JPS59102955A - Bisazo-type yellow dye - Google Patents

Abstract

NEW MATERIAL:The compound of formula I {Q<1> and Q<2> are (substituted) alkyl, cyano, trifluoromethyl, or carbamoyl of formula -CONR<3>R<4> [R<3> is H or (substituted) alkyl; R<4> is H, (substituted) alkyl, aryl, etc.]; Q<3> and Q<4> are H, halogen, (substituted) alkyl or (substituted) alkoxy; X is cation of nonmetallic atom; Y<1> and Y<2> are H, halogen, (substituted) alkyl or (substituted) alkoxy; R<1> and R<2> are H, (substituted) alkyl, etc.; a, b, m, n, p and q are 1-4; m+n and p+q are <=5}. USE:Yellow dye for dyeing the micro-color filter of color image-pikcup device such as color camera tube, solid-state color image-pickup element, etc. It has excellent dyeing property and fastness. PROCESS:The objective dye is prepared, e.g. by reacting the dye of formula II(M is alkali metal) with a halogenation agent, and reacting the resultant compound of formula III (Hal is halogen) with an organic base composed of plural nonmetallic atoms and a proton source (preferably water or an alcohol).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel bisazo yellow dye. More specifically, the present invention relates to a novel bisazo yellow dye with excellent dyeability and fastness.

Yellow pigments are useful as ordinary pigments, but they are also used in many applications as a component of three primary colors.

One such use is as a yellow dye for staining micro color filters of color imaging devices such as color image pickup tubes and color solid-state image sensors. This micro color filter is a color separation filter (colored resin film) prepared by dyeing a mosaic or striped filter element (resin film) made of a water-soluble polymer substance such as gelatin or casein with a desired dye. It is made up of a combination of colors and separates the light that enters the imaging device to enable color imaging.

By the way, the micro color filters used in color imaging devices have a large impact on the sensitivity, resolution, color reproducibility, etc. of the color imaging device, so various studies are being conducted on improving and controlling their 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 dyes used for dyeing must be carefully checked for dyeability, fastness, color characteristics, etc. It is also known that it is necessary to take this into account.

Furthermore, since solid-state imaging devices consist of flat ICs in which photoelectric conversion elements and scanning circuits are highly integrated, they are susceptible to impurities such as dirt, dust, and alkali metals. They strongly dislike pollution. Solid-state imaging devices contaminated with such impurities often do not exhibit predetermined characteristics.1. There is a problem in that it directly leads to a decrease 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.

Based on the above-mentioned technical background, the present invention is aimed at improving the dyeability of a colored resin film for manufacturing a micro color filter attached to an imaging device such as a solid-state imaging device and imaging quality.
The present invention provides a novel bisazo-based yellow dye with excellent fastness and color properties.

That is, the present invention is based on the general formula [■]: [However, Ql and Q2 may be the same or different from each other, and each is represented by an alkyl group, a substituted alkyl group, a cyano group, a trifluoromethyl group, or -CONR3R4. carbamoyl group (here, R3 represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and R4 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, or an aryl group, provided that R3 and R4 are directly or Q3 and Q4 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 represents a substituted alkoxy group; X represents a cation consisting of a nonmetallic atom; Y1 and Y2 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 represents a substituted alkoxy group; R1 and R2 may be the same or different and each is a hydrogen atom, an alkyl group, or a substituted alkyl group (provided that R1 and R2 are not directly connected to form a ring). a, b・m・n, p, and q each represent an integer from 1 to 4, provided that m and n
and the sum of p and q are each 5 or less. ]
It consists of a bisazo-based yellow pigment.

Next, the present invention will be explained in detail.

Ql in the above general formula [I] and the alkyl group, substituted alkyl group, cyan group, trifluoromethyl group, or carbamoyl group represented by -CONR3R4 represented by Ql are listed below.

The alkyl group has 1 to 20 carbon atoms, preferably 1 to 1O1
More preferred are 1 to 6 linear, branched or cyclic alkyl groups, such as methyl, ethyl, propyl, inpropyl, butyl, isobutyl, 5ec-butyl, pentyl group, hexyl group,
and cyclohexyl group.

A substituted alkyl group has 1 carbon number in the alkyl group.
~20, preferably 1-10, more preferably 1-6
The alkyl group has a substituent attached thereto, and examples of the substituent include a cyano group, an alkoxy group, a hydroxy group, and a carboxyl group.

