JP2000267296A - Method for developing material having photosensitive resin composition and apparatus therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for developing a photosensitive resin composition by which the deposition of a dissolved component is prevented even under low replenishment, the consumption of an alkali component is suppressed, the amount of waste liquor discharged is reduced and development quality is stably retained. SOLUTION: The fatigue of a developer due to the development of a photosensitive resin composition in a developing apparatus is detected, electric current is supplied between two electrodes by way of the developer in accordance with the degree of fatigue and development is carried out while retaining the activity of the developer. The fatigue of the developer may be detected by reading the processed area of a developed photosensitive material or measuring elapsed time in which processing is not carried out in the developing apparatus or a physical property value of the developer other than the pH (particularly a physical property value selected from the electric conductivity, specific gravity and opacity).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for developing a photosensitive resin composition carried on a lithographic printing plate, a printed wiring board or a substrate used for producing an integrated circuit. In particular, the present invention relates to a developing method and an apparatus capable of stably processing a material having a plurality of photosensitive resin compositions using an automatic developing group. In particular, the present invention relates to a developing method and a developing apparatus capable of performing a stable developing process when making a lithographic printing original plate such as a PS plate.

[0002]

2. Description of the Related Art In the manufacture of lithographic printing plates such as photosensitive lithographic printing plates (hereinafter sometimes abbreviated as PS plates), printed wiring boards, integrated circuits, and the like, a photosensitive resin composition provided on a substrate is used. And developing the material layer having the object. Since this development is performed by eluting a part of the material having the photosensitive resin composition into the alkaline developer,
The alkaline developing solution in the developing tank consumes an alkaline component and its activity decreases. Further, even if the material having the photosensitive resin composition is not developed, since the surface of the developer is always in contact with air, the developer absorbs carbon dioxide in the air, and the alkali contained in the solution is absorbed by the developer. The agent components are consumed and the activity is similarly reduced. In other words, in the development processing device,
The processing fatigue accompanying the development processing of the photosensitive resin composition and the aging degradation (or aging fatigue) caused by the contact between the developer and the air are simultaneously progressing to a different degree. If the deterioration proceeds beyond a certain level, proper development processing cannot be performed. Therefore, it is known that the deterioration is recovered by replenishing the development replenisher at appropriate times.

In order to prevent a decrease in the activity of a developer,
In general, a method of correcting the alkali consumption by supplying a replenisher containing an alkali agent or a buffer at a higher concentration than the developing solution in the developing tank is adopted. This so-called replenishment method is necessary to stably develop a large amount of the photosensitive resin composition using a developing apparatus, but also has the following problems.

[0004] 1) With the replenishment, the overflow is discharged from the developing tank and becomes a developing waste liquid. However, since it cannot be discharged to the sewer, it is necessary to take measures for disposal of the waste liquid. The disposal of the waste liquid is costly, and the disposal itself
With environmental impact. 2) Performing replenishment results in wasteful discharge of developer components such as an alkali agent in addition to the problem described in the preceding paragraph, and is economically burdensome. 3) The photosensitive resin composition eluted in the developing solution precipitates in the developing solution having a high salt concentration and adheres to a transport system such as a roller, which causes an abnormal transportability in the developing device or a stop of the developing device. . When the cleaning is performed to remove the precipitates, the development processing device is stopped, so that the productivity is reduced and the labor of the operation is increased. 4) Chemicals added as alkali agents or buffers (silicates, phosphates, etc.) increase the salt concentration, and the components dissolved from the photosensitive resin composition in the transport system or tank are likely to precipitate (especially silicates). .

As a countermeasure for the above 1) and 2), it is conceivable to add only necessary components to reduce the loss due to overflow. As a method of adding only the necessary components, a method of directly adding the consumed components to the developing solution in use can be considered, but this takes time to dissolve the developing solution and causes trouble, and at the same time, the above-described method is used. Problem 3)
Regarding (4) and (4), the problem is aggravated. Therefore, although there is some improvement with respect to (1) and (2), it is not a practical solution to the problem of replenishment.

On the other hand, it is well known that an inert electrode is immersed in an aqueous solution of a neutral salt to cause electrolysis of water to generate hydrogen ions at an anode and hydroxyl ions at a cathode.
Since the electrolysis of water does not increase the salt concentration, it is considered to be more preferable as a measure against the above 1) and 2). In fact, it is also known that the cathodicly generated hydroxyl ions can be used to increase the pH of the developer of the silver halide photographic material.

However, in developing a material having a photosensitive resin composition such as a photosensitive material for printing using a photodecomposition reaction of quinonediazide or diazo coupling of a diazonium salt, a method of supplying an alkali agent by electrolysis is generally used. Not used. The reason is that, even though it is called a developer, the developer for a material having a photosensitive resin composition has a fundamentally different composition from the developer for a silver halide photosensitive material, and the photosensitive resin composition Since the developer of the material containing the substance contains an organic polymer component eluted by making the photosensitive resin composition soluble in water and a siloxane-based resin component eluted from the aluminum base plate, the poisoning of the electrode is prevented. That is, it is easy to predict that it is difficult to sustain the electrolytic operation stably due to so-called organic contamination.

US Pat. No. 2,541,488 discloses a method for forming a azo image in which a dye is formed by a diazo coupling reaction using an electrolytically generated hydroxyl ion. Unlike the present invention, it is realized by a newly prepared reaction system which does not contain organic and inorganic resin components and which is free from the risk of poisoning, and contains various polymer components. It is a different system from the photosensitive resin composition of interest.

Another disadvantage of the development of a material having a photosensitive resin composition with replenishment is that it is difficult to maintain sufficient replenishment accuracy when the replenishment is controlled by pH in a conventional manner. In the practical range of developing solutions for materials having a photosensitive resin composition, the salt concentration is designed to be low and the pH is kept high in order to accelerate the dissolution of unnecessary composition components. Generation of various hydroxyl ions and hydrogen ions affects the performance of the developer. Nevertheless, since the pH of the developing solution was high, the change in pH was insensitive to the fluctuation of the alkali component concentration. Therefore, it is necessary to strictly take the allowable range of the control value of pH,
Heretofore, there has been a contrivance for maintaining a stable developing performance by suppressing a pH fluctuation by a large amount of replenishment. Moreover, the high replenishment rate also contributed to the prevention of precipitation of the eluted photosensitive resin composition components. In other words, the prevention of the fatigue of the developer and the prevention of the formation of precipitates and the reduction of the development replenisher and the waste liquid are incompatible with each other. It is.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to maintain the performance of a developing solution in a developing tank by using a developing processing apparatus while replenishing the developing solution. It is an object of the present invention to provide a developing method capable of solving the above-mentioned defects and reducing the amount of a developing replenisher or a replenisher and a developing waste solution, and constantly obtaining stable development quality. Specifically, it is a development method using a development processing apparatus, which is a photosensitive resin which does not precipitate dissolved components even at a small replenishment amount, can suppress the discharge amount of waste liquid, and can stably maintain development quality without being impaired. An object of the present invention is to provide a method for developing a material having a composition.

