JPS5965846A - Developing device - Google Patents

Abstract

PURPOSE:To enable adequate developing process by providing at least three conduits for conducting respectively a pH adjusting agent, reducing agent and metallic compd. to be replenished into a developing tank, joining these conduits to one conduit in the med-way and connecting the same to the developing tank. CONSTITUTION:A preliminary tank 24 is connected through a conduit 26 to a reducing tank 20. A pump 28 which is controllable of a number of rotation or rotating time and a flow rate regulating valve 30 are provided to the conduit 26. Three preliminary tanks 32, 34, 36 are connected through conduits 38, 40, 42 to a developing tank 22. Said conduits are joined to one conduit 44 just before the tank 22. Then, three kinds of liquids in the above-mentioned three tanks are admitted into the tank 22 under mixing and are uniformly dispersed in the tank 2, whereby the adequate developing process is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an apparatus for developing an image forming material through processes such as reduction and development.

As shown in FIG. 1, the image-forming material processed in the present invention comprises a support (10) provided with an image-forming layer (12).

Supports include glass, paper, plastic film,
Any material such as nonwoven fabric can be used, but polyester film, triacetate film, etc. are particularly suitable. These supports may be treated with corona discharge, if necessary.
An image forming layer is provided after performing adhesion improving treatment such as primer treatment.

The image forming layer is formed by dispersing, preferably dissolving, in a hydrophilic binder, a metal compound which is reduced to become metal development nuclei and a compound having a diazo group or an azide group.

As the binder, natural polymers such as gelatin, casein, glue, gum arabic, shellac, etc., carboxyl methyl cellulose, egg albumin, polyvinyl alcohol (partially saponified polyvinyl acetate), polyvinylpyrrolidone, polyethylene oxide, etc. are used. Materials other than those mentioned above can be used as long as they form an image forming layer and have such hydrophilicity that when they come into contact with a developer, the developer penetrates and physical development is possible.

Metal compounds that are reduced to give metal development nuclei include chlorides of responsible metals such as palladium, gold, silver, platinum, and copper;
Water-soluble salts such as nitrates, such as palladium chloride, silver nitrate, gold tetrahydrogen chloride, etc., which are contained in the activator solution for electroless plating, are used. Among these, water-soluble salts of palladium, gold, platinum, and copper, particularly water-soluble salts of palladium, are preferably used.

The image forming layer is preferably formed by mixing an aqueous solution of the above-mentioned metal compound (a commercially available actipator liquid for electroless plating can be used as is) with an aqueous binder solution together with a compound having a diazo group or an azide group, and applying the mixture. A liquid with a suitable viscosity of 10 to 1000 centiboise,
By coating this on a support and drying it, it is usually
．． It is obtained as a coating film with a thickness of 1 to 30 μm.

In addition to the water mentioned above, a mixed solvent of water and a water-miscible solvent such as a lower alcohol, ketone, or ether may also be used as the solvent.

As the compound having a diazo group or an azide group, for example, a water-soluble zinc chloride double salt, sulfate, or phosphate having a diazo group, or a diazo resin obtained from these are preferably used.

The image forming layer (12) contains the binder 100 described above.
part: 0.1 to 100 parts of metal compound, especially 1 to 100 parts
10 parts, 1 to 10 parts of a compound having a diazo group or a kl azide group
It is preferably included in a proportion of 100 parts, particularly 20 to 50 parts.

After forming the image forming layer, hardening treatment is desirably performed in order to suppress elution of the binder into the developer during physical development. Hardening treatment is performed using AA compounds such as potash bright bread, ammonium bright bread, nichrome bright bread, C such as chromium sulfate, etc.
By mixing a compound such as r compound in the coating solution for forming the image forming layer at a ratio of, for example, 0.1 to 50 parts per 100 parts of the paint, or by coating the aqueous solution on the image forming layer. will be carried out.

Next, to explain an image forming method using the image forming material, first, as shown in FIG.
For example, pattern exposure is performed through a transparent original ([4)]. As a result, the compound having a diazo group or an azide group is selectively decomposed in the exposed area (16) depending on the exposed area. As the light source, any light source that can decompose the diazo compound or azide compound described above can be used. For example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an arc lamp, a chemical lamp, a xenon lamp, an Ar laser, etc. can be used. Depending on the desired image gradation, for example, when using ultraviolet light having a center wavelength of 4050 m, exposure may be performed for 10 to 200 seconds at an intensity of I W/n11 to 300 W/m'.

