JP2009209343A - Ultraviolet ray absorbent and composition comprising the same - Google Patents

Abstract

［Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、互いに独立して水素原子または１価の置換基を表す。Ｒ^５及びＲ^６は、互いに独立して水素原子または１価の置換基を表す。Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は、互いに独立してヘテロ原子を表す。］
【選択図】なしA long-wave ultraviolet absorbing ability that not only improves the ultraviolet light durability of a common polymer material but also can suppress the decomposition of other unstable compounds by using the polymer material as an ultraviolet filter. The present invention provides a robust ultraviolet absorber that maintains a long-term.
An ultraviolet absorber having a molecular weight of 1000 or less and a molar extinction coefficient at a maximum absorption wavelength of 80000 or more, and an ultraviolet absorber comprising a compound represented by the following general formula (I).

[R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent. R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. X ¹ , X ² , X ³ and X ⁴ each independently represent a hetero atom. ]
[Selection figure] None

Description

  The present invention relates to an ultraviolet absorber and a composition containing the same.

Conventionally, ultraviolet absorbers have been imparted by sharing ultraviolet absorbers with various resins. An inorganic ultraviolet absorber and an organic ultraviolet absorber may be used as the ultraviolet absorber. Inorganic ultraviolet absorbers (see, for example, Patent Documents 1 to 3) are excellent in durability such as weather resistance and heat resistance, but are selected because the absorption wavelength is determined by the band gap of the compound. There is little degree of freedom, and there is nothing that can absorb the long wave ultraviolet (UV-A) region around 400 nm, and those that absorb the long wave ultraviolet rays have absorption up to the visible region, and are therefore colored.
On the other hand, since the organic ultraviolet absorber has a high degree of freedom in the structural design of the absorbent, it is possible to obtain various absorption wavelengths by devising the structure of the absorbent.

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

In contrast, benzophenone and benzotriazole UV absorbers have relatively good light resistance, and can be cut relatively clearly up to a long wavelength region by increasing the concentration and film thickness (see, for example, Patent Documents 6 and 7). .) However, when these ultraviolet absorbers are usually mixed and applied in a resin or the like, the film thickness is limited to about several tens of μm. When cutting to a long wavelength region with this film thickness, it is necessary to add an ultraviolet absorber at a considerably high concentration. However, there has been a problem that simply adding to a high concentration causes precipitation of ultraviolet absorbers and bleeding out due to long-term use. In addition, some benzophenone and benzotriazole ultraviolet absorbers have skin irritation properties and accumulation properties in the living body, and careful attention is required for use.
JP-A-5-339033 JP-A-5-345639 JP-A-6-56466 JP-A-6-145387 JP 2003-177235 A JP-A-2005-517787 JP-A-7-285927

  The object of the present invention is to solve the above-mentioned problems, not only to improve the ultraviolet light durability of the polymer material to be shared, but also to stabilize the other by using the polymer material as an ultraviolet filter. An object of the present invention is to provide an ultraviolet absorber capable of suppressing the decomposition of a compound and maintaining a long-wave ultraviolet absorbing ability without precipitation or bleed out for a long period of time.

  In the development of ultraviolet absorbers, the inventors have focused on heterocyclic compounds and repeated synthesis and evaluation in detail, and as a result, a single molecule that does not have multiple ultraviolet absorption structures and has a large molar extinction coefficient. It has been found that the above-mentioned problems can be solved by using it, and a novel heterocyclic compound having a specific structure having high light fastness that satisfies such physical properties and excellent in long-wave ultraviolet absorption ability has been found, and the present invention has been completed. It was.

［Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、互いに独立して水素原子または１価の置換基を表す。Ｒ^５及びＲ^６は、互いに独立して水素原子または１価の置換基を表す。Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は、互いに独立してヘテロ原子を表す。］
［７］前記一般式（Ｉ）におけるＲ^５及びＲ^６が、互いに独立してアルコキシ基、アリールオキシ基、アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、カルバモイルオキシ基、アミノ基、アシルアミノ基またはカルバモイルアミノ基であることを特徴とする、［６］項に記載の紫外線吸収剤。
［８］前記一般式（Ｉ）におけるＲ^１、Ｒ^２、Ｒ^３及びＲ^４のうち少なくとも１つが、ハメットの置換基定数σｐ値が０．２以上の置換基であることを特徴とする、［６］又は［７］項に記載の紫外線吸収剤。
［９］前記一般式（Ｉ）におけるＲ^１、Ｒ^２、Ｒ^３及びＲ^４のうち少なくとも１つが、シアノ基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルカルボニル基、アリールカルボニル基、アルキルスルホニル基またはアリールスルホニル基であることを特徴とする、［６］〜［８］のいずれか１項に記載の紫外線吸収剤。
［１０］前記一般式（Ｉ）におけるＸ^１、Ｘ^２、Ｘ^３及びＸ^４が硫黄原子であることを特徴とする、［６］〜［９］のいずれか１項に記載の紫外線吸収剤。
［１１］Ｒ^１とＲ^２との組及びＲ^３とＲ^４の組の少なくとも一方が環を形成しないことを特徴とする［６］〜［１０］のいずれか１項に記載の紫外線吸収剤。
［１２］Ｒ^１とＲ^２との組及びＲ^３とＲ^４の組のいずれも環を形成しないことを特徴とする［６］〜［１１］のいずれか１項に記載の紫外線吸収剤。
［１３］前記一般式（Ｉ）におけるＲ^１、Ｒ^２、Ｒ^３及びＲ^４のうち少なくとも１つが、炭素数６以上のアルコキシカルボニル基であることを特徴とする、［６］〜［１２］のいずれか１項に記載の紫外線吸収剤。
［１４］前記一般式（Ｉ）におけるＲ^５及びＲ^６が、炭素数２以上のアルコキシ基であることを特徴とする、［６］〜［１３］のいずれか１項に記載の紫外線吸収剤。
［１５］［１］〜［１４］のいずれか１項に記載の紫外線吸収剤を含む組成物。
［１６］［１］〜［１５］のいずれか１項に記載の紫外線吸収剤と高分子物質からなることを特徴とする高分子組成物。 The object of the present invention has been achieved by the following method.
[1] An ultraviolet absorber having a molecular weight of 1,000 or less and a molar extinction coefficient at a maximum absorption wavelength of 75,000 or more.
[2] The ultraviolet absorbent according to item [1], wherein the molecular weight is 350 or more and 950 or less, and the molar absorption coefficient at the maximum absorption wavelength is 78000 or more and 120,000 or less.
[3] The ultraviolet absorber according to the item [1] or [2], wherein the maximum absorption wavelength is 360 nm or more and the full width at half maximum is 60 nm or less.
[4] The ultraviolet absorbent according to any one of [1] to [3], wherein the maximum absorption wavelength is 370 nm or more and the half width is 10 nm or more and 45 nm or less.
[5] The ultraviolet absorber according to any one of [1] to [4], which is composed of a compound in which two heterocycles are condensed to one benzene ring.
[6] The ultraviolet absorbent according to item [5], comprising a compound represented by the following general formula (I).

[R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent. R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. X ¹ , X ² , X ³ and X ⁴ each independently represent a hetero atom. ]
[7] R ⁵ and R ⁶ in the general formula (I) are each independently an alkoxy group, aryloxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, amino group, acylamino The ultraviolet absorber according to item [6], which is a group or a carbamoylamino group.
[8] At least one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (I) is a substituent having a Hammett's substituent constant σp value of 0.2 or more, The ultraviolet absorber as described in the item [6] or [7].
[9] At least one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (I) is a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, The ultraviolet absorber according to any one of [6] to [8], which is an alkylsulfonyl group or an arylsulfonyl group.
[10] The ultraviolet absorber according to any one of [6] to [9], wherein X ¹ , X ² , X ³ and X ⁴ in the general formula (I) are sulfur atoms. .
[11] The ultraviolet absorber according to any one of [6] to [10], wherein at least one of the group of R ¹ and R ² and the group of R ³ and R ⁴ does not form a ring. .
[12] The ultraviolet absorber according to any one of [6] to [11], wherein neither the group of R ¹ and R ² nor the group of R ³ and R ⁴ forms a ring.
[13] At least one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (I) is an alkoxycarbonyl group having 6 or more carbon atoms, [6] to [12] The ultraviolet absorber of any one of these.
[14] The ultraviolet absorber according to any one of [6] to [13], wherein R ⁵ and R ⁶ in the general formula (I) are an alkoxy group having 2 or more carbon atoms. .
[15] A composition comprising the ultraviolet absorber according to any one of [1] to [14].
[16] A polymer composition comprising the ultraviolet absorber according to any one of [1] to [15] and a polymer substance.

In addition, compounds similar to the structure of the ultraviolet absorber of the present invention (for example, those in which R ¹ , R ² , R ³ and R ⁴ are all alkylthio groups in the general formula (I)) are, for example, charge transfer complexes Although it has been known for a long time as its structure, its usefulness as an ultraviolet absorber has not been reported. Further, the compound represented by the general formula (I) in which two heterocycles are condensed to a benzene ring is an analogous compound in which one heterocycle is condensed to a benzene ring (for example, Japanese Patent Publication No. SHO 49-11155). The molar extinction coefficient ε is more than twice that of the compound described in (1), that is, it is out of the relationship where it is considered that the ultraviolet absorption effect can be obtained simply by doubling the number of heterocycles. It was impossible to imagine that the compound represented by the general formula (I) exhibited excellent performance as an ultraviolet absorber.

Since the ultraviolet absorber satisfying the above physical properties of the present invention has a large molar extinction coefficient per molecular weight, a sufficient ultraviolet shielding effect can be obtained only by using a small amount. The benzotriazole compound and the triazine compound, which are general-purpose ultraviolet absorbers, have a great merit compared to the molar extinction coefficients of about 20,000 and about 60,000, respectively.
In addition, the ultraviolet absorbent comprising the compound represented by the general formula (I) of the present invention has an excellent effect of providing high light fastness, a high molar extinction coefficient ε and sharp absorption. The ultraviolet absorber of the present invention can be used as a composition, and the light stability of the polymer molded product can be enhanced by incorporating the ultraviolet absorber of the present invention into a polymer molded product such as plastic or fiber. .
Furthermore, the polymer material containing the ultraviolet absorbent according to the present invention can be used as a filter or a container for protecting contents that are sensitive to ultraviolet rays by utilizing the excellent ultraviolet absorbing ability.

Hereinafter, the present invention will be described in detail.
The ultraviolet absorbent according to the present invention has a molecular weight of 1,000 or less and a molar extinction coefficient at a maximum absorption wavelength of 75,000 or more. Since an ultraviolet absorber satisfying this physical property has a large molar extinction coefficient per molecular weight, a sufficient ultraviolet shielding effect can be obtained only by using a small amount.

  In order to obtain a large ultraviolet absorption effect only by using a small amount of the ultraviolet absorber, it is desirable that the light absorption of the ultraviolet absorber is large. As described in “Chemistry Seminar 9 Color Chemistry” by Sumio Tokita (Maruzen, 1982), pages 154 to 155, the intensity of light absorption, that is, the oscillator strength, is proportional to the integral of the molar extinction coefficient. The molar extinction coefficient is a value proportional to the square of the transition moment. Since the transition moment is expressed as a function of the distance vector as described in "Functional pigments" written by Shin Okawara, Ken Matsuoka, Tsuneaki Hirashima, Junjiro Kitao (Kodansha Scientific, 1992), Since a short wave absorbing compound composed of a short conjugated system has a small transition moment, light absorption is generally smaller as a short wave absorbing compound. In fact, the molar absorption coefficient at the maximum absorption wavelength of a general ultraviolet absorber is only about 1 to 30,000 for benzophenone and benzotriazole.

Further, the molar extinction coefficient at the maximum absorption wavelength varies depending on the shape of the absorption spectrum. That is, even if the light absorption is the same, the molar extinction coefficient differs between a sharp spectrum and a broad spectrum. In order to obtain a large molar extinction coefficient, a sharp spectrum, that is, a spectrum having a small half width is desirable. Moreover, since the ultraviolet absorber which gives a broad spectrum has absorption also in a wide region from the maximum absorption wavelength to the long wave side, the half width is small in order to effectively shield the long wave ultraviolet region without yellowish coloring. A UV absorber having a spectrum is preferred.
The molar extinction coefficient in the present invention is a desirable value as a physical property of the ultraviolet absorber, but is a value in a range that could not be reached so far.

  The molar extinction coefficient at the maximum absorption wavelength is more preferably 78,000 to 150,000, further preferably 85,000 to 120,000, and particularly preferably 90000 to 110,000.

  The full width at half maximum is preferably 60 nm or less, more preferably 50 nm or less, and further preferably 45 nm or less.

  It should be noted that the maximum absorption wavelength and the full width at half maximum defined in the present invention can be easily measured by those skilled in the art. The measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectroscopy II” (Maruzen, 1992), pages 180 to 186, edited by the Chemical Society of Japan. Specifically, the sample is dissolved in an appropriate solvent, and measured by a spectrophotometer using a cell made of quartz or glass and two cells for sample and control. The solvent to be used is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in addition to the solubility of the sample. Any solvent that satisfies the above conditions can be selected. In the present invention, measurement is performed using ethyl acetate (EtOAc) as a solvent.

The maximum absorption wavelength and half-value width of the dye in the present invention are values measured using a quartz cell having an optical path length of 10 mm by preparing a solution having a concentration of about 5 × 10 ⁻⁵ mol · dm ^{−3 using} ethyl acetate as a solvent. Is used.
The half width of the spectrum is described in, for example, “The Fourth Edition Experimental Chemistry Course 3 Basic Operation III” (Maruzen, 1991), page 154, edited by the Chemical Society of Japan. In the above-mentioned book, the half-value width is explained using an example in which the horizontal axis is taken on the wave number scale, but the half-value width in the present invention is the value obtained when taking the axis on the wavelength scale, The unit is nm. Specifically, it represents the width of an absorption band that is ½ of the absorbance at the maximum absorption wavelength, and is used as a value that represents the shape of the absorption spectrum.

  As an ultraviolet absorber having a large molar extinction coefficient, for example, it has a plurality of ultraviolet absorbing structures in one molecule such as a polymerized ultraviolet absorber described in JP-T-2006-526671 and JP-A-2007-507567. In some cases, it becomes an ultraviolet absorber having an apparent molar absorption coefficient. At the same time, however, the molecular weight has increased, so the extinction coefficient per UV absorber structure has not changed, and the low volatility effect of polymerization can be expected, but the problem of increased use has been solved. Absent.

  Although a smaller molecular weight is preferable, a minimum molecular structure is necessary as an ultraviolet absorber having desired performance. In the present invention, it has been found that a molecular weight of 1000 or less is sufficient in consideration of the molecular weight necessary for giving preferable physical properties from the molecular weight of an existing ultraviolet absorber. The molecular weight is more preferably 350 or more and 950 or less, further preferably 400 or more and 930 or less, and particularly preferably 500 or more and 910 or less.

  In addition, the molecular weight of the benzotriazole type compound which is a general purpose ultraviolet absorber is about 300, and the molar extinction coefficient is about 20,000. The molecular weight of the triazine compound is about 600, and the molar extinction coefficient is about 60,000. The relationship between the molecular weight defined by the present invention and the molar extinction coefficient at the maximum absorption wavelength cannot be achieved by combining conventional UV absorbers, but can be achieved for the first time by a novel UV absorber skeleton. it can.

The ultraviolet absorber of the present invention comprises the compound represented by the general formula (I).
In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, methyl, Ethyl), an aryl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenyl or naphthyl), a cyano group, a carboxyl group, or an alkoxycarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methoxy). Carbonyl), an aryloxycarbonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenoxycarbonyl), a substituted or unsubstituted carbamoyl group having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms) (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkyl having 1 to 20 carbon atoms (preferably 1 to 10) A sulfonyl group (for example, acetyl), an arylcarbonyl group having 6 to 20 (preferably 6 to 10) carbon atoms (for example, benzoyl), a nitro group, a substituted or unsubstituted amino group having 0 to 20 (preferably 0 to 10) carbon atoms Group (for example, amino, dimethylamino, anilino), acylamino group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, acetamido, ethoxycarbonylamino), sulfonamide having 0 to 20 carbon atoms (preferably 0 to 10) Group (for example, methanesulfonamide), imide group having 2 to 20 carbon atoms (preferably 2 to 10) (for example, succinimide, phthalimide), imino group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, benzylideneamino) , Hydroxy group, alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, methoxy), carbon An aryloxy group having 6 to 20 (preferably 6 to 10) aryloxy group (for example, phenoxy), an acyloxy group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, acetoxy), and 1 to 20 carbon atoms (preferably 1 to 1). 10) alkylsulfonyloxy group (for example, methanesulfonyloxy), arylsulfonyloxy group (for example, benzenesulfonyloxy) having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), sulfo group, and 0 to 20 carbon atoms (preferably 0). To 10) substituted or unsubstituted sulfamoyl groups (for example, sulfamoyl, N-phenylsulfamoyl), C 1-20 (preferably 1-10) alkylthio groups (for example, methylthio), C 6-20 (preferably Is 6-10) arylthio group (eg phenylthio), 1-20 carbon atoms (preferably 1-10) Alkylsulfonyl group (for example, methanesulfonyl), arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, benzenesulfonyl), 4- to 7-membered ring (preferably 5 to 6-membered ring) heterocyclic group (For example, pyridyl, morpholino) and the like. Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. Further, the substituents may be bonded to each other to form a ring.

