JP2008071862A - Silver halide photosensitive material for forming electromagnetic wave shielding film, electromagnetic wave shielding film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent electromagnetic wave shielding film, excellent in electromagnetic wave shielding performance and having high light transmittance as well as low surface resistivity while being prominent further in color reproducibility, through a manufacturing method employing silver halide photosensitive material for forming the electromagnetic wave shielding film. <P>SOLUTION: The silver halide photosensitive material for forming the electromagnetic wave shielding film is provided on the transparent substrate with a silver halide photosensitive layer, comprising silver halide grain having average grain size of ≥0.01 μm and ≤0.10 μm while whose silver/binder mass ratio is ≥2.0 and ≤20, and wave length which shows the maximum absorption concentration in a spectral absorption concentration in visible light exists in 400-450 nm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a silver halide photosensitive material for forming an electromagnetic wave shielding film that shields electromagnetic waves generated from electronic devices such as mobile phones, microwave ovens, CRTs, and flat panel displays, an electromagnetic wave shielding film, and a method for producing the same.

  In recent years, there has been an increasing use of electronic devices such as display devices used in mobile phones, personal computers, TVs, etc., but electromagnetic waves are generally emitted from these electronic devices, which It is known that so-called electromagnetic interference (EMI) occurs, such as malfunction of electrical equipment, failure, or the possibility of harming the human body.

  Along with this, there is an increasing need to reduce such EMI, and standards or regulations regarding the intensity of electromagnetic wave emission are established mainly in Europe and the United States, and recent electronic devices are required to meet these standards. Yes. In particular, equipment that requires visibility such as a CRT, a flat panel display, or a window glass needs to satisfy both electromagnetic wave shielding performance and transparency.

On the other hand, a method for producing a conductive mesh by utilizing exposure to photosensitive silver halide and a development process is known. In this method, a silver halide emulsion layer is exposed to light and developed to form a developed silver directly, which is then used as a catalyst to produce a conductive mesh, making it easy to form a mesh pattern. In addition, it is disclosed as a useful method capable of producing an electromagnetic shielding material in large quantities at a low cost (see, for example, Patent Documents 1 to 5). In these materials, it is preferable to use fine grains as the photosensitive silver halide and to increase the ratio of the silver halide to the photosensitive silver halide and the binder and the Ag / binder ratio as much as possible. .
WO 01/51276 pamphlet JP 2004-221564 A JP 2004-221565 A JP 2006-10895 A JP 2006-12935 A

  However, a silver halide photosensitive material having a high Ag / binder ratio using fine-grain photosensitive silver halide has a problem that unnecessary optical scattering such as irradiation and halation is likely to occur during exposure of the mesh pattern. In addition, it was found that the generation of static electricity was significant in the photosensitive material manufacturing process. The former is particularly remarkable in the case of high-energy short-time exposure such as laser light exposure. This is because the photosensitive silver halide is a fine particle of 0.10 μm or less, the Ag / binder ratio is high, the distance between the silver halides is small, and what is required as a support for an electromagnetic wave shielding material is high. It is presumed to be due to a synergistic effect of having a refractive index. The latter is presumed to be due to a decrease in the water content of the photosensitive material due to the small amount of binder.

  The present invention has been made in view of the above problems, and its purpose is excellent in electromagnetic wave shielding performance, that is, low surface specific resistance, high transparency (light transmission), and further sharpness of the mesh pattern. An object of the present invention is to provide an excellent transparent electromagnetic wave shielding film by a production method using a silver halide photosensitive material for forming an electromagnetic wave shielding film. Furthermore, it is to prevent the influence of static electricity generated during the production of the electromagnetic wave shielding film, and to improve the color reproducibility when the electromagnetic wave shielding film is mounted on the plasma display panel and operated.

  As a result of examining the optical behavior at the time of exposure in each layer in the silver halide light-sensitive material, the present inventors have used a specific dye and designed it so that its spectral absorption characteristics are within a certain range. It was found that a transparent electromagnetic wave shielding film having high transparency while maintaining electrical conductivity, excellent in the sharpness of the mesh pattern, hardly affected by static electricity, and excellent in color reproducibility can be obtained.

  That is, the object of the present invention is achieved by the following.

  1. A silver halide photosensitive layer containing silver halide grains having an average grain size of 0.01 μm or more and 0.10 μm or less on a transparent support, and having a silver / binder mass ratio of 2.0 or more and 20 or less, A silver halide photosensitive material for forming an electromagnetic wave shielding film, wherein a wavelength exhibiting a maximum absorption concentration in a spectral absorption concentration in visible light is 400 to 450 nm.

  2. 2. The silver halide photosensitive material for forming an electromagnetic wave shielding film as described in 1 above, wherein the silver halide photosensitive layer contains a dye having a spectral absorption maximum of 410 to 450 nm.

  3. 3. The silver halide photosensitive material for forming an electromagnetic wave shielding film as described in 1 or 2 above, wherein at least one non-photosensitive intermediate layer is provided between the transparent support and the silver halide photosensitive layer.

  4). 4. The silver halide photosensitive material for forming an electromagnetic wave shielding film as described in 3 above, wherein a dye having a spectral absorption maximum of 350 to 410 nm is contained in at least one of the transparent support and the non-photosensitive intermediate layer.

  5. 5. The silver halide photosensitive material for forming an electromagnetic wave shielding film as described in any one of 1 to 4 above, wherein a backing layer is provided on the opposite side of the transparent support from the silver halide photosensitive layer.

  6). 6. The silver halide photosensitive material for forming an electromagnetic wave shielding film as described in 5 above, further comprising a dye having a spectral absorption maximum of 410 to 450 nm in at least one of the transparent support, the non-photosensitive intermediate layer and the backing layer. A silver halide photosensitive material for forming an electromagnetic shielding film.

  7. 7. The halogen for forming an electromagnetic wave shielding film according to any one of 1 to 6 above, wherein a spectral absorption concentration at a wavelength indicating the maximum absorption concentration existing in 400 to 450 nm is 0.50 to 3.0. Silver halide photosensitive material.

  8). 8. The halogen for forming an electromagnetic wave shielding film according to any one of 4 to 7, wherein the dye having a spectral absorption maximum of 350 to 410 nm is any one of the following general formulas (I) to (III): Silver halide photosensitive material.

(In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, or an aryl group. R ₃ represents an alkyl group or an allyl group, and A and B represent —CN, —SO ₂ R ₁₁ , and —COOR ₁₂ , respectively. Or -CONR ₁₃ R ₁₄ , R ₁₁ and R ₁₂ each represent an alkyl group or an aryl group, and R ₁₃ and R ₁₄ each represent a hydrogen atom, an alkyl group or an aryl group.)

(Wherein R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom or an alkyl group, R ₈ represents an alkyl group or an allyl group, and R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group or aryl, respectively. And G represents an electron withdrawing group.)

(In the formula, R ₁₁ and R ₁₂ each represent an alkyl group or an acyl group, and A 1 and B 1 are each represented by —CN, —SO ₂ R ₁₃ , —COOR _14, or —CONR ₁₅ R ₁₆ , R ₁₃ , R ₁₄ Each represents an alkyl group or an aryl group, and R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group or an aryl group.)
9. 9. A step of exposing the silver halide photosensitive material for forming an electromagnetic wave shielding film according to any one of 1 to 8 above with a laser beam having an emission wavelength of less than 450 nm, and developing the exposed silver halide photosensitive material to form metallic silver An electromagnetic shielding film comprising: a step of forming a transparent portion and a light transmitting portion; and a step of forming a conductive metal portion by subjecting the metallic silver portion to at least one selected from physical development and plating. Production method.

  10. 10. An electromagnetic wave shielding film produced by the method for producing an electromagnetic wave shielding film as described in 9 above.

  According to the present invention, there are provided a silver halide photosensitive material for forming an electromagnetic wave shielding film having excellent electromagnetic wave shielding performance, high transparency, and further excellent mesh pattern sharpness, an electromagnetic wave shielding film, and a method for producing the same. be able to.

  Silver halide photosensitive material for forming an electromagnetic wave shielding film of the present invention (hereinafter, also simply referred to as a silver halide photosensitive material or a photosensitive material), a silver halide having an average grain size of 0.01 μm or more and 0.10 μm or less on a transparent support It has a silver halide photosensitive layer containing grains and a silver / binder mass ratio of 2.0 or more and 20 or less, and has a wavelength of 400 to 450 nm showing a maximum absorption concentration among spectral absorption concentrations in visible light. It exists in In the present invention, visible light refers to an electromagnetic wave region having a wavelength of 400 to 700 nm.

