JPH10237334A - Methine dye - Google Patents

Abstract

(57) [Problem] To provide a methine dye excellent in dyeing property and decolorization property. A methine dye having at least one substituent represented by the following general formula 1 in the molecule. Embedded image [In the formula, R ₁ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and n represents 1 to 4. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel methine dye effective for dyes, pharmaceuticals, spectral sensitizing dyes, etc., and more particularly, useful as a spectral sensitizing dye for use in silver halide photographic materials. It relates to pigments.

[0002]

2. Description of the Related Art Methine dyes have been applied and studied in various fields because of their advantages such as ease of synthesis, abundant variations, and high absorbance. Particularly in the field of silver halide photographic materials, many methine dyes have been known as spectral sensitizing dyes and desensitizing dyes, or filter dyes that absorb light of unnecessary wavelengths to prevent halation and irradiation. I have been.

[0003] Silver halide photographic light-sensitive materials are required to have high sensitivity in different specific wavelength ranges depending on the purpose of use. One of the techniques for producing such silver halide photographic light-sensitive materials is that various types of methine dyes are added to silver halide photographic emulsions as sensitizing dyes, and the wavelength is longer than the inherent photosensitive wavelength range of the silver halide. It is generally well known that the sensitivity in a particular wavelength range can be very effectively increased in a particular wavelength range.

When spectral sensitization is applied to a silver halide photographic emulsion by a dye, it must satisfy not only the spectral sensitizing effect and the increase in sensitivity but also the following requirements. . (1) The spectral sensitization range is appropriate. (2) Stable photographic characteristics are maintained during storage of the photosensitive material. (3) No contamination or fog due to the residual dye applied for spectral sensitization after development processing. (4) No bad interaction with other photographic additives.

In order to satisfy the above requirements, various types of methine dyes such as cyanine dyes and merocyanine dyes have been proposed. For example, He-
Sensitizing dyes corresponding to a red light source such as a Ne laser, a red LD, and a red LED are disclosed in US Pat. No. 4,965,183.
Nos. 5,116,722 and the like are proposed, and one of the features is that they have little residual color contamination after development processing.

However, even these sensitizing dyes do not completely satisfy the above requirements, and further improvement is required.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel methine dye having excellent dyeing properties and decolorization properties, and particularly to a photographic spectral sensitizing dye having a high sensitivity which satisfies the above requirements. Another object of the present invention is to provide an excellent dye which has little residual color contamination after development.

[0008]

As a result of various studies, the present inventors have found excellent dyes satisfying the above object by the following means.

(1) A methine dye having at least one substituent represented by the following general formula 5 in the molecule.

Embedded image [In the formula, R ₁ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and n represents 1 to 4. ]

(2) The methine dye according to (1), wherein the methine dye is represented by the following general formula 6, 7, or 8:

Embedded image [Wherein Z ₁ and Z ₂ each represent an atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ represents a trivalent group formed by connecting a substituted or unsubstituted methine group by an odd number of 7 or less conjugated double bonds. R ₂ and R ₃ represent a substituted or unsubstituted alkyl group or an aryl group, and at least one of them represents the above-mentioned general formula 5
Having a substituent represented by p and q each represent 0 or 1, and X ⁻ represents an anion for neutralizing the charge of the molecule. ]

Embedded image [Wherein Z ₁ , Z ₂ , R ₂ , R ₃ , and p have the same meanings as in the general formula 6. L ₂ represents a tetravalent group in which 6 or less substituted or unsubstituted methine groups are linked to form a conjugated double bond, and L ₃ represents 7 or less substituted or unsubstituted methine groups. It represents a trivalent group formed by connecting an odd number of conjugated double bonds. Y ₁ and Y ₂ are 5 or 6
A group of atoms necessary to form a membered nitrogen-containing heterocyclic ring;
_At least one of ₂ , R ₃ , Y ₁ and Y ₂ has a substituent represented by the above general formula (5). r represents 0 or 1,
X ^- represents an anion for neutralizing a molecule of the charge. ]