Next, the image forming layer (12) having a latent image in which a compound having a diazo group or an azide group is broken up in a pattern is brought into contact with the aqueous reducing agent solution by dipping or coating. As shown in Figure 3, metal development nuclei are generated almost uniformly in the image forming layer. As the reducing agent, a strong reducing agent such as stannous chloride, stannous sulfate, or sodium borohydrate is used. This reduction treatment varies depending on the strength of the reducing agent, but generally the reducing agent is
Using a reducing agent solution containing a concentration of 0 Vl, the reaction is carried out at room temperature or under heating for about 10 seconds to 400 seconds.

Further, a physical developer is brought into contact with the thus obtained image forming layer (12) having a latent image formed by selective decomposition of the compound having a diazo group or an azide group by dipping or coating, A visible image (18) as shown in FIG. 4 is formed in the exposed area, in which the metal in the developer is precipitated by reduction, centering on metal development nuclei.

As the physical developer, an aqueous solution containing a water-soluble reducible heavy metal salt and a reducing agent is used, if necessary, in a heated state.

As the reducible heavy metal salt, for example, water-soluble salts of Group IB metals such as nickel, cobalt, iron and chromium, and Group IB metals such as button are used alone or in combination. Suitable water-soluble reducible heavy metal salts include, for example, cobaltous chloride and cobaltous iodide.

These reducible heavy metal salts are contained in a physical developer solution, for example, 1
．． It is contained in a proportion of 0 to 100 Vl.

As the reducing agent, for example, hypophosphorous acid, sodium hypophosphite, etc. can be used.

These reducing agents may be added in the physical developer, for example, from 0.1 to 5
0 f! /l is used.

Some of the effective reducing agents contained in the physical developer overlap with the reducing agents responsible for the generation of metal development nuclei. Therefore, when using a physical developer that contains a relatively strong reducing agent, do not perform reduction treatment to prevent the generation of metal development nuclei after 5 exposures, but directly process with the physical developer to prevent the generation of metal development nuclei and physical development. They can also be done substantially simultaneously.

However, if the reaction is carried out in two stages, there is an advantage that the reduction reaction and the metal precipitation reaction can be controlled accurately by adjusting the temperature and reaction time, respectively.

In order to prevent the heavy metal ions generated by dissolving the reducible heavy metal salts from precipitating as hydroxides in the physical developer, for example, monocarboxylic acids; dicarboxylic acids: hydroxides such as malic acid and lactic acid are used. Quinicarboxylic acid; one or more complexing agents consisting of organic carboxylic acids such as conolilic acid, citric acid, aspartic acid, glycolic acid, tartaric acid, ethylenediaminetetraacetic acid, glyconic acid, sugar acid, and quinic acid. can be included. These complex chloride forming agents are used in the physical developer in a proportion of, for example, 1 to 1 Q OVl.

In addition, the physical developer contains PI- (regulators, buffers, preservatives, brighteners, interfacial agents, etc.) such as acids and bases to improve the storage stability and operability of the developer and the quality of the resulting images. An activator and the like are added as necessary according to a conventional method.

Alternatively, in addition to the above, the image forming material shown in FIG. 1 may be sequentially subjected to reduction treatment to prevent generation of metal development nuclei, pattern exposure treatment, and physical development treatment in this order. Compared to the image forming method described above, this method requires washing with water and drying before exposure, so there is a problem that the number of steps is increased, but the same image can be obtained in either case.

The image forming materials and image forming methods described above have many advantages as follows.

In other words, it has a light transmission density of 4 or more, and can form a black image with gradations as required. Also, since it uses a development inhibitor dissolution system, it has high resolution, and can be used as an alternative to images produced by silver salt photography. is obtained. Furthermore, since the image is a metal image, it can be corrected using a reducing solution such as Farmer's reducing solution consisting of red blood salt and sodium thiosulfate, or Kodak R-4. Taking advantage of these characteristics, the above image materials can be used as a substitute for lithium film or as a mask.
It is Noh. For example, the first development is performed in a nickel plating bath using a boron-based reducing agent, and the second development is performed in a high temperature nickel plating bath at 65 to 90°C using a reducing agent containing sodium hypophosphite or copper plating. If plating is performed under high-speed plating conditions, a metallic image with metallic luster can be formed on the binder surface. Moreover, the obtained image can be used for example with hydrochloric acid 5
Since the binder in the non-image area can be selectively removed by treating with a 5-chloride or nitric acid aqueous solution for 5 minutes, it can also be used as a printed circuit board.