In the carbamoyl group represented by the formula -〇〇NR3R4, R3 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 1O1, more preferably 1 to 6 carbon atoms, and 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. ．． More preferably, 1 to 6 alkyl groups have an I value substituent group, and R4 is a hydrogen atom, a carbon number of 1 to 20,
Preferably, an alkyl group having 1 to 10, more preferably 1 to 6 carbon atoms, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 1O1, more preferably 1 to 6 carbon atoms, and a benzyl group are preferable. Note that R3 and R4 may be bonded directly or via an oxygen atom to form a 5-6 ring. Among these carbamoyl groups, those in which both R3 and R4 are hydrogen atoms, and those in which one of R3 or R4 is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms are easily available. It is preferable because of its large size and good dyeability.

In addition, one or both of Ql and Ql has a carbon number of 1
-4 alkyl groups or cyano groups are preferred from the viewpoint of fastness as a dye. - In the above general formula [I], among the hydrogen atom, halogen atom, alkyl group, substituted alkyl group, alkoxy group, or substituted alkoxy group represented by Q3 and Q4, the halogen atom is particularly preferably a chlorine atom, and the alkyl group is , linear chain having 1 to 20 carbon atoms, preferably 1 to 1O1, more preferably 1 to 6 carbon atoms,
A branched or cyclic alkyl group, examples of which include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 5ec-butyl group, pentyl group, hexyl group, and cyclohexyl group. I can do it.

A substituted alkyl group, an alkoxy group, and a substituted alkoxy group in which the alkyl moiety contained in the substituted alkoxy group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms are generally used. Note that examples of the substituent include a cyan group, an alkoxy group, a hydroxy group, and a carboxyl group.

Examples of cations consisting of nonmetallic atoms represented by X in the above general formula [I] include protons (H+),
A cation derived from an aromatic heterocyclic base such as a pyridinium cation, which may contain a substituent, and a quinolinium cation, which may contain a substituent, and the general formula [ ]: % formula % [1 ] (However, R5, R6, R7 and R8 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 R5, H6, H7 and R in the general formula [I[] is a hydrogen atom, and the others are:
Lower alkyl group having 1 to 6 carbon atoms, or phenyl group (lower alkyl group having 1 to 6 carbon atoms, or lower alkyl group having 1 to 6 carbon atoms)
6, which may be substituted with a lower alkoxyl group).

Among the hydrogen atom, halogen atom, alkyl group, substituted alkyl group, alkoxy group, or substituted alkoxy group represented by Yl and Y2, the halogen atom is particularly preferably a chlorine atom, and the alkyl group has 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6 linear, monobranched or cyclic alkyl groups, examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 5ec- Butyl group, pentyl group,
Mention may be made of hexyl and cyclohexyl groups.

A substituted alkyl group, an alkoxy group, and a substituted alkoxy group in which the alkyl moiety contained in the substituted alkoxy group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms are generally used. Note that examples of the substituent include a cyan group, an alkoxy group, a hydroxy group, and a carboxyl group.

Of the hydrogen atom, alkyl group, or substituted alkyl group represented by R1 and R2, the alkyl group has 1 to 20 carbon atoms.
, preferably 1 to io, s and preferably 1 to 6 linear, branched or cyclic alkyl groups, examples of which include methyl group, ethyl group, propyl group, inpropyl group, butyl group. , inbutyl, 5ec-butyl, pentyl, hexyl and cyclohexyl.

The number of carbon atoms in the alkyl moiety contained in the substituted alkyl group is 1 to
20, preferably 1 to 10, more preferably 1 to 6 are generally used.

In addition, examples of the substituent include a cyan group, an alkoxyl group, a hydroxyl group, and a carboxyl group. When R1 and R2 are directly connected to form a ring, the ring is a 5- to 12-membered negative ring, preferably a 5- to 6-membered ring, and more preferably a 6-membered ring.

Next, examples of yellow dyes represented by the above general formula [I] and preferred in the present invention will be listed.

