WO2010038743A1 - Solid polymer material - Google Patents

Abstract

Disclosed is a solid polymer material comprising an ultraviolet absorber composition that comprises at least one ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and at least one ultraviolet absorber (B) having a maximum absorption wavelength of less than 360 nm.  The mass ratio of the ultraviolet absorber (A) to the ultraviolet absorber (B) is in the range of 1 : 1 to 1 : 100, and the ultraviolet absorber (A) is an auxiliary component.  The solid polymer material has a light transmittance of not more than 10% at 370 nm and not less than 70% at 410 nm.

Description

Solid polymer material

The present invention relates to a solid polymer material, and more particularly to a solid polymer material containing an ultraviolet absorber composition.

In addition to the purpose of preventing deterioration of the polymer material used as a base material, the UV absorber is used for the purpose of preventing deterioration of the contents due to UV light by using a polymer material containing the UV absorber as an UV cut filter. Is done. These UV cut filters can be used to protect the contents of packaging materials such as foods and pharmaceuticals, and as filters for plasma displays to protect infrared absorbers and pigments. It has been studied to be used for protecting dyes as a filter for dye-sensitized solar cells.

In such applications, polyester is often used as a substrate, and a method of blending an ultraviolet absorber is taken. If a large amount of UV absorber is blended in order to improve the cut performance of the UV cut filter, sublimation or decomposition of the UV absorber will occur during film formation, which will contaminate equipment such as molding rolls. May lead to decline.
Furthermore, there arises a problem that the ultraviolet absorber bleeds out on the film surface after film formation.
For such sublimation or decomposition, it has been shown that an ultraviolet absorber having a specific structure is used, but actually, contamination of equipment due to sublimation cannot be completely prevented (for example, Patent Document 1). And 2 etc.). Further, in order to prevent bleed out, it has been shown that a laminated polyester film is used. There is a need for a simple and effective method for reducing such sublimation and bleed out.

Also, the demand to cut to the long wave region of the ultraviolet region is increasing due to reasons such as protecting high-performance pigments, maintaining high weather resistance, and protecting the human body from harmful ultraviolet rays. Increasing the amount of UV absorber used can further cut the long wave region, but sublimation and bleed out are likely to occur, and yellowness becomes a problem. There is a demand for a method of cutting to a long wave region without increasing the amount of the ultraviolet absorber.

JP 2004-202899 A JP 2005-346999 A JP 2004-10875 A

The present invention provides an ultraviolet absorber composition capable of reducing the total amount of the ultraviolet absorber without reducing the ultraviolet shielding performance, reducing bleed out, and further reducing volatilization of the ultraviolet absorber in the film process. It is an object of the present invention to provide a solid polymer material containing the above.

As a result of detailed examination of compounds having absorption in the ultraviolet region, the present inventors have used ultraviolet absorbers having a specific structure having a maximum absorption wavelength at 360 to 400 nm as an auxiliary, so that the ultraviolet shielding performance is improved. It has been found that the total amount of the UV absorber can be reduced without dropping, reducing the bleed-out, and further reducing the volatilization of the UV absorber in the film process. The present invention has been made based on such findings.

According to the present invention, the following means are provided:
<1> An ultraviolet absorber composition comprising at least one ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and at least one ultraviolet absorber (B) having a maximum absorption wavelength of less than 360 nm. And the ratio of the ultraviolet absorber (A) to the ultraviolet absorber (B) is in the range of 1: 1 to 1: 100 by mass ratio, and the ultraviolet absorber (A) is used as an auxiliary. A solid polymer material having a light transmittance of 10% or less at 370 nm and 70% or more at 410 nm.
<2> The solid polymer material according to <1>, wherein the light transmittance is 5% or less at 370 nm and 70% or more at 410 nm.
<3> The solid polymer material according to <1> or <2>, wherein the ultraviolet absorber (B) is a benzotriazole, triazine, benzoxazinone, or benzophenone.
<4> The solid polymer material according to any one of <1> to <3>, wherein the ultraviolet absorber (A) is an ultraviolet absorber comprising a compound represented by the following general formula (1): .

[Het ¹ represents a divalent 5-membered or 6-membered aromatic heterocyclic residue. The aromatic heterocyclic residue may have a substituent.
X ^a , X ^b , X ^c and X ^d each independently represent a hetero atom. X ^a to X ^d may have a substituent.
Y ^a , Y ^b , Y ^c , Y ^d , Y ^e and Y ^f each independently represent a hetero atom or a carbon atom. Y ^a to Y ^f may have a substituent.
The ring bonded to Het ¹ may have a double bond at any position. ]
<5> In the general formula (1), a ring formed by X ^a , X ^b , Y ^a , Y ^b , Y ^c and a carbon atom, and X ^c , X ^d , Y ^d , Y ^e , Y ^f and carbon The solid polymer material according to <4>, wherein at least one of the rings formed by atoms is condensed.
<6> In the general formula (1), a ring formed by X ^a , X ^b , Y ^a , Y ^b , Y ^c and a carbon atom, and X ^c , X ^d , Y ^d , Y ^e , Y ^f and carbon The solid polymer material according to <4> or <5>, wherein at least one of the rings formed by the atoms is not a perimidine ring.
<7> The solid polymer material according to any one of <4> to <6>, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[Het ² is synonymous with Het ^{1 in the} general formula (1).
X ^2a , X ^2b , X ^2c and X ^2d have the same ^meanings as X ^a , X ^b , X ^c and X ^{d in the} general formula (1), respectively.
Y ^2b , Y ^2c , Y ^2e and Y ^2f have the same ^meanings as Y ^b , Y ^c , Y ^e and Y ^{f in the} general formula (1), respectively.
L ¹ and L ² each independently represent an oxygen atom, a sulfur atom or ═NR ^a (R ^a represents ^a hydrogen atom or a monovalent substituent).
Z ¹ and Z ² each independently represents an atomic group necessary for forming a ^4- to 8-membered ring together with Y ^2b and Y ^2c or Y ^2e and Y ^2f . ]
<8> The solid polymer material according to <7>, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

[Het ³ is synonymous with Het ^{2 in the} general formula (2).
X ^3a , X ^3b , X ^3c and X ^3d have the same ^meanings as X ^2a , X ^2b , X ^2c and X ^{2d in the} general formula (2), respectively.
R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g and R ^3h each independently represent a hydrogen atom or a monovalent substituent. ]
<9> The solid polymer material according to <8>, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).

[Het ⁴ is synonymous with Het ^{3 in the} general formula (3).
R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g and R ^4h are R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^{3f in the} general formula (3), respectively. , R ^3g and R ^3h . ]
<10> The solid polymer material according to <9>, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

[R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g and R ^5h are R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R in the general formula (4), respectively. It is synonymous with ^4f , ^R4g and ^R4h . R ⁵ⁱ and R ^5j each independently represent a hydrogen atom or a monovalent substituent. ]
<11> A film comprising the solid polymer material according to any one of <1> to <10>.

The solid polymer material of the present invention can maintain the ultraviolet shielding performance even when the total amount of the ultraviolet absorber used is reduced, can suppress the film haze due to bleed out, and further reduces the volatilization of the ultraviolet absorber. It can be kept low and contamination of equipment due to volatilization of the UV absorber in the film process can be prevented.

The above and other features and advantages of the present invention will become more apparent from the following description.

The solid polymer material of the present invention comprises an ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and an ultraviolet absorber (B) having a maximum absorption wavelength of less than 360 nm. Contains an agent composition. Preferably, the number of ultraviolet absorbers (A) is two or less, and the case where only one type is particularly preferred. The number of ultraviolet absorbers (B) is preferably two or less, and particularly preferably one.

