JPH08137053A - Solid processing agent for silver halide photographic material - Google Patents

Abstract

PURPOSE: To provide a solid processing agent for a silver halide photographic material, that is excellent in moisture resistance and has high solubility by containing a specific compound. CONSTITUTION: This solid processing agent for a silver halide photographic material contains a compound represented by the formula. In the formula, L<1> and L<2> may be the same or different, and are represented by -OR<1> or -NR<2> R<3> , R<1> , R<2> , and R<3> each represent hydrogen atom or an alkyl group, with L<1> and L<2> each having a total of four or more substituents in one molecule which are selected from the following A group: -SO3 M -OSO3 M and -COOM wherein M represents hydrogen atom, an alkali metal or ammonium. Further, L<1> and/or L<2> is preferably -NR<2> R<3> , and in particular both L<1> and L<2> are preferably -NR<2> R<3> . Also, at least either of R<2> or R<3> is preferably an alkyl group of 1 to 3 carbons, particularly an ethyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for a silver halide photographic light-sensitive material, and more particularly to a solid processing agent having a fluorescent whitening ability with improved moisture resistance and solubility.

[0002]

2. Description of the Related Art Various processing solutions such as a color developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution and a stabilizing solution are used for processing a silver halide photographic light-sensitive material such as a color photographic light-sensitive material. For simple preparation of these treatment liquids, necessary components are preliminarily prepared and then a concentrated liquid or a treatment agent processed into a compact form such as powder, granules or tablets is commercially available. The user can simply prepare the treatment liquid simply by dissolving these processed treatment agents in water or warm water.

Although there are advantages and disadvantages to each of the forms of the above-mentioned treatment agents, in recent years, in the industry, for the purpose of reducing the logistics cost and the reduction of waste, it is lighter and smaller in volume,
In addition, the advantages of solid processing agents such as powders, granules and tablets that can reduce the amount of plastic packaging materials such as polyethylene containers have been attracting attention. However, solid processing agents have a longer dissolution time than liquid processing agents, resulting in lower work efficiency, deliquescent or blocking due to their strong hygroscopicity, or the components react with each other due to moisture absorption. However, the present situation is that the application field is limited.

Various proposals have hitherto been made to alleviate the drawbacks of these solid processing agents. JP-A-51-6
No. 1837 proposes a method of incorporating a water-soluble polymer as a disintegrating agent in order to accelerate the dissolution of the tableting agent. Further, JP-A Nos. 2-109042 and 2-109
Nos. 043 and 4-221951 disclose a method for preventing moisture absorption by hermetically packing various granular treatment agents in a known moisture-proof packaging material such as a composite material of plastic and aluminum. Furthermore, JP-A-4-19655 and 4-2307
In No. 48, inert components are arranged in layers between easily reacting components, and polyvinylidene chloride, P
A method for improving the preservability by packaging with a moisture-proof material such as ET is disclosed, and in JP-A-5-88302, 5-100368, in order to prevent deterioration of the tablet-like treatment agent due to moisture absorption,
A method of packaging a water-soluble polymer sheet and then packaging it with a moisture-proof packaging material such as PET is disclosed.

By the way, in printing materials such as color paper among silver halide color photographic light-sensitive materials, the whiteness of the white background of the image is important, and therefore fluorescent whitening is performed to prevent stains such as yellowing. The agent is added to the processing liquid. Fluorescent whitening agents are often added to color developing solutions, but in order to improve the effect, not only color developing solutions but also bleaching solutions, bleach-fixing solutions, fixing solutions, stabilizing solutions, rinse solutions, etc. It is preferably added to the liquid. However, when a brightening agent is added to a solid processing agent, the solubility and hygroscopicity, which are the drawbacks of the solid processing agent, are further deteriorated, and in the technologies known to date, there are many problems in practical use. Became clear. For example, even if it is sealed with a moisture-proof material,
There is a high probability that these materials have pinholes,
In that case, it was found to absorb moisture in a short period of time. Also,
It has also been found that the treatment agent must be packaged with a moisture-proof material for each preparation, because the treatment agent immediately absorbs moisture when opened, and the packaging material cannot be sufficiently reduced in weight. In addition, in the actual dissolution work, weak agitation is performed in order to avoid splashing of liquid and entrainment of air, and under such agitation conditions, the solid processing agents manufactured by the conventional technique still have a long dissolution time. It turned out to be time consuming.

