JP2007088218A - Method for producing translucent electromagnetic wave shielding film, translucent electromagnetic wave shielding film obtained by the production method, film for display panel, optical filter for display panel, and plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a transparent electromagnetic shielding film excellent in durability, electromagnetic shielding properties and light transmittance and having a small light scattering at a low cost in large quantities, and a translucent electromagnetic shielding film and display film obtained thereby An optical filter for a display panel and a plasma display panel are provided.
A silver salt-containing layer provided on a transparent substrate is exposed and developed to form a metallic silver portion and a light transmitting portion, and the metallic silver portion is further subjected to physical development and / or plating. Forming a conductive metal part in which a conductive metal is supported on the metal silver part by processing, and applying a discoloration preventing process to the conductive metal part with an organic mercapto compound; Production method of electromagnetic wave shielding film, translucent electromagnetic wave shielding film obtained by the production method, display film having the same, optical filter for display panel, and plasma display panel.
[Selection figure] None

Description

  The present invention relates to electromagnetic waves generated from the front surface of a display such as a CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), FED (field emission display), microwave oven, electronic device, printed wiring board, etc. The present invention relates to a method for manufacturing a light-transmitting electromagnetic wave shielding film having a light-transmitting property, a light-transmitting electromagnetic wave shielding film obtained by the manufacturing method, a film for display panel, an optical filter for display panel, and a plasma display panel .

  2. Description of the Related Art In recent years, with the increase in use of various electric facilities and electronic application facilities, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly. The EMI has been found to cause malfunction and failure of electronic and electrical equipment. For this reason, electronic and electrical equipment is required to keep the intensity of electromagnetic wave emission within the standard or regulation.

  Although it is necessary to shield the electromagnetic wave in order to take measures against the EMI, it is obvious that a property that does not allow the metal electromagnetic wave to penetrate may be used. For example, a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, a method of covering the cable with a metal foil, and the like are adopted. However, in CRT, PDP, etc., since the operator needs to recognize characters displayed on the screen, transparency in the display is required. For this reason, in any of the above methods, the front surface of the display often becomes opaque, which is inappropriate as an electromagnetic wave shielding method.

Particularly, since PDP generates a large amount of electromagnetic waves as compared with CRT or the like, stronger electromagnetic shielding ability is required. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value. For example, in a translucent electromagnetic shielding material for CRT, the surface resistance value is required to be about 300 Ω / sq or less, whereas in a translucent electromagnetic shielding material for PDP, it is 2.5 Ω / sq or less. In consumer plasma televisions using PDPs, there is a high need for 1.5 Ω / sq or less, and a very high conductivity of 0.1 Ω / sq or less is more desirable.
Further, the required level for transparency is about 70% or more (total visible light transmittance) for CRT and 80% or more for PDP, and further higher transparency is desired.

  In order to solve the above problems, as shown below, various materials and methods have been proposed so far that achieve both electromagnetic shielding properties and light transmittance using a metal mesh having openings, A typical example is an etching mesh using a photolithography method. An etching mesh using a conventional photolithography method can be finely processed, and therefore has an advantage that a mesh with a high aperture ratio (high transmittance) can be created and strong electromagnetic wave emission can be shielded. On the other hand, the manufacturing process is complicated and has a problem of high cost, and improvement is demanded.

A method using the principle of silver salt photography has been proposed as a method for producing a metal mesh at a low cost corresponding to this demand.
For example, Patent Document 1 discloses a method for producing an electromagnetic wave shielding material by preparing a silver halide photosensitive material, exposing and developing it in a mesh shape, and further performing a plating treatment.

JP 2004-221564 A

The metal mesh obtained by using the silver salt photography method as described above can be manufactured with a smaller number of steps and can reduce the manufacturing cost compared to the manufacturing process of the etching mesh using photolithography. On the other hand, it had the following problems.
That is, the durability required for the electromagnetic shielding material used for the display is not sufficient, and improvement has been desired.

  The present invention has been made in view of such circumstances, and its object is to provide a low-cost transmissive electromagnetic shielding film having excellent durability, high electromagnetic shielding properties, small light scattering, and high light transmittance. It is providing the manufacturing method which can be manufactured in large quantities by. Moreover, the objective of this invention is providing the translucent electromagnetic wave shielding film obtained by the said manufacturing method. Still another object of the present invention is to provide a display film, an optical filter for a display panel, and a plasma display panel, each of which includes the translucent electromagnetic wave shielding film.

As a result of earnest investigation from the viewpoint of obtaining a light-transmitting electromagnetic wave shielding film that has excellent durability and high electromagnetic shielding properties and high transparency at the same time, the inventors have treated the durability with an organic mercapto compound. Has been found to be effective, the inventors have found that the above object can be effectively achieved by the following constitution, and have completed the present invention.
That is, the present invention is as follows.

