JP2008251275A - Treatment method and treatment device of conductive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treatment method and a treatment device of a conductive material high in conductivity and storage stability and capable of keeping the line width uniform. <P>SOLUTION: This is the treatment method of the conductive material in which a silver image is formed by exposing and treating a conductive material precursor having at least one layer of a silver halide emulsion layer on a support body, and in which in treating in a treatment method liquid containing at least one kind or more of either compound of a reducing material, water-soluble phosphorous oxo acid compound, or water-soluble halide, and a face having the silver image of the conductive material is conveyed and treated with no contact. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a processing method and a processing apparatus for a conductive material that can be used for applications such as an electronic circuit, an antenna circuit, an electromagnetic wave shielding material, and a touch panel.

  In recent years, with the rapid development of the information-oriented society, technologies related to information-related devices have rapidly advanced and become popular. Among them, the display device is used for televisions, personal computers, guidance displays for stations, airports, and other information. In particular, plasma displays have attracted attention in recent years.

  In such an information society, there is a concern about the influence of electromagnetic waves radiated from these display devices. For example, the influence on surrounding electronic devices and the influence on the human body are considered. In particular, the impact on human health is not negligible, and there is a need to reduce the strength of the electromagnetic field applied to the human body, and various transparent conductive materials have been developed to meet these requirements. Has been. For example, JP-A-9-53030, JP-A-11-122024, JP-A-2000-294980, JP-A-2000-357414, JP-A-2000-329934, JP-A-2001-38843, JP-A-2001-47549. JP-A-2001-51610, JP-A-2001-57110, JP-A-2001-60416, and the like.

  As a method for producing these conductive materials, a conductive metal such as silver, copper, nickel, or indium is formed on a transparent resin film by sputtering, ion plating, ion beam assist, vacuum deposition, or wet coating. A method of forming a metal thin film is generally used. In these conventional methods, since the construction method becomes extremely complicated, there has been a problem that the productivity is high and the productivity is poor.

  Another performance required for the transparent conductive material is conductivity and light transmittance. In order to increase the conductivity, it is necessary to form a metal thin film fine pattern having a certain width and thickness. At the same time, if the line width of the pattern made of a metal that blocks light is increased, the transmittance decreases. However, it is necessary to produce a fine metal pattern with sufficient conductivity, particularly a uniform pattern with a minimum necessary width, in order to satisfy both, but this cannot be satisfied by the conventional method.

  From the viewpoint of producing a uniform pattern, a method of using a silver salt photographic light-sensitive material containing a silver halide emulsion layer as a conductive material precursor has been proposed in recent years. For example, in International Publication No. 01/51276 pamphlet (Patent Document 1) and Japanese Patent Application Laid-Open No. 2004-221564 (Patent Document 2), a silver salt photographic light-sensitive material is subjected to image exposure and development treatment, and then subjected to metal plating treatment to be transparent. Proposals have been made for methods of manufacturing conductive materials. Similarly, a method using a silver complex diffusion transfer method has also been proposed as a method using a silver salt photosensitive material, for example, JP-A-2003-77350 (Patent Document 3).

  In the case of a conductive material using these various silver salt photographic light-sensitive materials as a conductive material precursor and higher conductivity is required, a metal plating process is performed. However, particularly when trying to perform electrolytic metal plating on a fine metal pattern, the resistance of the pattern is too high for electrolytic plating in the fine pattern, and only the power feeding portion may be plated. Therefore, there has been a demand for a conductive material using a silver salt photographic light-sensitive material capable of obtaining high conductivity even with a fine metal pattern and a method for producing the same so that the electrolytic metal plating process is made uniform.

  Furthermore, the conductivity of conductive materials using various silver salt photographic light-sensitive materials as the conductive material precursor may vary during storage. As an example in which this is a problem, there is a 1 / 4λ type electromagnetic wave absorber. The 1 / 4λ type wave absorber has a structure in which a transparent resistive film equal to 377Ω which is a characteristic impedance of free space is installed at a position separated by ¼ of the wavelength λ of the radio wave absorbed from the radio wave reflector. . A conductive material using silver salt photographic light-sensitive material as a conductive material precursor can make a highly transparent resistor, but the resistance is lost due to the previous problem of conductivity variation, and the performance of the radio wave absorber is preserved. Deteriorates inside. As can be seen from this example, there has been a demand for a conductive material that not only has sufficiently high conductivity but also has high storage stability and a method for manufacturing the same.

  As means for solving the above problems, Japanese Patent Application No. 2006-176037 disclosed that a conductive material precursor having at least one silver halide emulsion layer on a support was exposed and developed to form a silver image on the support. Later, a treatment method for a conductive material is proposed in which treatment is performed with a treatment solution containing at least one of a reducing substance, a water-soluble phosphorus oxoacid compound, and a water-soluble halide.

  By the way, when electroless plating and / or electrolytic plating is performed on metallic silver, which is a fine metal pattern of the conductive material obtained, it is very preferable if it can be manufactured by roll-to-roll from the viewpoint of productivity. Here, the treatment with a roll-to-roll means that a conductive material wound in a roll shape (hereinafter referred to as a conductive material roll) is subjected to a treatment such as electroless plating and / or electrolytic plating and then wound into a roll shape again. It is a method to take. Therefore, the conductive material precursor described in the above-mentioned Patent Documents 1 to 3 having at least one silver halide emulsion layer on the support is suitable from the viewpoint of obtaining a roll-shaped conductive material. JP-A-2006-190535 (Patent Document 4) and JP-A-2006-286410 (Patent Document 5) are known as various processing methods or processing apparatuses.

However, at least one of the reducing substance, the water-soluble phosphorus oxoacid compound, and the water-soluble halide is used by using a roll of a conductive material having metallic silver as a fine metal pattern on the support. When an attempt is made to produce efficiently by a method of treating with the treatment liquid containing the above and then winding it on a roll body, when the electroless plating and / or electrolytic plating is subsequently applied, the obtained metal pattern line It was difficult to keep the width uniform and was not satisfactory.
WO 01/51276 pamphlet JP 2004-221564 A JP 2003-77350 A JP 2006-190535 A JP 2006-286410 A

  Accordingly, an object of the present invention is to provide a processing method and a processing apparatus for a conductive material that have high conductivity and storage stability and can maintain a uniform line width.

The above object of the present invention has been achieved by the following processing method and processing apparatus.
1) A method for treating a conductive material in which a conductive material precursor having at least one silver halide emulsion layer on a support is exposed and developed to form a silver image, the following (I) to (I) III) Conductive material characterized in that when it is treated with a treatment liquid containing at least one type of compound according to any one of the above compounds, the surface having the silver image of the conductive material is conveyed and treated in a non-contact manner. Processing method.
(I) Reducing substance (II) Water-soluble phosphorus oxoacid compound (III) Water-soluble halide 2) A treatment apparatus used in the method for treating a conductive material according to 1) above, wherein the conductive material is in the form of a roll An unwinding section for holding the conductive material, a processing section for treating the conductive material with the treatment liquid, a drying section, and a winding section for winding the dried conductive material into a roll, The surface having the silver image of the conductive material is conveyed and processed in a non-contact manner from the time when the conductive material enters the processing section treatment tank to the time when it enters the washing section water washing tank. Conductive material processing equipment.
3) A processing apparatus used in the method for processing a conductive material according to 1) above, wherein a roll-out portion for holding the roll-shaped conductive material precursor, and developing the conductive material precursor with a developer. A developing section to be processed, a washing section for removing the silver halide emulsion layer of the conductive material precursor, a drying section, a processing section for processing the conductive material with the processing liquid, and a drying section; A winding portion for winding the dried conductive material into a roll shape, and from the time when the conductive material enters the treatment unit treatment tank until it enters the washing unit water washing tank, A conductive material processing apparatus for transporting and processing a surface having a silver image of a conductive material in a non-contact manner.

  According to the present invention, it is possible to provide a processing method and a processing apparatus for a conductive material that have high conductivity and storage stability and can maintain a uniform line width.

  By subjecting a metallic silver image derived from a silver salt photosensitive material to a treatment solution containing, for example, a water-soluble halide, a metallic silver image having high conductivity and high storage stability can be obtained. Hereinafter, this treatment is referred to as post-treatment, and the treatment liquid is referred to as post-treatment liquid.

  In the present invention, the conductive material precursor having at least one silver halide emulsion layer on the support may be developed after exposure by (1) development processing according to the silver salt diffusion transfer method, or (2) direct development. There are three development processing methods typified by development processing to be fixed later and (3) development processing according to the curing development method. The method (1) is, for example, the method described in JP-B-42-23745, the method (2) is, for example, the method described in US Pat. No. 6,706,165, and the method (3) is, for example, J. et al. Photo. Sci. Magazine No. 11 p 1, A. G. By Tull (1963) or “The Theory of the Photographic Process (4th edition, p326-327)”, T. H. It is described by James et al.

  In the method (1), an image is deposited by a development process by silver salt diffusion transfer development, and then the silver halide emulsion layer that is no longer needed is removed by a water washing removal process, and then the conductive material is dried by a drying process. As described above, the development process of the conductive material is basically composed of three processes. In the method (2), the direct development processing, fixing processing, water washing processing, and drying processing are the basic development processing steps. In the method (3), a curing development process, water washing removal, and a drying process are the basic components of the development process.

  The post-processing of the present invention is performed after image formation. Next, it will be described in which step the post-processing step of the present invention is performed. FIG. 6 is a conceptual diagram showing the order of the post-processing steps of the present invention. FIG. 6 shows the sequence of steps from unwinding the exposed roll-shaped conductive material processed by roll-to-roll through a series of processing steps to winding. Here, the development in FIG. 6 is shown as three development methods: (1) development by silver salt diffusion transfer, (2) direct development, and (3) curing development. (A) is a method in which post-processing is performed after the development step in any of the above methods (1), (2), and (3). After the post-treatment process, the treatment is performed in the order of fixing, water removal, water washing and drying treatment. FIG. 6B shows a method in which post-processing is performed after the development, fixing, or water washing removal process. After the post-treatment step, it is preferable to wash with water so that the components of the post-treatment liquid do not precipitate on the surface of the conductive material, and then dry treatment. FIG. 6 (c) shows a method in which post-processing is performed after development, fixing, water removal, and water washing steps. Also in the method (c), it is preferable to carry out washing and drying after the post-treatment step as in the method (b). FIG. 6 (d) shows a method in which post-processing is performed after development, fixing or water removal, water washing and drying. Also in the method (d), it is preferable to carry out water washing and drying treatment after the post-treatment step as in the methods (a), (b) and (c).

  By the way, in order to process in roll-to-roll in order to realize mass production, when the above processes (a), (b), and (c) are continuously performed, the conductive material being conveyed is wet. In this state, the post-treatment process is started, and the post-treatment liquid concentration management load increases due to dilution of the post-treatment liquid. Further, the post-treatment quality may be adversely affected. It is. Hereinafter, the processing apparatus (d) will be described in detail.

  The feature of the post-treatment method of the conductive material of the present invention is that the silver image surface imaged by the development processing is used from the time when the conductive material enters the processing section processing tank until it enters the washing section water washing tank. Transport and process in a non-contact state. Here, transporting the silver image surface in a non-contact state means that the silver image surface is not in contact with a fixed object such as a roll. In general, when transporting a continuously running support, it is simpler in terms of apparatus and tends to be employed when the support is conveyed by contacting the front and back of the support with a roll or the like. However, the contact-type conveyance cannot obtain the line width uniformity of the mesh pattern. In the present invention, by conducting non-contact conveyance of the silver image surface, a conductive material having high conductivity and storage stability and capable of keeping the line width uniform can be obtained.

  Embodiments of a post-treatment apparatus for a conductive material according to the present invention will be described below in detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an example of a post-processing apparatus of the present invention, which is an example in which the post-processing apparatus of the present invention is applied to a conductive material precursor processing apparatus. FIG. 1 shows a conductive material processing apparatus corresponding to the development processing methods (1) and (3) described above. In the description of FIG. 1, the developing unit 100 side is the upstream side, and the drying unit 6 side is the downstream side.

  In FIG. 1, the conductive material post-processing apparatus of the present invention includes a roll-shaped unwinding portion 16 of the conductive material precursor E and a developing portion that develops the conductive material precursor E with a developer 110. 100, a water washing part 101 for removing the silver halide emulsion layer of the conductive material precursor E, a drying part 102, a post-treatment part 4 for post-treatment by immersing the conductive material, and the conductive material The water-washing part 5 for carrying out the water-washing process of the property material, the drying part 6, and the winding-up part 18 for winding up the dried electroconductive material in roll shape are provided.