  Further, as a method for producing an electromagnetic wave shielding film, a step of exposing the silver halide photosensitive material for forming an electromagnetic wave shielding film with a laser beam having an emission wavelength of less than 450 nm, and developing the exposed silver halide photosensitive material to form a metallic silver portion And a light transmissive portion, and a step of forming the conductive silver portion by applying at least one selected from physical development and plating treatment to the metallic silver portion.

  Further, the electromagnetic wave shielding film is manufactured by the above manufacturing method.

  Hereinafter, the present invention will be described in detail.

[Silver halide photosensitive layer]
After the silver halide grains are developed into metal silver grains, the contact between the developed silver grains needs to be as large as possible in order to reduce the surface specific resistance and effectively block electromagnetic waves. For this purpose, it is preferable to increase the surface area ratio, and the smaller the silver halide grain size, the better. Accordingly, in the present invention, the average grain size of the silver halide grains is 0.01 μm or more and 0.10 μm or less in terms of equivalent sphere diameter. However, too small particles tend to aggregate and become agglomerated, and the contact probability is conversely reduced. Therefore, 0.02 to 0.10 μm is preferable, and 0.03 to 0.10 μm is more preferable. The equivalent spherical diameter of silver halide grains represents the diameter of grains having the same volume and having a spherical shape.

  The average grain size of silver halide grains is the temperature at the time of silver halide grain preparation, pAg, pH, addition rate of silver ion solution and halide ion solution, grain size control agent (for example, 1-phenyl-5-mercapto (Tetrazole, 2-mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.) can be appropriately combined and controlled.

In the present invention, an embodiment in which the value obtained by dividing the coating silver amount (g / m ² ) by the particle size (μm) is 6 or more and 25 or less is preferable. When a large amount of photosensitive silver halide having a relatively small particle size is used, this value tends to be larger than 25. In this case, the silver halide grains are likely to slip off from the coating at the edge portion when the film is cut. There is a tendency. Further, when a small amount of photosensitive silver halide having a relatively large particle diameter is used, this value tends to be smaller than 6, and in this case, the number of photosensitive silver halide grains in a unit area is reduced, so that It is because it is easy to fall.

  In the present invention, the shape of the silver halide grains is not particularly limited, and for example, spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, tetragonal flat plate, etc.), octahedron, tetrahedron It can be in various shapes such as shapes. In order to increase the sensitivity, tabular grains having an aspect ratio of 2 or more, 4 or more, and further 8 to 16 can be preferably used. The particle size distribution is not particularly limited, but a narrow distribution is preferable from the viewpoint of sharply reproducing the outline of the pattern during pattern formation by exposure and enhancing transparency while maintaining high conductivity. The particle size distribution of the silver halide grains used in the silver halide photosensitive material for forming an electromagnetic wave shielding film of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. It is. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (wherein S represents the standard deviation of the particle size distribution and R represents the average particle size)
The silver halide grains 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, Group 8-10 metal ions such as iron ion, rhodium ion, ruthenium ion and iridium ion are preferably used because the difference between the exposed portion and the unexposed portion tends to be clearly generated when the metal silver image is generated.

  These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. 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 potassium bromide rhodate and potassium iridate.

In the present invention, the content of the metal ion compound contained in the silver halide is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, and is preferably 10 ⁻⁹ to 10 ^−3. More preferably, it is mol / mol Ag.

  In order for silver halide grains to contain the above-described metal ions, each step during physical ripening of the metal compound before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains, etc. What is necessary is just to add in arbitrary places in. Moreover, in addition, the solution of a heavy metal compound can be continuously performed over the whole or a part of particle formation process.

  In the present invention, chemical sensitization performed on a photographic emulsion can be performed to further improve sensitivity. As chemical sensitization, for example, noble metal sensitization such as gold, palladium and platinum sensitization, chalcogen sensitization such as sulfur sensitization with inorganic sulfur or organic sulfur compounds, reduction sensitization such as tin chloride and hydrazine, etc. are used. be able to.

  The silver halide grains may be subjected to spectral sensitization. Preferable spectral sensitizing dyes include cyanine, carbocyanine, dicarbocyanine, complex cyanine, hemicyanine, styryl dye, merocyanine, complex merocyanine, holopolar dye, and the like. Can be used alone or in combination.

(binder)
In the silver halide photosensitive layer according to the present invention, the silver halide grains are uniformly dispersed, and the silver halide grains are supported on a support, and the silver halide photosensitive layer and other layers, or the support, A binder is used for the purpose of ensuring the adhesion of the resin. The binder that can be used in the present invention is not particularly limited, and both a water-insoluble polymer and a water-soluble polymer can be used, but a water-soluble polymer is preferably used from the viewpoint of improving developability.

  In the silver halide photosensitive material for forming an electromagnetic wave shielding film of the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  In the present invention, the silver / binder mass ratio of the silver halide photosensitive layer is 2.0 or more and 20 or less. This is to increase the contact area between the developed silver particles described above, and is preferably 2.5 or more and 15 or less, more preferably 3.0 or more and 10 or less.

(Spectral absorption characteristics)
The light transmittance and absorption density used in the description of the present invention will be described.

The light transmittance is a percentage (%) of the value of the intensity I of the light that has passed through the sample with respect to the measured light intensity I ₀ . The absorption concentration A is represented by the following formula.

A = −log (I / I ₀ )
In the present invention, the wavelength indicating the maximum absorption concentration in the visible light spectral absorption concentration of the silver halide photosensitive material for forming an electromagnetic wave shielding film is 400 to 450 nm. Moreover, it is preferable that the spectral absorption density | concentration is 0.50-3.0.

  That is, when the photosensitive material before exposure is measured with a spectral densitometer, in the visible light region (400 to 700 nm), the wavelength indicating the maximum absorption density is in the range of 400 to 450 nm, and the spectral absorption density is 0.00. It is preferable that it is 50-3.0. When the value is less than 0.50, the effect of the present invention is insufficient. The range of the spectral absorption concentration of 0.50 to 3.0 is a region where the effect can be sufficiently exerted, but 0.6 to 2.5 is particularly preferable.

  The silver halide photosensitive material has a non-photosensitive intermediate layer between a transparent support and a silver halide photosensitive layer, and at least the silver halide photosensitive layer contains a dye having a spectral absorption maximum of 410 to 450 nm. It is preferable that at least one of the transparent support and the non-photosensitive intermediate layer contains a dye having a spectral absorption maximum of 350 to 410 nm.

  Further, the silver halide photosensitive material has a backing layer on the opposite side of the silver halide photosensitive layer with respect to the transparent support, and at least the silver halide photosensitive layer has a spectral absorption maximum of 410 to 450 nm. A certain dye is contained, and the backing layer preferably contains a dye having a spectral absorption maximum of 350 to 410 nm.

  Furthermore, it is particularly preferable that at least one of the transparent support, the non-photosensitive intermediate layer and the backing layer further contains a dye having a spectral absorption maximum of 410 to 450 nm.

  The dye having a spectral absorption maximum of 410 to 450 nm and the dye having a spectral absorption maximum of 350 to 410 nm can be used without limitation as long as they have the spectral transmission characteristics. it can.

  In the present invention, the dye having a spectral absorption maximum of 350 to 410 nm is preferably represented by any one of the general formulas (I) to (III).

In the general formula (I), R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an aryl group. R ₃ represents an alkyl group or an allyl group, A and B are each represented by —CN, —SO ₂ R ₁₁ , —COOR ₁₂ or —CONR ₁₃ R ₁₄ , and R ₁₁ and R ₁₂ are each an alkyl group or an aryl group. R ₁₃ and R ₁₄ each represents a hydrogen atom, an alkyl group or an aryl group.

Alkyl groups include unsubstituted and substituted alkyl groups. Since there is a difference in the effect of the compound represented by the general formula depending on the number of carbon atoms of the above-described alkyl group (in the case of a substituted alkyl group, an alkylene group constituting the alkyl group), R ₁ and R ₂ have a number of 1 to 4, R ₃ is 1 to 6, especially those substituted with hydrophilic groups such as carboxylic acids or sulfonic acids or their salts, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are 1 Or 10 is preferred. Preferable examples of the above aryl group include an unsubstituted or substituted phenyl group. Further Representative examples of alkyl groups if detailed R _1, a methyl group, an ethyl group, n- propyl group, i- propyl and n- butyl group, an aryl group R ₁ Representative examples include phenyl group, tolyl group, xylyl group, methoxyphenyl group, chlorophenyl group and the like. As typical examples of the alkyl group represented by R ₂ , the same examples as the alkyl group represented by R ₁ can be given.