At least one of R ¹ , R ² , R ³ and R ⁴ preferably represents a substituent having a Hammett's substituent constant σp value of 0.2 or more.
Hammett's substituent constant σ value will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, J. et al. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill), “Areas of Chemistry”, No. 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195. The substituent having Hammett's substituent constant σp value of 0.2 or more in the present invention is an electron-attracting group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit of the σp value is not particularly limited, but is preferably 1.20 or less, and more preferably 1.00 or less.

Examples of substituents having Hammett's substituent constant σp value of 0.2 or more include a cyano group (0.66), a carboxyl group (—COOH: 0.45), and an alkoxycarbonyl group (—COOMe: 0.45). , Aryloxycarbonyl group (—COOPh: 0.44), carbamoyl group (—CONH ₂ : 0.36), alkylcarbonyl group (—COMe: 0.50), arylcarbonyl group (—COPh: 0.43), Examples include an alkylsulfonyl group (—SO ₂ Me: 0.72), an arylsulfonyl group (—SO ₂ Ph: 0.68), and the like. In the present specification, Me represents a methyl group, and Ph represents a phenyl group. The values in parentheses are the σp values of typical substituents in Chem. Rev. 1991, Vol. 91, pp. 165-195.

R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring. For example, when forming a ring with R ¹ and R ^2, it is not possible to define a σp value of R ¹ and R ^2, in the present invention the partial structure of each ring in R ¹ and R ² is substituted Assuming that the σp value in the case of ring formation is defined. For example, when a 1,3-indandione ring is formed, it is considered that R ¹ and R ² are each substituted with a benzoyl group. This is similarly defined even when a ring is formed by R ³ and R ⁴ .

At least one of R ¹ , R ² , R ³ and R ⁴ represents a substituent having a Hammett's substituent constant σp value of 0.2 or more, but a pair of R ¹ and R ² or R ³ and R ⁴ It is preferable that either one of the groups is a substituent. More preferably, ^three of R ¹ , R ² , R ³ and R ⁴ are this substituent. Particularly preferably, R ¹ , R ² , R ³ and R ⁴ are all the substituents.

At least one of R ¹ , R ² , R ³ and R ⁴ is more preferably —CN, —COOR ⁸ , —CONR ⁹ R ¹⁰ , —COR ¹¹ or —SO ₂ R ¹² (where, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom or a monovalent substituent). More preferred is —CN, —COOR ⁸ , —COR ¹¹ or —SO ₂ R ¹² . More preferred is -CN or -COOR ⁸ . Particularly preferred is -CN.
More preferably, at least one of R ¹ , R ² , R ³ and R ⁴ is an alkoxycarbonyl group having 6 or more carbon atoms. More preferably, it has 6 or more and 20 or less carbon atoms, and further preferably 6 or more and 12 or less carbon atoms. You may have a substituent in arbitrary positions on an alkoxy group. Examples of the substituent include those described above. Examples of the alkoxy group in the alkoxycarbonyl group include a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.

The combination of R ¹ and combination and ^{R 3} and ^{R 4} and ^{R 2} may be any combination satisfies the above conditions, the set and ^{R 3} and ^{R 4} in ^{R 1} and ^{R 2} More preferably, the sets are the same combination.

R ¹ and R ^{2 and} R ³ and R ⁴ may be bonded to each other to form a ring. The ring to be formed may be either a saturated or unsaturated hydrocarbon ring or a heterocyclic ring. However, a dithiol ring and a dithiolane ring are not formed. For example, as a ring containing a carbon atom to which R ¹ and R ² defined in the general formula (I) are bonded, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a pyrrolidine Ring, tetrahydrofuran ring, tetrahydrothiophene ring, oxazoline ring, thiazoline ring, pyrroline ring, pyrazolidine ring, pyrazoline ring, imidazolidine ring, imidazoline ring, piperidine ring, piperazine ring, pyran ring and the like. These may have a substituent at an arbitrary position. Examples of the substituent include the examples of the monovalent substituent described above. Examples of the divalent substituent include a carbonyl group and an imino group. When there are a plurality of substituents, they may be the same or different. Moreover, it may be a condensed ring or a spiro ring by bonding with substituents to form a ring.

Preferable examples of the combination of R ¹ and R ² or R ³ and R ⁴ are shown in the following Table 1, but the present invention is not limited thereto. In the present specification, Et represents an ethyl group, and Bu represents a butyl group. Me represents a methyl group, Ph represents a phenyl group, and Ac represents an acetyl group. The wavy line in the table indicates the binding site to the heterocycle in the general formula (I).

R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent described above.
Among them, hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylcarbonyl group, arylcarbonyl group, nitro group, amino group, acylamino group, sulfone Amide groups, hydroxy groups, alkoxy groups, aryloxy groups, acyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, sulfo groups, alkylthio groups, and arylthio groups are preferred. A hydrogen atom, a halogen atom, an amino group, an acylamino group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, and an arylthio group are more preferable. More preferred are an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acylamino group, a carbamoyloxy group, and a carbamoylamino group. An alkoxy group, an aryloxy group, and an acyloxy group are particularly preferable. An alkoxy group having 2 or more carbon atoms is particularly preferable.

  As an alkyl group in the case of an alkoxy group, a C1-C20 alkyl group is preferable, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group etc. are mentioned. A monovalent substituent may be present at any position on the alkyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. The alkyl group in the case of an alkoxy group is preferably an alkyl group having 3 to 20 carbon atoms. More preferably, it is a C5-C18 alkyl group. Particularly preferred is an alkyl group having 6 to 12 carbon atoms.

  In the case of an aryloxy group, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. A monovalent substituent may be present at any position on the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. The aryl group in the case of an aryloxy group is preferably an aryl group having 6 to 14 carbon atoms. More preferably, it is an aryl group having 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

  The acyl group in the case of an acyloxy group is preferably an acyl group having 1 to 20 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butanoyl group, a hexanoyl group, an octanoyl group, a benzoyl group, and a naphthoyl group. A monovalent substituent may be present at any position on the acyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. In the case of an acyloxy group, the acyl group is preferably an acyl group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 acyl group. Particularly preferred is an acyl group having 4 to 8 carbon atoms.

  The alkyl group in the case of the alkoxycarbonyloxy group is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group. A monovalent substituent may be present at any position on the alkyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. The alkyl group in the case of an alkoxycarbonyloxy group is preferably an alkyl group having 3 to 20 carbon atoms. More preferably, it is a C5-C18 alkyl group. Particularly preferred is an alkyl group having 6 to 12 carbon atoms.

  The aryl group in the case of the aryloxycarbonyloxy group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. A monovalent substituent may be present at any position on the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. The aryl group in the case of the aryloxycarbonyloxy group is preferably an aryl group having 6 to 14 carbon atoms. More preferably, it is an aryl group having 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

  The acyl group in the case of an acylamino group is preferably an acyl group having 1 to 20 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butanoyl group, a hexanoyl group, an octanoyl group, a benzoyl group, and a naphthoyl group. A monovalent substituent may be present at any position on the acyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. In the case of an acylamino group, the acyl group is preferably an acyl group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 acyl group. Particularly preferred is an acyl group having 4 to 8 carbon atoms.

  As the substituent on the nitrogen atom in the case of the carbamoyloxy group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are preferable. Examples thereof 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. The alkyl group and aryl group in the case of the carbamoyloxy group are preferably an alkyl group having 3 to 20 carbon atoms and an aryl group having 6 to 14 carbon atoms. More preferred are an alkyl group having 6 to 12 carbon atoms and an aryl group having 6 to 10 carbon atoms.

  As the substituent on the nitrogen atom in the case of the carbamoylamino group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are preferable. Examples thereof 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. The alkyl group and aryl group in the case of the carbamoylamino group are preferably an alkyl group having 3 to 20 carbon atoms and an aryl group having 6 to 14 carbon atoms. More preferred are an alkyl group having 6 to 12 carbon atoms and an aryl group having 6 to 10 carbon atoms.

R ⁵ and R ⁶ may be different from each other, but are preferably the same.

Preferable examples of R ⁵ or R ⁶ shown in Table 2 below, but the present invention is not limited thereto. In addition, the wavy line in a table | surface shows the coupling | bond part to the benzene ring in the said general formula (I).

X ¹ , X ² , X ³ and X ⁴ 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. Preferably, they are a nitrogen atom, an oxygen atom, and a sulfur atom. More preferably, they are a nitrogen atom and a sulfur atom. Particularly preferred is a sulfur atom.
X ¹ , X ² , X ³ and X ⁴ may be different from each other, but it is more preferable and particularly preferable that the set of X ¹ and X ² and the set of X ³ and X ⁴ are the same combination. Are all the same. Most preferably, all represent sulfur atoms.

Although it is shown in the following Table 3 for the combination of preferred embodiments of X ¹ and X ² or X ³ and X ^4, the present invention is not limited thereto. In the present specification, Ac represents an acetyl group. The wavy line in the table indicates the bonding site to the carbon atom to which R ¹ and R ² or R ³ and R ⁴ in general formula (I) are bonded.

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

In the general formula (Ia), R ^1a , R ^2a , R ^3a and R ^4a represent a monovalent substituent. However, at least one of R ^1a , R ^2a , R ^3a and R ^4a is a cyano group, an alkoxycarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), or 6 to 20 carbon atoms (preferably 6 to 6 carbon atoms). 10) aryloxycarbonyl group, carbamoyl group having 1 to 20 carbon atoms (preferably 1 to 10), alkylcarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), 6 to 20 carbon atoms (preferably 6 carbon atoms) 10) an arylcarbonyl group, a C1-C20 (preferably 1-10) alkylsulfonyl group or a C6-C20 (preferably 6-10) arylsulfonyl group.

Regarding the combination of (R ^1a , R ^2a ) and (R ^3a , R ^4a ), R ^1a , R ^2a , R ^3a and R ^4a may be a monovalent substituent in which at least one of these combinations does not form a ring. preferable. It is particularly preferable that (R ^1a , R ^2a ) and (R ^3a , R ^4a ) are monovalent substituents that do not form a ring in this combination. When a ring is not formed, there is an advantage that the long-wave ultraviolet absorption ability is excellent and yellowing of the compound itself can be suppressed. Further, as compared with the case of forming a ring, when no ring is formed, there is an advantage that the solubility in a solvent and the compatibility with a polymer are excellent.

  Specific examples of the monovalent substituent that does not form a ring in the present specification include a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methyl, ethyl), and 6 to 6 carbon atoms. 20 (preferably 6 to 10) aryl group (for example, phenyl, naphthyl), cyano group, C1-C20 (preferably 1-10) alkoxycarbonyl group (for example, methoxycarbonyl), C6-C20 (preferably Are 6 to 10) aryloxycarbonyl groups (for example, phenoxycarbonyl), substituted or unsubstituted carbamoyl groups (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethyl) having 1 to 20 carbon atoms (preferably 1 to 10). Carbamoyl), an alkylcarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (eg acetyl), 6 to 20 carbon atoms (preferably 6-10) arylcarbonyl group (for example, benzoyl), nitro group, substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms (preferably 0 to 10) (for example, sulfamoyl, N-phenylsulfamoyl), C1-C20 (preferably 1-10) alkylsulfonyl group (for example, methanesulfonyl), C6-C20 (preferably 6-10) arylsulfonyl group (for example, benzenesulfonyl), 4- to 7-membered ring ( Preferred examples thereof include 5- to 6-membered heterocyclic groups (for example, pyridyl and morpholino). Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different.

However, at least one of the monovalent substituents R ^1a , R ^2a , R ^3a and R ^4a is a cyano group, an alkoxycarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), and 6 to 20 carbon atoms. (Preferably 6-10) aryloxycarbonyl group, carbamoyl group having 1-20 carbon atoms (preferably 1-10), alkylcarbonyl group having 1-20 carbon atoms (preferably 1-10), 6-6 carbon atoms It is a 20 (preferably 6-10) arylcarbonyl group, a C1-C20 (preferably 1-10) alkylsulfonyl group, or a C6-C20 (preferably 6-10) arylsulfonyl group.

R ^1a , R ^2a , R ^3a and R ^4a are all a cyano group, an alkoxycarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), and an aryloxy group having 6 to 20 carbon atoms (preferably 6 to 10). Carbonyl group, C 1-20 (preferably 1-10) carbamoyl group, C 1-20 (preferably 1-10) alkylcarbonyl group, C 6-20 (preferably 6-10) aryl A substituent selected from a carbonyl group, an alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10) or an arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) is particularly preferable. More preferably, the combination of R ^1a and R ^2a and the combination of R ^3a and R ^4a are the same combination.

R ^5a and R ^6a are each an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10), an aryloxy group having 6 to 20 carbon atoms (preferably 6 to 10), and 1 to 20 carbon atoms (preferably 1 to 1 carbon atoms). 10) an acyloxy group, an alkoxycarbonyloxy group having 1 to 20 carbon atoms (preferably 1 to 10), an aryloxycarbonyloxy group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), and 1 to 20 carbon atoms (preferably Is a carbamoyloxy group having 1 to 10), an amino group having 0 to 20 (preferably 0 to 10) carbon atoms, an acylamino group having 1 to 20 (preferably 1 to 10) carbon atoms, and 1 to 20 carbon atoms (preferably 1-10) represents a carbamoylamino group.

R ^5a and R ^6a may further have a substituent. Examples of the substituent include the monovalent substituent described above. Examples of the divalent substituent include a carbonyl group and an imino group. When there are a plurality of substituents, they may be the same or different. Moreover, it may be a condensed ring or a spiro ring by bonding with substituents to form a ring.

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

The compound represented by the general formula (I) or (Ia) can be synthesized by any method. For example, a compound in which R ⁵ and R ⁶ in the general formula (I) are hydroxy intermediates is synthesized as a synthetic intermediate, synthesized by a reaction in which a desired substituent is introduced by alkylation or acylation. Can do.
The synthetic intermediate in which R ⁵ and R ⁶ in the general formula (I) are hydroxy groups, for example, when X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms, known patents and documents For example, Japanese Patent Application Laid-Open No. 63-225382 discloses a reference example on page 3 in the upper right column on the first line to the lower left column on the first line, Liebigs Ann. Chem., 1969, Vol. 726, pages 103-109, and can be synthesized with reference to page 109, lines 5 to 12 in the literature.
In addition, the compound represented by the general formula (I) is an experimental item from page 27, right column 27 of the Journal of Organic Chemistry, 1990, Vol. 55, pages 5347-5350, page 27, 1994, Volume 59, pages 3077-3081, page 3081, lines 11 to 16, Tetrahedron Letters, 1991, volume 32, pages 4897-4900, page 4897, line 9 to page 4899, line 3, 1977 Year 1, 26, 2225, Table 1, Tetrahedron, 1993, 49, 3035-3042, 3030 pages 11-20 and 3040 pages 22-38, Journal of the American Chemical Society, 1958, 80, 1662-1664, references 1664, right 6th to 15th line, 1995, 117, 9995-10002, reference 9996, right 12th to 9997 46th line on the left, 4th page, left 43th line to 45th right line of Japanese Patent Laid-Open No. 6-80672, Phosphorus, Sulfur, and Silicon, 1997, 120 & 121, 121-143 page 123 page 18th line Page 124 Third row, Chem. Commun., 2004, pp. 1758-1759, page 1758, left line 44-54, German Patent No. 3724852, page 4, line 46-5, page 16, line 16 100097 gazette, page 3 upper left row 3 to page 4, lower left row 4th row, Special Table Hei 5-506428 gazette page 12 lower right row 1 row to page 35 lower right row 1 row, etc. The compound can be synthesized with reference to the synthesis route of the compound having a similar structure.
Further, a bis (N, N-dialkyliminium) compound obtained by reacting a quinone with an N, N-dialkyldithiocarbamate salt (for example, a synthesis intermediate M-2 in Examples described later) is synthesized, It can also be synthesized by reacting an active methylene compound and a heterocyclic compound.

For example, the exemplary compound (1) is obtained by reacting disodium salt obtained by reacting carbon disulfide and malononitrile in the presence of sodium hydroxide with chloranil to synthesize a hydroquinone compound (synthetic intermediate B in Examples described later). It can be synthesized by reacting this with 2-ethylhexanoyl chloride in the presence of a base. The exemplified compound (2) can be synthesized by reacting a hydroquinone compound (synthesis intermediate B in Examples described later) and 2-ethylhexyl bromide in the presence of a base.
In addition, the hydroquinone compound (synthetic intermediate B in the examples described later) reacts 1,4-benzoquinone with potassium N, N-diethyldithiocarbamate to produce a bis (N, N-diethyliminium) compound (described later). It can also be synthesized by synthesizing the synthesis intermediate M-2) in the Examples and reacting it with malononitrile.
For example, Exemplified Compound (11) is obtained by reacting dipotassium salt obtained by reacting carbon disulfide and ethyl cyanoacetate in the presence of potassium hydroxide with chloranil to synthesize Exemplified Compound (72) and 2-ethylhexa It can be synthesized by reacting noyl chloride in the presence of a base. The exemplified compound (12) can be synthesized by reacting the exemplified compound (72) with 2-ethylhexyl bromide in the presence of a base.
The exemplified compound (72) can also be synthesized by reacting the synthetic intermediate M-2 and ethyl cyanoacetate in Examples described later.
The exemplified compound (59) can be synthesized by reacting a dipotassium salt obtained by reacting carbon disulfide and ethyl cyanoacetate in the presence of potassium hydroxide with hexafluorobenzene.
The exemplified compound (51) can be synthesized by reacting the exemplified compound (59) with sodium dodecanethiolate.