  In the post-processing apparatus shown in FIG. 1, the conductive material precursor roll 20 that has been exposed in advance is subjected to development processing for a predetermined time in the developing unit 100 while being unwound from the unwinding shaft 2 and transported, and the water-washing unit 101. The unnecessary silver halide emulsion layer and the like are removed, the moisture is dried in the drying unit 102, and at least one of the reducing substance, the water-soluble phosphorus oxoacid compound, and the water-soluble halide is used in the post-processing unit 4. A post-treatment is performed for a predetermined time with the treatment liquid 14 contained above, the water is washed in the water washing section 5, the moisture is dried in the drying section 6, and the paper is wound around the winding shaft 9. As a result, a conductive pattern having high conductivity and storage stability on the support and capable of keeping the line width uniform when electroless plating and / or electrolytic plating is performed thereafter is obtained. When a transparent support such as a plastic resin film is used as the support, a transparent conductive film can be obtained. Moreover, the bonding part of the process of bonding a protective film etc. after drying is provided as needed.

  In FIG. 1, a roll-shaped conductive material precursor roll 20 is mounted on the unwinding shaft 2 and is continuously unwound in the direction of the arrow and conveyed. The surface of the roll-shaped conductive material precursor roll 20 having the silver halide emulsion layer is wound in an inner volume. A tension control means 3, for example, a powder brake, is connected to the unwinding shaft 2 to control the tension applied to the conductive material precursor E in the development processing unit 100, the water washing unit 101, and the drying unit 102. The tension control means 3 is 40 to 150 N / m at the conductive material precursor E in order to suppress meandering, wrinkles and sagging of the conductive material precursor E in the development processing unit 100, the water washing unit 101, and the drying unit 102. The range of tension is applied, and the transport speed and tension of the conductive material precursor E are controlled and transported.

  Before the conductive material precursor E unwound from the roll-shaped conductive material precursor roll 20 is transported and enters the developing tank 109, the transport direction of the conductive material precursor E is reversed by the reverse roller 107. . The surface having the silver halide emulsion layer is conveyed in the developing tank 109 in a non-contact state by the reversing roller 107 and the reversing roller 108 described later. The development tank 109 is preferably a vertically long and thin tank as shown in FIG. 1, by reversing the transport direction while supporting the back surface of the conductive material precursor E with the reverse roller 108 provided in the lower part of the tank, The development time (the time of immersion in the developer) can be obtained with a small installation space.

  The capacity of the developing tank 109 varies depending on the width dimension of the conductive material precursor E, but about 30 to 130 liters is appropriate. More preferably, it is 50-100 liters. In the developing tank 109, the developing solution 110 is stored up to a predetermined level, and the developing solution consumed by the developing process is periodically replenished by a replenishing device (not shown). The developing tank 109 is adjusted to a predetermined temperature range by a constant temperature device (not shown).

  The conductive material precursor E discharged from the developing tank 109 is continuously developed in the air developing unit 111 and conveyed to the water washing unit 101. The water washing unit 101 includes a first water washing tank 103, a second water washing tank 104, a third water washing tank 105, and a rinse tank 106. The rinsing tanks 103, 104, 105, and the rinsing tank 106 are designed to clean the front and back surfaces of the conductive material precursor E that is continuously conveyed by shower nozzles 114, 117, 120, and 123, which will be described later. In order to prevent the quality of the conductive material precursor E from being scattered by shower water droplets and adhering to the water droplets, each tank is covered with a cover (not shown).

  An air knife 112 is installed at the inlet of the first water washing tank 103, and the hot water ejected from the shower nozzle 114 does not flow into the aerial development unit 111 along the conductive material precursor E that is continuously running. I am doing so. In order to stabilize the distance between the air knife and the conductive material precursor E and stabilize the effect of the air knife, a roller 137 is disposed under the air knife 112. Moreover, in order to stabilize the conveyance level of the electroconductive material precursor E, the rollers 138 and 139 are arrange | positioned in the washing tank. The rollers 137, 138, and 139 are preferably rubber rollers that do not slip when the conductive material precursor E is conveyed and are difficult to be damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The conductive material precursor E in the first water rinsing tank 103 is uniformly sprayed over the entire surface of the conductive material precursor E in the first water rinsing tank 114 by hot water ejected from the shower nozzle 114. The formed silver halide emulsion layer and the intermediate layer and protective layer provided as necessary are washed away with water to expose the metallic silver deposited on the physical development nuclei. Or the metal silver obtained by hardening image development is exposed. An air knife 113 is also installed at the outlet of the first rinsing tank 103 so that the hot water ejected from the shower nozzle 114 does not flow into the second rinsing tank 104. A shower nozzle 114 is also provided on the back surface of the conductive material precursor E, and the backing layer is removed by washing with water. In the figure, three shower nozzles 114 for spraying on the front and back sides of the conductive material precursor E conveyed to the first washing tank 103 are provided, but the shower pressure can be adjusted by a valve (not shown). Yes.

  Next, air knives 115, 116, 118, and 119 are installed at the inlet and the outlet of the second rinsing tank 104 and the third rinsing tank 105, respectively, to prevent mixing of the rinsing liquid with the adjacent tanks and downstream. The structure increases the cleanliness of the washing solution. Subsequently, an air knife 121 is also installed at the entrance of the rinsing tank 106 so that fresh ion-exchanged hot water (hereinafter referred to as hot pure water) ejected from the shower nozzle 123 does not flow into the third washing tank 105. The hot pure water ejected from the shower nozzle 123 of the rinsing tank 106 completely removes unnecessary portions that could not be removed up to the third water washing tank 105, thereby further improving the cleanliness of the front and back of the conductive material precursor E. . A sponge-like soft roll 122 is installed at the outlet of the rinsing tank 106 to prevent moisture adhering to the conductive material precursor from being brought into the drying unit 102. As described above, by providing air knives at the inlet and outlet between each washing tank, the washing water used for washing in each washing tank is not brought into the washing tank with high cleanliness downstream. As the tank is washed with water, the washing efficiency is higher, the sludge is reliably prevented from being attached, and a conductive material having a high commercial value can be obtained.

  The hot water ejected from the shower nozzle 114 of the first water washing tank 103 is stored in the first water washing storage tank 124 by a pipe (not shown), and is circulated and supplied to the shower nozzle 114 by the circulation pump 129. About 20-50 liters is suitable for the capacity | capacitance of the 1st washing storage tank 124. FIG. A filter 130 is installed in the hot water piping route to remove floating matters such as silver sludge and dust floating in the hot water. A heater (not shown) is installed in the first washing / reservoir 124 and the temperature is adjusted to about 35 to 45 ° C. Similarly, circulation pumps 131 and 133 and filters 132 and 134 are also installed in the second flush storage tank 125 and the third flush storage tank 126, and the capacity of the storage tank is equivalent to 20 to 50 liters, and a heater (not shown) is also provided. It is installed and the temperature is adjusted to about 35 to 45 ° C.

  The warm pure water ejected from the shower nozzle 123 of the rinsing tank 106 is stored in the rinse storage tank 127 through a pipe (not shown), and is circulated and supplied to the shower nozzle 123 by the circulation pump 135. The capacity of the rinse storage tank 127 is appropriately about 20 to 50 liters. The rinse storage tank 127 is provided with a circulation pump 135, a filter 136, and a heater (not shown), and the temperature is adjusted to about 30 to 40 ° C. The rinse storage tank 127 is provided with a replenishment supply port 128 from a warm pure water tank (not shown), and warm pure water is replenished by about 1 to 15 liters / minute. Preferably, it is 2-5 liters / minute.

  The rinse storage tank 127 is provided with an overflow liquid supply port 93 serving as an overflow liquid supply means. When a predetermined amount or more of warm pure water is stored, the rinse storage tank 127 overflows and is replenished to the third flush storage tank 126. An overflow liquid supply port 92 is also attached to the third flush storage tank 126, and the overflowed warm water is replenished to the second flush storage tank 125. An overflow liquid supply port 91 is also attached to the second flush storage tank 125, and the overflowed warm water is replenished to the first flush storage tank 124. The first flush storage tank 124 is also provided with an overflow port 90, and the overflowing hot water DW is drained. By replenishing only the rinse storage tank 127 with fresh warm pure water, the overflow water having a higher cleanness is sequentially supplied to the downstream washing tanks from the downstream side to realize the liquid saving of the replenishing liquid, In addition, because the air knives installed between each washing tank do not mix between the tanks, the washing water used for washing in each washing tank is not brought into the downstream washing tank with high cleanliness. Washing with high cleaning efficiency is performed, sludge adhesion is reliably prevented, and a conductive material with high commercial value can be obtained.

  A sufficient amount of warm water and warm pure water is sprayed on both the front and back surfaces of the conductive material precursor E in the water washing section 101, and the conductive material F from which unnecessary components are completely washed away is dried in the drying section 102. Blowing nozzles 152 are installed at the top and bottom of the drying unit 6, and the conductive material F is dried by warm air hitting the front and back of the conductive material F. Although the drying temperature should just be 30 degreeC or more, 40-65 degreeC is suitable from a viewpoint of productivity. Preferably, 50-60 degreeC is suitable. The conductive material F is conveyed to the post-processing unit 4 after passing through the nip roll pair 153 after the drying unit 102. Before and after the nip roll pair 153, the tension of the developing unit 100, the rinsing unit 101, and the drying unit 102 and the post-processing unit 4, the rinsing unit 5, and the drying unit 6 that are the subsequent processes are controlled separately.

  The conductive material F conveyed from the nip roll pair 153 is reversed in the conveyance direction by the reverse roller 11 before entering the post-treatment tank 13. The silver image surface is conveyed in a non-contact state in the post-processing tank by the reverse roller 11 and the reverse roller 12 described later. The post-treatment tank 13 is preferably a vertically long and thin tank as shown in FIG. 1, and is small by reversing the conveying direction while supporting the back surface of the conductive material F with the reverse roller 12 provided in the lower part of the tank. A sufficient amount of post-treatment time (time of immersion in the post-treatment liquid) can be obtained in the installation space.

  The capacity of the post-treatment tank 13 varies depending on the width of the conductive material F, but about 30 to 130 liters is appropriate. More preferably, it is 50-100 liters. The post-processing liquid 14 is stored in the post-processing tank 13 up to a predetermined liquid level, and the post-processing liquid consumed by the post-processing is periodically replenished by a replenishing device (not shown). The post-treatment tank 13 is adjusted to a predetermined temperature range by a thermostat (not shown). In the present invention, the time when the conductive material enters the processing section processing tank is the time A when the conductive material F enters the post-treatment liquid 14 in the post-processing tank 13 in FIG. This is the last roller with the reversing roller 11 in contact with the silver image surface before starting the post-processing. Also, the time until the silver image surface of the conductive material F enters the processing section processing tank is B until it enters the water washing section water washing tank, and the roller that contacts the silver image surface for the first time after being conveyed in a non-contact manner is the first. 1 is a roller 32 of the water washing tank 21.

  The feature of the post-processing apparatus of the conductive material of the present invention is that the silver image surface imaged by the development processing is from the time when the conductive material enters the processing section processing tank to the time when it enters the washing section water washing tank. Transport and process in a non-contact state. Moreover, conveying with a silver image surface being non-contact means not contacting a fixed object, such as a roll. A conductive material that has high conductivity and storage stability by non-contact conveyance of the silver image surface, and can maintain a uniform line width when electroless plating and / or electrolytic plating is performed thereafter. can get.

  The conductive material F discharged upward from the post-treatment tank 13 is conveyed horizontally or substantially downward from the roller 15 and sent to the water washing section 5. The water washing section 5 has a first water washing tank 21 and a second water washing tank 22. The washing tanks 21 and 22 store washing water 27 and 28, and are washed by immersion treatment with washing water on the front and back of the conductive material F that is continuously conveyed. As shown in FIG. 1, it is preferable that the rinsing water 27 and 28 in each tank is circulated by shower nozzles 23, 24, 25 and 26. In addition, each tank is covered with a cover (not shown) in order to prevent an increase in humidity in the processing apparatus room, scattering of shower water droplets, and quality abnormality of the conductive material F due to water droplet adhesion.

  In addition, a roller cleaning tab 17 is installed at the lower part of the roller 15 in order to prevent adhesion of the post-treatment liquid 14 on the surface of the roller 15, and the washing water 28 of the second washing tank 22 is periodically supplied in a fixed amount. It is supplied by a pump 46 and drains excess water from an overflow port (not shown).