Regarding the incorporation of an optical brightening agent in a solid processing agent, a tablet-like processing agent for color development containing a specific diaminostilbene type optical brightening agent and polyethylene glycol in JP-A-5-341468, JP-A-6-351
No. 30 discloses a tablet-like processing agent for color development which contains a specific diaminostilbene-based optical brightening agent and has a bulk density of 1.2 g / cm ² or more. Solubility of the tablet-like processing agent,
It is noted that the storage stability and strength were improved. However, it takes a long time for the actual dissolution work, and it absorbs moisture remarkably under storage conditions in which it is directly exposed to the outside air, and it has not been possible to solve the practical problem.

[0007]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a solid processing agent having excellent moisture resistance and high solubility. The second purpose is to reduce the logistics cost, storage space, and packaging waste by taking advantage of the solid processing agent.

[0008]

Means for Solving the Problems As a result of diligent studies on the above problems, the present inventor has found that the problems can be achieved by the following solid processing agents.

1. A solid processing agent for a silver halide photographic light-sensitive material, comprising a compound represented by the following general formula (I).

[0010]

Embedded image

In the general formula (I), L ¹ and L ² may be the same or different and are represented by --OR ¹ or --NR ² R ³ . Here, R ¹ , R ² and R ³ each represent a hydrogen atom or an alkyl group, and L ¹ and L ²
Has a total of four or more substituents selected from the following Group A in one molecule. Group A: -SO ₃ M, in -OSO ₃ M, -COOM above A group, M represents a hydrogen atom, an alkali metal, ammonium.

In the general formula (I), L ¹ and / or L
Preferably ² is -NR ² R ^3, it is particularly preferable that both of L ¹ and L ² is -NR ² R ^3. At least one of R ² and R ³ is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an ethyl group. Further, it is most preferable that one of R ² and R ³ is an alkyl group and the other is a hydrogen atom. When ^{one of} L ¹ and L ² is —OR ¹ , R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and both L ¹ and L ² are —OR ¹
In the case of, R ¹ has ¹ to ₃ carbon atoms substituted with a —SO ₃ M group.
Is preferably an alkyl group. R ¹ , R ² , R ³
The substituent of the group A for substituting the alkyl group of is —SO ₃ M,
-COOM are preferred, especially -SO ₃ M are preferable.
M is preferably a hydrogen atom or an alkali metal, and particularly preferably an alkali metal. Of the alkali metals, sodium is most preferred.

Preferred specific examples of the optical brightener of the general formula (I) used in the present invention are those in which L ¹ and L ² are represented by the following atomic groups.

[0014]

[Table 1]

[0015]

[Table 2]

Further, in the present invention, the solid processing agent is preferably the following. 2. A solid processing agent for a silver halide color photographic light-sensitive material, wherein the solid processing agent of 1 is a tablet processing agent obtained by press-molding a powder and / or granular processing agent component. .

The present invention will be described in detail below. In the present invention, the solid processing agent refers to a powder, a granule, a lump such as a tablet, which is composed of two or more kinds of components. These treatment agents may be a one-part type containing all the components necessary for the treatment liquid, or a separate type composed of a plurality of parts. It is preferable to configure. Here, the powder means that the formed particles have an average particle diameter of 100 μm.
The average particle size obtained by granulating the powder is 100 to 3000 μm. A tablet is a cylinder obtained by pressing powder or granules,
It refers to lumps such as spheres, cuboids, and cubes. From the viewpoint of effectively achieving the object of the present invention, the solid processing agent is preferably a tablet-shaped processing agent obtained by pressurizing a granulated product. From the viewpoint of accelerating dissolution, the size of the tablet-like treatment agent is preferably as small as possible without impairing handleability, and is preferably 1 g to 30 g in terms of weight, and particularly 2 g to 20 g.
g is preferred.