[0011]

As a means for satisfying both the above-mentioned requirement of a low replenishment amount and a low waste liquid discharge amount, and a requirement of a high development quality and a stable operation, the present inventors have proposed a method of supplying electricity to a tired developer. We examined whether it would be effective to activate them by doing so, and basically obtained a prospect. However, even if this method was feasible, it was considered that stable maintenance of the pH value was a problem in implementation, and we examined the appropriateness management means diligently, surprisingly monitoring the pH value and managing replenishment. Instead, the present inventors have found that the object can be achieved by selecting an appropriate index of the treatment solution fatigue degree and adjusting the replenishment rate in accordance with the fluctuation of the index, and arrived at the present invention based on this finding. did.

1. A developing method for sequentially developing a material having a plurality of sheets of a photosensitive resin composition with a developer, the method comprising detecting fatigue of the developer accompanying the development of the photosensitive resin composition, and detecting the detected fatigue. A method for developing a material having a photosensitive resin composition, characterized by maintaining the activity of a developer by applying a current between two electrodes via the developer according to the degree.

2. A method for developing a material having a plurality of photosensitive resin compositions, a developing means for processing the photosensitive resin composition with a developer, and a detecting means for detecting fatigue of the developer accompanying the development, Using a developing apparatus having means for supplying a current between two electrodes existing through a developer and supply means for replenishing the generated hydroxide ions to the developer, a plurality of sheets of the photosensitive resin composition are used. Are sequentially subjected to a developing treatment with a developing solution, the fatigue of the developing solution accompanying the development of the photosensitive resin composition is detected, and, depending on the detected degree of fatigue, the above-described current applying means is operated to generate hydroxyl ions. Is supplied to the developer to maintain the activity of the developer, the method for developing a material having the photosensitive resin composition as described in 1 above, wherein

3. The method for developing a material having a photosensitive resin composition according to the above item 1 or 2, wherein the method for detecting the fatigue of the developer accompanying the development is at least one selected from the following three: (1) Reading of the processing area of the material having the photosensitive resin composition (2) Integration of the time during which the development processing of the material having the photosensitive resin composition is not performed in the developing device (3) Storage in the developing device Measurement of electric conductivity (abbreviated as electric conductivity), specific gravity or opacity of the developed developer.

4. The fatigue of the developing solution caused by the development is calculated by integrating (1) the processing area of the material having the photosensitive resin composition and (2) the time during which the developing processing of the material having the photosensitive resin composition is not performed in the developing apparatus. 4. The method for developing a material having a photosensitive resin composition according to any one of the above items 1 to 3, wherein the method is determined by combining time.

5. A developing tank in the developing apparatus and a tank for supplying current to the developer through two electrodes are connected to each other by a pipe to form a circulation system. 5. A method for developing a material having the photosensitive resin composition according to any one of the above items 1 to 4, wherein the material is reused.

6. PH at which the developer contains silicate.
6. A method for developing a material having the photosensitive resin composition as described in any one of the above items 1 to 5, which is an aqueous alkaline solution of 0 or more.

[7] The washing water according to any one of the above items 1 to 6, wherein the washing water used in the washing or stopping step following the development step is in contact with the anode and is also in electrical contact with the developer through the diaphragm. A method for developing a material having a photosensitive resin composition.

8. The photosensitive resin composition as described in any one of the above items 1 to 7, wherein the diaphragm separating the electrode chambers of the two electrodes is a bivalent selective anion exchange membrane. Development processing method of the material having.

9. Developing means for sequentially processing the material having the photosensitive resin composition with a developing solution, detecting means for detecting fatigue of the developing solution accompanying development or aging of the developing solution, and between the two electrodes via the developing solution A developing apparatus for a material having a photosensitive resin composition, comprising: an energizing means for generating hydroxyl ions by energizing; and a circulating means for coupling the developing means and the energizing means.

That is, the feature of the present invention is that, unlike a development processing method using a known electrolysis generating means of an alkali component in a silver halide photographic material (for example, this example is found in an activator processing), it is accompanied by development. That is, a detecting means instead of a pH value for detecting the fatigue of the developer is used. Since the developing solution of the silver salt photosensitive material has a sufficient buffer capacity, and there is almost no irregular pH fluctuation not related to the fatigue of the developing solution.
In that case, a method of adjusting the pH to a standard value may be performed. However, in a developer for a material having a photosensitive resin composition, the pH is liable to fluctuate, which is incompatible with photographic performance, as described above, and the pH responds to a fluctuation in the amount of an alkali component due to development. Is insensitive, so it is not appropriate to control the alkali supply amount by the pH value. Therefore, there is a need for a detection means which does not depend on pH and which correctly reflects the degree of fatigue, and the present invention can be achieved by finding such a detection means.

Preferred detection means for detecting the fatigue of the developer, which is the key to the present invention, include the following three means. (1) Reading the processing area of the material having the photosensitive resin composition. For example, in the case of a positive photosensitive material, the photosensitive member o-
When quinonediazide is exposed to light, it becomes a carboxylic acid in a developer and dissolves, and thus consumes alkali. In a developer system with poor buffering capacity, the relationship between the consumption of alkali and the fluctuation of pH is not uniquely determined, whereas the amount of the photosensitive material processed corresponds to the amount of alkali agent consumed during development. Moreover, it is an index that can be read accurately. Therefore, when the processing amount of the photosensitive material is used as an index, the degree of fatigue of the developer can be accurately detected.

(2) An integrated value of the time during which the development processing is not performed in the development processing device. The developer for the material having the photosensitive resin composition usually has a pH.
12 or more, often 12.5 or more highly alkaline,
Moreover, since the salt concentration is low, the absorption rate of carbon dioxide in the air is high. As a result, the development activity is reduced correspondingly to the amount of the absorbed carbon dioxide gas. Therefore, the deterioration with time of the developer due to carbon dioxide gas progresses in proportion to the time during which the development processing is not performed in the development processing apparatus. Under such circumstances, the pH value is not an indicator of the deterioration over time due to the absorption of carbon dioxide gas because the salt concentration of the developing solution is low and the hydroxide ion concentration is high, and the developing process is performed. The accumulated time of the time not taken is an index for controlling the alkali supply amount, that is, an appropriate means for detecting the degree of fatigue. Here, "the development processing is not performed" means that the development is performed when the power of the development processing apparatus is turned on, the temperature and the replenishment system are ready, and the material of the photosensitive resin composition is fed, that is, the so-called This is the sum of both the case of the standby state and the case of the rest state where the power of the developing device is not turned on. There is no significant difference in the absorption rate of carbon dioxide between the standby state and the idle state where neither temperature control nor stirring of the developer is performed, so ignoring the slight difference between the two. Even if the total is integrated, there is no significant effect on the accuracy of the developer management. On the other hand, the detection of the degree of the fatigue of the developer due to the development processing is described above (1), and the detection of the degree of the fatigue of the developer due to the development processing and aging (standby and stop of the apparatus) is described below ( It is detected by the method of 3).