The solution for confirming the spectral absorption maximum wavelength is obtained by dissolving the ultraviolet absorbers (A) and (B) using an organic or inorganic solvent or water alone or a mixture thereof.
Examples of the organic solvent include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane), sulfoxide solvents (for example, dimethyl sulfoxide). Ureido solvents (eg tetramethylurea), ether solvents (eg dioxane, tetrahydrofuran, cyclopentylmethyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene, n-decane), Halogen solvents (eg, tetrachloroethane, chlorobenzene, chloronaphthalene), alcohol solvents (eg, methanol, ethanol, isopropyl alcohol, ethylene glycol, cyclohexanol, phenol), pyridi Solvent (eg pyridine, γ-picoline, 2,6-lutidine), ester solvent (eg ethyl acetate, butyl acetate), carboxylic acid solvent (eg acetic acid, propionic acid), nitrile solvent (eg acetonitrile), sulfone An acid solvent (for example, methanesulfonic acid), an amine solvent (for example, triethylamine, tributylamine), or the like can be used.
As the inorganic solvent, for example, sulfuric acid, phosphoric acid and the like can be used.

From the solubility point of the ultraviolet absorbers (A) and (B), an amide solvent, a sulfone solvent, a sulfoxide solvent, a ureido solvent, an ether solvent, a ketone solvent, a halogen solvent, a hydrocarbon solvent, Alcohol solvents, ester solvents, or nitrile solvents are preferred.

The concentration of the ultraviolet absorbers (A) and (B) for measurement is not particularly limited as long as the maximum wavelength of spectral absorption can be confirmed, and preferably 1 × 10 ⁻⁷ to 1 × 10 ¹³ mol / L. Range.
The temperature for measurement is not particularly limited, and is preferably 0 ° C. to 80 ° C.
The spectral absorption measurement device is not particularly limited, and an ordinary spectral absorption measurement device (for example, U-4100 spectrophotometer, trade name, manufactured by Hitachi High-Technologies Corporation) can be used.

The mixing ratio of the ultraviolet absorber (A) and the ultraviolet absorber (B) is 1: 1 to 1: 100, and the ultraviolet absorber (A) is used as an auxiliary. The ratio is preferably 1: 2 to 1:50, more preferably 1: 3 to 1:25. In this case, the mixing ratio is expressed as a mass ratio. By setting it within this range, it is further excellent in manufacturing suitability, and further, it is possible to obtain a desired transmittance at a predetermined absorption wavelength. For example, by containing an appropriate amount of the ultraviolet absorber (B), the transmittance at a wavelength of 370 nm is suitably obtained. This is preferable because it can be suppressed. Here, “auxiliary used” means that the ultraviolet absorber (B) is mainly used, and the ultraviolet absorber (A) is used in the same amount or less. is there.

First, the ultraviolet absorber (A) will be described in detail. The ultraviolet absorber (A) is an ultraviolet absorber having a maximum absorption wavelength of 360 to 400 nm, and is preferably an ultraviolet absorber made of the compound represented by the general formula (1).
In the general formula (1), Het ¹ represents a divalent 5-membered or 6-membered aromatic heterocyclic residue having at least one heteroatom. Het ¹ may be condensed.
Examples of the hetero atom include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. A hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. More preferably, they are a nitrogen atom and a sulfur atom. Particularly preferred is a sulfur atom. When two or more hetero atoms are present, they may be the same atom or different atoms.
Examples of the aromatic heterocyclic ring in which two hydrogen atoms are added to a divalent aromatic heterocyclic residue include pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine, Examples include pyrimidine, pyrazine, 1,3,5-triazine, furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,3,4-thiadiazole and the like. Preferred examples of the aromatic heterocycle include pyrrole, pyridine, furan and thiophene. More preferred are pyridine and thiophene. Particularly preferred is thiophene. Any position for removing the hydrogen atom of the aromatic heterocycle may be used. For example, the bonding positions in the hetero 5-membered ring compound pyrrole include the 2,3-position, 2,4-position, 2,5-position, 3,4-position, and 3,5-position. In addition, the bonding positions in the hetero 6-membered ring compound pyridine include the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 position and 3,6 position. It is done.

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

X ^a , X ^b , X ^c and X ^d each independently represent a hetero atom. Examples of the hetero atom include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. A hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. More preferably, they are a nitrogen atom and an oxygen atom. X ^a to X ^d may have a substituent. Examples of the substituent include the examples of the monovalent substituent R described above.

Y ^a , Y ^b , Y ^c , Y ^d , Y ^e and Y ^f each independently represent a hetero atom or a carbon atom. Examples of the atoms constituting Y ^a to Y ^f include a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. The atoms constituting Y ^a to Y ^f are preferably a carbon atom, a nitrogen atom and an oxygen atom, and more preferably a carbon atom and a nitrogen atom. More preferred is a carbon atom, and particularly preferred is a case where all represent a carbon atom. In addition, the atoms may be substituted, may be bonded with each other to form a ring, and may further be condensed. Examples of the substituent include the examples of the monovalent substituent R described above. The ring bonded to Het ¹ may have a double bond at any position.

The ring formed by X ^a , X ^b , Y ^a to Y ^c and a carbon atom, and the ring formed by X ^c , X ^d , Y ^d to Y ^f and a carbon atom (represented by Het ¹ above) At least one of the two rings bonded to the aromatic heterocyclic residue is preferably condensed. Moreover, it is preferable that at least one of the two rings is not a perimidine ring.

In Tables 1 to 6 below, the ring formed by X ^a , X ^b , Y ^a to Y ^c and the carbon atom is A, the aromatic heterocyclic residue represented by Het ¹ is Het, Specific examples of each ring are shown with B being a ring formed by X ^c , X ^d , Y ^d to Y ^f and a carbon atom.

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

Het ² has the same meaning as Het ^{1 in the} general formula (1). The same applies to the preferred case.

X ^2a , X ^2b , X ^2c and X ^2d are the same as X ^a , X ^b , X ^c and X ^{d in the} general formula (1), respectively, and are the same when preferred. X ^2a , X ^2b , X ^2c and X ^2d may be different from each other, but it is more preferable that X ^2a and X ^2b , and X ^2c and X ^2d each represent the same combination, particularly preferably X ^{In this case, 2a} and X ^2c represent an oxygen atom, and X ^2b and X ^2d represent a nitrogen atom.

Y ^2b , Y ^2c , Y ^2e and Y ^2f have the same ^meanings as Y ^b , Y ^c , Y ^e and Y ^{f in the} general formula (1), respectively. The same applies to the preferred case.

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

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

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

Het ³ has the same meaning as Het ^{2 in the} general formula (2). The same applies to the preferred case.

X ^3a , X ^3b , X ^3c and X ^3d have the same ^meanings as X ^2a , X ^2b , X ^2c and X ^{2d in the} general formula (2), respectively, and are the same when preferred. X ^3a , X ^3b , X ^3c and X ^3d may be different from each other, but it is more preferable that X ^3a and X ^3b , and X ^3c and X ^3d each represent the same combination, particularly preferably X ^{In this case, 3a} and X ^3c represent an oxygen atom, and X ^3b and X ^3d represent a nitrogen atom.

R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g and R ^3h each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent include the examples of the monovalent substituent R described above. Any two substituents of R ^3a to R ^3d and R ^3e to R ^3h may be bonded to each other to form a ring, and may further be condensed. R ^3a to R ^3h are preferably a hydrogen atom, an alkyl group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, or a hydroxy group, and more preferably a hydrogen atom or an alkoxy group having 10 or less carbon atoms. More preferred is a hydrogen atom, and particularly preferred is a case where all of R ^3a to R ^3h represent a hydrogen atom.

