JPS5995530A - How to harden gelatin - 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 a method for hardening gelatin. More specifically, the present invention relates to a method for accelerating the hardening of gelatin-containing photographic layers.

Generally, silver halide photographic light-sensitive materials include a silver halide emulsion layer coated on a support such as a film base such as cellulose ester, polyethylene terephthalate, or polystyrene, paper, waterproof paper, synthetic paper, or glass. Emulsion protective layer, filter layer, intermediate layer, undercoat layer, if necessary.
It consists of auxiliary layers such as an anti-halation layer and a banking layer. Photographic materials such as image-receiving elements without a silver halide emulsion layer are also known in the diffusion transfer process.

The layers constituting these photographic materials often mainly contain gelatin and/or gelatin derivatives.

However, the layer containing gelatin and/or gelatin derivatives (hereinafter referred to as gelatin-containing layer) has abrasion resistance,
Since they have poor dimensional stability, flexibility, and water resistance during photographic processing, gelatin hardeners are applied to these layers in order to maintain physical strength that can withstand practical use as elements constituting photographic light-sensitive materials. It requires the use of various additives, including: Aldehyde hardeners, which have been known for a long time, can provide a high degree of hardness, but deteriorate photographic properties.

Many non-aldehyde hardeners have been proposed for hardening gelatin-containing layers, but many of these hardeners thicken the photographic emulsion, making it difficult to coat. However, due to the slow curing speed, the coating layer required a long aging period, and attempts to accelerate curing by humidification may result in variations in hardness due to uneven temperature, and characteristics are often impaired.

Also, if a large amount of hardener is used to reach the required level of hardening in a short period of time, the hardening agent may adversely affect the photographic properties or cause the hardening to progress gradually over time, eventually resulting in hardening. This causes the so-called posterior dura mater phenomenon, which occurs when the membrane goes too far.
This is preferable since it significantly inhibits developability.

In order to solve one or more of these problems in the use of hardeners, auxiliary agents that increase the degree of hardening by hardeners or accelerate the curing speed, as well as their application methods, are known. For example, in Japanese Patent Publication No. 48-13709, a salt formed from a volatile acid and a nonvolatile alkali, such as sodium acetate, is used as an auxiliary agent to volatilize the acid during coating and drying to increase the pH within the gelatin layer. It has been shown that hardening agents can increase the degree of hardening. The auxiliary agent described in this patent, such as sodium acetate, can very effectively increase the degree of hardening, but the viscosity of the gelatin coating solution increases significantly over time, and the acid gradually volatizes even after the gelatin layer is formed. However, it has serious drawbacks, such as the fact that the pH within the layer increases too much, resulting in significant negative effects such as fog.

Furthermore, although the melting temperature of the seratin layer, which indicates the degree of hardening, is high, the mechanical strength of the gelatin layer is insufficient.

To explain this in more detail, as gelatin is hardened, the melting temperature and mechanical strength of the gelatin layer will change as the gelatin layer hardens.
(See the example of the above-mentioned Japanese Patent Publication No. 48-13709). However, all curing methods do not have the same or similar correlation with the above two parameters, and depending on the curing method, there are cases where the mechanical strength is high compared to the melting temperature, and some cases where the mechanical strength is high compared to the melting temperature. The opposite may be the case. The second reason for this mechanism is unknown. The high melting temperature means
For example, it is suitable for high-temperature processing, but it is generally not possible to increase the absorption amount of the processing liquid to an extremely high level. Therefore, it can be said that the higher the degree of hardening in Limit 9, the better.Therefore, it is desirable to use a gelatin hardening method that provides as high mechanical strength as possible when the degree of hardening is set to the desired melting temperature or liquid absorption amount. .

Furthermore, Japanese Patent Application Laid-open No. 51-9434 discloses that by simultaneously applying multiple layers of gelatin coating liquid containing alkali salts such as sodium acetate and sodium citrate or amines and gelatin coating liquid containing a hardening agent, It has been shown to promote dura mater.

Although this method is useful as an initial hardening acceleration method in a multilayer simultaneous coating method, it still has the drawbacks of increasing the pH within the coating layer due to volatile acids such as sodium acetate and low mechanical strength against melting temperature. ing. Others: JP-A-47-30088, JP-A-55-46745
Although various hardening aids are also described in the Japanese Patent Application Publication No. 2003-111003, published in 1993, published in 1993, published by J.D., 1993, 1993, 1993, 1993, 1993, 1993, and the like, they often gave unsatisfactory results as well.

The purpose of the present invention is to reduce the increase in viscosity of gelatin coating liquid over time, increase the degree of hardening due to melting temperature or liquid absorption amount,
It is another object of the present invention to provide a method for hardening gelatin which has a significantly high mechanical strength and which uses the minimum amount of hardening agent necessary to reach the desired saturation hardening level; It is an object of the present invention to provide a stable curing method for ceratin that can reach a saturation curing level in a short period of time and is free from post-curing development and fogging.