As the method for producing the granulated product, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation can be used. it can.

In the granulation, the solid treatment agent components are mixed, such as a one-agent granulation method in which all solid treatment agent components are mixed and granulated, and a separate granulation method in which the solid treatment agent components are granulated for each part. Depending on the method, a granulation method involving various mixing forms can be used, but the above-mentioned fractional granulation method is preferable from the viewpoint of the effect of the present invention.

The average particle size of the obtained granulated product is 100-80.
It is preferably 0 μm, and more preferably 200 to 750 μm. If the average particle size is smaller than 100 μm or larger than 800 μm, the above-mentioned granules are mixed and the components become non-uniform when compressed under pressure,
So-called segregation or weight deviation occurs, which is not preferable. Furthermore, the particle size distribution is ± 100 for 60% or more of the granulated particles.
Those within a deviation of ˜150 μm are preferred.

When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting machine may be used. it can. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity and handleability, a cylindrical type, so-called tablet is preferable.

The molding pressure in the case of pressure compression is 300 to
2,000 kg / cm ² is preferred, more preferably 500
~ 1,500 kg / cm ² , and more preferably 650
It is 1,200 kg / cm ² . If it is less than 300 kg / cm ² , the strength of the obtained solid is insufficient, and 2,000 kg / cm ²
When it exceeds the above range, the solubility of the obtained solid matter deteriorates.

The fluorescent brightening agent represented by the general formula (I) may be contained in the solid processing agent in only one kind or in combination of two or more kinds. Further, an optical brightener other than the present invention may be used in combination within a range that does not impair the effects of the present invention, but the amount thereof is less than 1/2 in molar ratio with respect to the optical brightener of the present invention. preferable. The ratio of the fluorescent whitening agent of the general formula (I) contained in the solid processing agent is preferably 1 to 30% by weight, particularly preferably 2 to 20%. The fluorescent whitening agent of the general formula (I) may be contained in a solid processing agent for any processing solution, but is preferably used for a color developing solution, a bleach-fixing solution, a bleaching solution, a fixing solution, a stabilizing solution and a rinse solution. A solid processing agent, particularly preferably a color developing solution, a bleach-fixing solution, and a stabilizing solution used for processing print materials such as color paper, color reversal paper and auto positive paper, and most preferably a solid processing agent. , A solid processing agent for a color developing solution of these printing materials. Among the fluorescent whitening agents of the general formula (I), SR of a specific example
-12, SR-27, SR-10, SR-8, SR-1
0 is preferable in terms of breadth of application and effect, and SR is particularly preferable.
-12, SR-27 and SR-10 are preferred, and SR-12 is most preferred.

The compound of the general formula (I) can be synthesized by a conventionally known method. For example, 4,4'-diaminostilbene-2,2'-disulfonic acid and cyanuric chloride are condensed to synthesize 4,4'-bistriazinylaminostilbene-2,2'-disulfonic acid, and then alcohols are also added. The comb can be synthesized by condensing amines. Specifically, Journal of Industrial Chemistry Vol. 60, No. 5, p.
604 (1957).

A synthesis example of the optical brightener is shown below. Synthesis of Compound (SR-12) 10.2 g of cyanuric chloride was dissolved in 100 ml of acetone, and 100 g of a 10% sodium diaminostilbenesulfonate aqueous solution was added dropwise over 20 minutes while cooling with ice.
During this period, the pH of the reaction solution of the sodium carbonate aqueous solution was adjusted to 5 to 7
Kept at. After continuing stirring for another 30 minutes, 100 g of an 18% taurine aqueous solution was added. Then, the mixture was heated to remove acetone, the internal temperature was adjusted to 95 ° C., and the mixture was stirred for 3 hours. During this period, the pH of the reaction solution was maintained at 6 or higher with an aqueous sodium carbonate solution. After the reaction was completed, the reaction mixture was cooled and salted out to give 12 g of pale yellow crystals.
I got It was confirmed from the mass spectrum and NMR that this was compound (SR-12). λ max = 348 nm (ε = 4.65 × 10 ⁴ , H ₂ O) Further, other compounds were synthesized by the same method as above.