  A roller 31 is installed lower than the roller 15 at the entrance of the first washing tank 21. This does not cause the post-treatment liquid 14 on the conductive material F conveyed after the roller 15 to stay, and for example, causes the post-treatment liquid 14 to flow toward the post-treatment tank 13 even if the post-treatment liquid 14 flows down. In addition, the roller 31 lower part is installed lower than the washing tank liquid level in order to prevent sticking of the roller surface. The rollers 32 and 33 are installed in the washing water stored in the first washing tank, and the silver image surface of the conductive material F is brought into contact with it and conveyed. Washing water circulating in the first washing tank ejected from the shower nozzles 23 and 24 is directed to the front and back of the conductive material F, respectively. The rollers 31, 32, 33, and 34 of the first rinsing tank 21 are preferably rubber rollers that do not slip during transportation and are not easily damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The conductive material F in the first water rinsing tank 21 is dipped, conveyed and washed by the stored water for washing. This prevents the front and back of the conductive material F in the first washing tank 21 from being crystallized by the components of the post-treatment liquid. In the figure, shower nozzles 23 and 24 that are sprayed on the front and back sides of the conductive material F conveyed to the first rinsing tank 21 are installed one by one, but the number is not particularly limited, and the shower pressure Can be adjusted by valves (not shown).

  A roller 34 is installed at the outlet of the first washing tank 21. The upper part of the roller 34 is set higher than the liquid level of the washing tank in order to drain the washing liquid. In addition, the lower part of the roller 34 is immersed in the washing tank liquid level to prevent the roller surface from sticking. The reason why the rinsing water 27 is not squeezed with the roller pair is to prevent the surface of the conductive material F from being damaged due to adhesion of the roller pair and entrainment of dust.

  Next, a roller 35 is installed at the entrance of the second washing tank 22. The roller 35 is preferably installed slightly higher than the previous roller 34. This is to prevent the flush water 28 in the second flush tank 22 from lowering the cleanliness than the flush water 27 in the first flush tank 21. The rollers 36 and 37 are installed in the rinsing water 28 stored in the second rinsing tank 22, so that the silver image surface of the conductive material F is brought into contact with the irrigated water. Flushing water 28 circulating in the second flushing tank, which is ejected from the shower nozzles 25 and 26, is directed to the front and back surfaces of the conductive material F, respectively. The rollers 35, 36, 37, and 38 of the second washing tank 22 are also preferably rubber rollers that do not slip during transportation and are not easily damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The shower nozzle 29 of the second washing tank 22 further improves the cleanliness of the surface of the conductive material F by directly jetting fresh ion exchanged water (hereinafter referred to as pure water) onto the surface of the conductive material. Then, it is replenished as flush water 28 in the second flush tank 22. Pure water is provided with a replenishment supply port 29 from a tank (not shown) and replenishes pure water at a rate of 0.1 to 10 liters / minute. Preferably, it is 0.15-5 liter / min. A sponge-like soft roller 39 is installed at the outlet of the second rinsing tank 22 so that moisture adhering to the conductive material F is not brought into the drying unit 6.

  The flush water 27 ejected from the shower nozzles 23 and 24 of the first flush tank 21 is circulated and supplied to the shower nozzles 23 and 24 by a pipe 40 and a circulation pump 42. The capacity of the first rinsing tank 21 is suitably about 10 to 50 liters. A filter 43 is installed in the flush water piping path to remove suspended matters such as dust floating in the flush water. As the flush water 27 in the first flush tank 21, pure water whose temperature is not adjusted is used. Similarly, a circulation pump 44 and a filter 45 are also installed in the second washing tank 22, and the capacity of the second washing tank is appropriately about 20 to 60 liters, and pure water whose temperature is not adjusted is used.

  The second flush tank 22 is provided with an overflow port 51. When the flush water 28 is stored in a predetermined amount or more, it overflows and is replenished to the first flush tank 21. The first flush tank 21 is also provided with an overflow port 50, and the flushed water D that has overflowed is drained. By replenishing only the second flushing tank 22 with fresh pure water, and replenishing the overflow water with high cleanness from the downstream to the upstream first flushing tank, liquid saving of the supplementary liquid is realized, and between each washing tank Since it is difficult to bring the washing water used for washing into the downstream washing tank having high cleanliness, washing with higher washing efficiency is performed in the downstream washing tank, and a conductive material with higher commercial value is obtained.

  After the post-treatment liquid adhering to both the front and back surfaces of the conductive material F is sufficiently washed and washed with water in the water washing section 5, the front and back surfaces of the conductive material F are dried in the drying section 6 and rolled on the winding shaft 9. Rolled up into a shape. Blowing nozzles 19 are installed at the top and bottom of the drying unit 6, and the conductive material F is dried by warm air hitting the front and back of the conductive material F. Although the drying temperature should just be 30 degreeC or more, 40-65 degreeC is suitable from a viewpoint of productivity. Preferably, 50-60 degreeC is suitable. A tension control means 10, such as a torque motor, that can drive and rotate the shaft is attached to the winding shaft 9. The tension is suitably in the range of 40 to 150 N / m.

  FIG. 2 shows another embodiment of the present invention, in which the development, fixing or water washing removal, water washing, and drying processes in FIG. It is a schematic sectional drawing which shows an example of the post-processing apparatus of this invention to process. In the description of the drawings of the present invention, the post-processing unit 4 side is upstream, and the drying unit 6 side is downstream.

  The conductive material processing apparatus of the present invention shown in FIG. 2 includes a roll-shaped unwinding portion 16 of the conductive material, a post-processing portion 4 that performs post-treatment by immersing the conductive material, and the conductive material. It has the water washing part 5 for performing a water washing process, the drying part 6, and the winding-up part 18 for winding up the dried electroconductive material in roll shape.

  In the post-processing apparatus shown in FIG. 2, the conductive material roll 1 that has been exposed and developed in advance is unwound from the unwinding shaft 2 and conveyed, while the post-processing unit 4 reduces the reducing substance, the water-soluble phosphoroacid compound, and A post-treatment is performed for a predetermined time with a treatment liquid 14 containing at least one compound of any one of water-soluble halides, followed by washing with a water washing section 5, drying moisture with a drying section 6, and applying to a winding shaft 9. It is wound up. As a result, a conductive pattern having high conductivity and storage stability on the support and capable of keeping the line width uniform when electroless plating and / or electrolytic plating is performed thereafter is obtained. When a transparent support such as a plastic resin film is used as the support, a transparent conductive film can be obtained. Moreover, the bonding part of the process of bonding a protective film etc. after drying is provided as needed.

  In FIG. 2, a roll-shaped conductive material roll 1 is mounted on an unwinding shaft 2 and is continuously unwound in the direction of the arrow and conveyed. The roll-shaped conductive material roll 1 has a silver image surface wound inside. A tension control means 3, for example, a powder brake, is connected to the unwinding shaft 2 to control the tension applied to the conductive material F in the post-processing unit 4, the water washing unit 5, and the drying unit 6. The tension control means 3 applies a tension in the range of 40 to 150 N / m to the conductive material F in order to suppress meandering, wrinkles and sagging of the conductive material F in the post-processing unit 4, the water washing unit 5 and the drying unit 6. The transport speed and tension of the conductive material F are controlled and transported.

  Before the conductive material F unwound from the roll-shaped conductive material roll 1 is transported and enters the post-treatment tank 13, the transport direction of the conductive material F is reversed by the reverse roller 11. The silver image surface is conveyed in a non-contact state in the post-processing tank by the reverse roller 11 and the reverse roller 12 described later. The post-treatment tank 13 is preferably a vertically long and thin tank as shown in FIG. 2, and is small by reversing the transport direction while supporting the back surface of the conductive material F with the reverse roller 12 provided in the lower part of the tank. A sufficient amount of post-treatment time (time of immersion in the post-treatment liquid) can be obtained in the installation space.

  The capacity of the post-treatment tank 13 varies depending on the width of the conductive material F, but about 30 to 130 liters is appropriate. More preferably, it is 50-100 liters. The post-processing liquid 14 is stored in the post-processing tank 13 up to a predetermined liquid level, and the post-processing liquid consumed by the post-processing is periodically replenished by a replenishing device (not shown). The post-treatment tank 13 is adjusted to a predetermined temperature range by a thermostat (not shown). In the present invention, similar to the conductive material processing apparatus of FIG. 1 described above, the time when the conductive material entered the processing section processing tank is the time when the conductive material F is in the post-processing liquid 14 of the post-processing tank 13 in FIG. This is the point A at the time of intrusion, and is the last roller where the reversing roller 11 contacts the silver image surface of the conductive material F before the start of post-processing. Also, the time until the silver image surface of the conductive material F enters the processing section processing tank is B until it enters the water washing section water washing tank, and the roller that contacts the silver image surface for the first time after being conveyed in a non-contact manner is the first. 1 is a roller 32 of the water washing tank 21.

  The feature of the post-processing apparatus of the conductive material of the present invention is that the silver image surface imaged by the development processing is from the time when the conductive material enters the processing section processing tank to the time when it enters the washing section water washing tank. Transport and process in a non-contact state. Moreover, conveying with a silver image surface being non-contact means not contacting a fixed object, such as a roll. A conductive material that has high conductivity and storage stability by non-contact conveyance of the silver image surface, and can maintain a uniform line width when electroless plating and / or electrolytic plating is performed thereafter. can get.

  The conductive material F discharged upward from the post-treatment tank 13 is conveyed horizontally or substantially downward from the roller 15 and sent to the water washing section 5. The water washing section 5 has a first water washing tank 21 and a second water washing tank 22. The washing tanks 21 and 22 store washing water 27 and 28, and are washed by immersion treatment with washing water on the front and back of the conductive material F that is continuously conveyed. As shown in FIG. 2, it is preferable that the rinsing water 27 and 28 in each tank is circulated by shower nozzles 23, 24, 25 and 26. In addition, each tank is covered with a cover (not shown) in order to prevent an increase in humidity in the processing apparatus room, scattering of shower water droplets, and quality abnormality of the conductive material F due to water droplet adhesion.

  In addition, a roller cleaning tab 17 is installed at the lower part of the roller 15 in order to prevent adhesion of the post-treatment liquid 14 on the surface of the roller 15, and the washing water 28 of the second washing tank 22 is periodically supplied in a fixed amount. It is supplied by a pump 46 and drains excess water from an overflow port (not shown).

  A roller 31 is installed lower than the roller 15 at the entrance of the first washing tank 21. This does not cause the post-treatment liquid 14 on the conductive material F conveyed after the roller 15 to stay, and for example, causes the post-treatment liquid 14 to flow toward the post-treatment tank 13 even if the post-treatment liquid 14 flows down. In addition, the roller 31 lower part is installed lower than the washing tank liquid level in order to prevent sticking of the roller surface. The rollers 32 and 33 are installed in the washing water stored in the first washing tank, and the silver image surface of the conductive material F is brought into contact with it and conveyed. Washing water circulating in the first washing tank ejected from the shower nozzles 23 and 24 is directed to the front and back of the conductive material F, respectively. The rollers 31, 32, 33, and 34 of the first rinsing tank 21 are preferably rubber rollers that do not slip during transportation and are not easily damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The conductive material F in the first water rinsing tank 21 is dipped, conveyed and washed by the stored water for washing. This prevents the front and back of the conductive material F in the first washing tank 21 from being crystallized by the components of the post-treatment liquid. In the figure, shower nozzles 23 and 24 that are sprayed on the front and back sides of the conductive material F conveyed to the first rinsing tank 21 are installed one by one, but the number is not particularly limited, and the shower pressure Can be adjusted by valves (not shown).

  A roller 34 is installed at the outlet of the first washing tank 21. The upper part of the roller 34 is set higher than the liquid level of the washing tank in order to drain the washing liquid. In addition, the lower part of the roller 34 is immersed in the washing tank liquid level to prevent the roller surface from sticking. The reason why the rinsing water 27 is not squeezed with the roller pair is to prevent the surface of the conductive material F from being damaged due to adhesion of the roller pair and entrainment of dust.