As a typical example of the aryl group of R _2, the same examples as the aryl group of R ₁ can be given. Representative examples of the alkyl group for R ₃ include methyl group, ethyl group, i-propyl group, n-butyl group, n-hexyl group, sulfoethyl group, carboxyethyl group, sulfatoethyl group, hydroxypropyl group, Examples thereof include a sulfopropyl group, a sulfobutyl group, a 2- (2-sulfatoethoxy) ethyl group, a benzyl group, and a sulfobenzyl group.

Typical examples of the alkyl group represented by R ₁₁ include a methyl group, an ethyl group, an i-propyl group, an n-butyl group, an n-hexyl group, a 2-ethylhexyl group, an n-dodecyl group, and a benzyl group. Can do. Representative examples of the aryl group for R ₁₁ include a phenyl group, a tolyl group, an ethylphenyl group, a t-butylphenyl group, a methoxyphenyl group, a chlorophenyl group, and the like. Representative examples of the alkyl group of R ₁₂ include a methyl group, an ethyl group, an n-butyl group, an n-pentyl group, a 2-ethylhexyl group, an n-octyl group, an n-dodecyl group, a 2-methoxyethyl group, A 3-methoxy-3-methylpropyl group, 2-phenoxyethyl group, benzyl group and the like can be mentioned. Representative examples of the aryl group for R ₁₂ include phenyl group, tolyl group, t-butylphenyl group, octylphenyl group, di-t-amylphenyl group, methoxyphenyl group, chlorophenyl group and the like. Typical examples of the alkyl group represented by R ₁₃ include a methyl group, an ethyl group, an n-butyl group, an n-hexyl group, an n-octyl group, and an n-dodecyl group. As a typical example of the alkyl group of R _14, the same examples as the alkyl group of R ₁₃ can be given. Typical examples of the aryl group for R ₁₄ include a phenyl group, a tolyl group, a methoxyphenyl group, a chlorophenyl group, and a trifluoromethylphenyl group.

Many of the compounds represented by the general formula (I) exhibit an absorption maximum at 400 nm or less in a methanol solution, and a compound having a desired absorption maximum can be selected by any combination of A and B. The selection of the combination of A and B in this sense is important, and it is selected from the group represented by —CN, SO ₂ R ₁₁ , —COOR ₁₂ or —CONR ₁₃ R ₁₄ , as already described. However, it is more desirable that A and B are selected from different groups. Further, it is more useful that one of A and B is selected from the group represented by —CN or —SO ₂ R _{11. In} this case, when R ₁ and R ₂ are both hydrogen atoms, a more preferable effect is obtained. can get.

In the general formula (II), R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom or an alkyl group, R ₈ represents an alkyl group or an allyl group, and R ₉ and R ₁₀ represent a hydrogen atom or an alkyl group, respectively. Group represents an aryl group, and G represents an electron withdrawing group.

Here, for example, an alkyl group includes unsubstituted and substituted alkyl groups, and an alkyl group having 1 to 20 carbon atoms is desirable. Preferable examples of the above aryl group include an unsubstituted or substituted phenyl group. In more detail, typical examples of the alkyl group of R ₄ , R ₅ , R ₆ and R ₇ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and the like. Typical examples of the alkyl group represented by R ₈ include methyl group, ethyl group, i-propyl group, n-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n- Decyl group, sulfoethyl group, carboxyethyl group, hydroxyethyl group, methoxyethyl group, sulfatoethyl group, sulfopropyl group, sulfobutyl group, 2- (2-sulfatoethoxy) ethyl group, benzyl group, sulfobenzyl group, etc. Can be mentioned.

Representative examples of the alkyl group represented by R ₉ and R ₁₀ include methyl group, ethyl group, i-propyl group, n-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group. Group, n-dodecyl group, benzyl group and the like. Typical examples of the aryl group represented by R ₉ and R ₁₀ include a phenyl group, an ethylphenyl group, an n-butylphenyl group, a chlorophenyl group, a cyanophenyl group, and a trifluoromethylphenyl group.

In the general formula (III), R ₁₁ and R ₁₂ each represents an alkyl group or an acyl group, A1 and B1 are each represented by —CN, —SO ₂ R ₁₃ , —COOR ₁₄ or —CONR ₁₅ R ₁₆ , and R ₁₃ And R ₁₄ each represents an alkyl group or an aryl group, and R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group or an aryl group.

The alkyl group represented by R ₁₁ and R ₁₂ has the same meaning as the alkyl group represented by R ₁ and R ₂ in formula (I). The acyl group represented by R ₁₁ and R ₁₂ is an acyl group from an aliphatic carboxylic acid or an aromatic carboxylic acid, and specifically includes an acetyl group, a propioniol group, and a benzoyl group.

  A1 and B1 are synonymous with A and B in the general formula (I).

  Specific examples of the compounds represented by the general formulas (I), (II), and (III) are shown below, but the present invention is not limited thereto.

  In the present invention, a known dye can be used as the dye having a spectral absorption maximum of 410 to 450 nm.

  For example, dyes represented by general formulas (I) to (III) described in JP-A No. 5-204092 and general formulas (1) to (3) described in JP-A No. 2000-257882 and general formula ( I), dyes represented by (II), compounds of I-48 to I-50 represented by general formula (I) described in JP-A-5-204092, and II-25 represented by general formula (II) -II-27 compound, III-39-III-41 compound represented by the same general formula (III) and AI-3, 1-1 represented by general formula (1) described in JP-A-2000-277578 1-40 and 1-51 to 1-60 compounds, 2-1 to 2-6 and 2-9 to 2-34 compounds represented by the same general formula (2), represented by the same general formula (3) Compounds of 3-1 to 3-62, compounds of I-1 to I-23 represented by the same general formula (I), II-2 to II-20 and dye-1 represented by formula (II).

(Addition amount, addition method)
The addition amount of the dyes represented by the general formula (I) ~ (III), preferably 0.001~3g / m ^2, more preferably from 0.005~0.6g / m ^2.

Further, as the amount of the dye spectral absorption maximum is 410～450Nm, preferably 0.01 to 10 g / m ^2, more preferably from 0.05 to 2.0 g / m ^2.

  In order to contain these dyes in the constituent layers, they may be dissolved in a low boiling point solvent and / or a high boiling point solvent, finely dispersed in a binder solution such as an aqueous gelatin solution using a surfactant, and then added. When the dye is water-soluble, it can be added as an aqueous solution.

  In order to contain these dyes in the support, they may be added and mixed directly to the support material in the support production process, or pellets previously kneaded into a part of the support material are formed, A known method such as mixing the required amount into the support material can be used without limitation.

(Electromagnetic wave shielding film with dye remaining)
Each of the above dyes may flow out and be removed from the photosensitive material in at least one selected from development processing, physical development and plating processing described later, but at least a part of the dye remains. In the formed electromagnetic wave shielding film, it is preferable that the spectral absorption maximum in visible light of the light transmitting portion of the electromagnetic wave shielding film exists in 400 to 450 nm.

  When the transparent electromagnetic wave shielding film having such spectral absorption characteristics is used for a display such as a PDP, for example, the color color reproducibility by BGR light is improved in order to suppress the light having a wavelength close to the ultraviolet ray emitted from the PDP. Has the effect of In this case, the spectral absorption density at 400 to 450 nm of the light transmissive portion of the electromagnetic wave shielding film is preferably 1.0 or less, more preferably 0.5 or less, and particularly preferably 0.05 or more and 0.40 or less.

(Layer structure)
The layer structure of the silver halide photosensitive material for forming an electromagnetic wave shielding film of the present invention basically comprises a transparent support and a silver halide photosensitive layer. Furthermore, it is preferable to provide various layers in consideration of not only high functionality, processing characteristics and durability as an electromagnetic wave shielding film but also the production efficiency and production stability of the silver halide photosensitive material.

  For example, a non-photosensitive intermediate layer is provided between the transparent support and the silver halide photosensitive layer, or a backing layer is provided on the opposite side of the transparent support from the silver halide photosensitive layer. It is preferable to provide a protective layer on the photosensitive layer. These layers may be composed of a plurality of layers. The dye relating to the present invention exhibits an excellent effect by being appropriately distributed and added to these layers.