Other objects and advantages of the present invention will be understood from the following description of the specification.

The above object of the present invention was achieved by using an alkali salt of oxydicarboxylic acid as a hardening aid for a non-aldehyde organic hardener as described below.

Oxydicarboxylic acids include DL-malic acid, L-malic acid, tartaric acid, dihydrotartaric acid, hydrogen tartrate, and the like. Alkali salt means an alkali metal salt such as sodium, potassium, lithium, etc.

Particularly useful organic hardeners for the present invention include active halogen type hardeners, active olefin type hardeners, epoxide type hardeners, aziridine type hardeners, and N-type hardeners such as those described in JP-A-55-46745. - Methylol-type hardeners, etc. As is well known, these hardeners do not provide sufficient hardening levels unless hardening aids are used, and it is difficult to reach a saturated hardening level, especially during a difficult period after application. Since the post-curing phenomenon is likely to occur, the effects of the present invention are more pronounced. Active halogen type hardeners are disclosed in, for example, Belgian patents 579,739 and 598.272, and West German patent 1.
, 130,283, West German Published Patent No. 1,9,00,79
1, U.S. Patent No. 2,169,513, U.S. Patent No. 2.732,
303, 297.61'50, 2,976,152
, 3.106,468, 3,542,549, 3
, 549,377, 3.645,743, 3,68
9,274, 3,701,664, British Patent 941,
998, 974,723, 990,275, 99
7,635, 1,022,656, same], 072,
008, 1.167, 207, Special Publication No. 39-1692
8, 47-33380 and the like.

Active olefin type hardeners are disclosed in, for example, West German Patent No. 872,
153, same 1. , 090427, same 1. ,100,94
2, 1.105,272, 1,622,260,
, U.S. Patent No. 257987L 3,255,000,
3,490,911, 3,640,720, 3,
642,486, 3,687,707, 3,749
, 573, British Patent No. 994,869, No. 1,054,1
23, 1,115,164, 1. ,158,263
, same 1. , 182,389, 1,183,648, Special Publication No. 44-23238, No. 47-8736, No. 47-2
This includes those described in patent specifications such as No. 5373.

Epoxide type hardeners are, for example, Belgian patent 578,
751, West German Patent No. 1,085,663, West German Patent No. 10913
22, 1,095,113, U.S. Pat. No. 2,726,1
62, 43f) 47,394, 3,091. ．． 513
, 3,179,517, and Japanese Patent Publication No. 34-7133.

For example, the aziridine type curing agent is described in Belgian Patent No. 575,
440, West German Patent No. 1,081,169, U.S. Patent No. 2.
327,760, 2,390,165, 2,950
, 197, 2.964,404, 2,983,6
11, 3,017,280. 3.220,848,
3,549,378, British Patent 797,321, Italian Patent 572,862, Japanese Patent Publication No. 33-/1212,
It includes those described in patent specifications such as No. 37-8790.

The amount of organic hardening agent used is 0.01 per gram of Seratin.
~i,o It can be arbitrarily changed within a range of about millimole.

The amount of the compound used as a hardening agent varies depending on the type of hardening agent and the type of emulsion, and there is a wide selection range, but it is approximately 0.
It is effective at about 1 to 2 mmol. Further, it may be added at any stage of preparing a coating solution for forming a gelatin film, but when added to a silver halide emulsion,
Generally, it is preferable to add it after the 241st formation of the silver halide emulsion.

Even if the hardening aid is added to a gelatin coating solution containing an organic hardening agent, the gelatin coating solution will not thicken and can be coated stably, and as described in JP-A-51-9434, ,
Another effective method is to contain a hardening aid and an organic hardener in separate ceratin coating solutions and apply them simultaneously in multiple layers. The pH of the gelatin composition containing the hardening agent and auxiliary agents is preferably from about 4 to about 8, particularly from about 5 to about 7.

The seratin-containing composition of the present invention may contain acid-treated seratin, improved latin, and derivative seratin in addition to lime-treated seratin, which is commonly used as seratin, and may further contain polyvinyl alcohol, polyvinylpyrrolidone, cellulose, In addition to water-soluble derivatives such as pun, it can also contain polymeric substances such as latex.

In addition to silver halide, there are also various additives necessary to compose photographic materials, such as stabilizers, antifoggants, toning agents, spreading agents, photosensitive dyes, coating aids, antihalation and irradiation dyes, and In addition to these dye fixing agents, physical development nuclei, color photographic materials, etc. can contain foggers, high boiling point oils, antioxidants, color staining and color mixing prevention agents, etc. The presence of substances does not limit the invention.

Examples are shown below.

Example 1 A silver chloroiodobromide gelatin emulsion having a composition of 65.5 mol of silver bromide and 34.0 mol of silver chloride to 0.5 mol of iodide and an average grain size of 0.45 μm was prepared using a neutral single jet. 1 piece prepared by the method.