1. By exposing and developing the silver salt-containing layer provided on the transparent substrate to form a metallic silver part and a light transmitting part, and further subjecting the metallic silver part to physical development and / or plating treatment A translucent electromagnetic wave shielding film characterized in that a conductive metal part in which a conductive metal is supported on the metal silver part is formed, and the conductive metal part is subjected to a discoloration prevention treatment with an organic mercapto compound. Production method.
2. The organic mercapto compound is represented by the following general formula (2): The manufacturing method of the translucent electromagnetic wave shielding film as described in any one of.
General formula (2)
Z-SM
[In General Formula (2), Z is an alkyl group, an aromatic group, or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² is a hydrogen atom or an alkali metal atom) Or an ammonium group), a group substituted with a substituent having at least one selected from the group consisting of an amino group and an ammonio group, or at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ]
3. The organic mercapto compound is one or more organic mercapto compounds selected from the following general formulas (1) and (3) to (5): Or 2. The manufacturing method of the translucent electromagnetic wave shielding film as described in any one of.
General formula (1)

[In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group,, ^{R 0} represents a substituent. L ¹ , L ² and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring through any of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Provided that at least one of ^{L 1,} L 2, ^{L 3} and ^{R 0} is representative of the -SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group). ]
General formula (3), general formula (4)

[In General Formulas (3) and (4), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group. However, R ₂₁ and R ₂₂ are not simultaneously a hydrogen atom, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group, and R ₂₅ represents a hydroxyl group (or a salt thereof), an amino group, an alkyl group, or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group, an acyl group, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group, an alkali metal atom, an aryl group or an aralkyl group. m represents 0, 1 or 2. n represents 2. ]
General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and Ma are a hydrogen atom, an alkali metal atom or ammonium, respectively. Represents a group. ]
4). 1. ~ 3. A translucent electromagnetic wave shielding film produced by the production method according to any one of the above.
5. Functional transparency with one or more functions selected from infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, UV protection properties, gas barrier properties, and display panel damage prevention properties 3. further comprising a layer; The translucent electromagnetic wave shielding film as described in 1.
6). 4). Or 5. A translucent electromagnetic wave shielding film as described in 1 above is used.
7). 6). An optical filter for a plasma display panel, characterized by using the film for a display panel described in 1.
8). 6). 6. Film for display panel as described in 7. A plasma display panel comprising the optical filter for plasma display panels described in 1.

ADVANTAGE OF THE INVENTION According to this invention, it can provide the manufacturing method which can manufacture the transmissive electromagnetic wave shielding film which is excellent in durability, has a high electromagnetic shielding property, and has a small light scattering and a high light transmittance at a low cost and in large quantities. . Moreover, according to this invention, the translucent electromagnetic wave shielding film obtained by the said manufacturing method, the film for displays which has this, the optical filter for display panels, and a plasma display panel can be provided.
Furthermore, surprisingly, the treatment with the organic mercapto compound in the present invention has an unexpected effect of preventing coloring.

Hereinafter, 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.

[Transparent substrate]
Examples of the transparent substrate used in the present invention include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and 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) A transparent plastic substrate such as can be used.
In the present invention, the transparent plastic substrate is preferably a polyethylene terephthalate film from the viewpoint of transparency, heat resistance, ease of handling, and cost. The thickness of the transparent plastic substrate is preferably 5 to 200 μm because the handleability is poor if it is thin, and the transmittance of visible light decreases if it is thick. More preferably, it is 10-130 micrometers, More preferably, it is 40-80 micrometers.

Since the electromagnetic shielding film for display panels requires transparency, it is desirable that the transparency of the transparent substrate is high. In this case, the total visible light transmittance of the transparent plastic substrate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. Moreover, in this invention, what was colored to such an extent that the objective of this invention is not disturbed as said transparent plastic base material can also be used.
The transparent plastic substrate in the present invention can be used as a single layer, but it can also be used as a multilayer film in which two or more layers are combined.

  In the present invention, a glass plate can also be used as the transparent substrate. Although the kind of glass plate is not specifically limited, When using as a use of the electromagnetic wave shielding film for a display, it is preferable to use the tempered glass which provided the reinforced layer on the surface. There is a high possibility that tempered glass can prevent damage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.

[Silver salt-containing layer]
In the present invention, a layer containing a silver salt (silver salt-containing layer) is provided on the transparent substrate. A silver salt content layer can contain a binder, a solvent, etc. besides silver salt.

<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, but 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 further described.
In the present invention, silver halide is used to function as an optical sensor. Techniques used in silver halide photographic films, photographic papers, printing plate-making films, emulsion masks for photomasks, etc. relating to silver halide can also be used as they are 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 is preferably 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.

  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. Can be.

The silver halide used in the present invention may further contain other elements. For example, in a photographic emulsion, it is also useful to dope metal ions used to obtain a high-contrast emulsion. In particular, transition metal ions such as rhodium ions and iridium ions are preferably used because a difference between an exposed portion and an unexposed portion tends to occur clearly when a metallic silver image is generated. Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such a ligand include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and the like. Specific examples of the compound include K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ .
In the present invention, the content of the rhodium compound and / or iridium compound contained in the silver halide is 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag with respect to the number of moles of silver in the silver halide. Preferably, it is 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 transmissive electromagnetic wave shielding film, and contribute to the reduction of production cost. 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 0.01-0.3 mol / mol Ag.
Examples of the Pd compound to be used include PdCl ₄ and Na ₂ PdCl ₄ .

