JP2002201046A - Reclaiming method of glass substrate, production method of dry plate and reclaiming apparatus of glass substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the cost of a glass substrate for a dry plate reducing waste materials by reusing the reclaimed glass substrate as a glass dry plate, according to reclaiming a used glass substrate or a defective glass substrate having a photosensitive emulsion layer or an undercoating layer, during producing process or after producing. SOLUTION: The glass substrate having at least one layer of a photosensitive emulsion layer, an antihalation layer or an undercoating layer is uncoating processed by the solution containing at least one kind of alkali compounds or at least two kinds of acid compounds, and the glass substrate is reclaimed by cleaning or inactivating if necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating a glass substrate (glass support) used for a photographic plate, a method for manufacturing a photographic plate using the same, and a glass substrate reproducing apparatus.

[0002]

2. Description of the Related Art A glass dry plate having a silver halide photographic emulsion layer on a glass substrate is excellent in dimensional stability. It is used as a photomask for laminated substrates. Such a glass dry plate is used to bake a fine pattern to form an original pattern, and then use the mask as a mask to contact and expose another glass dry plate to duplicate the pattern, or to transfer the original pattern by contact exposure to a substrate having a photoresist layer. To obtain a large number of photoresist patterns.

[0003] As described above, since high precision is required for a glass dry plate, a glass substrate used as a support is subjected to special screening by a glass maker, and further inspected by a dry plate maker. Only high-quality glass substrates with very few glass bubbles, foreign substances in glass, scratches, etc. are used.

[0004]

In spite of using a high quality and high price glass plate which has been subjected to the special inspection as described above, conventionally, the glass dry plate has not been used in the manufacturing process or in a storage state after manufacturing. Glass substrates that have become defective due to expiration or other reasons, or that have been used by a user,
It was just disposed of.

Accordingly, an object of the present invention is to recycle a glass substrate having a photosensitive emulsion layer or an undercoat layer, which has become a defective product during or after the manufacturing process or a used glass substrate,
An object of the present invention is to provide a method which can be reused as a glass plate. As a result, waste material (glass) can be reduced, and the cost of the glass substrate for a dry plate can be reduced.

It is a further object of the present invention to provide a method for producing a sufficiently high quality glass dry plate using a recycled glass substrate.

[0007]

As a result of various studies, the present inventors have found that a glass dry plate or a used glass dry plate that has been treated as a defective product during or after the manufacturing process, that is, a photosensitive emulsion layer or an undercoat layer. By treating the glass substrate having the above with an aqueous solution containing at least one alkali compound or an aqueous solution containing at least two acid compounds (hereinafter also referred to as “film removal”). And found that the glass substrate can be recycled. That is, the present invention has the following configuration.

(1) A glass substrate having at least one of a photosensitive emulsion layer, an antihalation layer and an undercoat layer is removed using an aqueous solution containing at least one alkali compound or at least two acid compounds. A method for reclaiming a glass substrate, comprising performing a film treatment. (2) A method for regenerating a glass substrate, wherein the glass substrate treated by the method described in (1) is washed at least once.

(3) A glass substrate treated by the method described in (1) or (2) above is treated with an aqueous solution containing at least one compound selected from a surfactant, a water-soluble polymer and an organic acid. A method of regenerating a glass substrate, wherein the glass substrate is subjected to a passivation treatment. (4) The method for recycling a glass substrate according to any one of the above (1) to (3), wherein the aqueous solution used for the film removal treatment is collected.

(5) A method for regenerating a glass substrate, wherein the glass substrate regenerated by the method according to any one of (1) to (4) is stored in a non-contact manner. (6) A method for producing a dry plate, comprising applying a photosensitive emulsion layer or an undercoat layer to a glass substrate regenerated by the method according to any one of (1) to (5).