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

Het ⁴ has the same meaning as Het ^{3 in the} general formula (3). The same applies to the preferred case.

R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g and R ^4h are R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^{3f in the} general formula (3), respectively. , R ^3g and R ^3h . The same applies to the preferred case.

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

Het ⁵ has the same meaning as Het ^{4 in the} general formula (4). The same applies to the preferred case.

R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g and R ^5h are R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^{4f in the} general formula (4), respectively. , R ^4g and R ^4h . The same applies to the preferred case.

R ⁵ⁱ and R ^5j each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent R described above. R ⁵ⁱ and R ^5j may be bonded to each other to form a ring or may be further condensed. R ⁵ⁱ and R ^5j are preferably a hydrogen atom, an alkyl group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, and a hydroxy group, and more preferably a hydrogen atom and an alkoxy group having 10 or less carbon atoms. More preferred is a hydrogen atom, and particularly preferred is a case where R ⁵ⁱ and R ^5j both represent a hydrogen atom.

The compound represented by any one of the general formulas (1) to (5) can be synthesized by any method. For example, publicly known patent documents and non-patent documents, for example, the example of page 4 left 43rd line to right 8th line of JP-A-2000-264879, page 4 right column 5th line 30 to 30 of JP-A-2003-155375. It can be synthesized with reference to the example of the line, “Bioorganic & Medicinal Chemistry”, 2000, Vol. 8, pp. 2095-2103, “Bioorganic & Medicinal Chemistry Letters”, 2003, Vol. 13, pages 4077-4080. For example, Exemplified Compound (15) can be synthesized by reacting 3,5-pyrazole dicarbonyl dichloride with anthranilic acid. The exemplified compound (32) can be synthesized by reacting 2,5-thiophene dicarbonyl dichloride with 4,5-dimethoxyanthranilic acid.

Specific examples of the compound represented by any one of the general formulas (1) to (5) are shown below, but the present invention is not limited thereto.

The compound represented by any one of the general formulas (1) to (5) can take a tautomer depending on the structure and the environment in which the compound is placed. Although the present invention is described in one of representative forms, tautomers different from those described in the present invention are also included in the compounds used in the present invention.

The compound represented by any one of the general formulas (1) to (5) may contain an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.). Good.

A polymer containing the structure of the compound represented by any one of the general formulas (1) to (5) in the repeating unit can also be suitably used in the present invention. The polymer may be a homopolymer or a copolymer composed of two or more types of repeating units. Further, it may be a copolymer containing other repeating units. Incidentally, the polymer containing the ultraviolet absorber structure in the repeating unit is described in JP-B-1-53455, JP-A-61-189530, and European Patent No. 27242. The description of these patent documents can be referred to for the method of obtaining the polymer.

Next, the ultraviolet absorber (B) will be described in detail. The ultraviolet absorber (B) is an ultraviolet absorber having a maximum absorption wavelength of less than 360 nm. Preferably it is 355 nm or less, More preferably, it is 350 nm or less.

The ultraviolet absorber (B) may have any structure as long as it satisfies the condition that the maximum absorption wavelength is less than 360 nm. For example, benzotriazole, triazine, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, acrylate, benzoate oxalate diamide, form, known as UV absorber structure Examples include amidine-based compounds and benzoxazinone-based compounds. Of these, benzotriazole, triazine, benzophenone, dibenzoylmethane, formamidine, and benzoxazinone compounds are preferred, and benzotriazole, triazine, benzophenone, and benzoxazinone compounds are further preferred. preferable. Most preferred are benzoxazinone compounds. These UV absorbers are, for example, Fine Chemical, May 2004, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999) 96- 140 pages, supervised by Shinichi Daikatsu, “Development of Polymer Additives and Environmental Measures” (CMC Publishing Co., Ltd., 2003), pages 54-64, published by Technical Information Association, “Polymer degradation / discoloration mechanism and its stabilization "Technology-Know-how" (Technical Information Association, 2006).

The benzotriazole-based compound is preferably a compound having a maximum absorption wavelength of less than 360 nm and represented by any of the following general formulas (IIa) or (IIb). (IIa) and (IIb) will be described in detail.

[In the general formula (IIa),
R ₁₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.
R ₁₂ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
R ₁₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a —COOR ₁₄ group (wherein R ₁₄ 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 ₁₁ represents a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted cycloalkyl, or a substituted or unsubstituted aryl group.
R ₁₁ 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 ₁₁ 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 An atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, methyl or ethyl), a carbon number of 6 to 20 (preferably Is an aryl group having 6 to 10) (eg phenyl, naphthyl), cyano group, carboxyl group, alkoxycarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10) (eg methoxycarbonyl), 6 to 20 carbon atoms (preferably Is a 6-10) aryloxycarbonyl group (for example, phenoxycarbonyl), a substituted or unsubstituted alkyl group having 0 to 20 carbon atoms (preferably 0 to 10). Vamoyl group (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, acetyl), 6 to 20 carbon atoms (preferably 6 to 6 carbon atoms) 10) an arylcarbonyl group (for example, benzoyl), a nitro group, a substituted or unsubstituted amino group (for example, amino, dimethylamino, anilino) having 0 to 20 carbon atoms (preferably 0 to 10), a carbon number of 1 to 20 ( Preferably 1-10) acylamino groups (eg acetamide, ethoxycarbonylamino),

C 0-20 (preferably 0-10) sulfonamide group (eg methanesulfonamide), C 2-20 (preferably 2-10) imide group (eg succinimide, phthalimide), C 1-20 (Preferably 1 to 10) imino group (eg benzylideneamino), hydroxy group, alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10) (eg methoxy), 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) ), An aryloxy group (eg phenoxy), an acyloxy group having 1 to 20 carbon atoms (preferably 1 to 10) (eg acetoxy), an alkylsulfonyloxy group having 1 to 20 carbon atoms (preferably 1 to 10) (eg 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 (preferably 6 to 10) carbon atoms (for example, phenylthio), an alkylsulfonyl group having 1 to 20 (preferably 1 to 10) carbon atoms (for example, methanesulfonyl), Examples include arylsulfonyl groups having 6 to 20 carbon atoms (preferably 6 to 10) (for example, benzenesulfonyl), heterocyclic groups having 4 to 7 members (preferably 5 to 6 members), such as pyridyl and morpholino. Can do.

R ₁₂ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₁₂ 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 ₁₂ 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 ₁₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a —COOR ₁₄ group (wherein R ₁₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, Or a substituted or unsubstituted aryl group. R ₁₃ 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 ₁₄ group (where R ₁₄ 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 ₁₁ and R ₁₂ 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 the case where T ₂ is directly bonded to the benzene ring without passing through L, that is, the 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 the general formula (a), m1 to m5 represent an integer of 0 to 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 preferred 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 —L—, —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 substituent —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, and 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 Combinations of ˜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—. Also preferred are combinations that are O— or —NH—CO—C ₃ H ₆ —CO—NH—.

Representative examples of the compound represented by the general formula (IIa) or (IIb) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-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'-Ok Ruoxyphenyl) benzotriazole, 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidylmethyl) -5′-methylbenzyl) phenyl) benzotriazole, 2- (3 ′ -Sec-butyl-5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis- (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3′-tert-butyl-5 ′-[ 2- (2-Ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-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) carbonyl] Ethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5) '-(2-Isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethyl Rubutyl) -6-benzotriazol-2-ylphenol], 2- [3′-t-butyl-5 ′-(2-methoxycarbonylethyl) -2′-hydroxyphenyl] -2H-benzotriazole and polyethylene glycol 300 Transesterification product with

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-3'-(1,1,3,3-tetramethylbutyl) -5 ' -(Α, α-dimethylbenzyl) -phenyl] benzotriazole and the like.