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 chemical sensitization, for example, noble metal sensitization such as gold sensitization, chalcogen sensitization such as sulfur sensitization, reduction sensitization or the like can be used.
Examples of emulsions that can be used in the present invention include color negatives described in Examples of JP-A-11-305396, JP-A-2000-321698, JP-A-13-281815, and JP-A-2002-72429. A film emulsion, a color reversal film emulsion described in JP-A No. 2002-214731, a color photographic paper emulsion described in JP-A No. 2002-107865, and the like can be suitably used.

<Binder>
In the silver salt-containing layer of the present invention, the binder can be used for the purpose of uniformly dispersing the silver salt particles and assisting the adhesion between the silver salt-containing layer and the transparent substrate. In the present invention, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but a water-soluble polymer is preferably used.
Examples of the binder include gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, polyhyaluron. An acid, carboxycellulose, etc. are mentioned. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.

  Content of the binder contained in the silver salt content layer of this invention is not specifically limited, It can determine suitably in the range which can exhibit a dispersibility and adhesiveness. The content of the binder in the silver salt-containing layer is preferably 1/4 to 100 in terms of Ag / binder volume ratio, more preferably 1/3 to 10, and more preferably 1/2 to 2. More preferably, it is most preferably 1/1 to 2. If the silver salt-containing layer contains a binder in an Ag / binder volume ratio of 1/4 or more, the metal particles can easily come into contact with each other in the physical development and / or plating process, and high conductivity can be obtained. Therefore, it is preferable.

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

[exposure]
In the present invention, the silver salt-containing layer provided on the transparent substrate 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, 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 (oscillation wavelength of about 1060 nm) is used. About 530 nm green laser, wavelength about 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (wavelength converted by LiNbO ₃ SHG crystal with waveguide inversion domain structure) Hitachi type No. HL6501MG) is preferably used.

  The method for exposing the silver salt-containing layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.

[Development processing]
In the present invention, after the silver salt-containing layer is exposed, development processing is further 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 a PQ developer, MQ developer, MAA developer, etc. can also be used. For example, CN-16, CR-56, CP45X, FD-3, Papitol manufactured by Fuji Film Co., Ltd. A developer such as C-41, E-6, RA-4, D-19, D-72 manufactured by KODAK, or a developer included in the kit, or a lith developer such as D-85 is used. be able to.
In the present invention, by performing the above exposure and development treatment, a metallic silver portion, preferably a patterned metallic silver portion is formed, and a light transmissive portion described later is formed.

  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.

  The developer used in the development process can contain an image quality improver for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as benzotriazole. In addition, it is also preferable to use polyethylene glycol, particularly when a lith developer is used.

  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, it is possible to support the conductive metal particles on the metallic part only by physical development or plating treatment, but it is also possible to support the conductive metal particles on the metallic silver part by combining physical development and plating treatment. it can.
“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 treatment 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 and copper chloride, formalin and glyoxylic acid as the reducing agent, EDTA and triethanolamine as the copper ligand, and other bath stabilization and plating film Examples of the additive for improving the smoothness 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, oxidation treatment is preferably performed on the metallic silver portion after the development treatment and the conductive metal portion formed after the physical development and / or plating 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. The oxidation treatment can be performed after exposure and development processing of the silver salt-containing 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 metallic 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.

  The light transmissive part in the present invention is formed together with the metal silver part by exposing and developing the silver salt-containing layer. The light transmissive portion is preferably subjected to an oxidation treatment after the development treatment, and further after the physical treatment or plating treatment, from the viewpoint of improving the transparency.

Next, the organic mercapto compound used in the present invention will be described.
Examples of the organic mercapto compound include alkyl mercapto compounds, aryl mercapto compounds, and heterocyclic mercapto compounds.

The organic mercapto compound is preferably a compound represented by the following general formula (2).
General formula (2)
Z-SM
[In General Formula (2), Z is an alkyl group, an aromatic group, or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² is a hydrogen atom or an alkali metal atom) Or an ammonium group), a group substituted with a substituent having at least one selected from the group consisting of an amino group and an ammonio group, or at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ]

  Moreover, as an organic mercapto compound, the compounds represented by the following general formulas (1) and (3) to (5) are also preferable.

General formula (1)

[In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group,, ^{R 0} represents a substituent. L ¹ , L ² and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring through any of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. However, at least one of L ¹ , L ² , L ³ and R ⁰ represents a —SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group). ]

General formula (3), general formula (4)

[In General Formulas (3) and (4), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group. However, R ₂₁ and R ₂₂ are not simultaneously a hydrogen atom, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group, and R ₂₅ represents a hydroxyl group, an amino group, an alkyl group or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group, an acyl group, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group, an alkali metal atom, an aryl group or an aralkyl group. m represents 0, 1 or 2. n represents 2. ]

General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and Ma are a hydrogen atom, an alkali metal atom or ammonium, respectively. Represents a group. ]

  The compound represented by the general formula (2) will be further described.

  In the general formula (2), the alkyl group represented by Z is preferably one having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms, the above-mentioned You may have a substituent other than a substituent. The aromatic group represented by Z is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms, and may have a substituent in addition to the above-described substituents. The heterocyclic group represented by Z is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and has 1 to 6 heteroatoms independently selected from nitrogen, oxygen and sulfur in one ring. It is a 5- or 6-membered ring and may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. Among the compounds represented by the general formula (2), a compound in which Z is a heterocyclic group having two or more nitrogen atoms is preferable.