(High contrast agent)
In the present invention, it is preferable that the photosensitive material has a high contrast in order to draw a conductive pattern with a clear edge. As the method, a method of increasing the silver chloride content to narrow the particle size distribution, or a hydrazine compound It is preferable to use a tetrazolium compound as a high contrast agent. The hydrazine compound is a compound having a —NHNH— group, and a typical one is represented by the following general formula (1).

General formula (1) T-NHNHCO-V, T-NHNHCOCO-V
In the formula, each T represents an optionally substituted aryl group or heterocyclic group. The aryl group represented by T includes a benzene ring or a naphthalene ring, and this ring may have a substituent. As a preferable substituent, a linear or branched alkyl group (preferably a methyl group having 1 to 20 carbon atoms). Group, ethyl group, isopropyl group, n-dodecyl group, etc.), alkoxy group (preferably C2-C21 methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably C2-C21 alkyl group). Acetylamino group, heptylamino group, etc.), aromatic acylamino group, and the like. In addition to these, for example, the substituted or unsubstituted aromatic ring as described above is -CONH-, -O-,- Also included are those bonded by a linking group such as SO ₂ NH—, —NHCONH—, —CH ₂ CH═N—, and the like. V represents a hydrogen atom, an optionally substituted alkyl group (methyl group, ethyl group, butyl, trifluoromethyl group, etc.), aryl group (phenyl group, naphthyl group), heterocyclic group (pyridyl group, piperidyl group, pyrrolidyl group) , Furanyl group, thiophene group, pyrrole group and the like).

  The above hydrazine compound can be synthesized with reference to the description in US Pat. No. 4,269,929. The hydrazine compound can be contained in the silver halide grain-containing layer, in the hydrophilic colloid layer adjacent to the silver halide grain-containing layer, or in another hydrophilic colloid layer.

  Particularly preferred hydrazine compounds are listed below.

(H-1): 1-trifluoromethylcarbonyl-2-{[4- (3-n-butylureido) phenyl]} hydrazine (H-2): 1-trifluoromethylcarbonyl-2- {4- [ 2- (2,4-di-t-pentylphenoxy) butyramide] phenyl} hydrazine (H-3): 1- (2,2,6,6-tetramethylpiperidyl-4-amino-oxalyl) -2- { 4- [2- (2,4-di-t-pentylphenoxy) butyramide] phenyl} hydrazine (H-4): 1- (2,2,6,6-tetramethylpiperidyl-4-amino-oxalyl)- 2- {4- [2- (2,4-di-t-pentylphenoxy) butyramide] phenylsulfonamidophenyl} hydrazine (H-5): 1- (2,2,6,6-tetramethylpiperidyl-4 − Amino-oxalyl) -2- {4- [3- (4-chlorophenyl-4-phenyl-3-thia-butanamide) benzenesulfonamido] phenyl} hydrazine (H-6): 1- (2,2,6 6-tetramethylpiperidyl-4-amino-oxalyl) -2- [4- (3-thia-6,9,12,15-tetraoxatricosanamide) benzenesulfonamide] phenylhydrazine (H-7): 1 -(1-methylenecarbonylpyridinium) -2- [4- (3-thia-6,9,12,15-tetraoxatricosanamide) benzenesulfonamide] phenylhydrazine chloride.

  When hydrazine is used as the thickening agent, an amine compound or a pyridine compound can be preferably used in order to enhance the reducing action of hydrazine. As the amine compound that promotes the reducing action of the hydrazine compound, it is particularly preferable that the molecule has at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds.

  In addition to the above-described amine compounds, pyridinium compounds and phosphonium compounds can also be preferably used as compounds that promote the reduction action of hydrazine. Since onium compounds are positively charged, they are considered to promote high contrast by adsorbing to negatively charged silver halide grains and accelerating electron injection from the developing agent during development. ing. For preferred pyridinium compounds, reference can be made to the bispyridinium compounds disclosed in JP-A-5-53231 and JP-A-6-242534. Particularly preferred pyridinium compounds are those in which a bispyridinium body is formed by linking at the 1-position or 4-position of pyridinium. The salt is preferably a chlorine ion, bromine ion or the like as a halogen anion, and other examples include boron tetrafluoride ion and perchlorate ion, but chlorine ion or boron tetrafluoride ion is preferable.

The hydrazine compound, amine compound, pyridinium compound, and tetrazolium compound are preferably contained in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol per mol of silver halide, particularly 1 × 10 ⁻⁴ to 2 × 10 ^−2. Mole is preferred.

(Support)
In the present invention, as a support, for example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfone (including polyethersulfone) film, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, etc. , Polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film, poly Methyl pentene film, polyether ketone film, polyether Ketone-imide film, a polyamide film, a fluororesin film, a nylon film, a polymethyl methacrylate film or an acrylic film or the like. In addition to these plastic films, quartz glass, soda glass, and the like can be used.

  Of these, cellulose triacetate film, polycarbonate film, polysulfone (including polyethersulfone), polyethylene terephthalate film, and polyethylene naphthalate film are preferably used.

  In the present invention, it is particularly preferable to use a polyethylene terephthalate film or a polyethylene naphthalate film that is a polyester film as the support from the viewpoints of transparency, isotropic properties, adhesiveness, durability, and the like.

  When the electromagnetic wave shielding film of the present invention is used for a display screen of a display, it is desirable that the support itself has high transparency because high transparency is required. In this case, the average transmittance in the visible light region of the plastic film or glass plate is preferably 85 to 100%, more preferably 90 to 100%. Moreover, in this invention, what colored the said plastic film or glass plate to the extent which does not interfere with the objective of this invention can also be used as a color tone regulator. The average transmittance of the visible light region is obtained by integrating the transmittances of the visible light region obtained by measuring the transmittance of the visible light region from 400 to 700 nm at least every 5 nm, and obtaining the average value thereof. Define. In measurement, the measurement aperture needs to be sufficiently larger than the mesh pattern described above, and is obtained by measuring at least 100 times larger than the mesh area of the mesh.

  Although there is no restriction | limiting in particular in the thickness of the support body used for this invention, it is preferable that it is 5-200 micrometers from a viewpoint of the maintenance of a transmittance | permeability and a handleability, and it is still more preferable that it is 30-150 micrometers.

  The transparent support according to the present invention can be colored by adding a dye. Examples of the method of adding the dye include a method of forming a film by adding the dye to a melt or solution of the support material, and a so-called dyeing method in which the dye is brought into contact with the film after forming the transparent support. When coloring the transparent support, it is preferable that the solubility parameters representing the compatibility of the support-forming polymer and the dye are close.

(Configuration of electromagnetic shielding film)
In the present invention, in order to provide high translucency and high electromagnetic wave shielding performance, a conductive mesh pattern is formed by drawing a lattice-like fine line pattern by exposure and then performing development processing, etc. It is preferable to use a shield film. The conductive metal part preferably has a line width of 20 μm or less and a line interval of 50 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 preferably less than 18 μm, more preferably less than 10 μm, and most preferably less than 7 μm.

  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 90% or more from the viewpoint of visible light transmittance. The aperture ratio is the proportion of the entire portion of the mesh without fine lines. For example, the aperture ratio of a square grid mesh with a line width of 10 μm and a pitch of 200 μm is 90%.

  In the present invention, it is also preferable to provide a photosensitive silver halide photosensitive layer on both sides of the support and to form a conductive pattern on each. In this case, it is preferable that the silver halide emulsion coated on each surface has sensitivity at different wavelengths by spectral sensitization. By giving sensitivity to different wavelengths on the front and back surfaces, it becomes possible to produce different conductive patterns on each surface, for example, to selectively shield against electromagnetic waves of different frequencies on the front and back surfaces. In addition, it is possible to form a conductive pattern.

(Production method)
With respect to the method for producing an electromagnetic wave shielding film of the present invention, (1) silver halide grains having an average grain size of 0.10 μm or less are contained on a transparent support, and the silver / binder mass ratio is 2.0 or more. A step of applying a silver halide photosensitive layer to form a silver halide photosensitive material for forming an electromagnetic wave shielding film; (2) at least one dye having a spectral absorption maximum at 350 to 450 nm simultaneously with or separately from the application. (3) a step of exposing the formed silver halide photosensitive material with a laser beam having an emission wavelength of less than 450 nm, and (4) development processing of the exposed silver halide photosensitive material. A step of forming a metallic silver portion and a light transmitting portion, and (5) applying at least one selected from physical development and plating treatment to the metallic silver portion, Step of forming, characterized by comprising the.

