KR790000865B1 - Silver Halide Photo Emulsion - Google Patents

Abstract

Ag halide-type photo. emulsions contg. >=1 merocyanine sensitizing dye(I; Z = atoms require to complete a benzoxazole or naphthoxazole ring, R1 = alkyl, aryl, R2 = alkyl, allyl, aryl, R3 = alkoxycarbonylalkyl, N-(N, N, N-trialkylammoniumalkyl)carbamoylalkyl, R2 = Ph when R3 = alkoxycarbonylalkyl, X = anion, and n = 0,1), are esp. sensitive in the green spectral region.

Description

Silver Halide Photo Emulsion

FIG. 1 shows the sensitizing dye (6) of the present invention in the silver salt iodide bromide used in Examples.

2 shows the sensitizing dye (2),

3 shows the sensitizing dye (5),

4 shows the sensitizing dye 16,

5 shows a photographic emulsion spectral sensitivity curve (where the vertical axis represents sensitivity and the horizontal axis represents wavelength) when the comparative dyes are added,

6 shows the spectral transmittance curve of Pitta (Ladden 58).

The present invention relates to a silver halide emulsion spectroscopically sensitized by a novel merocyanine pigment, and more particularly to a silver halide photographic emulsion having high green sensitivity. It is known to use a dimethine merocyanine pigment | dye as a spectroscopic sensitizer of a photo emulsion conventionally, but the sensitization capability is not enough. Accordingly, a first object of the present invention is to provide a silver halide photographic emulsion having a strong spectroscopic effect. A second object is to provide a silver halide photographic emulsion in which the manufactured photosensitive material is spectrally sensitized with little decrease in sensitivity even with time. In addition, the present invention provides a silver halide photographic emulsion in which a sensitizing dye having excellent solubility is increased without developing afterglow.

The present inventors have found that the above various objects can be achieved by incorporating a merocyanine pigment of the following structural formula into a silver halide photographic agent.

In the above structural formula, Z represents the atomic group necessary to form benzoxazole nucleus, naphthooxazole nucleus, naphthooxazole nucleus. Specific examples of these nuclei include benzoxazoles substituted with benzoxazole, halogen, alkyl, alkoxy, hydroxy, trichloromethyl, alkoxycarbonyl, acetyl or phenyl, 5-fluorobenzoxazole and 5-chlorobenzoxazole. Sol, 5-bromobenzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-trichloromethylbenzoxazole, 5-methoxycarbonylbenzoxox Sol, 5-acetylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 5- (Alpha)-naphthooxazole, (beta), (beta)-naphthooxazole, (beta)-naphthooxazole nucleus etc. are mentioned, such as chloro-6-methyl benzoxazole.

R ₁ is an alkyl group (unsubstituted or substituted alkyl group), for example methyl group, ethyl group, propyl group, butyl group, hydroxyalkyl group (e.g. β-hydroxyethyl group, γ-hydroxypropyl group), alkoxyalkyl group (e.g. β-methoxyethyl group, γ-methoxypropyl group, etc., acyloxyalkyl group (e.g., β-acetoxyethyl group, ω-propionyloxybutyl group, etc.), carboxyalkyl group (e.g., β-carboxyethyl group, ω-carboxy Butyl group, etc.), alkoxycarbonylalkyl group (e.g., methoxycarbonylmethyl group, β-methoxycarbonylethyl group, ω-ethoxycarbonylbutyl group, etc.), sulfoalkyl group (e.g., β-sulfoethyl group, γ-sulfo Propyl group, γ-sulfobutyl group, δ-sulfobutyl group, etc.), sulfate alkyl group (e.g. β-sulfate ethyl group, ω-sulfate butyl group, etc.), aralkyl group (e.g. benzyl group, phenethyl group, P-carboxybenzyl Group, P-carboxyphenethyl group, P-sulfobenzyl group, P-sulphophenethyl group, etc.), allyl group (for example, vinyl methyl group etc.), etc.,

R ₂ represents an alkyl group (eg methyl group, ethyl group, propyl group, butyl group, etc.), an allyl group (eg vinyl methyl group, etc.), an aryl group (eg phenyl group, P-sulfophenyl group, etc.),