(7) The method for producing a dry plate as described in the above item (6), wherein, before coating the photosensitive emulsion layer or the undercoat layer, foreign substances adhering to the recycled glass substrate are removed. (8) The method for producing a dry plate as described in (6) or (7) above, wherein the time from the end of regeneration of the glass substrate to the start of application of the photosensitive emulsion layer or the undercoat layer is optimized.

(9) A desorption treatment tank for removing the photosensitive emulsion layer or the undercoat layer on the glass substrate, a cleaning tank for cleaning the desorption-treated glass substrate, and a deactivation treatment for the desorption-cleaned glass substrate. An apparatus for regenerating a glass substrate, comprising a deactivation treatment tank and a collection tank for collecting a desorbed liquid in the desorption treatment tank.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The glass substrate (support) in the present invention is not particularly limited in glass composition, but may be soda lime glass, soda lime aluminum glass, soda lime glass, white crown glass, low expansion glass, alkali-free glass, synthetic quartz glass, Alkali glass and the like are preferred. If float glass is used, tin adhered during float glass production or glass cullet adhered during cutting remains on the glass surface, which becomes a defect during pattern formation, and is preferably removed by pretreatment. In addition, it is preferable that the surface is degreased in advance before the application of the coating liquid for a hydrophilic colloid layer, and a pretreatment for improving hydrophilicity is performed. The end face of the support is preferably polished for handling.

The glass substrate used in the present invention comprises various hydrophilic colloid layers such as a protective layer above the photosensitive emulsion layer and, if necessary, an undercoat layer (undercoat layer) below the emulsion layer. Have Further, a substrate provided with an antihalation layer on the back surface of the substrate may be used. Specific examples include high resolution, squirrel, lath, and dry plates such as bright room dry plates. As the photosensitive emulsion layer of the present invention, a silver halide emulsion layer usually used in this field can be used. In addition, various photographic additives (sensitizing dyes, hardeners, plasticizers, etc.) usually used in this field may be contained in the emulsion layer and other hydrophilic colloid layers.

In the present invention, a glass substrate having such a photosensitive emulsion layer or the like is converted into an aqueous solution containing at least one kind of alkali compound or at least two kinds of acid compounds (hereinafter, also referred to as a film removing solution). By immersion, the emulsion layer and the like can be eluted and removed from the glass substrate.

Examples of the alkali compound include sodium hydroxide, potassium hydroxide, sodium hypochlorite and the like. PH of aqueous solution containing alkali compound
Is preferably 12 to 14, more preferably 14, the liquid temperature is preferably 50 to 80 ° C, more preferably 70 to 80 ° C, and the concentration is preferably 5 to 20%, more preferably 10 to 15%. %. In this range,
The glass substrate can be stably removed. Examples of the mixed acid solution containing at least two kinds of acid compounds include ozone sulfuric acid, a mixed solution of sulfuric acid and nitric acid, and a mixed solution of sulfuric acid and potassium nitrate. The liquid temperature is preferably from 50 to 90C, more preferably from 70 to 90C.
It is preferable to use a stock solution having a pH of about 1.

The concentration of the desorbed solution can be controlled by neutralization titration. If necessary, a stirring operation or an ultrasonic operation may be performed to improve the film removal efficiency. Specific examples include bubbling with air or nitrogen gas, stirring with ultrasonic waves and rotating blades, and the like.

Silver is dissolved in the desorbed solution eluted from the emulsion layer and the like, and silver and a hydrophilic colloid (such as gelatin) float as a solid as many glass substrates are processed. It is preferable to collect the desorbed liquid and remove solids from the desorbed liquid by filtration or the like. This prevents failures due to foreign substances adhering to the glass substrate,
Silver can be recovered effectively. As a collection method,
Filtration and recovery using an alkali-resistant or acid-resistant cartridge filter can be used. In this case, the frequency of collection can be appropriately set by controlling the filtration pressure.
Silver can be recovered by burning the filter and the filter.