Embedded image [Wherein Z ₁ , R ₂ , and p have the same meanings as in General Formula 6, and L ₂ , Y ₁ , Y ₂ , and r have the same meanings as with General Formula 7, respectively. Y ₃ and Y ₄ represents an atomic group necessary for forming a 5 or 6-membered nitrogen-containing heterocyclic ring, R _2,
At least one of Y ₁ , Y ₂ , Y ₃ and Y ₄ has a substituent represented by the above general formula 1. m represents 0 or 1. ]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The methine dye of the present invention has a substituent represented by the general formula 5 in the dye molecule. Examples of such methine dyes include polynuclear methine dyes represented by cyanine, merocyanine, and rhodocyanine, oxonols, styryls, benzylidenes, and arylidenes. These methine dyes may have a cation for neutralizing the intramolecular charge, and may be an alkali metal ion (for example, sodium ion or potassium ion) or an optionally substituted ammonium ion (for example, ammonium ion). Ion, triethylammonium ion, pyridium ion, and morpholinium ion), and a heterocyclic onium ion that forms a cyanine dye. As the present invention, polynuclear methine dyes represented by cyanine, merocyanine and rhodocyanine are more preferable.

The substituent represented by the general formula 5 which is a feature of the present invention will be specifically described. In the formula, R ₁ is an optionally substituted alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
n-amyl group, β-hydroxyethyl group, γ-hydroxypropyl group, β-acetoxyethyl group, γ-acetoxypropyl group, β-methoxyethyl group, γ-methoxypropyl group, carboxymethyl group, β-carboxyethyl group Γ-carboxypropyl group, δ-carboxybutyl group, ω-carboxypentyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, β-methoxycarbonylethyl group, γ-methoxycarbonylpropyl group, δ-methoxycarbonylbutyl group, β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ
-A sulfobutyl group, a benzyl group, a phenethyl group, a p-carboxybenzyl group, a p-sulfophenethyl group, an allyl group, a propargyl group, a trifluoroethyl group and the like, an aryl group (for example, a phenyl group, a methoxyphenyl group,
Chlorophenyl group, nitrophenyl group, etc.) and heterocyclic group (for example, pyridyl group). Among these, a substituted or unsubstituted alkyl group or aryl group having 8 or less carbon atoms is preferable. n represents 1 to 4, and is preferably 1 or 2.

Next, the general formulas (6), (7) and (8) will be specifically described. In the formula, Z ₁ and Z ₂ each represent an atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring.
Specific examples of these nitrogen-containing heterocycles include, for example, an oxazoline ring, an oxazole ring, a benzoxazole ring,
Naphthoxazole ring, thiazoline ring, thiazole ring,
There are a thiazine ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a quinoline ring, a benzoquinoline ring, an indolenine ring, a benzoindolenine ring, a benzimidazole ring, a naphthymidazole ring, and the like. Furthermore, the carbon atoms of these heterocycles are halogen atoms (for example, chlorine atom, bromine atom, etc.),
Alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, n-amyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, n-propoxy group, etc.) , A hydroxy group, a trifluoromethyl group, a cyano group, an alkanesulfonyl group (for example, a methanesulfonyl group, an ethanesulfonyl group, etc.),
Sulfamoyl group (for example, sulfamoyl group, N, N
-A substituent such as a dimethylsulfamoyl group, a piperidinosulfonyl group, a morpholinosulfonyl group or the like, or an aryl group (eg, a phenyl group or a methoxyphenyl group) may be attached. Preferred of these are:
It has 12 or less carbon atoms including a substituent.