(3) Detection of the degree of fatigue based on physical values other than the pH value. On the other hand, physical property values other than the pH value can be used as physical property detection means. In a developing solution for a material having a photosensitive resin composition, an alkali component is consumed by a development process, and this should appear as a decrease in hydroxyl ions, that is, a decrease in pH, conductivity, an increase in specific gravity, and an increase in opacity. However, as described again, the pH value does not correctly reflect the degree of fatigue of the developer due to various confounding factors,
Physical property values other than the pH value respond to the degree of fatigue, and can be used as means for detecting the degree of fatigue. Preferred physical properties that can be used for this purpose are electrical conductivity (hereinafter conductivity), specific gravity and opacity. Among them, the electrical conductivity unexpectedly reflects the fatigue level well. Probably, the high alkali and low salt concentrations greatly contribute to the conductivity of the hydroxide ions, and it is considered to be advantageous as a detection means that the concentration is in a condition substantially corresponding to the conductivity.

The fatigue of the developing solution is caused by both processing fatigue due to processing of the material having the photosensitive resin composition and aging fatigue due to absorption of carbon dioxide gas in the environment when the development processing is not performed. Therefore, it is possible to further improve the alkali supply accuracy by obtaining a combination of the processing area of the material having the photosensitive resin composition and the integrated time over time in a state where the development processing is not performed even during standby. it can.

The electrolyte used for energization for supplying alkali is:
Although an aqueous salt solution may be prepared separately from the developing solution, it is unnecessary to use an actually used developing solution for at least the catholyte, since preparation of the electrolytic solution is unnecessary (or the amount can be significantly reduced). It can be directly connected to the bath, and therefore, it is also possible to guide the tired developer to the current-carrying tank and circulate the developer while activating the developer in the current-carrying tank. This is particularly advantageous because the amount of the developer discharged as waste can be greatly reduced within a range in which the organic substances (polymer compounds and the like) eluted in the developer do not occur.

During energization, hydroxyl ions are generated in the cathode chamber to activate the developer, while hydrogen ions are generated in the anode chamber. This hydrogen ion can also be used for the development processing. That is, as explained later,
In the washing step following the development of the material having the photosensitive resin composition, it can be used to promote washing, or can be used for a neutralization operation as a priming process before discharging the waste developing solution.

The above-mentioned defects relating to the development stability of the material having the photosensitive resin composition according to the present invention can be solved as follows. (1) The amount of chemicals used in the developer is reduced, and the amount of waste liquid discharged is reduced. (2) supply of alkali is controlled by an appropriate index,
The development quality is also maintained, and stable operation without precipitation of eluted components is performed in the developer circulation system. (3) When anodic water is used as a replenisher for washing with water, particularly for washing with low replenishment, the strength of the relief image in the non-eluted region increases.

Regarding the above-mentioned organic contamination of the electrode, that is, poisoning, in the method of the present invention, deterioration of electrolysis efficiency due to poisoning is not recognized. This surprising effect is attributed to the fact that the method of the present invention for controlling the supply of alkali with an appropriate index stabilizes the developing solution in the developing tank.
Further advantages and features of the present invention are further described in the following embodiments.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for developing a material having the photosensitive resin composition of the present invention will be described in detail. [Development] A developing solution (referred to as a developing solution) to which the developing method of the present invention can be applied is any developing solution widely used in the market, and includes materials having various photosensitive resin compositions, That is, it is used for developing any of photosensitive materials for lithographic printing, photosensitive materials for printed wiring boards, and photoresists for producing high-definition patterns such as integrated circuits. A particularly preferable application object is development of a photosensitive material for lithographic printing, and among them, it is used for development processing of a PS plate, particularly a positive photosensitive resin composition. First, a developer for a developing process for a material having the photosensitive resin composition will be described.

<Developer> A preferred developer for the material having the photosensitive resin composition used in the present invention is pH.
Is in the range of 9.0 to 14.0, preferably 12.0 to 1
The developer is in the range of 3.5. In this specification, a developer means a development initiator (a developer in a narrow sense) and a development replenisher unless otherwise specified. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium And inorganic alkali agents such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used. These alkali agents are used alone or in combination of two or more.

Among the above-mentioned alkaline aqueous solutions, a developer in which the effect of the present invention is further exhibited is an aqueous solution containing an alkali metal silicate and having a pH of 12 or more. The aqueous solution of the alkali metal silicate is composed of silicon oxide S which is a component of the silicate.
The ratio of iO ₂ and alkali metal oxide M ₂ O (generally [S
iO ₂ ] / [M ₂ O] molar ratio) and the concentration can be adjusted. For example, JP-A-54-620 can be used.
04 No. as disclosed in Japanese, SiO ₂ / Na ₂ O
Is from 1.0 to 1.5 (ie [SiO ₂ ] / [Na ₂
O] is 1.0 to 1.5) and the content of SiO ₂ is 1 to 4% by weight.
As described in JP-A-7-7427, [SiO
₂ ] / [M] is 0.5 to 0.75 (that is, [SiO ₂ ] /
[M ₂ O] is 1.0 to 1.5), the concentration of SiO ₂ is 1 to 4% by weight, and the developer is based on gram atoms of all alkali metals present therein. An aqueous solution of an alkali metal silicate containing at least 20% potassium by weight is preferably used.

Various surfactants and organic solvents can be added to the developer, if necessary, for the purpose of accelerating the developability, dispersing the development residue, and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

The above-mentioned surfactants can be used alone or in combination of two or more.
001 to 10% by weight, more preferably 0.01 to 5% by weight.

An organic solvent is further added to the developer if necessary. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1
-Propanol, 4-phenyl-1-butanol, 4-
Phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol,
-Methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine and the like can be mentioned. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

The developing solution may further contain a preservative, if necessary.
Coloring agents, thickeners, defoamers, water softeners, and the like can be included. Examples of the water softener include polyphosphoric acid and its sodium, potassium, and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, and 1,2-diaminocyclohexanetetraacetic acid. Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and - hydroxy data ene-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

The appropriate addition amount of such a water softener varies depending on the chelating ability thereof, the hardness of the hard water used and the amount of the hard water. 0.01 to 5% by weight, more preferably 0.0
It is in the range of 1-0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is more than this range, adverse effects on the image area such as color omission appear.