In the present invention, it is preferable that the glass substrate further subjected to the desorption treatment is washed at least once. This makes it possible to wash solids in the desorbing liquid that may adhere to and remain on the glass substrate surface. As the washing water, ordinary tap water may be used, but it is more preferable to neutralize the alkali or acidic glass substrate surface by the desorption treatment by washing with an acidic or alkaline treating solution. The washing treatment may be, for example, a multi-stage washing (commonly used in the development of photosensitive materials) in which one tank is divided into a plurality of sections and a backflow is prevented by a partition plate.

In the present invention, the desorbed glass substrate is further treated with an aqueous solution containing at least one compound selected from a surfactant, a water-soluble polymer and an organic acid (hereinafter referred to as an inactivating liquid). ) Is preferably used.

According to the present invention, the surface of the glass substrate from which the emulsion layer and / or the undercoat layer has been removed by the elimination liquid is very slightly etched, so that the glass surface is in a highly active state. For this reason, it has been found that residues of the emulsion and the like easily adhere to the glass surface, and after a certain period of time, a situation may occur in which the residues cannot be removed even after rewashing. In addition, since the glass surface is active, even if the glass is dried while being washed with water containing impurities, spots of water spots (water scorch) occur, and repelling or poor adhesion occurs even when an emulsion or the like is applied later. Turned out to be the cause. By treating with an aqueous solution containing the above surfactant and the like, the surface of the glass substrate is covered with a removable organic film, and the glass surface can be inactivated. It was found that a sufficiently reproducible surface state could be secured. Further, such an inactivating treatment also has an effect of cleaning foreign substances generated by the solid matter in the desorbed liquid adhering to the glass surface.

As the active ingredient of the deactivating liquid, a surfactant (preferably, an alkylbenzene sulfonate, polyethylene nonylphenyl ether, a nonionic surfactant such as a photographic drainer drywell solution, etc.) Examples include molecules (eg, polyvinyl alcohol, polyethylene glycol, etc.) and organic acids (eg, oxalic acid, butyric acid, glycolic acid, glyceric acid, etc.). The concentration is not particularly limited, but is about 0.3 to 5%. The temperature is preferably from 18 to 30C.

On the other hand, in the present invention, the glass substrate subjected to the desorption treatment is preferably stored in a non-contact manner. Normally, when storing glass, in order to prevent the occurrence of scratches and the like due to contact between the glasses, the glass sheet is stored with interleaving paper interposed therebetween. , The resin component and the like contained in the slip sheet were transferred to glass and became cloudy, so-called glass burning occurred. Therefore, the glass substrate subjected to the desorption treatment of the present invention is preferably stored in a non-contact manner. Specifically, a spacer or the like can be attached to both ends of the glass substrate, and the glass substrate can be stored so as not to contact the glass surface.

A photographic dry plate can be produced by applying a photosensitive emulsion layer and the like to the glass substrate regenerated according to the present invention in exactly the same manner as a normal glass substrate.
Before coating the emulsion layer or the like, it is preferable to remove foreign substances adhering to the glass substrate. Specifically, methods such as a chemical cleaning method and a physical cleaning method can be performed alone or in combination.

In the present invention, the activity of the surface of the glass substrate can be adjusted by the conditions of the desorption treatment and the inactivation treatment (the type of the liquid, the liquid temperature and the processing time).
In particular, by optimizing the waiting period (re-injection interval) from the end of the regenerating process to the start of emulsion coating according to the above-mentioned processing conditions, it is possible to manufacture a higher quality dry plate. The normal waiting period depends on the processing conditions, but when the inactivation treatment is not performed, it is preferably before the surface of the glass plate is dried, specifically, within 3 days, more preferably within 2 days. When the treatment is performed, it is preferably within 28 days, more preferably within 18 days. Within this range, a high-quality dry plate can be regenerated without causing the effects of water spots, burnt glass, and the like. Further, the step of regenerating the glass substrate and the step of manufacturing the glass dry plate can be performed continuously without substantially eliminating the waiting time.

