JPH0563762B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to color imaging devices such as color image pickup tubes and color solid-state imaging devices. For example, in a VTR camera, etc., in order to extract the color signal corresponding to the color image,
Color image pickup tubes in which a micro color filter is provided in the light receiving section have been commonly used. On the other hand, recently, as a device to replace the image pickup tube,
For example, various solid-state image sensors such as CCD, BBD, and MOS have been developed, and color solid-state image sensors, which combine solid-state image sensors and micro color filters, have been developed with the main purpose of miniaturizing the VTR cameras mentioned above. Practical applications are being considered, and some have already been put into practical use. A color solid-state image sensor is made up of a photoelectric conversion element, which is generally called a micropixel, and a flat image sensor integrated circuit (IC) that integrates a scanning circuit. It consists of a micro color filter in which several types of micro color separation filter elements (colored resin films) such as red, green, blue, cyan, magenta, and yellow are combined in a mosaic or stripe pattern. . Color solid-state image sensors are generally manufactured by a method called "bonding method" or "on-wafer method." Among these methods, the bonding method involves forming a color separation filter element corresponding to each pixel of a solid-state image sensor on a transparent support such as glass in advance to produce a micro color filter, and then bonding this to the surface of the solid-state image sensor. This method is used to create a color solid-state image sensor. Therefore, in this method, when adhering independently manufactured micro color filters to the surface of a solid-state image sensor, strict control is performed so that each color separation filter element accurately corresponds to each pixel of the solid-state image sensor. Operation is required. On the other hand, the on-wafer method is a method in which a micro color filter is formed directly on a solid-state image sensor. Therefore, this on-wafer method has the advantage that it can be incorporated into the manufacturing process of a solid-state image sensor, and that it facilitates the manufacture of a color solid-state image sensor. Note that the on-wafer method involves simultaneously manufacturing a large number of color solid-state image sensors by forming color separation filter elements corresponding to each pixel of each solid-state image sensor on a wafer on which a large number of solid-state image sensors are arranged. A single color solid-state image sensor is manufactured by cutting out a single solid-state image sensor (chip) from a wafer in which a large number of solid-state image sensors are arranged, and forming a color separation filter element on each chip. Although several methods (on-chip methods) are known, in this specification, any of these methods are included in the on-wafer method. By the way, the micro color filter in a color imaging device has a great effect on the sensitivity, resolution, color reproducibility, etc. of the color imaging device, and therefore various studies are being conducted on improving and controlling its various characteristics. Particular attention is paid to the selection of dyes for dyeing micro color filters, and in order to obtain excellent micro color filters, the dye properties, fastness, color characteristics, etc. of the dyes used for dyeing must be carefully selected. It is also known that it is necessary to take this into account. Furthermore, as mentioned above, solid-state image sensors are composed of flat ICs in which photoelectric conversion elements and scanning circuits are highly integrated, so they are susceptible to dirt, dust, alkali metals, etc. Contamination by impurities is highly disliked. A solid-state imaging device contaminated with such impurities often does not exhibit predetermined characteristics, which poses a problem that directly leads to a reduction in product yield. Therefore, in the process of attaching a micro color filter to a solid-state image sensor,
Great care is taken to avoid contamination with such impurities as much as possible. The present invention is based on the above technical background.