The developed printing plate is disclosed in JP-A-54-8 / 1979.
No. 002, No. 55-115045, No. 59-5843
As described in each of the publications such as No. 1 and the like, post-treatment is carried out with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and starch derivatives. The processing apparatus used in the present invention can perform these processes in various combinations. The lithographic printing plate obtained by such a process is mounted on an offset printing press and used for printing a large number of sheets. As a plate cleaner used for removing stains on a plate during printing, a conventionally known PS cleaner is used.
A plate cleaner for plates is used, for example, CL-
1, CL-2, CP, CN-4, CN, CG-1, PC
-1, SR, IC [Fuji Photo Film Co., Ltd.
Manufactured).

The form in which the hydroxide ion obtained by energization between the electrodes via the developing solution is used as an alkali component for replenishment is to introduce the developing solution energized in the cathode chamber into the replenishing tank.
Any method may be employed, such as replenishing the developing tank with the current supplied in the cathode chamber, or replenishing the developing chamber with the liquid supplied in the cathode chamber in the circulation path of the developing tank, but a particularly preferred embodiment is used.

<Development Processing Apparatus> In the present invention, except for the part relating to the electrolysis apparatus, any general-purpose or known development processing apparatus (also referred to as a development apparatus) on the market can be used. Usually, a developing tank necessary for dissolving an image-like alkali-soluble region of the material having the photosensitive resin composition in the developing solution is indispensable, but usually a rinsing tank for washing after development (washing) Tank), a desensitizing tank and a drying unit. Further, an apparatus in which the post-processes described above are combined is also used. The features of the present invention are that the use of hydroxide ions by energization as an alkali agent for replenishment and the use of a detection means independent of pH to know the degree of fatigue of the developing solution. Will be described.

FIG. 1 is a schematic diagram showing the structure of an electrolysis apparatus used in one embodiment of the present invention. In FIG.
The electrolytic device 1 includes an electrolytic bath 2, a pipe 12 for sending a catholyte to a developing tank of a developing device (not shown), and a pipe 13 for sending an anolyte to a developing stop tank of the developing device in the present embodiment. And a pipe 10 for replenishing the electrolytic solution to the electrolytic device. The electrolytic cell 2 is divided into an anode chamber 3 and a cathode chamber 4 by a diaphragm 5, and an anode 14 and a cathode 15 are provided in each of the electrolytic chambers. The flow of the liquid between the developing tank and the electrolytic chamber is indicated by an arrow. A direct current energizing voltage is applied to the anode 14 and the cathode 15 by voltage applying means 17 (a rectifier and an AC power supply, a battery, and applied voltage control, etc.). The control unit 16 manages energization. Fresh water 11 is piped to the liquid preparation tank 6 via a switching valve 8, and this pipe is also connected to an electrolytic cell via a level sensor 7. The liquid preparation tank is connected to the electrolytic chamber via a valve 9.

The diaphragm 5 has liquid permeability enough to ensure conductivity between the cathode chamber and the anode chamber, but the liquids in both tanks are not excessively mixed, and are not mixed with the developing solution or the anolyte. What is necessary is not to be invaded. Preferred diaphragm materials include:
Neutral porous membrane film (eg, unglazed pottery plate) which is not affected by the developing solution or anolyte, or polymer hydrophobic polyporous membrane [eg, commercially available Gore-Tex film (manufactured by Gore-Tex Corporation) ], Polymer permeable membrane [for example, commercially available MF (microfilter) membrane, UF (ultrafiltration) membrane, RO (reverse osmosis)
Membrane] can be used. In addition, an ion exchange membrane may be used, and an anion exchange membrane (product names include Selemion AMV / AMR manufactured by Asahi Glass Co., Ltd., anion type Aci
plex etc.), cation exchange membranes (Dafon Nafion,
Asahi Glass Co., Ltd. Flemion, cation type Aciple
x) are suitable for the purpose of the present invention. In particular, a bivalent selective anion exchange membrane is preferable because the anolyte solution and the catholyte solution are less likely to cross each other and the electric resistance is less increased.

As the electrode, any material can be used as long as the electrode is inert. Preferred anode materials include lead oxide, graphite, lead, platinum and the like, for example, a commercially available carbon sheet (Cresheet, manufactured by Kureha Chemical Industry Co., Ltd.). As the cathode material, stainless steel (SUS303, 316 or the like), copper, silver, graphite, lead, platinum or the like, for example, commercially available SUS316 (NTK316, manufactured by Nippon Metal Industry Co., Ltd.) can be used. Each of these electrode materials is commercially available. The electrolyte for the cathode compartment is
As described above, the developing solution is suitable, but it may be used after being diluted to some extent with water for the purpose of correcting the amount of evaporation while the development is continued.

Next, the operation of the electrolysis apparatus will be described. When a voltage is applied between the anode 14 and the cathode 15 and energization is performed, hydroxyl ions are generated in the cathode chamber and hydrogen ions are generated in the anode chamber, and change in the alkaline and acidic directions, respectively. The catholyte is supplied to the developing tank via the pipe 12 as a replenisher, and the developing activity in the developing tank is maintained and stable development is performed. On the other hand, in one embodiment of the present invention, in the apparatus shown in FIG. 1, the acidic electrolytic solution in the anode chamber is supplied to the developing stop tank in the developing apparatus and the alkaline electrolyte adhered to the developed photosensitive resin composition. , And the composition film is de-swelled to achieve physical strengthening. Further, washing may be performed at the same time. The anode compartment and the cathode compartment are separated by a diaphragm, so that direct mixing is prevented.

The solution preparation tank 6 substantially serves as both a solution preparation tank for preparing fresh developer and a storage tank for storing used developer for reuse. That is, fresh water 11 is supplied via the valve 8 and a developer is charged therein to prepare a developing solution. In addition, an overflow solution (not shown) returned from the developing tank may be stored. In any case, the developer prepared or stored in this tank is sent to the cathode chamber via the valve 10 and energized, and the alkali component (hydroxyl ions) is supplied to be in a replenisher state. Volume 1
The liquid is sent to the developing tank by 2 and replenishment is performed. on the other hand,
The anolyte can be adjusted in the solution adjusting tank 6 and supplied to the anode chamber by switching the piping system with a switching valve. Further, the level of the liquid in the anode chamber and the level of the cathode chamber are maintained constant by switching the level sensor 7 and the valve so that the fresh water 11 or the liquid in the liquid adjusting tank 6 is sent. A preferred embodiment is a developing method in which a used developing solution is stored in the solution preparation tank 6, activated in the composition of the replenisher in the electrolytic tank, and reused.

As the electrolyte for the anode compartment, a developer can be diverted. Alternatively, the electrolyte prepared by dissolving only an inorganic salt component in the developer composition in water may be used. May be used. In the latter case, there is also an advantage that the disposal cost can be reduced by disposing of the waste developer as the pH is already low. Energization is performed at a current density of 1 to 100 A / dm ² , preferably 1 to 50 A / d
m ² , more preferably in the range of ^{2 to} 20 A / dm ² . The applied voltage is adjusted so that the current density falls within this range. The value varies depending on the shape of the apparatus, particularly the distance between the electrodes, and the electrolyte concentration of the developing solution.
0V, preferably 3-10V. The electrode area varies depending on the substantial volume of the developing tank to be processed. However, it is almost appropriate to obtain the electrode area per 1 liter of the developing tank by proportional calculation, assuming that the electrode area is 1 dm ² . Under such a relationship between the electrode area and the amount of liquid in the developing tank, the energizing time is about 40 seconds with respect to the developing amount of 1 m ² of the photosensitive resin composition.

