JPWO2007001008A1 - Printed circuit board manufacturing method and printed circuit board - Google Patents

Abstract

Printed circuit board manufacturing method capable of forming a printed circuit board having high conductivity and a small number of pinholes into a thin line pattern, and capable of mass production at low cost with a low environmental load, and a photosensitive material for printed circuit boards obtained by the manufacturing method Provide. Furthermore, the present invention provides a photosensitive material that can achieve both plating progress and pressure resistance. An emulsion layer containing a silver salt emulsion provided on a support is exposed and developed to form a metallic silver portion and a light transmissive portion, and the metallic silver portion is further subjected to physical development and / or plating treatment. By doing so, a conductive metal portion in which conductive metal particles are supported on the metal silver portion is formed.

Description

  The present invention relates to a method for producing a printed circuit board used in the field of electronics industry, in particular, a flexible printed circuit board, a printed circuit board obtained by the production method, and a photosensitive material used for the production.

  As a conventional printed circuit board manufacturing method, a copper foil is bonded onto an insulator film using an adhesive, and a desired wiring pattern is formed by a subtractive method, and the adhesive film is bonded onto the insulator film. The substrate is roughly divided into a two-layer flexible substrate in which a desired wiring pattern is formed by a subtractive method or an additive method using a substrate directly provided with a base metal layer without using an agent.

Printed boards are classified into flexible boards and rigid boards depending on the material used for the insulating board. In the flexible substrate, the insulating substrate is composed of a material having high flexibility such as polyimide resin or polyester. On the other hand, in the rigid substrate, the insulating substrate is made of a material having high hardness such as glass epoxy resin.

In general, a three-layer flexible substrate with a simple manufacturing method dominates. However, with the recent increase in the density of electronic devices, a wiring board having a narrow wiring width is required. In the case of the above three-layer flexible substrate, a method of forming a wiring part by etching has been proposed (for example, Japanese Patent Application Laid-Open No. 2003-309336 (Patent Document 1)). However, in this method, the side surface of the wiring portion is etched, so-called side etching occurs, so that the cross-sectional shape of the wiring portion tends to become a trapezoid with a skirt spread, and thus etching is performed until electrical insulation between the wiring portions is ensured. If this is done, the wiring pitch width would become too wide, so there was a limit to reducing the wiring pitch. In addition, the manufacturing process is complicated and complicated, and the production cost is high, and the etching process has problems with environmental problems due to the treatment of waste liquid.

Since the skirt spread of the wiring portion by this side etching increases as the thickness of the copper foil increases, in order to reduce the spread and reduce the pitch, a 35 μm thick copper generally used conventionally is used. It was necessary to use a copper foil having a thickness of 18 μm instead of the foil. However, such a thin copper foil has a low rigidity and therefore has a poor handling property. Therefore, there is a problem that a reinforcing material such as an aluminum carrier has to be bonded to increase the rigidity. In addition, when this is done, there have been problems such as an increase in film defects such as variations in film thickness and occurrence of pinholes and cracks.

Therefore, as the thickness of the copper foil is reduced in order to reduce the pitch of the wiring portion, the manufacture of the wiring board becomes more difficult and the manufacturing cost increases. In particular, recently, there is an increasing demand for a wiring board having a wiring portion with a narrow pitch that cannot be manufactured without using a copper foil having a thickness of 10 μm or less and several μm, and the manufacturing cost of a three-layer flexible substrate is increasing. Is becoming a problem.

Then, the 2 layer flexible substrate which can form a copper coating directly on an insulator film, without giving an adhesive agent came to attract attention. Since the two-layer flexible substrate is a substrate in which a base metal layer is formed by dry plating or wet plating directly on an insulator film without an adhesive, and a copper conductor layer is formed by electroplating or the like. In addition, the thickness of the copper conductor film to be deposited can be adjusted to an arbitrary thickness.

Currently, a method for forming a base metal generally used to obtain this type of two-layer flexible substrate is a dry plating method. After a base metal layer is deposited on an insulator film, it is further dry-plated. Methods for forming a copper coating have been proposed (Japanese Patent Laid-Open No. 8-139448 (Patent Document 2), Japanese Patent Laid-Open No. 10-154863 (Patent Document 3). There are many pinholes with a size of several tens of μm to several hundreds of μm, and the thickness of the final copper film to be formed is about 0.2 to 0.5 μm. An exposed part due to a pinhole is generated, and in order to prevent this, it is necessary to repeat base formation or to apply a catalyst.

Also, with the recent increase in the density of electronic devices, a double-sided printed wiring board in which a conductor pattern is formed on both sides of an insulating substrate is often used. The conductor patterns on both sides of the double-sided printed wiring board are connected by metal plating or the like through holes (hereinafter referred to as through-hole portions) that penetrate the insulating substrate and the conductor patterns on both sides.

FIG. 1 is a cross-sectional view showing a manufacturing process of a conventional double-sided printed wiring board. As shown in FIG. 1A, metal foils 2a and 2b made of copper are formed on both surfaces of an insulating substrate 1. Next, as shown in FIG. 1B, through-hole portions 5 penetrating the metal foils 2a and 2b and the insulating substrate 1 are formed at predetermined positions.

Then, after applying a palladium catalyst to the insulating substrate 1 and the metal foils 2a and 2b, so-called electroless copper plating is performed, which is immersed in a copper plating solution. Thereby, as shown in FIG.1 (c), the electroless copper plating layer 3 is formed in the inner peripheral surface 5a of the through-hole part 5, and the surface of metal foil 2a, 2b. Thereby, the metal foil 2 a and the metal foil 2 b are electrically connected via the electroless copper plating layer 3.

However, the thickness of the electroless copper plating layer 3 is as thin as about 0.3 μm and the film quality is not good. Therefore, electrolytic copper plating is further performed. Thereby, the electrolytic copper plating layer 4 is formed on the electroless copper plating layer 3. The thickness of the electrolytic copper plating layer 4 is about 15 μm. In this way, the conductor layer 7 composed of the metal foils 2 a and 2 b, the electroless copper plating layer 3 and the electrolytic copper plating layer 4 is formed on both surfaces of the insulating substrate 1.

Next, as shown in FIG. 1D, an etching resist 6 having a desired shape is formed on the electrolytic copper plating layers 4 on both surfaces of the insulating substrate 1 by photolithography using a photomask. At this time, the etching resist 6 is formed on the electrolytic copper plating layer 4 in the peripheral portion 5b of the through-hole portion 5.

Subsequently, the electrolytic copper plating layer 4, the electroless copper plating layer 3, and the metal foils 2a and 2b are etched using the etching resist 7 as a mask. Thereby, as shown in FIG.1 (e), the conductor patterns 21a and 21b of the desired shape, the electroless copper plating layer 3, and the electrolytic copper plating layer 4 are formed. Finally, the etching resist 6 is removed.

In the double-sided printed circuit board formed by the above-described manufacturing method, even when the insulating substrate 1 is made of a material having a high flexibility, the conductor 7 becomes thick as about 25 μm, so that the flexibility is inferior.

Next, the prior art regarding the method of forming the electroconductive metal silver pattern using silver salt is demonstrated.
Photosensitive materials using silver salts have heretofore been mainly used as materials for recording and transmitting images and videos. For example, color negative film, black and white negative film, movie film, photographic film such as color reversal film, photographic printing paper such as color paper, black and white photographic paper, etc. Furthermore, it can be used that metal silver can be formed according to the exposure pattern Emulsion masks (photomasks) and the like that have been used are widely used. All of these are valuable in the image itself obtained by exposing and developing a silver salt, and use the image itself.

  On the other hand, since developed silver obtained from a silver salt is metallic silver, the conductivity of metallic silver can be used depending on the production method. Such a proposal has been scattered from old times until recently, and there are the following as examples disclosing a specific method for forming a conductive silver thin film. In the 1960s, Japanese Patent Publication No. 42-23746 (Patent Document 4) discloses a method of forming a metallic silver thin film pattern by a silver salt diffusion transfer method in which silver is deposited on physical development nuclei. A method of forming a conductive pattern by simply exposing and developing using an instant black-and-white slide film, using this principle as it is, is published in Analytical Chemistry, Vol. 72, Section 645, 2000. (Non-Patent Document 1) and International Publication WO 01/51276 (Patent Document 5).

However, with the methods described in the above two documents, it is difficult to obtain high conductivity, and it is insufficient for use as a printed circuit board material.
Further, specially prepared physical development nuclei are uniformly provided on the layer on which the conductive metal pattern is formed without distinction between exposed and unexposed areas. For this reason, there is a drawback that opaque physical development nuclei remain in the exposed portion where the metallic silver film is not formed, and the insulation is impaired. In addition, it is difficult to obtain high conductivity, and there has been a problem that insulation is impaired when a thick silver film is obtained to obtain high conductivity. Therefore, even if the above silver salt diffusion transfer method is used as it is, a printed board excellent in insulation and conductivity cannot be obtained.
In addition, when using a commercially available negative film without using the silver salt diffusion transfer method and imparting conductivity through development, physical development, and plating processes, in terms of conductivity and insulation, as a printed circuit board material It was insufficient for use.

JP 2003-309336 A Japanese Patent Laid-Open No. 8-139448 JP-A-10-154863 Japanese Patent Publication No.42-23746 International Publication WO 01/51276 Published by Analytical Chemistry, Volume 72, Section 645, 2000

As described above, the conventional printed circuit board and the manufacturing method thereof have problems. In order to narrow the wiring width due to the recent demand for higher wiring density, it is necessary to make the copper foil or copper film thinner. However, since pinholes deteriorate, both high-density wiring and pinholes are compatible. Difficult. Further, in the double-sided printed board, if a long through-hole plating time is taken in order to ensure conductivity, the conductor thickness is increased and the flexibility is impaired, and it is difficult to achieve both conductivity and flexibility.
Further, the conventional method of forming a conductive metal silver pattern using a silver salt sensitive material is insufficient for use as a printed circuit board material in terms of conductivity and insulation between conductive wires.
Furthermore, it is extremely advantageous not to provide a protective layer in order to perform physical development and / or plating processing quickly in a silver salt sensitive material, but silver salt photosensitive materials not provided with a protective layer are subject to external pressure. The impact is large and pressure characteristics need to be improved. In addition, with the increase in the density of electronic devices, different circuit wirings are separated from each other by a small interval for miniaturization. When an electrolyte such as water is interposed in this interval, an electrochemical reaction occurs. As a result, the copper ions dissolved from the copper alloy that is the material of the current-carrying portion on the high potential side are precipitated on the low potential side, and a short circuit occurs when the amount increases. This phenomenon is called migration. When such migration occurs, the circuit does not function normally. Therefore, it has been regarded as important from the viewpoint of reliability that such a migration phenomenon does not occur.
When a large amount of water-absorbing binder is present between circuit wirings, the migration resistance is poor, and a material with good migration resistance has been demanded from the viewpoint of reliability as the size is reduced as described above.

  The present invention has been made in view of such circumstances, and an object of the present invention is a printed circuit board material that has both high conductivity and high insulation at the same time, has no pinholes, and has good migration resistance, Provided a method that can easily form a thin line pattern and that can be manufactured in large quantities at a low cost with a low environmental load. Further, the influence of external pressure, which is extremely advantageous for the manufacturing, has been reduced (the pressure property has been improved). ) To provide a silver salt sensitive material. Furthermore, the other object of this invention is to provide the printed wiring board obtained by the said manufacturing method.

  As a result of intensive studies from the above viewpoint, the present inventors have found that the above object can be effectively achieved by the following production method and printed wiring board, and have completed the present invention.

That is, the object of the present invention is achieved by the following production method.
(1) A photosensitive material including an emulsion layer containing a silver salt emulsion provided on a support is exposed and developed to form a metallic silver portion and a light transmitting portion, and the metallic silver portion is further formed. Production of a printed circuit board having a conductive metal part and an insulating part, wherein a conductive metal part in which conductive metal particles are supported on the metal silver part is formed by physical development and / or plating treatment Method.
(2) A photosensitive material including an emulsion layer containing a silver salt emulsion provided on a support is exposed and developed to form a metallic silver portion and a light transmissive portion, and the metallic silver portion is physically treated A conductive metal part in which conductive metal particles are supported on the metal silver part is formed by developing and / or plating, and the light transmissive part and the conductive metal part are oxidized. The manufacturing method of the printed circuit board which has an electroconductive metal part and an insulating part.
(3) A photosensitive material including an emulsion layer containing a silver salt emulsion provided on a support is exposed and developed to form a metallic silver portion and an insulating portion, and the metallic silver portion and the insulating portion are formed. A conductive metal part having conductive metal particles supported on the metal silver part by oxidizing the conductive part and further physically developing and / or plating the metal silver part. For producing printed circuit board having conductive metal portion and insulating portion.
(4) A photosensitive material including an emulsion layer containing a silver salt emulsion provided on a support is exposed and developed to form a metallic silver portion and an insulating portion, and the metallic silver portion and the light After forming the conductive metal part carrying the conductive metal particles on the metallic silver part by oxidizing the transparent part and further physical development and / or plating the metallic silver part, the conductive part A method of manufacturing a printed circuit board having a conductive metal portion and a light-transmitting portion, wherein the metal portion and the insulating portion are oxidized.
(5) A photosensitive material including an emulsion layer containing a silver salt emulsion provided on a support is exposed and developed to form a metallic silver portion and an insulating portion, and the metallic silver portion is formed of Pd. A conductive metal part formed by supporting conductive metal particles on the metal silver part by performing a physical development and / or plating treatment on the metal silver part. For producing printed circuit board having conductive metal portion and insulating portion.

