JPH06503183A - Photographic silver halide development processing method, silver halide materials and solutions therefor - 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] Photographic silver halide development processing method, Silver halide materials and solutions therefor The present invention relates to photographic silver halide processing solutions, particularly color developers.

Color development parameters such as time, temperature, component content, pH etc. must be carefully controlled to obtain sensitometric results ( Understood. This usually requires strict control over temperature and color developer replenishment, for example. This means that it must be strictly controlled. The cost of such controls is commercially Obviously this is critical in operation.

U.S. Pat. No. 4,155,763 discloses aromatic amine color developing agents and pyrazo A compound consisting of 1-aryl-pyrapritone with two substituents at the 4-position of the lydone. A color developer is disclosed. This advantage is due to more robust image pigmentation and cheaper It is said to contain a certain amount of color developer.

The English abstract of Japanese Patent Application No. 62/178251 states that parafuconylene diamine Color developing agents and auxiliary developers, especially colors consisting of 1-phenyl-pyrazolidone - The developer is listed. Image formation is “highly sensitive” and creates “excellent gradation” It is stated that. It is also said that there is no effect of stirring.

The above two documents state that when a second developer is used in the color developer, the black and white developer In some cases even higher developing activity is obtained, for example when using a hydroquinone developing agent. The activity increases very strongly with the addition of metol or l-phenyl-pyrazolidone. It has been shown that it adds

The present invention provides a black and white developer of a type not previously disclosed for use in color developers. The presence of drugs can affect, for example, color developing agent concentration, bromide ion concentration. , provides a color development method that is not sensitive to changes in pH 1 development processing time and temperature. do.

According to the present invention, sensitometric results caused by changes in processing variables In the presence of one or a combination of black and white silver halide developing agents which reduce the variability of the fruit. , low variability and acceptable sensitometry consisting of color development. - A method for developing imagewise exposed silver halide color materials is provided which provides results. Ru.

A preferred black and white developing agent (also referred to herein as ETA (electron transfer agent)) is Metol or pyrazolidone. Many pyrazolidone developers have fewer shows some improvements in obtaining cytometric variations, but one that is particularly effective is the general formula :(In the formula, R1 and R1 are each hydrogen or an alkoxy group having 1 to 4 carbon atoms. , and R3 and R4 are each hydrogen or an alkyl group having 1 to 10 carbon atoms.

However, either one of R1 or R2 is an alkoxy group, or R8 or Each R4 is an alkyl group having 3 to 7 carbon atoms) has.

In the present invention (unlike the prior art), low activity conditions are presently used in E. TA not only accelerates but also decelerates high activity conditions, thereby Less variation in sensitometric results under both active conditions.

The black and white developer may be present either in the color developer or in the photographic material being processed. good. When contained in photographic materials, it remains in an inactive form until processing. It is preferable to For example, a black and white developer uses a developing solution (usually alkaline) to remove the material. ), the protective group (blocking group) that is removed by hydrolysis when immersed in Can be activated.

The present invention further provides a color developing agent and a general formula: Each is hydrogen or an alkyl group having 1 to 10 carbon atoms. However, R1 or R1 Either one of them is an alkoxy group, or one of R8 or R4 has 3 to 3 carbon atoms. 7 alkyl group) Provided is a photographic color developer comprising a black and white silver halide developing agent having the following properties.

Many ETAs have been shown to be useful for reducing sensitometric sensitivity to processing variables. Tested for efficacy. Using the decrease in sensitivity to development time as an example. different Three broad types of behavior can be observed for ETA, which are as follows: .

(1) With contrast Dmin increase caused by time and preservation of objective contrast. Reduced spread of sensitometry. Please refer to Figure 10 of the accompanying drawings.

(2) with contrast of Dmin increase caused by increasing time and contrast; Reduced sensitometric spread. Please refer to Figure 11 of the accompanying drawings.

(3) Although the decrease in sensitometric spread is small, even with a small Dmin control , with reduced contrast and still significant variability. See Figure 12 of the attached drawings. I want to be These results are clearly unacceptable especially with respect to increasing Dmin. stomach. Therefore, the use of type (3) ETA alone is not part of this invention.