Compound (SR-1) Light yellow powder λmax = 351 nm (ε = 5.10 × 10 ⁴ , H ₂ O) 〃 (SR-2) 〃 〃 = 352 nm (ε = 5.33 × 10 ⁴ , H ₂ O) 〃 (SR-3) 〃 〃 = 343 nm (ε = 5.11 × 10 ⁴ , H ₂ O) 〃 (SR-4) 〃 〃 = 351 nm (ε = 5.23 × 10 ⁴ , H ₂ O) 〃 (SR-5) 〃 〃 = 348 nm (ε = 4.78 × 10 ⁴ , H ₂ O) 〃 (SR-6) 〃 〃 = 348 nm (ε = 4.76 × 10 ⁴ , H ₂ O) 〃 (SR-7) 〃 〃 = 343 nm (ε = 4.86 × 10 ⁴ , H ₂ O) 〃 (SR-8) 〃 〃 = 345 nm (ε = 4.56 × 10 ⁴ , H ₂ O) 〃 (SR-9) 〃 = 343 nm (ε = 4.43 × 10 ⁴ , H ₂ O) 〃 (SR-10) 〃 〃 = 345 nm (ε = 4.99 × 10 ⁴ , H ₂ O) 〃 (SR-11) 〃 〃 = 351 nm (ε = 5.10 × 10 ⁴ , H ₂ O) 〃 (SR -13) 〃 〃 = 352 nm (ε = 5.68 × 10 ⁴ , H ₂ O) 〃 (SR-14) 〃 〃 = 353 nm (ε = 5.40 × 10 ⁴ , H ₂ O) 〃 (SR-15) 〃 = 350nm (ε = 5.98 × 10 ⁴ , H ₂ O) 〃 (SR-16) 〃 〃 = 349 nm (ε = 4.76 × 10 ⁴ , H ₂ O) 〃 (SR-17) 〃 〃 = 348 nm (ε = 4.77 × 10 ⁴ , H ₂ O) 〃 (SR-18) 〃 〃 = 349 nm (ε = 4.62 × 10 ⁴ , H ₂ O) 〃 (SR-19) 〃 〃 = 352 nm (ε = 4.91 × 10 ⁴ , H ₂ O) 〃 (SR-20) 〃 〃 = 351 nm (ε = 5.21 × 10 ⁴ , H ₂ O) 〃 (SR-21) 〃 = 350 nm (ε = 5.18 × 10 ⁴ , H ₂ O) 〃 (SR-22) 〃 = 352 nm (ε = 4.63 × 10 ⁴ , H ₂ O) 〃 (SR-23) 〃 〃 = 350 nm (ε = 4.78 × 10 ⁴ , H ₂ O) 〃 (SR-24) 〃 = 349 nm (ε = 5.12 × 10 ⁴ , H ₂ O) 〃 (SR-25) 〃 〃 = 353 nm (ε = 4.56 × 10 ⁴ , H ₂ O)

In the present invention, when the solid treating agent is a granule or a tablet, a water-soluble polymer compound such as soluble starch, dextrin, mannitol, hydroxymethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyethylene glycol, polyacrylamide, etc. is used as a binder. It is preferable to contain 0.1 to 10% by weight, particularly soluble starch, dextrin,
It is preferable to contain mannitol. Further, in order to improve the dissolution rate of the solid processing agent, it is preferable to include sodium paratoluenesulfonate, a polyethylene oxide-based nonionic surfactant, and an alkylbenzenesulfonic acid-based anionic surfactant, particularly for a color developing solution. In order to improve the dissolution rate of the color developing agent, it is preferable to add sodium paratoluenesulfonate in an amount ratio of 10 to 200 mol% with respect to the color developing agent. On the other hand, when the solid processing agent is powder and / or granules, JP-A-4-19655 and 4-23074
The vacuum packaging form described in No. 8 is preferable.