  Next, a roller 35 is installed at the entrance of the second washing tank 22. The roller 35 is preferably installed slightly higher than the previous roller 34. This is to prevent the flush water 28 in the second flush tank 22 from lowering the cleanliness than the flush water 27 in the first flush tank 21. The rollers 36 and 37 are installed in the rinsing water 28 stored in the second rinsing tank 22, so that the silver image surface of the conductive material F is brought into contact with the irrigated water. Flushing water 28 circulating in the second flushing tank, which is ejected from the shower nozzles 25 and 26, is directed to the front and back surfaces of the conductive material F, respectively. The rollers 35, 36, 37, and 38 of the second washing tank 22 are also preferably rubber rollers that do not slip during transportation and are not easily damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The shower nozzle 29 of the second rinsing tub 22 is used as the rinsing water 28 of the second rinsing tub 22 while further improving the cleanliness of the surface of the conductive material F by jetting pure water directly onto the surface of the conductive material. To be replenished. Pure water is provided with a replenishment supply port 29 from a tank (not shown) and replenishes pure water at a rate of 0.1 to 10 liters / minute. Preferably, it is 0.15-5 liter / min. A sponge-like soft roller 39 is installed at the outlet of the second rinsing tank 22 so that moisture adhering to the conductive material F is not brought into the drying unit 6.

  The flush water 27 ejected from the shower nozzles 23 and 24 of the first flush tank 21 is circulated and supplied to the shower nozzles 23 and 24 by a pipe 40 and a circulation pump 42. The capacity of the first rinsing tank 21 is suitably about 10 to 50 liters. A filter 43 is installed in the flush water piping path to remove suspended matters such as dust floating in the flush water. As the flush water 27 in the first flush tank 21, pure water whose temperature is not adjusted is used. Similarly, a circulation pump 44 and a filter 45 are also installed in the second washing tank 22, and the capacity of the second washing tank is appropriately about 20 to 60 liters, and pure water whose temperature is not adjusted is used.

  The second flush tank 22 is provided with an overflow port 51. When the flush water 28 is stored in a predetermined amount or more, it overflows and is replenished to the first flush tank 21. The first flush tank 21 is also provided with an overflow port 50, and the flushed water D that has overflowed is drained. By replenishing only the second flushing tank 22 with fresh pure water, and replenishing the overflow water with high cleanness from the downstream to the upstream first flushing tank, liquid saving of the supplementary liquid is realized, and between each washing tank Since it is difficult to bring the washing water used for washing into the downstream washing tank having high cleanliness, washing with higher washing efficiency is performed in the downstream washing tank, and a conductive material with higher commercial value is obtained.

  After the post-treatment liquid adhering to both the front and back surfaces of the conductive material F is sufficiently washed and washed with water in the water washing section 5, the front and back surfaces of the conductive material F are dried in the drying section 6 and rolled on the winding shaft 9. Rolled up into a shape. Blowing nozzles 19 are installed at the top and bottom of the drying unit 6, and the conductive material F is dried by warm air hitting the front and back of the conductive material F. Although the drying temperature should just be 30 degreeC or more, 40-65 degreeC is suitable from a viewpoint of productivity. Preferably, 50-60 degreeC is suitable. A tension control means 10, such as a torque motor, that can drive and rotate the shaft is attached to the winding shaft 9. The tension is suitably in the range of 40 to 150 N / m.

  Next, a conductive material post-processing apparatus according to another embodiment of the present invention will be described in detail with reference to the drawings. FIG. 3 is a schematic sectional view of the post-processing apparatus of the present invention. In the description of the drawings of the present invention, the post-processing section side is upstream and the drying section side is downstream.

  FIG. 3 shows a conductive material post-processing apparatus according to the present invention, a roll-shaped conductive material unwinding section 16, a post-processing section 4 for post-processing the conductive material with a shower nozzle, and the conductive material. The water washing part 5 for carrying out the water washing process, the drying part 6, and the winding-up part 18 for winding up the dried electroconductive material in roll shape are provided.

  In the post-processing apparatus shown in FIG. 3, the conductive material roll 1 that has been exposed and developed in advance is unrolled from the unwinding shaft 2 and conveyed, and is subjected to post-processing for a predetermined time by the post-processing unit 4 to be washed with water. The water is washed in the section 5, the moisture is dried in the drying section 6, and the film is wound around the winding shaft 9. As a result, a conductive pattern having high conductivity and storage stability on the support and capable of keeping the line width uniform when electroless plating and / or electrolytic plating is performed thereafter is obtained. When a transparent support such as a plastic resin film is used as the support, a transparent conductive film can be obtained. Moreover, the bonding part of the process of bonding a protective film etc. after drying is provided as needed.

  In FIG. 3, a roll-shaped conductive material roll 1 is mounted on the unwinding shaft 2, and is continuously unwound in the direction of the arrow and conveyed. The roll-shaped conductive material roll 1 has a silver image surface wound inside. A tension control means 3, for example, a powder brake, is connected to the unwinding shaft 2 to control the tension applied to the conductive material F in the post-processing unit 4, the water washing unit 5, and the drying unit 6. The tension control means 3 applies a tension in the range of 40 to 150 N / m to the conductive material F in order to suppress meandering, wrinkles and sagging of the conductive material F in the post-processing unit 4, the water washing unit 5 and the drying unit 6. The transport speed and tension of the conductive material F are controlled and transported.

  The conductive material F unwound from the roll-shaped conductive material roll 1 is conveyed, is horizontally conveyed by the roller 15, and enters the post-treatment tank 20. The post-treatment tank 20 performs a post-treatment on the surface of the conductive material F that is continuously conveyed by the post-treatment liquid 14 ejected from a shower nozzle 61 described later. The post-treatment tank 20 is covered with a cover (not shown) in order to prevent an increase in humidity in the processing apparatus chamber, splashing of shower water droplets, and quality abnormality of the conductive material F due to water droplet adhesion.

  An air knife 63 is installed at the inlet of the post-treatment tank 20 so that the post-treatment liquid 14 ejected from the shower nozzle 61 does not flow into the vicinity of the roller 15 along the conductive material F that is continuously running. I have to. In order to stabilize the distance between the air knife and the conductive material F and stabilize the effect of the air knife, a roller 64 is disposed under the air knife 63. Further, in order to stabilize the transport level of the conductive material F, rollers 65, 66, 67, 68, 69 and 70 are arranged in the post-treatment tank 20. The rollers 64, 65, 66, 67, 68, 69, and 70 are preferably rubber rollers that do not slip when the conductive material F is conveyed and are not easily damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The conductive material F in the post-treatment tank 20 is uniformly dispersed on the entire surface of the conductive material F in the post-treatment tank 20 by the post-treatment liquid 14 ejected from the shower nozzle 61. An air knife 71 is also installed at the outlet of the post-treatment tank 20 so that the post-treatment liquid 14 ejected from the shower nozzle 61 does not flow into the water washing section 5 in the next step. In the figure, six shower nozzles 61 for spraying on the surface of the conductive material F conveyed to the post-treatment tank 20 are installed, but the number is not particularly limited, and the shower pressure is a valve (not shown). Each can be adjusted.

  The post-treatment liquid 14 ejected from the shower nozzle 61 of the post-treatment tank 20 is stored in the post-treatment liquid storage tank 72 through a pipe (not shown), and is circulated and supplied to the shower nozzle 61 by a circulation pump 73. Although the capacity | capacitance of the post-processing liquid storage tank 72 changes also with the width dimensions of the electroconductive material F, about 20-130 liters is suitable. A filter 74 is installed in the post-treatment liquid piping path to remove floating substances such as dust floating in the post-treatment liquid. A heater (not shown) is installed in the post-treatment liquid storage tank 72 and is adjusted to a predetermined temperature. The liquid level is controlled by a liquid level sensor (not shown). When the liquid level drops, the post-treatment liquid 14 is replenished from the pipe 75. When the liquid level exceeds the level, the waste liquid W is discharged through the overflow port 76.

  In FIG. 3, the time when the conductive material enters the processing section processing tank is the time A when the conductive material F enters the post-treatment liquid 14 in the post-processing tank 20, and the silver image surface of the conductive material F The reverse roller 11 is the last roller that comes into contact before the start of post-processing. Also, the time until the silver image surface of the conductive material F enters the processing section processing tank is B until it enters the water washing section water washing tank, and the roller that contacts the silver image surface for the first time after being conveyed in a non-contact manner is the first. 1 is a roller 32 of the water washing tank 21.

  A feature of the post-processing apparatus of the conductive material according to the present invention is that at least during the post-processing, the silver image surface formed by the development processing is conveyed and processed in a non-contact state. Moreover, conveying with a silver image surface being non-contact means not contacting a fixed object, such as a roll. Non-contact conveyance of the silver image surface is highly conductive and storage stability. Furthermore, when conducting electroless plating and / or electrolytic plating, the conductive material can keep the line width uniform. Is obtained.

  The conductive material F discharged from the post-treatment tank 20 is sent to the water washing section 5. The water washing section 5 has a first water washing tank 21 and a second water washing tank 22. The washing tanks 21 and 22 store washing water 27 and 28, and are washed by immersion treatment with washing water on the front and back of the conductive material F that is continuously conveyed. Wash water 27 and 28 in each tank are circulated by shower nozzles 23, 24, 25 and 26. In addition, each tank is covered with a cover (not shown) in order to prevent an increase in humidity in the processing apparatus room, scattering of shower water droplets, and quality abnormality of the conductive material F due to water droplet adhesion.

  A roller 31 is installed horizontally with the roller 70 at the entrance of the first washing tank 21. In addition, the roller 31 lower part is installed lower than the washing tank liquid level in order to prevent sticking of the roller surface. The rollers 32 and 33 are installed in the washing water stored in the first washing tank, and the silver image surface of the conductive material F is brought into contact with it and conveyed. Washing water circulating in the first washing tank ejected from the shower nozzles 23 and 24 is directed to the front and back of the conductive material F, respectively. The rollers 31, 32, 33, and 34 of the first rinsing tank 21 are preferably rubber rollers that do not slip during transportation and are not easily damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The conductive material F in the first washing tank 21 is immersed and transported by the stored washing water and washed, and the front and back surfaces of the conductive material F in the first washing tank 21 are crystallized with components of the post-treatment liquid. It is a thing that prevents it. In the figure, shower nozzles 23 and 24 that are sprayed on the front and back sides of the conductive material F conveyed to the first washing tank 21 are provided one by one, but the number is not particularly limited, and the shower pressure Can be adjusted by valves (not shown).

  A roller 34 is installed at the outlet of the first washing tank 21. The upper part of the roller 34 is set higher than the liquid level of the washing tank in order to drain the washing liquid. The lower part of the roller 34 is immersed in the washing tank liquid level to prevent the roller surface from sticking. The reason why the rinsing water 27 is not squeezed with the roller pair is to prevent the surface of the conductive material F from being damaged due to adhesion of the roller pair and entrainment of dust.

  Next, a roller 35 is installed at the entrance of the second washing tank 22. The roller 35 is preferably installed slightly higher than the previous roller 34. This is to prevent the flush water 28 in the second flush tank 22 from lowering the cleanliness than the flush water 27 in the first flush tank 21. The rollers 36 and 37 are installed in the rinsing water 28 stored in the second rinsing tank 22, so that the silver image surface of the conductive material F is brought into contact with the irrigated water. Flushing water 28 circulating in the second flushing tank, which is ejected from the shower nozzles 25 and 26, is directed to the front and back surfaces of the conductive material F, respectively. The rollers 35, 36, 37, and 38 of the second washing tank 22 are also preferably rubber rollers that do not slip during transportation and are not easily damaged. As the rubber material, nitrile rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), silicone rubber, urethane rubber and the like are used.

  The shower nozzle 29 of the second rinsing tub 22 is used as the rinsing water 28 of the second rinsing tub 22 while further improving the cleanliness of the surface of the conductive material F by jetting pure water directly onto the surface of the conductive material. To be replenished. Pure water is provided with a replenishment supply port 29 from a tank (not shown) and replenishes pure water at a rate of 0.1 to 10 liters / minute. Preferably, it is 0.15-5 liter / min. A sponge-like soft roller 39 is installed at the outlet of the second rinsing tank 22 so that moisture adhering to the conductive material F is not brought into the drying unit 6.

  The flush water 27 ejected from the shower nozzles 23 and 24 of the first flush tank 21 is circulated and supplied to the shower nozzles 23 and 24 by a circulation pump 42 through a pipe 40. The capacity of the first rinsing tank 21 is suitably about 10 to 50 liters. A filter 43 is installed in the flush water piping path to remove suspended matters such as dust floating in the flush water. As the flush water 27 in the first flush tank 21, pure water whose temperature is not adjusted is used. Similarly, a circulation pump 44 and a filter 45 are also installed in the second washing tank 22, and the capacity of the second washing tank is appropriately about 20 to 60 liters, and pure water whose temperature is not adjusted is used.