(6) The method for producing a printed circuit board according to any one of (1) to (5) above, wherein the silver salt emulsion in the silver salt-containing layer is silver halide.
(7) The method for producing a printed circuit board according to (6), wherein the silver halide is mainly composed of silver chloride.
(8) The method for producing a printed circuit board according to (6) or (7), wherein the silver halide contains a rhodium compound and / or an iridium compound.
(9) The method for producing a printed circuit board according to any one of (6) to (8), wherein the silver halide contains Pd (II) ions and / or Pd metal.
(10) The method for producing a printed circuit board according to (9) above, wherein the silver halide contains Pd (II) ions and / or Pd metal in the vicinity of the surface layer of the silver halide grains.
(11) The method for producing a printed circuit board according to any one of (1) to (10) above, wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains an antioxidant. .
(12) The method for producing a printed circuit board according to any one of (1) to (10) above, wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains an oxidizing agent.
(13) The emulsion layer according to any one of (1) to (12) above, wherein the emulsion layer is substantially disposed on the uppermost layer, and the silver salt emulsion is substantially an unchemically sensitized emulsion. A method for manufacturing a printed circuit board.
(14) The above (1) to (1), wherein the emulsion layer is substantially the uppermost layer, and the silver salt emulsion is a silver halide emulsion having a silver iodide content of 1.5 mol% or less. 13) The printed circuit board manufacturing method according to any one of the above.
(15) The above (1) to (14), wherein the emulsion layer is substantially disposed on the uppermost layer, and the coating amount of the silver salt emulsion is 4 g / m ² or less in terms of silver amount. The manufacturing method of the printed circuit board in any one.
(16) The method for producing a printed circuit board as described in (15) above, wherein a weight ratio of Ag / binder in the emulsion layer is 1.5 or more.
(17) The method for producing a printed circuit board as described in 15 or 16 above, wherein a binder layer is provided below the emulsion layer.
(18) The above (15), wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains at least one of a matting agent, a slip agent, colloidal silica, and an antistatic agent. The printed circuit board manufacturing method in any one of-(17).
(19) A method for manufacturing a printed circuit board comprising any combination of (1) to (18) above.
(20) A method for producing a printed circuit board comprising the combination of any one of (1) to (18) above, wherein the swelling ratio of the insulating part is 150% or less.
(21) A method for producing a printed circuit board comprising any combination of the above (1) to (18), wherein the total coating amount of the binder including the emulsion layer is 2.5 g / m 2 or less. .
(22) The method for manufacturing a printed circuit board according to any one of (1) to (21), wherein the exposure is performed by a scanning exposure method using a laser beam.
(23) The method for producing a printed circuit board according to any one of (1) to (21), wherein the exposure is performed through a photomask.
(24) The method for producing a printed circuit board according to any one of (1) to (21), wherein the developer used in the development treatment of the silver salt-containing layer contains an image quality improver.
(25) The method for producing a printed circuit board according to any one of (1) to (21), wherein the developer used in the development treatment of the silver salt-containing layer is a lith developer.
(26) The mass of the metallic silver contained in the exposed portion after the development treatment is a content of 50% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. The manufacturing method of the printed circuit board in any one of said (1)-(25).

(27) The method for manufacturing a printed circuit board according to any one of (1) to (26), wherein the plating treatment is performed by electroless plating.
(28) The method for manufacturing a printed circuit board according to any one of (1) to (26), wherein the plating treatment is performed by electrolytic plating.
(29) The method for manufacturing a printed circuit board according to any one of (1) to (26), wherein the plating treatment is performed by electroless plating and subsequent electrolytic plating.
(30) The method for manufacturing a printed circuit board according to (27) or (29), wherein the electroless plating is electroless copper plating.
(31) The method for producing a printed circuit board according to any one of the above (1) to (30), wherein the gradation after the development treatment of the silver salt-containing layer exceeds 4.0.
(32) The method for producing a printed circuit board according to any one of (1) to (31), wherein the light-transmitting portion has substantially no physical development nucleus.

Furthermore, the object of the present invention is achieved by a printed board comprising the following aspects.
(33) A printed board having a conductive metal portion and a light-transmitting portion, which is obtained by the production method according to any one of (1) to (32).
(34) The printed wiring board according to (33), wherein the mass of silver is 50% by mass or more based on the total mass of the metal components contained in the conductive metal part.
(35) The printed wiring board according to (33), wherein the total mass of silver, copper, and palladium with respect to the total mass of the metal components contained in the conductive metal portion is 80% by mass or more.
(36) The printed wiring board according to any one of (31) to (35) above, wherein a line width of the conductive metal portion is 0.1 μm or more and less than 18 μm.
(37) The printed wiring board according to any one of (31) to (36), wherein a line width of the conductive metal portion is 0.1 μm or more and less than 14 μm.
(38) The printed wiring board according to any one of (31) to (37), wherein a line width of the conductive metal portion is 0.1 μm or more and less than 10 μm.
(39) The printed wiring board according to any one of (31) to (38), wherein a line width of the conductive metal portion is 0.1 μm or more and less than 7 μm.
(40) The printed wiring board according to any one of (31) to (37).

According to the present invention, a printed circuit board having high conductivity and few pinholes can be formed into a thin line pattern, and can be mass-produced at low cost with a low environmental load.
Moreover, the photosensitive material for producing a printed circuit board of the present invention is excellent in that there is no problem of fog. A printed circuit board material having good migration resistance can be obtained.

Further, as described with reference to FIG. 1 in the background art section, the conventional method increases the thickness of the conductor, resulting in the disadvantage of poor flexibility. However, the double-sided printed wiring board according to the present invention is manufactured. The method also eliminates this problem. FIG. 2 shows the manufacturing process of the double-sided printed wiring board according to the present invention.
As shown in FIG. 2A, both sides of the insulating substrate 1 have an emulsion layer containing a silver salt emulsion. Next, as shown in FIG.2 (b), the through-hole part 5 is formed in a predetermined position.

Thereafter, the emulsion layer is exposed and developed. As a result, as shown in FIG. 2C, silver images 81a and 81b are formed in the exposed portions, and insulating binders 82a and 82b are formed in the unexposed portions. Further, as shown in FIG. 2 (d), the electroless copper plating layer 3 is formed on the inner peripheral surface 5a of the through hole portion 5 and the surfaces of the silver images 81a and 81b, and the electrolytic copper plating layer 4 is further formed by electrolytic copper plating. It is formed. The conductor layer 7 thus formed has a thickness of ˜15 μm, and the flexibility of the double-sided printed wiring board is maintained.

It is the schematic of the manufacturing process of the double-sided printed circuit board by the prior art shown for the comparison. It is a schematic explanatory drawing of the manufacturing process of the double-sided printed circuit board by the manufacturing method of this invention. It is an electrode pattern figure for migration measurement. It is a circuit diagram for migration measurement.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Insulation board | substrate 2a, 2b Metal foil 3 Electroless copper plating layer 4 Electrolytic copper plating layer 5 Through-hole part 5a Inner peripheral surface 6 Etching resist 7 Conductive layer 21a, 21b Conductive pattern 81a, 81b Silver image 82a, 82b Insulating binder

First, the characteristics of the manufacturing method of the present invention will be described in comparison with other methods that are closest to the present invention that are conventionally known.
A method using a conventional silver salt diffusion transfer method (Analytical Chemistry, Vol. 72, Section 645, published in 2000 (Non-patent Document 1), International Publication No. WO 01/51276 (Patent Document 5) In the method))), since the physical development nucleus layer is uniformly provided on the metal image portion and the light transmitting portion, the physical development nucleus remains in the light transmitting portion in addition to the metal image portion. Therefore, the silver salt diffusion transfer method has the principle problem that the remaining physical development nuclei have electrical conductivity, so that the insulation is impaired.

  The above problem is a serious problem particularly in printed wiring board materials that require high insulation properties. In contrast, in the method of the present invention, metallic silver that functions as a physical development nucleus is generated only in the exposed portion and not in the unexposed portion that becomes the insulating portion. Have.

  On the other hand, in International Publication WO 01/51276 (Patent Document 5), without using the silver salt diffusion transfer method, a commercially available photographic film is used, and development, physical development, and plating processes are performed. It is described that conductivity can be imparted. Actually, it is possible to form a conductive metal film based on the above document, but in this case, both the conductivity and the insulation are inferior to the silver salt diffusion transfer method, such as a printed wiring board. It was insufficient for use as a printed wiring board material used in the above. Further, in the silver salt diffusion transfer method, a physical development nucleus layer for forming a metal image is specially provided, whereas in a commercially available photographic film, the physical development nucleus is in the silver halide emulsion layer. There are differences that are produced and buried in large amounts of binder.

Next, the manufacturing method and printed wiring board of the present invention will be described in more detail.
In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

Hereinafter, the photosensitive material for producing a printed circuit board of the present invention and a printed circuit board formed using the photosensitive material will be described in detail.
In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

<Photosensitive materials for printed circuit board>
[Support]
As the support of the photosensitive material used in the production method of the present invention, a plastic film, a plastic plate, a glass plate, or the like can be used.
Examples of the raw material for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, EVA; polyvinyl chloride, Vinyl resins such as polyvinylidene chloride; polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC) Etc. can be used.
The plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.

[Silver salt-containing layer]
The photosensitive material used in the production method of the present invention has an emulsion layer (silver salt-containing layer) containing a silver salt emulsion as an optical sensor on a support. A silver salt content layer can contain a binder, a solvent, etc. besides silver salt.
Preferably, the emulsion layer is substantially disposed on the uppermost layer. Here, “the emulsion layer is substantially the uppermost layer” not only means that the emulsion layer is actually disposed on the uppermost layer, but also the total thickness of the layers provided on the emulsion layer is 0. .5 μm or less. The total thickness of the layers provided on the emulsion layer is preferably 0.2 μm or less.
In addition to the silver salt, the emulsion layer may contain a dye, a binder, a solvent and the like as required. Hereinafter, each component contained in the emulsion layer will be described.
<Dye>
The light-sensitive material may contain a dye at least in the emulsion layer. The dye is contained in the emulsion layer as a filter dye or for various purposes such as prevention of irradiation. The dye may contain a solid disperse dye. Examples of the dye preferably used in the present invention include dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication are preferable. Further, (II-2) to (II-24) described in JP-A-7-152112, (III-5) to (III-18) described in JP-A-7-152112, and JP-A-7-152112. (IV-2) to (IV-7) described in the publication are also preferably used.

  In addition, as dyes that can be used in the present invention, solid fine particle dispersed dyes to be decolored during development or fixing processing include cyanine dyes, pyrylium dyes, and aminium dyes described in JP-A-3-138640. Can be mentioned. Further, as dyes that do not decolorize during processing, cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes not containing an acidic group described in JP-A-8-245902, and those described in JP-A-8-333519 Lake type cyanine dyes, cyanine dyes described in JP-A-1-266536, holopolar cyanine dyes described in JP-A-3-136638, pyrylium dyes described in JP-A-62-299959, JP-A-7-253039 Polymer type cyanine dyes described in JP-A No. 2-282244, solid fine particle dispersions described in JP-A No. 2-282244, light scattering particles described in JP-A No. 63-131135, Yb3 + compounds described in JP-A No. 9-5913 And ITO powder described in JP-A-7-113072. . In addition, dyes represented by general formula (F1) and general formula (F2) described in JP-A-9-179243, specifically, compounds F35 to F112 described in the same publication can also be used.

  Moreover, as said dye, a water-soluble dye can be contained. Such water-soluble dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and benzylidene dyes are particularly useful in the present invention. Specific examples of water-soluble dyes that can be used in the present invention include British Patent Nos. 584,609, 1,177,429, JP-A-48-85130, 49-99620, No. 49-114420, No. 52-20822, No. 59-154439, No. 59-208548, US Pat. No. 2,274,782, No. 2,533,472, No. 2 No. 3,956,879, No. 3,148,187, No. 3,177,078, No. 3,247,127, No. 3,540,887, No. 3 , 575,704 specification, 3,653,905 specification, and 3,718,427 specification.

  The content of the dye in the emulsion layer is preferably 0.01 to 10% by mass with respect to the total solid content, from the viewpoint of preventing irradiation and the like, and from the viewpoint of lowering sensitivity due to an increase in the amount added. More preferred is mass%.

<Silver salt>
Examples of the silver salt used in the present invention include inorganic silver salts such as silver halide and organic silver salts such as silver acetate. In the present invention, it is preferable to use silver halide having excellent characteristics as an optical sensor.

The silver halide preferably used in the present invention will be described.
In the present invention, it is preferable to use a silver halide excellent in characteristics as an optical sensor, and the technique used in a silver salt photographic film or photographic paper, a printing plate-making film, a photomask emulsion mask, etc. relating to silver halide, It can also be used in the present invention.

  The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halide mainly composed of AgCl, AgBr, and AgI is preferably used, and silver halide mainly composed of AgBr or AgCl is preferably used. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred are silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.

  Here, “silver halide mainly composed of AgBr (silver bromide)” refers to silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of AgBr may contain iodide ions and chloride ions in addition to bromide ions.

  The silver iodide content in the silver halide emulsion is preferably 1.5 mol% per mole of silver halide emulsion. By setting the silver iodide content to 1.5 mol%, fogging can be prevented and pressure characteristics can be improved. A more preferred silver iodide content is 1 mol% or less per mole of silver halide emulsion.

Silver halide is in the form of solid grains. From the viewpoint of image quality of the patterned metallic silver layer formed after exposure and development, the average grain size of silver halide is 0.1 to 1000 nm in terms of sphere equivalent diameter ( 1 μm) is preferred, 0.1 to 100 nm is more preferred, and 1 to 50 nm is even more preferred.
Incidentally, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.