  The compound represented by the general formula (I) or (Ia) may take a tautomer depending on the structure and the environment in which the compound is placed. Although described in one of the representative forms in the present specification, tautomers different from those described in the present specification are also represented by the general formula (I) or (Ia) used in the present invention. Included in compounds.

  The compound represented by the general formula (I) or (Ia) can be a cation or an anion with an appropriate counter ion depending on the structure and the environment in which the compound is placed. In the present specification, hydrogen ions are used as counter cations and hydroxide ions are used as counter anions as representative counter ions, but the general formulas used in the present invention also have counter ions other than these. It is contained in the compound represented by (I) or (Ia). There may be one type of counter ion, or a plurality of types having an arbitrary ratio.

The compounds represented by the general formula (I) are in the positions where R ¹ and R ² , R ³ and R ⁴ , X ¹ and X ² , X ³ and X ⁴ or R ⁵ and R ⁶ are different from each other. Can be replaced by geometric isomers. Even if only one of these geometric isomers is described in the present specification, other geometric isomers are also represented by the general formula (I) or (Ia) used in the present invention. It is contained in the compound. In addition, even when a geometric isomer mixture is obtained in the process of synthesis or purification, only the typical structure is described in this specification. In the case of a geometric isomer mixture, the abundance ratio may be any ratio between 0: 1 and 1: 0.

The compound represented by the general formula (I) or (Ia) may contain an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.).

  A polymer containing the structure of the compound represented by the general formula (I) or (Ia) as a UV-absorbing group in a repeating unit can also be suitably used in the present invention. Below, the example of the repeating unit containing the structure of the compound represented by the said general formula (I) or (Ia) is shown.

  It may be a homopolymer composed of the above repeating units or a copolymer composed of two or more kinds of repeating units. Further, it may be a copolymer containing other repeating units. Examples of other repeating units are shown below.

  Regarding the polymer containing the ultraviolet absorber structure in the repeating unit, JP-B-1-53455, page 4, lower left line 12 to page 13, upper left line 3, JP-A-61-189530, line 3 There are descriptions in the upper right 13th line to the 6th page lower 12th line and the 3rd page 40th line to the 8th page 13th line of the European Patent 27242. The description of these patent documents can be referred to for the method of obtaining the polymer.

  Although the maximum absorption wavelength of the ultraviolet absorber of this invention is not specifically limited, Preferably it is 280-400 nm, More preferably, it is 320-390 nm.

  The ultraviolet absorber of the present invention is suitably used as a composition comprising the same. Examples of the composition include a dispersion, a solution, a mixture, and a coated product.

  The ultraviolet absorber of the present invention can be used in the state of a dispersion dispersed in a dispersion medium. Hereinafter, the dispersion containing the ultraviolet absorbent according to the present invention will be described.

  Any medium may be used for dispersing the ultraviolet absorbent according to the present invention. For example, water, an organic solvent, a resin, a resin solution and the like can be given. These may be used alone or in combination.

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

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

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

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

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

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

  The content of the ultraviolet absorber in the dispersion containing the ultraviolet absorber of the present invention varies depending on the purpose of use and the form of use and cannot be uniquely determined, but may be any concentration depending on the purpose of use. Good. Preferably it is 0.001-80 mass% with respect to the whole quantity of a dispersion, More preferably, it is 0.01-50 mass%.

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

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

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

  Moreover, the ultraviolet absorber of this invention can be used in the state of a mixture with arbitrary compounds. Hereinafter, the mixture containing the ultraviolet absorber of the present invention will be described.

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

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

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

The polymer substance used in the polymer composition will be described. The polymeric material is a natural or synthetic polymer or copolymer. For example, the following are mentioned.
<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 Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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

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

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

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

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

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

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

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

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

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

<7> Graft copolymer of aromatic vinyl monomer such as styrene or α-methylstyrene, for example, styrene to polybutadiene, styrene to polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) to polybutadiene; Styrene, acrylonitrile and methyl methacrylate; 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, Polymers of halogen-containing vinyl compounds in particular, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers Halogen-containing polymers such as

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

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

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

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

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

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

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

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

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

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

<19> Polycarbonate and polyester carbonate.

<20> Polyketone.

<21> Polysulfone, polyethersulfone and polyetherketone.

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

<23> Dry and non-dry alkyd resins.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The polymer material containing the ultraviolet absorbent according to the present invention may contain an antioxidant, a light stabilizer, a processing stabilizer, an anti-aging agent, a phase, if necessary, in addition to the above-described polymer substance and the ultraviolet absorbent according to the present invention. Arbitrary additives such as a solubilizer may be appropriately contained.

The compounds according to the invention are particularly suitable for stabilizing organic materials against damage by light, oxygen or heat. Among them, the compound of the present invention is most suitable for use as a light stabilizer, particularly an ultraviolet absorber. Hereafter, the use as a ultraviolet absorber of the compound of this invention is demonstrated.
What is stabilized by the ultraviolet absorber of the present invention includes dyes, pigments, foods, beverages, body care products, vitamins, pharmaceuticals, inks, oils, fats, waxes, surface coatings, cosmetics, photographic materials, textiles and the like Examples include pigments, plastic materials, rubber, paints, polymer materials, polymer additives, and the like.
When the ultraviolet absorbent according to the present invention is used, the mode thereof may be any method. Although the ultraviolet absorber of the present invention may be used alone or as a composition, it is preferably used as a composition. Especially, it is more preferable that it is a polymeric material containing the ultraviolet absorber of this invention. Hereinafter, the polymer material containing the ultraviolet absorbent according to the present invention will be described.

The polymer material containing the ultraviolet absorbent according to the present invention uses the polymer material. The polymer material containing the ultraviolet absorbent according to the present invention may be formed only from the polymer substance, or may be formed by dissolving the polymer substance in an arbitrary solvent.
The polymer material containing the ultraviolet absorbent according to the present invention can be used for all applications in which a synthetic resin is used, but can be particularly suitably used for applications that may be exposed to sunlight or light including ultraviolet rays. . Specific examples include, for example, glass substitutes and surface coating materials thereof, housing, facilities, window glass for transportation equipment, coating materials for daylighting glass and light source protection glass, housing, facilities, window films for transportation equipment, housing, Inner and outer coating materials for facilities, transportation equipment, etc., and coating films formed by the coatings, alkyd resin lacquer coatings and coatings formed by the coatings, acrylic lacquer coatings and coatings formed by the coatings, Components for light sources that emit ultraviolet rays such as fluorescent lamps and mercury lamps, precision machinery, components for electronic and electrical equipment, materials for shielding electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, bottles, boxes, Blister, cup, special packaging, compact disc coat, agricultural or industrial sheet or film material, printed matter, dyed matter, dyed face Anti-fading agents, protective films for polymer supports (eg for plastic parts such as machinery and automotive parts), printed overcoats, inkjet media coatings, laminated matte, optical light films, safety glass / front glass Intermediate layers, electrochromic / photochromic applications, overlaminate films, solar heat control films, sunscreen creams, shampoos, rinses, hairdressing cosmetics, sportswear, stockings, hats and other textile products for textiles, curtains, carpets, Home interior products such as wallpaper, plastic lenses, contact lenses, medical devices such as artificial eyes, optical filters, backlight display films, prisms, mirrors, optical materials such as photographic materials, mold films, transfer stickers, graffiti prevention Film, tape, ink, etc. Bogu, signs, marking plate, and a marking device such as a surface coating material or the like.

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

Two or more types of ultraviolet absorbers of the present invention having different structures may be used in combination, or one or more types of ultraviolet absorbers having other structures may be used in combination. When two types (preferably three types) of ultraviolet absorbers are used in combination, ultraviolet rays in a wide wavelength region can be absorbed. In addition, when two or more kinds of ultraviolet absorbers are used in combination, the dispersion state of the ultraviolet absorber is also stabilized. Any ultraviolet absorber having a structure other than the ultraviolet absorber of the present invention can be used. For example, supervised by Shinichi Daikatsu, “Development of Polymer Additives and Environmental Measures” (CMC Publishing, 2003) Chapter 2, edited by Toray Research Center Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999) 2.3.1, and the like. For example, triazine, benzotriazole, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, acrylate, benzoic acid ester oxalic acid diamide, etc., known as UV absorber structures Compounds. For example, Fine Chemical, May 2004 issue, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Junichi Okachi Supervised “Development of Polymer Additives and Environmental Measures” (CM Publishing, 2003), pages 54-64, etc.
Preferred are benzotriazole, benzophenone, salicylic acid, acrylate, and triazine compounds. More preferred are benzotriazole, benzophenone and triazine compounds. Particularly preferred are benzotriazole and triazine compounds.

  The benzotriazole-based compound is preferably a compound having an effective absorption wavelength of about 270 to 380 nm and represented by any one of the following general formulas (IIa), (IIb) or (IIc).

（式中、Ｒ_４及びＲ_５は、互いに独立して１〜５個の炭素原子を有するアルキルを表す。Ｒ_４は、Ｃ_ｎＨ_{２ｎ＋１−ｍ}基と一緒になって、５〜１２個の炭素原子を有するシクロアルキル基を形成してもよい。ｍは１又は２を表す。ｎは２〜２０の整数を表す。Ｍは、−ＣＯＯＲ_６（ここで、Ｒ_６は、水素原子、１〜１２個の炭素原子を有するアルキル、アルキル部分及びアルコキシ部分に１〜２０個の炭素原子を有するアルコキシアルキル、またはアルキル部分に１〜４個の炭素原子を有するフェニルアルキルである。）を表す。）
で表される基であり、 [In the general formula (IIa),
R ₁ is a hydrogen atom, alkyl having 1 to 24 carbon atoms, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, cycloalkyl having 5 to 8 carbon atoms, or the following general formula:

(Wherein R ₄ and R ₅ independently represent an alkyl having 1 to 5 carbon atoms. R ₄ together with the C _n H _{2n + 1-m} group represents 5 to 12 A cycloalkyl group having a carbon atom may be formed, m represents 1 or 2, n represents an integer of 2 to 20, M represents —COOR ₆ (where R ₆ represents a hydrogen atom, 1 Represents an alkyl having -12 carbon atoms, an alkoxyalkyl having 1-20 carbon atoms in the alkyl and alkoxy moieties, or a phenylalkyl having 1-4 carbon atoms in the alkyl moiety. )
A group represented by

R ₂ is a hydrogen atom, a halogen atom, an alkyl having 1 to 18 carbon atoms, and a phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety;
R ₃ is a hydrogen atom, a chlorine atom, an alkyl or alkoxy having 1 to 4 carbon atoms, or —COOR ₆ (wherein R ₆ is as defined above).
However, at least one of R ₁ and R ₂ is other than a hydrogen atom. ]

であり、
また、ｎが２のときＴ_２は、式：

、又は−Ｏ−Ｔ_９−Ｏ−の基である。 [In the general formula (IIb),
T is a hydrogen atom or alkyl having 1 to 6 carbon atoms,
T ₁ is a hydrogen atom, a chlorine atom, or an alkyl or alkoxy having 1 to 4 carbon atoms,
n is 1 or 2,
When n is 1, T ₂ is a chlorine atom, -OT ₃ , or a formula:

And
When n is 2, T ₂ is represented by the formula:

Or a group of —O—T ₉ —O—.

であり、 (Wherein T ₃ is a hydrogen atom, alkyl having 1 to 18 carbon atoms and unsubstituted or substituted by 1 to 3 hydroxyl groups or by —OCOT ₆ , 3 to 18 Alkyl having 1 carbon atom, a continuous carbon-carbon bond interrupted once or several times by —O— or —NT ₆ — and unsubstituted or substituted by hydroxyl or —OCOT ₆ Cycloalkyl having 5 to 12 carbon atoms and unsubstituted or substituted by hydroxyl and / or alkyl having 1 to 4 carbon atoms, having 2 to 18 carbon atoms And unsubstituted or substituted by hydroxyl, alkenyl, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, or- H ₂ CH (OH) -T ₇ or

And

T ₄ and T ₅ , independently of one another, are a hydrogen atom, an alkyl having 1 to 18 carbon atoms, a 3 to 18 carbon atoms, and a continuous carbon — by —O— or —NT ₆ —. Alkyl in which the carbon bond is interrupted once or several times, cycloalkyl having 5 to 12 carbon atoms, phenyl, phenyl substituted by alkyl having 1 to 4 carbon atoms, 3 to 8 carbon atoms An alkenyl having a phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, or a hydroxyalkyl having 2 to 4 carbon atoms,

T ₆ is a hydrogen atom, an alkyl having 1 to 18 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, an alkenyl having 3 to 8 carbon atoms, phenyl, 1 to 4 carbon atoms Phenyl substituted by alkyl having, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety;

T ₇ is a hydrogen atom, an alkyl having 1 to 18 carbon atoms, phenyl that is unsubstituted or substituted by hydroxyl, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, or —CH ₂ OT ₈ ,
T ₈ is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, phenyl, alkyl having 1 to 4 carbon atoms Phenyl substituted by or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety,

T ₉ is alkylene having 2 to 8 carbon atoms, alkenylene having 4 to 8 carbon atoms, alkynylene having 4 carbon atoms, cyclohexylene, having 2 to 8 carbon atoms and- Alkylene in which the continuous carbon-carbon bond is interrupted once or several times by O—, or —CH ₂ CH (OH) CH ₂ O—T ₁₁ —OCH ₂ CH (OH) CH ₂ —, or —CH ₂ — _{C (CH 2 OH) 2 -CH} 2 - and is,

T ₁₀ is alkylene having 2 to 20 carbon atoms and in which successive carbon-carbon bonds can be interrupted once or several times by —O—, or cyclohexylene,

T ₁₁ is an alkylene having 2 to 8 carbon atoms, an alkylene having 2 to 18 carbon atoms and in which a continuous carbon-carbon bond is interrupted once or several times by —O—, 1, 3 -Cyclohexylene, 1,4-cyclohexylene, 1,3-phenylene, or 1,4-phenylene, or T ₁₀ and T ₆ together with two nitrogen atoms form a piperazine ring. Become. ]]

[In the general formula (IIc), R _{'2 is} C 1 _{-C 12} alkyl and k is a number from 1 to 4. ]

（式中、Ｒ＝３’−ｔｅｒｔ−ブチル−４’−ヒドロキシ−５’−２Ｈ−ベンゾトリアゾール−２−イルフェニル、２−［２’−ヒドロキシ−３’−（α，α−ジメチルベンジル）−５’−（１，１，３，３−テトラメチルブチル）−フェニル］ベンゾトリアゾール；２−［２’−ヒドロキシ−３’−（１，１，３，３−テトラメチルブチル）−５’−（α，α−ジメチルベンジル）−フェニル］ベンゾトリアゾール等を挙げることができる。 Typical examples of the compound represented by any one of the general formulas (IIa) to (IIc) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5). '-T-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5 '-Di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-5 ′-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (2 ′ -Hydroxy Cis-4′-octyloxyphenyl) 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′-hydroxy Phenyl) benzotriazole, 2- (3′-t-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3′-t-butyl) -5 ′-[2- (2-ethylhexyloxy) -carbonylethyl] -2′-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3′-tert-butyl-2′-hydride) Roxy-5 ′-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3′-t-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl) benzo Triazole, 2- (3′-t-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3′-t-butyl-5 ′-[2- ( 2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-t-butyl- 2′-hydroxy-5 ′-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2′-methylene-bis [4- (1,1,3 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], 2- [3′-t-butyl-5 ′-(2-methoxycarbonylethyl) -2′-hydroxyphenyl] -2H-benzotriazole Transesterification product of styrene and polyethylene glycol 300;

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

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

[In the general formula (III),
u is 1 or 2, and r is an integer from 1 to 3,
Substituent Y ₁ is, independently of _one another, a hydrogen atom, hydroxyl, phenyl or halogen, halogenomethyl, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 18 carbon atoms, —COO— (C _{1- C18} alkyl) substituted with 1-18 carbon atoms.

when u is 1, Y ₂ is alkyl having 1 to 18 carbon atoms, unsubstituted or phenyl substituted by hydroxyl, halogen, alkyl having 1 to 18 carbon atoms or alkoxy;
Having 1 to 12 carbon atoms and —COOH, —COOY ₈ , —CONH ₂ , —CONHY ₉ , —CONY ₉ Y ₁₀ , —NH ₂ , —NHY ₉ , —NY ₉ Y ₁₀ , —NHCOY ₁₁ , Alkyl substituted by -CN and / or -OCOY ₁₁ ;
It has 4 to 20 carbon atoms, the continuous carbon-carbon bond is interrupted by one or more oxygen atoms and is unsubstituted or substituted by hydroxyl or alkoxy having 1 to 12 carbon atoms Alkyl, alkenyl having 3 to 6 carbon atoms, glycidyl, unsubstituted or cyclohexyl substituted with hydroxyl, alkyl having 1 to 4 carbon atoms and / or —OCOY ₁₁ , Phenylalkyl, —COY ₁₂ or —SO ₂ Y ₁₃ having 1 to 5 carbon atoms and unsubstituted or substituted by hydroxyl, chlorine and / or methyl.