  The second flush tank 22 is provided with an overflow port 51. When the flush water 28 is stored in a predetermined amount or more, it overflows and is replenished to the first flush tank 21. The first flush tank 21 is also provided with an overflow port 50, and the flushed water D that has overflowed is drained. By replenishing only the second flush tank 22 with fresh pure water and replenishing highly clean overflow water from the downstream side to the first flush tank on the upstream side, it is possible to save liquid in the replenisher and Since washing water used for washing between tanks is difficult to bring into a highly clean water washing tank on the downstream side, water washing with higher washing efficiency is performed in the water washing tank on the downstream side, and a conductive material with high commercial value can be obtained. .

  After the post-treatment liquid adhering to both the front and back surfaces of the conductive material F is sufficiently washed and washed with water in the water washing section 5, the front and back surfaces of the conductive material F are dried in the drying section 6 and rolled on the winding shaft 9. Rolled up into a shape. Blowing nozzles 19 are installed at the top and bottom of the drying unit 6, and the conductive material F is dried by warm air hitting the front and back of the conductive material F. Although the drying temperature should just be 30 degreeC or more, 40-65 degreeC is suitable from a viewpoint of productivity. Preferably, 50-60 degreeC is suitable. A tension control means 10, such as a torque motor, that can drive and rotate the shaft is attached to the winding shaft 9. The tension is suitably in the range of 40 to 150 N / m.

  The post-treatment liquid of the present invention contains any of (I) a reducing substance, (II) a water-soluble phosphorus oxoacid compound, and (III) a water-soluble halide. As the reducing substance used in the post-treatment liquid of the present invention, a developing agent known in the field of photographic development can be used. These are described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979) 308119 (December 1989) or cited. Specifically, hydroquinone, potassium hydroquinone monosulfonate, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone and other polyhydroxybenzenes, ascorbic acid and its derivatives, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1 -3-Pyrazolidones such as phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, aminophenols such as paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylene Examples include polyaminobenzenes such as diamine, hydroxylamines, and the like. Among these, ascorbic acid having high water solubility and low toxicity is preferable. These reducing substances are preferably used as an aqueous solution of at least 1% by mass or more, preferably 5 to 30% by mass.

  In the present invention, the water-soluble phosphorus oxoacid compound includes phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid and the like, and salts thereof, and ester compounds of these phosphorus oxo acids. . Any water-soluble phosphorus oxo acid compound can be used as long as its solubility in water at 25 ° C. is at least 0.1% by mass or more. Specific examples of these water-soluble phosphorus oxoacid compounds include phosphates such as sodium phosphate, potassium phosphate and disodium phosphate, hypophosphites such as sodium hypophosphite, disodium dihydrogen pyrophosphate and the like. Esters of various known water-soluble phosphorus oxoacid compounds such as pyrophosphate, tripolyphosphate, hexametaphosphate, and other water-soluble phosphorus oxoacid compounds such as various phosphate esters such as polyoxyethylene alkyl ether phosphates and alkyl phosphates Can be used. Of these, inorganic water-soluble phosphorus oxoacid compounds and phosphates are preferred. These water-soluble phosphorus oxoacid compounds are preferably used as an aqueous solution of at least 5% by mass, preferably 10 to 30% by mass.

  The halogen used as the water-soluble halide in the present invention may be any of fluorine, chlorine, bromine and iodine, and is a compound having a solubility in water of at least 0.1% by mass at 25 ° C. Any compound can be used as long as it is capable of releasing. Examples of the water-soluble halide used in the post-treatment liquid of the present invention include hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, and other hydrochloric acids, chlorides such as sodium chloride, ammonium chloride, and rubidium chloride, and odors. Various inorganic halides such as bromides such as sodium iodide, potassium bromide and lithium bromide, iodides such as sodium iodide, fluorides such as sodium fluoride and potassium fluoride, dimethylamine hydrochloride and trimethylamine bromide And amine salts such as benzalkonium chloride, alkylpyridinium hydrochloride, imidazolinium hydrochloride, polyallylamine hydrochloride and diallyldimethylammonium chloride polymer. Among these, compounds capable of releasing chloride ions in an aqueous solution are preferable, and water-soluble inorganic chlorides such as sodium chloride and potassium chloride are particularly preferable. These water-soluble halides are preferably used in an aqueous solution of at least 1% by mass, preferably 5-30% by mass.

  The reducing substance, water-soluble phosphorus oxo acid compound, and water-soluble halide as components of the post-treatment liquid used in the present invention may be used alone or, for example, the same kind as the reducing substance and another reducing substance. A plurality of components may be mixed and used, or another type of component such as a reducing substance and a water-soluble halide may be mixed and used. Among these, it is most preferable to use a water-soluble halide having high efficiency of the post-treatment liquid and high storage stability and high process stability of the post-treatment liquid. The post-treatment temperature is preferably higher, but if it is not used below the Tg (glass transition temperature) of the substance used as the support for the conductive material, the conductive material will be stretched or cut during the treatment. Process with. The treatment temperature is preferably 30 ° C. or higher when using a water-soluble halide, 40 ° C. or higher when using other materials, more preferably 50 to 70 ° C., and even more preferably 60 to 70 ° C. for any material. To do. Although the treatment time depends on the components of the post-treatment, the treatment is carried out for 10 seconds or longer, preferably 30 seconds to 3 minutes.

  The pH of the post-treatment liquid of the present invention is 10 or less, preferably 4-9. In particular, when a reducing substance is used as a component of the post-treatment liquid, if the pH is high, the reducing substance in the post-treatment liquid is likely to be oxidized, and the storage stability of the post-treatment liquid is deteriorated. In the post-treatment liquid, the pH is preferably 8 or less. In order to adjust to a preferable pH, a known pH buffering agent can be used in the post-treatment liquid. In addition to these, the post-treatment liquid used in the present invention may contain a known surfactant, antifoaming agent, preservative and the like.

  Next, the conductive material of the present invention will be described. As described above, the method of developing the conductive material precursor of the present invention includes (1) development processing according to the silver salt diffusion transfer method, (2) development processing for fixing after direct development, and (3) development processing according to the curing development method. Three methods can be used. Hereinafter, the conductive material using the development processing method (1) in the present invention is type 1, the conductive material using the development processing method (2) is type 2, and the conductive material using the development processing method (3) is used. It abbreviates as Type 3 and will be described in order.

<Type 1>
The conductive material precursor having a silver halide emulsion layer is exposed, and then the silver halide grains in the image area, which is an unexposed area, are dissolved with a soluble silver complex salt forming agent to dissolve as a soluble silver complex salt. The soluble silver complex salt diffused up to the top is reduced with a reducing agent (developer) such as hydroquinone to deposit metallic silver to form an image. Thereafter, it is removed by washing with water, and the silver halide emulsion layer is washed away to form a pattern with a silver image on the substrate.

  The conductive material precursor has at least a physical development nucleus layer and a silver halide emulsion layer on the support in this order from the side closer to the support. Further, the non-photosensitive layer may have an outermost layer farthest from the support and / or an intermediate layer between the physical development nucleus layer and the silver halide emulsion layer. These non-photosensitive layers are layers having a water-soluble polymer as a main binder. As the water-soluble polymer mentioned here, any polymer can be selected as long as it easily swells with a developing solution and allows the developing solution to easily penetrate into the underlying silver halide emulsion layer and physical development nucleus layer.

  Specifically, gelatin, albumin, casein, polyvinyl alcohol, or the like can be used. Particularly preferred water-soluble polymers are proteins such as gelatin, albumin and casein. In order to sufficiently obtain the effect of the present invention, the binder amount of the non-photosensitive layer is preferably in the range of 20% by mass to 100% by mass, particularly 30% by mass with respect to the total binder amount of the silver halide emulsion layer. % To 80% by mass is preferable.

  These non-photosensitive layers may be added to known photographic additives as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989), if necessary. An agent can be included. Further, the film can be hardened with a crosslinking agent as long as the peeling of the silver halide emulsion layer after the treatment is not prevented.

As the physical development nuclei of the physical development nuclei layer in the type 1 conductive material precursor, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing sulfides with water-soluble salts such as palladium and zinc, and silver colloids and palladium sulfide nuclei are preferable. The fine particle layer of these physical development nuclei can be provided on the plastic resin film by vacuum deposition, cathode sputtering, or coating. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg / m ² in terms of solid content.

  The physical development nucleus layer may contain a hydrophilic binder. The amount of the hydrophilic binder is preferably about 10 to 500% by mass with respect to the physical development nucleus. As the hydrophilic binder, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like can be used. Preferred hydrophilic binders are proteins such as gelatin, albumin and casein.

  Examples of the physical development nucleus layer include inorganic compounds such as chromium alum, formalins, glyoxal, malealdehyde, aldehydes such as glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, 2,3- Aldehyde equivalents such as dihydroxy-1,4-dioxane, compounds having active halogen such as 2,4-dichloro-6-hydroxy-s-triazine salt and 2,4-dihydroxy-6-chloro-triazine salt , Divinyl sulfone, divinyl ketone, N, N, N-triacryloyl hexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups and epoxy groups in the molecule, and as a polymer hardener Contains one or more of various protein cross-linking agents (hardeners) such as dialdehyde starch It is preferable. Among these crosslinking agents, dialdehydes such as glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, and adipaldehyde are preferable, and glutaraldehyde is more preferable. The crosslinking agent preferably contains 0.1 to 30% by mass in the physical development nucleus layer, particularly 1 to 20% by mass, based on the total protein contained in the following base layer and physical development nucleus layer.

The type 1 conductive material precursor preferably has a base layer made of protein and latex between the physical development nucleus layer and the transparent support. It is preferable to further have an easy adhesion layer such as vinylidene chloride or polyurethane between the transparent support and the base layer. As the protein used for the base layer, gelatin, albumin, casein or a mixture thereof is preferably used. The protein content in the base layer is preferably 10 to 300 mg / m ² . The latex content used in the base layer is preferably 0.2 to 1.3 g / m ² .

  The physical development nucleus layer and the base layer can be applied by an application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating and the like.

  In the type 1 conductive material precursor, a silver halide emulsion layer is provided as an optical sensor. Techniques used for silver halide photographic films, photographic papers, printing plate-making films, photomask emulsion masks, and the like relating to silver halides can be used as they are.

  For formation of silver halide emulsion grains used in the silver halide emulsion layer, Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (such as forward mixing, reverse mixing, and simultaneous mixing) are used. (December 1989) can be used. Among them, the so-called controlled double jet method, which is a kind of simultaneous mixing method and keeps pAg in a liquid phase to be formed constant, is preferable in that silver halide emulsion grains having a uniform particle diameter can be obtained. In the present invention, the average grain size of preferable silver halide emulsion grains is 0.25 μm or less, particularly preferably 0.05 to 0.2 μm. There is a preferable range for the halide composition of the silver halide emulsion used in the present invention, and it is preferable that the chloride content is 80 mol% or more, and it is particularly preferable that 90 mol% or more is chloride.

  In the production of silver halide emulsions, group VIII such as sulfite, lead salt, thallium salt, rhodium salt or complex salt thereof, iridium salt or complex salt thereof in the process of silver halide grain formation or physical ripening as necessary. A metal element salt or a complex salt thereof may coexist. Further, it can be sensitized by various chemical sensitizers, and methods commonly used in the art such as sulfur sensitization method, selenium sensitization method and noble metal sensitization method can be used alone or in combination. In the present invention, the silver halide emulsion can be dye-sensitized as necessary.

  The silver halide emulsion layer is a layer having a water-soluble polymer as a binder, and the water-soluble polymer here is synonymous with the water-soluble polymer of the non-photosensitive layer described above, preferably gelatin. . The ratio of the amount of silver halide and the amount of gelatin contained in the silver halide emulsion layer is such that the mass ratio (silver / gelatin) of silver halide (silver equivalent) to gelatin is 1.2 or more, more preferably 1.5 or more. It is.

  In the silver halide emulsion layer, known photographic additives can be used for various purposes. These are described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) or cited.

For the type 1 conductive material precursor, it is preferable to use a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer as a halation or an irradiation prevention agent for improving the image quality. The antihalation agent is preferably a base layer or a physical development nucleus layer, or an intermediate layer provided as necessary between the physical development nucleus layer and the silver halide emulsion layer, or a back provided with a support interposed therebetween. It can be contained in the coating layer. An irradiation inhibitor is preferably contained in the silver halide emulsion layer. The amount added can be varied within a wide range as long as the desired effect can be obtained. For example, when it is contained in the backing layer as an antihalation agent, a range of about 20 mg / m ² to about 1 g / m ² is desirable and preferable. Is 0.5 g / m ² or more as the optical density at the maximum absorption wavelength.