The shape of the silver halide grains is not particularly limited, and may be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, tetragonal flat plate shape, etc.), octahedron shape, and tetrahedron shape. There can be a cube and a tetrahedron.
The silver halide grains may be composed of a uniform phase or a different surface layer. Moreover, you may have the localized layer from which a halogen composition differs in a particle | grain inside or surface.

  The silver halide emulsion which is a coating solution for an emulsion layer used in the present invention is described in P.I. Grafkides, Chimie et Physique Photographic (published by Paul Montel, 1967), G.K. F. Photographic Chemistry by Dufin (published by The Focal Press, 1966), V. L. It can be prepared using the method described in Making and Coating Photographic Emulsion (published by The Formal Press, 1964) by Zelikman et al.

That is, as a method for preparing the silver halide emulsion, either an acidic method, a neutral method, or the like may be used. As a method for reacting a soluble silver salt and a soluble halogen salt, a one-side mixing method, a simultaneous mixing method, Any of these combinations may be used.
As a method for forming silver particles, a method of forming particles in the presence of excess silver ions (so-called back mixing method) can also be used. Furthermore, as one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is generated, that is, a so-called controlled double jet method can be used.
It is also preferable to form grains using a so-called silver halide solvent such as ammonia, thioether or tetrasubstituted thiourea. A tetrasubstituted thiourea compound is more preferable as such a method, and is described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal type and a narrow grain size distribution, and is preferably used in the present invention. it can.
Further, in order to make the grain size uniform, as described in British Patent No. 1,535,016, Japanese Patent Publication No. 48-36890, and Japanese Patent Publication No. 52-16364, silver nitrate or halogenated A method of changing the alkali addition rate according to the particle growth rate, or a method of changing the concentration of the aqueous solution as described in British Patent No. 4,242,445 and JP-A-55-158124 It is preferable to grow silver quickly in a range not exceeding the critical saturation. The silver halide emulsion used for forming the emulsion layer in the present invention is preferably a monodispersed emulsion, and the coefficient of variation represented by {(standard deviation of grain size) / (average grain size)} × 100 is 20% or less, and more. It is preferably 15% or less, and most preferably 10% or less.

  The silver halide emulsion used in the present invention may be a mixture of a plurality of types of silver halide emulsions having different grain sizes.

The silver halide emulsion used in the present invention may contain a metal belonging to Group VIII or Group VIIB. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound, or the like. These compounds may be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and such pseudohalogens. In addition to ammonia, organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, etc.), urea, thiourea and the like can be mentioned.
In order to increase the sensitivity, doping of a metal hexacyanogenated complex such as K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ] or K ₃ [Cr (CN) ₆ ] is advantageous. Done.

A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium halide (III) compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt, a hexabromorhodium (III) complex salt, and a hexaamine rhodium (III). ) Complex salt, trizalatodium (III) complex salt, K ₃ Rh ₂ Br _{9 and the} like.
These rhodium compounds are used by dissolving in water or a suitable solvent, and are generally used in order to stabilize the rhodium compound solution, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, hydrofluoric acid). Or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is possible to add another silver halide grain previously doped with rhodium and dissolve it at the time of silver halide preparation.

Examples of the iridium compound include hexachloroiridium complex salts such as K ₂ IrCl ₆ and K ₃ IrCl ₆ , hexabromoiridium complex salts, hexaammineiridium complex salts, and pentachloronitrosyliridium complex salts.
Examples of the ruthenium compound include hexachlororuthenium, pentachloronitrosylruthenium, K ₄ [Ru (CN) ₆ ] and the like.
Examples of the iron compound include potassium hexacyanoferrate (II) and ferrous thiocyanate.

The above ruthenium and osmium are added in the form of water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855, etc. Preferable examples include hexacoordination complexes represented by the following formula.
[ML _6] - ⁿ
(Here, M represents Ru or Os, and n represents 0, 1, 2, 3 or 4.)
In this case, the counter ion is not important, and for example, ammonium or alkali metal ions are used. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.

[RuCl ₆ ] ⁻³ , [RuCl ₄ (H ₂ O ₂ )] ⁻¹ , [RuCl ₅ (NO)] ⁻² , [RuBr ₅ (NS)] ⁻² , [Ru (CO) ₃ Cl ₃ ] ^{− 2} , [Ru (CO) Cl ₅ ] ⁻² , [Ru (CO) Br ₅ ] ⁻² , [OsCl ₆ ] ⁻³ , [OsCl ₅ (NO)] ⁻² , [Os (NO) (CN) ₅ ] ^-2, [Os (NS) Br _5] ^-2, [Os _{(CN) 6]} ^-4, _{[Os (O) 2 (CN)} 5 ] ^-4.

The amount of these compounds added is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, and more preferably 10 ⁻⁹ to 10 ⁻³ mol / mol Ag.

In addition, in the present invention, silver halide containing Pd (II) ions and / or Pd metal can also be preferably used. Pd may be uniformly distributed in the silver halide grains, but is preferably contained in the vicinity of the surface layer of the silver halide grains. Here, Pd “contains in the vicinity of the surface layer of the silver halide grains” means that the Pd content is higher than the other layers within 50 nm in the depth direction from the surface of the silver halide grains. means.
Such silver halide grains can be prepared by adding Pd in the course of forming silver halide grains. After adding silver ions and halogen ions to 50% or more of the total addition amount, Pd Is preferably added. It is also preferred that Pd (II) ions be present in the surface layer of the silver halide by a method such as addition at the time of post-ripening.
The Pd-containing silver halide grains increase the speed of physical development and electroless plating, increase the production efficiency of a desired electromagnetic shielding material, and contribute to the reduction of production costs. Pd is well known and used as an electroless plating catalyst. However, in the present invention, Pd can be unevenly distributed on the surface layer of silver halide grains, so that extremely expensive Pd can be saved. is there.

In the present invention, the content of Pd ions and / or Pd metals contained in the silver halide is preferably 10 ^{−4 to} 0.5 mol / mol Ag with respect to the number of moles of silver in the silver halide. More preferably, it is 0.01 to 0.3 mol / mol Ag.
Examples of the Pd compound to be used include PdCl ₄ and Na ₂ PdCl ₄ .

The non-chemically sensitized emulsion according to the present invention will be described. In a silver halide photographic light-sensitive material, the silver halide emulsion is usually subjected to chemical sensitization. As a method of chemical sensitization, for example, a chemical sensitizer composed of a chalcogenite compound or a noble metal compound having a sensitivity sensitizing action for a photographic light-sensitive material cited in paragraph No. 0078 of JP-A No. 2000-275770 is halogenated. By adding to the silver emulsion. As the silver salt emulsion used in the light-sensitive material of the present invention, an emulsion that does not undergo such chemical sensitization, that is, an unchemically sensitized emulsion can be preferably used. A method for preparing an unchemically sensitized emulsion can be easily performed by not adding these chemical sensitizers to the emulsion. In addition, even when a compound containing chalcogenite or a noble metal is added to the emulsion, if the increase in sensitivity relative to the case where these are not added is small, the present invention regards this emulsion as non-chemical sensitization. In the present invention, a preferable method for preparing a non-chemically sensitized emulsion is to add an amount of a chemical sensitizer composed of chalcogenite or a noble metal compound, such that the increase in sensitivity due to the addition of these is less than 0.1. It is preferable to keep it at. The specific amount of chalcogenite or noble metal compound added is not limited, but as a preferred method for preparing an unchemically sensitized emulsion in the present invention, the total amount of these chemically sensitized compounds is 5 × per mole of silver halide. It is preferable to make it 10 ⁻⁷ mol or less, and it is more preferable not to add these compounds at all.

  In the present invention, in order to further improve the sensitivity as an optical sensor, chemical sensitization performed with a photographic emulsion can be performed. As the chemical sensitization method, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination. When the above chemical sensitization methods are used in combination, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization. A combination of a method and a gold sensitization method is preferable.

The sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the sulfur sensitizer, known compounds can be used. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. Can be used. Preferred sulfur compounds are thiosulfate and thiourea compounds. The amount of sulfur sensitizer added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, and is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. Preferably, it is 10 ^<-5 > ^-10 <^-3> mol.

  A known selenium compound can be used as the selenium sensitizer used for the selenium sensitization. That is, the selenium sensitization is usually carried out by adding unstable and / or non-labile selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used. In particular, it is preferable to use compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855.

  The tellurium sensitizer used for the tellurium sensitizer is a compound that generates silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide grain. The silver telluride formation rate in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640 No. 4-271341, No. 4-3333043, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.), P. 635 (1980). , Ibid 1102 (1979), ibid 645 (1979), Journal of Chemical Society Parkin Transaxi (J. Chem. Soc. Perkin. Trans.) Vol. 1, 2191 (1980), S. Compounds described in The Chemistry of Organic Selenium and Tellunium Compounds, Volume 1 (1986), Volume 2 (1987), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Companies Can be used. Particularly preferred are compounds represented by the general formulas (II), (III) and (IV) in JP-A-5-313284.

The amount of selenium sensitizer and tellurium sensitizer that can be used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, etc., but is generally 10 ⁻⁸ to 10 ⁻² per mole of silver halide. Mol, preferably about 10 ⁻⁷ to 10 ⁻³ mol. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used for gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, thioglucose gold (I), and thiomannose gold (I). About 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of silver halide grain formation or physical ripening.

  In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion by the method described in European Patent Publication (EP) 293917. The silver halide emulsion used in the preparation of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Combinations of different chemical sensitization conditions and different sensitivities) may be used. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.

The coating amount of the silver salt emulsion is preferably 4 g / m ² or less, more preferably ² g / m ² or less in terms of silver amount. By setting the coating amount of the silver salt emulsion to 4 g / m ² or less, fog is hardly generated and the pressure property can be improved.

<Binder>
In the emulsion layer, a binder can be used for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. In the present invention, 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.
Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyacrylic acid, and the like. Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.

The content of the binder contained in the emulsion layer is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited. As for the content of the binder in the emulsion layer, the Ag / binder weight ratio is preferably 1.5 or more, and more preferably 2.5 or more. When the Ag / binder weight ratio is 1.5 or more, the time required for the plating treatment can be shortened. The Ag / binder weight ratio is preferably 20 or less. On the other hand, in order to obtain good migration resistance, it is preferable that the total amount of binder on the side of the support including the emulsion layer is as small as possible. All binder - coating amount is preferably 2.5 g / ^{m 2} or less, more preferably 0.5 to 2.0 g / ^{m 2.}

<Solvent>
The solvent used for forming the emulsion layer is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, etc. , Esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.
The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of silver salt, binder and the like contained in the emulsion layer. Preferably there is.

<Antioxidant>
The emulsion layer according to the present invention preferably contains an antioxidant. Addition of an antioxidant to the emulsion layer makes it difficult for fog to occur and improves pressure characteristics.
The antioxidant used in the present invention preferably has a molecular weight of 330 or less. The lower limit is not particularly limited, but a molecular weight of 40 or more is preferable. Particularly preferred are those having a molecular weight of 200-330.

  Furthermore, the antioxidant used in the present invention is preferably a compound having an oxidation potential Eox of Eox ≦ 1.5 (V). More preferably, Eox ≦ 1.2 (V). More preferably, 0.3 ≦ Eox ≦ 0.8 (V). The oxidation potential Eox of the antioxidant can be easily measured by those skilled in the art. The method is described, for example, in a paper by A. Stanienda “Naturwissenschafften”, Volumes 47, 353 and 512 (1960), “P. Delahay” “New Instrumental Methods in Electrochemistry” (1954), published by Interscience Publishers, and “L. Mits. Graphic” "Techniques" (Polarographic Technologies) 2nd edition (1965), InterScience Pub Sshazu are described in, for example, (Interscience Publishers) company published. The value of Eox means the potential at which the compound is withdrawn at the anode in portammetry, and it is primarily related to the highest occupied electron energy level in the ground state of the compound.

Eox in the present invention is a value obtained from a polarographic half-wave potential under the conditions described below. That is, acetonitrile was used as the solvent for the antioxidant, 0.1N sodium perchlorate was used as the supporting electrolyte, the concentration of the antioxidant was 10 ⁻³ to 10 ⁻⁴ mol / liter, and the reference electrode was an Ag / AgCl electrode. The Eox was measured at 25 ° C. using a rotating platinum plate electrode.

  This antioxidant is most preferably added directly to the silver halide emulsion layer of the light-sensitive material according to the present invention, but it contains hydrophilic colloids such as an intermediate layer, a protective layer, a yellow filter layer, and an antihalation layer. You may add to the non-photosensitive layer used as a binder. It is also effective to add it to both the photosensitive emulsion layer and the non-photosensitive layer. When added to the photosensitive emulsion layer, the antioxidant may be added at any time from coating to processing, but is preferably added from chemical ripening to coating processing, more preferably after completion of chemical ripening. That's fine. Further, it may be added to the non-photosensitive layer and diffused throughout the constituent layers during coating.

The antioxidant may be added after dissolving in water or a lower alcohol, ester or ketone compatible with water, or a mixed solvent thereof. Further, it may be added after being dissolved in a high boiling point solvent. The addition amount is preferably in the range of 10 ⁻² to 10 ⁻⁸ mol per mol of silver halide, and particularly preferably in the range of 10 ⁻³ to 10 ⁻⁵ mol. What is necessary is just to select suitably according to a kind etc. When it is contained in the non-photosensitive layer, an aqueous solution of hydrophilic colloid containing an antioxidant is applied in the range of 0.01 to 50 g, more preferably in the range of 0.05 to 10 g, per 1 g of hydrophilic colloid. As a result, good results can be obtained. Moreover, although antioxidant may be used independently, you may use together.

  Specific examples of the antioxidant include the following compounds, but are not limited thereto.

A preferable antioxidant is represented by the following general formula (II).