Further, an apparatus for carrying out the glass substrate recycling method of the present invention will be described. Although the glass substrate regenerating apparatus of the present invention may essentially have a film-removing tank, the most preferred glass substrate regenerating apparatus includes a photosensitive emulsion layer or an undercoat layer on a glass substrate as shown in FIG. A desorption treatment tank 11 to be removed, a desorption liquid taken out of the desorption treatment tank 11, and a recovery tank 1 for preventing a high concentration desorption liquid from flowing out.
3. A cleaning tank 15 (1) for cleaning the desorbed glass substrate
5a and 15b) and an inactivation treatment tank (finishing tank) 17 for inactivating the glass substrate subjected to the desorption cleaning treatment. Further, it is preferable to have a terminal (load / unload) 19 for non-contact storage of the regenerated glass. Each tank is a tank for performing the above-described processing of the present invention, and various processing conditions (temperature, concentration, processing amount, processing time, etc.)
And means for transporting the glass substrate. It is preferable to adopt a closed system in the film removing process. Further, it is preferable that the washing tank has a multi-stage structure of two or more tanks, and more preferably water is supplied in the washing tank 15b.
It is preferable to employ a multi-stage washing method of draining water from 5a.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 A high-resolution soda lime and a light room dry plate were used as a glass dry plate, and a film removing treatment was performed using a sodium hydroxide aqueous solution as a film removing treatment solution. Sodium hydroxide concentration (6.25 to 25%), temperature for membrane removal (40 to 8)
(0 ° C.) and the film removal time (5 to 25 minutes) were variously changed as shown in Table 1, and the glass substrate was subjected to a regeneration treatment. In addition, in the film removal treatment tank, stirring was performed with a magnetic stirrer at 600 rpm. The desorption results are also shown in Table 1.

It should be noted that the removal of the film was confirmed by scratching the lattice pattern with a needle on the surface of the removed film and observing it with an optical microscope to confirm the presence or absence of the emulsion film. Observation was performed using a different light source for illumination, and two methods of determining the degree of film removal based on the interference color observed when the emulsion film remained were evaluated as follows. The same applies to the following embodiments. -Undercoat layer not peeled off (no detachment) x-Undercoat layer peeling residue slightly present △,-Emulsion layer and undercoat layer peeling completed (released)-

[0030]

[Table 1]

The emulsion layer and the undercoat layer are peeled from the glass substrate by using an aqueous solution of sodium hydroxide (film removal).
You can see that it can be done.

Example 2 The number of days after coating the emulsion on a glass substrate and the film-removing property were examined. That is, in the same manner as in Example 1, except that
As shown in Tables 2 and 3, as a glass dry plate to be treated, a glass dry plate having a different number of days since the application of the emulsion layer on the glass substrate was used under various desorption conditions (sodium hydroxide concentration,
(Desorption temperature and desorption time). The glass plates used were high resolution, squirrel, and bright room plates, and were not stirred in the desorption tank. Table 2 shows the results of the film removal of the raw dry plate (untreated dry plate) aged 0 to 2 days after the application of the emulsion, and Table 3 shows the raw dry plate (untreated dry plate) aged 3 years from the 10 days after the emulsion coating. ) And the result of film removal of the developed dry plate.

[0033]

[Table 2]

[0034]

[Table 3]

From the above results, it can be seen that the film can be satisfactorily removed from either a raw dry plate immediately after the emulsion coating or a developed dry plate three years after the emulsion coating.

Example 3 A regeneration treatment as shown in Table 4 was performed for each of the washing treatment, the inactivation treatment, and the presence or absence of non-contact storage. Table 4 shows the conditions for the film removal treatment (using an aqueous solution of sodium hydroxide as the film removal solution), the results of film removal and the results of water stain. The water stains in Table 4 are all water stains generated over time. When this water stain occurs, the undercoat and the emulsion are repelled and cannot be applied, or even if they can be applied, poor adhesion or poor surface condition occurs.