Coloring for the production of colored resin films for micro color filters attached to imaging devices such as solid-state imaging devices and imaging tubes has excellent dyeability, fastness, and color characteristics expressed by a specific general formula, and is made using alkali metals. It is characterized in that it is carried out using a dye that does not contain this in its molecular structure. That is, in the present invention, the colored resin film of the micro color filter has the general formula []: [However, Q ¹ and Q ² may be the same or different, and each represents an alkyl group, a substituted alkyl group,
Cyano group, trifluoromethyl group, or -
Carbamoyl group represented by CONR ³ R ⁴ (where
R ³ represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and R ⁴ represents a hydrogen atom, an alkyl group,
represents a substituted alkyl group, aralkyl group, or aryl group, in which R ³ and R ⁴ may be connected directly or via an oxygen atom to form a ring; Q ³ and Q ⁴ are mutually may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group; X represents a cation consisting of a nonmetallic atom; Y ¹ and Y ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group; R ¹ and R ² may be the same or different from each other; each represents a hydrogen atom, an alkyl group, or a substituted alkyl group; however, R ¹ and R ² may be directly connected to form a ring); and q are each 1
represents an integer of ~4, provided that the sum of m and n and the sum of p and q are each 5 or less. ] This is a color imaging device characterized by being colored with a dye represented by the following. Next, the present invention will be explained in detail. The present invention utilizes an alkali metal that has been conventionally used as a yellow pigment for dyeing the colored resin film of a micro color filter that is formed on the surface of the light receiving part of an imaging device such as a solid-state imaging device or an imaging tube. Instead of the yellow pigment contained, some or all of it can be replaced with the general formula []: It is characterized by the use of a novel yellow pigment represented by. In the above general formula [], each of the alkyl group, substituted alkyl group, cyano group, trifluoromethyl group or carbamoyl group represented by -CONR ³ R ⁴ represented by Q ¹ and Q ² will be described below. The alkyl group has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
10, more preferably 1 to 6 linear, branched or cyclic alkyl groups, examples of which include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group. , pentyl, hexyl, and cyclohexyl. A substituted alkyl group is one in which a substituent is attached to an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. For example, a cyano group, an alkoxy group, a hydroxy group, a carboxyl group, etc. can be mentioned. In the carbamoyl group represented by the formula -CONR ³ R ⁴ , R ³ is a hydrogen atom, a carbon number of 1 to 20,
Preferably, an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms, has a substituent attached, and R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 20 carbon atoms;
Preferably 1 to 10 alkyl groups, more preferably 1 to 6 alkyl groups with substituents, and benzyl groups are preferable. Note that R ³ and R ⁴ may be bonded directly or via an oxygen atom to form a 5- to 6-membered ring. Among these carbamoyl groups, R ³ and R ⁴
both of which are hydrogen atoms, and one of R ³ or R ⁴ is a hydrogen atom and the other one has 1 carbon atom
-4 alkyl groups are preferred because they are easily available and have good dyeability. In addition, it is preferable that one or both of Q ¹ and Q ² is an alkyl group having 1 to 4 carbon atoms or a cyano group from the viewpoint of fastness as a dye. In the above general formula [], among the hydrogen atom, halogen atom, alkyl group, substituted alkyl group, alkoxy group, or substituted alkoxy group represented by Q ³ and Q ⁴ , the halogen atom is particularly preferably a chlorine atom, and the alkyl group is , a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, examples of which include methyl group, ethyl group, propyl group, isopropyl group. , butyl group, isobutyl group,
Mention may be made of sec-butyl, pentyl, hexyl and cyclohexyl groups. The number of carbon atoms in the substituted alkyl group, alkoxy group, and the alkyl moiety contained in the substituted alkoxy group is 1 to 1.
20, preferably 1 to 10, more preferably 1 to 6
is generally used. In addition, as a substituent, for example, a cyano group, an alkoxy group,
Examples include hydroxy group and carboxyl group. In the above general formula [], examples of cations consisting of nonmetallic atoms represented by X include protons (H ⁺ ), pyridinium cations that may contain substituents, and Cations derived from aromatic heterocyclic bases such as norinium cations, and general formula []: (R ⁵ ) (R ⁶ ) (R ⁷ ) (R ⁸ )N ⁺ [] (However, R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic group). In addition, at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula [] is a hydrogen atom, and the others are a lower alkyl group having 1 to 6 carbon atoms, or a phenyl group ( (optionally substituted with a lower alkyl group having 1 to 6 carbon atoms or a lower alkoxyl group having 1 to 6 carbon atoms) is preferable. Hydrogen atoms and halogen atoms represented by Y ¹ and Y ² ,
Among alkyl groups, substituted alkyl groups, alkoxy groups, and substituted alkoxy groups, the halogen atom is particularly preferably a chlorine atom, and the alkyl group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. A linear, branched or cyclic alkyl group, examples of which are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, and cyclohexyl. The following groups can be mentioned. The number of carbon atoms in the substituted alkyl group, alkoxy group, and the alkyl moiety contained in the substituted alkoxy group is 1 to 1.
20, preferably 1 to 10, more preferably 1 to 6
is generally used. In addition, as a substituent, for example, a cyano group, an alkoxy group,
Examples include hydroxy group and carboxyl group. Among the hydrogen atoms, alkyl groups, and substituted alkyl groups represented by R ¹ and R ² , the alkyl group is a linear, branched, or cyclic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group and cyclohexyl group. The alkyl moiety contained in the substituted alkyl group generally has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. In addition, examples of the substituent include a cyano group, an alkoxy group, a hydroxy group, and a carboxyl group. When R ¹ and R ² are directly connected to form a ring, the ring is a 5- to 12-membered ring, preferably a 5- to 6-membered ring, and more preferably a 6-membered ring. Next, examples of the dye (yellow dye) represented by the above general formula [] and preferably used in the present invention will be given.