  A preferable compound represented by the general formula (2) is represented by the following formula (2-a).

In the general formula, Z is necessary for forming an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (pyrrole ring, imidazole ring, pyrazole ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc.). A compound having at least one —SM group or thione group, and from a hydroxyl group, a —COOM group, a —SO ₃ M group, a substituted or unsubstituted amino group, a substituted or unsubstituted ammonio group Having at least one substituent selected from the group consisting of In the formula, R ¹¹ and R ¹² are each independently a hydrogen atom, —SM group, halogen atom, alkyl group (including those having a substituent), alkoxy group (including those having a substituent), a hydroxyl group, -COOM group, -SO 3 _M group, (including those having a substituent) alkenyl group (including those having a substituent) amino group, (including those having a substituent) carbamoyl group, a phenyl group (substituted Including a group having a group), and R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5-membered ring or a 6-membered ring, preferably a nitrogen-containing heterocycle. M is synonymous with M defined in the general formula (2). Z is preferably a group that forms a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the -SM group or thione group, and the substituent includes a halogen atom, Lower alkyl groups (including those having substituents, preferably those having 5 or less carbon atoms such as methyl and ethyl groups), lower alkoxy groups (including those having substituents; carbons such as methoxy, ethoxy and butoxy) And a lower alkenyl group (including those having a substituent. Preferred are those having 5 or less carbon atoms), a carbamoyl group, a phenyl group, and the like. Furthermore, the compounds represented by the following formulas A to F in the general formula (2-a) are particularly preferable.

In the formula, R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently a hydrogen atom, —SM group, halogen atom, lower alkyl group (including those having a substituent. Carbon number such as methyl group, ethyl group, etc. 5 or less are preferred), a lower alkoxy group (including those having a substituent, preferably those having 5 or less carbon atoms), a hydroxy group, —COOM ² , —SO ₃ M ⁵ group, a lower alkenyl group ( Including those having a substituent, preferably those having 5 or less carbon atoms), an amino group, a carbamoyl group, and a phenyl group, at least one of which is an -SM group. M, M ² and M ⁵ each represent a hydrogen atom, an alkali metal atom or an ammonium group. In particular, hydroxy groups as substituents other than _{^{-SM, -COOM 2, -SO 3 M}} 5 group, it preferably has a water-soluble group such as an amino group.

The amino group represented by R ²¹ , R ²² , R ²³ , R ²⁴ represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

  Although the specific example of a compound represented by General formula (2) below is shown, it is not limited to these.

  The compounds represented by the general formulas (1) and (3) to (5) will be further described.

The compound represented by the general formula (1) will be described in detail. In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group, wherein the ^{R 0} is a substituent. L ^{1, L 2,} L ³ each independently represent a hydrogen atom, he represents a halogen atom or a carbon atom, a nitrogen atom, an oxygen atom, an optional substituent attached to the ring either sulfur or phosphorus atom, L ¹ ~L ³ may be the same or different. However, at least one of L ¹ , L ² , L ³ and R ¹ represents a —SM group (M is an alkali metal atom, a hydrogen atom, or an ammonium group).

Specific examples of the optional substituent represented by L ¹ , L ² , and L ³ and the substituent represented by R ⁰ include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), Alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing quaternized nitrogen atom (for example, pyridinio group), acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, Hydroxy group, alkoxy group (ethyleneoxy group or propyleneoxy group unit Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group , Hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino Group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, ( (Alkyl, aryl or heterocyclic) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, And a group containing a phosphoric acid amide or phosphoric acid ester structure. These substituents may be further substituted with these substituents.

More preferably, the arbitrary substituents represented by L ¹ , L ² and L ³ and the substituent represented by R ⁰ are a substituent having ⁰ to 15 carbon atoms, such as a chlorine atom, an alkyl group, an aryl group, a complex A cyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, a cyano group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group, an (alkyl, aryl or heterocyclic ring) amino group, a hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio Group, a sulfo group or a salt thereof, and a sulfamoyl group, and more preferably an alkyl group, an aryl group, a complex Group, alkoxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, alkoxy group, aryloxy group, acyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, hydroxyamino group, N-substituted saturated or unsaturated A saturated nitrogen-containing heterocyclic group, acylamino group, sulfonamido group, ureido group, thioureido group, sulfamoylamino group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, sulfo group or a salt thereof; Most preferred are amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylthio group, arylthio group, mercapto group, carboxy group or salt thereof, sulfo group or salt thereof. In the general formula (1), L ¹ , L ² , L ³ and R ⁰ may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In the general formula (1), at least one of L ¹ , L ² , L ³ and R ⁰ represents an —SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group). Here specifically the alkali metal atom is Na, K, Li, Mg, Ca, etc., it -S ^- present as a counter cation. M is preferably a hydrogen atom, an ammonium group, Na ⁺ , or K ⁺ , and particularly preferably a hydrogen atom. Of the compounds represented by the general formula (1), compounds represented by the following general formula (1-A) and general formula (1-B) are preferable.

