JP5450994B2 - Heterocyclic compounds - Google Patents

Description

  The present invention relates to a novel heterocyclic compound.

  As a heterocyclic compound, several compounds in which two heterocyclic rings are condensed to a benzene ring have been known so far (see, for example, Patent Documents 1 to 3 and Non-Patent Document 1). Many of these were reported as tetrathiafulvalene analogues, mainly because of their interest as charge transfer complexes. For this reason, most of the condensed heterocycles are dithiol rings, and most of them have a structure in which an alkyl mercapto group or a dithiol ring is substituted from the 2-position of the dithiol ring via exomethylene.

  In addition, the use of a compound having such a structure for various functional materials can be used as a charge transfer complex in an organic electrophotographic material (see, for example, Patent Document 2) or as a partial structure of an inert carbon free radical (for example, However, the structure is limited to a narrow range where desired performance can be exhibited. New compounds have not been found because the other uses have not been studied.

On the other hand, conventionally, UV absorbers are imparted by using UV absorbers in common 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 4 to 6) 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 7 and 8 in the long wave ultraviolet region have poor light resistance, and the absorption capacity decreases with time.

  In contrast, benzophenone-based and benzotriazole-based 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 9 and 10). .) 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.

  In recent years, as an image recording material, a material for forming a color image is mainly used. Specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer material, and the like. A silver halide photosensitive material, printing ink, recording pen, etc. are actively used. Further, a color filter is used for recording and reproducing a color image on an image pickup device such as a CCD in a photographing apparatus and on an LCD or PDP in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixing method and subtractive color mixing method are used to display or record full color images. In fact, there is no fast-acting dye that has absorption characteristics that can realize the above-mentioned conditions and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force. As the ink for ink jet recording, water-based ink, oil-based ink, pigment-dispersed ink, or solid (melting type) ink is used.
For the colorant used in such ink for ink jet recording, the solvent has good solubility or dispersibility, high density recording is possible, hue is good, light, heat, environment It is robust against active gases (oxidizing gases such as NOx, SOx, ozone, etc.), has excellent fastness to water and chemicals, has good fixability to image receiving materials, and is difficult to bleed, ink It is required to have excellent storage stability, no toxicity, high purity, and availability at low cost. However, it is extremely difficult to search for colorants that meet these requirements at a high level. In particular, it is strongly desired to have a good yellow hue, high solubility or dispersibility, fastness to light, humidity and heat, and in particular, fastness to light.

In thermal transfer recording, a thermal transfer material in which a heat-meltable ink layer is formed on a support (base film) is heated by a thermal head, the ink is melted and recorded on an image receiving material, and on the support. There is a method in which a heat-sensitive transfer material having a dye-donating layer containing a heat-transferable dye is heated by a thermal head to thermally transfer the dye onto the image receiving material. The latter thermal transfer system can change the transfer amount of the dye by changing the energy applied to the thermal head, so that gradation recording is easy and is particularly advantageous for high-color full-color recording. However, the heat transfer dyes used in this method have various limitations, and very few satisfy all the required performance.
The required performance includes, for example, favorable spectral characteristics for color reproduction, easy transfer, fastness to light and heat, fastness to various chemicals, and easy synthesis. It is easy to make a recording material for thermal transfer. However, the conventional dye compound proposed as having spectral characteristics preferable for color reproduction and being robust to light and heat is not at a satisfactory level, and further improvement is strongly desired.

  Since color filters are required to have high transparency, a method called a dyeing method in which coloring is performed using a dye has been performed. For example, a color filter can be produced by sequentially repeating a method of forming a pattern by pattern exposure and development of a dyeable photoresist and then dyeing with a filter color dye for all filter colors. In addition to the dyeing method, a color filter can be produced by a method using a positive resist. The color filter produced by these methods has a high transmittance and excellent optical characteristics because it uses a dye, but has limitations in light resistance, heat resistance, and the like. For this reason, the coloring agent which was excellent in various tolerances and high in transparency was desired. On the other hand, a method using an organic pigment having excellent light resistance and heat resistance in place of a dye is widely known, but it has been difficult to obtain optical characteristics like a dye with a color filter using the pigment.

The dyes and pigments used in each of the above applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under environmental conditions to be used, for example, light resistance, heat resistance, good resistance to oxidizing gases such as ozone, and the like. In addition, when the pigment is a pigment, it is substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but it is difficult to achieve both because they are in a trade-off relationship.
In addition, when using the pigment, in addition to having a particle size and a particle shape necessary for expressing the desired transparency, fastness under the environmental conditions used, such as light resistance, heat resistance, Good resistance to oxidative gases such as ozone, and other chemical fastness to organic solvents and sulfurous acid gas. Disperse even fine particles in the medium used, and stable dispersion. , Etc. are also required. In particular, there is a strong demand for pigments that have a good yellow hue, have high coloring power among light, wet heat, and active gases in the environment, and are fast to light.

  In other words, the required performance for pigments is wider than dyes that require performance as pigment molecules, and not only the performance as pigment molecules but also the above requirements as a solid (fine particle dispersion) as an aggregate of pigment molecules All performance needs to be satisfied. As a result, the group of compounds that can be used as pigments is extremely limited compared to dyes, and even if high-performance dyes are derived into pigments, there are only a few that can satisfy the required performance as fine particle dispersions. It cannot be developed. This is confirmed by the fact that the number of pigments registered in the color index is less than 1/10 of the number of dyes.

Azo pigments are widely used in printing inks, ink-jet inks, electrophotographic materials, and the like because they are excellent in hue and coloring power, which are color characteristics. Of these, the most typically used yellow azo pigments are diarylide pigments. Examples of diarylide pigments include C.I. I. Pigment Yellow 12, 13 and 17 and the like. However, since diarylide pigments are very inferior in fastness, especially light resistance, when the printed matter is exposed to light, the pigment is decomposed and discolored, which is not suitable for long-term storage of the printed matter.
For example, as a yellow pigment used for inkjet recording, C.I. I. Pigment Yellow 74, 128, and 155. Among these, P.I. Y. 74 gives a clear yellow color but fades in a short period when the printed matter is exposed to light. P. Y. 128 and P.I. Y. With respect to 155, the printed product has a relatively small discoloration when exposed to light, but it has a strong greenish color and is inferior in the color reproduction range by the subtractive color mixing method. Thus, there is no known yellow pigment for inkjet that can achieve both a clear yellow hue and fastness to light.
Further, as a yellow pigment used for coloring pixels of a color filter, C.I. I. Pigment Yellow 138 and 150. Among these, P.I. Y. 138 contains a lot of halogens having a concern about the environment as a molecular structure. P. Y. 150 contains a heavy metal (for example, nickel) which has an environmental concern. As described above, there is no known yellow pigment that has performance as a pigment for use in a color filter but does not have a concern for safety to the environment.

  On the other hand, condensed polycyclic pigments are generally excellent in light fastness and heat resistance, and are therefore used in resin coloring, color filters, inkjet inks, and the like. Representative examples include phthalocyanine pigments (for example, CI Pigment Blue 15: 3, CI Pigment Green 7), quinacridone pigments (for example, CI Pigment Violet 19, CI Pigment, etc.). Red 122 etc.), diketopyrrolopyrrole pigments (eg CI Pigment Red 254 etc.), anthraquinone pigments (eg CI Pigment Red 177 etc.). However, condensed polycyclic pigments have disadvantages that they are inferior in coloring power and dispersibility or have a high halogen content, which is a concern for safety.

  When expressing a full color using a subtractive color mixing method of three colors of yellow, magenta, and cyan, or four colors added with black, if a pigment with poor fastness is used for one color, the gray of the printed matter If the balance is changed and a pigment having poor color characteristics is used, the color reproducibility at the time of printing is lowered. Therefore, in order to obtain a printed matter that maintains high color reproducibility for a long period of time, a pigment dispersion having both color characteristics and fastness is desired.

  On the other hand, compounds represented by the following chemical formulas (S-1) to (S-5) are known as heterocyclic compounds (see, for example, Patent Document 11 and Non-Patent Document 2). These compounds were only of interest as components of charge transfer complexes and intermediates thereof. In fact, they hardly absorbed visible light in solution and were not intended for use as colored compounds.

Japanese Patent Laid-Open No. 63-150273 Japanese Patent Laid-Open No. 4-85547 Japanese translation of Japanese translation of PCT publication No. 5-506428 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 Japanese Patent Laid-Open No. 63-150273 "Journal of the American Chemical Society", 1995, 117, 9995-1202. Tetrahedron Letters, 1977, 26, 2223

  An object of the present invention is to provide a novel heterocyclic compound useful as a functional material such as a pharmaceutical, an agricultural chemical, a dye, a pigment, an ultraviolet absorber, and a liquid crystal, and a synthetic intermediate thereof.

The present inventors have conducted extensive studies on the synthesis of a heterocyclic compound in which two heterocyclic rings are condensed to a benzene ring. As a result, the inventors have found a heterocyclic compound having a specific structure that has not been known so far. It came to complete.
The object of the present invention has been achieved by the following methods [1] to [3] .
[1] A compound represented by the following general formula (I).

[In General Formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent —CN, —COOR ⁸ , —CONR ⁹ R ¹⁰ , —COR ¹¹ or —SO ₂ R ¹² . . Here, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom or a monovalent substituent selected from the following substituent group. R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring represented by the above general formulas (2) to (7). R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent selected from the following substituent group. X ¹ , X ² , X ³ and X ⁴ represent a sulfur atom.
However, R ¹ , R ² , R ³ and R ⁴ are all cyano groups, X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms, and R ⁵ and R ⁶ are both hydroxy groups or hydrogen atoms. Except when there is. R ¹ and R ³ are both hydrogen atoms, R ² and R ⁴ are both arylcarbonyl groups, X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms, and R ⁵ and R ⁶ are both Except when it is a hydroxy group.
In the general formulas (2) to (7), R ²¹ , R ²² , R ³¹ , R ³² , R ³⁴ , R ⁴¹ , R ⁴⁴ , R ⁵¹ , R ⁵² , R ⁶² , R ⁶⁴ , R ⁷³ and R ⁷⁴ are Independently of each other, it represents a hydrogen atom or a monovalent substituent selected from the following substituent group.
^{R 23, R 24, R 25} , R 33, R 34, R 35, R 43, R 45, R 53, R 54, R 63 each independently represent an oxygen atom, a sulfur atom or nitrogen atom .
Z ⁷¹ and Z ⁷² each independently represent —N═ or —C (R ⁷⁵ ) ═. Here, R ⁷⁵ represents a hydrogen atom or a monovalent substituent selected from the following substituent group.
In the general formula ^(2), when ^{R 23} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 21} or ^{R 22.} If R ²⁴ is a nitrogen atom, said nitrogen atom to form a ring with ^{R 22.} If R ²⁵ is a nitrogen atom, said nitrogen atom to form a ring with ^{R 21.}
In the general formula ^(3), when ^{R 33} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 31} or ^{R 32.} If a R ³⁵ nitrogen atoms, said nitrogen atom to form a ring with ^{R 31.}
In the general formula ^(4), when at least one of ^{R 43} and ^{R 45} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 41.}
In the general formula ^(5), when ^{R 53} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 52.} If R ⁵⁴ is a nitrogen atom, said nitrogen atom to form a ring with ^{R 51.}
In the general formula ^(6), when ^{R 63} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 62.}
<Substituent group>
Halogen atom, linear or branched alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, cyano group, carboxyl group, alkoxycarbonyl group having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms Carbonyl group, substituted or unsubstituted carbamoyl group having 0 to 20 carbon atoms, alkylcarbonyl group having 1 to 20 carbon atoms, arylcarbonyl group having 6 to 20 carbon atoms, nitro group, substituted or unsubstituted having 0 to 20 carbon atoms Amino groups, acylamino groups having 1 to 20 carbon atoms, sulfonamido groups having 0 to 20 carbon atoms, imide groups having 2 to 20 carbon atoms, imino groups having 1 to 20 carbon atoms, hydroxy groups, and those having 1 to 20 carbon atoms. Alkoxy group, aryloxy group having 6 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkylsulfonyloxy group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms Sulfonyloxy group, sulfo group, substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, carbon A number 6 to 20 arylsulfonyl group or a 4 to 7-membered heterocyclic group]
[2] R ⁵ and R ⁶ in the general formula (I) are each independently an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acylamino group, a carbamoyloxy group, or a carbamoyl group The compound according to [1], which is an amino group.
[3] A compound represented by the following general formula (I ′).

[In the general formula (I ′), R ¹ , R ² , R ³ And R ⁴ Represents a cyano group or an alkoxycarbonyl group having 1 to 20 carbon atoms.
R ₅ And R ₆ Independently represent an alkoxy group having 1 to 20 carbon atoms or an acyloxy group having 1 to 20 carbon atoms.
X ¹ , X ² , X ³ And X ⁴ Represents a sulfur atom. ]

[A1] A colored composition containing a compound represented by the following general formula (II).

(Wherein R ⁵ , R ⁶ Independently represent a hydrogen atom or a monovalent substituent selected from the substituent group in [1]. X ¹ , X ² , X ³ And X ⁴ Represents a sulfur atom. Y ¹ And Y ² Is a 4-7 membered ring Q together with the carbon atom to which each is attached. ¹ And Q ² Represents the atomic group necessary to form )
[A2] Ring Q in the general formula (II) ¹ And Q ² The coloring composition according to [A1], wherein are independently a heterocycle.
[A3] Ring Q in formula (II) ¹ And Q ² The coloring composition according to the above [A1] or [A2], in which are each independently a heterocycle containing a nitrogen atom.
[A4] Ring Q in the general formula (II) ¹ And Q ² The coloring composition according to any one of [A1] to [A3], in which are each independently a 5- to 6-membered heterocycle.
[A5] Ring Q in the general formula (II) ¹ And Q ² The coloring composition according to the above [A4], wherein are independently represented by any one of the general formulas (2) to (7) described in [1] or a tautomer thereof.

[A6] Formula at least one of ^{R 24} and ^{R 25} in (2), the general formula (3) ^{R 35} in the general formula (4) ^{R 53} in ^{R 45,} and the general formula (5) in the And at least one of R ⁵⁴ represents an oxygen atom, respectively, according to the above [ A5 ].
[A7] at least one of the ^{R 21} in the general formula (2), the general formula (3) ^{R 31} in the general formula (4) ^{R 51} and ^{R 52} in ^{R 41,} and the general formula (5) in the Are each a hydrogen atom, The coloring composition as described in said [ A6 ] or [ A7 ].

[ A8 ] In the general formula ( II ), R ⁵ and R ⁶ are each independently selected from the group consisting of a hydrogen atom, an alkoxy group, an acyloxy group, a cyano group, and a halogen atom, [ A1 ]-[ A8 ] The coloring composition of any one of.

The hetero compounds of the present invention are useful as functional materials such as pharmaceuticals, agricultural chemicals, dyes, pigments, ultraviolet absorbers, liquid crystals, organic semiconductors, organic conductors, organic electronic materials, medical diagnostic materials, and synthetic intermediates thereof.
In particular, the compounds of the present invention can be used as dyes, pigments, and ultraviolet absorbers that have high light fastness, a high molar extinction coefficient ε, and give sharp absorption. Among them, it is extremely excellent in long-wave ultraviolet absorbing ability and can be preferably used as an ultraviolet absorber. If the compound of the present invention having absorption in the visible region is used, a colored composition excellent in light fastness that does not contain heavy metals can be provided. By incorporating the compound of the present invention having absorption in the ultraviolet region into a polymer molded product such as plastic or fiber, the light stability of the polymer molded product can be enhanced. Furthermore, the polymer material containing the compound of the present invention having absorption in the ultraviolet region can be used as a filter or a container for protecting contents sensitive to ultraviolet rays by utilizing the excellent ultraviolet absorbing ability. In addition, the compound of the present invention can be preferably used as a liquid crystal compound or an optically anisotropic material by utilizing structural features having substituents in four directions perpendicular to each other on a plane from a strong central portion. By incorporating the compound of the present invention into a polymer material and processing it into a film, optical properties can be imparted to the film. Furthermore, the film containing the compound of the present invention can be used as a retardation plate, a polarizing plate, an optical compensation film, etc. by utilizing the imparted optical characteristics.

Hereinafter, the present invention will be described in detail.
First, the <substituent group> in the present application will be described.
The <substituent group> is a group consisting of the above-mentioned monovalent substituents, specifically, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carbon number of 1 to 20 (preferably 1-10) linear or branched alkyl group (for example, methyl, ethyl), aryl group (for example, phenyl, naphthyl) having 6 to 20 carbon atoms (preferably phenyl, naphthyl), cyano group, carboxyl group, carbon number 1 -20 (preferably 1-10) alkoxycarbonyl group (eg methoxycarbonyl), C6-C20 (preferably 6-10) aryloxycarbonyl group (eg phenoxycarbonyl), C0-20 (preferably 0-10) substituted or unsubstituted carbamoyl group (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), carbon number 1 20 (preferably 1-10) alkylcarbonyl group (for example, acetyl), C6-C20 (preferably 6-10) arylcarbonyl group (for example, benzoyl), nitro group, C0-20 (preferably 0) -10) substituted or unsubstituted amino group (for example, amino, dimethylamino, anilino), C1-C20 (preferably 1-10) acylamino group (for example, acetamido, ethoxycarbonylamino), C0-20 (Preferably 0 to 10) sulfonamide group (for example, methanesulfonamide), imide group having 2 to 20 carbon atoms (preferably 2 to 10) (for example, succinimide, phthalimide), 1 to 20 carbon atoms (preferably 1 to 1) 10) imino group (for example, benzylideneamino), hydroxy group, carbon number of 1-20 (preferably 1-10) An alkoxy group (for example, methoxy), an aryloxy group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenoxy), an acyloxy group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, acetoxy), carbon An alkylsulfonyloxy group having 1 to 20 (preferably 1 to 10) alkylsulfonyloxy group (for example, methanesulfonyloxy), an arylsulfonyloxy group having 6 to 20 carbon atoms (preferably 6 to 10) (for example, benzenesulfonyloxy), a sulfo group, C 0-20 (preferably 0-10) substituted or unsubstituted sulfamoyl groups (eg, sulfamoyl, N-phenylsulfamoyl), C 1-20 (preferably 1-10) alkylthio groups (eg, methylthio) ), An arylthio group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenylthio) An alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methanesulfonyl), an arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, benzenesulfonyl), and a 4 to 7-membered ring (preferably 5-6 membered ring) Hajime Tamaki (e.g. pyridyl, morpholino).
Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. Also but it may also be bonded with substituents together form a ring.