The triazine compound is preferably a compound having a maximum absorption wavelength of less than 360 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 ) _mf1 − (Lf ₂ ) _mf2 − (Lf ₃ ) _mf3 − (Lf ₄ ) _mf4 − (Lf ₅ ) _mf5 −

In the general formula (b), mf1 to mf5 represent an integer of 0 to 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 preferred 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 above-mentioned 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 is 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 —.

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-dimethylpheny ) -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-Butyloxypro Xyl) 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- Me Toxiphenyl) -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 a maximum absorption wavelength of less than 360 nm is preferable, and a compound represented by the following general formula (IVa) or (IVb) is preferable.

[In the general formula (IVa), X ₁ and X ₂ are independently of each other 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 ₁ 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 ₃ 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 ₃ represents a divalent substituent. ]

(General formula (IVa))
X ₁ and X ₂ 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 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 is represented. X ₁ and X ₂ 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, 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 ₁ and X ₂ 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 ₁ is 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 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 ₁ 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 substitution 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 ₁ 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 the 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 preferred 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 ₃ 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 ₃ 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 ₃ 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 ₃ represents a divalent substituent.
When tb is 2, specific examples of X ₃ 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 —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 ₁ 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 ₃ 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 A combination of an alkoxy 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 is preferable.

When tb is 2,
X ₁ 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 ₃ 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- -Diethylamino-2'-hexyloxycarbonylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Examples include benzophenone and 1,4-bis (4-benzyloxy-3-hydroxyphenoxy) butane.

The benzoxazinone compound is preferably a compound having a maximum absorption wavelength of less than 360 nm and represented by the following general formula (V).

(In the general formula (V), R ₁ represents a substituent, n ₁ represents an integer of 0 to 4, R ₂ represents an n ₂ valent substituent or linking group, and n ₂ represents 1 to 4) Represents an integer.)

In the general formula (V), R ₁ represents a substituent, and examples of the substituent are those exemplified as the substituent of the alkyl part of the above-mentioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group. The same thing is mentioned. R ₁ is preferably a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl 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 group, amino group, acylamino group, 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, aryl group Sicarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably halogen atom, alkyl group, aryl group, cyano group Group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryl Oxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfini Group, alkyl or arylsulfonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably halogen atom, alkyl group, aryl group, A hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an alkyl or an arylsulfonyl group, and more preferably a halogen atom or an alkyl group An aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group, more preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Group, 6 to 20 carbon atoms An aryloxy group, an alkylthio group having 1 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms, more preferably a chlorine atom, a fluorine atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, or a 6 to 10 carbon atoms. An aryl group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and an arylthio group having 6 to 10 carbon atoms, more preferably a chlorine atom or a fluorine atom An atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

n ₁ is preferably 0 to 3, more preferably 0 to 2, further preferably 0 or 1, and most preferably 0, that is, the benzene ring has no substituent.

R ₂ represents an n ₂ -valent substituent or linking group, and examples of the substituent include those of the alkyl moiety of the above-mentioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group. The same thing is mentioned. The linking group is one in which the substituent further has one or more bonds. R ₂ is preferably an aliphatic group, an aromatic group, and a linking group further having a bond, and more preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and these are divalent to tetravalent. A linking group, more preferably an alkyl group, an alkenyl group, an aryl group, and a linking group in which these are divalent to trivalent, more preferably an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, and a linking group in which these are divalent to trivalent, more preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 6 to 6 carbon atoms. 12 aryl groups, and these are divalent to trivalent linking groups, more preferably alkyl groups having 1 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, and continuous groups that are divalent to trivalent. More preferably methyl, ethyl, propyl, butyl, isopropyl, 2-butyl, benzyl, phenyl, 2-naphthyl, ethylene, trimethylene, 1,2-propylene, tetramethylene, 1,2-phenylene, 1, 3-phenylene, 1,4-phenylene, 2,6-naphthylene, and benzene-1,3,5-yl, more preferably methyl, ethyl, benzyl, phenyl, ethylene, trimethylene, 1,3-phenylene, 1 , 4-phenylene, benzene-1,3,5-yl, more preferably ethylene, trimethylene, 1,3-phenylene, 1,4-phenylene, benzene-1,3,5-yl, most preferably Is 1,4-phenylene.

n ₂ is preferably 1 to 3, more preferably 2 to 3, and most preferably 2.

As a representative example of the benzoxazinone compound, 2,2 '-(p-phenylene) di-3,1-benzoxazin-4-one can be given.

The salicylic acid compound is preferably a compound having a maximum absorption wavelength of about 290 to 330 nm, and representative 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 a maximum absorption wavelength of about 270 to 350 nm, and representative 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'-diph Nylacryloyl) oxy) -2,2-bis (((2′-cyano-3,3′-diphenylacryloyl) oxy) methyl) propane, N- (2-carbomethoxy-2-cyanovinyl) -2-methylindoline Etc.

The oxalic acid diamide compound preferably has a maximum absorption wavelength of about 250 to 350 nm. Typical examples thereof include 4,4′-dioctyloxyoxanilide, 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-t-butyl-2'-ethyloxanilide, 2-ethoxy-2'-ethyl-5,4'-di-t-butyloxa Nilide etc. can be mentioned.

The ultraviolet absorber (B) is particularly preferably a compound selected from the following compound group B. Compound group B is a group consisting of the following compounds (II-1) to (V-1).

[1] Compound (II-1) represented by the general formula (IIa) 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole (II-2) 2- ( 3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (II-3) 2- (2-hydroxy-5-t-octylphenyl) benzotriazole (II-4) 2-ethylhexyl -3- [3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (II-5) 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol (II-6) 2- (2H-benzotriazol-2-yl) -3-tert-butylphenol (II-7) 2- (2H-benzotriazo Ru-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1-3,3-tetramethylbutyl) phenol (II-8) 2- (2H-benzotriazole-2 -Yl) -3-methylphenol (II-9) 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol

[2] Compound (II-10) represented by the above general formula (IIb) 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3- Tetramethylbutyl) phenol]

[3] Compound (III-1) represented by the above general formula (III) 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3 , 5-triazine (III-2) 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine (III-3) 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl-4,6-bis ( 2,4-Dimethylphenyl) -1,3,5-triazine (III-4) 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol (III- 5) Bisethylhexyloxyphenol Triazine

[4] Compound (IV-1) represented by the above general formula (IV) Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate (IV-2) 2,2′-hydroxy-4,4′- Dimethoxybenzophenone (IV-3) 2-hydroxy-4-methoxybenzophenone (IV-4) 1,4-bis (4-benzoyl-3-hydroxyphenoxy) butane (IV-5) 2-hydroxy-4-octoxybenzophenone (IV-6) 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (IV-7) 2,2 ′, 4,4′-tetrahydroxybenzophenone

[5] Compound (V-1) represented by the general formula (V) 2,2 ′-(p-phenylene) di-3,1-benzoxazin-4-one

Compound (II-1) has the following structure, and is commercially available as trade name Tinuvin 328 (manufactured by Ciba Specialty Chemicals).
Compound (II-2) has the following structure, and is commercially available as trade name Tinuvin 326 (manufactured by Ciba Specialty Chemicals).
Compound (II-3) has the following structure, and is commercially available as trade name Tinuvin 329 (manufactured by Ciba Specialty Chemicals).
Compound (II-4) has the following structure, and is commercially available as trade name Tinuvin 109 (manufactured by Ciba Specialty Chemicals).
Compound (II-5) has the following structure and is commercially available as trade name Tinuvin 171 (manufactured by Ciba Specialty Chemicals).
Compound (II-6) has the following structure, and is commercially available as trade name Tinuvin PS (manufactured by Ciba Specialty Chemicals).
Compound (II-7) has the following structure, and is commercially available as trade name Tinuvin 928 (manufactured by Ciba Specialty Chemicals).
Compound (II-8) has the following structure, and is commercially available as trade name Tinuvin P (manufactured by Ciba Specialty Chemicals).
Compound (II-9) has the following structure, and is commercially available as trade name Tinuvin 234 (manufactured by Ciba Specialty Chemicals).
Compound (II-10) has the following structure, and is commercially available as trade name Tinuvin 360 (manufactured by Ciba Specialty Chemicals).