Dye-11 (X = pyridinium cation) [Dye-23 In the formula of Dye-1, X = NH4+ dye [Dye-3
] In the formula of dye-1, X = CH3N H3” (7)
Dye [Dye-4] In the formula of Dye-1, X=C2H5N)13" Dye [Dye-5] In the formula of Dye-1, X= (CH3) 2 N H2+ Dye [Dye-6] Dye- In the formula 1, X= (C2H'!3) 2NH2+
Dye [Dye-7] In the formula of Dye-1, X = (C2H5) 3NH+ Dye [Dye-8] [Dye-9] Dye [Dye-10] In the formula of Dye-1, [Dye-11 ] In the formula of dye-1, [dye-12] elemental [dye-15] In the formula of dye = 1, the dye where X=H+ [dye-16] (PyH+ represents a pyridinium cation, the same applies hereinafter) [dye- 17 [Dye-18] [Dye-19] [Dye-201 [Dye-21] (Y=CH3) [Dye-22] In the formula of Dye-21, Y=CH30-Dye [Dye-23
] In the formula of Dye-21, the dye with Y=C statement [Dye-24] [Dye-25] [Dye-26] In the formula of Dye-25, the dye with Y=CH3 U Dye-271 [Dye-28] The dye of general formula II used in the present invention is, for example,
General formula [■]: (However, M is an alkali metal ion, and the other symbols have the same meanings as in the case of general formula [I]) is reacted with a halogenating agent to form a dye represented by general formula [■]. IV]: (Hal is a halogenating agent, other symbols are -・n
After obtaining a compound represented by formula q (synonymous with the case of formula [11T]), an organic base or ammonia consisting of a plurality of nonmetallic atoms, and a proton source (preferably water or alcohol) are prepared therein. It can be manufactured by

Alternatively, by reacting the compound represented by general formula [IV] with a proton source (preferably water or alcohol) to form the corresponding sulfonic acid, and then reacting with an organic base consisting of a plurality of nonmetallic atoms or ammonia. , general formula CI] can also be obtained.

In addition, in the manufacturing method described in "2", from the viewpoint of operational simplicity and cost, M is sodium ion and Hal
is preferably a chlorine atom.

Examples of the halogenating agent used in the production method of item L include phosphorus oxychloride, phosphorus pentachloride, chlorosulfonic acid, and thionyl chloride.

In addition, the alcohol used as a proton source in the production method described in L has 1 to 6 carbon atoms (preferably 1
-4) Alcohols can be mentioned, examples of which include methanol, ethanol, 2-propanol, 2-methoxyethanol, and the like.

The compound represented by the general formula [N] described above, which is a raw material for manufacturing the yellow pigment represented by the general formula [I] used in the present invention, can be manufactured, for example, by the following route.

[V] [VI] [V11]
[VIII] (However, each symbol in each general formula above has the same meaning as in the case of general formula [I] above)
That is, the diamine represented by the general formula [V] is diazotized into a dianonium salt represented by the general formula [VI], and then this dianonium salt is converted into the general formula [VII],
The coupling component represented by [VIII] and l1ll
A compound of the above general formula [111] can be obtained by a 4th reaction. In addition, general formulas [VII] and [FI
The coupling components represented by [II] may be the same or different, and usually about 1 mole each is reacted with 2 moles of the diazonium salt.

These diazotization reactions and coupling reactions are described in German Patent Nos. 556480 and 4270.
It can be easily carried out by selecting conditions with reference to the description in the specification of No. 32.

Moreover, as specific examples of the compound of general formula [V] which becomes a raw material in the reaction indicated by "-", the following compounds can be mentioned.

R9t, the compound of formula [V] is known or is disclosed in German Patent Nos. 497,628 and 399,149.
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 [VII] and [VIII] include the following compounds.

SO, VIVl - These coupling components and other coupling components are described, for example, in "Sosetsu Synthetic Dyes" by Hiroshi M11guchi (Sankyo Publishing, 1970).

The coupling components represented by the general formulas [VII] and [VIII] are known or can be easily produced by a method similar to the method for producing known coupling components having similar structures.

The novel bisuane yellow dye represented by the general formula [I] of the present invention has particularly excellent fastness to resin films formed from gelatin and the like, and also has high fastness to heat, light, etc. Furthermore, since this new bisazo dye does not contain alkali metal atoms in its molecular structure, it is particularly useful as a yellow dye for dyeing microcolor filters of color solid-state image sensors, which are extremely sensitive to alkali metal contamination. .

Next, examples of the present invention will be shown. In addition, the dye numbers shown below correspond to each of the above-mentioned dye numbers.

[Example] Synthesis of Good $-1 (a) Sodium salt corresponding to Dye-1 (said Dye-1
Synthesis (Diazotization and Coupling Reaction) of X=Na+ in the formula The mixture was added to a mixture of 8mM and 35% river acid, and dissolved by heating. After cooling, this solution was added with an aqueous solution of sodium nitrite (NaNO30.7g/water 5mM).
was added dropwise at a temperature of 0° C. or lower, and the mixture was stirred for 20 minutes to obtain a diazonium salt solution.