[0037]

[Table 4]

From the above results, it can be seen that the inactivation treatment and the non-contact storage are effective in preventing the occurrence of water stain.

Example 4 A treatment was carried out in the same manner as in Example 1 except that an aqueous solution of sodium hypochlorite was used as a film removing treatment solution. Table 5 shows the results of the film removal. Here, all the types of the dry plates described in Table 5 are trade names of glass dry plates manufactured by Fuji Photo Film Co., Ltd., UM is a high-resolution dry plate, AK is a bright room dry plate, PF / KO is a squirrel dry plate, YA represents a lath dry plate.

[0040]

[Table 5]

From the above results, it can be seen that the film can be sufficiently removed even when an aqueous solution of sodium hypochlorite is used.

Example 5 Nos. 4-4, 4-5, and 4 which were subjected to film removal processing in Example 4
On -6, 4-12 and 4-13 glass substrates, the corresponding emulsions for UM, PF and AK plates were recoated. In addition, No. 4-7 which was subjected to the film removal treatment in Example 4
Was stored for 25 days, and the emulsion was recoated in the same manner as described above. Table 6 shows the results. Here, the evaluation of photographic properties is performed by exposing and developing through a wedge, and calculating its characteristic curve. This method is performed by rubbing the surface while the emulsion film is wet, or by scratching it in a lattice in a dry state after processing, attaching an adhesive tape, and evaluating the state of peeling of the emulsion film when this is peeled off. Was. Each ○
Indicates that it is equivalent to the case where it is applied to a normal product.

[0043]

[Table 6]

From the above results, it can be seen that when the result of film removal is insufficient, the adhesion is reduced when the emulsion is recoated and the glass substrate is reused. In addition, when burning occurs, the adhesiveness is reduced, and the coating liquid is easily repelled at the time of undercoating and emulsion coating.

Example 6 As shown in FIG. 1, a desorption treatment tank 11, a recovery tank 13, cleaning tanks 15a and 15b, an inactivation treatment tank (finishing tank) 17, and a terminal (load) for non-contact storage of regenerated glass The following operation was performed using a playback device having (unload) 19. For transport of the glass substrate, 10 to 20 glass plates (high resolution, squirrel, lath, and bright room plates having an emulsion layer and an undercoat layer on a glass substrate) are set in a stainless steel cassette. , In a dedicated transport device, by automatic control programmed in advance,
It carried out by carrying to each processing tank. Maximum processing size of glass substrate is 1000 × 1600mm, maximum load is 250
kg.

The desorption treatment tank 11 has a capacity of about 1500 liters, and has a function of increasing the desorption efficiency by agitating air by filtering the delamination residue by pump circulation. Desorption treatment tank 1
The processing liquid and processing conditions in 1 will be described later.

The recovery tank 13 is a step for recovering the desorbed liquid taken out of the film removal processing tank 11 so as to prevent a high-concentration desorbed liquid from flowing out. Treatment was performed at room temperature for 15 seconds using filtered water. The efficiency was improved by air stirring. In FIG. 1, the cleaning tank 15 includes a first tank (15a) and a second tank (15).
In the present embodiment, the tank is composed of three tanks as shown below, and the degassed glass is washed. The washing water supplied from the third washing tank is the second
It is designed to be introduced into the washing tank and use washing water efficiently. Filtration water was used as washing water, and each treatment was performed at room temperature for 15 seconds. The efficiency was improved by air stirring. In the finishing tank 17, the surface of the glass substrate that has been subjected to film removal and cleaning is inactivated with an inactivating liquid. As an inactivating liquid, a dry well solution of a photographic drainer of 0.3 to 0.5% was used and treated at room temperature for 15 seconds. The efficiency was improved by air stirring. When the glass dry plate was regenerated under the processing conditions shown in Table 7 below, a good glass substrate could be regenerated.