Compound (III-1) has the following structure, and is commercially available as trade name Tinuvin 460 (manufactured by Ciba Specialty Chemicals).
Compound (III-2) has the following structure, and is commercially available as trade name Cyasorb UV-116 (manufactured by Cytec).
Compound (III-3) has the structure shown below and is commercially available as trade name Tinuvin 405 (manufactured by Ciba Specialty Chemicals).
Compound (III-4) has the following structure, and is commercially available as trade name Tinuvin 1577 (manufactured by Ciba Specialty Chemicals).
Compound (III-5) has the following structure, and is commercially available as trade name Tinosorb S (manufactured by Ciba Specialty Chemicals).

Compound (IV-1) has the following structure, and is commercially available as trade name Uvinul A plus (manufactured by BASF).
Compound (IV-2) has the following structure, and is commercially available as trade name Uvinul 3049 (manufactured by BASF).
Compound (IV-3) has the following structure, and is commercially available as trade name Visorb 110 (manufactured by Kyodo Yakuhin Co., Ltd.).
Compound (IV-4) has the following structure, and is commercially available as trade name Seesorb 151 (manufactured by Cypro Kasei Co., Ltd.).
Compound (IV-5) has the following structure, and is commercially available as trade name Chimassorb 81 (manufactured by Ciba Specialty Chemicals).
Compound (IV-6) has the following structure, and is commercially available as trade name Uvinul MS40 (manufactured by BASF).
Compound (IV-7) has the following structure, and is commercially available as trade name Uvinul 3050 (manufactured by BASF).
Compound (V-1) has the structure shown below, and is commercially available as trade name Siasorb UV-3638 (manufactured by Cytec Industries).

In the present specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The alkyl group may have a branch or may form a ring. The number of carbon atoms of the alkyl group is preferably 1-20, and more preferably 1-18. The alkyl part of the substituted alkyl group is the same as the above alkyl group. The alkenyl group may have a branch or may form a ring. The alkenyl group has preferably 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The alkynyl group may have a branch or may form a ring. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

Examples of the substituent of the alkyl part of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group include a halogen atom (eg, chlorine atom, bromine atom, iodine atom), alkyl group [straight chain, branched, cyclic Represents a substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo Including [2,2,2] octane-3-yl) and tricyclo structures with more ring structures It is intended to. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ],

Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2 2] is intended to encompass oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or 6 A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2 Methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetra Decanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituent having 2 to 30 carbon atoms or Unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N -Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) Substituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy groups (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) Carbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino groups (preferably amino groups, substituted or unsubstituted alkyls having 1 to 30 carbon atoms) An amino group, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino),

An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, Carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino having 2 to 30 carbon atoms) Groups such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino groups (preferably substituted with 7 to 30 carbon atoms) Or an unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), Alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino) , Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, Echi Thio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having a carbon number) 2-30 substituted or unsubstituted heterocyclic thio groups such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl groups (preferably substituted or unsubstituted sulfamoyl having 0 to 30 carbon atoms) Groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N ′ -Phenylcarbamoyl) sulfamoyl),

A sulfo group, an alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, etc. , P-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Base A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxy Carbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n Octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl) N- (methylsulfonyl) carbamoyl),

An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphini ), A phosphinyloxy group (preferably having 2 carbon atoms) 30 substituted or unsubstituted phosphinyloxy groups, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino groups (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Phosphinylamino groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethyl Silyl, phenyldimethylsilyl).

Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

Examples of the substituent of the aryl part of the substituted aralkyl group are the same as the examples of the substituent of the following substituted aryl group.

In the present specification, the aromatic group means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. The number of carbon atoms in the aromatic group is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 20. Among them, the aryl group is preferably phenyl or naphthyl, particularly preferably phenyl.

The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group are the same as those described above as examples of the substituent of the alkyl portion of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group.

In the present specification, the heterocyclic group preferably contains a 5-membered or 6-membered saturated or unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. Examples of heteroatoms of the heterocycle include B, N, O, S, Se and Te. Heteroatoms are preferably N, O and S. The heterocyclic ring preferably has a valence (monovalent) in which the carbon atom is free (the heterocyclic group is bonded at the carbon atom). The number of carbon atoms of the heterocyclic group is preferably 1 to 40, more preferably 1 to 30, and still more preferably 1 to 20. Examples of the saturated heterocyclic ring include a pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring and a 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring include imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, benzoselenazole ring, pyridine ring, pyrimidine ring and quinoline ring. The heterocyclic group may have a substituent. Examples of the substituent are the same as those described above as examples of the substituent of the alkyl portion of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group.

The ultraviolet absorbers (A) and (B) used in the present invention may be present alone, but may be linked to each other in advance or by forming a bond in the composition. Moreover, it is good also as a copolymer which makes a monomer by couple | bonding a polymeric group, respectively, and polymerizes this, and contains a ultraviolet absorber (A) and (B) in a unit structure. Another monomer to which the ultraviolet absorbers (A) and (B) are not bonded 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 solid polymer material of the present invention may further contain a light stabilizer and an antioxidant.
Preferable examples of the light stabilizer and the antioxidant include compounds described in JP-A No. 2004-117997. Specifically, compounds described in paragraphs [0071] to [0111] in the middle of p29 of JP-A No. 2004-117997 are preferable. A compound represented by general formula (TS-I), general formula (TS-II), general formula (TS-IV) or general formula (TS-V) described in paragraph [0072] is particularly preferable.

The solid polymer material of the present invention may contain any compound as appropriate as other components depending on the purpose, in addition to the ultraviolet absorbent composition comprising the ultraviolet absorbent (A) and the ultraviolet absorbent (B). it can.

When used with a thermoplastic resin, the ultraviolet absorber may be added during the polymerization process of the thermoplastic resin or may be added after the polymerization. When added in a molten state to the thermoplastic resin after polymerization, the ultraviolet absorber may be added alone or in a state dispersed in a solvent or the like. The solvent used at this time may be any solvent that does not deteriorate the resin to be kneaded and disperses the ultraviolet absorber.

Such melt mixing can be performed by adding an ultraviolet absorber at a temperature equal to or higher than the melting temperature of the polymer using a melt mixing facility such as a single screw or twin screw extruder. When the dispersion is used, it can be carried out by adding the dispersion under pressure and then removing the organic solvent.

The ultraviolet absorber may be added to the molten state of the thermoplastic resin during film formation and kneaded. This method is a preferable method because the deterioration of the thermoplastic resin can be suppressed by reducing the heat history.

In the case of a thermoplastic polymer capable of melt polymerization, for example, a thermoplastic polyester such as polyethylene terephthalate or polyethylene naphthalate, a dispersion of an ultraviolet absorber may be added before or during the polymerization. The ultraviolet absorber may be added alone or may be added in a state dispersed in a solvent in advance. The solvent in this case is preferably a polymer raw material. The polymerization reaction may be carried out according to the usual polymer polymerization conditions.