  Although each of these processes may be batch-processed independently, it is preferable that each process is interlock | cooperating with respect to the continuous web from the drawing | feeding-out of a transparent support body. Finally, the formed electromagnetic shielding film may be obtained as a long roll, or the formed electromagnetic shielding film may be cut and integrated in a sheet form.

(Coating process)
A coating process is a process of apply | coating the said structural layer on a transparent support body. Examples of the coating method include a dip coating method, a spray coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, an inkjet coating method, or US Pat. No. 2,681,294. Examples include an extrusion coating method using a hopper described in the specification. In addition, if necessary, U.S. Pat. Nos. 2,761,791, 3,508,947, 2,941,898 and 3,526,528, Yuji Harasaki, “Coating The method of simultaneously applying two or more layers described in “Engineering” on page 253 (published by Asakura Shoten in 1973) can also be preferably used.

(Exposure process)
In the present invention, the photosensitive material is exposed to form a conductive pattern by performing at least one selected from development processing, physical development and plating processing described later. Examples of the light source used for exposure include light such as ultraviolet rays, visible rays, and infrared rays, and radiation such as electron beams and X-rays. Visible rays are used in terms of utilizing the characteristics of silver halide. preferable. In particular, it is preferable to use a light source having a narrow wavelength distribution because the formation of the electromagnetic shielding film can be efficiently controlled and can be stably manufactured.

  In the present invention, it is particularly preferable to perform exposure using a laser beam. Among various laser beams, a blue laser is preferable because of the photosensitive characteristics of silver halide. The emission wavelength is preferably 370 to 450 nm, particularly 415 to 440 nm.

Specifically, a helium / cadmium laser (about 442 nm), a blue semiconductor laser having an oscillation wavelength of 400 to 430 nm using an InGaN-based material, a GaAlAs-based (laser wavelength 850 nm) semiconductor laser, and a MgO: LiNbO ₃ SHG crystal. There is a laser (425 nm) extracted after wavelength conversion by the method, but a blue semiconductor laser is preferable from the viewpoint of compactness, low power consumption, stability, long life and the like. In particular, a blue semiconductor laser announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001 is preferred.

(Development processing)
In the present invention, after the photosensitive material is exposed, development processing is performed. The development process is preferably a so-called black-and-white development process that does not contain a color developing agent.

  As the developing solution, in addition to hydroquinones such as hydroquinone, sodium hydroquinonesulfonate, chlorohydroquinone and the like as developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1- Use in combination with pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate. Can do. In addition, it is preferable to use a reductone compound such as ascorbic acid or isoascorbic acid in combination with the superadditive developing agent without using hydroquinone.

  Further, sodium sulfite salt or potassium sulfite salt as a preservative, sodium carbonate salt or potassium carbonate salt as a buffering agent, diethanolamine, triethanolamine, diethylaminopropanediol or the like as a development accelerator can be appropriately used in the developing solution.

  The development processing solution used in the development processing can contain an image quality improving agent for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole.

  In the present invention, it is preferable that the development processing performed after exposure includes pre-fixing physical development. The term “physical development before fixing” as used herein refers to a process of reinforcing developed silver by supplying silver ions from outside the silver halide grains having a latent image by exposure before performing a fixing process described later. As a specific method for supplying silver ions from the developing solution, for example, a method of dissolving silver nitrate or the like in advance in a developing solution and dissolving silver ions, or sodium thiosulfate in the developing solution, Examples include a method in which a silver halide solvent such as ammonium thiocyanate is dissolved, unexposed silver halide is dissolved during development, and development of silver halide grains having a latent image is supplemented.

  In the present invention, it is preferable to use a formulation in which a silver halide solvent is dissolved in advance in a developing solution because a decrease in the transmittance of the film due to the occurrence of fogging in an unexposed portion can be suppressed.

  In the development processing in the present invention, after the development of the exposed silver halide grains, fixing processing is performed for the purpose of removing and stabilizing the unexposed silver halide grains. For the fixing treatment in the present invention, a fixer formulation used for photographic films, photographic papers and the like using silver halide grains can be used. The fixing solution used in the fixing process may use sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, or the like as a fixing agent. As a hardening agent at the time of fixing, aluminum sulfate, chromium sulfate, or the like can be used. As the fixing agent preservative, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing solution can be used, and citric acid, oxalic acid, and the like can be used.

  The washing water used in the present invention includes N-methyl-isothiazol-3-one, N-methyl-isothiazol-5-chloro-3-one, and N-methyl-isothiazole-4,5 as antifungal agents. -Dichloro-3-one, 2-nitro-2-bromo-3-hydroxypropanol, 2-methyl-4-chlorophenol, hydrogen peroxide and the like can be used.

(Physical development, plating)
In the present invention, it is preferable to perform at least one selected from a physical development process and a plating process in order to assist the contact between the developed silvers formed by the above-described development process and increase the conductivity. This is a process for improving the conductivity by supplying from the outside a conductive substance source not previously contained in the photosensitive material during or after the development process. The physical development can be performed by immersing a photosensitive material containing a silver halide emulsion having a latent image in a processing solution containing silver ions or silver complex ions and a reducing agent. In the present invention, physical development is defined not only when the development start point of physical development is the latent image nucleus but also when developed silver is the physical development start point, and this can be preferably used.

  In the present invention, various conventionally known plating methods can be used for the plating treatment. For example, electrolytic plating and electroless plating can be performed alone or in combination. Among these, electroless plating that does not cause plating unevenness due to current distribution unevenness can be preferably used. As a metal that can be used for electroless plating, for example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used, but the plating process is relatively easy and has high conductivity. It is particularly preferable to use copper electroless plating from the viewpoint of easily obtaining the properties.

  The above processing can be performed during development, at any timing after development, before fixing, and after fixing processing. However, from the viewpoint of maintaining high transparency of the film, it is preferably performed after the fixing processing.

  In the present invention, an embodiment in which the amount of metal applied by physical development or metal plating is 10 times or more and 100 times or less in terms of mass with respect to developed silver obtained by exposing and developing a photosensitive material is preferable. . This value can be determined by quantifying the metal contained in the photosensitive material by, for example, fluorescent X-ray analysis before and after physical development or metal plating. When the amount of metal imparted by physical development or metal plating is less than 10 times in terms of mass relative to developed silver obtained by exposing and developing a photosensitive material, the conductivity tends to decrease slightly. If it is more than 100 times, the transmittance tends to decrease due to metal deposition on unnecessary portions other than the conductive mesh pattern portion. In the present invention, it is preferable to perform both physical development and metal plating.

(Oxidation treatment)
In the present invention, it is preferable to carry out an oxidation treatment after the development treatment, physical development or plating treatment. By the oxidation treatment, unnecessary metal components can be ionized and dissolved and removed, and the transmittance of the film can be further increased.

  As a treatment liquid used for the oxidation treatment, for example, a treatment method using an aqueous solution containing Fe (III) ions, or hydrogen peroxide, persulfate, perborate, perphosphate, percarbonate, perhalogen A treatment liquid containing a conventionally known oxidant such as a method of treatment using an aqueous solution containing a peroxide such as an acid salt, a hypohalite, a halogenate, or an organic peroxide can be used. The oxidation process is preferably performed after the development process and before the plating process because the transmittance can be improved efficiently with a short time process, and particularly preferably after the physical development. It is.

(Blackening treatment)
In the present invention, it is preferable to perform a blackening treatment on the surface of the metal mesh from the viewpoint of preventing external light reflection on the surface of the electromagnetic wave shielding film. When the transparent electromagnetic wave shielding film subjected to such blackening treatment is used for, for example, a display such as a PDP, a reduction in contrast due to reflection of external light can be reduced and the color tone of the screen when not in use is kept black and high quality. Can be preferable.

  There is no restriction | limiting in particular as the method of a blackening process, A well-known method can be used individually or in combination suitably. For example, when the outermost surface of the conductive pattern is made of metallic copper, it is immersed in an aqueous solution containing sodium chlorite, sodium hydroxide, or trisodium phosphate, or oxidized, or copper pyrophosphate or pyrroline. A method of blackening by immersion in an aqueous solution containing potassium acid and ammonia and performing electrolytic plating can be preferably used. If the outermost layer of the conductive pattern is made of a nickel-phosphorus alloy film, it is immersed in an acidic blackening solution containing copper (II) chloride or copper (II) sulfate, nickel chloride or nickel sulfate, and hydrochloric acid. The method to do can be used preferably.