Type (1) is the preferred behavior exhibited by preferred compounds. type( 2) are other useful and advantageous properties in which an increase in contrast or a corresponding balance is desired. In certain cases, it may be preferable to type (1). To the present invention Also includes using a combination of ETAs. For example, type (2) and tie The combination with type (3) can give the same overall properties as type (1). Ta The combination of type (1) and type (3) also has a particularly wide spread of the sensitometric curve. Gives good results that are well controlled.

A useful group of type (1) ETAs of formula (I) is at least R1 and/or R2. one of which is an alkoxy group having 1 to 4 carbon atoms, such as -0CR, and R3 is hydrogen or is an alkyl group having 1 to 4 carbon atoms, such as -CHI, and R4 is hydrogen or A hydroxyalkyl group having 1 to 4 carbon atoms, such as -CHIOH.

A useful group of type (2) ETAs of formula (I) are those in which R', R'' and R3 are hydrogen. and R4 is an alkyl group having 3 to 7 carbon atoms, for example, CsH+ It is.

A preferred black and white developer is 1-(4-methoxyphenyl)-3-pyrazolidone, 1 -(3,4-dimethoxyphenyl)-3-pyrazolidone and l-phenyl-4- It is n-pentyl-pyrazolidone.

The black and white developing agent is contained in the developer in an amount of 5 g/L or less, preferably 0.05 to 0.5 g/L. may be present in concentrations within the range of When included in photographic materials, may be present in one or more layers of the photographic material. photographic materials. As mentioned above, it is a function of the pH of the processing solution. of a compound that releases it either as a function of silver halide development or as a function of silver halide development. It may be a shape.

In particular, due to the presence of black and white developing agents, development time and temperature, pH 1 bromide ion This is caused by variations in the concentration of the color developing agent (e.g. CD4) in the color developer. It has been found that the variability caused by straining is improved. Reduced sensitometric variation The risks further reduce the refill rate, thus reducing overflow and drainage. It means to become. Sometimes it is necessary to remove bromide ions from the developer. It can also be avoided.

Although the present invention is particularly applicable to color negative film processing, other processing methods, e.g. For example, it can also be applied to color photographic paper. The material to be processed must be from a support having at least one silver halide emulsion layer supporting a color coupler. Become. The term “associated therewith” as used herein has its ordinary meaning in the art. The coupler is It can be contained in the emulsion layer or a layer adjacent thereto. The preferred color material is , comprising one or more emulsion layers, each having a coupler associated with it, Three dye image-forming units, each sensitized to a different region of the spectrum Consisting of Typical color materials are sensitized to blue, green and red light, respectively yellow -, magenta and cyan image dyes.

Examples of color photographic materials and processing methods thereof include Kenneth Mason Pu. Published by En+sworth, Hants, UK Research Disclosure ), Section 308119 (December 1989).

The following examples are included for a better understanding of the invention.

Example 1 Color coupler (A) of formula dissolved in di-t-butyl phthalate (a pair of couplers dissolved in Tabular grains having an average grain area of 1.05 mμ2 including medium ratio = 1:0.5) A single layer coating of silver bromoiodide emulsion containing 1.0 g/rr (as silver)! and coupler 0.6g/rr! coated with.

The following basic color developer was used.

color developer diethyltriaminepentaacetic acid Pentasodium salt (40% w/w) 6.5m/potassium carbonate 37.3g Sodium bromide 1.3g Potassium iodide 1.2■ Hydroxyl ammonium sulfate 2.0g CD4 (color developing agent) 4.5 Add water to make 1.0 liter pl=to, 0 The table below shows the concentration of 1-(4-methoxyphenyl)-3-pyrazolidone and ．． Details of the development process at 8° C. for development time are shown.

The sensitometric results for these 12 development treatments were Figures 1.2 and 3 show a set of three time series for each level. show. In Figure 1 without ETA (control), the effect of time is D min, speed It provides a significant increase in sensitivity, Dmax and contrast. P.T. In Figure 2 at Ao, 1 g/L, the spread of sensitometry caused by time. The gap has decreased significantly. In Figure 3 at ETA 0.3g/L, the song The lines are coming together. The optimal level of ETA is probably 0.1-0.3 g/L. Dew.

The essential difference between this result and the expected one is that short processing times accelerate (as might be expected) as well as long processing times (which may be expected). unexpected).

This expected sensitometric spread from both high and low activity conditions No compression can also be achieved with other processing variables as shown in Examples 2 and 3 below. shown.