R ₃ is an alkoxy carbonylalkyl group (e.g., methoxycarbonylmethyl group, ethoxycarbonylmethyl group, etc.), an alkoxyalkyl group (e.g., hydroxymethoxymethyl group, 2-hydroxyethoxymethyl group, 2- (2-hydroxy) Ethoxy) ethyl group, 2- (2-acetoxyethoxy) ethyl group, acetoxymethoxymethyl group, etc.), N- (N, N-dialkylaminoalkyl) carbamoylalkyl group (e.g., N- [3- (N , N-dimethylamino) propyl] carbamoylmethyl group, N- [2- (N, N-diethylamino) ethyl] carbamoylmethyl group, N-[(3-morpholino) propyl] carbamoylmethyl group, N- [3- (piperidino) -propyl] carbamoylmethyl group, etc.), N- (N, N, N-trialkylammoniumalkyl) carbamoylalkyl group, such as N- [3- (N, N, N-trimethyl Ammonium) propyl] carbamoylmethyl group, N- [3- (N, N, N-triethylammonium) propyl] carbamoylmethyl group, N- [3- (N-methylmorpholinopropyl] carbamoylmethyl group, N- [3- (N-methylpiperidino) propyl] carbamoylmethyl group, such as N, N, N-trialkylammoniumalkyl group (e.g., N, N- Ethyl -N- methyl ammonium group, N, N, N- trimethyl-ammonium group and the like) to indicate. However, R ₃ is alkoxycarbonyl group when R ₂ is a phenyl group, X is, for example, acid anions chloride, bromide, Iodide, P-toluenesulfonate, methyl sulfate, ethyl sulfate and the like,

n represents 0 or 1.

Next, although the specific example of the novel merocyanine pigment | dye used for this invention was given, it is not limited only to this.

The new merocyanine sensitizing dyes of the present description can be used in combination with the pigments indicated in the patent specification below, and the oil agent can also be darkened (sensitivity is significantly increased). For example, French Patent No. 2,017,640, Patent No. 2,037,271, Patent No. 2,046,893, Belgian Patent No.765,244, Japanese Patent Application No. 43-4936, Japanese Patent Publication No. 45-25831, Japanese Patent Publication No. 46-1999, Patent Publication No. 43-4932, Patent Publication No. 43-4933, Patent Publication No. 46-18107, and the like.

A synthesis example of the compound used in the present invention is as follows.

Synthesis Example 1

1. Synthesis of Compound [4]

100 g of 2- (2-aminoethoxy) ethanol was added to 200 ml of ethyl acetate, and a solution obtained by dissolving 160 g of bromine acetate ethyl ester in 100 ml of ethyl acetate was added dropwise while stirring with water.

After an hour, the product was washed with ether, dissolved in 100 ml of water, and then reacted with reflux for 3 hours by adding a 300 ml solution of ethanol 80 g of phenylisocyanate.

Thereafter, ethanol was removed by distillation under reduced pressure, water was added, the precipitated oily substance was extracted with chloroform, dried, and chloroform was removed by distillation, and the crystals were filtered.

Recrystallization with ethanol gave 35 g of 1- (2-hydroxyethoxy) ethyl-3-phenyl-2-thiohydantoin having a melting point of 85 ° to 87 ° C.

To 4.0 g of 1- (2-hydroxyethoxy) ethyl-3-phenyl-2-thiohydantoin and 6.2 g of 2-acetanilide vinyl-3-ethylbenzoxazolidium iodide, 50 ml of ethyl alcohol and 4 ml of triethylamine were added. After addition, the mixture was allowed to react under reflux for 30 minutes, and the precipitated crystals were filtered out.

It was crystallized with methyl alcohol chloroform mixture to obtain 3.2 g of the red compound [4].

Synthesis Example 2

Synthesis of Compound [5]

To 4.0 g of 1- (2-hydroxyethoxy) ethyl-3-phenyl-2-thiohydantoin and 5.1 g of anhydro-2-anilidevinyl-3- (3-sulfo) propyl benzthioxazolilium hydroxide 100 ml of pyridine and 8 ml of piperidine were added and reacted by refluxing in an oil bath for one hour.

After cooling, ether was added to precipitate the pigment and washed several times with ether.