  In addition to the above-described method, blackening treatment can be performed by a method of finely roughening the surface, but from the viewpoint of maintaining high conductivity, blackening by oxidation rather than finer surface roughening is possible. The method of crystallization treatment is preferred.

(Near-infrared absorbing layer)
When the electromagnetic wave shielding film of the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), near infrared absorption, which is a layer containing a near infrared absorbing dye under the silver halide photosensitive layer. It is also preferred to provide a layer. In some cases, the near-infrared absorbing layer may be provided on the opposite side of the support to the silver halide grain layer side, or may be provided on both the silver halide grain layer side and the opposite side. A near-infrared absorbing layer can be provided between the silver halide grain layer containing silver halide and the support, or a near-infrared absorbing layer can be provided on the opposite side of the support as viewed from the silver halide grain layer. The former is preferred because it can be applied simultaneously with one side of the support.

  Specific examples of near-infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo And triallylmethane-based compounds. The PDP optical filter is required to have near-infrared absorptivity mainly for absorption of heat rays and noise prevention of electronic devices. For this purpose, a dye having a near-infrared absorption ability having a maximum absorption wavelength of 750 to 1100 nm is preferable, and a metal complex system, an aminium system, a phthalocyanine system, a naphthalocyanine system, a diimonium system, and a squalium compound system are particularly preferable.

  As the near-infrared absorbing dye, the diimonium compound is IRG-022, IRG-040 (above, manufactured by Nippon Kayaku Co., Ltd.), and the nickel dithiol complex compound is SIR-128, SIR-130, SIR-132, SIR-159. SIR-152, SIR-162 (manufactured by Mitsui Chemicals, Inc.), and phthalocyanine compounds may be commercially available products such as IR-10 and IR-12 (manufactured by Nippon Shokubai Co., Ltd.).

  For example, when the electromagnetic wave shielding film of the present invention is used in combination with an optical filter for a plasma display panel (PDP), in order to prevent a decrease in color reproducibility due to emission of bright lines of neon gas used for PDP, this measure is around 595 nm. The aspect containing the pigment | dye which absorbs the light of this is preferable.

  Specific examples of the dye that absorbs the specific wavelength include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, and methine. And well-known organic pigments and organic dyes such as isoindolinone, quinophthalone, pyrrole, thioindigo, and metal complex, and inorganic pigments. Of these, phthalocyanine-based and anthraquinone-based dyes are particularly preferably used because of their good weather resistance.

(UV absorbing layer)
In the present invention, it is preferable to use an ultraviolet absorber having a maximum absorption wavelength of less than 350 nm in order to avoid deterioration of the electromagnetic wave shielding film due to ultraviolet rays.

  As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S-triazine compounds, cyclic imino ester compounds, and the like can be preferably used. Of these, benzophenone compounds, benzotriazole compounds, and cyclic imino ester compounds are preferred. As what is blended with the polyester, a cyclic imino ester compound is particularly preferable. There are no particular restrictions on the layer added to these ultraviolet absorbers, but from the viewpoint of preventing the binder used in the silver halide photosensitive layer (mesh pattern layer) from being deteriorated by ultraviolet rays, it is added to the silver halide photosensitive layer. Or the aspect provided in the light source side rather than this layer is preferable.

  Preferred ultraviolet absorbers include benzotriazoles, for example, compounds represented by general formula [III-3] described in JP-A-1-250944, and general formula [III described in JP-A-64-66646. ], A compound represented by general formula [I] described in JP-A-4-16333, and JP-A-5-165144. The compounds represented by the general formulas (I) and (II) are preferably used.

  These ultraviolet absorbers are, for example, high-boiling organics typified by phthalates such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. It is preferable to add by dispersing in a solvent. Moreover, the aspect which adds these ultraviolet absorbers directly to a support body is also used preferably, In this case, the aspect as described in the Japanese translations of PCT publication No. 2004-531611 can also be used preferably, for example.

(Antireflection layer)
When the electromagnetic wave shielding film of the present invention is used for the purpose of protecting the display screen, it is preferable to provide an antireflection layer. As the antireflection layer, inorganic materials such as metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides, etc., can be used by vacuum deposition, sputtering, ion plating, ion beam assist, etc. A method of laminating a thin film in a layer or a multilayer, a method of laminating a resin having a different refractive index such as an acrylic resin or a fluororesin into a single layer or a multilayer can be used.

  In the present invention, in the transparent electromagnetic wave shielding film, when an antireflection layer is formed on the opposite side of the layer having a conductive pattern with the support of the electromagnetic wave shielding film sandwiched, the antireflection layer is first formed. After forming, the aspect which bonds a protective film and forms a conductive pattern layer after that is preferable. When the antireflection layer is formed after the conductive pattern is formed first, the efficiency of the plasma treatment and corona treatment performed to improve the adhesion between the antireflection layer and the support tends to be reduced. The embodiment in which the layer is formed first is preferred. In addition, when the antireflection layer is formed first, from the viewpoint of preventing the layer from being deteriorated by development, plating treatment, etc., a mode in which a conductive pattern layer is formed after pasting a protective film in advance is preferable. .

  As the protective film used in the present invention, a commercially available protective film can be used. From the viewpoint of facilitating coating of a photosensitive silver halide emulsion layer for forming a conductive pattern, the film is used. Is preferably 10 μm or more and 100 μm or less, particularly preferably 20 μm or more and 60 μm or less. If the thickness is less than 10 μm, the rigidity of the film is remarkably reduced, so that the work efficiency of the protection film is likely to be reduced, and if it is thicker than 100 μm, a failure such as a winding wrinkle is likely to occur when the film is wound. is there.

  Although there is no restriction | limiting in particular in the kind of adhesive used for a protective film, The thing which does not damage an antireflection film at the time of peeling, without altering an antireflection film is used preferably. From such a viewpoint, an acrylic or silicone adhesive is preferably used. Moreover, what is 0.08-0.6N / 25mm as the adhesive force is used preferably.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
(Preparation of EMP-1)
The following (A1 solution) and (B1 solution) were simultaneously added to 1 L of 0.5% gelatin aqueous solution kept at 35 ° C. while controlling the silver potential (EAg) = 85 mV and pH = 5.8, and the following (C1 Solution) and (D1 solution) were simultaneously added while controlling EAg = 85 mV and pH = 5.8. At this time, the silver potential was controlled using a 10% potassium bromide aqueous solution, and the pH was controlled using acetic acid or a sodium hydroxide aqueous solution.

(A1 solution)
Potassium bromide 104g
Potassium iodide 3.0g
1300ml with water
(B1 solution)
150 g silver nitrate
1360ml with water
(C1 liquid)
310g of potassium bromide
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium iodide 10 g
4000ml with water
(D1 solution)
480 g of silver nitrate
4200ml with water
After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. Thereafter, 2.0 mg of sodium thiosulfate per mol of silver halide was used for chemical sensitization at 40 ° C. for 80 minutes, and after completion of chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7- The photosensitive silver halide emulsion was obtained by adding 500 mg of tetrazaindene (TAI) per mole of silver halide and further adding 500 mg of the following sensitizing dye SD-1 per mole of silver halide. The average particle size was 0.04 μm, and the variation coefficient of the particle size distribution was 0.13.

0.40 g / m ^{2 of} butyl acrylate: styrene: glycidyl acrylate (40: 20: 40% by mass) latex on one side of a 120 μm thick polyethylene terephthalate film support subjected to plasma discharge treatment on both sides, hexamethylene A backing layer was provided by applying -1,6-bis (ethylene urea) at 0.01 g / m ² . Furthermore, 0.20 g / m ² of gelatin was coated on the other side as a non-photosensitive intermediate layer.

As a silver halide photosensitive layer on the non-light-sensitive intermediate layer, the above silver halide emulsion was coated with a silver coating amount of 0.75 g / m ² and a gelatin coating amount of 0.15 g / m ² (silver / binder ratio of 5. The photosensitive material 100 was prepared by applying the coating composition to (0) and then drying. In the preparation of the photosensitive material, a hardening agent (H-1: tetrakis (vinylsulfonylmethyl) methane) was added at a ratio of 50 mg per 1 g of gelatin. Further, as a coating aid, a surfactant (SU-2: di (2-ethylhexyl) sulfosuccinate / sodium) was added to adjust the surface tension.

