JPH04506579A - photographic silver chloride emulsion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to photographic silver chloride emulsions with improved storage stability.

Photographic silver chloride emulsions are widely used today in the production of photographic color negative paper materials. . As such materials age, their sensitometric performance decreases in speed sensitivity and and the minimum density (D,i,) increases, while its contrast decreases. do.

Known techniques to counter these drawbacks of silver halide emulsions generally include the use of small amounts of UK, consisting of adding a reducing agent such as aminohexose-reductones. The method described in Japanese Patent No. 1262127 is included.

However, there is a need to further improve the storage stability (shelf life) of silver chloride emulsions. Ru.

European Patent Specification No. 0246766 (US Patent No. 4782011) , blocked bisphenols are described as photographic dye image stabilizers.

These compounds were specifically contained in the silver chlorobromide emulsion.

According to the present invention, the phenolic hydroxyl having two bonded phenol rings, One hydrogen atom of the group is substituted with a blocking group that is a substituent other than hydrogen. and a bisphenol in which at least one of the phenol rings is substituted. At least the derivative has improved storage stability by containing the derivative therein. A light-sensitive silver chloride emulsion is provided comprising 90% silver chloride.

A blocking group is any group that does not affect the desired properties of the stabilizer. Good too.

The two phenolic rings of the stabilizer can be bonded directly through a single bond or between them through a bonding group. May be indirectly coupled. Preferably, the bond between the phenolic rings is one ring phenolic hydroxy groups of and blocked phenolic hydroxy groups of other rings. It is an ortho position regarding.

Preferably, each phenolic ring is independently unblocked, unblocked or blocked. Substituted in the ortho or para position with respect to the phenolic hydroxy group. substituent It is further preferred that the is present at both the ortho and para positions.

The bisphenol compound preferably has the general formula: (wherein R is alkyl, cyclo Alkyl, alkenyl, aryl, acyl, alkylsulfonyl or aryls is luphonyl, R' is a single bond, alkylene, alkylidene, heteroatom or sulfonyl a linking group selected from Each R1 is independently alkyl, alkoxy, alkenyl, cycloalkyl , represents one or more substituents selected from aryl or aryloxy or each R independently, together with the benzene ring to which it is attached, is a fused polycyclic aromatic Represents the atoms necessary to complete the group ring structure, and represents the alkyl, alkoxy, cycloalkyl, Kyl, alkylene, alkenyl, aryl, aryloxy and all acyl groups are optionally replaced) has.

Examples of blocking groups R are methyl, ethyl, propyl or butyl, cyclohexyl xyl, phenyl, acetyl or benzoyl.

Examples of linking groups R1 are methylene, butylidene, 3.5.5-trimethylhexylidene. ion, oxygen, sulfur or sulfonyl.

A particularly preferred group of bisphenol compounds has the general formula = (wherein R1 and R are As defined, and R, , R4, Rr; and R6 are each independently is a substituted or unsubstituted alkyl, alkenyl, cycloalkyl or cycloalkyl group ) has. Preferably, R3 and R4 are the same, and R5 and R- are the same .

Specific examples of bisphenols suitable for use in the present invention are as follows.

CH3CH2-c4H9-t CH3CH3 Blocked bisphenol derivatives include many commercially available blocked bisphenol derivatives. It can be easily prepared from corresponding compounds that have not been prepared. For example, aluminum bromide Acyl chloride, a Locking groups can be introduced into the unblocked parent bisphenol .

Examples of unblocked parent bisphenols from which stabilizers of the invention can be made include: As written.

The present invention also provides the phenolic hydroxyl having two linked phenolic rings. One hydrogen atom of the group is substituted with a blocking group that is a substituent other than hydrogen. , a bisphenol derivative in which at least one of the phenol rings is substituted, To provide a method for improving the storage stability of a silver chloride emulsion by incorporating silver chloride into the emulsion. Ru.

The present invention further provides a photographic material comprising a support having a layer of a light-sensitive silver chloride emulsion, comprising: , the material has two linked phenolic rings to improve its shelf life. , one hydrogen atom of the phenolic hydroxy group is a substituent other than hydrogen, is substituted with a locking group, and at least one of the phenol rings is substituted. A photographic material containing a bisphenol derivative is provided.

The silver chloride emulsion used in the present invention contains more than 90 mol% silver chloride, preferably Kuhoko's emulsion is substantially pure silver chloride.

Bisphenol compounds are added to silver chloride emulsions containing high boiling point bisphenols. It can be included as a dispersion of coupler solvent droplets. In small droplets like this may also contain a color coupler. Also, these include alcohol, e.g. For example, it may be contained as a solution in methanol.

The color coupler may be any type of coupler useful in color photographic materials. stomach. Examples of such coupler types include phenolic and naphtholic cyanogens. couplers, pyrazolidone and pyrazolotriazole magenta couplers and acyl Contains ruacetanilide yellow coupler.

Particularly good results have been obtained with pivaloylacetanilide couplers and especially with aryloxy It is obtained by having a coupling-off group. Such couplers are preferably is the general formula: (wherein R7 is one of the types found in couplers such as those described above or represents a further substituent, and R11 is a coupling-off group, preferably is an aryloxy group).

Emulsions, emulsion additives and couplers suitable for use in the emulsions and elements of this invention include: Research Disclosure +1 December 978, Section 17643, Kenneth MasonPublicat ions Ltd,, 12a North 5treet, Emsworth, 1lantsPOIO7D, U., published. In particular, Kap For information on the IV.

The following examples are included for a better understanding of the invention. Separate dispersions were prepared.