Also, when u is 2, Y ₂ is alkylene having 2 to 16 carbon atoms, alkenylene having 4 to 12 carbon atoms, xylylene, 3 to 20 carbon atoms, one or more continuous carbon by -O- atoms - carbon bond is interrupted, and / or alkylene substituted by _{hydroxyl, -CH 2 CH (OH) CH} 2 -O-Y 15 -OCH 2 CH (OH) CH 2, - _{CO-Y 16 -CO -, -} CO-NH-Y 17 -NH-CO-, or _{- (CH 2) m -CO 2 -Y} 18 -OCO- (CH 2) m.

(here,
m is 1, 2 or 3;
Y ₈ is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 18 carbon atoms, 3 to 20 carbon atoms, one or more oxygen or sulfur atoms, or —NT ₆ —. Alkyls interrupted by continuous carbon-carbon bonds and / or substituted by hydroxyl, having 1 to 4 carbon atoms and -P (O) (OY ₁₄ ) ₂ , -NY ₉ Y ₁₀ , or -OCOY ₁₁ and / or alkyl substituted by hydroxyl, alkenyl having 3-18 carbon atoms, glycidyl, or phenylalkyl having 1-5 carbon atoms in the alkyl moiety;
Y ₉ and Y ₁₀ are independently of each other alkyl having 1 to 12 carbon atoms, alkoxyalkyl having 3 to 12 carbon atoms, dialkylaminoalkyl having 4 to 16 carbon atoms, or 5 Cyclohexyl having ˜12 carbon atoms, or Y ₉ and Y ₁₀ together may be alkylene, oxaalkylene or azaalkylene having 3 to 9 carbon atoms,
Y ₁₁ is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, or phenyl;
Y ₁₂ is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, phenyl, alkoxy having 1 to 12 carbon atoms, phenoxy, having 1 to 12 carbon atoms Alkylamino or phenylamino,
Y ₁₃ is alkyl having 1 to 18 carbon atoms, phenyl, or alkylphenyl having 1 to 8 carbon atoms in the alkyl group;
Y ₁₄ is alkyl having 1 to 12 carbon atoms, or phenyl;
Y ₁₅ is alkylene having 2 to 10 carbon atoms, phenylene, or -phenylene-M-phenylene- (where M is —O—, —S—, —SO ₂ —, —CH ₂ — or a a _{a), - -C (CH 3)} 2.
Y ₁₆ is alkylene having 2 to 10 carbon atoms, oxaalkylene or thiaalkylene, phenylene, or alkenylene having 2 to 6 carbon atoms;
Y ₁₇ is alkylene having 2 to 10 carbon atoms, phenylene, or alkyl phenylene having 1 to 11 carbon atoms in the alkyl moiety, and Y ₁₈ is alkylene having 2 to 10 carbon atoms. Or alkylene having from 4 to 20 carbon atoms and having a continuous carbon-carbon bond interrupted once or several times by oxygen. ]]

  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-dimethylphenol L) -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-butyloxyp Poxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl]- 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-) Methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris (2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl) -1,3,5 -Triazine, 2- (2-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.

  The benzophenone-based compound is preferably a compound having an effective absorption wavelength of about 270 to 380 nm, and representative examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyl. Oxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxypropoxy) Benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-methoxy-2'-carboxybenzophenone 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4-diethylamino-2′-hexyloxycarbonylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetra Examples thereof include hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 1,4-bis (4-benzyloxy-3-hydroxyphenoxy) butane and the like.

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

  The acrylate compound is preferably a compound having an effective absorption wavelength of about 270 to 350 nm, and typical examples thereof include 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, ethyl 2-cyano-3,3- Diphenyl acrylate, isooctyl 2-cyano-3,3-diphenyl acrylate, hexadecyl 2-cyano-3- (4-methylphenyl) acrylate, methyl 2-cyano-3-methyl-3- (4-methoxyphenyl) cinnamate, butyl 2-cyano-3-methyl-3- (4-methoxyphenyl) cinnamate, methyl 2-carbomethoxy-3- (4-methoxyphenyl) cinnamate 2-cyano-3- (4-methylphenyl) acrylate, 1 , 3-Bis (2'-cyano-3,3'-diphenyl Acryloyl) oxy) -2,2-bis (((2′-cyano-3,3′-diphenylacryloyl) oxy) methyl) propane, N- (2-carbomethoxy-2-cyanovinyl) -2-methylindoline, etc. Can be mentioned.

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

  The addition amount of the ultraviolet absorber in the polymer material cannot be uniquely determined because it varies depending on the purpose of use and the form of use, but may be any concentration depending on the purpose of use. Preferably it is 0.001-10 mass% in a polymeric material, More preferably, it is 0.01-5 mass%.

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

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

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

  The packaging material containing the ultraviolet absorbent according to the present invention will be described. The packaging material containing the ultraviolet absorbent according to the present invention may be a packaging material made of any kind of polymer as long as it contains the compound represented by the general formula (I). For example, thermoplastic resins described in JP-A-8-208765, polyvinyl alcohol described in JP-A-8-151455, polyvinyl chloride described in JP-A-8-245849, and JP-A-10-168292. Polyesters described in JP-A No. 2004-285189, heat-shrinkable polyesters described in JP-A No. 2001-323082, styrene resins described in JP-A No. 10-298397, JP-A No. 11-315175, Examples thereof include polyolefins described in JP-A Nos. 2001-26081 and 2005-305745, and ROMPs described in JP-T-2003-524019. For example, a resin having an inorganic vapor-deposited thin film layer described in Japanese Patent Application Laid-Open Nos. 2004-50460 and 2004-243684 may be used. For example, the paper which apply | coated resin containing the ultraviolet absorber of Unexamined-Japanese-Patent No. 2006-240734 may be sufficient.

  The packaging material containing the ultraviolet absorbent according to the present invention may be used for packaging foods, beverages, drugs, cosmetics, personal care products, and the like. For example, for food packaging described in JP-A-11-34261, JP-A-2003-237825, colored liquid packaging described in JP-A-8-80928, and liquid preparation described in JP-A-2004-51174 Packaging, pharmaceutical container packaging described in JP-A-8-301363, JP-A-11-276550, sterilization packaging for medical products described in JP-A-2006-217781, and JP-A-7-287353 Photosensitive material packaging, photographic film packaging described in JP-A No. 2000-56433, UV-curable ink packaging described in JP-A No. 2005-178832, JP-A No. 2003-200996, JP-A No. 2006-323339 The shrink label etc. which are described in the gazette are mentioned.

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

  The packaging material containing the ultraviolet absorber of the present invention has not only ultraviolet shielding properties as described in, for example, JP-A Nos. 2001-26081 and 2005-305745, but also has other performances. May be. For example, those having gas barrier properties described in JP-A No. 2002-160321, those containing an oxygen indicator described in JP-A No. 2005-156220, and those described in JP-A No. 2005-146278, for example. And a combination of an ultraviolet absorber and an optical brightener.

  You may manufacture the packaging material containing the ultraviolet absorber of this invention using any method. For example, a method of forming an ink layer described in JP-A-2006-130807, for example, a method of melt extrusion 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-9-142539, for example, a method of dispersing an ultraviolet absorber in an adhesive described in JP-A-9-157626, and the like can be mentioned.

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

  The container containing the ultraviolet absorbent according to the present invention may be used for food, beverages, drugs, cosmetics, personal care products, shampoos and the like. For example, a liquid fuel storage container described in JP-A-5-139434, a golf ball container described in JP-A-7-289665, a food container described in JP-A-9-295664, and JP-A-2003-237825 Container, sake container described in JP-A-9-58687, drug-filled container described in JP-A-8-155007, beverage container described in JP-A-8-324572, JP-A-2006-298456 A container for oily foods described in JP-A-9-86570, a solution container for analytical reagents 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, JP-A-11-2765 No. 0, a pharmaceutical container described in JP-A-11-290420, a high-purity chemical liquid container described in JP-A-11-290420, a liquid container described in JP-A-2001-106218, and JP-A-2005-178832 UV curable ink containers, plastic ampules described in WO 04/93775 pamphlet, and the like can be mentioned.

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

  You may manufacture the container containing the ultraviolet absorber of this invention using any method. For example, a two-layer stretch blow molding method described in JP-A No. 2002-370723, a multilayer coextrusion blow molding method described in JP-A No. 2001-88815, and an outer side of a container described in JP-A No. 9-241407. A method of forming an ultraviolet absorbing layer, JP-A-8-91385, JP-A-9-48935, JP-A-11-514387, JP-A-2000-66603, JP-A-2001-323082, Examples thereof include a method using a shrinkable film described in JP-A-2005-105032 and a pamphlet of WO99 / 29490, a method using a supercritical fluid described in JP-A-11-255925, and the like.

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

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

  The use purpose of the paint containing the ultraviolet absorber of the present invention may be any use. For example, UV shielding paints described in JP-A-7-26177, JP-A-9-169950, JP-A-9-221163, JP-A-2002-80788, and UV-rays described in JP-A-10-88039. Near-infrared shielding 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 No. 2002-294165, JP-A No. 2000-273362, JP-A No. 2001-279189, The powder coating material described in JP-A-2002-271227 and the aqueous coating described in JP-A-2001-9357 Paints, water-based metallic paints, water-based clear paints, top coat paints used in automobiles, buildings and civil engineering products described in JP-A No. 2001-316630, curable paints described in JP-A No. 2002-356655, Coating film forming composition used for plastic materials such as automobile bumpers described in JP-A No. 2004-937, metal plate paint described in JP-A No. 2004-2700, and JP-A No. 2004-169182 Cured gradient coating film, coating material for electric wire described in JP-A-2004-107700, automotive repair coating described in JP-A-6-49368, JP-A-2002-38084, JP-A-2005-307161 Anionic electrodeposition paints described in JP-A-5-78606, JP-A-5-185031, JP-A-10-140089 No. 2000-509082, JP-T 2004-520284, WO 2006/097201, pamphlet for automobiles, JP-A 6-1945, steel plate paint, JP-A 6-313148 Stainless steel paints described in Japanese Patent Publication No. 7-3189, lamp insect repellent paint described in Japanese Patent Laid-Open No. 7-3189, ultraviolet curable paint described in Japanese Patent Laid-Open No. 7-82454, and antibacterial composition described in Japanese Patent Laid-Open No. 7-118576. Anti-fatigue paint described in JP-A No. 2004-217727, anti-fog paint described in JP-A No. 2005-314495, super-weather resistant paint described in JP-A No. 10-298493, Gradient paint described in Kaihei 9-241534, photocatalyst paint described in JP-A No. 2002-2335028, JP-A 2000-345 109, a stripping paint for concrete described in JP-A-6-346022, an anticorrosive paint described in JP-A-2002-167545, and a protective coating described in JP-A-8-324576 A water-repellent protective coating described in JP-A-9-12924, a sheet glass scattering-preventing coating described in JP-A-9-157581, an alkali-soluble protective coating described in JP-A-9-59539, Aqueous temporary protective coating composition described in JP-A-2001-181558, floor coating described in JP-A-10-183057, emulsion coating described in JP-A-2001-111508, JP-A-2001-262856 Two-component water-based paint described in JP-A-9-263729, one-component paint described in JP-A-9-263729, and JP-A-2001-288410. UV curable coating, electron beam curable coating composition described in JP-A-2002-69331, thermosetting coating composition described in JP-A-2002-80781, and JP-T-2003-525325 Water-based paint for baking lacquer, powder paint and slurry paint described in JP-A-2004-162021, repair paint described in JP-A-2006-233010, powder described in JP-T-11-51489 Examples thereof include paint water dispersions, plastic coatings described in JP-A Nos. 2001-59068 and 2006-160847, and electron beam curable coatings described in JP-A No. 2002-69331.

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

  The coating film containing the ultraviolet absorber of the present invention is a coating film containing an ultraviolet absorber composed of the compound represented by the general formula (I), and is formed using the above-described coating material containing the ultraviolet absorber of the present invention. It is a coating film.

  The ink containing the ultraviolet absorbent according to the present invention will be described. The ink containing the ultraviolet absorbent of the present invention may be any form of ink as long as it contains the compound represented by the general formula (I). Examples thereof include dye ink, pigment ink, water-based ink, and oil-based ink. Moreover, you may use for any use. For example, the screen printing ink described in JP-A-8-3502, the flexographic printing ink described in JP-T-2006-521941, the gravure printing ink described in JP-T-2005-533915, and JP-T-11-504955. Lithographic offset printing ink described in Japanese Patent Publication No. 2005, typographic printing ink described in Japanese Patent Publication No. 2005-533915, UV ink described in Japanese Patent Application Laid-Open No. 5-254277, EB ink described in Japanese Patent Application Laid-Open No. 2006-30596, etc. Is mentioned. Moreover, for example, it describes in Unexamined-Japanese-Patent No. 11-199808, WO99 / 67337 pamphlet, Unexamined-Japanese-Patent No. 2005-325150, Unexamined-Japanese-Patent No. 2005-350559, Unexamined-Japanese-Patent No. 2006-8811, Special table 2006-514130. Ink-jet inks, photochromic inks described in JP-A-2006-257165, thermal transfer inks described in JP-A-8-108650, masking inks described in JP-A-2005-23111, JP-A-2004-75888 And the fluorescent ink described in JP-A-7-164729, the DNA ink described in JP-A-2006-22300, and the like.

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

  The fiber containing the ultraviolet absorbent according to the present invention will be described. The fiber containing the ultraviolet absorbent according to the present invention may be a fiber made of any kind of polymer as long as it contains the compound represented by the general formula (I). For example, JP-A-5-117508, JP-A-7-119036, JP-A-7-196631, JP-A-8-188921, JP-A-10-237760, JP-A-2000-54287, Polyester fibers described in JP 2006-299428 A, JP 2006-299438 A, polyphenylene sulfide fibers described in JP 2002-322360 A, JP 2006-265770 A, JP 7-76580 A. Polyamide fibers described in JP 2001-348785 A, JP 2003-41434 A, JP 2003-239136 A, epoxy fibers described in WO 03/2661, pamphlet, JP 10-251981 A Aramid fiber, JP-A-6-22881 Polyurethane fiber according to JP-like cellulose fibers described in JP-T-2005-517822.

  You may manufacture the fiber containing the ultraviolet absorber of this invention by any method. For example, as described in JP-A-6-228818, a polymer containing the compound represented by the general formula (I) in advance may be processed into a fiber, for example, JP-A-5-9870, Even if it processed using the solution etc. which contain the compound represented by the said general formula (I) with respect to what was processed into the fiber form as described in Kaihei 8-188921 and Unexamined-Japanese-Patent No. 10-1587. Good. You may process using a supercritical fluid like Unexamined-Japanese-Patent No. 2002-212884 and Unexamined-Japanese-Patent No. 2006-16710.

  The fiber containing the ultraviolet absorber of the present invention can be used for various applications. For example, apparel described in JP-A-5-148703, lining described in JP-A-2004-285516, underwear described in JP-A-2004-285517, blanket described in JP-A-2003-339503, Socks described in JP-A No. 2004-11062, artificial leather described in JP-A No. 11-302982, insect-proof mesh sheet described in JP-A No. 7-289097, construction described in JP-A No. 10-1868 Mesh sheet, carpet described in JP-A-5-256464, moisture-permeable and waterproof sheet described in JP-A-5-193037, nonwoven fabric described in JP-A-6-114991, and JP-A-11-247028 JP, 2000-144583, and the sheet-like article which consists of a fiber as described in Unexamined-Japanese-Patent No. 2000-144453 Refreshing garments described in Japanese Patent Laid-Open No. 703, moisture-permeable waterproof sheets described in Japanese Patent Laid-Open No. 5-193037, flame retardant artificial suede-like structures described in Japanese Patent Laid-Open No. 7-18484, and Japanese Patent Laid-Open No. 8-41785. Resin tarpaulin described in the publication, film agent, exterior wall material, agricultural house described in JP-A-8-193136, building material net, mesh described in JP-A-8-269850, and JP-A-8-284063. Filter substrate described in Japanese Patent Publication No. 9-57889, an antifouling film agent disclosed in Japanese Patent Laid-Open No. 9-57889, a mesh fabric described in Japanese Patent Laid-Open No. 9-137335, a land net, and described in Japanese Patent Laid-Open No. Underwater net, extra fine fiber described in JP-A-11-247027, JP-A-11-247028, JP-A-7-310283, special table 2003-528 No. 74, a nonwoven fabric described in JP-A-2001-30861, an airbag base fabric described in JP-A-2001-30861, JP-A-7-324283, JP-A-8-20579, and JP-A-2003-147617. And the ultraviolet ray absorbing fiber product described.

  The building material containing the ultraviolet absorber of the present invention will be described. The building material containing the ultraviolet absorber of the present invention may be a building material made of any kind of polymer as long as it contains the compound represented by the general formula (I). For example, the vinyl chloride type described in JP-A-10-6451, the olefin type described in JP-A-10-16152, the polyester type described in JP-A-2002-161158, and JP-A-2003-49065. Examples thereof include polyphenylene ethers described above and polycarbonates described in JP-A No. 2003-160724.

  The building material containing the ultraviolet absorber of the present invention may be produced by any method. For example, it may be formed into a desired shape using a material containing the compound represented by the general formula (I) as described in JP-A-8-269850, or described in JP-A-10-205056, for example. A material containing a compound represented by the above general formula (I) may be laminated to form a compound represented by, for example, a compound represented by the above general formula (I) as described in JP-A-8-151457. For example, as described in JP-A No. 2001-172531, a coating layer containing a compound represented by the general formula (I) may be applied and formed.