The solid processing agent of the present invention is disclosed in JP-A 2-1.
09042, 2-109043, 4-221951
No., 4-19655, No. 4-230748, 5-88
It is preferable to wrap with the moisture-proof material described in No. 302, 5-100368. Furthermore, the technique applicable to the solid processing agents described in the above publications can be directly applied to the solid processing agent of the present invention. The solid processing agent of the present invention may be supplied to the processing tank after being dissolved in water or warm water in advance, or may be used in a method of directly supplying the processing agent to water and the processing agent separately, but powder and The former is preferred in the case of granules, and the latter method is preferred in the case of tablets.

Preferred treating solutions to which the present invention can be applied are described in JIII Journal of Technical Disclosure, Jpn. Pat. No. 94-4992, page 15, right column, line 15 to page 4, right column, line 7. ,
Particularly, as a preservative for the color developing solution, JP-A-3-1588
The sulfoalkyl-substituted hydroxylamines described in Nos. 49 and 3-174152 are preferable, and as a preservative for the fixing solution and the bleach-fixing solution, sulfinic acid derivatives such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid are preferable, Solid organic acids such as succinic acid and maleic acid are preferable as the pH buffer for the bleaching solution and the bleach-fixing solution.
Further, as a stabilizing solution, 1,2-benzisothiazoline-
It is preferable to contain a fungicide such as 3-one.

The light-sensitive material processed by using the solid processing agent of the present invention may be any color negative film, color paper, color reversal film, color reversal paper, movie color negative film, movie color positive film, color auto positive film or the like. Good, but color negative films and color papers are particularly preferable. Regarding these light-sensitive materials, JP-A-5-34887, column 1
27 line 40 to column 135 line 6, and
No. 2251, column 12, line 21 to column 25
The description in line 5 can be cited.

[0031]

The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 1) Preparation of color development replenishing tablet sample for color paper According to Example 1 of JP-A-5-341468, a tablet sample was prepared by the following method. Operation (A) 100.0 g of a developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β-methanesulfonamido) ethyl] aniline sulfate], a compound of the general formula (I) and A comparative compound (described in Table 3: 30.0 g) and sodium sulfite (3.7 g) were mixed with an air jet fine pulverizer to give an average particle diameter of 10 μm.
Grind to m. After granulating this fine powder in a commercial fluidized bed spray granulator for about 5 minutes at room temperature with 4.5 ml of water, the granulate is dried at 60 ° C. for 8 minutes.
Next, the granulated product is dried in vacuum at 40 ° C. for 120 minutes to almost completely remove water. The obtained granules were mixed with a commercially available shaker to obtain fine particles smaller than 100 μm and 80
Sieve oversized particles larger than 0 μm.

Procedure (B) Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 100.0 g, potassium bromide 0.3
g, 25 g of diethylenetriamine pentaacetic acid, 100 g of sodium p-toluenesulfonate, and the compound of the general formula (I) (described in Table 3, 30.0 g) are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 3.0 ml, and after granulation, it is dried at 50 ° C. for 10 minutes. Then granulate at 40 ° C. in vacuum for 1
Dry for 20 minutes to remove water almost completely. The obtained granulated product is sieved as in the operation (A).

Procedure (C) 350 g of potassium carbonate and 50 g of potassium hydroxide are pulverized in the same manner as in procedure (A) and then uniformly mixed with a commercially available mixer. Next, as in the operation (A), the amount of water sprayed is set to 200 ml, and granulation is performed. After the granulation, the granulated product is dried at 70 ° C for 15 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 120 minutes to almost completely remove water. The obtained granulated product is sieved as in the operation (A).

Operation (D) The granules prepared in the above operations (A) to (C) are heated at 25 ° C. for 4 hours.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. Furthermore polyethylene glycol (PE
G6000) and mix for 3 minutes. Next, the mixture was tableted with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, to a die with a diameter of 20 mm so that the filling amount per tablet was 2.87 g and the compression pressure was 700 kg / cm ² , and each tablet was 50 Tablet samples 1 to 14 were prepared for replenishing color development for individual color papers.