Next, the general formula (1-A) will be described in detail. R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, which is represented by the general formula (1) And L ¹ , L ² , and L ³ have the same meanings, and preferred ranges thereof are also the same. However, R ¹ and R ³ do not represent a hydroxy group. R ^{1 to} R ⁴ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group. R ¹ and R ² may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In general formula (1-A), at least one of R ^{1 to} R ⁴ is an —SM group, and more preferably at least two of R ^{1 to} R ⁴ are —SM groups. When at least two of R ^{1 to} R ⁴ are —SM groups, preferably R ⁴ and R ¹ , or R ⁴ and R ³ are —SM groups.

  In the present invention, among the compounds represented by the general formula (1-A), compounds represented by the following general formulas (1-A-1) to (1-A-3) are particularly preferable.

In the general formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent, and X represents a water-soluble group or a substituent substituted with a water-soluble group. In the general formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ²⁰ represents a hydrogen atom or an arbitrary substituent. In General Formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. However, R ¹⁰ and Y ¹ do not represent a hydroxy group.

Next, the compounds represented by the general formulas (1-A-1) to (1-A-3) will be described in detail.
In General Formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent. Here, the arbitrary substituents are the same as those described for R ^{1 to} R ^{4 in} the general formula (1-A). R ¹⁰ is preferably a mercapto group, a hydrogen atom, or a group selected from the following substituents having 0 to 15 carbon atoms. That is, amino group, alkyl group, aryl group, alkoxy group, aryloxy group, acylamino group, sulfonamido group, alkylthio group, arylthio group, alkylamino group, arylamino group and the like can be mentioned. In general formula (1-A-1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group means a group containing a dissociable group that can be partially or completely dissociated by an alkaline developer, or a salt such as a sulfonic acid or carboxylic acid and a salt thereof, an ammonio group, or the like. Includes a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonio group, a sulfonamido group, an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, Or the substituent containing these groups is represented. In the present invention, the active methine group means a methyl group substituted with two electron-withdrawing groups, specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy. Examples include groups such as carbonylmethyl. The substituent represented by X in the general formula (1-A-1) is the above-described water-soluble group or a substituent substituted with the above-mentioned water-soluble group, and the substituent has 0 carbon atoms. ˜15 substituents, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkyl, aryl or heterocyclic) amino group, an acylamino group, a sulfonamide group, Examples include ureido group, thioureido group, imide group, sulfamoylamino group, (alkyl, aryl or heterocyclic) thio group, (alkyl, aryl) sulfonyl group, sulfamoyl group, amino group and the like. 10 alkyl groups (especially methyl groups substituted with amino groups), aryl groups, aryloxy groups, amino groups, (alkyl, aryl, or Ring) amino group, an (alkyl, aryl or heterocyclic) group such as thio group.

Among the compounds represented by the general formula (1-A-1), a compound represented by the following general formula (1-A-1-a) is more preferable.
General formula (1-A-1-a)

Wherein ^{R 11} has the same meaning as ^{R 10} in formula (1-A-1), and the preferred range is also the same. R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. However, at least one of R ¹² and R ¹³ has at least one water-soluble group. Here, the water-soluble group is a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonio group, a sulfonamide group, an acylsulfamoyl group, or a sulfonylsulfamoyl group. Represents a group, an active methine group, or a substituent containing these groups, and preferred examples include a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, an amino group, and the like. R ¹² and R ¹³ are preferably an alkyl group or an aryl group, and when R ¹² and R ¹³ are an alkyl group, the alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, As the substituent, a water-soluble group, particularly a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ¹² and R ¹³ are an aryl group, the aryl group is preferably a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and the substituent is a water-soluble group, particularly a sulfo group (or a salt thereof). , A carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ¹² and R ¹³ represent an alkyl group or an aryl group, they may be bonded to each other to form a cyclic structure. A saturated heterocyclic ring may be formed by a cyclic structure.

In General Formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and has the same meaning as X in General Formula (1-A-1). In the general formula (1-A-2), the water-soluble group represented by Y ¹ or the substituent substituted with the water-soluble group is more preferably an active methine group or the following group substituted with a water-soluble group, That is, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group, and an aryl group. Y ¹ is more preferably an active methine group or an amino group (alkyl, aryl, or heterocyclic) substituted with a water-soluble group, wherein the water-soluble group includes a hydroxy group, a carboxy group or a salt thereof, sulfo A group or a salt thereof is particularly preferred. Y ¹ is particularly preferably an (alkyl, aryl, or heterocyclic) amino group substituted with a hydroxy group, a carboxy group (or a salt thereof), or a sulfo group (or a salt thereof), and —N (R ⁰¹ ) It is represented by (R ⁰² ) group. R ⁰¹ and R ⁰² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A), respectively, and preferred ranges thereof are also the same.

In the general formula (1-A-2), R ²⁰ represents a hydrogen atom or an arbitrary substituent, and here, the arbitrary substituent is the one described for R ^{1 to} R ^{4 in} the general formula (1-A). The same thing is mentioned. R ²⁰ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms. That is, a hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a hydroxylamino group and the like can be mentioned. R ²⁰ is most preferably a hydrogen atom.