Specific examples of the nitrogen-containing heterocyclic ring formed by Y ₁ , Y ₂ and Y ₃ , Y ₄ include, for example, an oxazolidine ring, a thiazolidine ring, an imidazolidine ring and a thiobarbituric acid ring. Examples of the nitrogen substituent of the heterocyclic ring include an alkyl group (for example, a methyl group, an ethyl group,
-Propyl group, i-propyl group, n-butyl group, n-amyl group, β-hydroxyethyl group, γ-hydroxypropyl group, β-acetoxyethyl group, γ-acetoxypropyl group, β-methoxyethyl group, γ -Methoxypropyl group, carboxymethyl group, β-carboxyethyl group, γ
-Carboxypropyl group, δ-carboxybutyl group, ω
-Carboxypentyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, β-methoxycarbonylethyl group, γ-methoxycarbonylpropyl group, δ
-Methoxycarbonylbutyl group, β-sulfoethyl group,
γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, benzyl group, phenethyl group, p-carboxybenzyl group, p-sulfophenethyl group, allyl group, propargyl group, etc.), aryl group (for example, phenyl group, A methoxyphenyl group), a heterocyclic group (for example, 2
-Pyridyl group, 2-thiazolyl group, 4-tetrahydropyranyl group, etc.). Among these, those having 12 or less carbon atoms including a substituent are preferred.

R ₂ or R ₃ is a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-amyl group, β
-Hydroxyethyl group, γ-hydroxypropyl group, β
-Acetoxyethyl group, γ-acetoxypropyl group, β
-Methoxyethyl group, γ-methoxypropyl group, carboxymethyl group, β-carboxyethyl group, γ-carboxypropyl group, δ-carboxybutyl group, ω-carboxypentyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, β -Methoxycarbonylethyl group, γ-methoxycarbonylpropyl group, δ-methoxycarbonylbutyl group, β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, benzyl group, phenethyl group, p-carboxy A benzyl group, a p-sulfophenethyl group, an allyl group, a propargyl group and the like; and an aryl group (eg, a phenyl group and a methoxyphenyl group). Among these, a substituted or unsubstituted alkyl group having 6 or less carbon atoms is preferable.

L ₁ or L ₃ is a trivalent group formed by connecting an optionally substituted methine group by an odd number of 7 or less conjugated double bonds (for example, = CH-, = CH-CH =
CH-, = CH-CH = CH-CH = CH-, = CH-
CH = CH-CH = CH-CH = CH-).
L ₂ is a tetravalent group in which an optionally substituted methine group is connected to form an even number of 6 or less conjugated double bonds (for example, = CH-CH =, = CH-CH = CH- CH
=, = CH-CH = CH-CH = CH-CH =, etc.). As a substituent of these methine groups, an alkyl group which may be substituted (for example, a methyl group, an ethyl group,
Benzyl group), aryl group (eg, phenyl group), alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.) ), An arylthio group (eg, a phenylthio group), a substituted amino group (eg, a piperidino group), or a halogen atom (eg, a chlorine atom, a bromine atom). Further, the substituents of the methine chain may form a ring as a 5- or 6-membered ring, and examples of such a ring include the following chemical formula 9.

Embedded image

P, q, and m represent 0 or 1, respectively.
p and q are preferably 0. r represents 0 or 1.

[0018] X ^- represents an anion for neutralizing a molecule of the charge. This supplies the number of negative charges necessary to neutralize the charge of the cation in the molecule, and may not be monovalent, but may be divalent or trivalent. Specific examples of such anions include halogen ions (for example,
F ⁻ , Cl ⁻ , Br ⁻ , I ^−, etc.), alkyl sulfate ions (eg, SO ₄ ²⁻ , HSO ₄ ⁻ , CH ₃ OSO ₃ ⁻ ),
Sulfonic acid ions (e.g., p-toluenesulfonic acid ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion, etc.), carboxylate ions (acetate ion, trifluoroacetate ion, oxalate ion, etc.),
Alternatively, PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , IO ₄ ⁻ , PO ₄
^3- , NO ₃ ^- and picrate ions.

Next, specific examples of the methine dye used in the present invention will be shown. However, the methine dye used in the present invention is not limited to these.