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[Table] The dyes of general formula [] used in the present invention are, for example, general formula []: (However, M is an alkali metal ion, and the other symbols have the same meanings as in the general formula [])
By allowing a halogenating agent to act on the pigment represented by
General formula []: After obtaining the compound represented by (Hal is a halogen atom and the other symbols are synonymous with the above general formula []), an organic base or ammonia consisting of multiple nonmetallic atoms and a proton are added to the compound. It can be produced by reacting with a source (preferably water or alcohol). Alternatively, a compound represented by the general formula [] may be used as a proton source (preferably water or alcohol).
A compound of general formula [] can also be obtained by reacting with a corresponding sulfonic acid and then reacting with an organic base consisting of a plurality of nonmetallic atoms or ammonia. In the above manufacturing method, from the viewpoint of operational simplicity and cost, it is desirable that M be a sodium ion and Hal be a chlorine atom. Examples of the halogenating agent used in the above production method include chlorinating agents such as phosphorus oxochloride, phosphorus pentachloride, chlorosulfonic acid, and thionyl chloride. In addition, the alcohol used as a proton source in the above production method has 1 to 6 carbon atoms.
(preferably 1 to 4) alcohols, examples of which include methanol, ethanol, 2-propanol, 2-methoxyethanol, and the like. The compound represented by the general formula [], which is a raw material for producing the yellow pigment represented by the general formula [] used in the present invention, can be produced, for example, by the following route. (However, each symbol in each general formula above is
In other words, the diamine represented by the general formula [] is diazotized to form a diazonium salt represented by the general formula [], and then this diazonium salt is converted into a diazonium salt represented by the general formula [], []. The compound of the above general formula [] can be obtained by sequentially reacting with the coupling components shown. The coupling components represented by the general formulas [] and [] may be the same or different from each other, and usually each has a content of about 1
mol is reacted with 2 moles of diazonium salt. These diazotization reactions and coupling reactions are described in German Patent No. 556480 and the same.
It can be easily carried out by selecting conditions with reference to the description in the specification of No. 427032. Further, as specific examples of the compound of the general formula [] that is a raw material in the above reaction, the following compounds can be mentioned. Compounds of general formula [ ] are known or
It can be produced according to the method for producing the above-mentioned exemplified compounds described in No. 358,398. Specific examples of the coupling components represented by the general formulas [] and [] include the following compounds.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] These coupling components and other coupling components are described, for example, in Hiroshi Horiguchi's ``Sosetsu Synthetic Dyes'' (Sankyo Publishing: published in 1970). The coupling components represented by the general formulas [ ] and [ ] are known or can be easily produced by a method similar to the method for producing known coupling components having similar structures. Conventionally known methods can be used to attach a colored resin film containing a dye represented by the general formula [ ] of the present invention to an imaging device to obtain a color imaging device equipped with a micro color filter. . For example, the following method can generally be used to attach a colored resin film to a solid-state image sensor to obtain a color solid-state image sensor equipped with a micro color filter. A photocurable resin solution such as dichromate gelatin is applied to the light receiving area of the solid-state image sensor to form a photocurable resin layer, and the surface of the photocurable resin layer is irradiated with light that has passed through an exposure pattern to form a photocurable resin layer. Produces mosaic or striped hardened areas. Next, this resin layer is washed with an appropriate solvent to dissolve and remove the uncured portion to obtain a mosaic or striped cured resin layer. A color separation filter element (colored resin film) is formed by dyeing with a yellow pigment represented by . Next, a color contamination prevention layer is formed on the color separation filter element formed in this way, and a photocurable resin layer is further formed thereon in the same manner, and the light that has passed through another exposure pattern is applied to the surface of the layer. irradiation to produce another mosaic or stripe-like hardened portion in the resin layer. Then, the uncured resin portion is removed in the same manner, and the cured resin layer is coated with another dye (for example, a dye that does not contain an alkali metal in the molecule, such as a cyan dye such as an organic base salt of copper phthalocyanine sulfonic acid). (preferably used) to form a color separation filter element (colored resin film). Further, if necessary, the operation for forming color separation filter elements is repeated to form a desired color separation filter group, and finally, a surface coating layer is formed to complete the formation of the micro color filter. Note that during or before or after each of the above operations, operations such as exposing the bonding pad part necessary for circuit formation may also be included.