The present inventors have developed a device for automatically carrying out development processing on the above image forming materials.
14).

This device consists of a tank that stores a reducing solution containing a reducing agent, a tank that stores a developer solution that contains a reducing agent and a metal compound, etc., which are connected in one direction, and a large number of rollers are installed in each tank. By driving the rollers, the image forming material on which the latent image has been formed travels and is immersed in the processing liquid in each tank. .

By using this device, sheet-like or continuous image-forming materials can be automatically developed and good images can be obtained, but each storage tank is configured to simply store processing liquid. As the number of sheets processed increases, the reducing agent and metal are consumed, resulting in a decrease in image density.・Also, the developer generally contains ammonia, Na, etc. to increase the metal precipitation rate.
Alkaline materials such as OH are often used), and in the development of the above-mentioned image materials, high-density images without capri can be quickly obtained using the above-mentioned alkaline materials. [2] However, when using this alkaline thread, especially ammonia, unless the pH is kept constant, the development speed cannot be controlled and good images cannot be obtained.

The present invention aims to solve the following problems associated with fatigue of the processing solution.The present invention measures the metal ion concentration and PII in the developer described above, and uses the values to determine the concentration of the developing bath. On the other hand, metal compounds and reducing agents.

The system is characterized in that the components in the eight tanks are controlled within a certain range by replenishing the pH control agent and, at the same time, replenishing the reducing agent in the reducing bath.

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a developing processing apparatus according to the present invention will be described below based on the drawings.゛FIG. 5 is a schematic diagram of the developing processing apparatus.

In the figure, (20) is a reducing tank in which a reducing agent solution is stored, and (22) is a developing tank in which a developing solution containing a reducing agent, a metal compound, etc. is stored. An image forming material (FIG. 2) having a latent image is sequentially immersed in each tank and subjected to development processing.

A reserve tank (24) is connected to the reduction tank (20) via a conduit (26). The tank (20) stores, for example, a 5-fold diluted aqueous solution of Knife Lad 7544-2 (manufactured by Okuno Pharmaceutical Co., Ltd.) as a reducing agent, and the tank (24) stores its undiluted solution. The conduit (26) is equipped with a pump (28) that can control the rotation speed or rotation time, and a flow rate adjustment valve (
30) is provided.

developing! (22) has three reserve tanks (32) (34)
(36) is Miki's conduit (38) (40) (42)
These conduits merge into a single conduit (44) before the tank (22). As a result, the three types of liquids in the three tanks are mixed and I! (2
2) Flow inside.

It will be uniformly dispersed in the tank.

In this case, the tank (22) contains non-ammony chemical nickel A.
(manufactured by Okuno Pharmaceutical Co., Ltd.) and 1/1 mixture of the same B (manufactured by the same company).
A doubly diluted aqueous solution is placed in the reserve tank (34), and the reserve tank (34) contains a stock solution of non-ammony chemical nickel B, which is a reducing agent for development, and the stock solution of non-ammony chemical nickel A, which is a metal compound solution for development, is placed in the reserve tank (36). However, the preliminary tank (32) contains a pH adjuster Na0)4 aqueous solution (for example, pH==
11) is included. The above conduit (38) (40)
(42) are respectively rotation speed or rotation time controlled pumps (
44) (46) (48) and flow rate adjustment valve (50)
(52) (54) are provided.

In addition, the tank (22) is provided with a tube # (51) for circulating the developer, one end of which is connected to the above-mentioned conductor %' (
44). Part of the liquid coming from conduit (44) flows directly towards N4 (22), and the remainder flows into conduit (5).
0) and is pumped by the pump (56).

It passes through a filter (58) and flows into the tank (22). Therefore, the above preliminary tanks (32) (34)
The liquid from (36) is more uniformly mixed and 411'/
(22) and subjected to development processing.

In addition, (6o) is a floating liquid storage tank, tank (20) (2
This is to receive the liquid that overflows from 2).