[0048]

[Table 7]

Example 7 A glass dry plate was regenerated under the same apparatus and processing conditions as in Example 6, with various changes in the presence or absence of the inactivation treatment and the number of days until the emulsion coating after the film removal treatment. The properties, adhesion and the presence or absence of water stain were evaluated. Table 8 shows the results.

[0050]

[Table 8]

From the above results, when the inactivation treatment is not carried out, within 3 days, preferably 2 days after the film removal treatment, and when the inactivation treatment is carried out, 28 days after the film removal treatment It is preferable to apply the emulsion layer and the like within, preferably within 18 days.

[0052]

According to the present invention, the emulsion and the undercoat layer can be effectively removed by treating the glass dry plate with the film removal treatment solution according to the present invention, and the glass substrate subjected to the film removal treatment can be reused in the same manner as a normal glass substrate. can do. That is, a glass dry plate having the same quality as that of the normal product can be obtained by coating the emulsion in the same manner as the normal product.

Further, by collecting the above-mentioned elimination liquid and removing solids from the elimination liquid by filtration or the like, a solid glass such as silver or a hydrophilic colloid (such as gelatin) dissolved and suspended in the elimination liquid is obtained. Failure can be prevented beforehand due to adhesion to the substrate, and silver can be effectively recovered.

Further, by subjecting the glass substrate subjected to the film removal treatment to a washing treatment, it is possible to wash and remove solids in the detachment liquid that may adhere to and remain on the surface of the glass substrate. In addition, by deactivating the glass substrate that has undergone film removal,
The surface of the glass substrate is covered with a film of an organic substance that can be removed again, so that even if a certain period of time has passed after the film removal treatment, a sufficiently reproducible surface state can be ensured, and the same foreign substance cleaning effect as described above can be obtained.

Further, the glass substrate subjected to the film removal treatment is stored in a non-contact manner, whereby the occurrence of glass burn is effectively prevented and the glass dry plate can be continuously regenerated.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus for performing a glass recycling method of the present invention.

[Explanation of symbols]

 11 Decoating treatment tank 13 Recovery treatment tank 15 Cleaning treatment tank 17 Inactivation treatment tank (finishing tank) 19 Load

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Nakamura 700, Konakacho, Sano City, Tochigi Pref.

Claims (9)

[Claims] A glass substrate having at least one of a photosensitive emulsion layer, an antihalation layer and an undercoat layer is removed using an aqueous solution containing at least one alkali compound or at least two acid compounds. A method for regenerating a glass substrate, comprising: performing a treatment. 2. A method for regenerating a glass substrate, wherein the glass substrate treated by the method according to claim 1 is washed at least once. 3. A glass substrate treated by the method according to claim 1 or 2 is deactivated using an aqueous solution containing at least one compound selected from a surfactant, a water-soluble polymer and an organic acid. A method for regenerating a glass substrate, comprising: performing a treatment. 4. The method for reclaiming a glass substrate according to claim 1, wherein the aqueous solution used for the film removal treatment is recovered. 5. A method for regenerating a glass substrate, wherein the glass substrate regenerated by the method according to claim 1 is stored in a non-contact manner. 6. A method for producing a dry plate, comprising applying a photosensitive emulsion layer or an undercoat layer to a glass substrate regenerated by the method according to claim 1. 7. The method for producing a dry plate according to claim 6, wherein foreign matters adhering on the recycled glass substrate are removed before coating the photosensitive emulsion layer or the undercoat layer. 8. The method for producing a dry plate according to claim 6, wherein the time from the end of regeneration of the glass substrate to the start of application of the photosensitive emulsion layer or the undercoat layer is optimized. 9. A desorption treatment tank for removing a photosensitive emulsion layer or an undercoat layer on a glass substrate, a cleaning tank for cleaning the desorption-treated glass substrate, and an inactivation treatment for the desorption-cleaned glass substrate. An apparatus for regenerating a glass substrate, comprising an activation treatment tank and a collection tank for collecting a desorbed liquid in the desorption treatment tank.