It is preferable that 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.
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.A. 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 cyano group (0.66), carboxyl group (—COOH: 0.45), alkoxycarbonyl group (—COOMe: 0.45), aryloxycarbonyl group ( -COOPh: 0.44), a carbamoyl group (-CONH _2: 0.36), an alkylcarbonyl group (-COMe: 0.50), an arylcarbonyl group (-COPh: 0.43), an alkylsulfonyl group (-SO ₂ Me: 0.72), or aryl Examples include a sulfonyl group (—SO ₂ Ph: 0.68). 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 .
In the present invention, the ring formed by combining R ¹ and R ² and R ³ and R ⁴ is the ring represented by the general formulas (2) to (7).

In the present invention, R ¹ , R ² , R ³ and R ⁴ are substituents having Hammett's substituent constant σp value of 0.2 or more .

That is, R ¹ , R ² , R ³ and R ⁴ are —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 selected from the above substituent group . More preferred is —CN, —COOR ⁸ , —COR ¹¹ or —SO ₂ R ¹² . More preferred is -CN or -COOR ⁸ . Particularly preferred is -CN.

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.

The rings formed by bonding R ¹ and R ^{2 and} R ³ and R ⁴ to each other will be described later. The substituents of these rings are monovalent substituents selected from the substituent group described above. A carbonyl group, an imino group, etc. are mentioned as a bivalent substituent like General formula (2)-(7) . 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.

Favorable examples and reference examples of the combination of R ¹ and ^{R 2} or ^{R 3} and ^{R 4} are shown in Table 1 below. 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 selected from the aforementioned substituent group . The monovalent substituent, among a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, a nitro Group, amino group, acylamino group, sulfonamido group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, sulfo group, alkylthio group and arylthio group 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. Alkoxy groups are even more preferred.

  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. In the case of an aryloxycarbonyloxy group, the aryl 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,} to display the sulfur atom.

In the present ^invention, X 1 to X ⁴ are both sulfur atoms, when they are hetero atoms, the ^{X 1} and ^{X 2} or ^{X 3} and Table 3 for reference for completely as examples of combinations of ^{X 4} It shows you.
Na us, in this 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) when used as an ultraviolet absorber.

In the general formula ^{(Ia), R 2a} and ^{R 4a} has the same meaning as ^{R 2} and ^{R 4} in Formula (I), the favorable examples thereof are also the same. R ^5a and R ^6a represent a monovalent substituent selected from the above substituent group . Preferably, an alkyl group having 1 to 20 (preferably 1 to 10) carbon atoms, an aryl group having 6 to 20 (preferably 6 to 10) carbon atoms, and a 4 to 7 membered ring (preferably 5 to 6 membered ring). It is a heterocyclic group. These may further have a substituent. Examples of the substituent include the monovalent substituents of the above-described substituent group . 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.

However, among the compounds represented by the general formula (I), R ¹ , R ² , R ³ and R ⁴ are all cyano groups, X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms, and A compound in which R ⁵ and R ⁶ are both a hydroxy group or a hydrogen atom is excluded from the scope of the present invention. Moreover, among the compounds represented by the general formula (I), R ¹ and R ³ are both hydrogen atoms, R ² and R ⁴ are both arylcarbonyl groups, and X ¹ , X ² , X ³ and X ⁴ are Compounds which are all sulfur atoms and R ⁵ and R ⁶ are both hydroxy groups are also excluded from the scope of the present invention.

Then, the case where the compound represented by the said general formula (I) is used as a coloring compound is demonstrated.
In the present invention, when the compound represented by the general formula (I) is used as a pigment, R ⁵ and R ⁶ are used from the viewpoint of imparting solvent resistance and water resistance by enhancing intramolecular and intermolecular interactions. A substituent having 5 or less carbon atoms or high planarity is preferred. Specifically, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms Group, aryloxy group, heterocyclic oxy group, acyloxy group having 2 to 5 carbon atoms, hydroxy group, halogen atom, nitro group, cyano group, amino group, mono / dialkylamino group having 1 to 5 carbon atoms, arylamino group A heterocyclic amino group, an alkoxycarbonyl group having 1 to 5 carbon atoms, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, preferably a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, A cyano group and a halogen atom are more preferable, and a hydrogen atom, a methoxy group, an ethoxy group, an acetoxy group, and a chlorine atom are particularly preferable because of ease of production. . The absorption maximum wavelength of the compound represented by the general formula (I) can be controlled by the electronic effect (electron donating property / electron attracting property) of R ⁵ and R ⁶ , so that it matches the target hue. Appropriate substituents can be selected.
In the present invention, when the compound represented by the general formula (I) is used as a dye, R ⁵ and R ⁶ are carbon atoms from the viewpoint of suppressing interaction between molecules and imparting affinity to a medium. It is preferably 6 or more and 36 or less, a bulky substituent, or a highly hydrophilic substituent. Specifically, hydrogen atom, alkyl group, cycloalkyl group, aryl group, heterocyclic group, acyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, hydroxy group, amino group, mono / dialkylamino Group, arylamino group, heterocyclic amino group, alkoxycarbonyl group having 1 to 5 carbon atoms, aryloxycarbonyl group, carboxyl group, sulfo group and phosphonic acid group are preferable, hydrogen atom, isopropyl group, t-butyl group, t -Amyl group, 2-ethylhexyl group, isopropyloxy group, t-butyloxy group, t-amyloxy group, 2-ethylhexyloxy group, pivaloyloxy group, 2-ethylhexanoyloxy group, hydroxy group, amino group, carboxyl group, sulfo group It is more preferable that the Child, t-butyloxy group, a 2-ethylhexyl group, 2-ethyl hexanoyl group are particularly preferred. The absorption maximum wavelength of the compound represented by the general formula (I) can be controlled by the electronic effect (electron donating property / electron attracting property) of R ⁵ and R ⁶ , so that it matches the target hue. Appropriate substituents can be selected.

In the present invention, when the compound represented by the general formula (I) is used as a pigment, R ¹ , R ² , R ³ , and R ⁴ may be used as solvent resistance or water resistance by increasing the intramolecular and intermolecular interactions. From the viewpoint of imparting properties, a substituent having 5 or less carbon atoms or high planarity is preferable. Further, in order to have a good optical property of absorbing visible light, the so-called donor with X ¹ to X ⁴ is a sulfur atom - so as to form an acceptor-type chromophore, electron-withdrawing substituent is preferred. Specifically, the acyl group having a carbon number of 2-5, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 5 carbon atoms, an aryloxycarbonyl group, a carbamoyl group, and any one selected from the group consisting of aryl-carbamoyl group The substituent is preferably selected from the group consisting of an acyl group having 2 to 5 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 5 carbon atoms, a carbamoyl group, and an arylcarbamoyl group. An acetyl group, a cyano group, a methoxycarbonyl group, an ethoxycarbonyl group, an N-phenylcarbamoyl group, and an N- (2-methoxyphenyl) carbamoyl group are particularly preferable.
In the present invention, when the compound represented by the general formula (I) is used as a dye, R ¹ , R ² , R ³ , and R ⁴ are used to suppress the interaction between molecules and impart affinity to a medium. From the standpoint of the above, a substituent having 6 to 36 carbon atoms, a bulky substituent, or a highly hydrophilic substituent is preferable. Further, in order to have a good optical property of absorbing visible light, the so-called donor with X ¹ to X ⁴ is a sulfur atom - so as to form an acceptor-type chromophore, electron-withdrawing substituent is preferred. Specifically, an acyl group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, and an arylcarbamoyl group, a carboxyl group, a sulfo group, and a phosphonic acid group are preferable, and a pivaloyl group, a cyano group, a t-butyloxycarbonyl group, 2- An ethylhexyloxycarbonyl group, a carbamoyl group, an N- (4-sulfophenyl) carbamoyl group, a mesitylcarbamoyl group, a carboxyl group, and a sulfo group are more preferable, and a t-butyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, and a carboxyl group are preferable. Particularly preferred.

In the present invention, at least one of the group of R ¹ and R ^{2 and} the group of R ³ and R ^{4 in} the general formula (I) is bonded to each other to form a ring, thereby increasing the conjugation length in the molecule. Since it is considered that the wavelength of extension and absorption maximum is extended to the visible region, it is preferable that at least one of them is bonded to each other to form a ring. This ring may be condensed with another ring, and may further have a substituent. Examples of such substituents are the same as the examples of the substituent group described above, and preferred forms are also the same.

When at least one of the group of R ¹ and R ^{2 and} the group of R ³ and R ^{4 in} the general formula (I) is bonded to each other to form a ring, the formed ring is aliphatic or aromatic. Although it may be a hydrocarbon ring or a heterocyclic ring, it is preferably a heterocyclic ring from the viewpoint of the optical properties and various fastnesses of the dye compound represented by the general formula (I), and further a nitrogen atom In view of the thermodynamic stability of the dye compound, it is more preferably a 5- to 6-membered ring.
For this reason, in this invention, the ring represented by General Formula (2)-(7) is formed.

From the viewpoints of optical properties and various fastness of the reduction compounds, when used as a colored compound, a compound represented by the following general formula (II) are good preferable.
Among these, the compound of this invention is a compound which satisfy | fills the prescription | regulation of the said general formula (I).

In general formula (II), R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.

When using a compound represented by one general formula (II) as a pigment, from the viewpoint as the R ⁵ and R ^6, to impart solvent resistance and water resistance by increasing the interaction between the intramolecular and carbon A substituent having a number of 5 or less or high planarity is preferred. Specifically, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms Group, aryloxy group, heterocyclic oxy group, acyloxy group having 2 to 5 carbon atoms, hydroxy group, halogen atom, nitro group, cyano group, amino group, mono / dialkylamino group having 1 to 5 carbon atoms, arylamino group A heterocyclic amino group, an alkoxycarbonyl group having 1 to 5 carbon atoms, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, preferably a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, A cyano group and a halogen atom are more preferable, and a hydrogen atom, a methoxy group, an ethoxy group, an acetoxy group, and a chlorine atom are particularly preferable because of ease of production. . The absorption maximum wavelength of the compound represented by the general formula (II) can be controlled by the electronic effect (electron donating property / electron attracting property) of R ⁵ and R ^6. Appropriate substituents can be selected.
When using a compound represented by one general formula (II) as a dye, as the R ⁵ and R ^6, inhibit the interaction between molecules, from the viewpoint of imparting affinity to the medium, 6 or more carbon atoms It is preferably 36 or less, a bulky substituent, or a highly hydrophilic substituent. Specifically, hydrogen atom, alkyl group, cycloalkyl group, aryl group, heterocyclic group, acyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, hydroxy group, amino group, mono / dialkylamino Group, arylamino group, heterocyclic amino group, alkoxycarbonyl group having 1 to 5 carbon atoms, aryloxycarbonyl group, carboxyl group, sulfo group and phosphonic acid group are preferable, hydrogen atom, isopropyl group, t-butyl group, t -Amyl group, 2-ethylhexyl group, isopropyloxy group, t-butyloxy group, t-amyloxy group, 2-ethylhexyloxy group, pivaloyloxy group, 2-ethylhexanoyloxy group, hydroxy group, amino group, carboxyl group, sulfo group It is more preferable that the Child, t-butyloxy group, a 2-ethylhexyl group, 2-ethyl hexanoyl group are particularly preferred. The absorption maximum wavelength of the compound represented by the general formula (II) can be controlled by the electronic effect (electron donating property / electron attracting property) of R ⁵ and R ^6. Appropriate substituents can be selected.

In one general formula ^{(II), X 1, X} 2, X 3, and ^{X 4} represents a sulfur atom. From the viewpoints of optical properties and various fastness of the compound represented by one general formula (II), the sulfur atom of the present application have particular preferred.

In one general formula ^{(II), Y 1, Y} 2 each represents a group of atoms necessary to form a ring ^Q 1, ^{Q 2} of the 4-7 membered together with the carbon atoms to which it is attached. Preferably, it represents a non-metallic atomic group necessary for forming a 4- to 7-membered ring Q ¹ or Q ² .

Rings Q ¹ and Q ² are 4- to 7-membered aliphatic or aromatic hydrocarbon rings or heterocycles, and may be condensed with other rings.

As substituents for R ^{1 to} R ⁶ and Q ¹ and Q ² , those known as substituents that generally enhance the interaction between molecules and improve pigment properties, specifically amide bonds such as benzimidazolone, It is also preferable to have a quinoxalinedione structure.

When the rings Q ¹ and Q ² are heterocycles, particularly electron-deficient heterocycles, the absorption maximum of the compound represented by the general formula (II) is shifted by a longer wavelength, and more preferable optical characteristics as a colored compound are exhibited. Therefore, the rings Q ¹ and Q ² in the present invention are preferably a heterocyclic ring, more preferably a heterocyclic ring containing a nitrogen atom, and from the viewpoint of thermodynamic stability of the compound, More preferably, it is a 5-6 membered ring.
Moreover , it is especially preferable that the rings Q ¹ and Q ² are represented by any one of the following general formulas (2) to (7) or a tautomer thereof. In general formula (II), rings Q ¹ and Q ² are compounds of the present invention in any of the following general formulas (2) to (7).
The rings represented by the general formulas (2) to (7) or tautomers thereof are electron-deficient heterocycles. For example, in the formula (2), R ²⁴ and / or R which are electron withdrawing groups are used. ²⁵ are connected by double bond conjugated with a hetero atom ^X 1 to X ^4, by hetero atoms ^X 1 to X ⁴ electron transition to the ^{R 24} and / or ^{R 25} occurs, particularly preferred as a coloring compound It is considered to exhibit optical characteristics.
Here, each of the “monovalent substituent” and the “substituent” defined in the ring structure represented by the general formulas (2) to (7) is a substituent selected from the above substituent group. Means group.

In the general formula (2), R ²¹ and R ²² each independently represent a hydrogen atom or a monovalent substituent.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (2) is used as a pigment, the substituent represented by R ²¹ and R ²² includes an intramolecular From the viewpoint of enhancing the interaction between molecules and imparting solvent resistance and water resistance, a substituent having 5 or less carbon atoms or a highly planar substituent is preferred. Specific examples of R ²¹ and R ²² include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, and aryl. It is preferably any substituent selected from the group consisting of an oxycarbonyl group, a carbamoyl group, and a sulfamoyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or a phenyl, It is particularly preferred.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (2) is used as a dye, the substituent on the hetero atom suppresses the interaction between molecules. From the viewpoint of imparting affinity to the medium, any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent is preferable. Specifically, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and a carboxyl group are preferable, and a t-butyl group, a t-amyl group, 2- An ethylhexyl group, a trifluoromethyl group, and a carboxyl group are more preferable, and a t-butyl group and a 2-ethylhexyl group are particularly preferable.

R ²³ , R ²⁴ and R ²⁵ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent .
Such heteroaryl atom, from the viewpoint of optical properties and various fastness of the compound represented by the general formula containing a ring structure represented by the general formula (2) (II), an oxygen atom, a nitrogen atom, sulfur is atomic preferable, and particularly preferably a at least one oxygen atom of the ^{R 24,} and ^{R 25.}
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (2) is used as a pigment, the substituent on the nitrogen atom may be an intramolecular or intermolecular interaction. From the viewpoint of imparting solvent resistance and water resistance by enhancing the resistance, a substituent having 5 or less carbon atoms or a highly planar substituent is preferred. Specifically, an alkyl group having 1 to 5 carbon atoms and an aryl group are preferable, a methyl group, an ethyl group, a propyl group, and a phenyl group are more preferable, and a methyl group is particularly preferable.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (2) is used as a dye, the substituent on the nitrogen atom suppresses the interaction between molecules. From the viewpoint of imparting affinity to the medium, any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent is preferable. Specifically, an alkyl group and an aryl group are preferable, a t-butyl group, a t-amyl group, a 2-ethylhexyl group, and a mesityl group are more preferable, and a t-butyl group and a 2-ethylhexyl group are particularly preferable.

Further, when R ²³ has a substituent, the substituent may be bonded to R ²¹ or R ²² to form a ring, and when R ²⁴ has a substituent, the substituent is bonded to R ^22. A ring may be formed, and when R ²⁵ has a substituent, the substituent may be bonded to R ²¹ to form a ring. As such a ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a dihydropyrimidine ring, and a dihydrotriazine ring are preferable.
However, in the present invention, when R ²³ is a nitrogen atom, the nitrogen atom is bonded to R ²¹ or R ²² to form a ring. When R ²⁴ is a nitrogen atom, the nitrogen atom is bonded to R ²² to form a ring. When R ²⁵ is a nitrogen atom, the nitrogen atom is bonded to R ²¹ to form a ring.