Here, in the present invention, the preliminary tank (24) (32) (34) (36
) to automatically feed consumable substances into the tank from the tank (
A portion of the developer is taken out from 22) and its pH and metal ion concentration are measured, and based on the results, the pumps (28), (44), (46), and (48) are driven to replenish the consumed amount. ing.

This is based on the findings of the present inventors as follows.

That is, the developing conditions for the image forming material are mainly influenced by four factors: pH 1 of the developer, concentration of the metal ion-concentrated reducing agent, and concentration of the reducing agent in the reducing tank. Of these, the concentration of metal ions and the concentration of the reducing agent change in relation to the development area, and the pH is the evaporation of alkaline components in the developer during development (when ammonia is used as a H regulator).
Alternatively, it changes with fatigue (when sodium hydroxide is used as a pH adjuster), and the situation is illustrated in FIG.

Figure 6 shows the changes in the degree of fatigue with respect to the processing area of the image forming material using sodium hydroxide, a mu-based chemical nickel developer, and a Siba nickel reducing solution (manufactured by Okuno Pharmaceutical Co., Ltd.). There is.

(1) Mix and prepare a photosensitive material coating liquid having the following composition in order from above.

Myabar+36 was applied onto a polyester film (Lumirror Q, -82 manufactured by Toshi Co., Ltd.) that had been subbed in advance and dried.

(2) After exposing the above image forming material with an ultra-high pressure mercury lamp (50
Development processing is carried out at a speed of mJ/c+li), 181nch/9)-.

(3) As the development process continues, the reducing agent concentration, Ni ion concentration, and pH in the developer, as well as the reducing agent concentration in the reducing tank, are measured for each predetermined development area and graphed.

(4) Set the limit value of the development area to obtain the allowable light transmission density to 0.
．． It is set to 8ηl. In the experimental example shown in the graph, if an image area of 0.8 m' is processed per 17 I of developer, the relative concentration of the reducing agent (sodium hypophosphite) in the developer decreases to 0.6. , the relative concentration of the reducing agent (boron-based) in the reducing solution has decreased to 0.98. Still, the relative concentration of Ni ions has decreased to 0.88 and the pH has decreased to 85.

The relative concentration is determined by dividing each component (Vl) after use by each component (Vl) in the reducing solution or developer before use.

As can be seen from FIG. 6, the development area is within the Ω range (0.0 to 0.8
In mVl, the tooth ion concentration and reducing agent concentration in the developing solution and the reducing agent in the reducing solution have an approximately linear function relationship. Generally, metal ion concentration can be measured relatively easily and quickly, but reducing agent concentration +X requires a long time to measure.

Therefore, in the present invention, the concentration and pH of metal ions such as Ni ions in the developer are continuously or periodically measured, and these values are set to the lower limits of their appropriate values (for example, relative concentration 0.88. Compare with PI18.5). And if it is lower than the appropriate value, pump (2B) (44) (
46) (48) and rotate each reserve tank (24) (3
2) (34) (From 3(3), pump the fresh developing reducing agent solution, same metal compound solution, and l) H regulator and reducing reducing agent solution into the tank (20×22), respectively.

As a result, if it is detected that the ion concentration and pi (reach the upper limit of the appropriate value (for example, relative concentration 0.95.p)! 1o), these pumps are stopped. In this case, the diversion control valve (28) (46)
The opening degree of (48) is determined by the three straight lines (A, B, C) in Figure 6.
), or the operating time or rotational speed of the pump is adjusted according to the gradient.

In FIG. 5, (62) is a conduit for measuring the metal ion concentration, etc., and is equipped with a pump (64) in the middle, as well as a pH measuring device (66) and a metal ion concentration measuring device (68). ). The liquid drained from the measuring device is collected in a drain liquid reservoir (70).

The metal ion concentration measuring device (68) is a commercially available device using a desired method such as redox potential method, spectroscopic absorption method, or titration method (for example, PP-4 manufactured by Rika Kenkyujo Co., Ltd.) and compared with the above appropriate value. A comparator (the company's gPp) that outputs a predetermined signal
-coN-i) etc. (not shown).

For example, the pH measuring device (66) is (NP made by Ikeda Rika Co., Ltd.).
H-550) and a comparator (not shown) similar to the above.

Next, the operation of the above-mentioned development processing apparatus will be described.