In General Formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. Y ² and R ³⁰ in formula (1-A-3) are the same groups as Y ¹ in formula (1-A-2) and R ^{20 in} formula (1-A-2), respectively. The range is also the same.

Next, the general formula (1-B) will be described in detail. ^R 5 to R ⁷ in the formula (1-B) has the same meaning as ^R 1 to R ⁴ of formula (1-A) independently, the preferred range thereof is also the same. Of the compounds represented by the general formula (1-B), the compound represented by the general formula (1-B-1) is particularly preferable.
Formula (1-B-1)

In the general formula (1-B-1), R ⁵⁰ has the same meaning as R ^{5 to} R ^{7 in the} general formula (1-B), and more preferably the general formulas (1-A-1) to (1-A- 3) a water-soluble group having the same meaning as X, Y ¹ , and Y ² or a group substituted with a water-soluble group. Furthermore, among the compounds of general formula (1-B-1), the compound represented by general formula (1-B-1-a) is most preferable.
General formula (1-B-1-a)

In the general formula (1-B-1-a), R ⁵¹ and R ⁵² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A-1-a), and preferred ranges thereof are also the same. .

  Specific examples of the compound represented by the general formula (1) are shown below, but the compound represented by the general formula (1) that can be used in the present invention is not limited to these.

In the general formula (3) and _(4), the alkyl group represented by _{R 21, R 22, R 23} , R 24 and _{R 25,} preferably 1 to 3 carbon atoms, such as methyl group, ethyl group And an alkyl group represented by R ₂₆ and R ₂₇ preferably has 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. The acyl group preferably has 1 to 18 carbon atoms, and examples thereof include an acetyl group and a benzoyl group. The alkyl group represented by M ₂₂ preferably has 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, and the aryl group preferably includes a phenyl group or a naphthyl group. The aralkyl group preferably has 15 or less carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

  Various synthetic methods are known for the compound represented by the general formula (3) or (4). For example, a Strecker amino acid synthesis method known as an amino acid synthesis method may be used. Is performed by alternately adding alkali and acetic anhydride in an aqueous solution.

  Next, although the specific example of a compound represented by General formula (3) or (4) is shown, this invention is not limited only to these.

The lower alkyl group represented by X _{40 in} the general formula (5) is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an isopropyl group. Next, although the example of a specific compound represented by General formula (5) is shown, it is not limited to these.

The organic mercapto compound used in the present invention is applied to the conductive metal part by, for example, immersing a transparent base material in which the conductive metal part is formed in the aqueous solution after making the aqueous solution. The organic mercapto compound aqueous solution used at this time is, for example, a compound represented by the above general formulas (1) to (5) at a concentration of 10 ⁻⁶ to 10 ⁻¹ mol in 1 liter, preferably 10 ^{−. It} is preferable to contain as a concentration of ⁵ to 10 ⁻² mol. The immersion time is 2 seconds to 30 minutes, preferably 5 seconds to 10 minutes.
The pH of the aqueous solution is preferably adjusted to 2 to 12 from the viewpoint of dissolving the organic mercapto compound, and the pH adjustment is not limited to ordinary alkalis and acids such as sodium hydroxide and sulfuric acid, but also as phosphoric acid and its buffer. A salt, carbonate, acetic acid or a salt thereof, boric acid or a salt thereof can be used.

[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 supporting the conductive metal particles on the metal silver portion by subjecting the metal silver portion formed by the above-described exposure and development processing to physical development or plating treatment.
Metal silver may be formed in an exposed part or in an unexposed part. The silver salt diffusion transfer method (DTR method) using physical development nuclei is to form metallic silver in unexposed areas. In the present invention, it is preferable to form metallic silver in the exposed portion in order to increase transparency.
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.

  In the conductive metal part, the conductive metal particles contained in the conductive metal part are copper particles from the viewpoint of increasing the contrast and preventing the conductive metal part from being oxidized and discolored over time. It is more preferable that at least the surface thereof is blackened. The blackening treatment can be performed using a method performed in the printed wiring board field. For example, blackening treatment is performed by treating at 95 ° C. for 2 minutes in an aqueous solution of sodium chlorite (31 g / l), sodium hydroxide (15 g / l), and trisodium phosphate (12 g / l). Can do.

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.

  Since the conductive metal portion in the present invention carries conductive metal particles, good conductivity can be obtained. For this reason, the surface resistance value of the translucent electromagnetic wave shielding film (conductive metal part) of the present invention is preferably 10Ω / sq or less, more preferably 2.5Ω / sq or less, and 1.5Ω. / Sq or less is more preferable, and 0.1 Ω / sq or less is most preferable.

When the conductive metal part in the present invention is used as a light-transmitting electromagnetic wave shielding film, a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a quadrangle such as a trapezoid, It is preferably a geometric figure combining (positive) hexagons, (positive) octagons, etc., and more preferably a mesh shape composed of these geometric figures.
In the present invention, it is most preferable to have a grid-like mesh form composed of squares.

  In the use of the translucent electromagnetic wave shielding film, the line width of the conductive metal part is preferably 20 μm or less, and the line interval is preferably 100 μm or more. The conductive metal portion may have a portion whose line width is wider than 20 μm for the purpose of ground connection or the like. Further, from the viewpoint of making the image inconspicuous, the line width of the conductive metal portion is more preferably less than 15 μm.