This was dissolved in ethanol, a methyl alcohol solution of sodium iodide was added to crystallize the pigment, and then filtered to obtain 4.5 g of an impure pigment. Recrystallization was performed twice with methyl alcohol chloroform mixture to give 2.5 g of the red compound [5].

Synthesis Example 3

Synthesis of Compound [18]

2.9 g of 2-methoxycarbonylmethyl-3-phenylthiohydantoin and 1.5 g of N, N-dimethyl aminopropylamine were reacted under heating for 3 hours at 130 ° C. in an oil bath, and the product was washed with ether after cooling. Then, 4 g of 2-acetanilide vinyl-3-ethylbenzoxazolium iodide, 50 ml of ethyl alcohol, and 2 ml of triethylamine were added thereto and reacted under reflux for 30 minutes. Precipitated crystals were filtered and recrystallized with ethyl alcohol chloroform solution to obtain 2.1 g of the compound [18].

Synthesis Example 4

Synthesis of Compound [23]

0.2 g of the compound [18] was dissolved in 30 ml of benzene, 0.8 ml of methyl iodide was added thereto, and the mixture was warmed and reacted for 10 minutes in a water bath. The precipitated crystals were filtered and washed with benzene to obtain 0.1 g of the compound [23].

The novel merocyanine dye of the present invention can be used not only for photosensitive materials for black and white photography, but also for color photosensitive materials composed of several layers, and is also resistant to the spectral sensitization effect caused by color dysfunction. It also diffuses into adjacent emulsion layers and does not act to increase or decrease the layers.

In particular, the merocyanine dye of the present invention is excellent in increasing the green sensitivity and the leaching phenomenon of the lithographic emulsion.

The spectroscopic sensitizing method according to the present invention is also useful for olso-type photo emulsions and photo-colored emulsions for internal color composed of several layers.

The silver halide photographic emulsion used in the present invention is precipitated by a conventional method, i.e., a single jet method, a double jet method, or a mixing method thereof, and may contain aged silver chloride, silver bromide, silver iodide, or mixed silver halide particles thereof. Preferred silver halide salts are silver bromide or silver iodide. The average diameter of the particles (eg measured by the projected area method numerical average) is preferably about 0.04 μ to about 2 μ.

The silver halide photographic emulsion used in the present invention is commonly used in chemical sensitization methods such as gold sensitization (eg, US Pat. Nos. 2,540,085, 2,597,856, 2,597,915, 2,399,083, etc.), and Group VIII metal ions. Increase / decrease (e.g., U.S. Pat.Nos. 1,574,944, 2,278,947, 2,440,206, 2,410,689, 3,189,458, 3,415,649, etc.), reduction or reduction (e.g., U.S. Patents 2,518,698, 2,419,974) , 2,983,610, etc.) or combinations thereof.

Specific chemical sensitizers include sulfur sensitizers such as arylthiocarbamide thiourea, sodium-thiosulfate or cystine, precious metal sensitizers such as potassium chloro oleate, oraz-thiosulfate and calcium chloroparadate, tin chloride and phenyl. Reducing sensitizers such as hydrazine and redductone; Moreover, you may apply sensitizers, such as a polyoxyethylene derivative, a polyoxypropylene derivative, and a derivative which has a quaternary-ammonium group. The oil agent of the present invention may contain a developing disorder preventive agent such as nitrobenzimidazole and ammonium chloroplatinate and a stabilizer such as 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. Moreover, you may contain coating agents, such as formaldehyde, chloram, 1-hydroxy-3, 5- dichloro triazine sodium, glyoxal, and dichloro acrolein, film-forming agents, saponins, and sodium alkylbenzenesulfonate.

When the silver halide emulsion used in the present invention is used in color photosensitive materials, color caplar and its dispersant are contained.

The silver halide photoemulsion used in the present invention is a protective colloid, in addition to gelatin, gelatin derivatives such as phthalated gelatin and gelatin halide, cellulose derivatives such as hydroxy-ethylcellulose and carboxymethylcellulose, soluble starch such as dextrin, polyvinyl alcohol , Hydrophilic polymers such as polyvinylpyrrolidone, polyacrylamide and polystyrenesulfonic acid, plasticizers for stabilization, latex polymers and matting agents. Finished emulsions are applied on a suitable support such as Baryta®, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, glass plate, and other plastic bases.