  The building material containing the ultraviolet absorber of the present invention can be used for various applications. For example, exterior building materials described in JP-A-7-3955, JP-A-8-151457, JP-A-2006-266042, wooden structures for building materials described in JP-A-8-197511, No. 9-183159, roofing material for building material, antibacterial building material described in JP-A-11-236734, base material for building material described in JP-A-10-205056, JP-A-11-300880 The antifouling building material described in the above, the flame retardant material described in JP 2001-9811 A, the ceramic building material described in JP 2001-172531, and the decorative building material described in JP 2003-328523 A, Japanese Patent Application Laid-Open Publication No. 2002-226864, Building Material Coated Article, Japanese Patent Application Laid-Open No. 10-6451, Japanese Patent Application Laid-Open No. 10-16152, Japanese Patent Application Laid-Open No. 2006-306020 Cosmetic material described in Japanese Patent Publication No. 8-269850, building material net described in Japanese Patent Application Laid-Open No. 9-277414, and building material described in Japanese Patent Application Laid-Open No. 10-1868. Mesh sheet for construction, film for building material described in JP-A-7-269016, film for cover described in JP-A-2003- 211538, JP-A-9-239921, JP-A-9-254345, A covering material for building materials described in Kaihei 10-44352, an adhesive composition for building materials described in JP-A-8-73825, a civil engineering building structure described in JP-A-8-207218, No. 82608, a coating material for walking paths, a sheet-like photocurable resin described in JP-A-2001-139700, and JP-A-5-253559. Protective coating for wood, cover for pushbutton switch described in JP-A-2005-294780, bonding sheet agent described in JP-A-9-183159, base material for building material described in JP-A-10-44352, Wallpapers described in JP 2000-226778 A, polyester films for covering described in JP 2003-111538 A, polyester films for forming members described in JP 2003-221606 A, JP 2004-3191 The flooring described in the gazette can be used.

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

  An image display device containing the ultraviolet absorbent according to the present invention will be described. The image display device containing the ultraviolet absorbent according to the present invention may be any one as long as it contains the compound represented by the general formula (I). 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, Japanese Patent Application Laid-Open No. 2000-223271, or a circular polarizing plate described in, for example, Japanese Patent Application Laid-Open No. 2005-189645 is necessary. A member containing an ultraviolet absorber may be used.

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

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

  You may manufacture the cover for solar cells containing the ultraviolet absorber of this invention by any method. For example, an ultraviolet absorbing layer described in JP-A No. 11-40833 may be formed, or layers each containing an ultraviolet absorber described in JP-A No. 2005-129926 may be laminated. It may be contained in the resin of the filler layer described in JP-A-91611, or a film may be formed from a polymer containing an ultraviolet absorber described in JP-A-2005-346999.

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

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

  Other examples of use include a light source cover for a lighting device described in JP-A-8-102296, JP-A-2000-67629, and JP-A-2005-353554, JP-A-5-272076, and JP-A-2003. Artificial leather described in JP-A-239181, sports goggles described in JP-A-2006-63162, deflection lenses described in JP-A-2007-93649, JP-A-2001-214121, JP-A-2001-214122 Hard coats for various plastic products described in JP-A-2001-315263, JP-A-2003-206422, JP-A-2003-25478, JP-A-2004-137457, and JP-A-2005-132999. Attaching outside the window described in JP-A-2002-36441 Hard coats, window covering films described in JP-A-10-250004, high-definition anti-glare hard coat films described in JP-A 2002-36452, and antistatic properties described in JP-A-2003-39607 Hard coat film, transparent hard coat film described in JP-A No. 2004-114355, anti-counterfeit book described in JP-A No. 2002-113937, and turf purpura inhibitor described in JP-A No. 2002-293706 A sealing agent for resin film sheet bonding described in JP-A-2006-274179, a light guide described in JP-A-2005-326661, a rubber coating agent described in JP-A-2006-335855, No. 10-34841, JP-A 2002-114879 Agricultural covering material, Special Table 2 Dyeing candles described in Japanese Patent Application Laid-Open No. 04-532306 and Japanese Translation of PCT International Publication No. 2004-530024, a fabric rinse composition described in Japanese Patent Application Publication No. 2004-525273, a prism sheet described in Japanese Patent Application Laid-Open No. 10-287804, Protective layer transfer sheet described in JP-A-2000-71626, photo-curable resin product described in JP-A-2001-139700, floor sheet described in JP-A-2001-159228, JP-A-2002-189415 A light-shielding printed label described in JP-A-2002-130591, an oil supply cup described in JP-A-2002-130591, a hard-coated article described in JP-A-2002-307619, and an intermediate transfer described in JP-A-2002-307845 Recording medium, artificial hair described in JP-A-2006-316395, WO99 / 29490 pamphlet A low-temperature heat-shrinkable film for labels described in JP-A No. 2004-352847, a fishing article described in JP-A No. 2000-224942, a microbead described in JP-A No. 8-208976, and -318592, a thin film described in JP-A-2005-504735, a heat-shrinkable film described in JP-A-2005-105032, and an input described in JP-A-2005-37642. Labels for molding, projection screens described in JP-A-2005-55615, JP-A-9-300537, JP-A-2000-25180, JP-A-2003-19776, JP-A-2005-74735 A decorative sheet according to claim 1, a hot melt adhesive according to JP-A-2001-207144, Table 2002-543265, JP 2002-543266, adhesive described in U.S. Pat. No. 6,225,384, electrodeposition coat, base coat described in JP-A-2004-35283, JP-A-7-268253 Wood surface protection described in Japanese Patent Laid-Open No. 2003-253265, Japanese Patent Laid-Open No. 2005-105131, Japanese Patent Laid-Open No. 2005-300962, and Japanese Patent No. 3915339 Glass, a flashlight described in JP-A-2005-304340, a touch panel described in JP-A-2005-44154, a sealing agent for resin film sheet bonding described in JP-A-2006-274197, and JP-A-2006 No. 89697, polycarbonate film coating, JP 2000-231 44 No. optical fiber tape described in Japanese, and the like solid wax described in JP-T-2002-527559.

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

The light resistance when used as a packaging / container application can be evaluated by the method of JIS-K7105 and a method referring to this. Specific examples thereof include light transmittance and transparency evaluation of a bottle body described in JP-A-2006-298456, sensory test evaluation of bottle contents after UV exposure using a xenon light source, and 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 No. 2005-105004, JP-A No. 2006-1568, visual evaluation of colorability, JP-A Nos. 7-40954 and 8 -151455, JP-A-10-168292, JP-A 2001-323082, Evaluation of UV transmittance described in JP-A No. 2005-146278, Evaluation of UV blocking rate described in JP-A No. 9-48935, JP-A No. 9-142539, JP-A No. 9-241407, JP-A No. 2004-243684 Evaluation of light transmittance described in JP-A-2005-320408, JP-A-2005-305745, and JP-A-2005-156220, and evaluation of viscosity of ink in an ink container described in JP-A-2005-178832. , Light transmittance evaluation described in JP-A-2005-278678, sample observation in a container after exposure to sunlight, color difference ΔE evaluation, UV transmittance evaluation after white fluorescent lamp irradiation described in JP-A-2004-51174, Light transmittance evaluation, color difference evaluation, light transmittance evaluation, haze value evaluation, color described in JP-A-2004-285189 Tone evaluation, yellowness evaluation described in JP2003-237825A, light shielding evaluation described in JP2003-20966, whiteness evaluation using L ^* a ^* b ^* color system color difference formula, Evaluation of yellowing using a color difference ΔEa ^* b ^* in a sample after exposure for each wavelength after the spectrum of xenon light described in Japanese Unexamined Patent Publication No. 2002-68322 is disclosed, ultraviolet absorption after ultraviolet exposure described in JP-A-2001-26081 Evaluation of film elongation after exposure using a sunshine weather meter described in JP-A-10-298397, evaluation of antibacterial properties after exposure to a xenon weather meter described in JP-A-10-237312, Evaluation of fading of packaging contents after irradiation with a fluorescent lamp as described in JP-A-239910, filling with salad oil as described in JP-A-9-86570 Evaluation of peroxide value and color tone of oil after exposure to fluorescent lamp on bottle, evaluation of absorbance difference after irradiation of chemical lamp described in JP-A-8-301363, and sunshine weather meter described in JP-A-8-208765 Surface glossiness retention after exposure, appearance evaluation, color difference after exposure using sunshine weatherometer described in JP-A-7-216152, bending strength evaluation, described in JP-A-5-139434 Examples include evaluation of light shielding ratio and evaluation of peroxide generation amount in kerosene.

The long-term durability when used for paints and coatings is JIS-K5400, JIS-K5600-7-5: 1999, JIS-K5600-7-6: 2002, JIS-K5600-7-7: 1999, JIS. -K5600-7-8: It can be evaluated by the method of 1999, JIS-K8741 and a method referring to this. Use specific examples thereof, the color difference ΔEa ^* b ^* in the color density and CIE ^L * ^a * ^{b *} color coordinates after exposure by a xenon light resistance test machine and UVCON apparatus described in JP-T-2000-509082, the residual gloss Evaluation, absorbance evaluation after exposure using a xenon arc light resistance tester to a film on a quartz slide described in JP-T-2004-520284, color density after exposure to a fluorescent lamp in a wax, UV lamp, 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 ^* , sun Evaluation of glossiness after exposure using a shine carbon arc light source, evaluation using a color difference ΔEa ^* b ^* after exposure using a metal weathering tester described in JP-A-2002-69331, gloss retention, Appearance evaluation, evaluation of gloss retention after exposure using a sunshine weatherometer described in JP 2002-38084 A, color difference after exposure using a QUV weather resistance tester described in JP 2001-59068 A Evaluation using ΔEa ^* b ^* , evaluation of gloss retention, gloss after exposure using a sunshine weatherometer described in JP-A No. 2001-115080, JP-A No. 6-49368, and JP-A No. 2001-262056 Retention rate evaluation, JP-A-8-324576, JP-A-9-12924, JP-A-9-169950, JP-A-9-24 Appearance evaluation after exposure using a sunshine weatherometer on a coated plate described in Japanese Patent No. 1534, JP-A-2001-181558, and after exposure using a sunshine weatherometer described in JP-A-2000-186234 Gloss retention rate, lightness value change evaluation, appearance evaluation of coating film deterioration state after exposure to Ducycle WOM for coating film described in JP-A-10-298493, UV of coating film described in JP-A-7-26177 Evaluation of transmittance, evaluation of UV blocking rate of coating film described in JP-A-7-3189, JP-A-9-263729, and evaluation of coating film using sunshine weatherometer described in JP-A-6-1945 Dew panel light control weather described in JP-A-6-313148 Evaluation of rust generation after exposure using a heater, strength evaluation of concrete against painted formwork after outdoor exposure described in JP-A-6-346022, color difference after outdoor exposure described in JP-A-5-185031 Evaluation using ΔEa ^* b ^* , cross-cut adhesion evaluation, surface appearance evaluation, gloss retention evaluation after outdoor exposure described in JP-A-5-78606, carbon arc light source described in JP-A-2006-63162 And yellowing degree (ΔYI) evaluation after exposure using.

The light resistance when used as an ink application can be evaluated by the method of JIS-K5701-1: 2000, JIS-K7360-2, ISO105-B02 and a method referring to this. Specifically, evaluation by measurement of color density and CIE L ^* a ^* b ^* color coordinates after exposure using an office fluorescent lamp and a fading tester described in JP-T-2006-514130; Electrophoretic evaluation after exposure to ultraviolet rays using a xenon arc light source described in JP 22300, density evaluation of printed matter using a xenon fade meter described in JP 2006-8811 A, 100 W described in JP 2005-23111 A Evaluation of ink detachability using a chemical lamp, evaluation of a residual ratio of a dye at an image forming site using a weather meter described in JP-A-2005-325150, and printed matter using an eye super UV tester described in JP-A-2002-127596 Chalking evaluation and discoloration evaluation, JP-A-11-199808, JP-A-8-108 The printed matter after xenon fade meter exposure described in 50 JP evaluation using the CIE ^L * ^a * ^{b *} color differences in the color coordinates ΔEa ^* b ^*, using a carbon arc light source described in JP-A-7-164729 For example, reflectivity evaluation after exposure.

  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, evaluation of photovoltaic efficiency of IV measurement 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-11-26185, Examples thereof include a discolored gray scale rating evaluation, color and appearance adhesion evaluation after exposure using a sunshine weather meter and a fade meter described in Japanese Unexamined Utility Model Publication No. 2000-144583.

The light resistance of the fiber and the fiber product is JIS-L1096: 1999, JIS-A5905: 2003, JIS-L0842, JIS-K6730, JIS-K7107, DIN75.202, SAEJ1885, SN-ISO-105-B02, AS / NZS4399. This method can be evaluated by the method described above and a method based on this method. JP-A-10-1587, JP-A-2006-299428, JP-A-2006-299438, UV transmittance evaluation, JP-A-6-228816, JP-A-7-76580, JP-A-8 JP-A-188921, JP-A-11-247028, JP-A-11-247027, JP-A-2000-144583, JP-A-2002-322360, JP-A-2003-339503, JP-A-2004-11062. Evaluation of blue scale discoloration after exposure using a xenon light source and a carbon arc light source described in JP No. 2003-147617, UV cut rate evaluation described in JP-A No. 2003-147617, and UV blocking described in JP-A No. 2003-41434 Carbage after dry cleaning described in JP-A-11-302982 After exposure blue scale discoloration evaluation using arc source, JP-A-7-119036 and JP-luminosity index after exposure using a fade-O-Meter described in JP-A-10-251981, the color difference based on psychometric chroma coordinates ΔE ^* Evaluation, tensile after exposure using UV tester and sunshine weather meter described in JP-A-9-57889, JP-A-9-137335, JP-A-10-1868, JP-A-10-237760 Strength Evaluation, Total Transmittance Evaluation, Strength Retention Rate Evaluation, Japanese Translation of PCT International Application No. 2003-528974, Japanese Patent Publication No. 2005-517822, and Japanese Patent Application Laid-Open No. HEI 8-8, JP-A-8-41785 and JP-A-8-193136. No. -20579, UV Protection Factor (UPF) evaluation, Japanese Patent Laid-Open No. 6-228818, Evaluation of discolored gray scale after exposure using a high-temperature fade meter as described in JP-A-7-324283, JP-A-7-196331, JP-A-7-18854, and JP-A-7-289097 Appearance evaluation after outdoor exposure, yellowness (YI) and yellowing degree (ΔYI) evaluation after ultraviolet exposure described in JP-A-7-289665, contract reflectance evaluation described in JP 2003-528974 A, etc. Can be given.

The light resistance of building materials can be evaluated by the method of JIS-A1415: 1999 and a method referring to this. Specifically, surface color tone evaluation after exposure using a sunshine weatherometer described in JP 2006-266402 A, carbon arc light source described in JP 2004-3191 A, JP 2006-306020 A Appearance evaluation after exposure using CPS, Appearance evaluation after exposure using Eye Super UV tester, Absorbance evaluation after exposure, Chromaticity after exposure, Color difference evaluation, CIE L ^* after exposure using metal hydride light source Evaluation using color difference ΔEa ^* b ^* in a ^* b ^* color coordinates, evaluation of gloss retention, JP-A-10-44352, JP-A-2003- 211538, JP-A-9-239921, JP-A-9- Haze value change evaluation after exposure using a sunshine weather meter described in Japanese Patent No. 254345, Japanese Patent Application Laid-Open No. 2003-221606, Evaluation of elongation retention using a tensile tester after exposure, evaluation of ultraviolet transmittance after immersion in a solvent described in JP-A No. 2002-161158, visual evaluation of appearance after exposure using an eye super UV tester, JP Gloss rate change evaluation after the QUV test described in JP-A No. 2002-226774, gloss retention evaluation after exposure using a sunshine weatherometer described in JP-A No. 2001-172531, JP-A No. 11-300088 Evaluation using color difference ΔEa ^* b ^* after exposure to ultraviolet light using the black light blue fluorescent lamp described, evaluation of adhesion retention after exposure using a cove con acceleration tester described in JP-A-10-205056, ultraviolet light Evaluation of barrier properties, appearance evaluation after outdoor exposure (JIS-A1410) described in JP-A-8-207218 and JP-A-9-183159 , Total light transmittance evaluation, haze change evaluation, tensile shear bond strength evaluation, total light transmittance evaluation after exposure using a xenon weather meter described in JP-A-8-151457, haze evaluation, yellowing degree evaluation And yellowing degree (ΔYI) after exposure using a sunshine weatherometer described in JP-A-7-3955, evaluation of residual ratio of ultraviolet absorber, and the like.

The light resistance when used as a recording medium can be evaluated by the method of JIS-K7350 and a method referring to this. Specifically, the background color difference change evaluation in the printed part after the fluorescent lamp irradiation described in JP-A No. 2006-167996, the xenon weather meter described in JP-A No. 10-203033 and JP-A No. 2004-181813 are used. Evaluation of residual image density by exposure used, evaluation of change in optical reflection density by exposure using xenon weather meter described in JP-A No. 2002-207845, Suntest CPS light fading test described in JP-A No. 2003-266926 Evaluation of yellowing degree by L ^* a ^* b ^* evaluation form after exposure using a machine, Fading evaluation after exposure using a fade meter described in JP-A No. 2003-145949, JP-A No. 2002-212237 Visual discoloration after exposure using the described xenon fade meter, Japanese Patent Application Laid-Open No. 2002-178625 Evaluation of color density retention after exposure to indoor sunlight described in the report, evaluation of color density retention after exposure using a xenon weather meter, C after exposure using a fade meter described in JP-A-2002-367227 / N evaluation, fog density evaluation after exposure to a fluorescent lamp described in JP-A-2001-249430, optical reflection density evaluation after exposure using a fluorescent lamp described in JP-A-9-95055, erasability evaluation, Color difference ΔE ^* evaluation after exposure using an atlas fade meter described in JP-A-9-309260, visual discoloration evaluation after exposure using a carbon arc fade meter described in JP-A-8-258415, JP Evaluation of retention rate of organic EL element color conversion characteristics described in Japanese Patent Application Laid-Open No. 2000-223271, and xenon fading tester described in Japanese Patent Application Laid-Open No. 2005-189645 The organic EL display luminance measurement evaluation after the exposure is mentioned.