  Examples of the transparent support used for the type 1 conductive material precursor include polyester resins such as polyethylene terephthalate, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride, polyimide resins, cellophane, and celluloid. A plastic resin film, a glass plate, etc. are mentioned.

  Examples of the method for producing a transparent conductive film using the type 1 conductive material precursor include formation of a silver thin film having a mesh pattern. In this case, the silver halide emulsion layer is exposed in a network pattern. As an exposure method, a transparent original having a network pattern and a silver halide emulsion layer are exposed in close contact with each other, or scanning is performed using various laser beams. There are exposure methods. In the above-described method of exposing with laser light, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm can be used.

  After exposing a transparent original having an arbitrary shape pattern such as a mesh pattern and the above precursor, or by scanning and exposing a digital image of an arbitrary shape pattern to the precursor with various laser light output machines, silver When processed with a salt diffusion transfer developer, physical development occurs, the silver halide in the unexposed areas is dissolved to form a silver complex salt, and reduced on the physical development nuclei to deposit metallic silver, thereby forming a silver thin film with a shape pattern. Obtainable. On the other hand, the exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After development, the silver halide emulsion layer, intermediate layer and protective layer which are no longer needed are washed away with water, and a silver thin film having a shape pattern is exposed on the surface.

  As a method for removing a layer provided on a physical development nucleus layer such as a silver halide emulsion layer after development, there is a method of removing by washing with water or transferring to a release paper. There are two methods for removing the water washing: a method of removing hot water using a scrubbing roller or the like while jetting it with a nozzle or the like, and a method of removing hot water by jetting with a nozzle or the like. Also, the method of transferring and peeling with release paper, etc., is to squeeze the excess alkali solution (silver complex diffusion transfer developer) on the silver halide emulsion layer in advance with a roller or the like, and remove the silver halide emulsion layer and the release paper. In this method, the silver halide emulsion layer and the like are transferred from a plastic resin film to a release paper and peeled off. As the release paper, water-absorbing paper or non-woven fabric, or paper having a water-absorbing void layer formed of a fine pigment such as silica and a binder such as polyvinyl alcohol on the paper is used.

  Next, a developing solution for silver salt diffusion transfer development will be described. The developer is an alkaline solution containing a soluble silver complex salt forming agent and a reducing agent. The soluble silver complex salt forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a compound for reducing the soluble silver complex salt to deposit metallic silver on the physical development nucleus. .

  Soluble silver complex forming agents used in the developer include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and sulfites such as sodium sulfite and potassium bisulfite. Salts, oxazolidones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, USP 5,200,294 As described, thioethers, 5,5-dialkylhydantoins, alkylsulfones, and the like, "The Theory of the Photographic Process (4th edition, p474-475)", by TH James. The compounds described can be mentioned.

  Among these soluble silver complex salt forming agents, alkanolamine is particularly preferable. A relatively low value is obtained for the surface resistance of the transparent conductive film developed with a processing solution containing an alkanolamine.

  Examples of the alkanolamine include N-aminoethylethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N-dimethylethanolamine, Examples include 3-aminopropanol and 2-amino-2-methyl-1-propanol.

  These soluble silver complex salt forming agents can be used alone or in combination.

  The reducing agent used in the developer is a development known in the field of photographic development as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989). The main drug can be used. For example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, ascorbic acid and its derivatives, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1- Examples include 3-pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, and the like. These reducing agents can be used alone or in combination.

  The content of the soluble silver complex salt forming agent is preferably 0.001 to 5 mol, more preferably 0.005 to 1 mol, per liter of the developer. The content of the reducing agent is preferably from 0.01 to 1 mol, more preferably from 0.05 to 1 mol, per liter of the developer.

  The pH of the developer is preferably 10 or more, and more preferably 11-14. In order to adjust to a desired pH, an alkali agent such as sodium hydroxide or potassium hydroxide, or a buffering agent such as phosphoric acid or carbonic acid is contained alone or in combination. The developer of the present invention preferably contains a preservative such as sodium sulfite or potassium sulfite.

<Type 2>
This is a method of performing direct development processing. For example, when using a negative emulsion, a silver halide grain of an optical sensor is exposed imagewise to form a latent image, and the latent image is used as a catalyst to reduce the silver halide with a reducing agent such as hydroquinone in the developer. Form silver. Thereafter, the unexposed silver halide is removed by a fixing process, and a pattern of silver particles held in an image-like binder is formed on the substrate.

  As the transparent support used for the type 2 conductive material precursor, the materials and performances described for the type 1 conductive material precursor can be used.

  In the type 2 conductive material precursor, a silver halide emulsion layer is provided on the support as an optical sensor. The halogen elements contained in the silver halide of the silver halide emulsion layer include chlorine, bromine, iodine and Any of fluorine may be used, and these may be combined. For the formation of silver halide emulsion grains, methods such as forward mixing, reverse mixing, and simultaneous mixing are used. Of these, the use of the controlled double jet method is preferred from the viewpoint of obtaining silver halide emulsion grains having a uniform grain size. The average grain size of preferable silver halide emulsion grains is 0.25 μm or less, particularly preferably 0.05 to 0.2 μm.

  The shape of the silver halide grains is not particularly limited. For example, the shape can be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagon flat plate shape, a triangular flat plate shape, a quadrangular flat plate shape, etc.), an octahedron shape, and a tetrahedron shape. Can be.

  In the production of silver halide emulsions, group VIII such as sulfite, lead salt, thallium salt, rhodium salt or complex salt thereof, iridium salt or complex salt thereof in the process of silver halide grain formation or physical ripening as necessary. A metal element salt or a complex salt thereof may coexist. Further, it can be sensitized by various chemical sensitizers, and methods commonly used in the art such as sulfur sensitization method, selenium sensitization method and noble metal sensitization method can be used alone or in combination. In the present invention, the silver halide emulsion can be dye-sensitized as necessary.

  The silver halide emulsion layer contains a binder. As the binder, both water-insoluble polymers and water-soluble polymers can be used as binders, but it is preferable to use water-soluble polymers. Preferred water-soluble polymers include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinyl amine, chitosan, polylysine, polyacrylic acid, poly Examples include alginic acid, polyhyaluronic acid, and carboxycellulose.

  In addition to the above water-soluble polymer, a polymer latex as a water-insoluble polymer can also be used for the silver halide emulsion layer. As the polymer latex, various known latexes such as homopolymers and copolymers can be used. Homopolymers include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene. Copolymers include ethylene / butadiene copolymers, styrene / butadiene copolymers, and styrene.・ P-methoxystyrene copolymer, styrene / vinyl acetate copolymer, vinyl acetate / vinyl chloride copolymer, vinyl acetate / diethyl maleate copolymer, methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene copolymer Polymer, methyl methacrylate / styrene copolymer, methyl methacrylate / vinyl acetate copolymer, methyl methacrylate / vinylidene chloride copolymer, methyl acrylate / acrylonitrile copolymer, methyl acrylate / butadiene copolymer Methyl acrylate-styrene copolymer, methyl acrylate-vinyl acetate copolymer, an acrylic acid-butyl acrylate copolymer, methyl acrylate-vinyl chloride copolymer, and butyl acrylate-styrene copolymer. The average particle size of the polymer latex used in the silver halide emulsion layer is preferably 0.01 to 1.0 [mu] m, more preferably 0.05 to 0.8 [mu] m.

  The polymer latex is preferably used at a mass ratio (polymer latex / water-soluble polymer) of 1.0 or less because the polymer latex has an adverse effect on coating properties when used in an excessive amount. In addition, regarding the total amount of polymer latex and water-soluble polymer contained in the silver halide emulsion layer, that is, the total amount of binder, if the amount of the binder is small, the coating property is adversely affected, and stable silver halide grains can also be obtained. On the other hand, if the amount is too large, the electroconductivity cannot be obtained unless a large amount of plating is performed, and the productivity is greatly affected. The mass ratio (silver / total binder) of the preferred silver halide (in terms of silver) and the total binder is 1.2 or more, more preferably 1.5 to 3.5.

  The silver halide emulsion layer of the conductive material precursor used for Type 2 is preferably hardened with a hardener. Examples of hardeners include inorganic compounds such as chromium alum, aldehydes such as formalin, glyoxal, malealdehyde and glutaraldehyde, N-methylol compounds such as urea and ethyleneurea, mucochloric acid, 2,3-dihydroxy- Aldehyde equivalent such as 1,4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salt, compound having active halogen such as 2,4-dihydroxy-6-chloro-triazine salt, divinyl Sulfone, divinyl ketone, N, N, N-triacryloyl hexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups or epoxy groups in the molecule, dialdehyde as a polymer hardener Research Disclosure Item 1764 for starch and others (November 1979) (December 1978) and 18716, can be used materials such as described in 308119 (December 1989). The hardener can be used alone or in combination. The hardener is preferably contained in an amount of 0.1 to 10% by weight, particularly 0.5 to 8% by weight, based on the binder contained in the silver halide emulsion layer.

  In the silver halide emulsion layer, known photographic additives similar to type 1 can be used for various purposes.

  If necessary, the type 2 conductive material precursor may be provided with a backing layer or an overlayer on the silver halide emulsion layer on the opposite side of the support from the silver halide emulsion layer. In addition, for the type 2 conductive material precursor, a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer, the same purpose as described for the type 1 conductive material precursor, It can be contained by the method.

  A method for producing a transparent conductive material using the type 2 conductive material precursor includes, for example, formation of a silver thin film having a mesh pattern. This is a type 1 silver salt diffusion transfer development. The exposure can be performed in the manner described.

  The developer used for the production of the type 2 conductive material in the present invention comprises a developing agent, a preservative, an alkali agent, and an antifoggant as a basic composition. Specific examples of the developing agent include hydroquinone, ascorbic acid, paraaminophenol, paraphenylenediamine, phenidone and the like. Some of these may be contained in the conductive material precursor. Examples of preservatives include sulfite ions. The alkaline agent is necessary for exhibiting the reducing ability of the developing agent, and is added so that the pH of the developer is 9 or more, preferably 10 or more. In addition, a buffering agent such as carbonate or phosphate is also used in order to keep the basicity stably. Furthermore, examples of the antifoggant added so that silver halide grains having no development nucleus are not reduced include bromide ions, benzimidazole, benzotriazole, 1-phenyl-5-mercaptotetrazole and the like.

  Furthermore, it is preferable for obtaining high conductivity to contain a soluble silver complex salt forming agent as a developer used in the production of the type 2 conductive material in the present invention. As a soluble silver complex forming agent. Specifically, thiosulfates such as ammonium thiosulfate and sodium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sulfites such as sodium sulfite and potassium hydrogen sulfite, 1,10-dithia-18 -Crown-6, thioethers such as 2,2'-thiodiethanol, oxadridones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, JP-A-9-171257 The mesoionic compounds described, 5,5-dialkylhydantoins, alkylsulfones, and others, “The Theory of the Photographic Process (4th edition, p474-475)”, written by TH James. Compounds.

  Of these soluble silver complex salt forming agents, alkanolamines are particularly preferred. Examples of the alkanolamine include diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N-dimethylethanolamine, 3-aminopropanol, 2- Amino-2-methyl-1-propanol etc. are mentioned.

  These soluble silver complex salt forming agents can be used alone or in combination. The amount of the soluble silver complex salt forming agent used is 0.1 to 40 g / liter, preferably 1 to 20 g / liter. The development processing temperature is usually selected from 15 to 45 ° C, more preferably 25 to 40 ° C.

  The fixing process is performed for the purpose of removing and stabilizing the silver salt in the undeveloped part. The fixing process can be performed by using a fixing process technique used in known silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, etc. And a fixing solution described in p321.

  Among them, a fixing solution containing a desilvering agent other than thiosulfate is preferable. In this case, as a desilvering agent, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sulfites such as sodium sulfite and potassium bisulfite, 1,10-dithia-18-crown-6, 2,2 ′ -Thioethers such as thiodiethanol, oxadoridones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, 5,5 -Dialkylhydantoins, alkylsulfones, and other compounds described in "The Theory of the Photographic Process (4th edition, p474-475)", TH James.

  Among these desilvering agents, alkanolamine is particularly preferable. Alkanolamine has the same meaning as the soluble silver complex forming agent described in the diffusion transfer developer. Further, although thiocyanate has a high desilvering ability, it is not preferable to use it from the viewpoint of safety to the human body.