Next, management of the developer by energization will be described. As described above, the fatigue detection means for reading the degree of the fatigue of the developer and leading to the replenishment is based on the development processing amount, the integration time during which the developing device is in the standby and rest states, Physical properties of the developer other than
Preferably, the reading is performed by one of the electric conductivity, the specific gravity, and the opacity, or one of the three methods for reading the electric conductivity, or a combination thereof.

In the case where the detection of the degree of fatigue of the developer is based on the development processing amount, a processing amount integrating device for the photosensitive resin composition is installed in the development processing device by measurement using an infrared sensor or contact measurement. The processing amount is obtained as an area from the time during which the composition is sent into the developing tank, the width of the composition, and the transport speed, and is integrated. The information on the development processing amount obtained here is sent to the control unit 16 of the electrolysis apparatus shown in FIG. Such a processing amount integrating device is known,
It has also been adopted.

When the detection of the degree of fatigue of the developer is based on the cumulative time of the elapsed time during which the developing process is not performed, the pH of the developer and the amount of the alkali component are substantially reduced by the carbon dioxide gas in the air. Is a correction to This correction is performed by a timer that records the operating state of the developing device, the time when the developing device is turned on and in a standby state,
And the time during which the developing device is stopped is integrated and recorded. In a typical embodiment of the present invention, in the operation for correcting the influence of carbon dioxide, a voltage is applied to the electrolytic layer every time the integrated value of the standby time exceeds 4 hours, and an electrolytic current is supplied. If the development processing apparatus is in a halt, the halt time is accumulated, and when the power of the development processing apparatus is turned on next, power is supplied for a length corresponding to the integration time up to that time.

In the case where the electric conductivity is selected and managed as the physical property value, the electric conductivity meter is installed at an appropriate place in the circulating system of the developing solution, but is installed in the developing tank or in the stirring and circulating portion of the developing tank. Is preferred. The information related to the fatigue of the developer is sent to the control unit 16 in FIG. 1 to manage the voltage application time to the electrodes.

When the energization time is controlled by the processing amount of the photosensitive resin composition, the voltage application time is controlled by the processing amount of 1 m ^2.
It is a standard to set the amount of current to 600 coulombs. Of course, it depends on the thickness of the coating tank for the photosensitive resin composition and the amount of the eluted components (therefore, the amount of exposure, etc.), and it is needless to say that adjustment according to the actual working conditions is necessary. When the energization time is controlled by the integration time of the standby time and the halt time of the developing device, the voltage application time is set to 4 hours for the integration time of both the standby time and the halt time in the average-scale development processing device. A guideline is that the amount be 600 coulombs. Since the concentration of carbon dioxide in the indoor environment varies depending on the seasonal variation, the content of the work being performed in parallel, the ventilation of the work place, and the like, it is needless to say that further adjustment is necessary in the actual place.

When the energization time is controlled by the electric conductivity of the developing solution in use, the change in electric conductivity is controlled so as to be within 5% of a standard value, preferably within 2%, more preferably within 1%. It is desirable to control the electrolysis time. In the average composition of the developer to which the present invention is applied, the conductivity is 40,000 to 6
10,000 μs / cm. The conductivity of the developer is 50,000 μs / cm
In the case of (1), the fluctuation in 1% is 500 μs / cm, which is a value that can be accurately read by a conductivity meter.
Fluctuations in electrical conductivity are accompanied by an increase or decrease in alkali metal ions accompanying the dissolution of the photosensitive resin composition, so that they correspond only to changes in hydrogen ion concentration, and are more logarithmic as a measure of fatigue of the developer than the corresponding pH value. Sensitive. To explain the specific energization operation and replenishment management, the conductivity meter constantly monitors the conductivity of the developing solution during the operation of the developing apparatus.
Is transmitted to the control device. Conductivity value is 1 of standard value
1, that is, 500 μs / cm, the controller of FIG. 1 applies a voltage between the electrodes 14 and 15 according to the information. When the energization time reaches 20 seconds, the energization amount becomes 300 coulombs. At this point, if the conductivity returns to within 1% of the standard value, the applied voltage is cut off.
If it has not returned to within%, energization is continued until the next control cycle. The energization and replenishment management are performed by such a control sequence.

The above three replenishment management methods may be used alone or in combination. From the viewpoint of the stability of the developing process, it is most preferable to use three types of replenishment control in combination. Next, it is preferable to combine the management based on the conductivity management, or the management based on the information on the development processing amount and the information on the accumulated time of the operable time. When the specific gravity or opacity, which is a physical property value other than the electric conductivity, is used for detecting the degree of fatigue of the developer, since all of these physical property values change with development, the first physical property value is used. A change value from that value is read based on (initial value), and the energization time is adjusted according to the value.

During energization, hydroxyl ions are generated in the cathode chamber to activate the developer, while hydrogen ions are generated in the anode chamber. This hydrogen ion can also be used for the development processing. That is, in the washing step following the development of the material having the photosensitive resin composition, when an anolyte containing hydrogen ions generated on the anode chamber side by energization is added to the washing water, excessive dissolution of the insoluble portion of the photosensitive resin composition occurs. Swelling is suppressed, the physical strength is also reinforced, and water washing is performed effectively. At this time, the components eluted during the development process may become insoluble in the washing wastewater and precipitate, in which case the components are separated from the waste liquid as far as the sediment is concerned, and disposal of the waste liquid is easy. become. As another method of using the anolyte, a used developer can be used as the anolyte to neutralize the alkali component and reduce the addition at the time of disposal of the waste liquid.

In another embodiment of the present invention, two electrolytic cells are provided, one of which is sufficient to compensate for the deterioration over time due to the absorption of carbon dioxide gas in the air when the developing process is not performed. The amount of current to be applied is always set to the amount
The base may be of a function-sharing type in which two electrolytic cells are energized only when the development processing is performed so as to compensate for fatigue caused by the development processing. By making the system cope with the fatigue of the developing process and the fatigue of the developing solution over time, it is possible to design a developing device with an electrolytic device having a low electric capacity. In this case, the electrolytic device for compensating for the influence of carbon dioxide gas absorption is always energized regardless of whether the developing process is being performed or is stopped. Compensation for the carbon dioxide absorption that occurs also does not occur, of course. In addition, the electrolytic device for compensating for the fatigue of the developing solution accompanying the developing process, even if the amount of the developing process is adopted as the means for detecting the degree of fatigue of the developing solution, the physical properties such as conductivity, specific gravity, opacity, etc. May be adopted.