The sensitizing dye used for this invention is added as an organic solvent which can be melt | dissolved in aqueous solution or water, for example, methanol, ethanol, methyl cellosolve, pyridine, etc.

The amount of addition is usually used in the amount of spectroscopically decreasing, for example, 5 × 10 ^-3 mol to 1 × 10 ^-6 mol of the sensitizing dye per mol.

Next, examples of the present invention will be described. However, this embodiment is not limited only.

EXAMPLE

By the double jet method, the silver halide bromide (0.25 mol% iodine content, 16.5 mol% bromine content) is obtained by desalting and physically aging as physical aging according to a conventional method in which silver halide particles are precipitated. The average diameter of the silver halide particles contained in this emulsion is 0.4 µm, and 1.18 mol of silver halide is contained in 1 kg of this emulsion. 1 kg of this emulsion is weighed into a bottle, put into a 50 ° C. temperature bath and dissolved. In order to compare with the sensitizing dye according to the present invention, methanol solutions of sensitizing dyes (see above) were respectively added in a predetermined amount (see Table 1), followed by mixing and stirring at 40 ° C. 10 ml of 0.1% by weight aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, 10 ml of 1% by weight aqueous solution of 1-hydroxy-3,5-dichlorotriazine was added, and then again. 10 ml of an aqueous 1% by weight sodium dodecylbenzenesulfonate solution was added and stirred.

露光)한다. 한편 2,666°K의 텅그스텐광원을 갖는 회절격자형 분광사진기를 사용하여 스펙트로 그람을 얻기 위한 노광을 하였다. 다음 조성의 현상액(FD-3)을 사용하여, 20℃로 2분간 현상하고, 정지(停止), 정착, 수세하여 일정한 흑백상을 갖는 스트립스를 얻었다. 이것을 후지샤싱 후이루무사제의 S형 농도계를 사용하여 농도측정하여 녹색필타 감도(SG) 및 현상장애를 얻었다. 감도를 결정한 광학농도의 기준점은 [현상장애 + 0.20]이었다.This oil agent was apply | coated and dried to the cellulose triacetate film base so that the thickness of a dry film might be set to 5 micrometers, and the sample of the photosensitive material was obtained. This film sample was cut into strips, one of which was attached to a green filter (laten-58) as a light source, using a photometer with a light source with a color temperature of 5,400 ° K.

光. On the other hand, using a diffraction grating spectrophotometer having a tungsten light source of 2,666 ° K was exposed to obtain a spectrogram. It developed at 20 degreeC for 2 minutes using the developing solution (FD-3) of the following composition, and stopped, fixed and washed with water, and obtained the strips which have a constant black-and-white image. The concentration was measured using an S-type densitometer manufactured by Fujishashi Furumu Co., Ltd. to obtain green filter sensitivity (SG) and developing disorder. The reference point of the optical density that determined the sensitivity was [development disorder + 0.20].

Composition of developer (FD-3)

500 ml of water

Metol 2g

40 g of sodium sulfite

Hydroquinone 4g

8 g of sodium carbonate (1H ₂ O)

1 g potassium bromide

Add 1 liter of water.

When using, add the same amount of water.

The obtained results are shown in the first table as relative values.

As apparent from the results of the spectrogram shown in Tables 1 and 5, the sensitizing dyes according to the present invention had superior green sensitivities to the pigments for comparison.

TABLE 1

The numerical value of a 1st table | surface is a sensitivity at the time of adding an optimal amount of each pigment | dye, and is a nonsensitivity at the time of making green sensitivity of the comparative pigment | dye 100.

Claims (1)

A silver halide photographic emulsion comprising at least one intermediate dye of the following structural formula.

In the above structural formula Z represents an atomic group necessary to form benzoxazolehex, naphthooxazole nucleus, R ₁ represents an alkyl group or an allyl group, R ₂ represents an alkyl group, an aryl group, an allyl group, R ₃ is an alkoxy carbonyl alkyl group, alkoxyalkyl group, N- (N, N-dialkylaminoalkyl) carbamoylalkyl group, N- (N, N, N-trialkylammoniumalkyl) carbamoylalkyl group, N, N, N -Trialkylammonium alkyl group. Provided that when R ₃ is an alkoxycarbonylalkyl group, R ₂ represents a phenyl group, X represents acid anion, n represents 0 or 1.

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