In the formula, Z ₁₁ represents an atomic group necessary for forming a carbocycle or a heterocycle, and preferred specific examples of the carbocycle include a benzene ring and a naphthalene ring, and preferred specific examples of the heterocycle are Includes a seven-membered ring containing an oxygen atom as a hetero atom. Specific examples of the substituent that can be substituted on these rings include an alkyl group, an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, and a sulfonic acid group.

Among the compounds of the general formula (II), compounds having at least one sulfonic acid group (sulfonate) on the aromatic carbocyclic ring are particularly preferable. Specific preferred specific examples of the antioxidant include the specific examples II- (19), II- (22), II- (39) and the like. As the antioxidant having a molecular weight of 330 or less, the following antioxidants (1) and (2) are also preferable in addition to the compound represented by the general formula (II).
(1) One of the substituents at the 2-position is a group selected from a hydroxy group, an amino group and a substituted amino group, the other is a hydrogen atom, and one of the substituents at the 3-position is a hydroxy group, an amino group, and A 2-cyclopenten-1-one derivative, which is a group selected from substituted amino groups, and the other is a hydrogen atom.
(2) One of the substituents at the 2-position is a group selected from a hydroxy group, an amino group and a substituted amino group, the other is a hydrogen atom, and one of the substituents at the 3-position is a hydroxy group, an amino group, and A 2-cyclohexen-1-one derivative, which is a group selected from substituted amino groups, and the other is a hydrogen atom. In (1) and (2), more preferably a compound in which the 2-position is a hydroxy group and the 3-position is an amino group or a substituted amino group. Among (1) and (2), (1) is preferable, and among them, the 3-position is pyrrolidin-1-yl, piperidin-1-yl or morpholin-1-yl and the 2-position is a hydroxy group Is most preferred. Specific examples include (II)-(48) and (II)-(49) of the exemplified compounds.

<Oxidizing agent>
The emulsion layer according to the present invention preferably contains an oxidizing agent. By adding an oxidizing agent to the emulsion layer, fogging is less likely to occur and the pressure property can be improved.
The addition amount is preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol / mol Ag, more preferably in the range of 1 × 10 ^{−6 to} 5 × 10 ⁻³ mol / mol Ag mole, but the addition amount is silver halide. It can be appropriately selected depending on the kind of the oxidizing agent and the kind of the oxidizing agent.
The oxidizing agent refers to a compound having an action of acting on metallic silver and converting it into silver ions. In particular, a compound that converts very fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H ₂ O _{2 , 2Na 2 SO 4 · H 2} O 2 · 2H 2 O), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (eg, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3H ₂ O, 4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ · 6H ₂ O], permanganate (e.g., KMnO _4), oxygen acid salts, such as chromates _{(e.g., K 2 Cr 2 O 7)} , a halogen element such as iodine and bromine, perhalogenates ( Eg potassium periodate) and high valent metal salts ( Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, potassium cyanoferric acid potassium). N-bromosuccinimide, chloramine T, chloramine B).

  A particularly preferred oxidizing agent used in the present invention is a thiosulfonate compound represented by the following general formula (XX), (XXI) or (XXII), and the most preferred general formula is the general formula (XX) It is a compound represented by

Formula (XX) R—SO ₂ SM
Formula (XXI) R—SO ₂ S—R ¹
Formula _{(XXII) R-SO 2 S} -L m -SSO 2 -R 2

In general formula (XX), (XXI) or (XXII), R, R ¹ and R ² may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, and m is 0 or 1. The compound represented by general formula (XX) to general formula (XXII) may be a polymer containing a divalent group derived from the structure represented by (XX) to (XXII) as a recurring unit. When possible, R, R ¹ , R ² and L may be bonded to each other to form a ring.

  When silver is present, thiosulfonic acid oxidizes silver by the following reaction formula to form silver sulfide. Gahler, Veroff wiss. Photo lab Wolfen X, 63 (1965).

RSO ₂ SM + 2Ag → RSO ₂ M + Ag ₂ S
It has been experimentally confirmed that such oxidation occurs. Hereinafter, the thiosulfonate compound will be described.

When R, R ¹ and R ² are aliphatic groups, they are saturated or unsaturated, linear, branched or cyclic aliphatic hydrocarbon groups, preferably alkyl groups having 1 to 22 carbon atoms, carbon These are an alkenyl group and an alkynyl group having a number of 2 to 22, and these may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl. Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl.

The aromatic group of R, R ¹ and R ² includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R ¹ and R ² is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium and having at least one carbon atom. Yes, preferably a 3- to 6-membered ring, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole , Tetrazole, oxadiazole, and thiadiazole ring.

Examples of the substituent for R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy), and an aryl group (eg, phenyl, naphthyl, tolyl). , Hydroxy group, halogen atom (for example, fluorine, chlorine, bromine, iodine), aryloxy group (for example, phenoxy), alkylthio group (for example, methylthio, butylthio), arylthio group (for example, phenylthio), acyl group (for example, acetyl, Propionyl, butyryl, valeryl), sulfonyl groups (eg, methylsulfonyl, phenylsulfonyl), acylamino groups (eg, acetylamino, benzoylamino), sulfonylamino groups (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy (E.g., acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group, _-SO 2 SM group, (M is a monovalent cation) _-SO 2 ^{R 1} group can be mentioned.

The divalent linking group represented by L is an atom or atomic group containing at least one selected from C, N, S and O. Specifically, it is composed of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, —S—, —NH—, —CO—, —SO ₂ — alone or a combination thereof.

L is preferably a divalent aliphatic group or a divalent aromatic group. L is a divalent aliphatic group for _{example, - (C 2 H 2)} n - (n = 1~12), - CH 2 -CH = CH-CH 2 -,

  Xylene group. Examples of the divalent aromatic group include a phenylene group and a naphthylene group.

  These substituents may be further substituted with the substituents described so far.

  M is preferably a metal ion or an organic cation. Examples of the metal ions include lithium ions, sodium ions, and potassium ions. Examples of the organic cation include ammonium ions (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), and guanidyl groups.

  Specific examples of the compound represented by the general formula (XX), (XXI) or (XXII) are shown below, but are not limited thereto.

  Compounds of the general formula (XX), (XXI) or (XXII) are described in JP 54-1019; British Patent 972,211; Journal of Organic Chemistry, Vol. 53, page 396 (1988). Can be synthesized.

The compound represented by the general formula (XX), (XXI) or (XXII) is preferably added at 10 ⁻⁷ to 10 ⁻¹ mol per mol of silver salt. Furthermore, the addition amount of 10 ⁻⁶ to 10 ⁻² , particularly 10 ⁻⁵ to 10 ⁻³ mol / mol Ag is preferable.

  In order to add the compound represented by the general formula (XX), (XXI) or (XXII) during grain formation, a method usually used when an additive is added to the emulsion can be applied. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or sparingly soluble in water is an appropriate organic solvent miscible with water, such as alcohols, glycols, ketones, esters, and amides. Thus, it can be added as a solution obtained by dissolving in a solvent that does not adversely affect photographic characteristics.

  The compound represented by the compound (XX), (XXI) or (XXII) may be added at any stage during grain formation of the silver salt emulsion, before chemical sensitization or during production.

  Although it may be added to the reaction vessel in advance, compound (XX), (XXI) or (XXII) is added in advance to an aqueous solution of a water-soluble silver salt or water-soluble alkali halide, and these aqueous solutions are used to form particles. May be. It is also preferable to add the compound (XX), (XXI) or (XXII) in several portions during the particle production process, or to add it continuously for a long time.

<Matting agent>
The emulsion layer according to the present invention preferably contains a matting agent. By adding a matting agent to the emulsion layer, fogging is less likely to occur and the pressure property can be improved. The addition amount is preferably in the range of 5 to 400 mg / ^{m 2,} but more preferably a range of 10 to 200 mg / ^{m 2,} amount added can be appropriately selected depending on the type of matting agent.
Examples of the matting agent include compounds described in JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15.

<Slip agent>
The emulsion layer according to the present invention preferably contains a slip agent. By adding a slipping agent to the emulsion layer, fogging is less likely to occur and the pressure property can be improved.
Examples of useful slip agents include British Patent Nos. 955,061, 1,143,118, U.S. Pat. Nos. 3,042,522 and 3,080,317. , No. 4,004,927, No. 4,047,958, No. 3,489,576, and JP-A-60-140341. No. 2,454,043, No. 2,732,305, No. 2,976,148, No. 3,206,311, German Patent No. No. 1,284,295, No. 1,284,294, higher fatty acid type, higher fatty alcohol type, higher fatty acid amide type slip agent, British Patent No. 1,263,722, Described in US Pat. No. 3,933,516 Of higher fatty acid esters, higher fatty alcohols described in U.S. Pat. Nos. 2,588,765, 3,121,060, and British Patent 1,198,387. Examples include ether slip agents, taurine slip agents described in US Pat. Nos. 3,502,437 and 3,042,222, and the like. Specific examples are shown below, but the slipping agent that can be used in the present invention is not limited thereto.

The optimum amount of the slip agent used varies depending on the amount of gelatin applied to the outermost layer and the type of matting agent, but is 5 to 200 mg, preferably 15 to 150 mg per 1 m ^{2 on} one side.

<Colloidal silica>
The emulsion layer according to the present invention preferably contains colloidal silica. By adding colloidal silica to the emulsion layer, fogging is less likely to occur, and pressure properties can be improved. The addition amount is preferably in the range of 0.01 to 2.0, more preferably in the range of 0.1 to 0.6, with respect to the binder (eg, gelatin) in the addition layer, but the addition amount is It can be selected appropriately.
The colloidal silica (colloidal silica) preferably used in the present invention refers to a colloid of silica fine particles having an average particle diameter of 1 nm or more and 1 μm or less, and disclosed in JP-A-53-112732 and JP-B-57-009051. Reference can be made to those described in JP-A-57-51653. These colloidal silicas can be prepared and used by a sol-gel method, or commercially available products can be used. In the case of preparing colloidal silica by the sol-gel method, Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Ricky D. et al. Badley et al; Langmuir 6, 792-801 (1990), Color Material Association, 61 [9] 488-493 (1988). In addition, when using a commercially available product, SNOWTEX-XL (average particle size 40-60 nm), SNOWTEX-YL (average particle size 50-80 nm), SNOWTEX-ZL (average particle size) manufactured by Nissan Chemical Co., Ltd. 70-100 nm), PST-2 (average particle size 210 nm), MP-3020 (average particle size 328 nm), Snowtex 20 (average particle size 10-20 nm, SiO ₂ / Na ₂ O> 57), Snowtex 30 ( Average particle size 10-20 nm, SiO ₂ / Na ₂ O> 50), Snowtex C (average particle size 10-20 nm, SiO ₂ / Na ₂ O> 100), Snowtex O (average particle size 10-20 nm, SiO ₂ / _{Na 2} O> 500) or the like can be preferably used (the weight content of sodium hydroxide and silicon dioxide and _{SiO 2} / Na 2 O, where Sodium hydroxide is a representation in terms of Na 2 _O, are described in the catalog). When using a commercial item, SNOWTEX-YL, SNOWTEX-ZL, PST-2, MP-3020, and SNOWTEX C are particularly preferable. The main component of colloidal silica is silicon dioxide, but it may contain alumina or sodium aluminate as a minor component, and as a stabilizer, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia. Or an organic base such as tetramethylammonium.

  As the colloidal silica of the present invention, colloidal silica having an elongated shape having a thickness of 1 to 50 nm and a length of 10 to 1000 nm described in JP-A-10-268464, JP-A-9-218488, or JP-A-Hei. Composite particles of colloidal silica and organic polymer described in JP-A-10-111544 can also be preferably used.

<Antistatic agent>
The emulsion layer according to the present invention preferably contains an antistatic agent. By adding an antistatic agent to the emulsion layer, fogging is less likely to occur and pressure properties can be improved.
As the antistatic layer, a conductive substance-containing layer having a surface resistivity of 10 ¹² Ω or less in an atmosphere of 25 ° C. and 25% RH can be preferably used. As the antistatic agent preferable in the present invention, the following conductive substances can be preferably used.
A conductive substance described in JP-A-2-18542, page 2, lower left line 13 to page 3, upper right line 7th line. Specifically, the metal oxides described in the second lower right line on page 2 to the lower right tenth line of the same publication, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication . Needle-like metal oxides described in US Pat. No. 5,575,957, paragraphs 0045 to 0043 of JP-A-10-142727, paragraphs 0013 to 0019 of JP-A-11-223901, and the like can be used.

The conductive metal oxide particles used in the present invention include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO _3, and composite oxides thereof, and these metal oxides Furthermore, metal oxide particles containing different atoms can be mentioned. As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ , and MgO are preferable, SnO ₂ , ZnO, In ₂ O ₃ and TiO ₂ are preferable, and SnO ₂ is particularly preferable. preferable. Examples containing a small amount of foreign atoms, Al or In, Sb Sn, and against SnO ₂ with respect to Nb or Ta, _In 2 _{O 3} with respect to TiO _2, Nb or different, such as halogen element to ZnO An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. When the added amount of the different element is less than 0.01 mol%, it becomes difficult to impart sufficient conductivity to the oxide or composite oxide, and when it exceeds 30 mol%, the degree of blackening of the particles increases, Not suitable because the antistatic layer is dark. Therefore, in the present invention, the material of the conductive metal oxide particles is preferably one containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

As the conductive metal oxide particles containing a small amount of the dissimilar atom, SnO ₂ particles are preferred antimony-doped, SnO ₂ particles are preferred which are particularly doped antimony 0.2-2.0 mol%.

  There is no restriction | limiting in particular about the shape of the electroconductive metal oxide used for this invention, A granular form, needle shape, etc. are mentioned. Moreover, the average particle diameter represented by the spherical equivalent diameter is 0.5-25 micrometers.