After physical ripening, desalination is performed depending on water conditions, gelatin is added,
Next, sodium thiosulfate was added to perform chemical sensitization, and then a stabilizer and a surfactant were added to finish the emulsion.

Gelatin of this emulsion xIIffiD, o, after adding x millimoles of the following hardening agent, it was subdivided into 1 part (blank without auxiliary agent), 1 part sodium tartrate (sample A), and the remainder 1 part each. 1 mmol of each of the following comparative aids B to F (samples B to F) was added per 1 g of gelatin.

Hardener - 2-oxy-4,6-dichloro-8-)riazine (Na
Auxiliary agent B for salt comparison Sodium acetate C Sodium citrate D Sodium benzoate E Sodium hydrogen carbonate F - Sodium succinate G...Disodium phosphate 3. Apply the 8 types of emulsion coating solutions obtained in this manner to a photographic paper base covered with polyethylene layers on both sides as silver nitrate.
0117m, gelatin 5.011/rrl and dried. The pH of the emulsion layer was adjusted to 6.0. These samples were heated at 35°C for 1 day, 10 days, and 50°C.
Those stored at 80% RH for 7 days were immersed in a 2% sodium carbonate aqueous solution at 20°C for 10 minutes to reduce the sphere diameter to 0.
A 5 mm ball point needle was placed on the emulsion film surface, and when the sample surface was translated at a speed of laR/sec, the load (I) of the ball point needle that caused damage to the gelatin film was measured. The results are shown in Cloth-1.

Table 1 In addition, the melting point of the above sample in a 2% aqueous sodium carbonate solution was investigated. Since all samples other than the samples heated at 35°C for 1 day were 90°C or higher, only the samples heated at 35°C for 1 day are shown in Table 2.

Table 2 The results in Table 1 show that sample A of the present invention using sodium tartrate has higher film strength in a short period of time than comparative samples B to G using other alkali salts. Also,
It is also understood from Tables 1 and 2 that the mechanical strength of the samples of the present invention is high even though there is no significant difference in melting temperature.

Furthermore, Table 3 shows the emulsion film PH value of each sample after heating.

Table-3 Sample AXC! It can be seen that , F and G are stable with small PH changes. As the pH increases, disadvantages such as fogging occur, and when the pH increases to about 7 or more, significant fogging occurs. It is also understood that Samples BXD and E have a significant adverse effect on photographic properties.Example 2 The organic hardening agent described in JP-A-51-9434, Denka-55-46745 was added to gelatin II at 9.0%. A 5% gelatin aqueous solution containing .13 mmol was prepared at pH 5.5 (solution A
~F) COOH=OH2 / \ cocm=aHt OHt N HOOOOL0HtSOtOH=OLOH
! OH C! &0H 8f Meanwhile, gelatin II, sodium tartrate (solution 2)
Or a 5% gelatin aqueous solution containing 1 mmol of sodium acetate (solution Y) and a 5% gelatin aqueous solution without it (
Solution X) was prepared.

On a corona discharge treated polyethylene laminate support, using a slide hopper type extrusion coating device, the hardening agent-containing gelatin solutions A to F were applied at 601/d (moisture) and the bath solutions x to z at 201// The solutions A to F were combined in the same manner as i, and multilayer coating was performed at the same time so that the solutions A to F were on the side closer to the support.

These samples were left at 35° C. (no humidity conditioning) and 50° C. in an 80-inch dish, and then the film strength was measured in the same manner as in Example 1. The results are shown in Table 4.

Table 4 The results in Table 4 show that sodium tartrate has the same effect as Example 1 on various organic hardeners.

Example 3 The film strength and melting temperature were investigated according to the method of Example 1, except that sodium salts of DL-malic acid and dihydroxytartaric acid were used as hardening aids, and are shown in Table 5.

Table-5 Procedural amendment (voluntary) Showa S and year //71. , 2δ day 4 car ii'l - Director-General Kazuo Wakasugi 1, Indication of the case 1981 Patent Application No. 2o633δ 2,
Name of the invention: Senna 7's hard-bore Otomanmemi 3, relationship with the case of the person who made Micho Patent Applicant's address: 4-2, Shiratama-chome, Maruno, Chiyoda-ku, Tokyo Name (598) Company 4 Agent Address Address: 4-2, 3-1 Marunouchi, Chiyoda-ku, Tokyo 100
No. Mitsubishi Paper Mills Co., Ltd. 5, date of the amendment order, Showa year, month, day 6, number of inventions increased by the amendment, 7, moon of the amendment (1), day after day, tea 2, shellfish, 71st point r (zuiyu) ε

Claims (1)

[Claims] (1) A gelatin hardening method characterized by using a non-aldehyde organic hardener and an alkali salt of an oxydicarbono acid.