[0020]

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[0021]

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[0038]

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[0041]

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[0042]

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[0043]

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[0046]

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[0047]

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[0048]

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[0049]

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The following are typical synthesis examples. Other exemplified compounds can be prepared in the same manner, or for example, in Frances M. H.
amer “Cyanine Dyes and Related Compounds” (196
4, published by Interscience Publishers), etc., and can be easily synthesized with reference to a conventionally known method.

Synthesis of ## STR32 ## Anhydro-2- (4-ethoxy-3-methyl-1,3-butadienyl) -3- (2-sulfoethyl) benzoxazolium hydroxide 1.69 g in 2- (phenylsulfonyl) 2.02 g of ethoxycarbonylmethyl rhodanine
And methanol (60 ml) were added, and while stirring at room temperature, 0.5 g of triethylamine was added and reacted for 30 minutes. After the completion of the reaction, the precipitated crystals were collected by filtration. The obtained crystals are washed with methanol and then with acetone, and then dried to a melting point of 254 ° C.
2.16 g of (decomposed) deep blue-violet crystals were obtained. The maximum absorption value of the methanol solution was 569 nm.

The silver halide photographic emulsion in which the methine dye of the present invention is used as a spectral sensitizing dye can be prepared by a conventional method such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide or chloroiodobromide. Any of silver halide and the like may be used.

In order to add the methine dye of the present invention as a sensitizing dye to these silver halide photographic emulsions, an organic solvent such as methanol, ethanol, acetone, cellosolve, pyridine, dimethylformamide or the like which is arbitrarily miscible with an aqueous solution or water can be used. The solvent can be added alone or as a solution of a mixed solvent. It is generally preferred that these sensitizing dyes be added to the silver halide photographic emulsion immediately after the completion of the second ripening. The amount of addition varies depending on the type of sensitizing dye or the type of silver halide photographic emulsion, but it can be used in a wide range of about 4 to 1,200 mg per 100 g in terms of silver nitrate.

The silver halide photographic emulsion in which the methine dye of the present invention is used as a sensitizing dye can be prepared by noble metal sensitization, sulfur sensitization,
Reduction sensitization and sensitization combined with them or addition of a polyalkylene oxide-based compound or the like may be performed.

The silver halide photographic emulsion in which the methine dye of the present invention is used as a sensitizing dye may be spectrally sensitized by using another sensitizing dye, for example, a known cyanine or merocyanine dye, if necessary. , Further stabilizers, surfactants, hardeners, optical brighteners, ultraviolet absorbers by known methods,
Additives such as filter dyes, antiirradiation dyes, antihalation dyes, preservatives, plasticizers, matting agents, color couplers and the like can be included. Further, when used for a photosensitive material for stabilization processing, it may contain a developing agent or a precursor thereof.

The protective colloid of a silver halide photographic emulsion in which the methine dye of the present invention is used as a sensitizing dye includes:
In addition to gelatin, there may be mentioned gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, soluble starch, and water-soluble polymers.

As a support to which a silver halide photographic emulsion in which the methine dye of the present invention is used as a sensitizing dye is coated, for example, baryta paper, paper laminated with plastic, synthetic paper, cellulose triacetate, polyethylene terephthalate, etc. A resin film or the like can be used. These supports may be provided with an undercoat layer and an antihalation layer, if necessary, by a known method.