  In order to obtain conductivity, for example, soluble salts (eg, chloride, nitrate, etc.), vapor deposited metal layers, ionic polymers as described in US Pat. Nos. 2,861,056 and 3,206,312 or US Pat. It is also possible to use insoluble inorganic salts as described in No. 1.

The antistatic layer containing such conductive metal oxide particles is preferably provided as an undercoat layer on the back surface, an undercoat layer of the emulsion layer, or the like. The addition amount is preferably 0.01 to 1.0 g / m ² in total on both sides.
The internal resistivity of the photosensitive material is preferably 1.0 × 10 ⁷ to 1.0 to 10 ¹² Ω in an atmosphere of 25 ° C. and 25% RH.

  In the present invention, in addition to the conductive material, JP-A-2-18542, page 4, upper right 2nd line, page 4 lower-right lower 3rd line, JP-A-3-39948, page 12, lower left 6 By using together the fluorine-containing surfactant described in the lower right line on page 13 of the same publication from the line, even better antistatic properties can be obtained.

<Other additives>
There are no particular restrictions on the various additives used in the light-sensitive material in the present invention, and for example, those described in the following publications can be preferably used.

1) Nucleation promoter The nucleation promoter is represented by the general formulas (I), (II), (III), (IV), (V), (VI) described in JP-A-6-82934. Compounds, general formulas (II-m) to (II-p) and compound examples II-1 to II in page 9, upper right column, line 13 to page 16, upper left column, line 10 of JP-A-2-103536. -22, and compounds described in JP-A-1-179939.

2) Spectral sensitizing dye As the above spectral sensitizing dye, JP-A-2-12236, page 8, lower left column, line 13 to the lower right column, line 4 and JP-A-2-103536, page 16, lower right column 3 Spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and JP-A-5-11389 are listed from the first line to the lower left column, line 20, from page 17. It is done.

3) Surfactant As the surfactant, JP-A-2-12236, page 9, upper right column, line 7 to lower-right column, line 7 and JP-A-2-18542, page 2, lower-left column, line 13 From the eyes, the surfactants described on page 18, lower right column, line 18 can be mentioned.

4) Antifoggant As the antifoggant, JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, Further, thiosulfinic acid compounds described in JP-A-1-237538 can be mentioned.

5) Polymer Latex Examples of the polymer latex include those described in JP-A-2-103536, page 18, lower left column, lines 12 to 20.

6) Compound having an acid group Examples of the compound having an acid group include compounds described in JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1.
7) Hardener As a specific method for arbitrarily controlling the swelling ratio of the emulsion layer and other binder layers in the present invention, there is a method using an inorganic or organic gelatin hardener alone or in combination. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen Compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalogen acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholinyl, carbonyl-3-pyridinio) methanesulfonate), Haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination.
Other examples include the compounds described in JP-A-2-103536, paragraph 18, upper right column, lines 5 to 17;
The above hardener may be added to the emulsion layer coating solution, or it may be dipped in the hardener solution at any timing during the printed circuit board manufacturing process (for example, after development processing or after plating processing) to cause hardening. May be.
From the viewpoint of migration resistance, it is preferable that the swelling ratio of the insulating portion after the plating treatment is low. The swelling ratio of the insulating part is preferably 150% or less, and more preferably 50 to 150%.

8) Black spot preventive agent The above black spot preventive agent is a compound that suppresses the occurrence of spot-like developed silver in unexposed areas. For example, U.S. Pat. No. 4,956,257 and JP-A-1-118832. And the compounds described in the publication No ..
9) Redox compounds As redox compounds, compounds represented by general formula (I) of JP-A-2-301743 (especially compound examples 1 to 50), pages 3 to 20 of JP-A-3-174143 are disclosed. Examples include general formulas (R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in JP-A-5-257239 and 4-278939. .
10) Monomethine Compound Examples of the monomethine compound include compounds of the general formula (II) of JP-A-2-287532 (especially Compound Examples II-1 to II-26).
11) Dihydroxybenzenes The compounds described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and European Patent Publication EP452772A can be mentioned.

[Binder layer]
The light-sensitive material according to the present invention preferably has a binder layer below the emulsion layer. Here, the lower layer means that the distance from the support is closer and located on the same plane. In the present invention, a binder layer comprising a hydrophilic colloid layer can be preferably placed below the silver salt emulsion layer.
Gelatin is advantageously used as the binder, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other synthetic hydrophilic polymer materials such as single or copolymer are used. be able to. As gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used. In the light-sensitive material of the present invention, when a binder layer is provided below the silver salt emulsion layer, the preferred binder layer thickness is in the range of 0.2 μm to 2 μm, more preferably in the range of 0.5 μm to 1 μm.

<Method for producing conductive film>
A method for producing a conductive film suitable as a light-transmitting electromagnetic wave shielding film using the above photosensitive material will be described.
In the method for producing a conductive film of the present invention, a photosensitive material having an emulsion layer containing a photosensitive silver halide salt is exposed on a support and subjected to a development treatment, whereby an exposed area and an unexposed area are respectively obtained. A metallic silver part and a light-transmitting part are formed, and a conductive metal is supported on the metallic silver part by further subjecting the metallic silver part to physical development and / or plating treatment.
The conductive film obtained by the present invention is not limited to a metal formed on a support by pattern exposure, but may be a film formed by surface exposure.

The method for producing a conductive film of the present invention includes the following three forms depending on the photosensitive material and the form of development processing.
(1) A mode in which a photosensitive silver halide black-and-white photosensitive material not containing physical development nuclei is chemically developed or thermally developed to form a metallic silver portion on the photosensitive material.
(2) An embodiment in which a photosensitive silver halide black-and-white photosensitive material containing physical development nuclei in a silver halide emulsion layer is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
(3) A photosensitive silver halide black-and-white photosensitive material that does not contain physical development nuclei and an image-receiving sheet having a non-photosensitive layer that contains physical development nuclei are overlaid and diffused and transferred to develop a metallic silver portion on the non-photosensitive image-receiving sheet. Form formed on top.
The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive film such as a light-transmitting electromagnetic wave shielding film is formed on the photosensitive material. The resulting developed silver is chemically developed silver or heat developed and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.
In the above aspect (2), in the exposed portion, the silver halide grains close to the physical development nucleus are dissolved and deposited on the development nucleus, whereby a light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film is formed on the photosensitive material. A translucent conductive film such as is formed. This is also an integrated black-and-white development type. Since the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a spherical shape with a small specific surface.
In the above aspect (3), the silver halide grains are dissolved and diffused in the unexposed area and deposited on the development nuclei on the image receiving sheet, whereby a light transmitting electromagnetic wave shielding film or a light transmitting conductive film is formed on the image receiving sheet. A translucent conductive film such as a film is formed. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.
In any embodiment, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer system, negative development processing is possible by using an auto-positive type photosensitive material as the photosensitive material). .
The chemical development, thermal development, dissolution physical development, and diffusion transfer development referred to here have the same meanings as are commonly used in the art, and a general textbook of photographic chemistry such as Shinichi Kikuchi, “Photochemistry” (Kyoritsu) Published by publisher), C.I. E. K. It is described in “The Theory of Photographic Process, 4th ed.” Edited by Mees. Although this case is a liquid processing, a thermal development method is also applied as a development method for other applications. For example, Japanese Patent Application Laid-Open Nos. 2004-184893, 2004-334077, 2005-010752, Japanese Patent Application Nos. 2004-244080, and 2004-085655 can be applied.

[exposure]
In the present invention, the silver salt-containing layer provided on the support is exposed. The exposure can be performed using electromagnetic waves. Examples of the electromagnetic wave include light such as visible light and ultraviolet light, and radiation such as X-rays. Furthermore, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.

  Examples of the light source include scanning exposure using a cathode ray (CRT). The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one or two or more of a red light emitter, a green light emitter, and a blue light emitter are used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used. An ultraviolet lamp is also preferable, and g-line of a mercury lamp, i-line of a mercury lamp, etc. are also used.

  In the present invention, exposure can be performed using various laser beams. For example, the exposure in the present invention is a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using high-density light can be preferably used, and a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be used. In order to make the system compact and inexpensive, the exposure is preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal. In order to design an apparatus that is particularly compact, inexpensive, long-life, and highly stable, it is preferable to perform exposure using a semiconductor laser.

Specifically, as a laser light source, a blue semiconductor laser with a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (with an oscillation wavelength of about 1060 nm) waveguide-like inverted domain structure about 530nm green laser taken out by wavelength conversion by the SHG crystal of LiNbO ₃ having a red semiconductor laser having a wavelength of about 685 nm (Hitachi type No.HL6738MG), red semiconductor laser having a wavelength of about 650 nm ( Hitachi type No. HL6501MG) is preferably used.

[Development processing]
In the present invention, after the emulsion layer is exposed, further development processing is performed. The development processing can be performed by a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like. The developer is not particularly limited, but PQ developer, MQ developer, MAA developer and the like can also be used. Commercially available products include, for example, CN-16, CR-56, CP45X, FD manufactured by Fuji Film Co., Ltd. -3, Papitol, a developer such as C-41, E-6, RA-4, D-19, D-72 manufactured by KODAK, or a developer included in the kit can be used. A lith developer can also be used.
As the lith developer, KODAK D85 or the like can be used. In the present invention, by performing the above exposure and development processing, a metal silver portion, preferably a patterned metal silver portion, is formed in the exposed portion, and a light transmissive portion described later is formed in the unexposed portion.

  In the production method of the present invention, a dihydroxybenzene developing agent can be used as the developer. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, hydroquinone monosulfonate, and the like, and hydroquinone is particularly preferable. Examples of the auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene developing agent include 1-phenyl-3-pyrazolidones and p-aminophenols. As the developer used in the production method of the present invention, a combination of a dihydroxybenzene developer and 1-phenyl-3-pyrazolidones; or a combination of a dihydroxybenzene developer and p-aminophenols is preferably used.

As a developing agent combined with 1-phenyl-3-pyrazolidone or a derivative thereof used as an auxiliary developing agent, specifically, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like.
Examples of the p-aminophenol auxiliary developing agent include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine and the like. Among them, N-methyl-p-aminophenol is preferable. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter, but in the present invention, it is particularly preferably used at 0.23 mol / liter or more. More preferably, it is the range of 0.23-0.6 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.23-0.6 mol / liter, more preferably 0.23-0. It is preferable to use 5 mol / liter, and the latter in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter to 0.003 mol / liter.

  In the present invention, both the development initiator and the development replenisher have a property that “the pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.5 or less”. preferable. As a method of confirming that the development starting solution or development replenisher used has this property, the pH of the development starting solution or development replenisher to be tested is adjusted to 10.5, and then sodium hydroxide is added to 1 liter of this solution. 0.1 mol was added, and the pH value of the liquid at this time was measured. In the production method of the present invention, it is particularly preferable to use a development starter and a development replenisher whose pH value rises to 0.4 or less when the above test is performed.

  As a method for imparting the above properties to the development initiator and the development replenisher, a method using a buffer is preferably used. Examples of the buffer include carbonates, boric acid described in JP-A-62-286259, saccharides (for example, saccharose), oximes (for example, acetoxime), and phenols described in JP-A-60-93433. (For example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like can be used, and carbonate and boric acid are preferably used. The amount of the buffer (particularly carbonate) used is preferably 0.25 mol / liter or more, and particularly preferably 0.25 to 1.5 mol / liter.

  In the present invention, the pH of the development initiator is preferably 9.0 to 11.0, and particularly preferably 9.5 to 10.7. The pH of the developer replenisher and the pH of the developer in the developer tank during continuous processing are also in this range. As the alkali agent used for pH setting, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

  In the production method of the present invention, when processing 1 square meter of the photosensitive material, the content of the developer replenisher in the developer is 323 ml or less, preferably 323 to 30 ml, particularly 225 to 50 ml. The development replenisher may have the same composition as the development starter, or it may have a higher concentration than the starter with respect to the components consumed in the development.

  In the developing solution for developing the light-sensitive material in the present invention (hereinafter, both the development starting solution and the developing replenisher may be simply referred to as “developing solution”), commonly used additives (for example, retaining agents) are used. (Constant, chelating agent). Examples of the preservative include sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The sulfite is preferably used in an amount of 0.20 mol / liter or more, and more preferably 0.3 mol / liter or more. However, since an excessive amount of the sulfite causes silver stain in the developer, the upper limit is It is desirable to be 1.2 mol / liter. Particularly preferred is 0.35 to 0.7 mol / liter. Further, as a preservative for a dihydroxybenzene developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Here, the ascorbic acid derivative includes ascorbic acid and its stereoisomer erythorbic acid and its alkali metal salts (sodium and potassium salts). As the ascorbic acid derivative, sodium erythorbate is preferably used in terms of material cost. The addition amount of the ascorbic acid derivative is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10, with respect to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as the preservative, it is preferable that the developer does not contain a boron compound.

  In addition to the above, additives that can be used in the developer include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide; diethanolamine, triethanolamine, etc. A development accelerator such as alkanolamine, imidazole or a derivative thereof, or a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be included as an antifoggant or a black pepper inhibitor. Specific examples of the benzimidazole compound include 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5 -Nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, sodium 4-[(2-mercapto-1,3,4-thiadiazol-2-yl) thio] butanesulfonate, 5- Examples include amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The content of these benzimidazole compounds is usually from 0.01 to 10 mmol, more preferably from 0.1 to 2 mmol, per liter of developer.

Further, various organic and inorganic chelating agents can be used in combination in the developer. As said inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
Examples of the above organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acileic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid. Examples thereof include, but are not limited to, acid, itaconic acid, malic acid, citric acid, and tartaric acid.

  Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, Triethylenetetramine hexaacetic acid, 1,3-diamino-2-propanol tetraacetic acid, glycol ether diamine tetraacetic acid, other publications of JP-A Nos. 52-25632, 55-67747, 57-102624, and others Examples thereof include compounds described in JP-A-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3,214,454 and 3,794,591, and West German Patent Publication No. 2227639, Research Disclosure, Vol. 181, Item. 18170 (May 1979 issue) and the like.
Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid and the like. In addition, Research Disclosure No. 18170, JP-A-57-208554, No.54. -61125, 55-29883 gazette and 56-97347 gazette etc. can be mentioned.

  Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241, and 55-65955. Nos. 55-65956, and the above-mentioned compounds disclosed in Research Disclosure No. 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts.

The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol per liter of the developer.

  Further, the compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, and JP-A-4-362294 can be used as a silver stain preventing agent in the developer. it can. Moreover, the compound of Unexamined-Japanese-Patent No. 61-267759 can be used as a solubilizing agent. Further, the developer may contain a color toning agent, a surfactant, an antifoaming agent, a hardening agent, and the like as necessary. The development processing temperature and time are related to each other and are determined in relation to the total processing time. In general, the development temperature is preferably from about 20 ° C. to about 50 ° C., more preferably from 25 to 45 ° C. The development time is preferably 5 seconds to 2 minutes, more preferably 7 seconds to 1 minute 30 seconds.

  From the viewpoint of developer transport cost, packaging material cost, space saving, and the like, it is also preferred that the developer be concentrated and diluted before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

  The development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. For the fixing process in the present invention, a fixing process technique used for a silver salt photographic film, photographic paper, a printing plate-making film, a photomask emulsion mask, or the like can be used.

Preferred components of the fixing solution used in the fixing step include the following.
That is, sodium thiosulfate, ammonium thiosulfate, if necessary, tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyrone, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid Etc. are preferably included. From the viewpoint of environmental protection in recent years, it is preferable that boric acid is not included. Examples of the fixing agent for the fixing solution used in the present invention include sodium thiosulfate and ammonium thiosulfate. Ammonium thiosulfate is preferable from the viewpoint of fixing speed, but sodium thiosulfate may be used from the viewpoint of environmental protection in recent years. Good. The amount of these known fixing agents used can be appropriately changed, and is generally about 0.1 to about 2 mol / liter. Most preferably, it is 0.2-1.5 mol / liter. In the fixing solution, a hardening agent (for example, a water-soluble aluminum compound), a preservative (for example, sulfite, bisulfite), a pH buffer (for example, acetic acid), a pH adjuster (for example, ammonia, sulfuric acid) ), Chelating agents, surfactants, wetting agents, fixing accelerators.

Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. A known antifoaming agent may be added to the fixing solution.
Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include thiourea derivatives described in JP-B Nos. 45-35754, 58-122535, and 58-122536; alcohols having a triple bond in the molecule; Examples include thioether compounds described in US Pat. No. 4,126,459; mesoionic compounds described in JP-A-4-229860, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid, boric acid, phosphate, sulfite, and the like. Inorganic buffers can be used. As the pH buffer, acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing an increase in pH of the fixing agent due to bringing in the developer, and is preferably 0.01 to 1.0 mol / liter, more preferably 0.02 to 0.6 mol / liter. Use degree. The pH of the fixing solution is preferably from 4.0 to 6.5, particularly preferably from 4.5 to 6.0. Further, as the dye elution accelerator, compounds described in JP-A No. 64-4739 can also be used.

  Examples of the hardener in the fixing solution of the present invention include water-soluble aluminum salts and chromium salts. A preferred compound as the hardener is a water-soluble aluminum salt, and examples thereof include aluminum chloride, aluminum sulfate, potash and vane. A preferable addition amount of the hardener is 0.01 mol to 0.2 mol / liter, and more preferably 0.03 to 0.08 mol / liter.

The fixing temperature in the fixing step is preferably about 20 ° C. to about 50 ° C., more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is preferably 600 ml / ^{m 2} or less with respect to the processing of the photosensitive material, more preferably 500 ml / ^{m 2} or less, 300 ml / ^{m 2} or less is particularly preferred.

The light-sensitive material that has been subjected to development and fixing processing is preferably subjected to water washing treatment or stabilization treatment. In the water washing treatment or the stabilization treatment, the washing water amount is usually 20 liters or less per 1 m ^{2 of the} light-sensitive material, and can be replenished in 3 liters or less (including 0, ie, rinsing with water). For this reason, not only water saving processing is possible, but also piping for self-installing equipment can be dispensed with. As a method for reducing the replenishment amount of washing water, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. When this multi-stage countercurrent method is applied to the production method of the present invention, the photosensitive material after fixing is gradually processed in contact with the normal direction, that is, in the direction of the processing solution not contaminated with the fixing solution. Furthermore, efficient washing with water is performed. Moreover, when performing water washing with a small amount of water, it is more preferable to provide the washing tank of a squeeze roller and a crossover roller as described in Unexamined-Japanese-Patent No. 63-18350, 62-287252, etc. In addition, various oxidizer additions and filter filtration may be combined to reduce the pollution load that becomes a problem at the time of washing with a small amount of water. Furthermore, in the above method, a part or all of the overflow liquid from the washing bath or stabilization bath produced by replenishing the washing bath or stabilization bath with water subjected to the fouling means according to the treatment, As described in JP-A-60-235133, it can also be used for a processing solution having a fixing ability, which is a previous processing step. In addition, water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles that are likely to occur during washing with a small amount of water and / or to prevent the processing agent component adhering to the squeeze roller from being transferred to the processed film. Also good.

  In the washing treatment or stabilization treatment, a dye adsorbent described in JP-A-63-163456 may be installed in a washing tank in order to prevent contamination with a dye eluted from the photosensitive material. In the stabilization treatment following the water washing treatment, baths containing the compounds described in JP-A-2-2013357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446 are disclosed. May be used as the final bath of the light-sensitive material. At this time, ammonium compounds, metal compounds such as Bi, Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines and surfactants are added as necessary. It can also be added. Water used in the water washing process or stabilization process includes tap water, water deionized, halogen, UV germicidal lamps, and water sterilized by various oxidizing agents (such as ozone, hydrogen peroxide, and chlorates). It is preferable to use it. Further, washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. The bath temperature and time at the water washing treatment or the stabilization temperature are preferably 0 to 50 ° C. and 5 seconds to 2 minutes.

  In order to store the processing solution such as the developer and the fixing solution used in the present invention, it is preferable to store the packaging solution having a low oxygen permeability described in JP-A-61-73147. Moreover, when reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with the air. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,795 and 3,545,971 and the like, and is simply referred to as a roller-conveying processor in this specification. In addition, the roller transport type processor is preferably from four steps of development, fixing, washing and drying, and in the present invention, other steps (for example, stop step) are not excluded, but it is best to follow these four steps. preferable. Moreover, four steps by a stable process may be used instead of the water washing process.

  In each of the above steps, a component obtained by removing water from the composition of the developing solution or the fixing solution may be supplied as a solid, dissolved in a predetermined amount of water and used as a developing solution or a fixing solution. Such a form of treating agent is called a solid treating agent. As the solid processing agent, powder, tablet, granule, powder, lump or paste is used. A preferred form of the treatment agent is a form described in JP-A-61-259921 or a tablet. For example, JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, British Patent No. 1,213,808, etc. Can be manufactured. Furthermore, the granule treating agent can be produced by a general method described in, for example, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735 and JP-A-3-393939. Further, powder processing agents are generally described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured in a conventional manner

The bulk density of the solid processing agent is preferably 0.5 to 6.0 g / cm ³ and particularly preferably 1.0 to 5.0 g / cm ^{3 in} view of its solubility.

  In preparing the solid processing agent, at least two kinds of mutually reactive particulate materials among the materials constituting the processing agent are replaced with at least one intervening separation layer made of a material inert to the reactive material. Alternatively, a method may be employed in which reactive substances are placed in layers so as to be separated into layers, a bag that can be vacuum-packed is used as a packaging material, and the bag is evacuated and sealed. Here, “inert” means that the substances do not react under normal conditions in the package when they are in physical contact with each other or that there is no significant reaction. The inert material may be inactive in the intended use of the two reactive materials, apart from being inert to the two mutually reactive materials. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react in direct contact with each other in the developer, they can be stored in the package for a long time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. In addition, hydroquinone or the like is briquetted to reduce the contact area with sodium hydroxide, so that the storage stability is improved and the mixture can be used. Bags made from an inert plastic film, a laminate of plastic material and metal foil are used as packaging materials for these vacuum packaging materials.

  The mass of the metallic silver contained in the exposed portion after the development treatment is preferably a content of 50% by mass or more, and 80% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. More preferably. If the mass of silver contained in the exposed portion is 50% by mass or more based on the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity can be obtained.

  The gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0. When the gradation after the development processing exceeds 4.0, the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high. Examples of means for setting the gradation to 4.0 or higher include the aforementioned doping of rhodium ions and iridium ions.

[Physical development and plating]
In the present invention, for the purpose of imparting conductivity to the metal silver portion formed by the exposure and development processing, physical development and / or plating treatment for supporting the conductive metal particles on the metal silver portion is performed. In the present invention, the conductive metal particles can be supported on the metallic silver portion by only one of physical development and plating. However, the combination of physical development and plating is used to convert the conductive metal particles to metallic silver. It can also be carried on the part. A metal silver portion subjected to physical development and / or plating is referred to as a “conductive metal portion”.
“Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to deposit metal particles. This physical phenomenon is used for instant B & W film, instant slide film, printing plate manufacturing, and the like, and the technology can be used in the present invention.
Further, the physical development may be performed simultaneously with the development processing after exposure or separately after the development processing.

In the present invention, the plating process can be performed using electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating. For the electroless plating in the present invention, a known electroless plating technique can be used. For example, an electroless plating technique used for a printed wiring board can be used, and the electroless plating is an electroless copper plating. Preferably there is.
Chemical species contained in the electroless copper plating solution include copper sulfate, copper chloride, reducing agent, formalin, glyoxylic acid, copper ligand, EDTA, triethanolamine, etc., bath stabilization and plating Examples of the additive for improving the smoothness of the film include polyethylene glycol, yellow blood salt, and bipyridine.
Examples of the electrolytic copper plating bath include a copper sulfate bath and a copper pyrophosphate bath.

  The plating speed at the time of plating in the present invention can be performed under moderate conditions, and high-speed plating of 5 μm / hr or more is also possible. In the plating treatment, various additives such as a ligand such as EDTA can be used from the viewpoint of improving the stability of the plating solution.

[Oxidation Treatment] In the present invention, it is preferable to subject the metal silver portion after the development treatment and the conductive metal portion formed by physical development and / or plating treatment to an oxidation treatment. By performing the oxidation treatment, for example, when a metal is slightly deposited on the light transmissive portion, the metal can be removed and the light transmissive portion can be made almost 100% transparent.
Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment. As described above, the oxidation treatment can be performed after exposure and development processing of the emulsion layer, or after physical development or plating treatment, and may be performed after development processing and after physical development or plating treatment.

  In the present invention, the metal silver portion after the exposure and development treatment can be further treated with a solution containing Pd. Pd may be a divalent palladium ion or metallic palladium. This treatment can accelerate electroless plating or physical development speed.

[Conductive metal part]
Next, the conductive metal part in the present invention will be described.
In the present invention, the conductive metal portion is formed by subjecting the metal silver portion formed by the above-described exposure and development processing to physical development or plating treatment, and supporting the conductive metal particles on the metal silver portion.
As the conductive metal particles supported on the metal part, in addition to the above-mentioned silver, copper, aluminum, nickel, iron, gold, cobalt, tin, stainless steel, tungsten, chromium, titanium, palladium, platinum, manganese, zinc, rhodium And particles of metals such as these, or alloys of these in combination. From the viewpoint of conductivity, cost, etc., the conductive metal particles are preferably copper, aluminum or nickel particles. Moreover, when providing magnetic field shielding properties, it is preferable to use paramagnetic metal particles as the conductive metal particles.

The conductive metal part preferably contains 50% by mass or more, and more preferably 60% by mass or more of silver with respect to the total mass of the metal contained in the conductive metal part. When silver is contained in an amount of 50% by mass or more, the time required for physical development and / or plating can be shortened, productivity can be improved, and cost can be reduced.
Furthermore, when copper and palladium are used as the conductive metal particles forming the conductive metal part, the total mass of silver, copper and palladium is 80% by mass or more based on the total mass of the metal contained in the conductive metal part. It is preferable that it is 90 mass% or more.

  The line width of the conductive metal portion is preferably less than 15 μm, more preferably less than 10 μm, and most preferably less than 7 μm.

The light transmissive part in the present invention preferably has substantially no physical development nucleus from the viewpoint of improving the transparency. Unlike the conventional silver complex diffusion transfer method, the present invention does not require diffusion after dissolving unexposed silver halide and converting it to a soluble silver complex compound. It has substantially no nucleus.
Here, “substantially no physical development nuclei” means that the abundance of physical development nuclei in the light-transmitting portion is in the range of 0 to 5%.

  The thickness of the metallic silver portion provided on the support before physical development and / or plating can be appropriately determined according to the coating thickness of the silver salt-containing layer coating applied on the support. The thickness of the metallic silver part is preferably 30 μm or less, more preferably 20 μm or less, further preferably 0.01 to 9 μm, and most preferably 0.05 to 5 μm. Moreover, it is preferable that a metal silver part is pattern shape. The metallic silver part may be a single layer or a multilayer structure of two or more layers. When the metallic silver portion has a pattern shape and has a multilayer structure of two or more layers, different color sensitivities can be imparted so that it can be exposed to different wavelengths. Thereby, when the exposure wavelength is changed and exposed, a different pattern can be formed in each layer.