  These desilvering agents can be used alone or in combination. The amount of the desilvering agent used is preferably 0.01 to 5 mol, more preferably 0.1 to 3 mol per liter of the fixing solution in total of the desilvering agent.

  In addition to the desilvering agent, the fixing solution may contain sulfite or bisulfite as a preservative, and acetic acid, borate amine, phosphate, or the like as a pH buffer. In addition, water-soluble aluminum (for example, aluminum sulfate, aluminum chloride, potassium alum) as a hardening agent, dibasic acid (for example, tartaric acid, potassium tartrate, sodium tartrate, sodium citrate, lithium citrate) as an aluminum precipitation inhibitor , Potassium citrate and the like). The preferred pH of the fixing solution varies depending on the type of desilvering agent, and in particular when the amine is used, it is 8 or more, preferably 9 or more. The fixing processing temperature is usually selected between 10 ° C. and 45 ° C., more preferably 18 ° C. to 30 ° C.

<Type 3>
This is a method using a curing development method. In this method, a silver halide grain of an optical sensor is exposed imagewise to form a latent image, and when this is used as a catalyst to reduce silver halide, a reducing agent whose oxidized form such as hydroquinone has a hardening action on gelatin. The metal silver is formed at the same time as the gelatin around the metal silver is hardened to form an image, and then washed away with water to wash away the non-hardened portion. Silver particles are held in the binder as in type 2, but only the support remains in the non-image area.

  As the transparent support used for the conductive material precursor used for type 3, the same transparent support used for the type 1 and type 2 conductive material precursors can be used.

  In the type 3 conductive material precursor used in the present invention, a silver halide emulsion layer is provided on a support as an optical sensor.

  As the silver halide in the present invention, the same silver halide as that used for the type 2 conductive material precursor can be used.

  In the present invention, the silver halide emulsion layer contains a binder. In the present invention, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but it is preferable to use a water-soluble polymer. Preferred binders in the present invention include, for example, proteins such as gelatin and casein, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polysaccharides such as starch, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine. , Polyacrylic acid, alginic acid, hyaluronic acid, carboxycellulose and the like. Of these water-soluble polymers, proteins such as gelatin are preferred.

  In the present invention, a polymer latex as a water-insoluble polymer can be used in addition to the above water-soluble polymer in the silver halide emulsion layer. As the polymer latex, various known latexes such as homopolymers and copolymers can be used. Homopolymers include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, isoprene, etc., and copolymers include ethylene butadiene, styrene butadiene, styrene p-methoxystyrene, Styrene / vinyl acetate, vinyl acetate / vinyl chloride, vinyl acetate / diethyl maleate, methyl methacrylate / acrylonitrile, methyl methacrylate / butadiene, methyl methacrylate / styrene, methyl methacrylate / vinyl acetate, methyl methacrylate / vinylidene chloride, methyl acrylate / acrylonitrile, Methyl acrylate / butadiene, methyl acrylate / styrene, methyl acrylate / vinyl acetate, acrylic acid / butyl acrylate, methyl acrylate Relate vinyl chloride, butyl acrylate-styrene and the like. The average particle size of the polymer latex used in the present invention is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.8 μm.

With respect to the total amount of water-soluble polymer and polymer latex contained in the silver halide emulsion layer in the present invention, that is, the total amount of binder, if the amount of the binder is small, the coating property is adversely affected, and stable silver halide grains are also obtained. On the other hand, if the amount is too large, it is difficult to obtain conductivity, and the productivity is greatly affected. The mass ratio (silver / total binder) between the preferred silver halide (in terms of silver) and the total binder is 0.5 or more, more preferably 1.5 to 3.5. Moreover, a preferable total binder amount is 0.05-3 g / m < ² > or more, More preferably, it is 0.1-1 g / m < ² >.

  Similar to the type 2 conductive material precursor, known photographic additives can be used for the silver halide emulsion layer for various purposes.

  For type 3 conductive material precursors, if necessary, an over layer on the backing layer or silver halide emulsion layer on the opposite side of the support and a lower layer below the silver halide emulsion layer. A pulling layer or the like can be provided. Further, a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer can be contained as well as the type 1 and type 2 conductive material precursors.

For the over layer and the undercoat layer of the type 3 conductive material precursor, the same binder as in the silver halide emulsion layer can be used. The preferred binder amount varies depending on the purpose of use of each layer. In particular, when the layers are cured in an image form using a curing development process and it is desired to leave only necessary portions, for example, an electroless plating is applied to the over layer. In the case of containing catalyst nuclei, etc., since the curing reaction occurring in the silver halide emulsion layer is used, it is preferably as thin as possible. The preferred amount is 0.1 g / m ² or less, more preferably 0.05 to 0. 0.001 g / m ² . Further, the over layer and the undercoat layer can contain a known surfactant, development inhibitor, irradiation prevention dye, pigment, matting agent, lubricant and the like.

  It is particularly preferred that the type 3 conductive material precursor contains a hardened developer. Curing developers include polyhydroxybenzenes such as hydroquinone, catechol, chlorohydroquinone, pyrogallol, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dimethylhydroquinone, 2,3- Dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-dimethylhydroquinone, 4-phenylcatechol, 4-t-butylcatechol, 4-s-butylpyrogalol, 4,5-dibromocatechol, 2,5-diethylhydroquinone, 2,5-silibenzoylaminohydroquinone and the like. In addition, aminophenol compounds such as N-methyl-paraaminophenol, paraaminophenol-2,4-diaminophenol, parabenzylaminophenol, 2-methyl-paraaminophenol, 2-hydroxymethyl-paraaminophenol, etc. For example, known curing developers described in JP-A-2001-215711, JP-A-2001-215732, JP-A-2001-312031, and JP-A-2002-62664 can be used. Benzene substituted with a hydroxyl group at least in the 1,2-position or 1,4-position is preferred. Further, these curable developers can be used in combination. Further, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3- It is also possible to use a reducing agent used for a known photographic developer such as pyrazolidone and 1-parachlorophenyl-3-pyrazolidone in combination with the above-described cured developer.

  These hardened developing agents may be contained in any layer of the conductive material precursor, but are preferably contained in the silver halide emulsion layer or the undercoat layer, and particularly in the silver halide emulsion layer. preferable. A preferable amount to be contained is an amount sufficient to make the water-soluble binder of the silver halide emulsion layer water-resistant, and thus varies depending on the amount of the water-soluble binder used. A preferable amount of the hardened developer is 0.01 to 0.5 mmol / water-soluble binder 1 g, more preferably 0.1 to 0.4 mmol / water-soluble binder 1 g. These hardened developers may be dissolved in the coating solution or contained in each layer, or may be dissolved in an oil dispersion and contained in each layer.

The type 3 conductive material precursor preferably contains a swelling inhibitor. In the present invention, the swelling inhibitor is used to prevent the water-soluble binder from swelling when the conductive material precursor is processed with a hardened developer, to prevent blurring of the image, to increase transparency, and to increase conductivity. Used for. Whether or not it acts as a swelling inhibitor is determined by checking whether gelatin precipitation occurs by adding a swelling inhibitor of 0.35 mol / liter to a 5% aqueous gelatin solution at pH 3.5. All the chemicals that cause the occurrence of swelling act as swelling inhibitors. Specific examples of the swelling inhibitor include inorganic salts such as sodium sulfate, lithium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, magnesium chloride, sodium chloride, manganese chloride, and magnesium phosphate. Or, for example, benzenesulfonic acid, diphenylsulfonic acid, 5-sulfosalicylic acid, paratoluenesulfonic acid, phenol disulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, 1,5-naphthalenesulfonic acid, 1-hydroxy-3 Sulfonic acids such as 1,6-naphthalenedisulfonic acid and dinaphthylmethanesulfonic acid, such as polyvinylbenzenesulfonic acid, a copolymer of maleic anhydride and vinylsulfonic acid, and a polymer precipitant such as polyvinylacrylamide Examples include compounds used. These swelling inhibitors may be used alone or in combination, but it is preferable to use inorganic salts, particularly sulfates. These swelling inhibitors may be contained in any layer of the conductive material precursor, but are particularly preferably contained in the silver halide emulsion layer. The preferred content of these swelling inhibitors 0.01 to 10 g / m ^2, still more preferably 0.1-2 g / m ^2.

  Examples of the method for producing a transparent conductive material using the type 3 conductive material precursor include formation of a silver thin film having a mesh pattern, which has been described in the above type 1 and type 2. It can be exposed by the method.

  In type 3, the conductive material precursor is exposed and then cured and developed. Cured developers include alkaline substances such as potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, or amine compounds, thickeners such as carboxymethylcellulose, development aids such as 3-pyrazolidinones, fog. Inhibitors such as potassium bromide, development modifiers such as polyoxyalkylene compounds, silver halide solvents such as thiosulfate, thiocyanate, cyclic imide, thiosalicylic acid, mesoionic compounds and the like are included. be able to. The pH of the developer is usually 10-14. Preservatives used in ordinary silver salt photographic developers, such as sodium sulfite, have the effect of stopping the curing reaction by curing development, so in the cured developers in the present invention, the preservative is used in an amount of at least 20 g / liter or less, The amount used is preferably 10 g / liter or less.

  The type 3 cured developer contains a cured developer when the conductive material precursor does not contain a cured developer. As the hardened developer, the same hardened developer as that contained in the conductive material precursor can be used. A preferable content of the hardened developer is 1 to 50 g / liter. When the hardened developer is contained in the developer, the preservability is poor and the air is immediately oxidized. Therefore, it is preferable to dissolve in an alkaline aqueous solution immediately before use.

  The type 3 curable developer preferably contains a swelling inhibitor. As the swelling inhibitor, the same swelling inhibitor as that contained in the conductive material precursor can be used. The content of a preferred swelling inhibitor is 50 to 300 g / liter, preferably 100 to 250 g / liter.

As a method for performing the type 3 curing and developing treatment, an immersion method or a coating method may be used. In the immersion method, for example, the conductive material precursor is conveyed while being immersed in a treatment liquid stored in a large amount in a tank, and in the coating method, for example, the treatment liquid is 40 to 40 on the conductive material precursor. About 120 ml / m ^{2 is} applied. In particular, when a curable developer containing a curable developer is used, it is preferable to use a coating method and avoid repeated use of curable development.

  The type 3 curing and developing treatment conditions are as follows. The development temperature is 2 to 30 ° C, and 10 to 25 ° C is more preferable. The development time is 5 to 30 seconds, preferably 5 to 10 seconds.

  The step of manufacturing the type 3 conductive material includes a step of removing the silver halide emulsion layer in the light transmitting portion and exposing the support surface. Since the main purpose of this step is to remove the silver halide emulsion, the processing solution used in this step contains water as the main component. The treatment liquid may contain a buffer component. Moreover, a preservative can be contained in order to prevent the removed gelatin from being spoiled. As a method of removing the silver halide emulsion, there are a method of rubbing with a sponge or the like, a method of peeling off by applying a roller to the film surface and slipping, a method of winding the roller in contact with the film surface and the like. As a method of applying the treatment liquid stream to the silver halide emulsion surface, a shower method, a slit method or the like can be used alone or in combination. Also, a plurality of showers and slits can be provided to increase the removal efficiency.

  In Type 3, after removing the non-image area silver halide emulsion layer to produce a silver image, a stronger silver image can be produced by processing with a solution containing a hardener well known to those skilled in the art. . Various hardeners such as aldehydes such as chrome alum and formalin, ketones such as diacetyl, mucochloric acid and the like can be used. In Type 3, the conductive material precursor is treated with a physical developer containing a silver halide solvent after the curing and developing treatment to increase the silver in the metallic silver cured by the curing and developing, thereby obtaining conductivity. .

  In the present invention, the conductive material produced by any one of the type 1, type 2 and type 3 methods is subjected to plating for various purposes such as obtaining higher conductivity or changing the color tone of the silver image. As the plating treatment in the present invention, electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating can be used. The degree of conductivity imparted by the plating process varies depending on the application to be used. For example, for use as an electromagnetic shielding material for PDP, the surface resistance value is 2.5Ω / □ or less, preferably 1.5Ω / □. The following are required:

  In the present invention, when the electroless plating treatment is performed, the activation treatment can be performed with a solution containing palladium for the purpose of promoting the electroless plating. Palladium may be in the form of a divalent palladium salt or a complex salt thereof, or may be metallic palladium. However, it is preferable to use a palladium salt or a complex salt thereof in view of the stability of the liquid and the stability of the treatment.