2) Evaluation of Moisture Resistance Each of 25 tablet samples obtained by the above operation was stored for 3 weeks in a constant temperature and humidity room adjusted to 25 ° C. and 70% relative humidity, which is a practical storage condition on the market. , Weight change before and after storage (%)
The hygroscopicity was evaluated and listed in Table 3. Next, 20 tablets each before and after storage were dissolved in 1 liter each of water, and the concentration of the developing agent CD-3 in the solution was measured by high performance liquid chromatography to show the residual ratio of the developing agent after storage to that before storage. (%) Was measured and is also shown in Table-3. 3) Evaluation of dissolution rate Each of 10 tablet samples obtained by the above operation was added to 1 liter of hot water at 35 ° C, and while maintaining the temperature, all the tablets were prepared while rotating the propeller of the stirrer at a speed of 50 rpm. The time until complete dissolution was measured. This dissolution method is
It approximates the practical working conditions in the market.
This measurement was repeated 3 times, and the average value of 3 times is shown in Table 3 as the dissolution time.

[0037]

[Table 3]

[0038]

[Table 4]

As shown in Table 3, the fluorescent whitening agent represented by the general formula (I) of the present invention has less hygroscopicity than the comparative compound, as can be seen from the small change in weight before and after storage. It is small and the residual rate of developing agent is high. From these two results, it is clear that the tablet sample prepared using the optical brightener of the general formula (I) of the present invention has excellent moisture resistance. Also, the dissolution time is significantly shorter than that of the comparative example, and it is clear that the solubility is improved.

Example 2 1) Preparation of bleach-fixing replenishing granules for color paper Operation (E) Ethylenediaminetetraacetic acid ferric potassium monohydrate 550
g and 20 g of ethylenediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (A) of Example 1. The amount of water sprayed is 25.0
After granulating, it is dried at 60 ° C. for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product. The granules obtained are passed through a shaker to pass through fine particles smaller than 300 μm and particles larger than 1000 μm.

Procedure (F) 1770 g potassium thiosulfate, 200 sodium sulfite
g, 60 g of potassium bromide, 100 g of each compound of the general formula (I) and comparative compound, p-toluenesulfinic acid 20
g and 200 g of soluble starch are pulverized and granulated in the same manner as in the operation (A) of Example 1. The amount of water sprayed is 15.0 ml, and after granulation, it is dried at 60 ° C. for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product. Then, in the same manner as in the operation (E), 300 μm to 100 μm
Sieve particles outside the 0 μm range.

Operation (G) The granules prepared in the above operations (E) and (F) are treated at 25 ° C.
10 using a mixer in a room where the humidity is controlled to 40% RH or less.
The ingredients were mixed uniformly for 1 minute to prepare bleach-fixing replenishment granules 1 to 10 for color paper.

2) Evaluation of Moisture Resistance 1000 g of each of the granule samples obtained by the above operation was stored for 2 weeks in a constant temperature / humidity chamber adjusted to a practical storage condition of 25 ° C. and a relative humidity of 70%. The weight change (%) was measured in the same manner as in Example 1. Further, the total amount of the granules after storage and 1000 g of the granules before storage were dissolved in 10 liters of water, the concentration of sodium sulfite in the solution was measured by high performance liquid chromatography, and the residual ratio was the same as in Example 1. (%) Was measured. The above results are shown in Table-5. 3) Evaluation of dissolution rate 200 g of each of the granule samples obtained by the above operation was added to 2 liters of hot water at 35 ° C., while rotating at a speed of 50 rpm while maintaining the temperature, until all the granules were completely dissolved. The time was measured. This measurement was repeated twice and the average value of the two times was shown as the dissolution time in Table-5.