  As other evaluation methods, it can be evaluated by the method of JIS-K7103 and ISO / DIS9050 and a method based on this method. Specifically, the appearance evaluation of the polycarbonate-coated film described in JP-A-2006-89697 after exposure with a UV tester, the blue scale evaluation after exposure to UV rays in artificial hair described in JP-A-2006-316395, Evaluation of treatment contact with water after exposure using the accelerated weathering tester described in JP 2006-335855 A, projection screen after exposure using the weathering tester described in JP-A-2005-55615 Visual evaluation of images projected on the surface of the specimen after exposure using a sunshine weather meter and a metal weather meter described in Japanese Patent Application Laid-Open No. 2005-74735, visual evaluation of changes in design properties, Japanese Patent Application Laid-Open No. 2005-326661 Appearance visual evaluation after lighting exposure using the described metal lamp reflector, JP-A-2002-18 No. 415, evaluation of light transmittance of a bottle label described in JP-A No. 2004-352847, evaluation of polypropylene deterioration after exposure under humidity conditions using a xenon weather meter described in JP-A No. 2003-19776, Evaluation of deterioration of hard coat film, evaluation of deterioration of substrate, evaluation of hydrophilicity, evaluation of scratch resistance, and evaluation of scratch resistance using sunshine weatherometers described in JP-A-2002-36441 and JP-A-2003-25478 Evaluation of gray scale color difference of artificial leather after exposure using a xenon lamp light source described in JP-A-239181, evaluation of liquid crystal device characteristics after exposure using a mercury lamp described in JP-A 2003-253265, JP-A 2002-239181 Evaluation of adhesion after exposure using a sunshine weatherometer described in Japanese Patent No. 307619 , Turf violet spot evaluation described in JP-A No. 2002-293706, UV exposure evaluation after exposure using a xenon arc light source described in JP-A No. 2002-114879, tensile strength evaluation, JP-A No. 2001-139700 Evaluation of concrete adhesion speed described in Japanese Laid-Open Patent Publication No. 2001-315263, post-exposure appearance evaluation using a sunshine weatherometer described in Japanese Patent Application Laid-Open No. 2001-315263, and evaluation of coating film adhesion Evaluation of yellowing degree and adhesion after exposure using a carbon arc light source described in JP-A-214122, Adhesion performance evaluation using an ultraviolet fade meter described in JP-A-2001-207144, JP-A-2000-67629 Insect flying suppression evaluation at the time of lighting as described in JP-A-10-19496 Evaluation of yellowing degree (ΔYI) of laminated glass using Eye Super UV tester described, QUV irradiation described in JP-A-8-318592, surface appearance evaluation after performing moisture resistance test, gloss retention evaluation, special Evaluation of color difference with time using a dew panel light control weather meter described in Kaihei 8-208976, glossiness after wood substrate application after exposure using a xenon weatherometer described in JP-A-7-268253 (DI), yellowness index (YI) evaluation, ultraviolet irradiation described in JP-T-2002-5443265, JP-A-2002-543266, UV-absorption rate evaluation after repeating darkness, JP-T-2004-532306 Examples include dye fading color difference ΔE evaluation after exposure to ultraviolet rays described in the publication.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Such suitable preservatives include, for example, phenoxyethanol, formaldehyde solutions, parabens, pentanediol or sorbic acid and preservatives listed in Schedule 6, Parts A and B of the Cosmetics Regulations.

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

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

  See, for example, the publication “Kosmetschie Farbemittel”, Verlag Chemie, Weinheim, 1984, published by Farbstoffcommunication der Deutschen Forschungsgemeinschaft. Substances suitable and approved for cosmetic purposes, such as edited in 81-106, may be used as colorants. The colorant is usually used at a concentration of 0.001 to 0.1% by weight based on the total mixture.

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

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

The cosmetic preparation containing the ultraviolet absorbent according to the present invention includes, as an auxiliary agent, an antifoaming agent such as silicone, a structural substance such as maleic acid, a solubilizer such as ethylene glycol, propylene glycol, glycerin or diethylene glycol, latex, Opacifying agents such as styrene / PVP or styrene / acrylamide copolymers, complexing agents such as EDTA, NTA, β-alanine diacetic acid or phosphonic acid, propane / butane mixtures, N ₂ O, dimethyl ether, CO ₂ , N ₂ Or propellants such as air, so-called couplers such as oxidative dye precursors, and developer components, thioglycolic acid and its derivatives, reducing agents such as thiolactic acid, cysteamine, thiomalic acid or α-mercaptoethanesulfonic acid, or excess Hydrogen oxide, potassium bromide or sodium bromide Any oxidizing agent may include.

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

The cosmetic formulation containing the ultraviolet absorber of the present invention can be contained in various cosmetic preparations. For example, the following preparations are particularly preferred:
-Skin care preparations, for example skin cleansing and cleansing preparations in the form of tablets or liquid soaps, synthetic detergents or cleaning pastes;
Bath preparations such as liquids (foam baths, milk, shower preparations) or solid bath preparations such as bath cubes and bath salts;
-Skin care preparations such as skin emulsions, multi-emulsions or skin oils;
-Cosmetic personal care preparations such as facial makeup in the form of a day cream or powder cream, white (powder or solid), blusher or cream make-up, eye care preparations such as eye shadow preparations, mascara, eyeliner, eye Cream or eye-fix cream; lip care preparations such as lipsticks, lip glosses, lip contour pencils; nail care preparations such as nail lacquers, nail lacquer removers, nail hardeners or cuticle removers;
-Foot care preparations such as foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or octopus preparations;
-Light protection preparations such as sun milk, lotions, creams or oils, sunblocks or tropicals, pretanning preparations or after-sun preparations;
-Skin tanning preparations, eg self-tanning creams;
-Decolorizing preparations, for example preparations for bleaching the skin, or whitening preparations;
-Insect repellents such as insect repellent oils, lotions, sprays or sticks;
-Deodorants such as deodorizing sprays, pump sprays, deodorant gels, sticks or roll-on;
An antiperspirant, such as an antiperspirant stick, cream or roll-on;
-Preparations for cleansing and caring for damaged skin, such as synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;
-Hair removal preparations (hair removal) as chemicals, for example hair removal powders, liquid hair removal preparations, hair removal preparations in the form of creams or pastes, hair removal preparations in gel form or aerosol foams;
-Shaving preparations such as shaving soap, foam shaving cream, non-foamed shaving cream, foams and gels, pre-shave preparations for dry shaving, aftershave or aftershave lotion;
-Fragrance preparations, such as fragrances (eau de cologne, eau de tore, eau de parphane, parfant aret, parphane), fragrance oils or fragrance creams; and-cosmetic hair treatment preparations, such as shampoos and conditioners Hair care preparations, eg pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, strong hair treatments, hair structuring preparations, eg hair wave preparations for permanent waves (hot waves , Mild wave, cold wave), hair straightening preparation, liquid setting preparation, hair foam, hair spray, bleach preparation, eg hydrogen peroxide solution, lightening Pooh, bleaching creams, bleaching powder, bleaching paste or oil, temporary, semi-permanent hair color or permanent hair color, natural hair color, such as preparations or henna or chamomile, including the auto-oxidation dye.

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

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

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

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

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

In the cosmetic preparation containing the ultraviolet absorbent according to the present invention, in the embodiment of the cosmetic preparation for hair, for example, the following hair cosmetic formulations may be used.
a ₁ ) Consisting of a UV absorber of the present invention, PEG-6-C ₁₀ oxo alcohol and sorbitan sesquioleate, water, and any desired quaternary ammonium compound such as 4% mincamidopropyldimethyl A self-emulsifying raw material formulation to which 2-hydroxyethylammonium chloride or Quaternium 80 is added,
a ₂ ) Consisting of the UV absorber of the present invention, tributyl citrate and PEG-20-sorbitan monooleate, water, and any desired quaternary ammonium compound such as 4% mincamidopropyldimethyl- A self-emulsifying raw material formulation to which 2-hydroxyethylammonium chloride or Quaternium 80 is added,
b) Quad-doped solutions of the UV absorber of the present invention in butyl triglycol and tributyl citrate;
c) A mixture or solution of the UV absorber of the present invention with n-alkylpyrrolidone.

  When the UV absorber of the present invention is used as a cosmetic preparation, for example, cream, gel, lotion, alcoholic and aqueous / alcoholic solution, water-containing emulsion, oil-containing emulsion, wax / fat composition, stick preparation, powder or ointment It can be used by containing. By using the ultraviolet absorbent of the present invention, it is possible to provide a cosmetic preparation which is excellent in long-wave ultraviolet absorbing ability and can maintain this absorbing ability for a long period of time. Examples of the ultraviolet absorber of the present invention include compounds of the general formula (I) or (Ia). For example, in order to improve spreadability to the skin and solubility in silicone oil as an oil component, It may be a silicone derivative represented by the formula (Ib). The general formula (Ib) will be described in detail below.

は一般式（Ｉｂ）構造中のＲ^１ｂ、Ｒ^２ｂ、Ｒ^３ｂ、Ｒ^４ｂ、Ｒ^５ｂ、Ｒ^６ｂ、Ｘ^１ｂ、Ｘ^２ｂ、Ｘ^３ｂおよびＸ^４ｂの任意の位置から、１個もしくは複数個の水素原子または１価の置換基を取り除くことで１価の置換基とした残基を表し、これが連結基Ｗと連結している。 In the general formula (Ib), R ^1b , R ^2b , R ^3b , R ^4b , R ^5b and R ^6b have the same meanings as R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , The same applies to the preferred case. X ^1b , X ^2b , X ^3b and X ^4b are synonymous with the aforementioned X ¹ , X ² , X ³ and X ^4, and are the same when preferred.

Is one or more from any position of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , X ^1b , X ^2b , X ^3b and X ^{4b in} the structure of general formula (Ib) This represents a residue which has been converted to a monovalent substituent by removing a hydrogen atom or a monovalent substituent, which is connected to the linking group W.

R ^{b1 to} R ^b9 are the same or different groups and have 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group, 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Represents an aryl group, a hydroxyl group or a hydrogen atom.

  W represents a divalent linking group. This linking group is composed of carbon atoms and atoms or atomic groups composed of heteroatoms such as nitrogen atoms, sulfur atoms and oxygen atoms. For example, alkylene group (for example, methylene, ethylene, propylene, butylene, pentylene), arylene group (for example, phenylene, naphthylene), alkenylene group (for example, ethenylene, propenylene), alkynylene group (for example, ethynylene, propynylene), amide group , Ester group, sulfoamide group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Va)-(Va represents a hydrogen atom or a monovalent substituent) As the monovalent substituent, the aforementioned E can be mentioned), a heterocyclic divalent group (for example, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4- A diyl group or a quinoxaline-2,3-diyl group). It represents a linking group having 1 to 20 carbon atoms. The above linking group may further have a monovalent substituent E. These linking groups may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring).

  W is preferably an alkylene group having 10 or less carbon atoms, an arylene group having 15 or less carbon atoms, a divalent linking group containing an ether group having 10 or less carbon atoms, or a divalent linking group containing an amide group having 10 or less carbon atoms. , A divalent linking group containing an amino group having 10 or less carbon atoms. More preferably, it is a divalent linking group containing an alkylene group having 5 or less carbon atoms, an arylene group having 10 or less carbon atoms, and an ether group having 5 or less carbon atoms. Particularly preferred is an alkylene group having 4 or less carbon atoms.

  m1, m2, and m3 represent the number of [—O—Si—] bonds and are integers of 0 or more. Preferably it is an integer of 0-10 as m1-m3, More preferably, it is an integer of 0-6. n represents an integer of 0 to 5. When n is 2 or more, W may be the same or different. Preferably it is an integer of 0-3. More preferably, it is 0 or 1. p represents the number of substitutions for the residue and represents an integer of 1 to 5. p is preferably 1 to 3, and more preferably 1 or 2.

Of the residues bonded to the linking group W, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b or R ^6b is preferably an ester group, an amide group, a carbonyl group, a sulfoamide group, a sulfonate group, or a ureido group , A sulfonyl group, a sulfinyl group, a residue obtained by removing a hydrogen atom or a monovalent substituent, and more preferably an ester group, an amide group, a sulfoamide group, a sulfonic acid ester group In particular, in the case of an ester group or an amide group, it is a residue that is a monovalent substituent by removing a hydrogen atom or a monovalent substituent.

  Preferred specific examples of the compound represented by the general formula (Ib) are shown below, but the present invention is not limited thereto.

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

Synthesis example 1
(Preparation of exemplary compound (1))
80 g of sodium hydroxide was dissolved in 800 ml of ethanol, and a solution of 66 g of malononitrile in 100 ml of ethanol was added under ice-cooling, followed by 76 g of carbon disulfide. The mixture was reacted at room temperature for 1 hour, and the obtained solid was filtered and washed with ethanol to obtain 166 g of the following synthetic intermediate A (yield 89%).
12.3 g of chloranil was dispersed in 100 ml of N, N-dimethylacetamide, a solution of the following synthetic intermediate A in 50 ml of water was added under ice cooling, and the mixture was reacted at room temperature for 6 hours. Water was added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 15 g of the following synthetic intermediate B (yield 78%).
1.16 g of the following synthetic intermediate B is dispersed in 5 ml of N, N-dimethylacetamide, 0.84 ml of 2,6-lutidine is added, and then 1.11 ml of 2-ethylhexanoyl chloride is added. Reacted for hours. Water was added to the reaction solution, and the resulting solid was filtered, washed with water, purified and recrystallized to obtain 0.6 g of Exemplified Compound (1) (yield 31%).
MS: m / z 638 (M +).
¹ H NMR (CDCl ₃ ) δ 0.98 (t, 6H), 1.09 (t, 6H), 1.35-1.90 (m, 16H), 2.68 (m, 2H).
¹³ C NMR (CDCl ₃ ) δ 11.96, 13.96, 22.61, 25.21, 29.75, 31.36, 47.14, 68.79, 111.54, 130.41, 136.51, 171.32, 175.38.
λmax = 380 nm (EtOAc), ε = 77600

Synthetic intermediate B could also be prepared by the following method.
N-methylpyrrolidone was added to the synthetic intermediate M-2 and malononitrile, and the mixture was stirred at an internal temperature of 80 ° C. for 4 hours in a nitrogen atmosphere. Cool to room temperature and add 1N hydrochloric acid with stirring. The precipitated crystals were filtered and washed with water to obtain a synthetic intermediate B.
Even when the synthetic intermediate B synthesized in this way was used, the exemplified compound (1) could be prepared in the same manner as described above.
Synthesis intermediate M-2 was prepared by the method shown below.
100 ml of N-methylpyrrolidone was added to 40 g (0.113 mol) of potassium diethyldithiocarbamate (53% aqueous solution). Next, 60 ml of acetic acid was added with stirring under ice cooling. Under ice-cooling, 24.5 g (0.226 mol) of 1,4-benzoquinone was added in portions. After stirring at room temperature for 2 hours, 150 ml of acetone was added. The precipitated crystals were filtered and washed with acetone to obtain 23.9 g of Exemplified Compound M-2 (yield 68.0%).
Further, the synthesis intermediate M-2 could be synthesized also by the following method.
38.4 g (0.17 mol) of sodium diethyldithiocarbamate trihydrate was dissolved in 19 ml of water and 180 ml of N-methylpyrrolidone, and subsequently 90 ml of acetic acid was added with stirring under water cooling. Under water cooling, 18.4 g (0.17 mol) of 1,4-benzoquinone was added over 30 minutes at an internal temperature of 25 ° C. or lower. After stirring at room temperature for 2 hours, 9.2 g (0.085 mol) of 1,4-benzoquinone was added, and further stirred at room temperature for 2 hours. 60 ml of acetone was added, and the precipitated crystals were filtered and washed with acetone to obtain 35 g of synthetic intermediate M-2 (yield 63%).
MS: m / z 402 (M +).
¹ H NMR (CD ₃ COOD) δ 1.51 (t, 12H), 3.99 (s, 8H), 6.70 (s, 8H).

Synthesis example 2
(Preparation of exemplary compound (2))
1.16 g of the above synthetic intermediate B was dispersed in 5 ml of N, N-dimethylacetamide, 1.24 ml of 2-ethylhexyl bromide was added, followed by addition of 1 g of potassium carbonate, and reacted at 60 ° C. for 5 hours. Water was added to the reaction solution, and the resulting solid was filtered, washed with water, and purified to obtain 0.5 g of Exemplified Compound (2) (yield 27%).
MS: m / z 610 (M +).
λmax = 381 nm (EtOAc), ε = 78000

Synthesis example 3
(Preparation of exemplary compound (72))
22.4 g of potassium hydroxide was dissolved in 250 ml of ethanol, and 21.3 ml of ethyl cyanoacetate was added under ice-cooling, followed by 15.2 g of carbon disulfide. The mixture was reacted at room temperature for 1 hour, and the obtained solid was filtered and washed with ethanol to obtain 36.5 g of the above synthetic intermediate C (yield 69%).
6.1 g of chloranil was dispersed in 50 ml of N, N-dimethylacetamide, a solution of the above synthetic intermediate C in 25 ml of water was added under ice-cooling, and reacted at room temperature for 5 hours. Water was added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 15 g of Compound (72) (yield 78%).
MS: m / z 480 (M +).