A thermoplastic resin containing an ultraviolet absorber at a relatively high concentration of 0.5 to 50% by mass obtained by the above method can be used as a master batch and further kneaded with a thermoplastic resin to which no ultraviolet absorber is added. A target ultraviolet absorber-containing polymer can be obtained.

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.

As a device for obtaining a dispersion of the ultraviolet absorbent composition, a high-speed stirring disperser having a large shearing force, a disperser giving high-intensity ultrasonic energy, or the like can be used. Specifically, there are a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic distortion ultrasonic generator, an emulsifying device having a Paulman whistle, and the like. A high-speed stirring type disperser preferable for use in the present invention is a high-speed rotation (500 to 15,000 rpm) in a liquid in which a main part such as a dissolver, polytron, homomixer, homoblender, ket mill, or jet agitator is dispersed. A dispersion machine of a type that preferably has a speed of 2,000 to 4,000 rpm. The high-speed agitating disperser that can be used in the present invention is also called a dissolver or a high-speed impeller disperser, and has a saw-tooth shape on a shaft that rotates at high speed as described in Japanese Patent Application Laid-Open No. 55-129136. It is also a preferable example to wear an impeller obtained by alternately bending the plates in the vertical direction.

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

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

The boiling point of the high-boiling organic solvent is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. The melting point of the high-boiling organic solvent is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower. Examples of the high-boiling organic solvent include phosphate ester, phosphonate ester, benzoate ester, phthalate ester, fatty acid ester, carbonate ester, amide, ether, halogenated hydrocarbon, alcohol and paraffin. Phosphate esters, phosphonate esters, phthalate esters, benzoate esters and fatty acid esters are preferred.
As for the method of adding the ultraviolet absorbent composition used in the present invention, JP-A-58-209735, JP-A-63-264748, JP-A-4-191851 and JP-A-8-272058, and British Patent No. 2016017A. You can refer to the specification.

In the present invention, an ultraviolet ray absorbing composition used in the present invention alone can provide a practically sufficient ultraviolet shielding effect, but a white pigment having a strong hiding power, such as titanium oxide, can be obtained when more stringency is required. May be used in combination. Further, 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 preference. For applications where transparency or white color is important, a fluorescent brightening agent may be used in combination. Examples of the optical brightener include those commercially available, 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 may be conveniently modified with other ester, ether, amine or silyl ether groups. These catalyst systems are usually named Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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

<3> Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / propylene Te-1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer, Ethylene / cycloolefin copolymers (eg ethylene / norbornene like COC (Cyclo-Olefin Copolymer)), ethylene / 1-olefin copolymers in which 1-olefins are 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, LLDP / EAA and alternating or random polyalkylene / carbon monoxide copolymers and their other polymers, for example mixtures of polyamide.

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

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

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

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

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

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

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

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

<7> Graft copolymer of aromatic vinyl monomer such as styrene or α-methylstyrene, eg styrene to polybutadiene, styrene to polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) to polybutadiene; Styrene, acrylonitrile and methyl methacrylate; styrene and maleic anhydride to polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide to polybutadiene; styrene and maleimide to polybutadiene; styrene and alkyl acrylate or methacrylate to polybutadiene; ethylene / propylene / dienter Styrene and acrylonitrile as polymer; polyalkyl acrylate Known as styrene and acrylonitrile to 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 with impact resistance improved with butylacrylate.

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

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

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

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

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

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

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

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

<18> Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or 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 acrylate, urethane acrylate or polyester acrylate.

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

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

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

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

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

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

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

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

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

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

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

The solid polymer material of the present invention may contain any of antioxidants, light stabilizers, processing stabilizers, anti-aging agents, compatibilizers and the like as necessary in addition to the above-described polymer substance and ultraviolet absorber composition. These additives may be appropriately contained.

The solid polymer material of the present invention uses the polymer substance. The solid polymer material of the present invention may be formed only from the polymer substance and the ultraviolet absorber composition, or may be formed by dissolving the polymer substance in an arbitrary solvent.

The solid polymer material of the present invention has a light transmittance of 10% or less at 370 nm and 70% or more at 410 nm. Preferably, it is 5% or less at 370 nm and 70% or more at 410 nm. More preferably, it is 1% or less at 370 nm and 70% or more at 410 nm. Although there is no particular lower limit at 370 nm, it is practical that it is 0.0001% or more. Moreover, although there is no upper limit in particular in 410 nm, it is practical that it is 98% or less. The measurement of light transmittance is not particularly limited. For example, a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation can be used.

The solid 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 and other cosmetics, sportswear, stockings, hats and other clothing textiles and fibers, curtains , Carpets, wallpaper and other home interior goods, plastic lenses, contact lenses, artificial eyes and other medical instruments, optical filters, prisms, mirrors, photo 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.

As the shape of the solid polymer material of the present invention, any shape such as 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, etc. It may be.

Since the solid polymer material of the present invention contains a composition comprising the ultraviolet absorbers (A) and (B), it has excellent light resistance (ultraviolet light fastness). No bleed out due to precipitation or long-term use. 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 solid polymer material of the present invention is used as an ultraviolet absorption filter or an ultraviolet absorption film, the polymer substance is preferably transparent. Examples of transparent polymer materials include cellulose esters (eg, diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, Polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic) Polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethyl methacrylate, syndiotactic polystyrene Emissions, polysulfone, polyether sulfone, polyether ketone, polyether 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 solid polymer material of the present invention will be described. The packaging material containing the solid polymer material of the present invention may be a packaging material made of any kind of polymer as long as it contains the ultraviolet absorbers (A) and (B). 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 solid polymer material 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 solid polymer material of the present invention may be, for example, a transparent packaging body described in JP-A-2004-51174, or, for example, a light-shielding packaging body described in JP-A-2006-224317. There may be.

The packaging material containing the solid polymer material of the present invention has not only ultraviolet shielding properties as described in, for example, JP-A-2001-26081 and JP-A-2005-305745, but also other performances. May be. For example, those having gas barrier properties described in 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.

The packaging material containing the solid polymer material of the present invention may be manufactured using any method. For example, a method of forming an ink layer described in JP-A-2006-130807, for example, a method of melt-extruding and laminating a resin containing an ultraviolet absorber described in JP-A-2001-323082 and JP-A-2005-305745 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 solid polymer material of the present invention will be described. The container containing the solid polymer material of the present invention may be a container made of any kind of polymer as long as it contains the ultraviolet absorbers (A) and (B). 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 use of the container containing the solid polymer material of the present invention may contain any foods, beverages, drugs, cosmetics, personal care products, shampoos and the like. For example, a liquid fuel storage container described in JP-A-5-139434, a golf ball container described in JP-A-7-289665, a food container described in JP-A-9-295664, and JP-A-2003-237825 Container, sake container described in JP-A-9-58687, drug-filled container described in JP-A-8-15507, beverage container described in JP-A-8-324572, JP-A-2006-298456 , A container for oily food described in JP-A-9-86570, a solution container for analytical reagent described in JP-A-9-113494, an instant noodle container described in JP-A-9-239910, and JP-A-11- No. 180474, JP-A 2002-68322, JP-A 2005-278678, light-resistant cosmetic container described in JP-A-11-276550, pharmaceutical container described in JP-A-11-290420 Containers for high-purity chemical liquids, containers for liquid agents described in JP-A-2001-106218, containers for ultraviolet curable inks described in JP-A-2005-178832, containers for WO04 / 93775 For example, the plastic ampules described on the frets.

The container made of the solid polymer material of the present invention has not only ultraviolet blocking properties as described in, for example, JP-A-5-305975 and JP-A-7-40954, but also has other performances. 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.