Since these operations are not directly related to the present invention,
The explanation will be omitted. Further, by subjecting each colored resin film to a surface modification treatment for preventing color staining, it is also possible to omit the provision of the color stain preventing layer. The novel yellow dye represented by the general formula [] has excellent dyeing properties for resin films formed from gelatin, etc., and has high fastness to heat, light, etc. The color imaging device of the present invention including the dyed colored resin film has high sensitivity, resolution, color reproducibility, durability, etc., and is a practically excellent color imaging device. In particular, regarding a color solid-state image sensor equipped with a micro color filter made of a colored resin film colored with the novel yellow dye represented by the above-mentioned general formula [], the solid-state image sensor part is different from the conventional one. Compared to the case where alkali metal-containing dyes are used, it is much more effectively protected from contamination by harmful alkali metal components, and there is a significant risk that the resulting color solid-state image sensor will no longer exhibit the desired characteristics. Because it decreases to
This results in a color solid-state image sensor that is excellent in practical use. Next, examples of the present invention will be shown. The dye-1 (yellow dye) used in the following examples was produced by the method described in "Production Example 1" below, and corresponds to the above-mentioned dye-1. Further, dyes-2 to 28 (yellow dyes) can also be produced by the same method, and similarly correspond to each of the above-mentioned dye numbers. Production Example 1 (a) Synthesis of a sodium salt corresponding to Dye-1 (X = Na ⁺ in the formula of Dye-1) (diazotization and coupling reaction) 1 mole of cyclohexanone and 2 moles of aniline were condensed. 26.6 g of the obtained 4,4'-cyclohexylidene bis(aniline) was mixed with 15 ml of water and 2.8 ml of 35% hydrochloric acid.
The mixture was added to the mixture and heated to dissolve. After cooling, add sodium nitrite aqueous solution (NaNO ₃ 0.7g/
5 ml of water was added dropwise at a temperature below 0° C., and the mixture was stirred for 20 minutes to obtain a diazonium salt solution. Separately, 1-(2-chloro-5-sulfophenyl)
-3-Methyl-5-pyrazolone sodium salt
5.77 g of sodium hydroxide, 0.9 g of sodium hydroxide, and 2.5 g of sodium acetate were added to 20 ml of water, and the above diazonium salt solution was added dropwise while stirring the mixture at a temperature of 0° C. or lower. The precipitated crystals were collected by filtration, washed with water, and then air-dried to obtain 7.2 g of a sodium salt corresponding to the target dye-1. (b) Chlorination reaction 6.0g of the sodium salt obtained in (a) above was added with N,
The mixture was dissolved in N-dimethylacetamide, and 12 ml of phosphorus oxychloride was added dropwise thereto while cooling on ice. Next, 20 ml of acetonitrile was added, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with water, and then washed with acetonitrile. The amount of sulfonyl chloride obtained was 5.0 g. (c) Synthesis of dye-1 The above sulfonyl chloride (5.0g) was mixed with N,N
-Dissolved in 25 ml of dimethylacetamide, and 5 ml of pyridine was added dropwise to this solution with stirring. Then,
1 ml of water was added to this solution, and the mixture was stirred at room temperature for 80 minutes. Add 40 ml of water and 35% hydrochloric acid (40 ml) to this reaction solution.
ml) were added dropwise. The precipitated crystals were collected by filtration, washed with dilute hydrochloric acid, and then dried in the air. In this way, 4.0 g of dye-1 (yellow dye) was obtained. According to the measurement results of atomic absorption spectroscopy, the Na content of this dye-1 was 0.07% by weight, and the K content was 0.03% by weight or less. (d) Identification of the basic skeleton of dye-1 The sulfonyl chloride obtained by the same method as in (b) above was added to 28% ammonia water to cause a reaction, and then the precipitated crystals were collected by filtration. The crude crystals were purified by silica gel column chromatography to obtain crystals with a melting point of 215-220°C. this crystal
FDMS (field desorption mass spectroscopy)
When the sample was multiplied, a parent peak was shown at m / e = 863. In normal EIMS, m / n = 549, 521, 287,
Fragment peaks were shown at 252, 206, 126, and 189, respectively. From the above mass spectrum data and the structure of the raw material compound, the above crystal was identified as having the following structure. In addition, from the above structure, the structure of the sulfonyl chloride produced in (b) can be confirmed, and
It was confirmed that the dye obtained above corresponds to the above-mentioned dye-1. In addition, the dyes-2 to 14 can be synthesized by replacing pyridine with other corresponding bases in the above production examples, and the dyes-15 to 28 can be synthesized by replacing pyridine with other corresponding bases.