  The thickness of the conductive metal part is preferable as the use of the electromagnetic shielding material for the display because the viewing angle of the display increases as the thickness decreases. It is preferably 1 μm or more and 20 μm or less, more preferably 1 μm or more and 13 μm or less, further preferably 2 to 10 μm, and most preferably 3 to 7 μm. Moreover, it is preferable that a metal silver part is pattern shape. The metal part may be a single layer or a multilayer structure of two or more layers.

  The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. Further, the “aperture ratio” is a ratio of a portion having no fine line forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 10 μm and a pitch of 200 μm is 90%. In addition, although there is no restriction | limiting of an upper limit in particular regarding the aperture ratio of the metal silver part in this invention, As said aperture ratio, it is preferable that it is 98% or less from the relationship between a surface resistance value and a line | wire width value.

[Light transmissive part]
The “light transmitting part” in the present invention means a part having transparency other than the conductive metal part in the light transmitting electromagnetic wave shielding film. As described above, the transmittance in the light transmissive part is 90% or more, preferably the transmittance indicated by the minimum value of the transmittance in the wavelength region of 380 to 780 nm excluding the contribution of light absorption and reflection of the transparent substrate. 95% or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.

The light transmissive part of 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 is preferable that 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%.

[Functional membrane]
The translucent electromagnetic wave shielding film obtained by the production method of the present invention as described above may be provided with a functional transparent layer having a desired function, if necessary. For example, display panel applications include infrared-shielding layers composed of infrared-absorbing compounds and metals; hard-coating layers that are not easily scratched; antireflection with antireflection properties adjusted for refractive index and film thickness Non-glare layer or anti-glare layer with antiglare properties such as glare prevention function; Antistatic layer; Antifouling layer with function of easily removing dirt such as fingerprints; Layer that cuts UV rays; Gas barrier A layer having a property; for example, a display panel breakage preventing layer having a function of preventing glass scattering when the glass is broken can be provided. These functional layers may be provided on the conductive metal part, or may be provided on the opposite side of the conductive metal part via a transparent substrate.

  Some of the functional transparent layers will be further described.

The layer having infrared shielding properties, for example, the near infrared absorbing layer is a layer containing a near infrared absorbing dye such as a metal complex compound, or a silver sputtered layer. Here, the silver sputter layer can cut light of 1000 nm or more from near infrared rays, far infrared rays to electromagnetic waves by alternately laminating dielectric layers and metal layers on the substrate by sputtering or the like. The dielectric layer includes a transparent metal oxide such as indium oxide or zinc oxide as a dielectric. The metal contained in the metal layer is generally silver or a silver-palladium alloy. The sputtered silver layer generally has a structure in which about 3, 5, 7 or 11 layers are laminated, starting from the dielectric layer.
In the PDP, the phosphor that emits blue light has a characteristic of emitting red light in addition to blue, but has a problem that a portion to be displayed in blue is displayed in a purplish color. . The layer having a color tone adjusting function that absorbs visible light in the specific wavelength range is a layer that corrects the colored light as a countermeasure, and contains a dye that absorbs light in the vicinity of 595 nm.

  As a method of forming an antireflection layer imparted with antireflection properties, metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides are used in order to suppress reflection of external light and suppress a decrease in contrast. A method of laminating an inorganic substance such as a single layer or multiple layers by a vacuum deposition method, a sputtering method, an ion plating method, or an ion beam assist method, or a single layer or a resin having a different refractive index such as an acrylic resin or a fluororesin There is a method of laminating on a functional layer in multiple layers. Moreover, the film which gave the antireflection process can also be affixed on a film | membrane.

  As a method for forming the non-glare layer or the anti-glare layer, a method of forming a fine powder such as silica, melamine, or acrylic into an ink and coating the surface can be used. At this time, the ink can be cured by thermal curing or photocuring. In addition, a film that has been subjected to non-glare treatment or anti-glare treatment can be attached to the film.

The translucent electromagnetic wave shielding film of the present invention is particularly useful as a display panel film because it has good electromagnetic wave shielding properties and translucency. The film for a display panel comprising the translucent electromagnetic wave shielding film of the present invention can be used as an optical filter for a plasma display panel, for example, by providing the functional transparent layer. These members can be applied to the front surface of displays such as CRT, PDP, liquid crystal, and EL, microwave ovens, electronic devices, printed wiring boards, and the like, and are particularly useful for PDP.
The PDP of the present invention has high electromagnetic shielding ability, high contrast and high brightness, and can be produced at low cost.