[0058]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 A 0.05% DMF solution of sensitizing dye 13 and sensitizing dye 40 in comparison with sensitizing dye 13 according to the present invention was added to a silver chloride emulsion prepared by a conventional method for producing a silver halide photographic emulsion. 2ml / gAg
Was added. These emulsions were aged in a bath at 40 ° C. for 45 minutes to stabilize the spectral sensitizing effect. Thereafter, predetermined amounts of a stabilizer, a surfactant, and a hardener were added, and then the mixture was applied to a polyethylene-laminated paper support, dried, and aged at 35 ° C. overnight. Then, it was cut into an appropriate size to obtain a test sample. Each of the samples thus obtained was wedge-exposed based on the ISO method, developed with a D-72 developer (US Eastman Kodak Co., Ltd., developer formulation) at 20 ° C. for 90 seconds, stopped, fixed, and After washing with water and drying, strips having a predetermined black-and-white image were obtained. MACHBETH-T manufactured by Macbeth Corporation
Density was measured using a D504 densitometer to evaluate sensitivity, fog and residual color. The reference point of the optical density at which the sensitivity was determined was [fog + 0.70]. The white light sensitivity is a relative value when the sensitivity of a sample to which no sensitizing dye was added was defined as 100, and the red sensitivity was a ratten gelatin filter No. manufactured by Eastman Kodak Company. Using 29,
The values are shown as relative values when the sensitivity value of Comparative Sensitizing Dyeing 40 is 100. For the residual color, the hue of the unexposed portion was visually evaluated. "5" represents the best quality and "1" represents the worst quality. The results are shown in Table 1.

[0060]

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[0061]

[Table 1]

Example 2 Sensitivity, fog and residual color were evaluated in the same manner as in Example 1 except that sensitizing dyeing 30 of the present invention and sensitizing dyeing 41 in comparison were used. The results are shown in Table 2.

[0063]

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[0064]

[Table 2]

Example 3 1.2 ml / g of a 0.025% DMF solution of the sensitizing dye of the present invention was compared with the sensitizing dyes 32, 33, and 34 of the present invention.
The sensitivity, fog and residual color were evaluated in the same manner as in Example 1 except that Ag was added. The results are shown in Table 3.

[0066]

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[0067]

[Table 3]

As is evident from Tables 1, 2 and 3, the methine dye of the present invention has higher sensitivity as a sensitizing dye than the comparative sensitizing dye, and has less fog and less residual color contamination after processing. It can be seen that it has good photographic characteristics.

[0069]

The methine dye of the present invention has excellent dyeing properties and decolorization properties, and particularly when used as a spectral sensitizing dye for a silver halide photographic light-sensitive material, there is little residual color due to dye contamination, and A silver halide photographic light-sensitive material having high sensitivity can be obtained.

Claims (2)

[Claims] 1. A methine dye having at least one substituent represented by the following general formula 1 in the molecule. Embedded image [In the formula, R ₁ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and n represents 1 to 4. ] 2. The methine dye according to claim 1, wherein the methine dye is represented by the following general formula 2, 3, or 4. Embedded image [Wherein Z ₁ and Z ₂ each represent an atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ represents a trivalent group formed by connecting a substituted or unsubstituted methine group by an odd number of 7 or less conjugated double bonds. R ₂ and R ₃ represent a substituted or unsubstituted alkyl group or aryl group, and at least one of them represents the above-mentioned general formula 1
Having a substituent represented by p and q each represent 0 or 1, and X ⁻ represents an anion for neutralizing the charge of the molecule. ] [Wherein Z ₁ , Z ₂ , R ₂ , R ₃ , and p have the same meanings as in the general formula ₂ . L ₂ represents a tetravalent group in which 6 or less substituted or unsubstituted methine groups are linked to form a conjugated double bond, and L ₃ represents 7 or less substituted or unsubstituted methine groups. It represents a trivalent group formed by connecting an odd number of conjugated double bonds. Y ₁ and Y ₂ are 5 or 6
A group of atoms necessary to form a membered nitrogen-containing heterocyclic ring;
_At least one of ₂ , R ₃ , Y ₁ and Y ₂ has a substituent represented by the above general formula 1. r represents 0 or 1,
X ^- represents an anion for neutralizing a molecule of the charge. ] [Wherein Z ₁ , R ₂ , and p have the same meanings as in the general formula ₂ , and L ₂ , Y ₁ , Y ₂ , and r have the same meanings as in the general formula 3. Y ₃ and Y ₄ represents an atomic group necessary for forming a 5 or 6-membered nitrogen-containing heterocyclic ring, R _2,
At least one of Y ₁ , Y ₂ , Y ₃ and Y ₄ has a substituent represented by the above general formula 1. m represents 0 or 1. ]