In the general formula (3), R ³¹ , R ³² and R ³⁴ each independently represent a hydrogen atom or a monovalent substituent.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a pigment, the substituent represented by R ³¹ includes intramolecular and intermolecular From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, the substituent is preferably a substituent having 5 or less carbon atoms or a highly planar substituent. Specific examples of R ³¹ include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, and an aryloxycarbonyl group. It is preferably any substituent selected from the group consisting of carbamoyl group and sulfamoyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or phenyl, and a hydrogen atom. Particularly preferred.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a dye, the substituent represented by R ³¹ is an intermolecular interaction. From the viewpoint of suppressing and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and a carboxyl group are preferable, and a t-butyl group, a t-amyl group, 2- An ethylhexyl group, a trifluoromethyl group, and a carboxyl group are more preferable, and a t-butyl group and a 2-ethylhexyl group are particularly preferable.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a pigment, the substituent represented by R ³² includes intramolecular and intermolecular From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, the substituent is preferably a substituent having 5 or less carbon atoms or a highly planar substituent. Specific examples of R ³² include a hydrogen atom, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, a nitro group, a cyano group, an alkoxycarbonyl group having 1 to 5 carbon atoms, an aryloxycarbonyl group, and a carbamoyl group. And a substituent selected from the group consisting of sulfamoyl groups, more preferably a hydrogen atom, a cyano group, an acetyl group, or a carbamoyl group, and particularly preferably a hydrogen atom or a cyano group.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a dye, the substituent represented by R ³² includes an intermolecular interaction. From the viewpoint of suppressing and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, an aryl group, a heterocyclic group, an acyl group, and a carbamoyl group are preferable, a pivaloyl group, a carbamoyl group, and a phenyl group are more preferable, and a carbamoyl group is particularly preferable.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a pigment, the substituent represented by R ³⁴ includes intramolecular and intermolecular From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, a substituent having 5 or less carbon atoms or a substituent having high planarity is preferable. Specifically, R ³⁴ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, an alkoxy group having 1 to 5 carbon atoms, an acylamino group having 2 to 5 carbon atoms, or a carbamoyl group. Atom, methyl group, ethyl group, methoxy group, ethoxy group, acetylamino group, carbamoyl, N-methylcarbamoyl group are more preferable, and methyl group, ethyl group, methoxy group, ethoxy group, and acetylamino group are particularly preferable. .
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a dye, the substituent represented by R ³⁴ suppresses the interaction between molecules. From the viewpoint of imparting affinity to the medium, the substituent is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, an alkyl group, an aryl group, an alkoxy group, a carboxyl group, and an amino group are preferable, and a t-butyl group, a t-amyl group, a t-butyloxy group, a 2-ethylhexyloxy group, and a carboxyl group are more preferable, and t A butyl group is particularly preferred.

R ³³ and R ³⁵ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent .
Such heteroaryl atom of the general formula in terms of optical properties and various fastness of the compound represented by the general formula (II) containing a ring structure represented by (3), an oxygen atom, a nitrogen atom, sulfur it is atomic preferable, and particularly preferably R ³⁵ is an oxygen atom.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a pigment, the substituent on the nitrogen atom includes an intramolecular and intermolecular interaction. From the viewpoint of imparting solvent resistance and water resistance by enhancing the resistance, a substituent having 5 or less carbon atoms or a highly planar substituent is preferred. Specifically, an alkyl group having 1 to 5 carbon atoms and an aryl group are preferable, a methyl group, an ethyl group, a propyl group, and a phenyl group are more preferable, and a methyl group is particularly preferable.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (3) is used as a dye, the substituent on the nitrogen atom suppresses the interaction between molecules. From the viewpoint of imparting affinity to the medium, any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent is preferable. Specifically, an alkyl group and an aryl group are preferable, a t-butyl group, a t-amyl group, a 2-ethylhexyl group, and a mesityl group are more preferable, and a t-butyl group and a 2-ethylhexyl group are particularly preferable.

Further, when R ³³ has a substituent, the substituent may be bonded to R ³¹ or R ³² to form a ring. When R ³⁵ has a substituent, the substituent may be bonded to R ³¹ to form a ring. As such a ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a dihydropyrimidine ring, and a dihydrotriazine ring are preferable.
However, in the present invention, when R ³³ is a nitrogen atom, the nitrogen atom is bonded to R ³¹ or R ³² to form a ring. In the case of R ³⁵ nitrogen atom, the nitrogen atom is bonded to R ³¹ to form a ring.

In the general formula (4), R ⁴¹ and R ⁴⁴ each independently represent a hydrogen atom or a monovalent substituent.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (4) is used as a pigment, the substituent represented by R ⁴¹ may be an intramolecular or intermolecular molecule. From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, the substituent is preferably a substituent having 5 or less carbon atoms or a highly planar substituent. Specific examples of R ⁴¹ include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an aryloxycarbonyl group, It is preferably a substituent selected from the group consisting of a carbamoyl group and a sulfamoyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or phenyl, and particularly preferably a hydrogen atom. preferable.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (4) is used as a dye, the substituent represented by R ⁴¹ may be an intermolecular interaction. From the viewpoint of suppressing and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, R ⁴¹ is preferably an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a carboxyl group, and a t-butyl group or a t-amyl group. 2-ethylhexyl group, trifluoromethyl group and carboxyl group are more preferable, and t-butyl group and 2-ethylhexyl group are particularly preferable.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (4) is used as a pigment, the substituent represented by R ⁴⁴ includes intramolecular and intermolecular From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, a substituent having 5 or less carbon atoms or a substituent having high planarity is preferable. Specifically, R ⁴⁴ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, an alkoxy group having 1 to 5 carbon atoms, an acylamino group having 2 to 5 carbon atoms, or a carbamoyl group. Atom, methyl group, ethyl group, methoxy group, ethoxy group, acetylamino group, carbamoyl, N-methylcarbamoyl group are more preferable, and methyl group, ethyl group, methoxy group, ethoxy group, and acetylamino group are particularly preferable. .
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (4) is used as a dye, the substituent represented by R ⁴⁴ includes an intermolecular interaction. From the viewpoint of suppressing and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, R ⁴⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carboxyl group or an amino group, more preferably a t-butyl group, a t-amyl group, a t-butyloxy group, a 2-ethylhexyloxy group or a carboxyl group. T-Butyl group is preferred, and particularly preferred.

R ⁴³ and R ⁴⁵ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent .
Such a hetero atom includes an oxygen atom, a nitrogen atom, a sulfur atom, from the viewpoint of optical properties and various fastnesses of the compound represented by the general formula (II) including the ring structure represented by the general formula (4). Child is preferred , and it is particularly preferred that R ⁴⁵ represents an oxygen atom.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (4) is used as a pigment, the substituent on the nitrogen atom may be an intramolecular or intermolecular interaction. From the viewpoint of imparting solvent resistance and water resistance by enhancing the resistance, a substituent having 5 or less carbon atoms or a highly planar substituent is preferred. Specifically, an alkyl group having 1 to 5 carbon atoms and an aryl group are preferable, a methyl group, an ethyl group, a propyl group, and a phenyl group are more preferable, and a methyl group is particularly preferable.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (4) is used as a dye, the substituent on the nitrogen atom suppresses the interaction between molecules. From the viewpoint of imparting affinity to the medium, any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent is preferable. Specifically, an alkyl group and an aryl group are preferable, a t-butyl group, a t-amyl group, a 2-ethylhexyl group, and a mesityl group are more preferable, and a t-butyl group and a 2-ethylhexyl group are particularly preferable.

Further, when at least one of R ⁴³ and R ⁴⁵ has a substituent, the substituent may be bonded to R ⁴¹ to form a ring. As such a ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a dihydropyrimidine ring, and a dihydrotriazine ring are preferable.
However, in the present invention, when at least one of R ⁴³ and R ⁴⁵ is a nitrogen atom, the nitrogen atom is bonded to R ⁴¹ to form a ring.

In the general formula (5), R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent substituent.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (5) is used as a pigment, the substituent represented by R ⁵¹ and R ⁵² includes an intramolecular From the viewpoint of enhancing the interaction between molecules and imparting solvent resistance and water resistance, a substituent having 5 or less carbon atoms or a highly planar substituent is preferable. Specific examples of R ⁵¹ and R ⁵² include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, and aryloxy It is preferably any substituent selected from the group consisting of a carbonyl group, a carbamoyl group, and a sulfamoyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or phenyl, and a hydrogen atom. It is particularly preferred.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (5) is used as a dye, the substituent represented by R ⁵¹ and R ⁵² may be an intermolecular molecule. From the viewpoint of suppressing the interaction and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, R ⁵¹ and R ⁵² are preferably an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a carboxyl group, a t-butyl group, t -Amyl group, 2-ethylhexyl group, trifluoromethyl group and carboxyl group are more preferred, and t-butyl group and 2-ethylhexyl group are particularly preferred.

R ⁵³ and R ⁵⁴ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent .
Such heteroaryl atom, from the viewpoint of optical properties and various fastness of the compound represented by the general formula containing a ring structure represented by the general formula (5) (II), an oxygen atom, a nitrogen atom, sulfur is atomic preferable, and particularly preferably a at least one oxygen atom of the ^{R 53,} and ^{R 54.}
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (5) is used as a pigment, the substituent on the nitrogen atom may be an intramolecular or intermolecular interaction. From the standpoint of enhancing solvent resistance and imparting solvent resistance and water resistance, a substituent having 5 or less carbon atoms or a highly planar substituent is preferred. Specifically, an alkyl group having 1 to 5 carbon atoms and an aryl group are preferable, a methyl group, an ethyl group, a propyl group, and a phenyl group are more preferable, and a methyl group is particularly preferable.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (5) is used as a dye, the substituent on the nitrogen atom suppresses the interaction between molecules. From the viewpoint of imparting affinity to the medium, any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent is preferable. Specifically, an alkyl group and an aryl group are preferable, a t-butyl group, a t-amyl group, a 2-ethylhexyl group, and a mesityl group are more preferable, and a t-butyl group and a 2-ethylhexyl group are particularly preferable.

In addition, when R ⁵³ has a substituent, the substituent may be bonded to R ⁵² to form a ring, and when R ⁵⁴ has a substituent, the substituent is bonded to R ⁵¹ to form a ring. May be. As such a ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a dihydropyrimidine ring, and a dihydrotriazine ring are preferable.
However, in the present invention, when R ⁵³ is a nitrogen atom, the nitrogen atom is bonded to R ⁵² to form a ring. When R ⁵⁴ is a nitrogen atom, the nitrogen atom is bonded to R ⁵¹ to form a ring.

In the general formula (6), R ⁶² and R ⁶⁴ each independently represent a hydrogen atom or a monovalent substituent.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (6) is used as a pigment, the substituent represented by R ⁶² includes an intramolecular and intermolecular From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, the substituent is preferably a substituent having 5 or less carbon atoms or a highly planar substituent. Specific examples of R ⁶² include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, a heterocyclic group, an acyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an aryloxycarbonyl group, It is preferably a substituent selected from the group consisting of a carbamoyl group and a sulfamoyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or phenyl, and particularly preferably a hydrogen atom. preferable.
In the present invention, examples of the substituent case, represented by R ⁶² to use formula containing a ring structure represented by the general formula (6) compounds represented by (II) as the dye, the interaction between molecules From the viewpoint of suppressing and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specific examples of R ⁶² include an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and a carboxyl group, and a t-butyl group and a t-amyl group. 2-ethylhexyl group, trifluoromethyl group and carboxyl group are more preferable, and t-butyl group and 2-ethylhexyl group are particularly preferable.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (6) is used as a pigment, the substituent represented by R ⁶⁴ is an intramolecular or intermolecular molecule. From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, the substituent is preferably a substituent having 5 or less carbon atoms or a highly planar substituent. Specifically, R ⁶⁴ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, an alkoxy group having 1 to 5 carbon atoms, an acylamino group having 2 to 5 carbon atoms, or a carbamoyl group. Atom, methyl group, ethyl group, methoxy group, ethoxy group, acetylamino group, carbamoyl, N-methylcarbamoyl group are more preferable, and methyl group, ethyl group, methoxy group, ethoxy group, and acetylamino group are particularly preferable. .
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (6) is used as a dye, the substituent represented by R ⁶⁴ is an intermolecular interaction. From the viewpoint of suppressing and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, R ⁶⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carboxyl group or an amino group, more preferably a t-butyl group, a t-amyl group, a t-butyloxy group, a 2-ethylhexyloxy group or a carboxyl group. T-Butyl group is preferred, and particularly preferred.

R ⁶³ represents an oxygen atom, a sulfur atom or a nitrogen atom which may have a substituent .
Such heteroaryl atom, from the viewpoint of optical properties and various fastness of the compound represented by the general formula containing a ring structure represented by the general formula (6) (II), an oxygen atom, a nitrogen atom, sulfur it is atomic preferable, and particularly preferably R ⁶³ is an oxygen atom.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (6) is used as a pigment, the substituent on the nitrogen atom may be an intramolecular or intermolecular interaction. From the standpoint of enhancing solvent resistance and imparting solvent resistance and water resistance, a substituent having 5 or less carbon atoms or a highly planar substituent is preferred. Specifically, an alkyl group having 1 to 5 carbon atoms and an aryl group are preferable, a methyl group, an ethyl group, a propyl group, and a phenyl group are more preferable, and a methyl group is particularly preferable.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (6) is used as a dye, the substituent on the nitrogen atom suppresses the interaction between molecules. From the viewpoint of imparting affinity to the medium, any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent is preferable. Specifically, an alkyl group and an aryl group are preferable, a t-butyl group, a t-amyl group, a 2-ethylhexyl group, and a mesityl group are more preferable, and a t-butyl group and a 2-ethylhexyl group are particularly preferable.

Further, when R ⁶³ has a substituent, the substituent may be bonded to R ⁶² to form a ring. As such a ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a dihydropyrimidine ring, and a dihydrotriazine ring are preferable.
However, in the present invention, when R ⁶³ is a nitrogen atom, the nitrogen atom is bonded to R ⁶² to form a ring.

Z ⁷¹ and Z ⁷² in the general formula (7) each independently represent —N═ or —C (R ⁷⁵ ) ═.
R ⁷³ and R ⁷⁴ each independently represent a hydrogen atom or a monovalent substituent.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (7) is used as a pigment, the substituents represented by R ⁷³ and R ⁷⁴ include intramolecular and From the viewpoint of enhancing the interaction between molecules and imparting solvent resistance and water resistance, it is preferably a substituent having 5 or less carbon atoms or a highly planar substituent. Specific examples of R ⁷³ and R ⁷⁴ include an aryl group, a heterocyclic group, an acyl group having 1 to 5 carbon atoms, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 5 carbon atoms, an aryloxycarbonyl group, and a carbamoyl group. Arylcarbamoyl group is preferred, phenyl group, acetyl group, cyano group, methoxycarbonyl group, ethoxycarbonyl group, carbamoyl group, N-phenylcarbamoyl group, N- (2-methoxyphenyl) carbamoyl group is more preferred, cyano group, A methoxycarbonyl group, an ethoxycarbonyl group, and a carbamoyl group are particularly preferable.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (7) is used as a dye, the substituent represented by R ⁷³ and R ⁷⁴ may be an intermolecular From the viewpoint of suppressing the interaction and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, R ⁷³ and R ⁷⁴ are preferably an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, a cyano group, a carbamoyl group, or a carboxyl group,
Phenyl group, t-butyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclohexyloxycarbonyl group, (2,6-di (t-butyl) -4-methylcyclohexyl) oxycarbonyl group, cyano group, carboxyl group and more Preferably
A t-butyloxycarbonyl group, a (2,6-di (t-butyl) -4-methylcyclohexyl) oxycarbonyl group, a cyano group, and a carboxyl group are particularly preferable.

R ⁷⁵ represents a hydrogen atom or a monovalent substituent.

In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (7) is used as a pigment, the substituent represented by R ⁷⁵ is an intramolecular or intermolecular molecule. From the viewpoint of enhancing the interaction and imparting solvent resistance and water resistance, the substituent is preferably a substituent having 5 or less carbon atoms or a highly planar substituent. Specific examples R ^75, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an aryl group, a heterocyclic group, an alkoxy group having 1 to 5 carbon atoms, 2 carbon atoms 5 acyl groups, C2-C5 alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfamoyl groups are preferred, hydrogen atoms, methyl groups, ethyl groups, phenyl groups, p-methoxyphenyl groups, methoxy groups, ethoxy groups And more preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group.
In the present invention, when the compound represented by the general formula (II) including the ring structure represented by the general formula (7) is used as a dye, the substituent represented by R ⁷⁵ is an intermolecular interaction. From the viewpoint of suppressing and imparting affinity to the medium, it is preferably any of a substituent having 6 to 36 carbon atoms, a bulky substituent, and a highly hydrophilic substituent. Specifically, R ⁷⁵ is preferably an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, a carboxyl group, a carbamoyl group, or a sulfamoyl group, a t-butyl group, a t-amyl group, 2 -Ethylhexyl group, t-butyloxy group, 2-ethylhexyloxy group, amino group, and carboxyl group are more preferable, and t-butyl group, 2-ethylhexyl group, t-butyloxy group, and 2-ethylhexyloxy group are particularly preferable.

In the present invention, R ⁵ and R ⁶ are each independently a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (I). An acyloxy group having 2 to 9 carbon atoms, a hydroxy group, a halogen atom, a cyano group, an amino group, a monoalkylamino group having 1 to 9 carbon atoms, an alkoxycarbonyl group having 1 to 9 carbon atoms, a sulfamoyl group, or a carbamoyl group. ^Te, R 1 to R ⁴ is an acyl group having a carbon number of 2-9, a nitro group, a cyano group, an alkoxycarbonyl group having 1 to 9 carbon atoms, a sulfamoyl group, a carbamoyl group, or an arylcarbamoyl group are preferred,
R ⁵ and R ⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 2 to 9 carbon atoms, a cyano group, or a halogen atom, and R ^{1 to} R ⁴ are independently of one another, an acyl group having a carbon number of 2-9, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 9 carbon atoms, a carbamoyl group, an arylcarbamoyl group are more preferable.

In the present invention, the dye compound represented by the general formula (I) is a dye compound represented by the general formula (II), and R ⁵ and R ⁶ are each independently a hydrogen atom, carbon An alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 2 to 9 carbon atoms, a hydroxy group, a cyano group, or a halogen atom, wherein the rings Q ¹ and Q ² are any one of the general formulas (2) to (7) or It is also preferred that the tautomer, wherein X ^{1 to} X ⁴ are sulfur atoms,
The dye compound represented by the general formula (I) is a dye compound represented by the general formula (II), and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkoxy having 1 to 6 carbon atoms. A group, an acyloxy group having 2 to 9 carbon atoms, a cyano group, or a halogen atom, and the rings Q ¹ and Q ² are any one of the general formulas (2) to (7) or a tautomer thereof, It is also more preferable that X ^{1 to} X ⁴ are sulfur atoms.