[Photosensitive Materials to be Applied] Materials having a photosensitive resin composition to which the present invention can be applied include photosensitive materials for lithographic printing, photosensitive materials for printed wiring boards, and high-definition patterns such as integrated circuits. May be used. Particularly preferred are photosensitive materials for lithographic printing,
Among them, the PS plate is a positive photosensitive resin composition.

Any positive photosensitive resin composition can be used as long as it has a change in solubility or swelling in a developer before and after exposure, and is often used as a PS plate. Preferred photosensitizers include o-quinonediazide compounds. For example, in the case of a positive photosensitive resin composition containing an alkali-soluble resin and an o-quinonediazide compound,
The o-quinonediazide compound is preferably a compound having at least one o-quinonediazide group, which increases the solubility in an aqueous alkali solution by actinic light.

Compounds having a quinonediazide group of this type are known to have various structures.
r, `` Light-Sensitive Systems '' (John Wiley & Sons, I
nc, published in 1965) on pages 336 to 352. As the positive photosensitive resin composition, various hydroxyl compounds and o-benzoquinonediazide or o-
Sulfonic acid esters of naphthoquinonediazide are preferred.

The positive photosensitive resin composition, other than the above-mentioned o-quinonediazide, includes:
A chemically amplified photosensitive resin composition in which a compound which is insoluble in water but soluble in alkali and whose alkali-soluble group is protected by an acid-decomposable group is combined with a photoacid generator can be used. The photosensitive resin composition incorporating the chemical amplification system is used as a lithographic printing material and photoresist for integrated circuits and other high-definition microfabrication. It is done.

As the photoacid generator used in the chemical amplification system, known photoacid generators can be used. A group of compounds used as photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and micro-resists. And a mixture thereof that generates an acid by the light can be appropriately selected and used.

In a chemically amplified photosensitive resin composition, a compound which is water-insoluble but alkali-soluble and used in combination with a photoacid generator and whose alkali-soluble group is protected by an acid-decomposable group is- C—O—C— or —C
It is a compound having a -O-Si- bond, and the following examples can be given. (A) comprising at least one orthocarboxylic acid ester and / or carboxylic acid amide acetal group, wherein the compound can have polymerizability, said group being as a crosslinking element in the main chain or as a lateral substituent (B) oligomeric or polymeric compounds containing recurring acetal and / or ketal groups in the main chain,
(C) a compound containing at least one enol ester or N-acylaminocarbonate group, (d) a cyclic acetal or ketal of β-ketoester or β-ketoamide,

(E) a compound containing a silyl ether group,
(F) a compound containing a silyl enol ether group, (g)
The aldehyde or ketone component is added to the developer in an amount of 0.
Monoacetals or monoketals having a solubility of 1 to 100 g / l, (h) tertiary alcohol ethers, and (i) tertiary allylic or benzylic alcohol carboxylic acid esters and carbonates.

Examples of the synthetic resin which is insoluble in water and soluble in an alkaline aqueous solution (hereinafter referred to as alkali-soluble resin) include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde cocondensation resin, phenol-modified xylene resin,
In addition to a copolymer of polyhydroxystyrene, polyhalogenated hydroxystyrene, N- (4-hydroxyphenyl) methacrylamide, a copolymer of hydroquinone monomethacrylate, a sulfonylimide polymer described in JP-A-7-28244, And carboxyl group-containing polymers described in JP-A-7-36184. Other acrylic resins containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, acrylic resins having a sulfonamide group described in JP-A-2-866, and urethane-based resins, Various alkali-soluble polymer compounds can also be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
0 to 20,000 and number average molecular weight of 200 to 60,00
0 is preferred. These alkali-soluble polymer compounds may be used alone or in combination of two or more, and are used in an amount of 80% by weight or less of the total composition.

Next, a material having a photopolymerizable photosensitive resin composition, which is one of the materials having a photosensitive resin composition used in the present invention, will be described. The photopolymerizable photosensitive resin composition used in the present invention, as its main component,
Compounds containing an ethylenic double bond capable of addition polymerization, photopolymerization initiators, etc., and if necessary, compounds such as thermal polymerization inhibitors are added.

The compound containing an addition-polymerizable double bond is
It can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds, for example, monomers, prepolymers, ie, dimers, trimers and oligomers, or mixtures thereof. And those having a chemical form such as a copolymer thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of carboxylic acids and aliphatic polyamine compounds.

The photopolymerization initiator contained in the photopolymerizable photosensitive resin composition used in the present invention may be selected from various photopolymerization initiators known in patents and literatures, depending on the wavelength of the light source used, or A combination system of two or more photopolymerization initiators (photopolymerization initiation system) can be appropriately selected and used. For example, when using light near 400 nm as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine,
Benzophenone and the like are widely used.

The present invention provides a positive PS plate using the above-mentioned quinonediazide or a compound having an alkali-soluble group protected by an acid-decomposable group, a negative PS plate using a photopolymerization system, and the following type: It can be similarly used for a lithographic printing plate material and a resist for producing a printed wiring or an integrated circuit. (1) Negative lithographic printing plate material using diazo resin (2) Negative lithographic printing plate material using photocrosslinkable resin (3) Alkali-soluble binder, acid generator, acid (heat) crosslinkable compound Negative type laser direct drawing type lithographic printing material including (4) a positive type laser further containing an alkali-soluble binder, a substance which is thermally decomposable and substantially degrades the solubility of the alkali-soluble binder when not decomposed. Direct-drawing lithographic printing materials

The coating amount (solid content) of the image forming layer obtained after coating and drying varies depending on the application, but is preferably 0.5 to 5.0 g / m ² for a general lithographic printing plate precursor. 0.5-1.5 g / m < ² > is more preferable. The thickness of the film is 0.01 to 100 μm, preferably 0.1 to 10 μm, and more preferably 0.3 to 1 μm.

[Support] The photosensitive resin composition is coated on a support according to the purpose. A dimensionally stable plate is used for the support. Examples of the substrate that can be used in the present invention include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, nickel, stainless steel, etc.), plastic film (For example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and the above metal was laminated or deposited. Paper or plastic films are included.

The thickness of the substrate used in the present invention is about 0.05 mm to 0.6 mm, preferably 0.1 mm to 0.2 mm.
4 mm, particularly preferably 0.15 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove the rolling oil on the surface.

[Plate making] The lithographic printing plate prepared as described above is usually subjected to image exposure and development processing. <Image Exposure> Examples of the light source of the active light beam used for the image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. Examples of the laser beam include a helium-neon laser, an argon laser, a krypton laser, a helium-cadmium laser, and a KrF excimer laser. In the laser direct-writing printing plate, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser and a semiconductor laser are particularly preferable.

The printing original plate composed of the above-mentioned materials is immersed in, for example, a developing solution stored in a developing tank when it is conveyed to a developing unit via a heating unit of a processing apparatus, and is subjected to a developing process. .