  In the present invention, a metallic silver portion having a desired thickness is formed by controlling the coating thickness of the silver salt-containing layer, and the thickness of the layer made of conductive metal particles can be freely controlled by physical development and / or plating treatment. Therefore, even a printed board having a thickness of less than 5 μm, preferably less than 3 μm can be easily formed.

  In the conventional method using etching, it was necessary to remove and discard most of the metal thin film by etching, but in the present invention, a pattern containing only a necessary amount of conductive metal is provided on the support. Therefore, it is sufficient to use only the minimum amount of metal, which is advantageous from the viewpoints of reducing the manufacturing cost and the amount of metal waste.

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
(Emulsion A adjustment)
・ 1 liquid:
750 ml of water
20g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
5 ml of potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution)
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7 ml
Potassium hexachloroiridate (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used for the three liquids were respectively KCl 20% aqueous solution and NaCl 20% aqueous solution. And heated at 40 ° C. for 120 minutes.

To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes while stirring to form 0.16 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitation agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated. Next, about 3 liters of the supernatant was removed (first water wash). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. 30 g of gelatin was added to the emulsion after washing and desalting, adjusted to pH 5.6 and pAg 7.5, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemical sensitization was performed to obtain an optimum sensitivity at 0 ° C., and 100 mg of 1,3,3a, 7-tetraazaindene as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative It was. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain diameter of 0.22 μm and a coefficient of variation of 9% was obtained. (Finally, the emulsion had pH = 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg / m ³ , and viscosity = 60 mPa · s.)

(Preparation of coated sample 1-1)
Sample 1-1 was coated on a polyethylene terephthalate film support having a moisture-proof undercoat containing vinylidene chloride on both sides as shown below so as to have a constitution of UL layer / emulsion layer / protective layer lower layer / protective layer upper layer protective layer. It was created. The preparation method, coating amount and coating method of each layer are shown below.
<Emulsion layer>
Emulsion A was subjected to spectral sensitization by adding sensitizing dye (sd-1) 5.7 × 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag and compound (Cpd-3) 8.0 × 10 ⁻⁴ mol / mol Ag were added and mixed well.
Then, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 90 mg / m ² , colloidal silica having a particle size of 10 μm of 15 wt% with respect to gelatin, aqueous latex (aqL-6) 100 mg / m ² m ² , 150 mg / m ^{2 of} polyethyl acrylate latex, 150 mg of latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (weight ratio 88: 5: 7) / M ² , core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63) , Shell: styrene / 2-acetoxyethyl acrylate (weight ratio 84/16), core / shell ratio = 50/50) 150 mg / m ² , 4 wt% of compound (Cpd-7) with respect to ceftin was added, and The coating solution pH was adjusted to 5.6 using acid. Thus Ag3.4g / ^{m 2} The emulsion layer coating solution was prepared on the following support was coated to a gelatin 1.1 g / ^{m 2.}

<Protective layer upper layer>
Gelatin 0.3g / m ²
Amorphous silica matting agent having an average of 3.5 μm 25 mg / m ²
Compound (Cpd-8) (gelatin dispersion) 20 mg / m ²
Colloidal silica with a particle size of 10-20 μm (Nissan Chemical Snowtex C)
30 mg / m ²
Compound (Cpd-9) 50 mg / m ²
Sodium dodecylbenzenesulfonate 20 mg / m ²
Compound (Cpd-10) 20 mg / m ²
Compound (Cpd-11) 20 mg / m ²
Preservative (Proxel (trade name, manufactured by ICI Co., Ltd.)) 1 mg / m ²

<Protective layer lower layer>
Gelatin 0.5g / m ²
1,5-dihydroxy-2-benzaldoxime 10 mg / m ²
Polyethyl acrylate latex 150mg / m ²
Compound (Cpd-13) 3 mg / m ²
Preservative (Proxel) 1.5mg / m ²

<UL layer>
Gelatin 0.5g / m ²
Polyethyl acrylate latex 150mg / m ²
Compound (Cpd-7) 40 mg / m ²
Compound (Cpd-14) 10 mg / m ²
Preservative (Proxel) 1.5mg / m ²

  In addition, the coating liquid of each layer added the thickener represented by the following structure (Z), and adjusted the viscosity.

The sample used in the present invention has a back layer and a conductive layer having the following composition.
<Back layer>
Gelatin 3.3 g / m ²
Compound (Cpd-15) 40 mg / m ²
Compound (Cpd-16) 20 mg / m ²
Compound (Cpd-17) 90 mg / m ²
Compound (Cpd-18) 40 mg / m ²
Compound (Cpd-19) 26 mg / m ²
1,3-divinylsulfonyl-2-propanol 60 mg / m ²
Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ²
Liquid paraffin 78mg / m ²
Compound (Cpd-7) 120 mg / m ²
Calcium nitrate 20mg / m ²
Preservative (Proxel) 12mg / m ²

<Conductive layer>
Gelatin 0.1 g / m ²
Sodium dodecylbenzenesulfonate 20 mg / m ²
SnO ₂ / Sb (9/1 weight ratio, average particle diameter 0.25 μ) 200 mg / m ²
Preservative (Proxel) 0.3 mg / m ²

<Support>
Undercoat layers of the following composition on both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were coated with a first layer and a second layer.

<Undercoat layer 1>
Core-shell type vinylidene chloride copolymer (1) 15 g
2,4-dichloro-6-hydroxy-s-triazine 0.25 g
Polystyrene fine particles (average particle size 3μ) 0.05g
Compound (Cpd-20) 0.20 g
Colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.)
0.12g
100g with water
Further, a coating solution adjusted to pH = 6 by adding 10 wt% KOH was applied at a drying temperature of 180 ° C. for 2 minutes so that the dry film thickness was 0.9 μm.

<2nd undercoat layer>
1g of gelatin
Methylcellulose 0.05g
Compound (Cpd-21) 0.02 g
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g
Proxel 3.5 × 10 ⁻³ g
Acetic acid 0.2g
100g with water
This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

<Application method>
A slide bead coater is maintained on the support with the above subbing layer on the emulsion layer side, starting from the side closer to the support, in the order of the UL layer, emulsion layer, protective layer lower layer and protective layer upper layer at 35 ° C. Apply a multilayer coating while adding a hardener solution according to the method, and after passing through a cold air set zone (5 ° C), in the order of the conductive layer and back layer from the side closer to the support on the side opposite to the emulsion surface, While adding a hardener solution by a coater method, simultaneous multilayer coating was performed, and the solution was passed through a cold air set zone (5 ° C.). When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both sides were simultaneously dried in the drying zone.

The obtained coated sample 1-1 contains a silver halide emulsion having a silver iodide content of 1.5% or less, which is a silver salt preferably used in the photosensitive material for forming a conductive film of the present invention, in the emulsion layer. . The silver salt coating amount is 3.4 g / m ² in terms of silver, and is the silver salt coating amount preferably used for the photosensitive material for forming a conductive film of the present invention. The emulsion layer has an Ag / binder weight ratio of 1.8, which corresponds to an Ag / binder ratio of 1.5 or more which is preferably used in the photosensitive material for forming a conductive film of the present invention. Further, in the emulsion layer of the coated sample 1-1, sodium benzenethiosulfonate which is an oxidant preferably used for the emulsion layer of the photosensitive material for forming a conductive film of the present invention, and the photosensitive material for forming a conductive film of the present invention. Hydroquinone, which is an antioxidant preferably used in the emulsion layer, and colloidal silica preferably used in the emulsion layer of the photosensitive material for forming a conductive film of the present invention. However, since the coated sample 1-1 has two protective layers above the emulsion layer, it does not correspond to the photosensitive material for forming a conductive film of the present invention.

(Preparation of coated sample 1-2)
For coated sample 1-1, sodium benzenethiosulfonate, which is an oxidizing agent preferably used for the emulsion layer of the photosensitive material for forming a conductive film of the present invention, and the emulsion layer of the photosensitive material for forming a conductive film of the present invention. Hydroquinone, which is a preferred antioxidant, and colloidal silica, which is preferably used in the emulsion layer of the photosensitive material for forming a conductive film of the present invention, are removed, and a protective upper layer and a protective lower layer are not applied, and a protective upper layer is further removed. A sample different from the coated sample 1-2 was prepared only by adding the surfactants Cpd-9 and Cpd-10 used for the coating to the emulsion layer so as to have the same coating amount as the coated sample 1-1. did.

(Preparation of coated samples 1-3 to 1-5)
A sample that differs from the coated sample 1-2 only in that hydroquinone, which is an antioxidant preferably used in the emulsion layer of the photosensitive material for forming a conductive film of the present invention, is added to the emulsion layer in the same amount as the coated sample 1-1. To obtain a coated sample 1-3. Moreover, with respect to the coating sample 1-3, coating samples differing only in that the antioxidants were changed to the compounds and coating amounts shown in Table 1 below were prepared, and coating samples 1-4 to 1-5 were obtained, respectively. .

(Preparation of coated sample 1-6)
For the coated sample 1-2, a sample that differs only in that the emulsion was changed to an unchemically sensitized emulsion was prepared by not adding sodium thiosulfate and chloroauric acid at the time of preparing the emulsion. Got.

(Preparation of coated samples 1-7 to 1-9)
With respect to the coated sample 1-2, sodium benzenethiosulfonate, which is an oxidizing agent preferably used in the emulsion layer of the photosensitive material for forming a conductive film of the present invention, is added in the same amount and at the same time as the coated sample 1-1. Samples that differ only in the addition were prepared to obtain coated samples 1-7. Moreover, the coating samples which differ only in having changed the oxidizing agent into the compound and addition amount of Table 1 with respect to the coating sample 1-7 were created, and the coating samples 1-8 and 1-9 were obtained, respectively.

(Preparation of coated sample 1-10)
With respect to the coating sample 1-2, a coating sample different from the coating sample 1-1 only in that the colloidal silica used in the coating sample 1-1 was added to the emulsion layer in the same amount as the coating sample 1-1 was prepared, and a coating sample 1-10 was obtained. .

(Preparation of coated samples 1-11 to 1-13)
For the coated sample 1-2, the same amorphous silica matting agent as that used for the upper layer of the protective layer of the coated sample 1-1, which is a matting agent preferably used for the emulsion layer of the photosensitive material for forming a conductive film of the present invention ( Samples differing only in the addition of an average of 3.5 μm) into the emulsion layer in Table 1 were prepared to obtain coated samples 1-11. Also, with respect to the coated sample 1-11, samples different from the coated sample 1-11 only in that the matting agent was changed to the compounds and coating amounts shown in Table 1 were prepared, and coated samples 1-12 and 1-13 were obtained.

(Preparation of coated samples 1-14 to 1-15)
A sample different from the coated sample 1-2 in that only the amount of the slip compound (Cpd-9) preferably used in the emulsion layer of the photosensitive material for forming a conductive film of the present invention was added to the emulsion layer in Table 1 was prepared. Thus, a coated sample 1-14 was obtained. Moreover, the sample which differs only in having changed the sliding agent into the compound and coating amount which are shown in Table 1 with respect to the application sample 1-14 was created, and the application sample 1-15 was obtained.

(Preparation of coated sample 1-16)
Without coating the protective layer upper layer and the protective layer lower layer on the coated sample 1-1, the amorphous silica matting agent preferably used for the photosensitive film-forming photosensitive material of the present invention, and the conductive property of the present invention. Sliding agents preferably used for photosensitive materials for film formation are added to the emulsion layer in the amounts shown in Table 1, and Cpd-9 and Cpd-10 are added to the emulsion layer so as to have the same coating amount as the coated sample 1-1. A sample different from that described above was prepared and designated as a coated sample 1-16. The amorphous silica matting agent used here was the same as that used for the upper layer of the protective layer of the coated sample 1-1, with an average of 3.5 μm.

(Preparation of coated sample 1-17)
A coated sample 1-17 was obtained by preparing a sample different from the coated sample 1-16 only in that the amount of potassium iodide added during emulsion preparation was changed to 9.4 g.

(Preparation of coated sample 1-18)
For coated sample 1-16, a sample that differs only in that the emulsion was changed to an unchemically sensitized emulsion was prepared by not adding sodium thiosulfate and chloroauric acid during emulsion preparation. Got.

(Preparation of coated samples 1-19 to 1-20)
Samples different from the coated sample 1-16 only in changing the coating flow rate of the emulsion layer were prepared, and samples 1-19 and 1-20 were obtained. Samples of the coated silver amount shown in Table 1 were obtained.

  The following exposure, development, and plating treatments were performed on the coated samples 1-1 to 1-20 thus obtained.

(Exposure and development processing)
A grid-like pattern capable of giving a developed silver image of line / space = 15 μm / 285 μm (pitch 300 μm) was exposed to the dried coating film using an image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd. At this time, the exposure amount was adjusted to be optimal for each sample.
For each sample after exposure, a developer (A) and a fixer (B) having the following prescription are used, and an FG-680AG automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) is used and the developing condition is 35 ° C. and 30 ″. Was processed.

-Developer (A) formulation The composition per liter of the concentrated solution is shown.
Potassium hydroxide 60.0g
Diethylenetriamine / pentaacetic acid 3.0g
Potassium carbonate 90.0g
Sodium metabisulfite 105.0g
Potassium bromide 10.5g
Hydroquinone 60.0g
5-methylbenzotriazole 0.53g
4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.3 g
Sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate
0.15g
0.45 g of sodium 2-mercaptobenzimidazole-5-sulfonate
Sodium erythorbate 9.0g
Diethylene glycol 7.5g
pH 10.79
In use, the mother liquor is diluted at a ratio of 1 part water to 2 parts of the concentrate, the pH of the mother liquor is 10.65, and the replenisher is at a ratio of 3 parts water to the 4 parts of the concentrate. The pH of the diluted replenisher was 10.62.