  For the electroless plating in the present invention, known electroless plating techniques such as electroless nickel plating, electroless cobalt plating, electroless gold plating, and silver plating can be used. In order to obtain this, it is preferable to perform electroless copper plating.

  The electroless copper plating solution in the present invention includes copper sources such as copper sulfate and copper chloride, reducing agents such as formalin, glyoxylic acid, potassium tetrahydroborate, and dimethylamine borane, EDTA, diethylenetriaminepentaacetic acid, Rochelle salt, glycerol, Soerythritol, Adenyl, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 1,3-diaminopropan-2-ol, glycol ether diamine, triisopropanolamine, tri It contains a copper complexing agent such as ethanolamine, a pH adjusting agent such as sodium hydroxide, potassium hydroxide and lithium hydroxide. In addition, polyethylene glycol, yellow blood salt, bipyridyl, o-phenanthroline, neocuproine, thiourea, cyanide, and the like can also be added as additives for improving bath stabilization and plating film smoothness. The plating solution is preferably aerated to increase stability.

  As described above, various complexing agents can be used in electroless copper plating. However, copper oxide co-deposits depending on the type of complexing agent, which greatly affects the conductivity, or with copper ions such as triethanolamine. It is known that a complexing agent having a low complex stability constant tends to precipitate copper, making it difficult to produce a stable plating solution or plating replenisher. Therefore, the complexing agents usually used industrially are limited, and in the present invention, the selection of the complexing agent is particularly important as the composition of the plating solution for the same reason. Particularly preferable complexing agents include EDTA and diethylenetriaminepentaacetic acid, which have a large stability constant of copper complex. Examples of plating solutions using such a complexing agent include high-temperature types used in the production of printed circuit boards. There is electroless copper plating. The method of high-temperature type electroless copper plating is described in detail in “Electroless plating basics and applications” (ed. In high-temperature type plating, the treatment is usually performed at 60 to 70 ° C., and the treatment time varies depending on whether or not the electrolytic plating is performed after the electroless plating. Usually, the electroless plating treatment is performed for 1 to 30 minutes, preferably 3 to 20 minutes. By doing so, the object of the present invention can be achieved.

  When electroless plating treatment other than copper is performed in the present invention, for example, a method described in “Plating Technology Guidebook” (edited by Tokyo Sheet Metal Cooperative Technical Committee, 1987) p406 to 432 can be used.

  In the present invention, electrolytic plating can also be applied. As the electroplating method, a known plating method such as copper plating, nickel plating, zinc plating, tin plating or the like can be used. As the method, for example, “Plating Technology Guidebook” (edited by Tokyo Sheet Metal Cooperative Association Technical Committee, 1987). (Year) described method can be used. Which plating method is used depends on the use of the conductive material to be manufactured, but when plating is performed in order to further increase the conductivity, copper plating or nickel plating is preferable. Preferred examples of the copper plating method include a copper sulfate bath plating method and a copper pyrophosphate bath plating method, and preferred nickel plating methods include a Watt bath plating method and a black plating method.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but it is needless to say that the present invention is not limited by this description. In the description, unless otherwise specified,% represents mass%.

A conductive material precursor using the silver salt diffusion transfer method was prepared as follows. A 100 μm thick polyethylene terephthalate film was used as the transparent support. Before applying the physical development nucleus layer, an undercoat layer made of vinylidene chloride is applied to this film, and gelatin 50 mg / m ² and latex (Dainippon Ink & Chemicals, Inc. WLS210) 35% by weight dispersion A base layer containing 1 g / m ² was applied and dried. Next, a physical development nucleus layer made of palladium sulfide was applied to a solid content of 0.4 mg / m ² and dried. Subsequently, the silver halide emulsion layer was coated on the physical development nucleus layer so as to be 3.0 g / m ^{2 in} terms of silver and dried, and the conductive material precursor was wound into a roll. A physical development nucleus and a silver halide emulsion layer made of palladium sulfide were prepared according to Example 1 of the aforementioned Japanese Patent Application Laid-Open No. 2004-172041.

  The precursor roll 500 m thus obtained is adhered by a 50 cm square transmission original having a mesh pattern with a fine line width of 20 μm and a lattice interval of 250 μm through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source. The exposure was processed for 500 m. The exposed pattern is connected by providing two silver images having a width of 20 mm and a length of 50 mm between the patterns so that a plating process performed later can be performed. Thereafter, the film was immersed in the following developer at 20 ° C. for 90 seconds, then washed with warm water at 40 ° C. and dried. Thus, a 500-m roll conductive material roll having a silver thin film formed in a mesh pattern was obtained.

<Developer>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
Add water to bring the total volume to 1000 ml and adjust to pH = 12.2.

  In the post-processing apparatus shown in FIG. 2, each conductive material roll 1 having a volume of 500 m on which the mesh-patterned silver thin film obtained as described above is formed is unwound from the unwinding shaft 2 and conveyed. The post-treatment is carried out by immersing in the post-treatment liquid shown in Table 1 at 60 ° C. for 90 seconds in the processing unit 4, washed with pure water at 20 ° C. in the water washing unit 5, and dried with warm air at 60 ° C. in the drying unit 6 And wound on the winding shaft 9. Conductive material roll 500m winding was processed for each post-treatment liquid to obtain conductive materials A1 to A3.

  As a comparative example, the conductive materials A1 to A3 are the same as those shown in FIG. 4 except that a post-processing apparatus that performs post-processing by transporting the silver image surface in contact with the roll during the immersion processing in the post-processing tank is used. As a result, conductive materials A4 to A6 were produced.

  The surface resistivity of the conductive material on which the mesh-patterned silver thin film obtained as described above was formed was measured according to JIS K 7194 using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. The results obtained are summarized in Table 2. In addition, the sample used for the measurement is the first mesh pattern of 500 m rolls for each of A1 to A6.

  Further, the conductive material on which the mesh-patterned silver thin film was formed was placed in a heating chamber at 60 ° C. for 1 week, and the subsequent surface resistance value was measured. The obtained results are also shown in Table 2 in terms of the value of how many percent of the original surface resistance value before heating was taken as 100%. In addition, the sample used for the measurement is the first mesh pattern of 500 m rolls for each of A1 to A6.

The conductive materials A1 to A6 were subjected to nickel plating at a temperature of 45 ° C. and a current density of 4 A / dm ² using the following nickel plating solution. The mesh pattern fine line width of the obtained conductive material was photographed with a digital microscope (KH-3000 manufactured by Hilox Co., Ltd.), and the width of the fine line was measured. The measurement is the first mesh pattern and the last mesh pattern of each conductive material of 500 m. Each sample of 50 cm square is measured at 10 points, and the range of line width fluctuation is shown in Table 2 as the line width after plating.

<Prescription of nickel plating solution>
Nickel sulfate 240 g / liter Nickel chloride 45 g / liter Boric acid 30 g / liter pH = 4.5

  From the results in Table 2, when processing with a post-treatment liquid containing a reducing substance, a water-soluble phosphorus oxoacid compound, and a water-soluble halide, the silver image surface of the conductive material is conveyed and processed in a non-contact state. Thus, a conductive material having high conductivity and storage stability and having a stable mesh pattern fine line width after plating was obtained.

  The following processing was performed using the post-processing apparatus of FIG. The post-processing apparatus in FIG. 3 includes a roll-shaped conductive material unwinding section 16 so as to be processed by a roll-to-roll, a post-processing section 4 for post-processing the conductive material with a shower nozzle, and the conductive material. The water-washing part 5 for carrying out the water-washing process of the property material, the drying part 6, and the winding-up part 18 for winding up the dried electroconductive material in roll shape are provided.

A conductive material precursor to be fixed after direct development was prepared as follows. A 100 μm thick polyethylene terephthalate film was used as the transparent support. An undercoat layer made of vinylidene chloride was applied to the film, and a base layer containing 50 mg / m ² of gelatin was applied thereon and dried. Next, 1 g of gelatin and 50 mg of a hardener (glyoxal 40% aqueous solution) are added to the above-described silver halide emulsion, and the resultant is applied and dried so as to be 3.0 g / m ^{2 in} terms of silver. The body was rolled up.

  The precursor roll 500 m thus obtained is adhered by a 50 cm square transmission original having a mesh pattern with a fine line width of 20 μm and a lattice interval of 250 μm through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source. The exposure was processed for 500 m. The exposed pattern is connected by providing two silver images having a width of 20 mm and a length of 50 mm between the patterns so that a plating process performed later can be performed. Thereafter, development processing was performed using the developer and the fixing solution described in Example 1 of JP-A-2004-221564 to obtain a 500 m conductive material roll having a silver thin film formed in a mesh pattern.

  In the post-processing apparatus of FIG. 3, each conductive material roll 1 having a volume of 500 m on which the mesh-patterned silver thin film obtained as described above is formed is unwound from the unwinding shaft 2 and conveyed. The post-treatment liquid shown in Table 1 is ejected from the shower nozzle at 60 ° C. for 60 seconds in the treatment tank 20, and the water is washed with pure water at 20 ° C. in the water washing section 5, and warm air at 60 ° C. in the drying section 6. Thus, moisture is dried and wound on the winding shaft 9. Conductive material B1-B3 was produced by processing one 500 m roll of conductive material roll for each post-treatment liquid. This was evaluated and the results shown in Table 3 were obtained.

  As a comparison, during the shower nozzle processing by the post-processing tank 20 shown in FIG. 5, the conductive materials B4 to B6 are processed by a post-processing device that performs post-processing by carrying the silver image surface in contact with the inlet and outlet rolls. Was made. This was evaluated in the same manner as in Example 1, and as a result, the results shown in Table 3 were obtained.

  From the results in Table 3, when processing with a post-treatment liquid containing a reducing substance, a water-soluble phosphorus oxoacid compound, and a water-soluble halide, the silver image surface of the conductive material is conveyed and processed in a non-contact state. Thus, a conductive material having high conductivity and storage stability and having a stable mesh pattern fine line width after plating was obtained.

  The conductive pattern obtained by the processing method and processing apparatus of the present invention can be used for conductive materials used for applications such as electromagnetic wave shielding films and touch panels.

Schematic sectional view showing an example of the post-processing apparatus of the present invention Schematic sectional view showing an example of the post-processing apparatus of the present invention Schematic sectional view showing an example of the post-processing apparatus of the present invention Schematic sectional view showing an example of a conventional post-processing apparatus Schematic sectional view showing an example of a conventional post-processing apparatus The conceptual diagram which shows the process order which processes the post-process of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive material roll 2 Unwinding shaft 3 Tension control means 4 Post-processing part 5 Water washing part 6 Drying part 8 Winding roll 9 Winding shaft 11 Reverse roller 13 Post-processing tank 14 Post-processing liquid 15 Roller 16 Unwinding part 17 Roller Washing tab 18 Winding part 19 Outlet nozzle 21 First washing tank 22 Second washing tank 23 Shower nozzle 27 Washing water 31 Roller 39 Roller pair 42 Circulation pump 43 Filter 50 Overflow port 61 Shower nozzle 63 Air knife F Conductive material

Claims (3)

A method for treating a conductive material obtained by exposing and developing a conductive material precursor having at least one silver halide emulsion layer on a support to form a silver image, wherein the following (I) to (III): When processing with the processing liquid containing at least 1 or more types of compound in any one of these, the surface which has the silver image of this electroconductive material is conveyed and processed in non-contact, The process of the electroconductive material characterized by the above-mentioned Method.
(I) Reducing substance (II) Water-soluble phosphorus oxoacid compound (III) Water-soluble halide   A processing apparatus used in the method for processing a conductive material according to claim 1, wherein an unwinding unit that holds the conductive material in a roll shape, a processing unit that processes the conductive material with the processing liquid, It has at least a drying unit and a winding unit for winding the dried conductive material into a roll shape, from the time when the conductive material enters the processing unit treatment tank until it enters the washing unit washing tank. In the meantime, the conductive material processing apparatus is characterized in that the surface having the silver image of the conductive material is conveyed and processed in a non-contact manner.   A processing apparatus for use in the conductive material processing method according to claim 1, wherein a roll-out portion that holds the conductive material precursor in a roll shape and the conductive material precursor is developed with a developer. A developing unit, a washing unit for removing the silver halide emulsion layer of the conductive material precursor, a drying unit, a processing unit for treating the conductive material with the processing solution, and a drying unit. A winding part for winding the conductive material into a roll shape, and the conductive material is in a period from the time when the conductive material enters the treatment tank to the time when it enters the washing tank. A conductive material processing apparatus for transporting and processing a surface having a silver image of a material in a non-contact manner.

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