It can also be synthesized by a method similar to the above production example. The cyan dye used for dyeing the microfilter colored resin film of the color solid-state image sensor of the present invention is a copper phthalocyanine dye (cyan dye-A) that does not substantially contain alkali metal and is synthesized according to the following production example. It is. Production example 2 After adding 10 g of copper phthalocyanine into 130 g of chlorosulfonic acid in portions at a temperature of 50°C or less,
The reaction mixture was stirred at 130°C for 4 hours. After stirring, the reaction mixture was cooled to 35°C and poured into 800ml of ice water. The precipitated crystals were collected by filtration, washed with water,
Dry. In this way, copper phthalocyanine tetrasulfonyl chloride (13 g) was obtained. The above copper phthalocyanine tetrasulfonyl chloride (13 g) was dissolved in 200 ml of methanol, and 34 ml of pyridine was added dropwise to this solution while stirring. The solution was then refluxed for 1 hour at room temperature. After the reflux was completed, the reaction solution was cooled, and the precipitated crystals were collected by filtration, washed with methanol, and then dried. 12 g of cyan dye-A of the formula: (CuPc)-( _SO3 -PyH ⁺ ) ₄ (where Pc represents phthalocyanine and PyH ⁺ represents a pyridinium cation) was thus obtained. According to the measurement results of atomic absorption spectroscopy, the Na content of this cyan dye-A was 0.02% by weight, and
The K content was less than 0.02% by weight. Example 1 A 0.7 micron thick layer was placed on the smoothing layer of a CCD type solid-state image sensor (the surface of which is provided with a protective layer made of phosphosilicate glass and a smoothing layer made of a transparent organic polymer compound). A chromic acid gelatin photocurable resin layer was provided, and a mask (exposure pattern) consisting of a mosaic pattern was placed thereon to perform contact exposure. Next, the exposed resin layer was washed with hot water to elute and remove the uncured portions of the resin, leaving a cured resin layer consisting of mosaic-like convex portions. This cured dye layer was dyed with dye-1 to prepare a colored (yellow) resin film. Next, 1,4-ethyl p-phenylene diacrylate was applied on the colored resin film thus formed.
A color stain prevention layer is formed using bis(β-hydroxyethoxy)cyclohexane, a photocurable resin layer is formed on top of it in the same manner, and the surface is irradiated with light that has passed through another exposure pattern. Then, another mosaic-like cured portion was generated in the resin layer. Then, in the same manner, the uncured resin portion was removed and the cured resin layer was dyed with cyan dye-A to prepare a colored (cyan) resin film. Finally, p-ethyl phenylene diacrylate-
A micro color filter portion is formed by forming a surface coating layer using 1,4-bis(β-hydroxyethoxy)cyclohexane,
A color solid-state image sensor was obtained. Examples 2 to 12 Color solid-state imaging devices were obtained in the same manner except that the colored resin film and the dye for dyeing the colored resin film were changed to the dyes listed in Table 1, respectively.
In addition, each dye used in the following examples corresponds to the above-mentioned dye number.

[Table] Table 2 shows the melting point and alkali metal content of the yellow dye used in each example.

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Claims (1)

[Claims] 1. The colored resin film of the micro color filter has the general formula []: [However, Q ¹ and Q ² may be the same or different, and each represents an alkyl group, a substituted alkyl group,
Cyano group, trifluoromethyl group, or -
Carbamoyl group represented by CONR ³ R ⁴ (where
R ³ represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and R ⁴ represents a hydrogen atom, an alkyl group,
represents a substituted alkyl group, aralkyl group, or aryl group, in which R ³ and R ⁴ may be connected directly or via an oxygen atom to form a ring; Q ³ and Q ⁴ are mutually may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group; X represents a cation consisting of a nonmetallic atom; Y ¹ and Y ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group; R ¹ and R ² may be the same or different from each other; each represents a hydrogen atom, an alkyl group, or a substituted alkyl group; however, R ¹ and R ² may be directly connected to form a ring); and q are each 1
represents an integer of ~4, provided that the sum of m and n and the sum of p and q are each 5 or less. ] A color imaging device characterized by being colored with a dye represented by: 2. The color imaging device according to claim 1, wherein the color imaging device is a color solid-state imaging device. 3. The color imaging device according to claim 1, wherein X in the general formula [] is a cation derived from an aromatic heterocyclic base. 4. The color imaging device according to claim 3, wherein X in the general formula [] is a pyridinium cation which may include a substituent. 5. The color imaging device according to claim 3, wherein X in the general formula [] is a quinolinium cation which may include a substituent. 6 X in the general formula [] is the general formula []: (R ⁵ ) (R ⁶ ) (R ⁷ ) (R ⁸ )N ⁺ [] (However, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each 3. The color imaging device according to claim 1, wherein the two groups are hydrogen atoms, aliphatic groups, or aromatic groups, which may be the same or different. 7. The color imaging device according to any one of claims 1 to 2, wherein X in the general formula [] is a hydrogen atom.