[0074]

EXAMPLES Hereinafter, the embodiments and effects of the present invention will be further described with reference to Examples, but the present invention is not limited thereto. In the following examples, a PS plate making material “VS” (manufactured by Fuji Photo Film Co., Ltd.) for offset printing of an anodized aluminum support was used as the material having the photosensitive resin composition. The exposure was performed using a xenon arc discharge lamp (with a UV filter such as soda glass removed) having a continuous spectrum of 2500 W according to JIS Z8902 using a light wedge with a step of 0.2. A metrological exposure was performed. This discharge lamp is a quartz glass tube, and the ultraviolet component is not absorbed by the tube wall.

An alkaline developing solution used in the developing step was prepared as follows. (Preparation of alkali developing solution)

Formulation of alkali developing solution 2.4% by weight of potassium hydroxide 1.8% by weight of silicon dioxide Nonionic surfactant (PEG-1000, manufactured by Wako Pure Chemical Industries) 0.8% by weight 3.0% by weight of potassium citrate % Water 92.0% by weight The pH of the developer is 13.03. Its conductivity is 49
It was 500 μs / cm.

The developing apparatus used was a commercially available developing apparatus for a PS plate to which an electrolysis apparatus with a control device (16 in FIG. 1) was connected as shown in FIG. This development processing apparatus has a development bath of immersion bath type, a washing bath, and a desensitization treatment bath, and the respective processing times are 15, 10,
10 seconds. The following tests were performed using the PS plate material, the sensitometric exposure method, the developing solution, and the developing apparatus shown above. The evaluation of the development result was performed as follows using the developed light wedge image. In other words, the standard sensitivity is set to 0 using the number of the step where the composition is recognized as remaining without being dissolved, and the number of steps deviated from the standard is converted into a step to shift one step. Was set as 0.2. When shifted to the high sensitivity side, the sensitivity value was displayed with a plus sign, and when shifted to the low sensitivity side, the sensitivity value was indicated with a minus sign. Hereinafter, this sensitivity display is referred to as relative light wedge sensitivity.

(Example 1) In this example, the degree of fatigue of the developing solution due to the developing process was determined based on the developing amount obtained from the developing amount integrating device provided in the developing device. Each time the PS plate sample was developed by 3 m ² (depending on the type of the photosensitive resin composition), a voltage was applied to the electrode by a signal from a control device (16 in FIG. 1) attached to the electrolytic cell, and a current density of 5 A / dm ² and current value 15A,
After two minutes of electrolysis (a current of 1800 coulombs), the circuit is cut off. The development processing was performed with a total processing amount of 60 m ² while taking out a development sample for evaluation every time the development processing was performed by 15 m ² by this apparatus. The relative light wedge sensitivity was less than 0.2 of the standard sensitivity from the beginning to the end of the development, that is, the number of steps of the sensitivity point was the same as the number of the standard development samples. That is, during development processing of PS plate samples as large as 60 m ² , the sensitivity was kept constant by the method of the present invention. In addition, no precipitate was observed in the developer.

(Embodiment 2) In this embodiment, the degree of fatigue of the developing solution when the developing processing apparatus is in a halt state is determined.
The developer was managed by the electrolysis apparatus based on the integrated pause time obtained from the pause time integrating device provided in the developing apparatus, and based on this value. The PS processing was stopped for 2 days without developing the PS plate sample by turning off the power of the developing apparatus. Each time the standing time reaches 5 hours, a voltage is applied to the electrode by a signal from a control device (16 in FIG. 1) attached to the electrolytic cell, and a current density of 5 A / dm ² and a current value of 15 A, 2
After electrolysis for 1 minute (electricity 1800 coulombs),
The circuit breaks. After developing the reference PS plate sample, after leaving it for 2 days, the PS plate sample of the same lot was immediately developed without adjusting the developing solution in the developing tank. Sample comparisons were made. The relative light wedge sensitivity of both is 0.2 of the standard sensitivity.
Less, ie, the number of steps of the sensitivity point was the same.

(Embodiment 3) In this embodiment, the degree of fatigue of the developing solution due to the developing process is determined by the value of the conductivity of the developing solution obtained from a conductivity meter provided in the developing tank of the developing apparatus. went. Each time the conductivity changes (decreases) by 495 μs / cm with the development of the PS plate sample, a voltage is applied to the electrode by a signal from a control device (16 in FIG. 1) attached to the electrolytic cell, and a current density of 5 A / Current value 1 at dm ²
After electrolysis at 5 A for 2 minutes (electricity of 1800 coulombs), the circuit is cut off. During this time, the change in the electric conductivity is 495 μs / cm of the initial electric conductivity of the developer.
If it does not recover within this time, further voltage application is automatically performed every two minutes. Each time 15 m ² development processing was performed by this apparatus, a development processing with a total processing amount of 60 m ² was performed while taking out a development sample exposed to a light wedge for evaluation. The relative light wedge sensitivity was less than 0.2 of the standard sensitivity from the beginning to the end of the development, that is, the number of steps of the sensitivity point was the same as the number of the standard development samples. In addition, no precipitation of the dissolved components was observed.

(Embodiment 4) In this embodiment, an embodiment will be described in which a method for developing a material having the photosensitive resin composition of the present invention is performed by using an integrated apparatus of an electrolysis apparatus and a development processing apparatus. FIG. 2 is a diagram showing an integrated apparatus of the electrolysis apparatus and the development processing apparatus used in the present invention. The same display numbers are used for the same portions throughout FIGS. The cathode chamber 4 of the electrolysis device 2 also serves as a developing tank, and the developer filled in the tank is also a catholyte, and the photosensitive resin composition is fed along the transport path shown by arrows 28-28 '. While developing the cathode 1
5 is also responsible for the reaction of reducing water to produce hydroxyl ions, and as a result, the mechanism at the cathode compensates for the consumption of hydroxide ions by development. The anode compartment 3 is separated from the cathode compartment by a diaphragm 5, and the catholyte flows into the anode compartment over the upper part of the diaphragm serving as a weir and undergoes electrolytic oxidation. As a result, electrolytic oxidation of organic components and generation of hydrogen ions occur, which is accompanied by a decrease in pH. The anolyte is discharged from the electrolysis device as a developing waste liquid through the discharge hole 42. On the other hand, the developing solution in the cathode chamber 4 is circulated with stirring by the circulating pump 40 by the circulating pump 40 to adjust the temperature and stir the developing solution.

In this example, except that the apparatus shown in FIG. 2 was used, the development of the photosensitive resin composition (PS plate material for offset printing "VS") was carried out in the same manner as in the development processing method of Example 3. Processing was performed. 15
Each time the m ² development processing was performed, a development processing with a total processing amount of 60 m ² was performed while taking out the development sample exposed to the light wedge for evaluation. The relative light wedge sensitivity was 0% of the standard sensitivity from the beginning to the end of the development. .2, that is, the number of steps at the sensitivity point was the same as the number of steps of the standard development sample. In addition, no precipitation of the dissolved components was observed.