  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
An emulsion containing silver iodobromide grains (I = 2 mol%) having an average equivalent sphere diameter of 0.05 μm and containing 7.5 g of gelatin per 60 g of Ag in an aqueous medium was prepared. At this time, the Ag / gelatin volume ratio was 1/1, and a low molecular weight gelatin having an average molecular weight of 20,000 was used as the gelatin species.
In this emulsion, K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ were added so as to have a concentration of 10 ⁻⁷ (mol / mol silver), and silver bromide grains were doped with Rh ions and Ir ions. . After adding Na ₂ PdCl ₄ to this emulsion and further performing gold-sulfur sensitization using chloroauric acid and sodium thiosulfate, together with the gelatin hardener, the coating amount of silver was 1 g / m ^2. It was coated on polyethylene terephthalate (PET). The PET used was hydrophilized before application. Via a lattice-shaped photomask (line / space = 195 μm / 5 μm (pitch 200 μm), space is a lattice-shaped photomask) capable of giving a developed silver image of line / space = 5 μm / 195 μm to the dried coating film After exposure using an ultraviolet lamp, development was performed at 25 ° C. for 45 seconds using the following developer, and further a fixing treatment (super Fujifix: manufactured by Fuji Photo Film Co., Ltd.) was performed for 3 minutes. Rinse with pure water.

[Developer composition]
The following compounds are contained in 1 liter of developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

Further, plating solution (copper sulfate 0.06 mol / L, formalin 0.22 mol / L, triethanolamine 0.12 mol / L, polyethylene glycol 100 ppm, yellow blood salt 50 ppm, α, α′-bipyridine 20 ppm is contained. The electroless copper plating process was performed at 45 ° C. using an electroless Cu plating solution having a pH of 12.5. However, ppm is synonymous with mg / L. Furthermore, the anti-discoloration treatment was carried out with an aqueous solution containing 0.1 mol / L of the compound of the present invention described in Table 1. In addition, this process was performed by immersing in said aqueous solution for 3 minutes.
After the discoloration preventing treatment, the sample of the present invention was obtained by washing with water and drying.

(Comparative Example 1)
A sample was prepared in the same manner as in Example 1 except that no discoloration prevention treatment was performed.

<Evaluation method>
(Surface resistance)
The surface resistivity was measured with a Mitsubishi Chemical resistivity meter Loresta.
The sample described in Table 1 below was 0.3Ω / □.
(Moisture and heat resistance / discoloration of conductive metal parts)
A two-day wet heat resistance test was performed under the conditions of 80 ° C. and 90% RH, and the discoloration of the conductive metal part after the test was visually evaluated. The discoloration was determined by observing the phenomenon that the color of metallic copper changes from green to brown, thereby determining the resistance to moist heat.
Those in which discoloration was observed were rated as x, and those in which discoloration was not recognized were marked as ◯.
(Coloring of heat-resistant / light-transmitting parts)
A heat resistance test was conducted at 100 ° C. for one week, and a test piece with a decrease in transmittance of 410 nm after the test of 3% or more was evaluated as x.

  As can be seen from Table 1, it was found that the sample of the present invention shown in Example 1 hardly causes discoloration of the metal wire portion. Furthermore, surprisingly, it has been found that the treatment in the present invention has an unexpected effect of preventing coloration on a light-transmitting part that is not considered to rust because it does not form a conductive metal part. did.

Claims (8)

  By exposing and developing the silver salt-containing layer provided on the transparent substrate to form a metallic silver part and a light transmitting part, and further subjecting the metallic silver part to physical development and / or plating treatment A translucent electromagnetic wave shielding film characterized in that a conductive metal part in which a conductive metal is supported on the metal silver part is formed, and the conductive metal part is subjected to a discoloration prevention treatment with an organic mercapto compound. Production method. The said organic mercapto compound is represented by following General formula (2), The manufacturing method of the translucent electromagnetic wave shielding film of Claim 1 characterized by the above-mentioned.
General formula (2)
Z-SM
[In General Formula (2), Z is an alkyl group, an aromatic group, or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² is a hydrogen atom or an alkali metal atom) Or an ammonium group), a group substituted with a substituent having at least one selected from the group consisting of an amino group and an ammonio group, or at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ] The translucent electromagnetic wave shield according to claim 1 or 2, wherein the organic mercapto compound is one or more organic mercapto compounds selected from the following general formulas (1) and (3) to (5). A method for producing a membrane.
General formula (1)

[In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group,, ^{R 0} represents a substituent. L ¹ , L ² and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring through any of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. However, at least one of L ¹ , L ² , L ³ and R ⁰ represents a —SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group). ]
General formula (3), general formula (4)

[In General Formulas (3) and (4), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group. However, R ₂₁ and R ₂₂ are not simultaneously a hydrogen atom, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group, and R ₂₅ represents a hydroxyl group (or a salt thereof), an amino group, an alkyl group, or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group, an acyl group, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group, an alkali metal atom, an aryl group or an aralkyl group. m represents 0, 1 or 2. n represents 2. ]
General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and Ma are a hydrogen atom, an alkali metal atom or ammonium, respectively. Represents a group. ]   The translucent electromagnetic wave shielding film manufactured by the manufacturing method in any one of Claims 1-3.   Functional transparency with one or more functions selected from infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, UV protection properties, gas barrier properties, and display panel damage prevention properties The translucent electromagnetic wave shielding film according to claim 4, comprising a layer.   A film for a display panel, wherein the translucent electromagnetic wave shielding film according to claim 4 or 5 is used.   An optical filter for a plasma display panel, wherein the display panel film according to claim 6 is used.   A plasma display panel comprising the film for display panel according to claim 6 or the optical filter for plasma display panel according to claim 7.