The general formula (I) is particularly preferably a so-called donor-acceptor type in order to enhance the interaction between molecules to impart solvent resistance and water resistance and to have good optical properties to absorb visible light. From the viewpoint of a chemical structure that forms a chromophore, the following general formulas (8) to (13).

In General formula (8), R ^<81> , R ^<82> , R ^<83> , R ^<84> is a hydrogen atom and a C1-C5 alkyl group each independently. R ⁸⁵ and R ⁸⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkylcarbonyl group having 1 to 5 carbon atoms. R ⁸⁷ and R ⁸⁸ are each independently an oxygen atom or a sulfur atom.

In the general formula (9), R ⁹¹ and R ⁹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁹² and R ⁹⁸ are each independently a hydrogen atom, a cyano group, or a carbamoyl group. R ⁹³ and R ⁹⁹ each independently represents an oxygen atom or a sulfur atom. R ⁹⁴ and R ⁹¹⁰ are an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms.

In General Formula (10), R ¹⁰¹ and R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ¹⁰² and R ¹⁰⁷ are an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. R ¹⁰³ and R ¹⁰⁸ each independently represents an oxygen atom or a sulfur atom. R ¹⁰⁵ and R ¹⁰⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkylcarbonyl group having 1 to 5 carbon atoms.

In General formula (11), R ^<111> , R ^<112> , R ^<113> , R ^<114> is a hydrogen atom, a C1-C5 alkyl group, and a phenyl group each independently. R ¹¹⁵ and R ¹¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms.

In General Formula (12), R ¹²¹ and R ¹²³ are each independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. R ¹²² and R ¹²⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. R ¹²⁵ and R ¹²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkylcarbonyl group having 1 to 5 carbon atoms.

In General Formula (13), R ¹³¹ , R ¹³² , R ¹³⁴ , and R ¹³⁷ are each independently an alkoxycarbonyl group having 2 to 5 carbon atoms or a cyano group. R ¹³³ and R ¹³⁸ are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. R ^{135, R 136} are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, Ru alkylcarbonyl der of 1 to 5 carbon atoms.

Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto. In the present specification, Pr represents a propyl group, and Hex represents a hexyl group.
Here, the compounds (75) to (77), (102), (103), (1-1) to (1-22), (2-11) to (2-18), (6-4), (6-8) to (6-11) are reference examples.

The compound represented by the general formula (I) can be synthesized by any method. For example, a compound in which R ⁵ and R ⁶ in the above general formula (I) are hydroxy groups is synthesized as a synthetic intermediate, synthesized by a reaction in which a desired substituent is introduced by alkylating or acylating the compound. 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. Sho 63-225382, page 3, upper right row, first line to lower left row, 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 above general formula (I) is a journal of Organic Chemistry, 1990, Vol. 55, pages 5347-5350, literature, page 5349, page 27, experimental section from right, line 1994, 59, 3077-3081, 3081 pages, lines 11-16, Tetrahedron Letters, 1991, 32, 4897-4900 pages, 4897, lines 9-4899, lines 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, 1664 pages right 6th to 15th line, 1995, 117, 9995-10002, 9996 pages right 12th to 9997 pages 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.
Also, a bis (N, N-dialkyliminium) compound obtained by reacting a quinone with an N, N-dialkyldithiocarbamate salt (for example, synthetic intermediate M-2 in the Examples of the present application) was 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 the present example). 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 (synthetic intermediate B in Examples of the present application) and 2-ethylhexyl bromide in the presence of a base.
The hydroquinone compound (synthetic intermediate B in the examples of the present application) was reacted with 1,4-benzoquinone and potassium N, N-diethyldithiocarbamate to give a bis (N, N-diethyliminium) compound (implemented in the present application). It can also be synthesized by synthesizing the example synthetic intermediate M-2) and reacting it with malononitrile.
For example, Exemplified Compound (11) is prepared by reacting dipotassium salt obtained by reacting carbon disulfide with 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 synthesis intermediate M-2 of Example of the present application synthesized as described above with ethyl cyanoacetate.
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 compounds of the present invention can take tautomers depending on the structure and the environment in which they are placed. Although described in this specification in one of the representative forms, tautomers different from those described in the present specification are also included in the compounds of the present invention.

  Depending on the structure and the environment in which it is placed, the compounds of the invention can be cations or anions with appropriate counterions. In the present specification, hydrogen ions are used as counter cations or hydroxide ions are used as counter anions as typical counter ions. However, compounds having other counter ions are also included in the compounds of the present invention. One type of counter ion may be used, or a plurality of types having an arbitrary ratio may be used.

When the compounds of the present invention are different in 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 , the positions of each other are interchanged. Can be. Even when only one of the geometric isomers is described in the present specification, other geometric isomers are also included in the compound of the present invention. Further, even when a geometric isomer mixture is obtained in the process of synthesis or purification, only a representative structure thereof 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 of the present invention may contain isotopes (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O and the like).

The hetero compounds of the present invention are useful as functional materials such as pharmaceuticals, agricultural chemicals, dyes, pigments, ultraviolet absorbers, liquid crystals, and synthetic intermediates thereof.
In particular, the compounds of the present invention can be used as dyes, pigments, and ultraviolet absorbers that have high light fastness, a high molar extinction coefficient ε, and give sharp absorption. Among them, it is extremely excellent in long-wave ultraviolet absorbing ability and can be preferably used as an ultraviolet absorber. By using the compound of the present invention having absorption in the visible range together with a polymer material, a colored product having excellent hue and fastness can be provided. By incorporating the compound of the present invention having absorption in the ultraviolet region into a polymer molded product such as plastic or fiber, the light stability of the polymer molded product can be enhanced. Furthermore, the polymer material containing the compound of the present invention having absorption in the ultraviolet region can be used as a filter or a container for protecting contents sensitive to ultraviolet rays by utilizing the excellent ultraviolet absorbing ability. Further, the compound of the present invention has substituents in four directions perpendicular to each other on a plane from a strong central portion. By utilizing this structural feature, it can be preferably used as a liquid crystal compound or an optically anisotropic material. By incorporating the compound of the present invention into a polymer material and processing it into a film, optical properties can be imparted to the film. Furthermore, the film containing the compound of the present invention can be used as a retardation plate, a polarizing plate, an optical compensation film, etc. by utilizing the imparted optical characteristics.
Hereafter, the use as a ultraviolet absorber of the compound of this invention is demonstrated.

A compound similar to the structure of the compound 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)) is, for example, the structure of a charge transfer complex However, 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 as large as that of the compound described in (1), that is, it is out of the relationship where it is considered that the number of UV absorption effect can be obtained by simply doubling two heterocycles. It was impossible to imagine that the compound represented by the general formula (I) exhibited excellent performance as an ultraviolet absorber.

  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 molar extinction coefficient at the maximum absorption wavelength is preferably 78000 to 150,000, more preferably 85,000 to 120,000, and particularly preferably 90000 to 110,000. The compound of the present invention having a maximum absorption wavelength and a molar extinction coefficient within the above ranges have excellent long-wave ultraviolet absorption ability.

A person skilled in the art can easily measure the maximum absorption wavelength. 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 molar extinction coefficient uses the definition described in, for example, “New Edition Experimental Chemistry Course 9 Analytical Chemistry [II]” (Maruzen, 1977), page 244, etc., edited by the Chemical Society of Japan. It can be obtained together with the absorption wavelength.

  The compound of the present invention as an ultraviolet absorber 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 compound of the present invention as an ultraviolet absorber can be used in the form of a dispersion dispersed in a dispersion medium. Hereinafter, the dispersion containing the compound of the present invention as an ultraviolet absorber will be described.

  Any medium can be used for dispersing the compound of the present invention as an ultraviolet absorber. 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 of the dispersion medium used when the compound of the present invention is used as an ultraviolet absorber include hydrocarbons such as pentane, hexane and octane, aromatics such as benzene, toluene and xylene, diethyl ether, Ethers such as 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, Amides such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, amines such as triethylamine and tributylamine, carboxylic acids such as acetic acid and propionic acid, salts Methylene, halogen-based, such as chloroform, tetrahydrofuran, heterocyclic ring system, such as pyridine, and the like. These can be used in combination at any ratio.

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

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

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

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

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

The compound of the present invention as an ultraviolet absorber can be used in the form of a solution dissolved in a liquid medium. Hereinafter, the solution containing the compound of the present invention as an ultraviolet absorber will be described.
Any liquid may be used for dissolving the compound of the present invention as the ultraviolet absorber. 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 containing the compound of the present invention as an ultraviolet absorber may additionally contain any compound. Examples thereof include dyes, pigments, ultraviolet absorbers, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, and metals. Other than the compound of the present invention as an ultraviolet absorber, it does not necessarily have to be dissolved.

  The content of the ultraviolet absorber in the solution containing the compound of the present invention as an ultraviolet absorber 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 0.001-30 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 compound of this invention as an ultraviolet absorber can be used in the state of a mixture with arbitrary compounds. Hereinafter, the mixture containing the compound of the present invention as an ultraviolet absorber will be described.

  The mixture containing the compound of the present invention as an ultraviolet absorber 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 them, a polymer material containing the compound of the present invention as an ultraviolet absorber 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 compound of the present invention as an ultraviolet absorber can be contained in a polymer substance by various methods. When the compound of the present invention as an ultraviolet absorber has compatibility with a polymer material, the compound of the present invention as an ultraviolet absorber can be directly added to the polymer material. The compound of the present invention as an ultraviolet absorber may be dissolved in an auxiliary solvent having compatibility with the polymer material, and the solution may be added to the polymer material. The compound of the present invention as an ultraviolet absorber may be dispersed in a high boiling point organic solvent or polymer, and the dispersion may be added to the polymer substance. Further, the dispersion may be coated on the surface of the polymer material.

The boiling point of the high-boiling organic solvent is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. The melting point of the high-boiling organic solvent is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower. Examples of the high-boiling 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 compound of the present invention as an ultraviolet absorber, JP-A-58-209735, JP-A-63-264748, JP-A-4-191851, JP-A-8-272058, and British Patent No. 2016017A. You can refer to the description.

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

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

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

<3> Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / propylene Te-1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer, Ethylene / cycloolefin copolymers (e.g., ethylene / norbornene, such as COC (Cyclo-Olefin Copolymer)), ethylene / 1-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> A graft copolymer of an 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, In particular, polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers Halogen-containing polymers such as

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

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

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

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

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

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

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

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

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

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

<19> Polycarbonate and polyester carbonate.

<20> Polyketone.

<21> Polysulfone, polyethersulfone and polyetherketone.

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

<23> Dry and non-dry alkyd resins.

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

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

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

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

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

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

<30> based on pure monomeric compounds or natural and synthetic organic materials which are mixtures of said compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or synthetic esters (for example phthalates, adipates, phosphates or trimellitates) Oils, fats and waxes, and mixtures of synthetic esters and mineral oil in any mass ratio, typically 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 when the compound of the present invention is used as an ultraviolet absorber 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 when the compound of the present invention is used as an ultraviolet absorber is preferably a thermoplastic resin.

  The polymer material containing the compound of the present invention as an ultraviolet absorber includes an antioxidant, a light stabilizer, a processing stabilizer, and an anti-aging agent as necessary in addition to the above-described polymer substance and the ultraviolet absorber of the present invention. Any additive such as a compatibilizer 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.
Stabilized by the compounds of the present invention as UV absorbers are dyes, pigments, foods, beverages, body care products, vitamins, pharmaceuticals, inks, oils, fats, waxes, surface coatings, cosmetics, photographic materials, Examples include woven fabrics and pigments thereof, plastic materials, rubber, paints, polymer materials, polymer additives, and the like.
When the compound of the present invention is used as an ultraviolet absorber, the method may be any method. Although the compound of the present invention may be used alone or as a composition as an ultraviolet absorber, it is preferably used as a composition. Among these, a polymer material containing the compound of the present invention as an ultraviolet absorber is more preferable. Hereinafter, a polymer material containing the compound of the present invention as an ultraviolet absorber will be described.

The polymer material containing the compound of the present invention as an ultraviolet absorber is formed using the polymer material. The polymer material containing the compound of the present invention as an ultraviolet absorber 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 compound of the present invention as an ultraviolet absorber can be used for all applications in which a synthetic resin is used, but is particularly suitable for applications that may be exposed to sunlight or light including ultraviolet rays. Can be used. 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 packaging materials for facilities, transportation equipment and the like, coating films formed by the coating materials, alkyd resin lacquer coating materials and coating films formed by the coating materials, acrylic lacquer coating materials and coating films formed by the coating materials, 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 / windshields 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 items 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.

  The shape of the polymer material containing the compound of the present invention as an ultraviolet absorber is flat membrane, powder, spherical particles, crushed particles, bulk continuum, fibrous, tubular, hollow fiber, granular, plate, porous Any shape such as a shape may be used.

Two or more compounds of the present invention having different structures may be used in combination, or a compound of the present invention as an ultraviolet absorber and one or more ultraviolet absorbers having other structures may be used in combination. When two types (preferably three types) of ultraviolet absorbers are used in combination, ultraviolet rays in a wide wavelength region can be absorbed. In addition, when two or more kinds of ultraviolet absorbers are used in combination, the dispersion state of the ultraviolet absorber is also stabilized. Any ultraviolet absorber having a structure other than the compound of the present invention can be used as the ultraviolet absorber. 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- continuous carbon by O-- alkylene carbon bond is interrupted once or several times, 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 compound is preferably a compound having an effective absorption wavelength of about 290 to 330 nm, and representative examples thereof include phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, dibenzoylresorcinol, bis ( 4-t-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxysalicylate, hexadecyl 3,5-di-t-butyl-4- Hydroxy salicylate and the like can be mentioned.

  The acrylate compound is preferably a compound having 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, 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%.

  Although a sufficient ultraviolet shielding effect can be obtained practically only with the compound of the present invention as an ultraviolet absorber, a white pigment having a strong hiding power, such as titanium oxide, may be used in combination when more strictness is required. . In addition, when the appearance and color tone become problems, or a small amount (0.05% by mass or less) of a colorant can be used in combination depending on the preference. For applications where transparency or white color is important, a fluorescent brightening agent may be used in combination. Examples of the 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.

  The polymer material containing the compound of the present invention as an ultraviolet absorber has excellent light resistance (fastness to ultraviolet light), and precipitation of the ultraviolet absorber and bleeding out due to long-term use do not occur. In addition, since the polymer material containing the compound of the present invention as an ultraviolet absorber has an excellent long-wave ultraviolet absorption ability, it can be used as an ultraviolet absorption filter or a container, and can protect compounds that are weak against 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 a polymer material containing the compound of the present invention as an ultraviolet absorber is used as an ultraviolet absorption filter or an ultraviolet absorption film, the polymer material is preferably transparent. Examples of transparent polymer materials include cellulose esters (eg, diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, Polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic) Polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethyl methacrylate, syndiotactic polystyrene Emissions, polysulfone, polyether sulfone, polyether ketone, polyether 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 compound of the present invention as an ultraviolet absorber can also be used as a transparent support, and the transmittance of the transparent support is preferably 80% or more, more preferably 86% or more.

  A packaging material containing the compound of the present invention as an ultraviolet absorber will be described. The packaging material containing the compound of the present invention as an ultraviolet absorber 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 compound of the present invention as an ultraviolet absorber may package any 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 compound of the present invention as an ultraviolet absorber may be, for example, a transparent package described in JP-A-2004-51174, or a light-shielding package described in JP-A-2006-224317, for example. It may be.

  The packaging material containing the compound of the present invention as an ultraviolet absorber has not only ultraviolet shielding properties as described in, for example, JP-A-2001-26081 and JP-A-2005-305745, but also other performances. You may have it. 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.

  The packaging material containing the compound of the present invention as an ultraviolet absorber may be produced using any method. For example, a method of forming an ink layer described in JP-A-2006-130807, for example, a method of melt-extruding and laminating a resin containing an ultraviolet absorbent 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.

  A container containing the compound of the present invention as an ultraviolet absorber will be described. The container containing the compound of the present invention as an ultraviolet absorber 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 use of the container containing the compound of the present invention as an ultraviolet absorber may contain foods, beverages, drugs, cosmetics, personal care products, shampoos and the like. For example, a liquid fuel storage container described in JP-A-5-139434, a golf ball container described in JP-A-7-289665, a food container described in JP-A-9-295664, and JP-A-2003-237825 Container, sake container described in JP-A-9-58687, drug-filled container described in JP-A-8-155007, 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.

  A container containing the compound of the present invention as an ultraviolet absorber not only has ultraviolet blocking properties as described in, for example, JP-A-5-305975 and JP-A-7-40954, but also has other performances. It may be. 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.

  A container containing the compound of the present invention as an ultraviolet absorber may be produced by 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 compound of the present invention as an ultraviolet absorber will be described. The paint containing the compound of the present invention as an ultraviolet absorber may be a paint 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 intended use of the paint containing the compound of the present invention as an ultraviolet absorber may be any application. For example, UV shielding paints described in JP-A-7-26177, JP-A-9-169950, JP-A-9-221163, JP-A-2002-80788, and UV-rays described in JP-A-10-88039. Near-infrared shielding 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 compound of the present invention as an ultraviolet absorber is generally composed of a paint (including a transparent resin component as a main component) and an ultraviolet absorber, but preferably 0 to 20% by mass of the ultraviolet absorber based on the resin. Of the composition. 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 compound of the present invention as an ultraviolet absorber is a coating film containing an ultraviolet absorber composed of the compound represented by the general formula (I), and a paint containing the compound of the present invention as the ultraviolet absorber. It is the coating film formed using.

  The ink containing the compound of the present invention as an ultraviolet absorber will be described. The ink containing the compound of the present invention as an ultraviolet absorber 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 an ink containing the compound of the present invention as an ultraviolet absorber 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 compound of the present invention as an ultraviolet absorber will be described. The fiber containing the compound of the present invention as an ultraviolet absorber 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.

  The fiber containing the compound of the present invention as an ultraviolet absorber may be produced 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 compound of the present invention as an ultraviolet absorber 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. 10-165045. 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 compound of the present invention as an ultraviolet absorber will be described. The building material containing the compound of the present invention as an ultraviolet absorber 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.