[0044]

[Table 5]

As shown in Table 5, the granules to which the comparative compound was added had a high hygroscopicity and were deliquescent and were lost in the form of granules. The residual rate of sodium sulfite is also low. On the other hand, the granules using the optical brightener of the present invention had a reduced hygroscopicity, did not reach the deliquescent state of the granules, and had no handling problem. In addition, the residual rate of sodium sulfite is clearly improved. Furthermore, regarding the dissolution time,
While none of the comparative examples dissolved within 30 minutes, in the present invention, all dissolved within 20 minutes, and a clear improvement effect was observed.

Example 3 1) Preparation of tablet for stable replenishment for color paper Operation (H) 10 g of potassium carbonate, 1-hydroxyethane-1,1-
200 g of sodium diphosphonate is pulverized and granulated in the same manner as in the operation (A) of Example 1. The amount of water sprayed is 1.0 ml
After granulation, the granules are dried at 70 ° C. for 3 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Procedure (I) The compound of the general formula (I) and the comparative compound (150 g), sodium sulfite (300 g), zinc sulfate heptahydrate (20 g) and ethylenediaminetetraacetic acid (150 g) were pulverized and prepared in the same manner as in Example 1 (A). Grain. The amount of water sprayed is 10.0 ml, and after granulation, it is dried at 65 ° C. for 5 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 8 hours to almost completely remove the water content of the granulated product.

Operation (J) The granules prepared in the above operations (H) and (I) were treated at 25 ° C.
10 using a mixer in a room where the humidity is controlled to 40% RH or less.
Mix evenly for a minute. Then, the mixture was mixed with a tablet press modified from Kikusui Seisakusho's Tough Press Collect 1527HU.
Compressing tableting was performed with the filling amount per tablet being 5 g to prepare a necessary amount of stable supplement tablets for color paper. 2) Evaluation of Moisture Resistance Twenty-five tablet samples obtained by the above operation were stored under the same conditions as in Example 1 for 4 weeks, and moisture absorption was evaluated by the same method. Next, 5 tablets each before and after storage were dissolved in 1 liter each of water, and the concentration of sodium sulfite in the solution was measured by the iodometric titration method, and the residual rate (%) was measured in the same manner as in Example 1 below. .
The above results are shown in Table-6. 3) Evaluation of solubility 10 tablet samples each obtained by the above operation were added to 2 liters each of hot water at 35 ° C., dissolution time was measured in the same manner as in Example 1, and the results are shown in Table 6. Posted.

[0049]

[Table 6]

As shown in Table 6, it is clear that the use of the optical brightener of the present invention can significantly improve the moisture resistance and the solubility even in the stable supplement tablet.

Example 4 Sample No. 1 of Example 1 Operation (D) for 1 and 14
50 g of soluble starch dried in vacuum at 40 ° C. for 120 minutes was added, and the same procedure as in Example 1 was repeated. 1B and 14B were produced. Sample No. 1,
14, 1B and 14B were stored in a constant temperature and constant humidity chamber adjusted to 25 ° C. and a relative humidity of 70% for 5 weeks, and the weight change and the residual ratio of the color developing agent were measured as in Example 1. The results were as follows. Sample No. Weight change (%) Residual rate (%) 1 9.0 97.5 Invention 1B 6.2 99.0 Invention 14 23.5 72.6 Comparative Example 14B 23.0 73.0 Comparative Example From the above results It is clear that the inclusion of soluble starch can further improve the moisture resistance.

[0052]

EFFECT OF THE INVENTION Moisture resistance is excellent and solubility can be remarkably improved.

Claims (2)

[Claims] 1. A solid processing agent for a silver halide photographic light-sensitive material, comprising a compound represented by the following general formula (I). Embedded image In the general formula (I), L ¹ and L ² may be the same or different and are represented by —OR ¹ or —NR ² R ³ . Here, R ¹ , R ² and R ³ each represent a hydrogen atom or an alkyl group, and L ¹ and L ^{2 each} have 4 or more substituents selected from the following group A in one molecule. . Group A: -SO ₃ M, in -OSO ₃ M, -COOM above A group, M represents a hydrogen atom, an alkali metal, ammonium. 2. The solid for a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a tablet-shaped processing agent obtained by pressurizing a powder and / or granular processing agent component. Processing agent.