Separately, ■-(2-chloro-5-sulfophenyl)-3-
5.77 g of sodium salt of methyl-5-pyrazolone, 0.9 g of sodium hydroxide, and 2.5 g of sodium acetate.
was added to 20mJ1 of water, and this was added to 11it below O'C.
The above diazonium salt solution was added dropwise while stirring at 30°C. The precipitated crystals were collected by filtration, washed with water, and then air-dried to obtain 7.2 g of thorium salt corresponding to the desired dye-1.

(b) Chlorination reaction 6.0 g of the sodium salt obtained in the above (a) was mixed with N and N
- 12 mJ1 of phosphorus oxychloride was added dropwise to the solution while it was dissolved in dimethylacetamide and cooled on ice. Next, 20 mu 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 obtained sulfonyl chloride is 5.
It was 0g.

(C) Synthesis of dye-1 The above sulfonyl chloride (5.0 g) was added to N.

It was dissolved in 25mM of N-dimethylacetamide, and 5mM of pyridine was added dropwise to this solution while stirring.

Next, 1 mM of water was added to this solution, and the mixture was stirred IW at room temperature for 80 minutes. To this reaction solution, 40mM water and 35% hydrochloric acid (40m) were sequentially 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.

(d) Identification of basic skeleton of dye-1 Sulfonyl chloride obtained by the same method as in (b) above was added to 28% aqueous ammonia to carry out the reaction, and then the precipitated crystals were collected by filtration. This crude crystal was purified by silica gel column chromatography, and the melting point was 215-22.
Crystals at 0°C were obtained.

This crystal was subjected to F DMS (field desorpt).
When subjected to ion mass 5 spectroscopy, it showed a peak of m/e = 863i. In normal EIMS, m/e = 549.521,28
Fragment peaks were shown at 7.252.206.126.189, respectively.

Based on the mass spectral data and the structure of the starting compound, the above crystal was identified as having the following structure.

Furthermore, from the above structure, the structure of the sulfonyl chloride produced in (b) could be confirmed, and it was also confirmed that the dye obtained above corresponded to the above-mentioned dye-1.

In addition, the above dyes 2 to 14 can be synthesized by replacing pyridine with another corresponding base in the production procedure described in ``2'', and dyes 15 to 28 can also be synthesized by following the above production example. It could be synthesized using a similar method.

Patent applicant Fuji Photo Film Co., Ltd. Agent Patent attorney Yasuo Yanagawa

Claims (1)

[Claims] ■. General formula [English]: [However, Ql and Q2 may be the same or different from each other and may be 1. ), an alkyl group, a substituted alkylcyano group, a trifluoromethyl group, or a car/<moyl group represented by LyoCONR3R4 (where R3 is a hydrogen atom, an alkyl group, or a substituted alkyl group R4 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, or a 4-yl group, provided that R3 and R4
may be connected directly or via an oxygen atom to form a ring): Q3 and Q4 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 , represents an alkoxy group, or a substituted alkoxy group; X represents a cation consisting of a nonmetallic atom; yl and Y2 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group; , represents an alkoxy group, or a substituted alkoxy group; R1 and R2 may be the same or different, and each is a hydrogen atom, an alkyl group, or a substituted alkyl group (provided that R1 and R2 are directly connected to form a ring) a. b, m. n. p, and q
each represents an integer from 1 to 4, provided that the sum of m and n and the sum of P and q are each 5 or less. ] A bisazo dye represented by. 2. The bisazo yellow dye according to claim 1, wherein X in the general formula [I] is a cation derived from an aromatic heterocyclic base. 3. The bisazo yellow dye according to claim 2, wherein X in the 3°-.119 formula [E] is a pyridinium cation which may contain a substituent. 4. The bisazo yellow dye according to claim 2, wherein X in the general formula [I] is a quinolinium cation which may contain a substituent. 5゜X in general formula [I] is general formula [■] : (R5) (
R6)(R7)(R8)N+ [II] (However, R, R, R7 and R8 may be the same or different and represent a hydrogen atom, an aliphatic group or an aromatic group) The bisazo yellow pigment according to claim 1, which is characterized by: 6. The Bisara-based violet dye according to claim 1, wherein X in the general formula [I] is a hydrogen atom.