  A building material containing the compound of the present invention as an ultraviolet absorber 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.

  A building material containing the compound of the present invention as an ultraviolet absorber can be used in 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.

  A recording medium containing the compound of the present invention as an ultraviolet absorber will be described. The recording medium containing the compound of the present invention as an ultraviolet absorber may be any 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 compound of the present invention as an ultraviolet absorber will be described. The image display device containing the compound of the present invention as an ultraviolet absorber 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 No. 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 compound of the present invention as an ultraviolet absorber will be described. The solar cell to which the compound of the present invention is applied as an ultraviolet absorber 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. There is a problem in that the dye that has 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 compound of the present invention as an ultraviolet absorber may be composed of any kind of polymer. For example, polyester described in JP-A-2006-310461, thermosetting transparent resin described in JP-A-2006-257144, α-olefin polymer described in JP-A-2006-210906, JP-A-2003-168814 Polypropylene described in the publication, polyethersulfone described in JP-A-2005-129713, acrylic resin described in JP-A-2004-227843, transparent fluororesin described in JP-A-2004-168057, etc. Can be mentioned.

  You may manufacture the cover for solar cells containing the compound of this invention as a ultraviolet absorber 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 containing the compound of the present invention as an ultraviolet absorber may have any shape. Films and sheets described in JP-A-2000-91610 and JP-A-11-261085, for example, a laminated film described in JP-A-11-40833, a cover glass structure described in JP-A-11-214736, and the like Is mentioned. The sealing material described in JP 2001-261904 A may contain an ultraviolet absorber.

  The glass and glass film containing the compound of the present invention as an ultraviolet absorber will be described. The glass and glass coating containing the compound of the present invention as an ultraviolet absorber 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, and 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 the 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 package contents after irradiation with fluorescent lamp described in JP-A-239910, filling with salad oil 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 Japanese Patent No. 22300, density evaluation of printed matter using a xenon fade meter described in Japanese Patent Application Laid-Open No. 2006-8811, 100 W described in Japanese Patent Application Laid-Open No. 2005-23111 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, Japanese Patent Application Laid-Open No. HEI 8-8, 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-7-196631, 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 organic EL element color conversion characteristic retention rate 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 compounds of the invention as UV absorbers can also be used as cosmetic preparations. Subsequently, the use of the compound of the present invention as an ultraviolet absorber as a cosmetic preparation will be described in detail.
Cosmetic formulations containing the compounds according to the invention as UV absorbers are for example in the form of creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat compositions, stick formulations, powders or ointments, As further auxiliaries and additives, mild surfactants, overfat agents, pearl essence waxes, consistency regulators, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, active ingredients of biological origin , Deodorant active ingredient, anti-dandruff agent, film forming agent, swelling agent, further UV light protection factor, antioxidant, hydrotropic agent, preservative, insect repellent, self-tanning agent, solubilizer, perfume oil, coloring Additional agents, antibacterial agents and the like 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 such 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 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 thickeners include, 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 glycol, 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 compounds according to the invention as UV absorbers, in addition to primary photoprotective substances, secondary antioxidants that interfere with the photochemical reaction chain induced when UV rays penetrate the skin or hair Photoprotective 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 (e.g., pmol to [mu] mol / kg) , As well as (metal) chelating agents (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, bili Bottles, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (eg Ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherol and its derivatives (eg, vitamin E acetate), vitamin A and derivatives (eg, vitamin A palmitate), and benzoin coniferyl benzoate, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, resinous nordihydroguaiaretic acid, nor Hydroguayretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, N- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] sulfanilic acid ( And salts thereof (eg disodium salt), zinc and derivatives thereof (eg ZnO, ZnSO ₄ ), selenium and derivatives thereof (eg selenium methionine), stilbene and derivatives thereof (eg stilbene oxide, trans-stilbene oxide) and Suitable derivatives of the active ingredient according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids). Mention may also be made of HALS (= “hindered amine light stabilizers”) compounds. The amount of antioxidant present is 0.001 to 30% by weight, preferably 0.01 to 3% by weight, based on the weight of the UV absorber.

  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. Typical examples are as follows:
-Glycerin;
-Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycol having an average molecular weight of 100 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, such as 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.

  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, pine), resins 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, lyrial, rilal, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hezion, Sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandine oil, mascatel 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. Substances recognized and suitable for cosmetic purposes, such as edited in 81-106, may be used as colorants. The colorant is usually used at a concentration of 0.001 to 0.1% by weight based on the total mixture.

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

  Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. The 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.

A cosmetic preparation containing the compound of the present invention as an ultraviolet absorber comprises, as an auxiliary agent, an antifoaming agent such as silicone, a structural substance such as maleic acid, a solubilizing agent such as ethylene glycol, propylene glycol, glycerin or diethylene glycol, Latex, opacifier such as styrene / PVP or styrene / acrylamide copolymer, complexing agent such as EDTA, NTA, β-alanine diacetic acid or phosphonic acid, propane / butane mixture, N ₂ O, dimethyl ether, CO ₂ , Propellants such as N ₂ or 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 hydrogen peroxide, potassium bromide or odor It may contain an oxidizing agent such as sodium.

  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.

Cosmetic formulations containing the compounds of the invention as UV absorbers can be included 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, funny (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;
-Deodorizing agents 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 as chemicals (hair removal), eg 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 parfum, parfant aret, parfum), 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, lightning 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 compound of the present invention as an ultraviolet absorber is preferably an agent formulated in cosmetics in the form of encapsulating the compound of the present invention as an ultraviolet absorber in a microcapsule. 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) (specially 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 cosmetic preparations containing the compounds of the invention as UV absorbers, particularly preferred embodiments of cosmetic preparations for the skin are light protection preparations such as milk, lotions, creams, oils, sunblocks or tropicals. Pretanning 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 cosmetic preparations containing the compounds according to the invention as UV absorbers, hair preparations as described above for hair treatment, in particular in the form of shampoos and hair conditioners, are particularly preferred as embodiments of cosmetic preparations for hair. Products, hair care preparations, eg 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 is there. 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 mass%, sodium laureth-2-sulfate 12.0 mass%, cocamidopropyl betaine 4.0 mass%, sodium chloride 3.0 mass%, and water. 100%.

In the cosmetic preparation containing the compound of the present invention as an ultraviolet absorber, in the form of a cosmetic preparation for hair, for example, the following hair cosmetic formulations may be used.
a ₁ ) Consisting of a compound of the invention as a UV absorber, PEG-6-C ₁₀ oxo alcohol and sorbitan sesquioleate, water, and any desired quaternary ammonium compound, eg 4% mink A self-emulsifying raw material formulation to which amidopropyldimethyl-2-hydroxyethylammonium chloride or Quaterium 80 is added,
a ₂ ) Consisting of a compound of the invention as an ultraviolet absorber, tributyl citrate and PEG-20-sorbitan monooleate, water, and any desired quaternary ammonium compound, eg 4% mincamide A self-emulsifying raw material formulation to which propyldimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added,
b) quad-doped solutions of the compounds of the invention as UV absorbers in butyl triglycol and tributyl citrate;
c) Mixtures or solutions of the compounds according to the invention as UV absorbers with n-alkylpyrrolidones.

  When the compounds according to the invention as UV absorbers are used as cosmetic preparations, for example creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, water-containing emulsions, oil-containing emulsions, wax / fat compositions, stick formulations, It can be used by containing in powder or ointment. 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 compound of the present invention as an ultraviolet absorber include compounds of the general formula (I) or (Ia). For example, in order to improve the spreadability to the skin and the solubility in silicone oil which is an oil component. Or a silicone derivative represented by the following general 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 that has been converted to a monovalent substituent by removing a hydrogen atom or a monovalent substituent, and this is linked 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 which is a monovalent substituent by removing a hydrogen atom or a monovalent substituent.

Then, the case where the compound of this invention is used as a coloring composition is demonstrated.
The coloring composition using the compound of the present invention refers to a pigment dispersion, an ink for ink jet recording, an ink sheet for thermal transfer recording, a color filter, a writing pen, a colored plastic, and other ink liquids.
The coloring composition using the compound of the present invention can be effectively used particularly as an ink for inkjet recording, an ink sheet for thermal transfer recording, and a color filter.

The coloring composition using the compound of the present invention contains at least one kind of medium, and the medium may be an aqueous medium or a non-aqueous medium. In view of the above, an aqueous coloring composition containing an aqueous medium is preferable.
In the coloring composition using the compound of the present invention, as an aqueous medium, a mixture containing water as a main component and optionally containing at least one hydrophilic organic solvent can be used.

Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol, diethylene glycol, Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether Ter, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate triethylene glycol monoethyl ether, ethylene glycol monophenyl ether Glycol derivatives such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine, etc. Derivatives, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1, 3-dimethyl-2-imidazolidinone, acetonitrile, acetone are preferred,
More preferred are alcohols, polyhydric alcohols, glycol derivatives, 2-pyrrolidone,
More preferably, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, hexanediol, glycerin, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-pyrrolidone,
Particularly preferred are ethylene glycol, diethylene glycol, hexanediol and glycerin.
The amount of the hydrophilic organic solvent is 0.1 to 50% by weight with respect to the whole coloring composition from the viewpoint of viscosity, surface tension, easiness of volatilization, safety to living organisms and environment, and the like. It is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight.

  In the coloring composition using the compound of the present invention, the dye compound represented by the general formula (I) is uniformly dissolved in the medium or dispersed and contained in the medium from the viewpoint of handleability. It is preferable. Here, the dye compound represented by the general formula (I) is dispersed in the medium when the compound represented by the general formula (I) is in a fine particle state and is suspended or suspended in the medium. It means being in a state.

  In the coloring composition using the compound of the present invention, when the coloring compound represented by the general formula (I) is dispersed in the medium, it is represented by the general formula (I) obtained by the above production method. The dye compound is desirably post-treated. Examples of post-processing methods include, for example, solvent particle milling process such as solvent salt milling, salt milling, dry milling, solvent milling, acid pasting, solvent heat treatment, etc., resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

  The dye compound represented by the general formula (I) of the present invention is preferably subjected to a solvent heating treatment as a post-treatment. As the solvent used for the solvent heat treatment, a solvent having a boiling point higher than the temperature during the heat treatment is preferable. Specifically, water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, alcohol solvents such as isopropanol and isobutanol, N, N-dimethylformamide , N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other polar aprotic organic solvents, glacial acetic acid, pyridine, and mixtures thereof are preferred.

By the above operation, the dye compound represented by the general formula (I) gives a regular crystal, which can be recognized from, for example, an X-ray diffraction pattern. As described in “Basics of X-ray Crystallography” (1973, Maruzen), according to Scherrer's formula, the full wave height half-width of the peak of the X-ray diffraction diagram (hereinafter referred to as half-width) Is inversely proportional to the average grain size.
In the present invention, it is preferable that the half-width of the maximum peak in the X-ray diffraction pattern of the solid is 0.40 ° or less in the previous stage in which the coloring compound represented by formula (I) is used as the coloring composition. More preferably, it is 0.30 ° or less. By forming large crystals, the fastness of the coloring composition is improved, and the dispersion stability is improved by reducing the active surface.
In the case where the maximum peak in the X-ray diffraction diagram is composed of a plurality of adjacent peaks, it can be determined from another appropriate single peak.

  The colored dispersion composition using the compound of the present invention preferably further includes at least one of a surfactant and a dispersant, and more preferably further includes at least one of a dispersant. By further including a surfactant and a dispersant, the dispersibility of the dye compound represented by formula (I) and the quality of the image formed using the colored composition can be improved.

  The dispersant in the present invention is not particularly limited as long as it is a compound capable of dispersing the dye compound represented by the general formula (I) in a medium. For example, the dispersant described in “Pigment Dispersion Technology, Surface Treatment, Usage of Dispersant and Evaluation of Dispersibility (published by Technical Information Society 1999)” and the like can be suitably used in the present invention. In the present invention, from the viewpoint of dispersion stability, a surfactant or a hydrophilic polymer is preferable.

  Examples of the surfactant include anionic, nonionic, cationic and amphoteric surfactants, and any surfactant may be used, but it has an affinity for the pigment and the aqueous medium, respectively. From the viewpoint, it is preferable to use an anionic or nonionic surfactant.

Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester are preferred,
Stearates, palmitates, oleates, linoleates, dodecylbenzenesulfonates, dodecyltrimethylammonium salts are more preferred,
Sodium oleate and sodium dodecylbenzenesulfonate are particularly preferred.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based surfactant, silicon-based surfactant and the like are preferable,
Polyoxyethylene butyl ether, sorbitan laurate, and glycerin laurate are more preferable.
Specifically, the hydrophilic polymer is preferably a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, an acrylate-acrylic acid copolymer, or polyvinylpyrrolidone,
Styrene-acrylic acid copolymers and phenyl acrylate-acrylic acid copolymers are more preferred.
Further, the molecular weight of these hydrophilic polymers is preferably in the range of 300 to 100,000, more preferably in the range of 500 to 50,000, and particularly preferably in the range of 1000 to 10,000. By setting the molecular weight to 300 or more, it can be stably adsorbed to the pigment to impart dispersibility, and by setting the molecular weight to 100000 or less, the viscosity of the colored dispersion composition can be freely controlled.
The acid value of these hydrophilic polymers is preferably in the range of 10 to 400, more preferably in the range of 30 to 300, and particularly preferably in the range of 50 to 200. . When the acid value is 10 or more, sufficient hydrophilicity is obtained, and when the acid value is 400 or less, sufficient affinity for the pigment can be obtained.
The amount of the surfactant or the hydrophilic polymer in the coloring composition is not particularly limited as long as the dye compound represented by the general formula (I) can be dispersed in the medium. For example, it can be 0.1 to 200% by mass relative to the dye compound represented by the general formula (I), and is 1 to 100% by mass from the viewpoint of dispersion stability and quality control of the colored composition. Is preferable, and it is more preferable that it is 2-50 mass%.

  The non-aqueous colored dispersion composition is obtained by dispersing the dye compound represented by the general formula (I) in a non-aqueous vehicle (non-aqueous medium). Resins used in non-aqueous vehicles are, for example, petroleum resins, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber , Phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin , Drying oil, synthetic drying oil, styrene / maleic acid resin, styrene / acrylic resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin chlorinated polypropylene, butyral resin, vinylidene chloride resin and the like. A photocurable resin may be used as the non-aqueous vehicle.

  Examples of the solvent used in the non-aqueous vehicle include aromatic solvents such as toluene, xylene, and methoxybenzene, and acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N Methyl-2-pyrrolidone, aniline, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as γ- butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid.

  The colored dispersion composition using the compound of the present invention can be obtained by dispersing the dye compound represented by the above general formula (I) and an aqueous or non-aqueous medium using a dispersion apparatus. Examples of the dispersing device that can be used include a ball mill, a sand mill, a bead mill, a roll mill, a jet mill, a paint shaker, an attritor, an ultrasonic disperser, and a disper.

  In the coloring composition using the compound of the present invention, when the dye compound represented by the general formula (I) is contained as a pigment, the volume average particle diameter of the pigment is preferably 10 nm or more and 250 nm or less. At this time, when the colored dispersion composition of the present invention is used for a colored body that transmits light such as a color filter, it is more preferable that the average particle diameter is relatively small in order to obtain a highly transparent composition. Specifically, the volume average particle size of the pigment is more preferably from 10 nm to 80 nm, further preferably from 10 nm to 50 nm, and particularly preferably from 10 nm to 30 nm. In addition, when the colored composition of the present invention is applied to a substrate such as a printing ink and used as a colored body that reflects light, in order to impart dispersion stability and fastness to light and heat, Further, in order to improve the hiding power, it is more preferable that the average particle diameter is relatively large. Specifically, the volume average particle size of the pigment is more preferably from 40 nm to 250 nm, further preferably from 50 nm to 200 nm, and particularly preferably from 60 nm to 150 nm. The volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the colorant. In the present invention, a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) was used as a measuring device for the volume average particle diameter of the pigment. The measurement was performed according to a predetermined measuring method by placing 3 ml of the pigment dispersion in a measuring cell. As parameters to be input at the time of measurement, ink viscosity was used as the viscosity, and pigment density was used as the density of the dispersed particles.

  It is preferable that the density | concentration of the coloring compound represented by general formula (I) or (II) contained in the coloring composition using the compound of this invention is the range of 1-35 mass%, and 2-25 mass%. More preferably, it is the range. When the density is 1% by mass or more, a sufficient image density can be obtained when the colored composition is used as an ink. Moreover, stability of a composition becomes more favorable because a density | concentration is 35 mass% or less. That is, in the case of a dispersion composition, sedimentation due to reaggregation can be prevented, and in the case of a dissolved composition, precipitation can be prevented.

  Applications of the colored composition using the compound of the present invention include image recording materials for forming images, particularly color images. Specifically, ink-jet recording inks described in detail below, thermal recording materials (for example, thermal transfer recording ink sheets), pressure-sensitive recording materials, recording materials using electrophotography, transfer-type silver halides. A photosensitive material, printing ink, a recording pen, etc. are mentioned. Preferred are inkjet recording inks, thermal recording materials, and recording materials using an electrophotographic method, and more preferred are inkjet recording inks.