The container made of the solid polymer material of the present invention may be manufactured 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 film made of the solid polymer material of the present invention will be described. The coating film containing the solid polymer material of the present invention may be a coating film composed of any component as long as it contains the ultraviolet absorbers (A) and (B). 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 formed from a paint in which a main agent, a curing agent, a diluent, a leveling agent, a repellant, and the like are arbitrarily blended.

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. Furthermore, in addition to these components, a coating material containing a leveling agent such as an acrylic resin or a silicone resin, an anti-fogging agent such as a silicone type or an acrylic type, or the like as required can be used.

The use purpose of the coating film containing the solid polymer material of the present invention may be any application. The coating film containing the solid polymer material of the present invention can be formed by the following paint. 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 coating film containing the solid polymer material of the present invention is preferably formed under the following conditions. Generally, it is composed of a paint (including a transparent resin component as a main component) and an ultraviolet absorber, and preferably has a composition of more than 0% by mass and not more than 20% by mass with respect to the resin. The thickness at the time of application is preferably 2 to 1000 μm, more preferably 5 to 200 μm. The method of applying these paints is arbitrary, but there are a spray method, a dipping method, a roller coat method, a flow coater method, a flow coating method and the like. Drying after application varies depending on the paint components, but it is preferably performed at room temperature to 120 ° C for about 10 to 90 minutes.

The coating film containing the solid polymer material of the present invention is a coating film containing the ultraviolet absorbers (A) and (B), and is a coating film formed using a paint containing the ultraviolet absorber.

The solid polymer material of the present invention includes any form obtained by using ink. 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 ink contains the ultraviolet absorbers (A) and (B), and examples thereof include dye ink, pigment ink, water-based ink, and oil-based ink. Moreover, what is used for any use may be used. 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.

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

The solar cell cover including the solid polymer material of the present invention will be described. The solar cell applied in the present invention may be a solar cell comprising any type of element such as a crystalline silicon solar cell, an amorphous silicon solar cell, and a dye-sensitized solar cell. In crystalline silicon solar cells and amorphous silicon solar cells, a cover material is used as a protective member for imparting antifouling, impact resistance and durability as described in JP-A-2000-174296. 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 including the solid polymer material of the present invention may be made of any kind of polymer. For example, polyester described in JP-A-2006-310461, thermosetting transparent resin described in JP-A-2006-257144, α-olefin polymer described in JP-A-2006-210906, JP-A-2003-168814 Polypropylene described in the publication, polyethersulfone described in JP-A-2005-129713, acrylic resin described in JP-A-2004-227843, transparent fluororesin described in JP-A-2004-168057, etc. Can be mentioned.

The solar cell cover including the solid polymer material of the present invention may be manufactured by any method. For example, an ultraviolet absorbing layer described in JP-A-11-40833 may be formed, or layers containing respective ultraviolet absorbers described in JP-A-2005-129926 may be laminated, or JP2000-2000A may be laminated. May be contained in the resin of the filler layer described in JP-A-91611, or a film may be formed from a polymer containing an ultraviolet absorber described in JP-A-2005-346999.

The solar cell cover including the solid polymer material 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, transparent film 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 described in JP-A-10-287804, 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, Floor sheet described in JP-A-2001-159228, water droplet adhesion prevention and heat-ray blocking properties described in JP-A-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, and a hard coating-coated article 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 shrinkability for labels described in WO99 / 29490 pamphlet, JP-A-2004-352847 Film, fishing gear described in JP-A-2000-224942, microbead described in JP-A-8-208976, pre-coated metal plate described in JP-A-8-318592, JP-A-2005-504735 The thin film described in the above, the heat-shrinkable film described in JP-A-2005-105032, the label for in-mold molding described in JP-A-2005-37642, the projection screen described in JP-A-2005-55615, Kaihei 9-300537, JP 2000-25180, JP 2003-19776, 2005-74735 Decorative sheet described in the above, 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 of the bottle body described in JP-A-2006-298456, transparency evaluation, sensory test evaluation of bottle contents after exposure to ultraviolet rays using a xenon light source, JP-A-2000-238857 Evaluation of haze value after irradiation with xenon lamp described in JP-A-2006-224317, evaluation of haze value as halogen lamp light source described in JP-A-2006-224317, use of 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 include color difference after exposure using a sunshine weatherometer, evaluation of bending strength, evaluation of shading 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 coating applications is JIS-K5400, JIS-K5600-7-5: 1999, JIS-K5600-7-6: 2002, JIS-K5600-7-7: 1999, JIS-K5600 It can be evaluated by the method of -7-8: 1999, JIS-K8741 and a method based on this method. 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, the 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 No. 22300, density evaluation of printed matter using a xenon fade meter described in JP-A-2006-8811, 100W described in JP-A-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 the xenon fade meter exposure described in Japanese Patent Application Publication No. 11-199808 and Japanese Patent Application Publication No. 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.

Other evaluation methods can be evaluated by the methods of JIS-K7103 and ISO / DIS9050 and methods 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 evaluation of design changes, JP-A-2005-326761 Appearance visual evaluation after lighting exposure using the described metal lamp reflector, evaluation of light transmittance of bottle label described in JP 2002-189415 A, JP 2004-352847 A, JP 2003-19776 A 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, evaluation of 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.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

(Preparation of ultraviolet absorber-containing pellets A to C)
100 g of the exemplary compound (1) as an ultraviolet absorber was added to 1 kg of polyethylene terephthalate resin (PET), and the mixture was stirred for 1 hour with a stainless steel tumbler. This mixture was melt-mixed at 280 ° C. with a twin-screw kneading extrusion kneader to produce pellets A by a conventional method.
100 g of the exemplary compound (21) as an ultraviolet absorber was added to 1 kg of polyethylene terephthalate resin (PET), and the mixture was stirred with a stainless steel tumbler for 1 hour. This mixture was melt-mixed at 280 ° C. with a twin-screw kneading extrusion kneader to produce pellets B by a conventional method.
100 g of the exemplary compound (V-1) as an ultraviolet absorber was added to 1 kg of polyethylene terephthalate resin (PET), and the mixture was stirred with a stainless steel tumbler for 1 hour. This mixture was melt-mixed at 280 ° C. with a twin-screw kneading extrusion kneader to produce pellets C by a conventional method.
The exemplary compounds (1), (21) and (V-1) were measured for absorption spectra using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The maximum absorption wavelength was 375, respectively. 374 and 346 nm.

Example 1
Polyethylene terephthalate resin (PET), pellets A and pellets C are melted and mixed at 280 ° C. in a biaxial kneading extrusion kneader at a ratio of 98% by mass, 1% by mass, and 1% by mass, and an unstretched sheet by an injection molding machine. And biaxially stretching to obtain a film having a thickness of 100 μm.

Example 2
An injection molding machine in which polyethylene terephthalate resin (PET), pellets A, and pellets C were melt-mixed at 280 ° C. in a biaxial kneading extrusion kneader at a ratio of 97.2 mass%, 0.8 mass%, and 2 mass%. To make an unstretched sheet, and further biaxially stretched to obtain a film having a thickness of 100 μm.

Example 3
An injection molding machine in which polyethylene terephthalate resin (PET), pellets A, and pellets C are melt mixed at 280 ° C. with a biaxial kneading extrusion kneader at a ratio of 94.5% by mass, 0.5% by mass, and 5% by mass. To make an unstretched sheet, and further biaxially stretched to obtain a film having a thickness of 100 μm.

Example 4
Polyethylene terephthalate resin (PET), pellets B, and pellets C are melted and mixed at 280 ° C. in a biaxial kneading extrusion kneader at a ratio of 98% by mass, 1% by mass, and 1% by mass, and an unstretched sheet by an injection molding machine. And biaxially stretching to obtain a film having a thickness of 100 μm.