The exemplified compound (72) could also be prepared as follows.
N-methylpyrrolidone was added to the synthetic intermediate M-2 and ethyl cyanoacetate, and the mixture was stirred at an internal temperature of 70 ° C. for 3 hours in a nitrogen atmosphere. Cool to room temperature and add methanol followed by acetic acid with stirring. The precipitated crystals were filtered and washed with methanol to obtain Exemplary Compound (72).

Synthesis example 4
(Preparation of exemplary compound (11))
1.44 g of Exemplified Compound (72) is dispersed in 5 ml of N, N-dimethylacetamide, 0.84 ml of 2,6-lutidine is added, followed by 1.11 ml of 2-ethylhexanoyl chloride, and 5 ml at room temperature. Reacted for hours. Water was added to the reaction solution, and the resulting solid was filtered, washed with water, and purified to obtain 0.16 g of Exemplified Compound (11) (yield 8%).
MS: m / z 720 (M +).
¹ H NMR (CDCl ₃ ) δ 0.98 (t, 6H), 1.09 (t, 6H), 1.35-1.90 (m, 16H), 2.61-2.72 (m, 2H).
¹³ C NMR (CDCl ₃ ) δ 11.96, 13.96, 22.61, 25.21, 29.75, 31.36, 47.14, 68.79, 111.54, 130.41, 136.51, 171.32, 175.38.
λmax = 381 nm (EtOAc), ε = 92900

Synthesis example 5
(Preparation of Exemplified Compound (12))
1.44 g of Exemplified Compound (72) was dispersed in 5 ml of N, N-dimethylacetamide, 1.24 ml of 2-ethylhexyl bromide was added, followed by 1.0 g of potassium carbonate, and reacted at 60 ° C. for 5 hours. . Water was added to the reaction solution, and the resulting solid was filtered, washed with water, and purified to obtain 0.5 g of Exemplified Compound (12) (yield 24%).
MS: m / z 704 (M +).
¹ H NMR (CDCl ₃ ) δ 0.90-1.05 (m, 12H), 1.38 (t, 6H), 1.40-1.85 (m, 18H), 4.02-4.10 (m, 4H), 4.30-4.42 (m, 4H ).
¹³ C NMR (CDCl ₃ ) δ 11.98, 13.91, 12.25, 14.25, 22.70, 25.25, 29.71, 31.43, 47.16, 62.55, 111.54, 130.41, 136.51, 171.73.
λmax = 382 nm (EtOAc), ε = 87600

Synthesis Example 6
(Preparation of exemplary compound (24))
Exemplified compound (24) was obtained in a yield of 4% in the same manner as in Synthesis Example 3 and Synthesis Example 5 except that pivaloylacetonitrile was used instead of ethyl cyanoacetate.
MS: m / z 729 (M +).
¹ H NMR (CDCl ₃ ) δ 0.91-1.05 (m, 12H), 1.34-1.48 (m, 26H), 1.50-1.69 (m, 8H), 1.81-1.91 (m, 2H), 4.10-4.18 (m , 4H).
λmax = 399 nm (EtOAc), ε = 96000

The exemplified compound (24) could also be prepared as follows.
Exemplified compound (24) was obtained in a yield of 4% in the same manner as in Synthetic Example 5, except that exemplified compound (139) was used instead of exemplified compound (72). Exemplary compound (139) was prepared as follows.
100 ml of N-methylpyrrolidone was added to 12.4 g (0.02 mol) of synthetic intermediate M-2 and 6.0 g (0.048 mol) of pivaloyl acetonitrile. Stirring was performed for 4 hours at an internal temperature of 80 ° C. in a nitrogen atmosphere. After cooling to room temperature, 30 ml of 1N hydrochloric acid was added with stirring. The precipitated crystals were filtered and washed with water to obtain 9.4 g of Exemplified Compound (139) (yield 98.0%).
¹ H NMR (DMSO-d ₆ ) δ 1.32 (s, 18H).

Synthesis example 7
(Preparation of Exemplified Compound (74))
Exemplified compound (74) was synthesized in the same manner as in Synthesis Example 3, except that 3-hydroxy-3-methylbutyl cyanoacetate was used instead of ethyl cyanoacetate.
MS: m / z 596 (M +).
¹ H NMR (DMSO-d ₆ ) δ 1.16 (s, 12H), 1.79 (t, 4H), 4.30 (t, 4H), 3.70-4.90 (br, 2H), 10.0-11.5 (br, 2H).

The exemplified compound (74) could also be prepared as follows.
50 ml of N-methylpyrrolidone was added to 8.0 g (0.0128 mol) of synthetic intermediate M-2 and 4.8 g (0.028 mol) of 3-hydroxy-3-methylbutyl cyanoacetate. The mixture was stirred for 3 hours at an internal temperature of 80 ° C. in a nitrogen atmosphere. Cool to room temperature and add 30 ml of ethyl acetate and 50 ml of water. While stirring, 2.5 ml of concentrated hydrochloric acid was added. The precipitated crystals were filtered, washed with ethyl acetate and water to obtain 7.3 g of Exemplified Compound (74) (yield 95.5%).

Synthesis example 8
(Preparation of exemplary compound (104))
3.0 g of Exemplified Compound (74) was dispersed in 10 ml of tetrahydrofuran (THF), 2.6 g of 4- (4-ethylcyclohexyl) cyclohexanecarbonyl chloride and 0.8 g of pyridine were added and reacted at 60 ° C. for 5 hours. Water was added to the reaction solution, and the resulting solid was filtered, washed with water, and purified to obtain 1.8 g of Exemplified Compound (104) (yield 35%).
MS: m / z 1046 (M +).
λmax = 386nm (CH ₂ Cl ₂ ), ε = 99900

Synthesis Example 9
(Preparation of exemplary compound (86))
Exemplified compound (86) was obtained in a yield of 52% in the same manner as in Synthesis Example 3, except that 2-ethylhexyl cyanoacetate was used instead of ethyl cyanoacetate.
MS: m / z 649 (M +).
¹ H NMR (DMSO-d ₆ ) δ 0.78-0.97 (m, 12H), 1.20-1.45 (m, 16H), 1.54-1.70 (m, 2H), 4.05-4.20 (m, 4H).

The exemplified compound (86) could also be prepared as follows.
30 ml of N-methylpyrrolidone was added to 8.0 g (0.02 mol) of the synthetic intermediate M-2 and 5.7 g (0.029 mol) of 2-ethylhexyl cyanoacetate. Stirring was performed for 3 hours at an internal temperature of 70 ° C. in a nitrogen atmosphere. After cooling to room temperature, 40 ml of methanol and then 8 ml of acetic acid were added with stirring. The precipitated crystals were filtered and washed with methanol to obtain 8.0 g of Compound (86) (yield 96.0%).

Synthesis Example 10
(Preparation of Exemplified Compound (81))
Exemplified compound (81) was obtained in a yield of 18% in the same manner as in Synthesis Example 4 except that exemplified compound (86) was used instead of exemplified compound (72).
MS: m / z 900 (M +).
¹ H NMR (CDCl ₃ ) δ 0.81-0.95 (m, 12H), 1.02 (t, 6H), 1.12 (t, 6H), 1.22-1.54 (m, 24H), 1.61-1.92 (m, 10H), 2.61-2.72 (m, 2H), 4.12-4.28 (m, 4H).
λmax = 381 nm (EtOAc), ε = 99000

Synthesis Example 11
(Preparation of Exemplified Compound (82))
Exemplified compound (82) was obtained in a yield of 32% in the same manner as in Synthesis Example 5, except that exemplified compound (86) was used instead of exemplified compound (72).
MS: m / z 873 (M +).
¹ H NMR (CDCl ₃ ) δ 0.82-1.06 (m, 24H), 1.25-1.61 (m, 32H), 1.62-1.81 (m, 4H), 4.01-4.08 (m, 4H), 4.12-4.23 (m , 4H).
λmax = 383 nm (EtOAc), ε = 92000

Synthesis Example 12
(Preparation of exemplary compound (87))
Exemplified Compound (87) was obtained in a yield of 18% in the same manner as in Synthesis Example 5, except that Exemplified Compound (74) was used instead of Exemplified Compound (72).
MS: m / z 821 (M +).
¹ H NMR (CDCl ₃ ) δ 0.81-1.08 (m, 12H), 1.32 (s, 14H), 1.34-1.45 (m, 8H), 1.46-1.72 (m, 8H), 1.73-1.85 (m, 2H ), 1.98 (t, 4H), 4.04-4.09 (m, 4H), 4.48 (t, 4H).
λmax = 383 nm (EtOAc), ε = 92000

Synthesis Example 13
(Preparation of exemplary compound (88))
Except for using Exemplified Compound (86) in place of Exemplified Compound (72) and using dimethyl sulfate in place of 2-ethylhexyl bromide, Exemplified Compound (88) was prepared in a yield of 19% in the same manner as in Synthesis Example 5. Obtained.
MS: m / z 677 (M +).
¹ H NMR (CDCl ₃ ) δ 0.83-0.92 (dt, 12H), 1.25-1.50 (m, 16H), 1.62-1.74 (m, 2H), 4.02 (s, 6H), 4.15-4.27 (m, 4H ).
λmax = 383 nm (EtOAc), ε = 92000

Synthesis Example 14
(Preparation of exemplary compound (121))
Exemplified compound (121) was obtained in a yield of 55% in the same manner as in Synthesis Example 3, except that t-butyl cyanoacetate was used instead of ethyl cyanoacetate.
MS: m / z 537 (M +)

The exemplified compound (121) could also be prepared as follows.
Synthetic intermediate M-2 (3.1 g) was dispersed in 20 ml of N-methylpyrrolidone, and then 1.69 g of t-butyl cyanoacetate was added, followed by reaction at 80 ° C. for 6 hours. After cooling to room temperature, yellow powder was obtained by adding 5 ml of acetic acid and 20 ml of methanol. This was recrystallized from methanol to obtain the exemplified compound (121) in a yield of 55%.

Synthesis Example 15
(Preparation of exemplary compound (122))
Exemplified compound (122) was obtained in a yield of 15% in the same manner as in Synthesis Example 5, except that exemplified compound (121) was used in place of exemplified compound (72).
MS: m / z 760 (M +)
¹ H NMR (CDCl ₃ ) δ 0.93-1.08 (m, 12H), 1.42 (s, 18H), 1.51-1.67 (m, 16H), 1.79-1.88 (m, 2H), 4.08-4.15 (m, 4H )

Synthesis Example 16
(Preparation of exemplary compound (130))
1.06 g of Exemplified Compound (86) was dispersed in 10 ml of N, N-dimethylacetamide, 0.44 g of 2-bromoethanol was added, and then 0.66 g of potassium carbonate was added, followed by reaction at 80 ° C. for 4 hours. . An aqueous hydrochloric acid solution was added to the reaction solution, and the resulting solid was filtered and washed with water, followed by ethanol recrystallization to obtain 0.65 g of Exemplified Compound (130) (yield 55%).
MS: m / z 736 (M +)
¹ H NMR (CDCl ₃ ) δ 0.87-0.99 (m, 12H), 1.25-1.48 (m, 16H), 1.61-1.78 (m, 2H), 4.01-4.06 (m, 4H), 4.16-4.22 (m , 4H), 4.25-4.32 (m, 4H)

Synthesis Example 17
(Preparation of Exemplified Compound (131))
Exemplified compound (131) was obtained in a yield of 18% in the same manner as in Synthesis Example 16 except that 2-iodopropane was used instead of 2-bromoethanol.
MS: m / z 734 (M +)
¹ H NMR (CDCl ₃ ) δ 0.85-0.97 (m, 12H), 1.25-1.50 (m, 16H), 1.62-1.73 (m, 2H), 4.17-4.25 (m, 4H), 4.65-4.77 (m , 2H)

Synthesis Example 18
(Preparation of Exemplified Compound (132))
Exemplified compound (132) was obtained in a yield of 45% in the same manner as in Synthesis Example 16, except that 2-bromoethyl benzoate was used instead of 2-bromoethanol.
MS: m / z 945 (M +)
¹ H NMR (CDCl ₃ ) δ 0.85-0.99 (m, 12H), 1.27-1.50 (m, 16H), 1.65-1.76 (m, 2H), 4.17-4.24 (m, 4H), 4.45-4.52 (m , 4H), 4.63-4.70 (m, 4H), 7.42-4.60 (m, 6H), 8.05-8.12 (m, 4H)

Synthesis Example 19
(Preparation of exemplary compound (123))
Exemplified compound (123) was obtained in a yield of 72% in the same manner as in Synthesis Example 3, except that iso-butyl cyanoacetate was used instead of ethyl cyanoacetate.
MS: m / z 536 (M +)

The exemplified compound (123) could also be prepared as follows.
Exemplified compound (123) was obtained in a yield of 49% in the same manner as in the reaction using Synthesis Intermediate M-2 in Synthesis Example 14 except that iso-butyl cyanoacetate was used instead of t-butyl cyanoacetate. It was.

Synthesis Example 20
(Preparation of exemplary compound (124))
Exemplified compound (124) was obtained in a yield of 24% in the same manner as in Synthesis Example 5, except that exemplified compound (123) was used in place of exemplified compound (72).
MS: m / z 760 (M +)
¹ H NMR (CDCl ₃ ) δ 0.90-1.10 (m, 24H), 1.30-1.68 (m, 16H), 1.70-1.84 (m, 2H), 1.99-2.14 (m, 2H), 4.00-4.12 (m , 8H)

Synthesis Example 21
(Preparation of exemplary compound (125))
Exemplified compound (125) was obtained in a yield of 63% in the same manner as in Synthesis Example 3, except that 2-cyano-N, N′-dimethylacetamide was used in place of ethyl cyanoacetate.
MS: m / z 478 (M +)

The exemplified compound (125) could also be prepared as follows.
Except for using 2-cyano-N, N′-dimethylacetamide in place of t-butyl cyanoacetate, similar to the reaction using Synthesis Intermediate M-2 in Synthesis Example 14 with a yield of 59%. Compound (125) was obtained.

Synthesis Example 22
(Preparation of Exemplified Compound (126))
Exemplified compound (126) was obtained in a yield of 1% in the same manner as in Synthesis Example 5, except that exemplified compound (125) was used instead of exemplified compound (72).
MS: m / z 703 (M +)
¹ H NMR (CDCl ₃ ) δ 0.90-1.14 (m, 12H), 1.28-1.70 (m, 16H), 1.71-1.85 (m, 2H), 3.01-3.32 (s, 12H), 3.95-4.08 (m , 4H)

Synthesis Example 23
(Preparation of exemplary compound (127))
Exemplified compound (127) was obtained in a yield of 6% in the same manner as in Synthetic Example 4, except that exemplified compound (125) was used instead of exemplified compound (72) and triethylamine was used instead of 2,6-lutidine. It was.
MS: m / z 731 (M +)
¹ H NMR (CDCl ₃ ) δ 0.95-1.02 (t, 6H), 1.10-1.14 (t, 6H), 1.40-1.55 (m, 8H), 1.75-1.93 (m, 8H), 2.60-2.69 (s , 2H), 3.01-3.30 (s, 12H)

Synthesis Example 24
(Preparation of exemplary compound (128))
Exemplified compound (128) was obtained in a yield of 88% in the same manner as in Synthesis Example 3, except that 2-cyano-N- (2-methoxyphenyl) acetamide was used in place of ethyl cyanoacetate.
MS: m / z 634 (M +)

The exemplified compound (128) could also be prepared as follows.
89% yield in the same manner as in the reaction using Synthesis Intermediate M-2 in Synthesis Example 14 except that 2-cyano-N- (2-methoxyphenyl) acetamide was used instead of t-butyl cyanoacetate. Example compound (128) was obtained.

Synthesis Example 25
(Preparation of exemplary compound (129))
Exemplified compound (129) was obtained in a yield of 1% in the same manner as in Synthesis Example 5, except that exemplified compound (128) was used in place of exemplified compound (72).
MS: m / z 859 (M +)
¹ H NMR (CDCl ₃ ) δ 0.90-1.14 (m, 12H), 1.28-1.70 (m, 16H), 1.71-1.89 (m, 2H), 3.90 (s, 6H), 4.01-4.11 (m, 4H ), 6.82-6.90 (m, 2H), 6.91-7.00 (m, 2H), 7.02-7.09 (m, 2H), 8.30-8.35 (m, 2H), 8.41 (s, 2H)

Synthesis Example 26
(Preparation of exemplary compound (133))
Exemplified compound (133) was obtained in a yield of 84% in the same manner as in Synthesis Example 3, except that benzoylacetonitrile was used instead of ethyl cyanoacetate.
MS: m / z 544 (M +)

The exemplified compound (133) could also be prepared as follows.
Exemplified Compound (133) was obtained in a yield of 85% in the same manner as in the reaction using Synthesis Intermediate M-2 of Synthesis Example 14 except that benzoylacetonitrile was used instead of t-butyl cyanoacetate.