In addition, the coloring composition using the compound of the present invention includes a color filter for recording / reproducing a color image used in a solid-state imaging device such as a CCD, a display such as an LCD or PDP, and a dyeing solution for dyeing various fibers. It can also be applied to.
In the coloring composition using the compound of the present invention, when the compound represented by the general formula (I) is dissolved in the medium,
It is preferable that the medium is water alone, water containing 1 to 40% by weight of a hydrophilic organic solvent, or a polymer binder and the compound represented by the general formula (I) is in the range of 1 to 50% by weight,
The medium is water alone or water containing 1 to 40% by mass of at least one of ethylene glycol, propylene glycol, glycerin, hexanediol and N-methylpyrrolidone, and the compound represented by the general formula (I) is 1 to 50 More preferably within the range of mass%,
It is particularly preferable that the medium is water alone or water containing 1 to 30% by mass of glycerin, and the compound represented by the general formula (I) is in the range of 1 to 40% by mass.
In the colored composition of the present invention, when the compound represented by the general formula (I) is dispersed in the medium,
The medium is water alone or water containing 1 to 40% by weight of a hydrophilic organic solvent, and the compound represented by the general formula (I) is in the range of 1 to 50% by weight, and the hydrophilic polymer or interface The active agent is preferably contained in an amount of 1 to 100% by mass relative to the compound represented by the general formula (I),
The medium is water alone or water containing 1 to 40% by mass of at least one of ethylene glycol, propylene glycol, glycerin, hexanediol and N-methylpyrrolidone, and the compound represented by the general formula (I) is 1 to 50 A styrene-acrylic acid copolymer, a phenyl acrylate-acrylic acid copolymer, polyvinyl pyrrolidone, sodium oleate, sodium dodecylbenzenesulfonate, or polyethylene glycol within the range of mass% It is more preferable to contain 1-100 mass% with respect to the compound represented by (I),
The medium is water alone or water containing 1 to 30% by mass of glycerin, and the compound represented by the general formula (I) is in the range of 1 to 40% by mass, and a styrene-acrylic acid copolymer, It is particularly preferable that 1 to 100% by mass of sodium oleate, sodium dodecylbenzenesulfonate, or polyethylene glycol is contained with respect to the compound represented by the general formula (I).

[Ink for inkjet recording]
Next, an ink for ink jet recording (ink jet recording material) using the compound of the present invention will be described.
Ink for inkjet recording using the compound of the present invention (hereinafter sometimes referred to as “ink”) includes at least one dye compound represented by the general formula (I) described above, Preferably, it can further comprise a water-soluble solvent, water and the like. Moreover, you may comprise using the coloring composition (preferably pigment dispersion) of the said invention as it is.

  The content ratio of the colored composition (preferably pigment dispersion) in the ink using the compound of the present invention is 1 from the viewpoint of the hue, color density, saturation, transparency, etc. of the image formed on the recording medium. The range of -100 mass% is preferable, the range of 3-20 mass% is especially preferable, The range of 3-10 mass% is the most preferable among these.

It is preferable that 0.1 to 20 parts by mass of the coloring compound (pigment) represented by the general formula (I) is contained in 100 parts by mass of the ink using the compound of the present invention. The content is more preferably 10 parts by mass or less and more preferably 1-10 parts by mass.
In addition, the ink using the compound of the present invention may contain other pigments in addition to the coloring compound (pigment) represented by the general formula (I). When two or more kinds of pigments are used in combination, the total content of the pigments is preferably within the above range.

  The ink using the compound of the present invention can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Furthermore, the ink using the compound of the present invention can simultaneously use another pigment in addition to the coloring compound (pigment) represented by the general formula (I). Applicable yellow pigments (eg CI PY-74, CI PY-128, CI PY-155, CI PY-213), applicable magenta pigments (eg CI PV-19, CI PR-122) Any applicable cyan pigment (for example, CI PB-15: 3, CI PB-15: 4) should be used. Can do. Further, examples of applicable black materials include disazo, trisazo, and tetraazo pigments, as well as carbon black dispersions.

As the water-soluble solvent used in the ink jet recording ink using the compound of the present invention, polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents and the like are used.
Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerin.

  Examples of the polyhydric alcohol derivative include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diglycerin. And ethylene oxide adducts.

  Examples of the nitrogen-containing solvent include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine. Examples of alcohols include alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol. Examples of the solvent include thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like. In addition, propylene carbonate, ethylene carbonate, or the like can be used.

  The water-soluble solvent used in the ink using the compound of the present invention may be used alone or in combination of two or more. The content of the water-soluble solvent is 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 40% by mass or less of the entire ink. By setting the content of the water-soluble solvent in the ink to 1% by mass or more, a sufficient optical density can be obtained. On the other hand, when the content is 60% by mass or less, an increase in the viscosity of the ink can be suppressed, and the stability of the ejection characteristics of the ink can be improved.

Preferred physical properties of the ink for ink jet recording using the compound of the present invention are as follows.
The surface tension of the ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 35 mN / m or less. By setting the surface tension to 20 mN / m or more, liquid overflow to the nozzle surface of the recording head can be suppressed. On the other hand, by setting it to 60 mN / m or less, the permeability to the recording medium after printing can be improved, and the drying time is shortened.
The surface tension is a value measured using a Wilhelmy surface tension meter in an environment of 23 ° C. and 55% RH.

The viscosity of the ink is preferably from 1.2 mPa · s to 8.0 mPa · s, more preferably from 1.5 mPa · s to less than 6.0 mPa · s, still more preferably from 1.8 mPa · s to 4. It is less than 5 mPa · s. By setting the viscosity to 8.0 mPa · s or less, the discharge property is improved. On the other hand, long-term jetting property becomes favorable by setting it as 1.2 mPa * s or more.
The viscosity (including those described later) was measured using a rotational viscometer Rheomat 115 (manufactured by Contraves) at 23 ° C. and a shear rate of 1400 s ⁻¹ .

  In addition to the components described above, water is added to the ink in the range of the above-described preferable surface tension and viscosity. The amount of water added is not particularly limited, but is preferably 10% by mass to 99% by mass, and more preferably 30% by mass to 80% by mass with respect to the entire ink.

  Furthermore, the ink for ink jet recording using the compound of the present invention, if necessary, for the purpose of property control such as improvement of ejection properties, cellulose such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, etc. Derivatives, polysaccharides and their derivatives, other water-soluble polymers, acrylic polymer emulsions, polyurethane emulsions, polymer emulsions such as hydrophilic latex, hydrophilic polymer gels, cyclodextrins, macrocyclic amines, dendrimers, crown ethers, urea And derivatives thereof, acetamide, silicon-based surfactants, fluorine-based surfactants, and the like can be used.

In order to adjust conductivity and pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, 2-amino-2-methyl Nitrogen-containing compounds such as -1-propanol, alkaline earth metal compounds such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid and nitric acid, strong acid and weak alkali salts such as ammonium sulfate, and the like can be used.
Furthermore, a pH buffer, an antioxidant, an antifungal agent, a viscosity modifier, a conductive agent, an ultraviolet absorber, and the like can be added as necessary.

The ink for ink jet recording using the compound of the present invention can be used in an image forming method by an ink jet recording method. As the ink jet recording method, a known method can be applied without particular limitation.
The ink jet recording method supplies energy to ink for ink jet recording, and images on known image receiving materials such as plain paper, resin-coated paper, ink jet special paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. Is formed.
Further, there is no limitation on the ink jet recording method, and a known method, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, An acoustic ink jet method in which an electrical signal is converted into an acoustic beam and ink is irradiated and ink is ejected by using radiation pressure, and a thermal ink jet method in which ink is heated to form bubbles and the generated pressure is used is used. be able to.

[Ink sheet for thermal transfer recording]
An ink sheet for thermal transfer recording using the compound of the present invention contains at least one dye compound represented by the general formula (I). The thermal transfer recording ink sheet generally has a structure in which a dye-donating layer is formed on a support, and the dye-donating layer contains a dye compound represented by formula (I). The ink sheet for thermal transfer recording of the present invention prepares an ink liquid by dissolving the dye compound represented by the general formula (I) in a solvent together with a binder, or by dispersing in fine particles in a solvent, It can be produced by coating an ink liquid on a support and drying it appropriately to form a dye-donating layer. In addition to the dye compound represented by the general formula (I), other dye compounds may be used simultaneously.

In order to apply the thermal transfer recording ink sheet to a thermal transfer recording material capable of recording a full color image, a cyan ink sheet containing a heat diffusible cyan dye capable of forming a cyan image, and a magenta image are formed. It is preferable that a magenta ink sheet containing a heat-diffusible magenta dye capable of forming a yellow ink sheet and a yellow ink sheet containing a heat-diffusible yellow dye capable of forming a yellow image are sequentially coated on a support. In addition, an ink sheet containing a black image forming substance may be further formed as necessary.
As a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image, for example, those described in JP-A-3-103477 and JP-A-3-150194 are preferably used. it can. As a magenta ink sheet containing a heat-diffusible magenta dye capable of forming a magenta image, for example, those described in JP-A-2-123166 can be preferably used. As a yellow ink sheet containing a heat diffusible yellow dye capable of forming a yellow image, for example, those described in JP-A-1-225559 can be preferably used.

(Support)
As the support for the thermal transfer recording ink sheet, any conventionally used support for an ink sheet can be appropriately selected and used. For example, the material described in paragraph No. 0050 of JP-A-7-137466 can be preferably used. The thickness of the support is preferably 2 to 30 μm.

(Dye-donating layer)
The binder resin that can be used in the dye-donating layer of the thermal transfer recording ink sheet has high heat resistance, and when heated, the dye compound represented by the general formula (I) and other dye compounds are image receiving materials. The type is not particularly limited as long as it does not hinder the transition. For example, what is described in paragraph number 0049 of JP-A-7-137466 can be given as a preferred example. As the solvent for forming the dye-donating layer, a conventionally known solvent can be appropriately selected and used, and those described in Examples of JP-A-7-137466 can be preferably used.
The content of the dye compound represented by the general formula (I) in the dye-donor layer is preferably ^{0.03~1.0g / m 2, 0.1~0.6g / m} 2 is more preferable. Further, the thickness of the dye-donating layer is preferably 0.2 to 5 μm, and more preferably 0.4 to 2 μm.

(Functional layer)
The ink sheet for thermal transfer recording may have a layer other than the dye-donating layer as long as the effect of the present invention is not excessively inhibited. For example, it may have an intermediate layer between the support and the dye-donating layer, or it may have a back layer on the support surface opposite to the dye-donating layer (hereinafter also referred to as “back surface”). There may be. Examples of the intermediate layer include an undercoat layer and a diffusion prevention layer (hydrophilic barrier layer) for preventing diffusion of the dye compound represented by formula (I) and other dye compounds in the direction of the support. Can do. Examples of the back layer include a heat resistant slip layer, and can prevent adhesion of the thermal head to the ink sheet.

[Thermal transfer recording method]
When performing thermal transfer recording using the thermal transfer recording ink sheet, a heating means such as a thermal head and an image receiving material are used in combination. That is, thermal energy is applied to the ink sheet from the thermal head in accordance with the image recording signal, and the dye compound represented by the general formula (I) and other dye compounds in the portion where the thermal energy is applied are transferred to the image receiving material and fixed. The thermal transfer recording method is characterized in that image recording is performed as a result. The image receiving material usually has a structure in which an ink receiving layer containing a polymer is provided on a support. As the configuration and materials used of the image receiving material, for example, those described in paragraph numbers 0056 to 0074 of JP-A-7-137466 can be preferably used.

〔Color filter〕
A color filter using the compound of the present invention contains at least one dye compound represented by the general formula (I). As a method for forming a color filter, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, JP-A-4-17553, and the like. As described above, there is a method of forming a pattern with a photoresist added with a colorant. Any of these methods may be used as a method for introducing the dye compound represented by the general formula (I) of the present invention into a color filter, and a preferable method is disclosed in JP-A-4-175754. After applying a positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a colorant and a solvent onto a substrate, the method described in JP-A-6-35182 and JP-A-6-35182. A method for forming a color filter comprising exposing through a mask, developing the exposed portion to form a positive resist pattern, exposing the entire surface of the positive resist pattern, and then curing the exposed positive resist pattern Can be mentioned. Further, a black matrix is formed according to a conventional method, and an RGB primary color system or Y.I. M.M. A C-complementary color filter can be obtained.

Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above publication can be preferably used.
Further, the content of the dye compound represented by the general formula (I) contained in the color filter is preferably 5 to 80% by weight, and more preferably 10 to 60% with respect to the total weight of the filter layer.

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

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
Synthesis intermediate B can also be synthesized 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.
Using the synthetic intermediate B synthesized in this way, the exemplary compound (1) could be synthesized in the same manner.
Synthesis intermediate M-2 was synthesized by the following method.
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%).
Alternatively, 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).

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

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 resulting 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 the mixture was 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 Exemplified Compound (72) (yield 78%).
MS: m / z 480 (M +).
The exemplified compound (72) can 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).

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

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

Example 6
(Preparation of Exemplified Compound (24))
Exemplified compound (24) was obtained in a yield of 4% in the same manner as in Example 3 and 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) can also be prepared as follows.
To 12.4 g (0.02 mol) of the synthetic intermediate M-2 and 6.0 g (0.048 mol) of pivaloylacetonitrile, 100 ml of N-methylpyrrolidone was added. 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).
Exemplified compound (24) was obtained in a yield of 4% in the same manner as in Example 5, except that exemplified compound (139) was used instead of exemplified compound (72).

Example 7
(Preparation of Exemplified Compound (74))
Exemplified compound (74) was synthesized in the same manner as in 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) can also be prepared as follows.
50 ml of N-methylpyrrolidone was added to 8.0 g (0.0128 mol) of the synthetic intermediate M-2 and 4.8 g (0.028 mol) of 3-hydroxy-3-methylbutyl cyanoacetate. Stirring was performed 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%).

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

Example 9
(Preparation of exemplary compound (86))
Exemplified compound (86) was obtained in a yield of 52% in the same manner as in 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) can also be prepared as follows.
30 ml of N-methylpyrrolidone was added to 8.0 g (0.02 mol) of 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 Exemplified Compound (86) (yield 96.0%).

Example 10
(Preparation of Exemplified Compound (81))
Exemplified compound (81) was obtained in a yield of 18% in the same manner as in 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

Example 11
(Preparation of Exemplified Compound (82))
Exemplified compound (82) was obtained in a yield of 32% in the same manner as in 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

Example 12
(Preparation of exemplary compound (87))
Exemplified compound (87) was obtained in a yield of 18% in the same manner as in 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

Example 13
(Preparation of exemplary compound (88))
Exemplified Compound (88) was obtained in a yield of 19% in the same manner as in Example 5 except that Exemplified Compound (86) was used instead of Exemplified Compound (72) and dimethyl sulfate was used instead of 2-ethylhexyl bromide. 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

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

Example 15
(Preparation of exemplary compound (122))
Exemplified compound (122) was obtained in a yield of 15% in the same manner as in Example 5 except that exemplified compound (121) was used instead 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 )

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)

Example 17
(Preparation of Exemplified Compound (131))
Exemplified compound (131) was obtained in a yield of 18% in the same manner as in 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)

Example 18
(Preparation of Exemplified Compound (132))
Exemplified compound (132) was obtained in a yield of 45% in the same manner as in 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)

Example 19
(Preparation of exemplary compound (123))
Exemplified compound (123) was obtained in a yield of 72% in the same manner as in Example 3 except that iso-butyl cyanoacetate was used instead of ethyl cyanoacetate.
MS: m / z 536 (M +)
The exemplified compound (123) can also be prepared as follows.
Exemplified compound (123) was obtained in a yield of 49% in the same manner as in the reaction using synthetic intermediate M-2 of Example 14 except that iso-butyl cyanoacetate was used instead of t-butyl cyanoacetate. It was.

Example 20
(Preparation of exemplary compound (124))
Exemplified compound (124) was obtained in a yield of 24% in the same manner as in Example 5 except that exemplified compound (123) was used instead 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)

Example 21
(Preparation of exemplary compound (125))
Exemplified compound (125) was obtained in a yield of 63% in the same manner as in 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) can also be prepared as follows.
Except for using 2-cyano-N, N′-dimethylacetamide in place of t-butyl cyanoacetate, similar to the reaction using the synthetic intermediate M-2 in Example 14 with a yield of 59%. Compound (125) was obtained.

Example 22
(Preparation of Exemplified Compound (126))
Exemplified compound (126) was obtained in a yield of 1% in the same manner as in 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)

Example 23
(Preparation of exemplary compound (127))
Exemplified compound (127) was obtained in a yield of 6% in the same manner as in 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)

Example 24
(Preparation of exemplary compound (128))
Exemplified compound (128) was obtained in a yield of 88% in the same manner as in 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) can also be prepared as follows.
The yield was 89% in the same manner as in the reaction using the synthetic intermediate M-2 in Example 14 except that 2-cyano-N- (2-methoxyphenyl) acetamide was used instead of t-butyl cyanoacetate. Example compound (128) was obtained.

Example 25
(Preparation of exemplary compound (129))
Exemplified compound (129) was obtained in a yield of 1% in the same manner as in Example 5, except that exemplified compound (128) was used instead 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)

Example 26
(Preparation of exemplary compound (133))
Exemplified compound (133) was obtained in a yield of 84% in the same manner as in Example 3, except that benzoylacetonitrile was used instead of ethyl cyanoacetate.
MS: m / z 544 (M +)
The exemplified compound (133) can 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 Example 14 except that benzoylacetonitrile was used instead of t-butyl cyanoacetate.

Example 27
(Preparation of exemplary compound (134))
Exemplified compound (134) was obtained in a yield of 5% in the same manner as in 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)

Example 28
(Preparation of exemplary compound (135))
Exemplified compound (135) was obtained in a yield of 46% in the same manner as in Example 3, except that phenylsulfonylacetonitrile was used instead of ethyl cyanoacetate.
MS: m / z 616 (M +)
The exemplified compound (135) can 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 Example 14 except that phenylsulfonylacetonitrile was used instead of t-butyl cyanoacetate.

Example 29
(Preparation of Exemplified Compound (136))
Exemplified compound (136) was obtained in a yield of 6% in the same manner as in 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)

Example 30
(Preparation of exemplary compound (137))
Exemplified compound (137) was obtained in 49% yield in the same manner as in Example 3, except that methylsulfonylacetonitrile was used instead of ethyl cyanoacetate.
MS: m / z 492 (M +)
The exemplified compound (135) can also be prepared as follows.
Exemplified compound (135) was obtained in a yield of 53% in the same manner as in the reaction using synthetic intermediate M-2 of Example 14 except that methylsulfonylacetonitrile was used instead of t-butyl cyanoacetate.