Similar results were obtained when coated with the same emulsion and processed with the same solution; was found in couplers (B) and (C) with

Example 2 Sodium bromide levels from 0.45 to 2.15 g/L and 0.0.1 and 0.3 g A set of experiments at ETA levels of /L were performed on the same coatings as above. The result The results are shown in Figures 4.5 and 6. Again, the change in bromide ion level at zero level of ETA There is significant sensitometric broadening caused by oxidation, increasing ETA levels. This is reduced as shown in FIGS. 5 and 6. Optimal level of PTA Probably 0. 'l-0,3 A single layer coating of silver bromoiodide emulsion as described in Example 1, The development time was set to 2.2 while varying the CD4 and PTA concentrations as shown in Table 2 below. Tested according to the method of Example 1 except that the time was kept constant for 5 minutes.

The sensitometric results for these 15 development treatments are shown in Figures 7.8 and 9. This is shown as a set of three CD4 level series. Figure 7 without ETA (control) The influence of CD4 level is Dmin, speed sensitivity, Dmax and control. It is to give a significant increase at the end. Figure 8 at ETA 0.1g/L , the sensitometric spread caused by CD4 was greatly reduced. are doing. In Figure 9 for PTAo, 3g/, the curves are again separated, but especially The contrast is even better than the control in similarity.

Similar results were obtained with other couplers ( Found in B) and (C).

Submission of translation of written amendment (Article 184-8 of the Patent Act) June 11, 1993

Claims (12)

[Claims] 1. Reduces variability in sensitometric results caused by changes in processing variables Color development in the presence of one or a combination of black and white silver halide developing agents to reduce reduces variability and gives acceptable sensitometric results. A method for developing imagewise exposed silver halide color materials. 2. The black and white developing agent has the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R1 and R2 are each hydrogen or an alkoxy group having 1 to 4 carbon atoms, and R3 and R4 are each hydrogen or is an alkyl group having 1 to 10 carbon atoms, and either one of R1 or R2 is an alkyl group having 1 to 10 carbon atoms. koxy group, or one of R3 or R4 is an alkyl group having 3 to 7 carbon atoms. ) The method according to claim 1, comprising: 3. At least one of R1 and/or R2 is an alkoxy group having 1 to 4 carbon atoms; , R3 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R4 is hydrogen or carbon The method according to claim 2, wherein the hydroxyalkyl group is a number 1 to 4 hydroxyalkyl group. 4. R1, R2 and R3 are hydrogen, and R4 is an alkyl group having 3 to 7 carbon atoms The method according to claim 2. 5. The black and white developing agent is 1-(4-methoxyphenyl)-3-pyrazolidone, 1- (3,4-dimethoxyphenyl)-3-pyrazolidone or 1-phenyl-4-n -pentyl-pyrazolidone. 6. Any one of claims 1 to 5, wherein a black and white developing agent is present in the color developer. The method described in Section 1. 7. Black and white developing agent is present in the color developer at a concentration of 0.05-0.5 g/L , the method according to claim 6. 8. The black and white developing agent is present in the silver halide color material and the active form is removed during the development process. Any one of claims 1 to 5, which is contained in an inert form released from The method described in section. 9. Color developing agent and general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R1 and R2 are each hydrogen or an alkoxy group having 1 to 4 carbon atoms, and R3 and R4 are each hydrogen or is an alkyl group having 1 to 10 carbon atoms, and either one of R1 or R2 is an alkyl group having 1 to 10 carbon atoms. Coxy group, or one of R3 or R4 is an alkyl group having 3 to 7 carbon atoms. ) A photographic color developer consisting of a black and white silver halide developing agent. 10. At least one of R1 and/or R2 is an alkoxy group having 1 to 4 carbon atoms. R3 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R4 is hydrogen or a carbon atom. The color developer according to claim 9, which is a hydroxyalkyl group having a prime number of 1 to 4. Image liquid. 11. R1, R2 and R3 are hydrogen, and R4 is alkyl having 3 to 7 carbon atoms 10. The method according to claim 9, wherein 12. The black and white developing agent is 1-(4-methoxyphenyl)-3-pyrazolidone, 1 -(3,4-dimethoxyphenyl)-3-pyrazolidone or 1-phenyl-4- The compound according to any one of claims 9 to 11, which is n-pentyl-pyrazolidone. How to put it on.