Coupler (A) is combined with a quarter of its weight of dibutyl phthalate and 2-(2-butylphthalate). ethyl acetate. Between the two dispersions In addition, the following block toxins were added at a concentration, by weight, equal to half the concentration of the coupler. Contains phenol. The fourth dispersion contains the same concentration and Comparison formula: %formula%) bisphosphate ester.

Each dispersion was mixed with a blue-sensitive silver chloride emulsion and deposited on a resin-coated paper support. On top, the silver and coupler coverages are each 0.18g/rr? and 0.40g/% It was coated so that

To evaluate the sensitometric performance, a piece of fresh coating was exposed to RA4 Treated with chemistry. Another piece was exposed at 50 °C and 50 °C for 1 week before being similarly exposed and processed. %RH and warmed in the dark.

The table below shows the Dl, 7 and Co of freshly coated and warmed pieces from each coating. We will show you what we think about Trust. Columns marked with “Δ” indicate new samples and warm samples. This shows the difference between the Taking the coating without any additives as a reference , two blocked bisphenols have a range of Dl, 7 increase and Reduce contrast loss. Comparison of bisphosphate esters with opposite effects It was shown by Le.

1-11 0.09 0.17 +0.08 2.71 2.26 -0.45 I -150,090,26+0.17 2.60 2.04 -0.56 14 A dispersion was prepared containing compound 1-11 with the coupler described below.

I also made a dispersion of each coupler only. In each dispersion, the same weight of ethyl acetate and half its weight of dibutyl phthalate. dissolved in. When present, bisphenols are included at half the weight of the coupler. I let it happen. The oil solution was prepared in an aqueous gelatin solution using ultrasonic stirring as in Example 1. It was dispersed into

Each dispersion containing coupler (B) is mixed with a red-sensitive silver chloride emulsion and Silver and coupler coverages were 239 mg/rrl and 239 mg/rrl, respectively, on oil-coated paper support. It was coated so that it was 425 mg/rrr. Red sensitized milk with second pair of coatings The same component coatings were used, except that a blue sensitized emulsion (as used in Example 1) was used instead of a blue emulsion. Made from a dispersion with a covering amount.

Similarly, a dispersion of coupler (C) is mixed with a green sensitized silver chloride emulsion. They were coated with silver and coupler coverages of 285 mg/I and 447 mg/I, respectively.

To evaluate the sensitometric performance, a specimen of the fresh coating was exposed to light and RA 4 Chemically treated. Separate pieces from each coating were exposed for 50 days for 8 days before being exposed and processed. Warm in the dark at °C and 50% RH.

The table below shows the D min of freshly coated and warmed pieces from each coating. Show the appearance of The column marked with “Δ” indicates the difference between the two sets due to warm treatment. It emphasizes the differences between All coatings show an increase in D wh i * in warm conditions. , and the magnitude of this increase is always reduced by the presence of bisphenols.

(Thus, the advantageous effects of the present invention may be due to the color sensitivity of the emulsion or the couplers it contains. It shows that it does not depend on

Red (B) None 0.138 0.178 +0.040 Red (B ) Ah Ri 0.136 0.157 +0.021! -1' -1 It has two bonded phenolic rings, and one of its phenolic hydroxy groups is water. When an elementary atom is substituted with a blocking group that is a substituent other than hydrogen, phenol Containing therein a bisphenol derivative in which at least one ring is substituted. Containing at least 90% silver chloride, its shelf life is improved by A photosensitive silver chloride emulsion.

International Jury＠&-

Claims (10)

[Claims] 1. It has two bonded phenol rings, and one of the phenolic hydroxy groups The hydrogen atom is substituted with a blocking group that is a substituent other than hydrogen, and the A bisphenol derivative in which at least one of the nor rings is substituted, Contains at least 90% silver chloride, which has improved storage stability. Photosensitive silver chloride emulsion. 2. Bisphenol derivatives have general formulas: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I ) (wherein R is alkyl, cycloalkyl, alkenyl, aryl, acyl, alkylsulfonyl or arylsulfonyl, R1 is a single bond, alkylene, alkylidene, heteroatom or sulfonyl and each R2 is independently alkyl, alkyl, or From lukoxy, alkenyl, cycloalkyl, aryl or aryloxy represents one or more selected substituents, or each R independently represents a bond to which it is attached. The benzene ring represents the atoms necessary to complete the fused polyaromatic ring structure. 2. The photosensitive emulsion according to claim 1, having the following properties: 3. Bisphenol derivatives have general formulas: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I I) (wherein R1 and R are as defined above, and R3, R4, R5 and and R6 each independently represent substituted or unsubstituted alkyl, alkenyl, cycloa (alkyl or aryl group) The photosensitive emulsion according to claim 1 or 2, having the following. 4. Claim No. 3 in which R3 and R4 are the same and R5 and R6 are the same The photosensitive emulsion according to item 3. 5. Claims 1-4 comprising substantially pure silver chloride. Photosensitive emulsion. 6. Further comprising a color coupler, according to any one of claims 1 to 5. photosensitive emulsion. 7. Claims in which the coupler is a yellow, cyan or magenta dye-forming coupler 6. The photosensitive emulsion according to item 6. 8. The coupler is acylacetanilide, phenolic, naphtholic, or pyrazoli 7. The photosensitive emulsion according to claim 6, which is a don or pyrazoloazole coupler. 9. Bisphenol as defined in any one of claims 1 to 4 comprising at least 90% silver chloride, containing a derivative therein. A method for improving the storage stability of silver chloride emulsions. 10. In order to improve the preservability of the material, any one of claims 1 to 4 may be used. containing therein at least a bisphenol derivative as defined in paragraph 1. A photographic material comprising a support having a layer of a light-sensitive silver chloride emulsion consisting of 90% silver chloride. fee.