Example 31
(Preparation of exemplary compound (138))
Exemplified compound (138) was obtained in a yield of 4% in the same manner as in 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 )

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 )

Example 33
(Preparation of exemplary compound (3-1))

4.0 g of sodium hydroxide was suspended in 45 ml of ethanol, 6.4 g of barbituric acid was added, and the mixture was heated to reflux for 2 hours with stirring. After cooling to room temperature, 3.0 ml of carbon disulfide was added and stirred at 40 ° C. for 2 hours. The crystals were separated by filtration to obtain 11.2 g of compound (b).
A solution prepared by dissolving 1.23 g of chloranil in 18 ml of N, N-dimethylacetamide and cooling 2.48 g of compound (b) in 5 ml of water was added dropwise. The resulting black solution was stirred at room temperature for 5 hours. Further, 5 ml of water was added, and after cooling to 3 ° C., the crystals were separated by filtration. The extract was washed with cold water and dried to obtain 2.04 g of exemplary compound (3-1) (yellow crystals).
Infrared absorption spectrum (cm ⁻¹ ): 3430-3450 (s, br), 1718 (s), 1647 (s), 1431 (s), 1348 (m), 582 (m)
The exemplified compound (3-1) can also be prepared as follows.
Synthetic intermediate M-2 (1.22 g) and barbituric acid (0.77 g) were suspended in dimethyl sulfoxide (100 ml), stirred for 5 hours while heating to 80 ° C. under a nitrogen stream, and then cooled to room temperature. After dissolving once, the newly precipitated solid was filtered off. It was washed with dimethyl sulfoxide and then with water and dried to obtain 1.01 g of exemplary compound (3-1) (yellow crystals).

Example 34
(Preparation of exemplary compound (3-2))
0.51 g of exemplary compound (3-1) was suspended in 10 ml of N, N-dimethylacetamide, and 0.28 ml of dimethyl sulfate and 0.70 ml of diisopropylethylamine were added. The suspension was stirred at 70 ° C. for 4 hours and then cooled to room temperature. The precipitate was filtered off and washed with dimethylacetamide, water and methanol. This was dried to obtain 0.31 g of exemplified compound (3-2) (pale yellow green crystal).
Infrared absorption spectrum (cm ⁻¹ ): 3430-3450 (s, br), 1718 (s), 1645 (s), 1556 (w), 1431 (s), 1350 (m)

Example 35
(Preparation of exemplary compound (3-3))
0.51 g of exemplary compound (3-1) was suspended in 10 ml of dimethyl sulfoxide, and 1.4 ml of acetic anhydride was added. Further, when 2.0 ml of triethylamine was added, the crystals were dissolved to obtain a uniform solution. This solution was stirred at 70 ° C. for 4 hours, and the precipitated crystals were separated by filtration. The extract was washed with dimethyl sulfoxide and water and dried to obtain 0.40 g of exemplary compound (3-3) (pale yellow crystals).
Infrared absorption spectrum (cm ⁻¹ ): 3430-3450 (s, br), 1780 (m), 1720 (s), 1647 (s), 1446 (s), 1356 (m), 1146 (m), 573 (s)

Example 36
(Preparation of exemplary compound (3-4))

4.0 g of sodium hydroxide was suspended in 45 ml of ethanol, 7.2 g of thiobarbituric acid was added, and the mixture was heated to reflux for 2 hours with stirring. After cooling to room temperature, 3.0 ml of carbon disulfide was added and stirred at 40 ° C. for 2 hours. The crystals were separated by filtration to obtain 12.6 g of compound (c).
A solution prepared by dissolving 1.23 g of chloranil in 18 ml of N, N-dimethylacetamide and cooling 2.64 g of compound (c) in 5 ml of water was added dropwise while cooling to 10 ° C. The solution was stirred at room temperature for 5 hours. Further, 5 ml of water was added, and after cooling to 3 ° C., the crystals were separated by filtration. The extract was washed with cold water and dried to obtain 1.99 g of exemplary compound (3-4) (yellowish brown crystals).
Infrared absorption spectrum (cm ⁻¹ ): 3430-3450 (s, br), 3109 (m), 3018 (m), 2901 (m), 1660 (m), 1616 (s), 1531 (s), 1443 (s), 1161 (s)
The exemplified compound (3-4) can also be prepared as follows.
Synthetic intermediate M-2 (1.24 g) and thiobarbituric acid (0.90 g) were suspended in dimethyl sulfoxide (50 ml), stirred for 4 hours while heating to 80 ° C. under a nitrogen stream, and then cooled to room temperature. The precipitated solid was separated by filtration, washed with dimethyl sulfoxide, water and methanol in this order, and dried to obtain 0.55 g of exemplary compound (3-4) (yellowish brown crystals).

Example 37
(Preparation of exemplary compound (3-6))
1.09 g of exemplified compound (3-4) was suspended in 10 ml of dimethyl sulfoxide, and 0.42 ml of acetic anhydride was added. Further, when 0.84 ml of triethylamine was added, the crystals were dissolved to obtain a uniform solution. This solution was stirred at 70 ° C. for 6 hours, and the precipitated crystals were separated by filtration. The extract was washed with dimethyl sulfoxide and water and dried to obtain 0.40 g of exemplary compound (3-6) (yellow-orange crystals).
Infrared absorption spectrum (cm ⁻¹ ): 3430-3450 (m, br), 3114 (m), 3022 (m), 2897 (m), 1784 (w), 1628 (s), 1533 (m), 1433 (s), 1155 (s)

Example 38
(Preparation of exemplary compound (3-33))

4.0 g of sodium hydroxide was suspended in 45 ml of ethanol, 8.7 g of 3-methyl-1-phenyl-5-pyrazolone was added, and the mixture was heated to reflux for 2 hours with stirring. After cooling to room temperature, 3.0 ml of carbon disulfide was added and stirred at 40 ° C. for 2 hours. The crystals were separated by filtration to obtain 13.6 g of compound (d).
A solution prepared by dissolving 1.23 g of chloranil in 18 ml of N, N-dimethylacetamide and dissolving 2.94 g of compound (d) in 5 ml of water was added dropwise while cooling to 10 ° C. The solution was stirred at room temperature for 5 hours. Further, 5 ml of water was added, and after cooling to 3 ° C., the crystals were filtered off. The extract was washed with cold water and dried to obtain 2.12 g of exemplary compound (3-33) (yellow crystals).
Infrared absorption spectrum (cm ⁻¹ ): 3400-3420 (br, m), 1643 (m), 1594 (w), 1497 (s), 1335 (m)
Moreover, exemplary compound (3-33) can be prepared also as follows.
1.24 g of compound (M-2) and 1.05 g of 3-methyl-1-phenyl-2-pyrazolin-5-one are suspended in 100 ml of dimethyl sulfoxide and stirred for 3 hours while heating to 80 ° C. under a nitrogen stream. After that, it was cooled to room temperature. To the obtained uniform solution, 10 ml of a 1 mol / L hydrochloric acid aqueous solution was added, and the precipitated solid was separated by filtration and washed with water and then with methanol. By drying, 1.90 g of Exemplified compound (3-33) (yellow crystals) was obtained.

Example 39
(Preparation of exemplary compound (140))
Exemplified compound (140) was obtained in a yield of 53% in the same manner as in the reaction using synthetic intermediate M-2 of Example 6 except that diethyl malonate was used instead of pivaloylacetonitrile.
MS: m / z 574 (M +).

Example 40
(Preparation of Exemplified Compound (141))
Exemplified compound (141) was obtained in the same manner as in the reaction using synthetic intermediate M-2 in Example 7 except that ethyl phenylsulfonylacetate was used instead of 3-hydroxy-3-methylbutyl cyanoacetate.
MS: m / z 710 (M +).

Example 41
(Preparation of exemplary compound (3-35))
10.9 g of the exemplified compound (3-33) was suspended in 360 ml of N, N-dimethylacetamide, and 7.7 ml of dimethyl sulfate was added. Further, 0.1 ml of triethylamine and 7.5 g of potassium carbonate were added, and the solution was stirred at 80 ° C. for 8 hours. Further, 3.8 ml of dimethyl sulfate was added and stirred at 80 ° C. for 3 hours, and the precipitated crystals were separated by filtration. After washing with N, N-dimethylacetamide, it was suspended in 50 ml of water and stirred at 100 ° C. for 1 hour. The solid was filtered off and washed with water. By drying, 6.5 g of Exemplified compound (3-35) (yellow-orange crystals) was obtained.
MS: m / z 630 (M +).

Example 42
(Preparation of Exemplified Compound (3-41))
Synthetic intermediate M-2 (3.1 g) and 3-acetylamido-1-phenyl-2-pyrazolin-5-one (2.4 g) are suspended in 20 ml of dimethyl sulfoxide and heated to 80 ° C. under a nitrogen stream for 5 hours. After stirring, it was cooled to room temperature. To the obtained uniform solution, 10 ml of a 1 mol / L hydrochloric acid aqueous solution was added, and the precipitated solid was separated by filtration and washed with water and then with methanol. By drying, 3.0 g of Exemplified Compound (3-41) (yellow crystal) was obtained.
MS: m / z 688 (M +).

Example 43
(Preparation of exemplary compound (3-56))
0.69 g of the exemplified compound (3-41) was suspended in 20 ml of N, N-dimethylacetamide, and 0.43 ml of dimethyl sulfate was added. Further, 0.1 ml of triethylamine and 0.41 g of potassium carbonate were added, the solution was stirred at 80 ° C. for 7 hours, and the precipitated crystals were separated by filtration. The resultant was washed with N, N-dimethylacetamide and water and dried to obtain 0.40 g of exemplary compound (3-56) (yellow-orange crystals).
MS: m / z 716 (M +).

Example 44
(Preparation of exemplary compound (3-57))
1.03 g of the exemplified compound (3-41) was suspended in 10 ml of tetrahydrothiophene-1,1-dioxide, and 1.4 ml of acetic anhydride was added. Further, 2.0 ml of triethylamine and 0.02 g of N, N-dimethylaminopyridine were added, the solution was stirred at 100 ° C. for 6 hours, and the precipitated crystals were separated by filtration. The product was washed with methanol and dried to obtain 0.85 g of exemplary compound (3-57) (yellow orange crystals).
MS: m / z 772 (M +).

Example 45
(Preparation of Exemplified Compound (3-58))
After suspending 1.55 g of synthetic intermediate M-2 and 1.40 g of 1,2-diphenyl-pyrazolidine-3,5-dione in 20 ml of dimethyl sulfoxide and stirring for 3 hours while heating to 80 ° C. under a nitrogen stream And cooled to room temperature. To the obtained uniform solution, 5 ml of 1 mol / L hydrochloric acid aqueous solution was added, and the precipitated solid was separated by filtration and washed with water and then with methanol. By drying, 1.60 g of Exemplified compound (3-58) (yellow crystals) was obtained.
MS: m / z 758 (M +).

Example 46
(Preparation of exemplary compound (3-59))
1.52 g of the exemplified compound (3-58) was suspended in 20 ml of N, N-dimethylacetamide, and 1.14 ml of dimethyl sulfate was added. Further, 0.90 ml of 1,8-diazabicyclo [5.4.0] -7-undecene was added, the solution was stirred at 100 ° C. for 7.5 hours, and the precipitated crystals were separated by filtration. It was washed with N, N-dimethylacetamide, water and methanol and dried to obtain 1.21 g of Exemplified compound (3-59) (yellow-orange crystals).
MS: m / z 786 (M +).

Example 47
(Preparation of exemplary compound (3-60))

2 g of benzene-1,2,4,5-tetrathiol (synthesized by the method described in Journal of Organic Chemistry, 1985, Vol. 50, page 2397) was mixed with 2 g of sodium hydroxide and 20 ml of water. Under a nitrogen stream, 2.5 ml of carbon disulfide was dropped and reacted at 70 ° C. for 6 hours. After cooling, the precipitated solid was filtered off. Washing with methanol and drying yielded 1.3 g of synthetic intermediate α.
Synthetic intermediate α0.87 g and ethyl iodide 0.73 ml were mixed and reacted at 50 ° C. for 12 hours. After cooling, 10 ml of acetic acid, 1 ml of pyridine and 1.57 g of 3-methyl-1-phenyl-2-pyrazolin-5-one were added and reacted at 100 ° C. for 10 hours. After cooling, the precipitated solid was filtered off. The product was washed with methanol and dried to obtain 0.8 g of exemplary compound (3-60).
MS: m / z 571 (M +)
IR (KBr) 3700-3300, 1520, 1420,
1330, 1280, 1060, 1040, 1020, 880, 510 cm ^-1 .

Example 48
(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.

Example 49
(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 804 (M +).

Example 50
(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 912 (M +).

Example 51
(Preparation of exemplary compound (3-63))
2.48 g of the above synthetic intermediate M-2 and 1.79 g of 3-carbamoyl-1-phenyl-2-pyrazolin-5-one were suspended in 20 ml of dimethyl sulfoxide, and heated to 80 ° C. under a nitrogen stream. After stirring for 5 hours, it was cooled to room temperature. To the obtained uniform solution, 10 ml of 1N hydrochloric acid aqueous solution was added, and the precipitated solid was separated by filtration and washed with water and then with methanol. It dried and obtained 4 g of exemplary compound (3-63).
MS: m / z 660 (M +).

Example 52
(Preparation of Exemplified Compound (3-45))
The above synthetic intermediate M-2 (1.24 g) and synthetic intermediate B-34 (0.82 g) were suspended in 100 ml of dimethyl sulfoxide, stirred for 12 hours while heating to 90 ° C. under a nitrogen stream, and then cooled to room temperature. To the obtained uniform solution, 10 ml of 1N hydrochloric acid aqueous solution was added, and the precipitated solid was separated by filtration and washed with water and then with methanol. By drying, 1 g of exemplary compound (3-45) was obtained.
MS: m / z 526 (M +).

Reference 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-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 longer wave length of λmax, a molar extinction coefficient ε of 2 times or more, and a half-value width reduced from about 40 nm to about 27 nm, giving 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 turned out that the compound represented by the said general formula (I) of this invention has the outstanding ultraviolet absorptivity.

Reference 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) 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 apparent from the results in Table 5, it was found that the compound of the present invention is less decomposed by light irradiation and has higher light fastness than existing UV absorbers having absorption in the UV-A region. .

(Reference Example 2A-1)
0.40 g of the exemplified compound (3-3) obtained as described above was suspended in 8 ml of N, N-dimethylacetamide and stirred at 100 ° C. for 3 hours. This suspension was filtered while hot, and the solid on the filter paper was washed with N, N-dimethylacetamide, water and methanol and then dried to obtain 0.40 g of a yellow-orange solid. This solid is a powder X-ray diffraction pattern (RINT manufactured by Rigaku Corporation) by CuKα ray irradiation.
Measured according to 2000 (trade name). The same applies hereinafter) and is characterized by the following diffraction angle 2θ.
High intensity: 23.3 ° (half-width 0.39 °), medium intensity: 9.9 °, 10.6 °, 17.6 °, 19.1 °, 21.4 °, 30.1 °

(Reference Example 2A-2)
The same operation as in Reference Example 2A-1 was carried out except that 0.40 g of Exemplified Compound (3-1) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of a yellowish green solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 5.0 °, 26.1 ° (half-value width 0.50 °), 26.9 ° (half-value width 0.41 °), medium strength: 12.9 °, 15.7 °, 20.8 °, 25.1 °

(Reference Example 2A-3)
The same operation as in Reference Example 2A-1 was carried out except that 0.40 g of Exemplified Compound (3-6) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of a brown solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High strength: 25.3 ° (half-value width 1.14 °), medium strength: 8.5 °, 12.5 °

(Reference Example 2A-4)
The same operation as in Reference Example 2A2-1 was performed, except that 0.40 g of Exemplified Compound (3-38) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of a yellow solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
The exemplified compound (3-38) was synthesized in the same manner as in the above synthesis example.
High intensity: 8.9 ° (half-value width 0.32 °), 25.6 ° (half-value width 0.42 °), medium strength: 10.7 °, 14.3 °, 22.1 °

(Reference Example 2A-5)
The procedure of Reference Example 2A-1 was repeated except that 0.40 g of Exemplified Compound (3-34) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1, 0.40 g of a brown solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
In addition, what was synthesize | combined like the said synthesis example was used for exemplary compound (3-34).
High intensity: 8.8 ° (half width 0.54 °) Medium intensity: 15.4 °, 16.1 °, 25.0 °, 25.6 °

(Reference Example 2A-6)
The same operation as in Reference Example 2A-1 was carried out except that 0.40 g of Exemplified Compound (3-35) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of a yellow solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 8.9 ° (half-value width 0.32 °), 25.6 ° (half-value width 0.42 °), medium strength: 10.7 °, 14.3 °, 22.1 °

(Reference Example 2A-7)
The same operation as in Reference Example 2A-1 was performed except that 0.40 g of Exemplified Compound (2-15) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of a solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
In addition, what was synthesize | combined like the said synthesis example was used for exemplary compound (2-15).
High strength: 9.9 ° (half-value width 0.60 °), medium strength: 15.1 °, 20.0 °

(Reference Example 2A-8)
The procedure of Reference Example 2A-1 was repeated except that 0.40 g of Exemplified Compound (3-45) was used instead of Exemplified Compound (3-3) in Example 2-1. 0.40 g of a green solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
The exemplified compound (3-45) was synthesized in the same manner as in the above synthesis example.
High intensity: 24.4 ° (half-value width 0.84 °) Medium intensity: 8.7 °, 16.8 °, 22.0 °

(Reference Example 2A-9)
The same operation as in Reference Example 2A-1 was carried out except that 0.40 g of Exemplified Compound (3-56) was used in place of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of an orange solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High strength: 8.9 ° (half width 0.53 °)

(Reference Example 2A-10)
The same operation as in Reference Example 2A-1 was carried out except that 0.40 g of Exemplified Compound (3-59) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of a yellow solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High Intensity: 10.1 ° (Half Width 0.31 °), 24.8 ° (Half Width 0.29 °), Medium Strength: 21.5 °, 26.7 °

(Reference Example 2A-11)
The procedure of Reference Example 2A-1 was repeated except that 0.40 g of Exemplified Compound (3-57) was used instead of Exemplified Compound (3-3) in Reference Example 2A-1. 0.40 g of an orange solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High strength: 8.3 ° (half-value width 0.29 °), medium strength: 15.6 °, 25.0 °

Also, the same as Reference Example 2A-1 except that 0.40 g of the compounds listed in Tables 6-1 to 6-2 below were used instead of the exemplified compound (3-3) in Reference Example 2A-1. The operation was performed.