(Production of photosensitive materials 101 to 108)
As shown in Table 1, with respect to the photosensitive material 100, a predetermined amount of each dye is added to each of the silver halide photosensitive layer, the non-photosensitive intermediate layer, the support, and the backing layer, thereby preparing the photosensitive material 101. -108 were produced.

  With respect to each of the silver halide light-sensitive materials 100 to 108 for forming a transparent electromagnetic wave shielding film thus obtained, the spectrophotometer (U-3210: (Manufactured by Hitachi, Ltd.). The measurement was handled under a safety light in consideration of the occurrence of baked silver.

  Each sample was processed into a roll with a width of 35 cm and a length of 120 m, and unwound to another core at a speed of 20 m / min in an atmosphere of 23 ° C. and 20% RH. The effect of peeling and charging was investigated.

  With respect to the silver halide photosensitive materials 100 to 108 for forming an electromagnetic wave shielding film manufactured as described above, a laser beam having an oscillation wavelength of 440 nm so that the line width is 10 μm and the distance between the lines is 240 μm. After mesh exposure using a blue semiconductor laser diode manufactured by Nichia Corporation), development processing was performed at 25 ° C. for 60 seconds using the following developer (DEV-1), and then the following fixing solution ( FIX-1) was used for fixing treatment at 25 ° C. for 120 seconds, followed by washing with water. Furthermore, physical development was performed at 25 ° C. for 5 minutes using the following physical developer (PD-1), followed by washing with water. Then, after being immersed in a Pd catalyst solution (CAT-1) at 25 ° C. for 30 seconds, it was washed with water and further subjected to electroless copper plating treatment at 45 ° C. for 10 minutes using a plating solution (PL-1). Shield films S100 to S108 were produced.

(DEV-1: Developer)
500 ml of pure water
Metol 2g
80 g of anhydrous sodium sulfite
Hydroquinone 4g
4g borax
Sodium thiosulfate 10g
Potassium bromide 0.5g
Add water to bring the total volume to 1L.

(FIX-1: Fixer)
750 ml of pure water
Sodium thiosulfate 250g
Anhydrous sodium sulfite 15g
Glacial acetic acid 15ml
Potash alum 15g
Add water to bring the total volume to 1L.

(PD-1: Physical developer)
800ml of pure water
Citric acid 5g
Hydroquinone 7g
Silver nitrate 3g
Add water to bring the total volume to 1L.

(CAT-1: Pd catalyst solution)
Palladium sulfate 20mg
Add water to bring the total volume to 1L.

(PL-1: plating solution)
Copper sulfate 0.04 mol Formaldehyde (37%) 0.08 mol Sodium hydroxide 0.10 mol Triethanolamine 0.05 mol Polyethylene glycol 100 ppm
Add water to bring the total volume to 1L.

  With respect to each of the transparent electromagnetic wave shielding films S100 to S108 having a conductive metal mesh portion obtained in this way, the spectral absorption characteristics of the light transmitting portion are measured with a spectrophotometer (U-3210: Hitachi, Ltd.). (Manufactured by Seisakusho). Moreover, the sharpness of the mesh pattern of the metallic silver mesh part was measured by scanning using a Sakura Microdensitometer M-5 type (former Konica Corporation), and a relative comparison was performed. The larger the value, the better the sharpness.

  Further, the surface specific resistance value and the transmittance were measured using a resistivity meter Loresta GP (MCP-T610 type: manufactured by Dia Instruments Co., Ltd.) and a spectrophotometer (U-3210: manufactured by Hitachi, Ltd.), respectively. did.

Further, the formed mesh was observed with a magnifying glass, and the number of defective points per 1 m ² such as generation of irregular patterns due to peeling electrification and mesh breakage was examined.

○: 1 or less Δ: 2 to 5 ×: 6 or more.

  Furthermore, each of the transparent electromagnetic wave shielding films S100 to S108 was applied to a state where only the electromagnetic wave shielding mesh of a plasma television manufactured by Pioneer Corporation was peeled off, and the color reproducibility was visually evaluated.

A: Calm color reproducibility and high saturation, extremely good B: Good color reproducibility B: Slightly inferior due to the cold color as a whole X: Bluish tendency is observed in the black part and glare is observed in the white part, which is poor.

  From the result of Table 2, since transparent electromagnetic wave shielding film S102-S108 which satisfy | fills the requirements of this invention has formed the mesh with high sharpness, it had high light transmittance and low surface specific resistance. Furthermore, it was found that the plasma display panel is excellent in color reproducibility.

  Electromagnetic wave shielding performance is evaluated by data on surface specific resistance, but practical measurement of electromagnetic wave shielding performance was performed by a method based on ASTM D 4935. In the range of 30 to 1,000 MHz, the comparative sample 100 was insufficient at about 20 dB, but all the samples of the present invention had an electromagnetic wave shielding effect of 30 dB or more and showed good performance.

Example 2
Sample No. 1 of Example 1 Samples in which the photosensitive layer dye No. 106 was changed to an equivalent application amount of A-4 and the intermediate layer dye I-8 was changed to equivalent application amounts of I-15, II-4, and III-5, respectively. 201, 202, 203 and sample No. Samples obtained by changing 108 photosensitive layer dye to equivalent application amount A-5 and changing the backing layer dye II-1 to equivalent application amounts I-15, II-4 and III-5, respectively 204, 205, 206.

  These sample Nos. When evaluation similar to Example 1 was implemented with respect to 201-206, as shown in Table 3, the equivalent effect was acquired. Therefore, in the present invention, since the spectral absorption maximum in the visible light region of the photosensitive material is set to 400 to 450 nm, it is possible to combine various known dyes, and in the visible light region of the photosensitive material. It can be seen that when the spectral absorption maximum is 400 to 450 nm, the effect of the present invention is exhibited regardless of the dye used.

Example 3
Table 4 shows the immersion time in the Pd catalyst solution (CAT-1) and the immersion time in the plating solution (PL-1) in the transparent electromagnetic wave shielding films S104 and S107 produced from the photosensitive materials 104 and 107 in Example 1. Transparent electromagnetic wave shielding films S301 to S308 were produced in the same manner except that the changes were made as shown in FIG.

  In the production of the transparent electromagnetic wave shielding films S301 to S308, (DEV-1), (FIX-1) and the developed silver amount after completion of the development of the silver halide at the stage where the washing with water was completed by fluorescent X-ray analysis. Quantitatively, after that, when the processing of (PD-1), (CAT-1) and (PL-1) was completed, the fluorescent X-ray analysis was performed again, and the physical development silver amount and the copper plating amount were quantified. Using the amount of metal thus determined, the ratio of the amount of metal applied by physical development or metal plating to the amount of developed silver obtained by exposing and developing the photosensitive material was determined as a mass ratio.

  Evaluation similar to Example 1 was implemented with respect to the transparent electromagnetic wave shielding film S301-S308 produced in this way. The results are shown in Table 4.

  From the results in Table 4, a transparent electromagnetic wave shielding film in which the amount of metal applied by physical development and metal plating is less than 10 times in terms of mass relative to developed silver obtained by exposing and developing a photosensitive material. Although S301 was able to obtain high transmittance and low surface specific resistance, the surface specific resistance was slightly higher than that of the other transparent electromagnetic wave shielding film of the present invention which is 10 times or more in terms of mass.

  Further, the transparent electromagnetic wave shielding film S305 in which the amount of metal applied by physical development and metal plating is greater than 100 times in terms of mass with respect to developed silver obtained by exposing and developing a photosensitive material has high transmittance. Although the rate and the low surface specific resistance were obtained, the transmittance was slightly lower than that of other transparent electromagnetic wave shielding films of the present invention smaller than 100 times in terms of mass.

  The amount of metal that satisfies the requirements of the present invention and is imparted by physical development and metal plating is 10 to 100 times in terms of mass with respect to developed silver obtained by exposing and developing the photosensitive material. Certain transparent electromagnetic wave shielding films S302, S303, S306, and S307 have a particularly high transmittance and a low surface specific resistance, and are understood to be a preferable aspect of the present invention.