-Fixing liquid (B) prescription The prescription per 1 L of the concentrated liquid is shown.
360g ammonium thiosulfate
Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.09g
Sodium thiosulfate pentahydrate 33.0g
Sodium metasulfite 57.0g
Sodium hydroxide 37.2g
Acetic acid (100%) 90.0g
Tartaric acid 8.7g
Sodium gluconate 5.1g
Aluminum sulfate 25.2g
pH 4.85
In use, it is diluted at a ratio of 2 parts of water to 1 part of the concentrated liquid. The pH of the working solution is 4.8. The replenisher used after same dilution as above using liquid-sensitive material 1 m ² per was performed at 258Ml.

(Plating treatment)
The film having a silver image for mesh pattern obtained by the above development treatment is subsequently immersed in an activation solution and an electroless copper plating solution having the following composition, whereby electroless copper plating is applied on the mesh pattern silver image. gave. Here, the activation treatment was performed at 35 ° C. for 5 minutes. The electroless copper plating was performed at 35 ° C. for a period of time until the copper plating thickness reached 2 μm.

(Activation solution composition): 0.2 g of PdCl ₂ per liter
HCl (2N aqueous solution) 25.6 ml
Add water to dissolve the above to 1 L.

(Electroless copper plating solution composition):
Copper sulfate 0.06 mol / L
Formalin 0.22 mol / L
Triethanolamine 0.12 mol / L
Polyethylene glycol 100ppm
Yellow blood salt 50ppm
Aqueous solution containing 20 ppm α, α'-bipyridine pH = 12.5

(Evaluation 1)
With respect to the obtained conductive thin film, plating progress and pressure resistance were evaluated by the following methods.
(1) Plating progress The plating thickness after plating was measured by cross-sectional SEM photography. From the relationship between the plating thickness obtained for each sample and the plating time, the time required for plating until the plating thickness reached 2 μm was determined by interpolation.

(2) Pressure resistance Prior to the above exposure, the occurrence frequency of the metal formed in a non-exposed part when the surface of each sample was rubbed with a cyclone scrub was observed with an optical microscope and ranked as follows.
<Evaluation>
5: Almost no metal formation in the non-exposed area, and very favorable level.
4: Although metal formation in the non-exposed area is rarely observed, it is a preferable level.
3: A level at which metal formation in the non-exposed area is rarely observed.
2: Level at which metal formation in non-exposed areas is observed.
1: Level at which metal formation is frequently observed in non-exposed areas.
When the metal formation level is an intermediate level of any of the above evaluation values, the evaluation value is determined by the average value of the corresponding evaluation values.

  The obtained evaluation results are shown in Table 1.

  From Table 1, the excellent effect of the present invention can be known. That is, it is shown in Table 1 that the time required for plating is significantly reduced for all of the samples of the present invention compared to the case of using the coated sample 1-1 which is a comparative sample, and the sample of the present invention is used. It can be seen that the conductive film can be formed quickly. On the other hand, it is shown in Table 1 that the pressure resistance may deteriorate when the sample of the present invention is used. Table 1 shows that the deterioration of the pressure resistance can be improved by using an antioxidant, an oxidizing agent, a matting agent, a sliding agent, and colloidal silica that can be preferably used in the light-sensitive material of the present invention. Has been. Table 1 shows that the use of an unchemically sensitized emulsion, which is one of the preferred embodiments of the present invention, can improve pressure resistance. Table 1 also shows that the pressure resistance can be improved by using an emulsion having a limited silver iodide content, which is one of the preferred embodiments of the present invention.

[Example 2]
(Preparation of coated samples 2-1 to 2-7)
Sample 2-1 was obtained by exactly the same method as Sample 1-18 used in Example 1.
Samples were prepared by changing the amount of gelatin in the emulsion layer and the coating amount of the emulsion layer and the UL layer as shown in Table 2 for the coated sample 2-1, and samples 2-1 to 2-7 were obtained.

  Each of the obtained samples was subjected to the same exposure, development, activation and plating as in Example 1 to evaluate the plating progress and pressure resistance.

Next, the migration resistance was evaluated by the following procedure.
First, the photosensitive material is exposed, developed, and plated using a metal mask negative so as to have the migration measurement electrode pattern shown in FIG. 3, and then dipped in a potassium alum solution to adjust the film thickness. It was. The degree of hardening was adjusted by the concentration of potassium alum solution and the immersion time.
Next, the migration measurement electrode produced as described above was incorporated in the circuit of FIG. 4 and a voltage of DC 5 V was applied in an environment of 65 ° C. and 95% RH. From the time of application of this voltage, the time course of the voltage across the resistor R ₁ and recorded in the recorder. The migration current was calculated from this measurement result, and the time required for 0.2 ampere or more was measured.

In addition, as an evaluation of the degree of hardening, the swelling ratio of the insulating portion was determined as follows. That is, the total thickness (d ₀ ) of the insulating part was measured, the part was immersed in distilled water at 25 ° C. for 1 minute, the swollen thickness (Δd) was measured, and the swelling rate (%) = Δ It was determined by the calculation formula of _d ÷ d ₀ × 100. Thickness can be measured by the same principle as an electric micrometer described in JIS B7536. For example, it can be measured with an electronic micrometer (K306 type) manufactured by Anritsu Electric Co., Ltd.

  The results are shown in Table 2.

  From Table 2, the excellent effect of the present invention can be known. That is, it is shown in Table 2 that the pressure resistance can be improved within a limited range of the applied silver amount, which is one of the preferred embodiments of the present invention. Table 2 shows that the required plating time can be further shortened by setting the limited Ag / binder ratio of the emulsion layer, which is one of the preferred embodiments of the present invention. Table 2 shows that the pressure resistance is improved by the application of the UL layer located on the support side of the emulsion layer, which is one of the preferred embodiments of the present invention. Although the reduction in the amount of coated silver tends to lead to an increase in the time required for plating, the amount of coated silver is reduced by setting the limited Ag / binder ratio of the emulsion layer, which is one of the preferred embodiments of the present invention. It is shown in Table 2 that the increase in the time required for plating accompanying the above can be reduced.

  The comparative example of this example means a comparative example for claim 20. In the comparative example, the rising of the migration current is observed after 300 to 500 minutes after the voltage application. On the other hand, in the present invention, there is no rise in migration current even after 300 to 500 minutes after voltage application, and no rise in migration current is observed after 1000 minutes.

  Observing the electrode portion after 400 minutes from the voltage application, in the comparative example, dendritic precipitates can be confirmed from the negative electrode to the positive electrode. However, in the present invention, there is almost no growth of dendritic precipitates.

Example 3
For each of the samples 1-1 to 1-20 prepared in Example 1, the spectral sensitizing dye SD-1 is changed to the following SD-2, Cpd-14 is changed to the following Cpd-YF, and the back layer Samples different from each other only in that the coating was not performed were prepared, and Samples 3-1 to 3-20 were obtained. Here, the coating amount of SD-2 and Cpd-YF was the same amount (mol / m ² ) as SD-1 and Cpd-14, respectively.
The obtained sample was exposed through a mesh photomask having a maximum line width of 10 μm and a lattice interval of 300 μm with a contact printer using a high-pressure mercury lamp as a light source, and then the same development processing, activation, and By carrying out the plating treatment, the plating progress and pressure resistance were evaluated. When the same evaluation as in Example 1 was performed, the excellent effect of the present invention was confirmed.

Example 4
Each sample prepared in Example 3 was exposed to a mesh pattern having a line width of 15 μm and a pitch of 300 μm using an image setter (Cobalt8 manufactured by ESCHER-GRAD, laser wavelength 410 nm) equipped with a blue semiconductor laser. . Each of the exposed samples was subjected to the same development processing, activation, and plating processing as in Example 1.
When the conductivity of each sample obtained was examined, the resistance (resistance between conductors separated by 10 cm) was 0 to 0.01 (Ω) in any sample, and it was effective for printed circuit boards. It was confirmed. According to the present invention, it is possible to provide a photosensitive material preferable for producing a printed circuit board with improved pressure resistance and reduced plating time. Moreover, a printed wiring board can be preferably manufactured by using the photosensitive material of the present invention.

Example 5
By applying no conductive layer to the coated sample 2-1 of Example 2, a sample different only in that the antistatic layer was not provided was prepared, and a coated sample 5-1 was obtained.
The obtained coated sample 5-1 and coated sample 2-1 were subjected to the same exposure, development, activation and plating as in Example 2. However, when evaluating the pressure resistance, the front and back surfaces of the sample were overlapped and rubbed rather than the Kicron scrubber, and the occurrence frequency of the metal formed in the non-exposed portion was evaluated. When observed using an optical microscope as in Example 1, the pressure resistance of sample 2-1 was level 5, and the pressure resistance of sample 5-1 was level 3. In Sample 5-1, no antistatic layer was provided, so that foreign matters such as dust were observed on the surface of the sample, and it was estimated that the pressure resistance deteriorated. It was shown that the present invention becomes more effective by the installation of the antistatic layer.

[Comparative Example 1]
As a sample for a comparative example, a commercially available two-layer type flexible substrate was used. This flexible substrate had a structure in which a copper electroless plating was formed on a polyimide resin film (thickness 50 μm), and a copper plating layer was further formed thereon.

[Comparative Example 2]
A commercially available three-layer type flexible substrate was used as a comparative sample. This flexible substrate had a configuration in which an adhesive layer made of an acrylic resin adhesive was formed on a polyimide resin film (thickness 50 μm), and a rolled copper layer was further formed thereon.

(Evaluation 2)
A sample that is different from the coated sample 2-1 only in that the support was changed to a polyimide resin film, exposed to light, and then subjected to the same development, activation, and plating as in Example 1. For the flexible substrates of Comparative Examples 1 and 2, the number of pinholes generated for each conductive film was examined. Regarding the number of pinholes, the number of pinholes generated within an area of 10 cm × 10 cm was counted using a transmission microscope. The evaluation results are shown in Table 3, respectively.

(Evaluation 3)
About the flexible substrate of Comparative Examples 1-2, the electroconductive film (DFR "HL-020" by Fuji Photo Film Co., Ltd.) was each laminated | stacked on the thin film metal layer using the laminator. Next, the DFR was exposed at 50 mJ through a counter comb-shaped negative pattern (S / L = 50 μm / 50 μm).
Then, it developed with Na2CO3 (1% concentration) aqueous solution, and also etched with the cupric chloride solution for 50 seconds. Furthermore, DFR remaining with acetone was removed. Next, a layer containing a solder resist (manufactured by Du Pont) was formed on the patterned copper thin film metal layer and the exposed undercoat layer by screen printing (thickness, about 20 μm), and 150 ° C. Heat treatment was performed for 1 hour to prepare each printed circuit board on which a fine pattern comb-shaped circuit was formed.

Example 6
After the same exposure as in the above evaluation 3 was performed on the coated sample 2-1 in Example 2, the same development processing, activation, and plating processing as in Example 1 were performed, and a comb-shaped circuit with a fine pattern was formed. A printed circuit board was created.

A DC voltage of 5 V was applied to each printed circuit board prepared above, and the insulation resistance between the wirings was measured. The evaluation results are shown in Table 3 below.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on June 27, 2005 (Japanese Patent Application No. 2005-186790), the contents of which are incorporated herein by reference.

Claims (17)

A photosensitive material including an emulsion layer containing a silver salt emulsion provided on a support is exposed and developed to form a metallic silver portion and an insulating portion, and the metallic silver portion is further subjected to physical development and A method for producing a printed circuit board, comprising: forming a conductive metal portion in which conductive metal particles are supported on the metal silver portion by plating. The method of manufacturing a printed circuit board according to claim 1, wherein the insulating portion has substantially no physical development nucleus. The method for producing a printed circuit board according to claim 1, wherein the emulsion layers are provided on both sides of the support. The said support body has flexibility, The manufacturing method of the printed circuit board as described in any one of Claims 1-3 characterized by the above-mentioned. The method for manufacturing a printed circuit board according to any one of claims 1 to 4, wherein the support is polyethylene terephthalate (PET). 6. The method for producing a printed circuit board according to claim 1, wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains an antioxidant. The method for producing a printed circuit board according to claim 1, wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains an oxidizing agent. The printed board according to any one of claims 1 to 7, wherein the emulsion layer is substantially disposed on the uppermost layer, and the silver salt emulsion is substantially unchemically sensitized grains. Method. The printed circuit board according to any one of claims 1 to 8, wherein the emulsion layer is substantially disposed on the uppermost layer, and the silver salt emulsion has a silver iodide content of 1.5 mol% or less. Manufacturing method. The said emulsion layer is arrange | positioned substantially at the uppermost layer, and the coating amount of the said silver salt emulsion is 4 g / m < ² > or less in conversion of silver amount, The Claim 1 characterized by the above-mentioned. Manufacturing method for printed circuit boards. The method for producing a printed circuit board according to claim 10, wherein the weight ratio of Ag / binder in the emulsion layer is 1.5 or more. The method for producing a printed circuit board according to claim 10, wherein a binder layer is provided below the emulsion layer. 13. The emulsion layer according to claim 1, wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains at least one of a matting agent, a slip agent, colloidal silica, and an antistatic agent. A method for producing a printed circuit board according to claim 1.   The method for producing a printed circuit board according to any one of claims 1 to 13, wherein a swelling ratio of the insulating part is 150% or less. The total binder coating amount on a side of the emulsion layer on the support including the emulsion layer is 2.5 g / m ² or less, according to any one of claims 1 to 13. A method for manufacturing a printed circuit board. A method for producing a printed circuit board comprising the combination according to any one of claims 1 to 15. The photosensitive material for printed circuit board production which can manufacture a printed circuit board with the manufacturing method as described in any one of Claims 1-16.

Images