Reference Example 3-1
-Preparation of aqueous colored dispersion composition-
In a zirconia container with a total content of 12 ml,
-0.25 g of solid of exemplary compound (3-3) obtained according to Example 35 above
・ Sodium oleate 0.05g
・ Glycerin 0.50g
・ Deionized water 4.20g
Was put together with 10 g of zirconia beads having a diameter of 0.1 mm and pulverized using a planetary ball mill (Fritsch Japan Co., Ltd., P-7 type) (rotation speed: 300 rpm, pulverization time: 3 hours). When the beads were separated from the mixture in the container by decantation after pulverization, a pigment dispersion composition (coloring composition) containing 5.0% of the exemplified compound (3-3) in a fine particle state was obtained.
The dispersion composition diluted 30 times with deionized water was measured by a dynamic light scattering method (Nikkiso Microtrack UPA-150).

The same operations as in Reference Example 3-1 were performed except that the solids listed in Tables 7-1 to 7-3 below were used instead of the solid of the exemplified compound (3-3) in Reference Example 3-1. As a result, a pigment dispersion composition (coloring composition) containing 5.0% of the compound in a fine particle state was obtained.
The colored compositions listed in Tables 7-1 to 7-3 all have a volume average particle size of less than 300 nm, and are stable dispersions that do not generate precipitates even when left at room temperature for 1 month. It was.

Reference Example 4-1
-Preparation of aqueous dye composition-
2.5 g of deionized water was added to 0.25 g of Exemplified Compound (4-4), and 8 mol / L potassium hydroxide aqueous solution was added with stirring to adjust to pH = 9 and completely dissolved. Here, 0.50 g of glycerin and deionized water were added to make a total of 5.00 g. When this was passed through a filter having a pore diameter of 0.45 μm, an aqueous coloring composition containing 5.0% of the exemplary compound (4-4) was obtained.

  In Reference Example 4-1, the same operation as in Reference Example 4-1 was carried out except that the compounds listed in Table 8 below were used instead of the exemplified compound (4-4). An aqueous coloring composition containing the above compound was obtained.

(Reference Example 5-1)
-Preparation of solvent-based dye composition-
4.75g of methyl ethyl ketone was added to 0.25g of exemplary compound (1-16), and it was made to melt | dissolve completely, stirring. When this was passed through a filter having a pore diameter of 0.45 μm, a solvent-based coloring composition containing 5.0% of the exemplary compound (1-16) was obtained.
(Reference Example 5-2) to (5-18), Comparative Example (5-1) (5-2)
In Reference Example 5-1, the same operation as in Reference Example 5-1 was carried out except that the compounds listed in Table 9 below were used instead of the exemplified compound (1-16). A solvent-based coloring composition containing the above compound was obtained.

(Light fastness of colored composition coating)
When the optical density of the coated material containing the exemplary compound (3-3) obtained according to Reference Example 3-1 was measured using a reflection-type spectrocolorimetric densitometer (XRite 938, XRite) Then, using a bar coater, an ink-jet exclusive paper (Epson Co., Ltd. photomat paper) was applied to prepare a coated product.
Similarly, the coating material of the pigment dispersion composition obtained according to Reference Examples 3-2 to 3-69 and Comparative Examples 3-1 to 3-3 was produced.
Next, using a xenon fading tester, each coated material was irradiated with xenon light (170,000 lux, transmitted through a 325 nm filter) for 2 weeks. The optical density after irradiation was measured, the residual ratio was calculated, and the light fastness was evaluated. The results are shown in Tables 10-1 to 10-3. In Tables 10-1 to 10-3, the coloring power is ◎ when the pigment solid content concentration required to obtain an optical density of 1.0 is less than 1.2%, and more than 1.2% and less than 3.0%. 3.0% or more and less than 5.0% is indicated by Δ, and 5.0% or more is indicated by ×.
In addition, the light fastness is evaluated as ○ when the residual ratio is 90% or more, Δ when 70% or more and less than 90%, and × when 70% or less.

From Tables 10-1 to 10-3, the colored dispersion composition containing the compound of the present invention has excellent light fastness even though it does not contain heavy metals that have high coloring power and are concerned about safety. You can see that
Reference Example-Light Fastness Evaluation of Aqueous Dye Composition Coatings-
When the optical density of the coated material containing the exemplified compound (4-4) obtained according to Reference Example 4-1 is measured using a reflection type spectrocolorimeter (XRite 938, XRite). Then, using a bar coater, an ink-jet exclusive paper (Epson Co., Ltd. photomat paper) was applied to prepare a coated product.
Similarly, the coating material of the aqueous | water-based coloring composition obtained according to Reference Examples 4-2 to 4-9 and Comparative Examples 4-1 to 4-2 was produced.
Next, using a xenon fading tester, each coated material was irradiated with xenon light (170,000 lux, transmitted through a 325 nm filter) for 4 days. The optical density after irradiation was measured, the residual ratio was calculated, and the light fastness was evaluated. The results are shown in Table 11. In Table 11, the coloring power is ◎, less than 0.8%, less than 2.0%, less than 2.0%, and more than 2.0%. Less than 0% is indicated by Δ, and 3.0% or more is indicated by ×.
In addition, the light fastness is evaluated as ○ when the residual ratio is 90% or more, Δ when 70% or more and less than 90%, and × when 70% or less.

  From Table 11, it can be seen that the aqueous coloring composition containing the compound of the present invention has excellent light fastness even though it does not contain a heavy metal having high coloring power and concerns about safety.

-Evaluation of light fastness of coatings of solvent-based dye compositions-
When the optical density of the coated product containing the exemplary compound (1-16) obtained according to Reference Example 5-1 is measured using a reflection type spectrocolorimeter (XRite 938, XRite). Then, using a bar coater, an ink-jet exclusive paper (Epson Co., Ltd. photomat paper) was applied to prepare a coated product.
Similarly, the coating material of the solvent-based coloring composition obtained according to Reference Examples 5-2 to 5-18 and Comparative Examples 5-1 to 5-3 was produced.
Next, using a xenon fading tester, each coated material was irradiated with xenon light (170,000 lux, transmitted through a 325 nm filter) for 4 days. The optical density after irradiation was measured, the residual ratio was calculated, and the light fastness was evaluated. The results are shown in Table 12. In Table 12, the coloring power is ◎ when the dye concentration is less than 0.8% necessary for obtaining an optical density of 1.0, ◯ when it is 1.0% or more and less than 2.0%, and 2.0% or more. Less than 0% is indicated by Δ, and 3.0% or more is indicated by ×.
In addition, the light fastness is evaluated as ○ when the residual ratio is 90% or more, Δ when 70% or more and less than 90%, and × when 70% or less.

  From Table 12, it can be seen that the aqueous coloring composition containing the compound of the present invention has excellent light fastness even though it has high coloring power and does not contain a heavy metal that is concerned about safety.

[Reference Example 6-1]
<Preparation of inkjet ink>
In a zirconia container with a total content of 12 ml,
-0.50 g of the solid of the compound (3-34) obtained according to Example 36 above,
・ 0.10 g of sodium oleate,
-4.40 g of deionized water,
Was put together with 10 g of zirconia beads having a diameter of 0.1 mm and pulverized using a planetary ball mill (Fritsch Japan Co., Ltd., P-7 type) (rotation speed: 300 rpm, pulverization time: 3 hours). After completion of the pulverization, the beads were separated from the mixture in the container by decantation to obtain a pigment dispersion composition (coloring composition) containing 10% of the compound (3-34) in a fine particle state.
The following components were added to and mixed with the pigment dispersion composition (colored composition) thus obtained to prepare an ink for ink jet recording (containing 5% of the compound (3-34)).

~ Ink composition ~
10% pigment dispersion composition 50 parts Glycerol 10 parts 2-pyrrolidone 5 parts 1,2-hexanediol 2 parts Triethylene glycol monobutyl ether 2 parts Propylene glycol 0.5 parts Deionized water 30.5 Part

The ink-jet ink thus obtained was refilled into a cartridge of an ink-jet printer (PX-V600, trade name, manufactured by Seiko Epson Corporation), and ink-jet paper painting mat finish (trade name, manufactured by Fuji Film Co., Ltd.) on the same machine. A solid image was recorded.
The reflection spectrum of the obtained image is shown in FIG. It can be seen from FIG. 1 that the image formed with the ink jet recording ink of the present invention has excellent spectral characteristics with sharp absorption. Further, when the light fastness of the obtained image was evaluated in the same manner as in Reference Example 3-1, an excellent residual rate was shown.
In Reference Example 6-1, Reference Example, except that the solids listed in Tables 13-1 to 13-3 below were used in place of the solid of Example Compound (3-3) obtained according to Example 35. When an operation similar to that of 6-1 was performed, an inkjet recording ink (coloring composition) containing 5.0% of the compound was obtained. These were stable inks that did not cause precipitation even at room temperature for one month.
To 0.50 g of Exemplified Compound (4-4), 3.5 g of deionized water was added, and 8 mol / L potassium hydroxide aqueous solution was added with stirring to adjust to pH = 9 and completely dissolved. Deionized water was added here to make a total of 5.00 g.
The following components were added to and mixed with the coloring composition thus obtained, and passed through a filter having a pore size of 0.45 μm to prepare an ink for ink jet recording (containing 5% of the compound (4-4)). .
~ Ink composition ~
・ 10% coloring composition 50 parts ・ Glycerin 10 parts ・ 2-pyrrolidone 5 parts ・ 1,2-hexanediol 2 parts ・ Triethylene glycol monobutyl ether 2 parts ・ Propylene glycol 0.5 parts ・ Deionized water 30.5 parts Ink for inkjet recording was produced by performing the same operation as described above except that the compounds listed in Tables 13-1 to 13-3 below were used instead of the exemplified compound (4-4).

-Evaluation of pigment-dispersed inkjet ink-
Inkjet ink is refilled into a cartridge for an inkjet printer (PX-V600, trade name, manufactured by Seiko Epson Corporation), and a solid image is printed on the inkjet paper painting mat finish (trade name, manufactured by Fuji Film Co., Ltd.) on the same machine. Recorded.
This sample was irradiated with xenon light (170,000 lux, transmitted through a 325 nm filter) for 2 weeks using a xenon fading tester. The optical density after irradiation was measured, the residual ratio was calculated, and the light fastness was evaluated. In Tables 14-1 to 14-3, as for light fastness, a residual ratio of 90% or more is indicated by ◯, 70% or more and less than 90% by Δ, and less than 70% by ×.
Regarding the coloring power, the obtained solid image has an optical density of 2.0 or more, ◯, 1.5 or more and less than 2.0, ◯, 1.0 or more and less than 1.5, or less than 1.0. It is said.
In addition, regarding ink stability, a case where no precipitate is formed after each ink is left at room temperature for one month is indicated by ◯, and a case where a precipitate is generated is indicated by x.
In addition, regarding the ejectability, the obtained solid image is visually observed, and “O” indicates that no streak is not ejected and “x” indicates that the streak is recognized.
The above results are shown in Tables 14-1 to 14-3.

  That is, it can be seen that the ink-jet ink of the present invention has excellent ink stability and ejection properties, and has both high coloring power and light fastness.

(Reference Example 7-1)
-Preparation of water-based inkjet ink-
To 0.50 g of Exemplified Compound (4-4), 3.5 g of deionized water was added, and 8 mol / L aqueous potassium hydroxide solution was added with stirring to adjust to pH = 9 and completely dissolved. Deionized water was added here to make a total of 5.00 g.
The following components were added to and mixed with the coloring composition thus obtained, and passed through a filter having a pore size of 0.45 μm to prepare an ink for ink jet recording (containing 5% of the compound (4-4)). .
~ Ink composition ~
・ 10% coloring composition 50 parts ・ Glycerin 10 parts ・ 2-pyrrolidone 5 parts ・ 1,2-hexanediol 2 parts ・ Triethylene glycol monobutyl ether 2 parts ・ Propylene glycol 0.5 parts ・ Deionized water 30.5 parts

(Reference Examples 7-2) to (7-9), Comparative Examples (7-1) to (7-2)
Ink for ink-jet recording was carried out in the same manner as in Reference Example 7-1 except that the compounds listed in Table 15 below were used instead of the exemplified compound (4-4) in Reference Example 7-1. Was made.

-Evaluation of water-based inkjet ink-
Inkjet ink is refilled into a cartridge for an inkjet printer (PM-980C, trade name, manufactured by Seiko Epson Corporation), and a solid image is printed on the inkjet paper painting mat finish (trade name, manufactured by Fujifilm Corporation) on the same machine. Recorded.
This sample was irradiated with xenon light (170,000 lux, transmitted through a 325 nm filter) for 4 days using a xenon fading tester. The optical density after irradiation was measured, the residual ratio was calculated, and the light fastness was evaluated. In Table 16, as for light fastness, a residual rate of 90% or more is indicated by ◯, 70% or more and less than 90% is indicated by Δ, and less than 70% is indicated by ×.
Regarding the coloring power, the obtained solid image has an optical density of 2.0 or more, ◯, 1.5 or more and less than 2.0, ◯, 1.0 or more and less than 1.5, or less than 1.0. It is said.
In addition, regarding ink stability, a case where no precipitate is formed after each ink is left at room temperature for one month is indicated by ◯, and a case where a precipitate is generated is indicated by x.
In addition, regarding the ejectability, the obtained solid image is visually observed, and “O” indicates that no streak is not ejected and “x” indicates that the streak is recognized.
The above results are shown in Table 16.

  That is, it can be seen that the ink-jet ink of the present invention has excellent ink stability and ejection properties, and has both high coloring power and light fastness.

It is a reflection spectrum of an inkjet recording image.

Claims (3)

The compound represented by the following general formula (I).

[In General Formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent —CN, —COOR ⁸ , —CONR ⁹ R ¹⁰ , —COR ¹¹ or —SO ₂ R ¹² . . Here, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom or a monovalent substituent selected from the following substituent group. R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring represented by the above general formulas (2) to (7). R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent selected from the following substituent group. X ¹ , X ² , X ³ and X ⁴ represent a sulfur atom.
However, R ¹ , R ² , R ³ and R ⁴ are all cyano groups, X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms, and R ⁵ and R ⁶ are both hydroxy groups or hydrogen atoms. Except when there is. R ¹ and R ³ are both hydrogen atoms, R ² and R ⁴ are both arylcarbonyl groups, X ¹ , X ² , X ³ and X ⁴ are all sulfur atoms, and R ⁵ and R ⁶ are both Except when it is a hydroxy group.
In the general formulas (2) to (7), R ²¹ , R ²² , R ³¹ , R ³² , R ³⁴ , R ⁴¹ , R ⁴⁴ , R ⁵¹ , R ⁵² , R ⁶² , R ⁶⁴ , R ⁷³ and R ⁷⁴ are Independently of each other, it represents a hydrogen atom or a monovalent substituent selected from the following substituent group.
^{R 23, R 24, R 25} , R 33, R 34, R 35, R 43, R 45, R 53, R 54, R 63 each independently represent an oxygen atom, a sulfur atom or nitrogen atom .
Z ⁷¹ and Z ⁷² each independently represent —N═ or —C (R ⁷⁵ ) ═. Here, R ⁷⁵ represents a hydrogen atom or a monovalent substituent selected from the following substituent group.
In the general formula ^(2), when ^{R 23} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 21} or ^{R 22.} If R ²⁴ is a nitrogen atom, said nitrogen atom to form a ring with ^{R 22.} If R ²⁵ is a nitrogen atom, said nitrogen atom to form a ring with ^{R 21.}
In the general formula ^(3), when ^{R 33} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 31} or ^{R 32.} If a R ³⁵ nitrogen atoms, said nitrogen atom to form a ring with ^{R 31.}
In the general formula ^(4), when at least one of ^{R 43} and ^{R 45} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 41.}
In the general formula ^(5), when ^{R 53} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 52.} If R ⁵⁴ is a nitrogen atom, said nitrogen atom to form a ring with ^{R 51.}
In the general formula ^(6), when ^{R 63} is a nitrogen atom, said nitrogen atom to form a ring with ^{R 62.}
<Substituent group>
Halogen atom, linear or branched alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, cyano group, carboxyl group, alkoxycarbonyl group having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms Carbonyl group, substituted or unsubstituted carbamoyl group having 0 to 20 carbon atoms, alkylcarbonyl group having 1 to 20 carbon atoms, arylcarbonyl group having 6 to 20 carbon atoms, nitro group, substituted or unsubstituted having 0 to 20 carbon atoms Amino groups, acylamino groups having 1 to 20 carbon atoms, sulfonamido groups having 0 to 20 carbon atoms, imide groups having 2 to 20 carbon atoms, imino groups having 1 to 20 carbon atoms, hydroxy groups, and those having 1 to 20 carbon atoms. Alkoxy group, aryloxy group having 6 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkylsulfonyloxy group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms Sulfonyloxy group, sulfo group, substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, carbon A number 6 to 20 arylsulfonyl group or a 4 to 7-membered heterocyclic group] R ⁵ and R ⁶ in the general formula (I) are each independently an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acylamino group, a carbamoyloxy group, or a carbamoylamino group. The compound according to claim 1, wherein The compound represented by the following general formula (I ').

[In General Formula (I ′), R ¹ , R ² , R ³ and R ⁴ represent a cyano group or an alkoxycarbonyl group having 1 to 20 carbon atoms.
R ₅ and R ₆ each independently represent an alkoxy group having 1 to 20 carbon atoms or an acyloxy group having 1 to 20 carbon atoms.
X ¹ , X ² , X ³ and X ⁴ represent a sulfur atom. ]

Images