Example 4
In the production of the transparent electromagnetic wave shielding films S101 and S106 produced in Example 1, oxidation treatment and blackening treatment were performed as shown in Table 5 to produce transparent electromagnetic wave shielding films S401 to S406.

  The oxidation treatment uses the following oxidation treatment solution (OX-1) between the physical development treatment and the Pd catalyst treatment. The blackening treatment is performed at 45 ° C. for 120 seconds, and the blackening treatment is performed after the treatment with the plating solution (PL-1). The treatment was performed at 80 ° C. for 120 seconds using the treatment liquid (BP-1).

  For the transparent electromagnetic wave shielding films S401 to S406 thus obtained, after measurement of surface specific resistance value, measurement of light transmittance at the opening, and forced degradation test for one month at 50 ° C. and 70% RH The light transmittance was measured. Further, the transparent electromagnetic wave shielding film on which the conductive pattern was formed was placed on a black paper and the film was observed from the opposite side to visually evaluate whether or not metallic gloss reflection was observed. The results are shown in Table 5.

(OX-1: oxidation treatment liquid)
Potassium ferricyanide 0.1g
Add water to bring the total volume to 1L.

(BP-1: Blackening treatment liquid)
Sodium chlorite aqueous solution (76%) 40g
Sodium hydroxide 5g
Add water to bring the total volume to 1L.

  From the results of Table 5, it can be seen that the metallic gloss reflection is sufficiently prevented in the preferred embodiment of the present invention, and the color tone of the screen when the display is not used can be kept black and high quality.

Example 5
In the production of the photosensitive material 106 produced in Example 1, instead of the backing layer on the polyethylene terephthalate support, 1 part by mass of the ultraviolet absorber (UV-1) was replaced with polyvinyl acetal (ESREC BM-S: Sekisui Chemical Co., Ltd. ( Photosensitive material in the same manner except that it was dissolved in an ethyl acetate / methyl ethyl ketone mixed solvent (mixing ratio 2: 1) together with 20 parts by mass and then coated so that UV-1 was 0.2 g / m ^2. 501 was produced, and a transparent electromagnetic wave shielding film S501 was produced using the same method as the transparent electromagnetic wave shielding film S106.

  The transparent electromagnetic wave shielding films S106 and 501 thus obtained were irradiated with light for 24 hours at 70,000 Lx in an environment of 24 ° C. and 60% RH using a Xe fade meter, and light transmission before forced deterioration was performed. The light transmittance after forced deterioration with respect to the transmittance was obtained. In addition, the occurrence of cracks after storage was evaluated and used as a measure of durability. The results are shown in Table 6.

  From the results in Table 6, it can be seen that the transparent electromagnetic wave shielding film S501 having at least one ultraviolet absorbing layer has improved durability of the coating against light irradiation, and is a particularly preferred embodiment of the present invention.

Example 6
<< Preparation of antireflection film (AR-1) >>
An antireflection film No. 1 described in Example 1 of JP-A-2005-338550. 14, the support was changed from a cellulose ester film to a polyethylene terephthalate film (thickness: 120 μm), and the backcoat layer was <A-1>, <A described in Example 1 of JP-A-10-039448 -2> solution, a layer having a dry film thickness of 0.8 μm is provided on the side close to the support using the <A-1> solution, and a dry film thickness of 0.8 μm is used on the outermost layer using the <A-2> solution. An antireflection film AR-1 was produced in the same manner except that it was coated to provide a 1 μm layer.

[Preparation of transparent electromagnetic wave shielding films S601 to S603]
After the protective film as shown in Table 7 was bonded to the antireflection processed surface side of the antireflection film AR-1 produced in this way, the same method as the production of the transparent electromagnetic wave shielding film S106 of Example 1 on the back surface side. Processing was performed to produce transparent electromagnetic wave shielding films S601 to S603.

[Preparation of transparent electromagnetic wave shielding film S604]
An antireflection layer was provided on the back surface of the transparent electromagnetic wave shielding film S106 produced in Example 1 in the same manner as in the production of the above antireflection film (AR-1) to produce a transparent electromagnetic wave shielding film S604.

  Evaluation similar to Example 1 was implemented with respect to the transparent electromagnetic wave shielding film S601-S604 obtained in this way. Further, the state of the antireflection layer after completion of the transparent electromagnetic wave shielding film was visually observed.

Protect film (PF-1): EC-700 manufactured by Sumilon Co., Ltd.
Protective film (PF-2): Hitachi Chemical Co., Ltd. L-5030

  As a result, the transparent electromagnetic wave shielding films S601 to S604 of the present invention all show high transmittance and low surface specific resistance, and the change in transmittance after the forced deterioration test is small, especially for the layer having a conductive pattern. The transparent electromagnetic wave shielding films S602 and S603, which have an antireflection layer on the opposite side of the film support, and after the antireflection layer is formed and bonded to the protective film, are formed with the conductive pattern layer. It turns out that it is a preferable aspect of this invention which can provide the transparent electromagnetic wave shielding film which has the favorable anti-reflective layer, without producing generation | occurrence | production of the reflection nonuniformity in a layer, or the fall of a radiation prevention function.

Claims (10)

A silver halide photosensitive layer containing silver halide grains having an average grain size of 0.01 μm or more and 0.10 μm or less on a transparent support, and having a silver / binder mass ratio of 2.0 or more and 20 or less, A silver halide photosensitive material for forming an electromagnetic wave shielding film, wherein a wavelength exhibiting a maximum absorption concentration in a spectral absorption concentration in visible light is 400 to 450 nm. The silver halide photosensitive material for forming an electromagnetic wave shielding film according to claim 1, wherein the silver halide photosensitive layer contains a dye having a spectral absorption maximum of 410 to 450 nm. 3. The silver halide photosensitive material for forming an electromagnetic wave shielding film according to claim 1, wherein at least one non-photosensitive intermediate layer is provided between the transparent support and the silver halide photosensitive layer. The silver halide photosensitive material for forming an electromagnetic wave shielding film according to claim 3, wherein a dye having a spectral absorption maximum of 350 to 410 nm is contained in at least one of the transparent support and the non-photosensitive intermediate layer. The silver halide photosensitive material for forming an electromagnetic wave shielding film according to any one of claims 1 to 4, further comprising a backing layer on the opposite side of the transparent support from the silver halide photosensitive layer. . The dye having a spectral absorption maximum of 410 to 450 nm is further contained in at least one of the transparent support, the non-photosensitive intermediate layer and the backing layer in the silver halide photosensitive material for forming an electromagnetic wave shielding film according to claim 5. A silver halide photosensitive material for forming an electromagnetic wave shielding film. 7. The electromagnetic wave shielding film forming device according to claim 1, wherein a spectral absorption concentration at a wavelength indicating a maximum absorption concentration existing in 400 to 450 nm is 0.50 to 3.0. 8. Silver halide photosensitive material. 8. The electromagnetic wave shielding film formation according to claim 4, wherein the dye having a spectral absorption maximum of 350 to 410 nm is any one of the following general formulas (I) to (III): Silver halide photosensitive material.

(In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, or an aryl group. R ₃ represents an alkyl group or an allyl group, and A and B represent —CN, —SO ₂ R ₁₁ , and —COOR ₁₂ , respectively. Or -CONR ₁₃ R ₁₄ , R ₁₁ and R ₁₂ each represent an alkyl group or an aryl group, and R ₁₃ and R ₁₄ each represent a hydrogen atom, an alkyl group or an aryl group.)

(Wherein R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom or an alkyl group, R ₈ represents an alkyl group or an allyl group, and R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group or aryl, respectively. And G represents an electron withdrawing group.)

(In the formula, R ₁₁ and R ₁₂ each represent an alkyl group or an acyl group, and A 1 and B 1 are each represented by —CN, —SO ₂ R ₁₃ , —COOR _14, or —CONR ₁₅ R ₁₆ , R ₁₃ , R ₁₄ Each represents an alkyl group or an aryl group, and R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group or an aryl group.) A step of exposing the silver halide photosensitive material for forming an electromagnetic wave shielding film according to any one of claims 1 to 8 with a laser beam having an emission wavelength of less than 450 nm, and developing the exposed silver halide photosensitive material to form a metal An electromagnetic wave shielding film comprising: a step of forming a silver portion and a light transmitting portion; and a step of forming a conductive metal portion by subjecting the metal silver portion to at least one selected from physical development and plating. Manufacturing method. An electromagnetic wave shielding film produced by the method for producing an electromagnetic wave shielding film according to claim 9.