The developing tank (22) and the reducing tank (20) are filled with a developing solution and a reducing solution in advance, respectively, and are filled with a developing solution and a reducing solution, respectively, by the operation of the pump (56).
! 7. The developer is circulating.

Therefore, the image forming material is stored in the reducing tank (20) and the developing tank (22).
They are soaked one after another and developed, and this process is repeated for several sheets or meters.

Further, the pump (64) is driven to partially extract the developer, and the PH1 metal ion concentration is measured by the measuring devices (66) and (68), respectively, and compared with the appropriate value.

If the measured value becomes lower than the appropriate value due to repeated development processing, output is generated from each device, which rotates the pumps (44), (46), and (48), and discharges each reserve tank (
32) (34) A pH adjusting solution, a fresh reducing solution, and a metal compound solution are supplied from (36) into the developing tank (22),
Fresh reducing liquid is also supplied from the container (24) into the υ reduction tank (20) by the pump (28). Then, if the freshness in the developer solution returns to its original state with these replenishing solutions, recovery is recognized as the metal ion concentration and pII value reaching the appropriate values, and each pump ( 28)
(44), (46), and (48) are stopped.

In this way, by repeating the above-described operations, proper development can always be carried out automatically.

The developed image forming material is then subjected to hardening and washing processes as required.

As described above, the development processing apparatus according to the present invention comprises a developing tank storing a developing solution containing a reducing agent and a metal compound, and a reducing tank storing a reducing solution containing a reducing agent. In the development processing apparatus for forming materials, at least three conduits are provided to respectively guide a pH adjusting agent, a reducing agent, and a metal compound to be replenished into the developer tank, and these conduits are used as one conduit midway into the developer tank. A pH measuring device and a metal ion concentration 61+1 determining device are connected to the reducing tank, and a conduit for guiding a reducing agent to be supplied into the reducing tank is connected to the reducing tank, and a pH measuring device and a metal ion concentration 61+1 determining device are connected to the reducing tank, respectively, and measure the pH 1 and metal ion concentration of the developer in the developing tank. Each of the conduits is equipped with a pump that rotates in response to the output of the pH measuring device and the metal ion concentration measuring device when the measured values fall below the appropriate values, and a pump is attached to the developing tank. The invention is characterized in that it is provided with a developer circulation device comprising a pump and a conduit extending from the conduit to other parts of the developer tank.

Therefore, according to the present invention, it is possible to use a reduction method and a developer that are always in an appropriate state for development processing.

Furthermore, since the reducing agent and the like can be mixed during the process and replenished into the developing tank, appropriate development processing can be carried out even during the replenishment of the liquid.

Furthermore, since a portion of the above replenishment is collected and sent to the developer tank, it is possible to make the developer solution uniform in the developer tank, and to properly measure its pH, etc. be effective.

[Brief explanation of the drawing]

1 to 4 show an example of an image forming material processed by the development processing apparatus according to the present invention. FIG. 1 is a schematic cross-sectional view of the image forming material 44 before image printing, and FIG. A similar cross-sectional view of the same material during image printing (;0 cross-section; FIG. 1 and FIG. 3 are subjected to reduction processing in a developing processing device), and FIG. 4 is a similar cross-sectional view of the same material subjected to visual processing. Figure 5 is related to the present invention.
FIG. 7 is an explanatory diagram of the configuration of a filter development processing apparatus ρ-example. ). Figure 6 is an example of a developer fatigue level measurement graph.

Claims (1)

[Claims] In an image forming material development processing apparatus comprising a developing tank storing a developing solution containing a reducing agent and a metal compound, and a reducing tank storing a reducing solution containing a reducing agent,
At least three conduits are provided for respectively supplying a pH adjuster, a reducing agent, and a metal compound to be supplied into the developer tank, and these conduits are connected to the developer tank as one conduit midway, and the 74-component tank is connected to the developer tank. A conduit for introducing a reducing agent to be supplied into the developer tank is connected to the reduction tank, and a Pal measurement device and a metal ion concentration measurement device are installed to measure the pH and metal ion concentration of the developer in the developer tank, respectively. The conduit contains the above py al! A pump is provided which rotates in response to the output when the measured values by the 1-determining device and the metal ion concentration measuring device fall below the appropriate values, and a conduit that connects to the developer tank leads to other parts of the developer tank. The above-mentioned device is characterized in that it is provided with a developer circulation device composed of a conduit and a pump.