Example 5
An injection molding machine in which polyethylene terephthalate resin (PET), pellets B, and pellets C are melt-mixed at 280 ° C. in a biaxial kneading extrusion kneader at a ratio of 97.2 mass%, 0.8 mass%, and 2 mass%. To make an unstretched sheet, and further biaxially stretched to obtain a film having a thickness of 100 μm.

Comparative Example 1
Polyethylene terephthalate resin (PET) 90% by mass, pellet C 10% by mass in a biaxial kneading extrusion kneader melted and mixed at 280 ° C. to make an unstretched sheet with an injection molding machine, and further biaxially stretched to obtain a thickness A 100 μm film was obtained.

Table 7 shows a list of produced films.

<Evaluation>
(1) Ultraviolet shielding characteristics For a wavelength of 250 to 400 nm, a double beam spectrophotometer (U-2001, trade name, manufactured by Hitachi, Ltd.) is used to measure the transmittance, and the ultraviolet transmittance at a wavelength of 380 nm is defined as a shielding characteristic. did.
(2) The color tone (L ^* a ^* b ^* ) of one film sample was measured by a transmission method using a color tone spectral color difference meter (ZL-2000, trade name, manufactured by Nippon Denshoku).
(3) Haze change According to JIS K7136, the haze value of the film was measured using Nippon Denshoku Industries Co., Ltd. haze meter NDH2000 (brand name). Furthermore, the haze after heat-treating the film at 150 ° C. for 30 minutes was measured by the same method, the amount of change in haze value before and after the heat treatment was measured by the same method, and the amount of change in haze value before and after the heat treatment was evaluated.
Evaluation criteria A: Change in haze value ≦ 1.0%
○: 1.0% <Haze value change ≦ 2.5%
X: 2.5% <Haze value change amount (4) Volatility After heating 100 g of each film at 280 ° C. for 30 minutes, the mass change was measured to determine the ease of volatilization of the UV absorber in the film process. .
(5) Light resistance Each film was irradiated with light with an illuminance of 170,000 lux with a xenon lamp (manufactured by Eagle Engineering), and the remaining amount of the ultraviolet absorbent after 50 hours was measured. The measurement was performed at 380 nm using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation.
Residual amount (%) = 100 × (100−transmittance after irradiation) / (100−transmittance before irradiation)
The results are shown in Table 8 below.

As is apparent from Table 8, the solid polymer materials (Examples 1 to 5) containing the composition composed of the ultraviolet absorbers (A) and (B) of the present invention contained the ultraviolet absorber (B) alone. Compared with the case of using (Comparative Example 1), the transmittance of 380 nm is the same level and the color tone is the same even though the total amount of UV absorber used is reduced by 45 to 80% by mass. It was a level. From this, it was found that the solid polymer material of the present invention has the same ultraviolet shielding performance even when the total amount of ultraviolet absorber used is reduced.
The change in film haze after heating represents the ease of bleeding out, but the rate of change in Examples 1 to 5 was lower than that in Comparative Example 1. From this, it was found that the solid polymer material of the present invention can keep the film haze due to bleed out low.
Further, the volatility of Examples 1 to 5 is significantly lower than that of Comparative Example 1, and the solid polymer material of the present invention can suppress the volatilization of the UV absorber when heated at 280 ° C. I understood it.

From the above results, the solid polymer material containing the ultraviolet absorbent composition according to the present invention has the same ultraviolet shielding performance even when the total amount of ultraviolet absorbent used is reduced, and the film haze caused by bleed-out As a result, it was found that the volatility of the UV absorber was also kept low.

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

This application claims priority based on Japanese Patent Application No. 2008-253715 filed in Japan on September 30, 2008, which is hereby incorporated herein by reference. Capture as part.

Claims (11)

1. An ultraviolet absorber composition comprising at least one ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and at least one ultraviolet absorber (B) having a maximum absorption wavelength of less than 360 nm; The ratio of the ultraviolet absorber (A) to the ultraviolet absorber (B) is in the range of 1: 1 to 1: 100 by mass ratio, and the solid absorber to which the ultraviolet absorber (A) is used as a supplement is used. A solid polymer material which is a molecular material and has a light transmittance of 10% or less at 370 nm and 70% or more at 410 nm.
2. The solid polymer material according to claim 1, wherein the light transmittance is 5% or less at 370 nm and 70% or more at 410 nm.
3. The solid polymer material according to claim 1 or 2, wherein the ultraviolet absorber (B) is benzotriazole, triazine, benzoxazinone, or benzophenone.
4. The solid polymer material according to any one of claims 1 to 3, wherein the ultraviolet absorber (A) is an ultraviolet absorber comprising a compound represented by the following general formula (1).
   

   

   [Het ¹ represents a divalent 5-membered or 6-membered aromatic heterocyclic residue. The aromatic heterocyclic residue may have a substituent.
   X ^a , X ^b , X ^c and X ^d each independently represent a hetero atom. X ^a to X ^d may have a substituent.
   Y ^a , Y ^b , Y ^c , Y ^d , Y ^e and Y ^f each independently represent a hetero atom or a carbon atom. Y ^a to Y ^f may have a substituent.
   The ring bonded to Het ¹ may have a double bond at any position. ]
5. In the general formula (1), a ring formed by X ^a , X ^b , Y ^a , Y ^b , Y ^c and a carbon atom, and X ^c , X ^d , Y ^d , Y ^e , Y ^f and a carbon atom are formed. The solid polymer material according to claim 4, wherein at least one of the rings to be condensed is condensed.
6. In the general formula (1), a ring formed by X ^a , X ^b , Y ^a , Y ^b , Y ^c and a carbon atom, and X ^c , X ^d , Y ^d , Y ^e , Y ^f and a carbon atom are formed. The solid polymer material according to claim 4 or 5, wherein at least one of the rings formed is not a perimidine ring.
7. The solid polymer material according to any one of claims 4 to 6, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
   

   

   [Het ² is synonymous with Het ^{1 in the} general formula (1).
   X ^2a , X ^2b , X ^2c and X ^2d have the same ^meanings as X ^a , X ^b , X ^c and X ^{d in the} general formula (1), respectively.
   Y ^2b , Y ^2c , Y ^2e and Y ^2f have the same ^meanings as Y ^b , Y ^c , Y ^e and Y ^{f in the} general formula (1), respectively.
   L ¹ and L ² each independently represent an oxygen atom, a sulfur atom or ═NR ^a (R ^a represents ^a hydrogen atom or a monovalent substituent).
   Z ¹ and Z ² each independently represents an atomic group necessary for forming a ^4- to 8-membered ring together with Y ^2b and Y ^2c or Y ^2e and Y ^2f . ]
8. The solid polymer material according to claim 7, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).
   

   

   [Het ³ is synonymous with Het ^{2 in the} general formula (2).
   X ^3a , X ^3b , X ^3c and X ^3d have the same ^meanings as X ^2a , X ^2b , X ^2c and X ^{2d in the} general formula (2), respectively.
   R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g and R ^3h each independently represent a hydrogen atom or a monovalent substituent. ]
9. The solid polymer material according to claim 8, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).
   

   

   [Het ⁴ is synonymous with Het ^{3 in the} general formula (3).
   R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g and R ^4h are R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^{3f in the} general formula (3), respectively. , R ^3g and R ^3h . ]
10. The solid polymer material according to claim 9, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).
    

    

    [R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g and R ^5h are R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R in the general formula (4), respectively. It is synonymous with ^4f , ^R4g and ^R4h . R ⁵ⁱ and R ^5j each independently represent a hydrogen atom or a monovalent substituent. ]
11. A film comprising the solid polymer material according to any one of claims 1 to 10.