Synthesis Example 27
(Preparation of exemplary compound (134))
Exemplified compound (134) was obtained in a yield of 5% in the same manner as in Synthesis Example 5, except that exemplified compound (133) was used instead of exemplified compound (72).
MS: m / z 770 (M +)
¹ H NMR (CDCl ₃ ) δ 0.95-1.01 (t, 6H), 1.04-1.12 (t, 6H), 1.51-1.69 (m, 16H), 1.82-1.92 (m, 2H), 4.15-4.21 (m , 4H), 7.49-7.62 (m, 6H), 7.98-8.03 (m, 4H)

Synthesis Example 28
(Preparation of exemplary compound (135))
Exemplified compound (135) was obtained in a yield of 46% in the same manner as in Synthesis Example 3, except that phenylsulfonylacetonitrile was used instead of ethyl cyanoacetate.
MS: m / z 616 (M +)

The exemplified compound (135) could also be prepared as follows.
Exemplified compound (135) was obtained in a yield of 44% in the same manner as in the reaction using Synthesis Intermediate M-2 of Synthesis Example 14 except that phenylsulfonylacetonitrile was used instead of t-butyl cyanoacetate.

Synthesis Example 29
(Preparation of Exemplified Compound (136))
Exemplified compound (136) was obtained in a yield of 6% in the same manner as in Synthesis Example 5, except that exemplified compound (135) was used instead of exemplified compound (72).
MS: m / z 842 (M +)
¹ H NMR (CDCl ₃ ) δ 0.85-1.13 (m, 12H), 1.40-1.70 (m, 16H), 1.75-1.86 (m, 2H), 3.92-4.12 (td, 4H), 7.54-7.64 (m , 4H), 7.66-7.73 (m, 2H), 7.98-8.03 (m, 4H)

Synthesis Example 30
(Preparation of exemplary compound (137))
Exemplified compound (137) was obtained in 49% yield in the same manner as in Synthesis Example 3, except that methylsulfonylacetonitrile was used instead of ethyl cyanoacetate.
MS: m / z 492 (M +)

The exemplified compound (137) could also be prepared as follows.
Exemplified compound (137) was obtained in a yield of 53% in the same manner as in the reaction using Synthesis Intermediate M-2 of Synthesis Example 14 except that methylsulfonylacetonitrile was used instead of t-butyl cyanoacetate.

Synthesis Example 31
(Preparation of exemplary compound (138))
Exemplified compound (138) was obtained in a yield of 4% in the same manner as in Synthesis Example 5, except that exemplified compound (137) was used instead of exemplified compound (72).
MS: m / z 928 (M +)
¹ H NMR (CDCl ₃ ) δ 0.84-1.04 (m, 12H), 1.32-1.61 (m, 16H), 1.72-1.83 (m, 2H), 3.21 (s, 6H), 4.01-4.025 (m, 4H )

Synthesis Example 32
(Preparation of exemplary compound (7))
1.93 g of synthetic intermediate B was suspended in 20 ml of tetrahydrofuran, and 1.1 ml of acetic anhydride was added. Further, 2.1 ml of triethylamine was added, and the mixture was heated to reflux for 3 hours. The precipitate in the reaction mixture was filtered off, washed with tetrahydrofuran and dried to obtain 0.84 g of exemplary compound (7) (pale yellow crystals).
Infrared absorption spectrum (cm ^-1 ): 2216 (s), 1795 (s), 1479 (s), 1423 (m), 1369 (m), 1144 (s)
¹ H NMR (CDCl ₃ ) δ 0.84-1.04 (m, 12H), 1.32-1.61 (m, 16H), 1.72-1.83 (m, 2H), 3.21 (s, 6H), 4.01-4.025 (m, 4H )

Synthesis Example 33
(Preparation of exemplary compound (140))
Exemplified compound (140) was obtained in a yield of 53% in the same manner as in the reaction using Synthesis Intermediate M-2 of Synthesis Example 6 except that diethyl malonate was used instead of pivaloylacetonitrile.
MS: m / z 574 (M +).

Synthesis Example 34
(Preparation of Exemplified Compound (141))
Exemplified compound (141) was obtained in the same manner as in the reaction using Synthesis Intermediate M-2 in Synthesis Example 7 except that ethyl phenylsulfonylacetate was used in place of 3-hydroxy-3-methylbutyl cyanoacetate.
MS: m / z 710 (M +).

Synthesis Example 35
(Preparation of exemplary compound (142))
2 g of synthetic intermediate A was dissolved in 5 ml of N, N-dimethylacetamide and 0.5 ml of water, 1 g of tetrafluoroterephthalonitrile was added, and the mixture was reacted at room temperature for 6 hours. Water was added to the reaction solution, and the resulting solid was filtered, washed with water, purified and recrystallized to obtain 1.2 g of Exemplified Compound (142) (yield 59%).
MS: m / z 404 (M-).
¹³ C NMR (CDCl ₃ ) δ 69.42, 103.99, 111.75, 112.47, 139.19, 173.47.

Synthesis Example 36
(Preparation of exemplary compound (143))
13 g of Exemplified Compound (86) was dissolved in 50 ml of N, N-dimethylacetamide, 6.7 ml of triethylamine was added under a nitrogen stream, and 3.7 ml of methanesulfonyl chloride was added dropwise little by little. The resulting reaction solution was allowed to react overnight at room temperature. The reaction liquid was added to ice water, concentrated hydrochloric acid was added to the resulting liquid mixture to adjust the acidity, and the resulting solid was filtered and washed with water to obtain an exemplary compound (143).
MS: m / z 805 (M +).

Synthesis Example 37
(Preparation of exemplary compound (144))
1.95 g of Exemplified Compound (86) was dissolved in 30 ml of methylene chloride, 1.25 ml of triethylamine was added while cooling in an ice bath under a nitrogen atmosphere, and then 1.48 ml of trifluoromethanesulfonic anhydride was added dropwise little by little. The resulting reaction solution was reacted at room temperature for 6 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate, dried over sodium sulfate, and concentrated to give Exemplified Compound (144).
MS: m / z 913 (M +).

Example 1
A sample solution was prepared by dissolving 1 mg of the exemplified compound (1) in 100 ml of ethyl acetate. Similarly, sample solutions were prepared for the exemplary compounds (2), (11), (12), (24), (81), (82), (87) and (88). Also, 2 mg of Comparative Compound 1 was dissolved in 100 ml of ethyl acetate to prepare a sample solution. Similarly, sample solutions were prepared for Comparative Compound 2 (Exemplary Compound VIII described in JP-B No. 49-11155), 11 and 12. Each sample solution was measured for UV spectrum in a 1 cm quartz cell using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. From the obtained spectrum chart, the maximum absorption wavelength, the molar absorption coefficient (ε) at the maximum absorption wavelength, and the half width (the width of the absorption band at half the absorbance at the maximum absorption wavelength) were calculated. The results are shown in Table 4 below.

As is apparent from the results in Table 4, the compound is represented by the above general formula (I) in which two heterocycles are condensed to a benzene ring with respect to a comparative compound in which one heterocycle is condensed to a benzene ring. The compound has a long wave of λmax, a molar extinction coefficient ε of 2 or more, a half width of about 40 nm to about 27 nm, and gives a strong and sharp absorption spectrum near the boundary with the visible region of the ultraviolet region. The compound represented by the general formula (I) has an excellent performance as an ultraviolet absorber because it is considered that the compound is simply considered to have two heterocycles and double the ultraviolet absorption effect. I found out. Therefore, it was found that the ultraviolet absorbent according to the present invention comprising the compound represented by the general formula (I) has an excellent absorption ability.
Spectra of exemplary compound (12) and comparative compound 12 are shown in FIG.

Example 2
5 mg of Exemplified Compound (1) was dissolved in 100 ml of ethyl acetate, and further diluted with ethyl acetate so that the absorbance was in the range of 0.95 to 1.05 to prepare a sample solution. Similarly, sample solutions were prepared for the exemplary compounds (2), (11), (12), (24), (81) and (82) and the comparative compounds A and B. The absorbance of each sample solution was measured in a 1 cm quartz cell using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The cell in which the sample solution was sealed was irradiated with light with a xenon lamp from which the UV filter was removed so that the illuminance was 170,000 lux, and the remaining amount of the ultraviolet absorber after irradiation for 1 week was measured. The remaining amount was calculated according to the following formula.
Residual amount (%) = 100 × (100−transmittance after irradiation) / (100−transmittance before irradiation)
The transmittance is a value measured at the maximum absorption wavelength of each compound. The results are shown in Table 5 below.

  As is clear from the results in Table 5, the ultraviolet absorbent according to the present invention is less likely to be decomposed by light irradiation and has high light fastness compared to existing ultraviolet absorbents having absorption in the UV-A region. all right.

Example 3
About Exemplified Compounds (11), (12), (81), (82), (83) and (85), 100 mg is weighed and mixed with 900 mg of MEK (2-butanone) and ethyl acetate to dissolve it. I investigated. The determination of solubility was performed by the following two methods.
<1> The presence or absence of insoluble matter is visually observed.
<2> After filtering with a 0.25 μm microfilter, the filtrate was diluted 1000 times and the absorbance was measured, and compared with the molar extinction coefficient measured separately with about 5 × 10 ⁻⁵ mol · dm ⁻³ solution. If it is 95% or less, it is determined that there is an insoluble matter.
The results are shown in Table 6. In addition, the case where it melt | dissolved is represented as (circle) and the case where there existed an insoluble part is represented as x.

As can be seen from the results in Table 6, the exemplified compounds (81), (82), (83) having an alkoxycarbonyl group having 6 or more carbon atoms in R ¹ , R ² , R ³ and R ⁴ in the general formula (I) And in the case of (85), it turns out that it is excellent in solubility compared with exemplary compound (11) and (12) in the case of less than 6 carbon atoms. This is remarkably shown in the difference between Exemplified compounds (12) and (83) having the same molecular weight but different only in the positions of the 2-ethylhexyl group and the ethyl group, and R ¹ , R ² , R ³ and R ⁴ It shows that the effect on solubility is large.

Example 4
3 mg of each of Exemplified Compounds (11), (12), (81) and (82) was weighed in a cylindrical aluminum dish having a diameter of 2 mm and a height of 2 mm, heated in an oven at 280 ° C. for 30 minutes, and then heated to room temperature. Left to cool. From the mass change before and after heating, the mass reduction rate by heating was investigated. The mass reduction rate was obtained by the following formula.
Mass reduction rate (%) = (mass before heating−mass after heating) / (mass before heating) × 100
The results are shown in Table 7.

As can be seen from the results in Table 7, Exemplified Compounds (12) and (82) in which R ⁵ and R ⁶ in General Formula (I) are alkoxy groups are compared with (11) and (81), which are acyloxy groups. It can be seen that the mass loss due to heating is small. The influence on the mass reduction by heating of R ⁵ and R ⁶ is large, indicating that an alkoxy group is preferable.

Example 5
(Preparation of sunscreen cream (301-308))
1. Preparation of sunscreen cream [A]
Numerical value (mass%)
Polyglycerin / stearoyl sodium lactate mixture 2.5
Behenyl alcohol 2.5
Squalane 4.0
Glyceryl tri-2-ethylhexanoate 3.0
2-Ethylhexyl paramethoxycinnamate 6.0
Ultraviolet absorbing compound 2.0

[B]
Numerical value (mass%)
Preservative appropriate amount 1,3-butylene glycol 5.0
Xanthan gum (2% aqueous solution) 15.0
Total amount with purified water 100.0

<Preparation method>
Both A and B were heated to 70 to 80 ° C. and dissolved uniformly. A was added to B, stirred at 5,000 rpm for 7 minutes with a homomixer while maintaining at 80 ° C., cooled with paddle stirring, stopped at 35-30 ° C., and allowed to stand. A sample using the exemplified compound (1) as the ultraviolet absorbing compound (sample 301), a sample using the exemplified compound (11) as the ultraviolet absorbing compound (sample 302), and a sample using the exemplified compound (12) as the ultraviolet absorbing compound ( Sample 303), sample using exemplified compound (24) as ultraviolet absorbing compound (sample 304), sample using exemplified compound (81) as ultraviolet absorbing compound (sample 305), and exemplified compound (82) as ultraviolet absorbing compound The sample used (sample 306), the sample using the comparative compound X as the ultraviolet absorbing compound (sample 307), and the sample using the comparative compound Y as the ultraviolet absorbing compound (sample 308), and mixing in the above formulation did. The comparative compound Y represents the same compound as the comparative compound B.

2. Evaluation of sunscreen cream <Evaluation method>
Above 1. The following evaluations were performed on the creams (samples 301 to 308) prepared in (1).
On a slide glass, it apply | coated so that it might become ² mg / cm <2> of cream, and was dried for 60 minutes. A light irradiation experiment was conducted using a merry-go-round type xenon fading tester. The xenon photogen was irradiated with light from the coated surface side for 200 hours using a 500 W lamp. After light irradiation, the cream was dissolved in DMSO, and the remaining amount was measured by HPLC. In the evaluation, the remaining amount after irradiation was calculated with no light irradiation as 100. The results are shown in Table 8.

  As is clear from the results in Table 8, in the samples 307 and 308 containing the comparative compound X or Y, the residual amount of the UV absorber after irradiation for 200 hours is low and the light resistance is poor, whereas the general formula (I In the samples 301 to 306 containing the compound represented by), 90% or more of the ultraviolet absorber remained even after 200 hours of light irradiation, and it was found that the sample was excellent in light resistance. From this, it can be seen that the cosmetic preparation containing the ultraviolet absorbent of the present invention is excellent in long-wave ultraviolet absorbing ability and can maintain this absorbing ability for a long period of time.

Example 6
(Preparation of polymer-kneaded UV agent-containing polymer film (401-404))
Exemplified compounds (81) and (82) were added to 15 g of polyethylene terephthalate so that the transmittance at 400 nm would be 1% when a 50 μm film was formed, melted and kneaded at 265 ° C., and then cooled and stretched to obtain a UV agent. Containing films (401) and (402) were produced. Further, in the system using the comparative compound Za and the comparative compound 12 instead of the exemplified compound, the same was kneaded and formed into films to prepare UV agent-containing films (403) and (404).

(Evaluation)
The sample was evaluated for coloration by measuring the transmittance at 420 nm, 440 nm, and 460 nm and visually. The results are shown in Table 9.

  As is clear from the results in Table 9, the sample (403) containing the comparative compound Za is colored more yellow than the samples (401) and (402) using the exemplified compounds 81 and 82 of the present invention. In addition, coloring was also observed in the sample (404) using the comparative compound 12 having a short maximum absorption compared to the exemplary compound because the amount of sample adjustment increased. From this, it can be seen that the film using the ultraviolet absorbent of the present invention is a film that absorbs the UV-A region effectively without being colored.

FIG. 1 shows the spectra of Exemplified Compound (12) and Comparative Compound 12 in Example 1.

Claims (16)

  An ultraviolet absorber having a molecular weight of 1,000 or less and a molar extinction coefficient at a maximum absorption wavelength of 75,000 or more.   The ultraviolet absorber according to claim 1, wherein the molecular weight is 350 or more and 950 or less, and the molar extinction coefficient at the maximum absorption wavelength is 78000 or more and 120,000 or less.   The ultraviolet absorber according to claim 1 or 2, wherein the maximum absorption wavelength is 360 nm or more and the half width is 60 nm or less.   The ultraviolet absorber according to any one of claims 1 to 3, wherein the maximum absorption wavelength is 370 nm or more and the half width is 10 nm or more and 45 nm or less.   The ultraviolet absorber according to any one of claims 1 to 4, comprising a compound in which two heterocycles are condensed to one benzene ring. The ultraviolet absorber according to claim 5, comprising a compound represented by the following general formula (I).

[R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent. R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. X ¹ , X ² , X ³ and X ⁴ each independently represent a hetero atom. ] R ⁵ and R ⁶ in the general formula (I) are independently of each other an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, an amino group, an acylamino group, or a carbamoyl group. The ultraviolet absorber according to claim 6, which is an amino group. 7. At least one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (I) is a substituent having a Hammett's substituent constant σp value of 0.2 or more, Or the ultraviolet absorber of 7. In the general formula (I), at least one of R ¹ , R ² , R ³ and R ⁴ is a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, or an alkylsulfonyl group. Or it is an arylsulfonyl group, The ultraviolet absorber of any one of Claims 6-8 characterized by the above-mentioned. The ultraviolet absorbent according to claim 6, wherein X ¹ , X ² , X ³ and X ⁴ in the general formula (I) are sulfur atoms. The ultraviolet absorber according to any one of claims 6 to 10, wherein at least one of a set of R ¹ and R ² and a set of R ³ and R ⁴ does not form a ring. 12. The ultraviolet absorber according to claim 6, wherein neither the group of R ¹ and R ² nor the group of R ³ and R ⁴ forms a ring. 13. The method according to claim 6, wherein at least one of R ¹ , R ² , R ^3, and R ^{4 in} the general formula (I) is an alkoxycarbonyl group having 6 or more carbon atoms. The ultraviolet absorber as described in. 14. The ultraviolet absorbent according to claim ⁶ , wherein R ⁵ and R ⁶ in the general formula (I) are an alkoxy group having 2 or more carbon atoms.   The composition containing the ultraviolet absorber of any one of Claims 1-14.   A polymer composition comprising the ultraviolet absorber according to any one of claims 1 to 15 and a polymer substance.

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