(Example 5) In this example, the photosensitive resin composition of the present invention was prepared using an apparatus in which the catholyte of the electrolytic apparatus used in the present invention and the developing solution of the developing apparatus formed a circulation system. One embodiment in which the development processing of the material is performed will be described.
FIG. 3 is a schematic diagram of a developing apparatus incorporating an electrolytic apparatus used in the method of the present invention, and is a diagram of an apparatus in which a cathode chamber of the electrolytic apparatus and an electrolytic tank of the developing apparatus form a circulation system. The cathode chamber 4 of the electrolysis apparatus 2 forms a circulation system by the developing tank 54 of the development processing apparatus 53, the liquid supply pipe 51, the liquid supply pipe 52, and the circulation pump 50, and is activated by the hydroxide ions electrolytically generated in the cathode chamber. The discharged developer flows into the developing tank by the circulation pump 50. The developer develops the photosensitive resin composition that is sent along the transport path shown by arrows 28-28 '. As a result, the consumption of the hydroxide ions by the development is compensated by the generation at the cathode. The anode compartment 3 is separated from the cathode compartment by a diaphragm 5, and the catholyte flows into the anode compartment over the upper part of the diaphragm serving as a weir and undergoes electrolytic oxidation. As a result, electrolytic oxidation of organic components and generation of hydrogen ions occur, which is accompanied by a decrease in pH. The anolyte is discharged from the electrolysis device as a developing waste liquid through the discharge hole 42.

In this embodiment, except that the apparatus shown in FIG. 3 was used, the development of the photosensitive resin composition (PS plate making material for offset printing "VS") was carried out in the same manner as in the developing method of Embodiment 3. Processing was performed. 15
Each time the m ² development processing was performed, a development processing with a total processing amount of 60 m ² was performed while taking out the development sample exposed to the light wedge for evaluation. The relative light wedge sensitivity was 0% of the standard sensitivity from the beginning to the end of the development. .2, that is, the number of steps at the sensitivity point was the same as the number of steps of the standard development sample. In addition, no precipitation of the dissolved components was observed.

[0085]

According to the present invention, there is provided a method for developing a material having a photosensitive resin composition which detects the degree of fatigue of a developing solution, performs electrolysis of water according to the degree of replenishment, and controls the replenishment of the developing solution. The amount of development replenisher, and thus the amount of development waste solution, can be reduced, and there is no precipitation of insoluble matter in the developer, and stable development processing quality in which the sensitivity of the material having the photosensitive resin composition is maintained. Can be kept.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a configuration of a water electrolysis apparatus according to the present invention.

FIG. 2 is a schematic view of an integrated apparatus of an electrolysis apparatus and a development processing apparatus used in one embodiment of the present invention.

FIG. 3 is a schematic view of a developing apparatus incorporating an electrolytic device used in one embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolyzer 2 Electrolysis tank 3 Anode chamber 4 Cathode chamber 5 Diaphragm 6 Liquid regulating tank 7 Level sensor 8 Valve 9 Valve 10 Switching cock 11 Water 12 Catholyte liquid supply pipe 13 Anolyte liquid supply pipe 14 Anode 15 Cathode 16 Control part 17 Power supply device 28, 28 'Photosensitive resin composition transport path 40 Circulation pump 41 Circulation path 42 Discharge hole 50 Circulation pump 51 Liquid feed pipe 52 Liquid feed pipe 53 Developing device 54 Developing tank

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Takashi Nakamura 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H096 AA06 AA25 AA26 BA03 BA10 GA09 GA22 LA25 5F046 LA09 LA14 LA19

Claims (9)

[Claims] 1. A developing method for sequentially developing a material having a plurality of sheets of a photosensitive resin composition with a developing solution, wherein a fatigue of the developing solution accompanying the development of the photosensitive resin composition is detected. A method of developing a material having a photosensitive resin composition, wherein the activity of the developing solution is maintained by applying a current between the two electrodes via the developing solution in accordance with the detected degree of fatigue. 2. A method for developing a material having a plurality of photosensitive resin compositions, comprising: developing means for processing the photosensitive resin composition with a developer; and detecting fatigue of the developer accompanying the development. Detecting means for detecting the presence of
Using a developing apparatus having a means for supplying a current between the two electrodes and a supplying means for replenishing the generated hydroxide ions to the developing solution, a plurality of sheets of the photosensitive resin composition are sequentially subjected to the developing treatment with the developing solution. Application, to detect the fatigue of the developer accompanying the development of the photosensitive resin composition, according to the detected degree of fatigue,
The method for developing a material having a photosensitive resin composition according to claim 1, wherein the energizing means is operated to supply the generated hydroxyl ions to the developing solution to maintain the activity of the developing solution. 3. The photosensitive resin composition according to claim 1, wherein the method for detecting the fatigue of the developer accompanying the development is at least one selected from the following three: Material development processing method. (1) Reading of the processing area of the material having the photosensitive resin composition (2) Integration of the time during which the development processing of the material having the photosensitive resin composition is not performed in the developing device (3) Storage in the developing device Measurement of electric conductivity (abbreviated as electric conductivity), specific gravity or opacity of the developed developer. 4. The method according to claim 1, further comprising the steps of: (1) treating an area of the material having the photosensitive resin composition; and (2) developing the material having the photosensitive resin composition in the developing apparatus. The method for developing a material having a photosensitive resin composition according to any one of claims 1 to 3, wherein the method is obtained by combining the accumulated time of the unreacted time and the accumulated time. 5. A developing tank in the developing apparatus and a tank for supplying a developing solution through two electrodes are connected to each other by a pipe to form a circulation system. The method for developing a material having a photosensitive resin composition according to any one of claims 1 to 4, wherein the liquid is activated by being energized and reused. 6. The developer according to claim 1, wherein said developer contains silicate and has a pH of 12.0.
The method for developing a material having the photosensitive resin composition according to any one of claims 1 to 5, wherein the method is an alkaline aqueous solution as described above. 7. The method according to claim 1, wherein the washing water used in the washing or stopping step following the developing step is in contact with the anode and is also in electrical contact with the developing solution via the diaphragm. A method for developing a material having the photosensitive resin composition according to claim 1. 8. The photosensitive resin composition according to claim 1, wherein the diaphragm partitioning the respective electrode chambers of the two electrodes is a bivalent selective anion exchange membrane. A method for developing a material having: 9. A developing means for sequentially processing a material having a photosensitive resin composition with a developing solution, a detecting means for detecting fatigue of the developing solution accompanying development or the aging of the developing solution, and a developing solution. Developing a material having a photosensitive resin composition, comprising: an energizing means for generating hydroxyl ions by energizing between two electrodes; and a circulating means for coupling the developing means and the energizing means. Processing equipment.