WO2007102393A1 - Method for manufacturing electromagnetic wave shielding film and electromagnetic wave shielding film - Google Patents
Method for manufacturing electromagnetic wave shielding film and electromagnetic wave shielding film Download PDFInfo
- Publication number
- WO2007102393A1 WO2007102393A1 PCT/JP2007/053900 JP2007053900W WO2007102393A1 WO 2007102393 A1 WO2007102393 A1 WO 2007102393A1 JP 2007053900 W JP2007053900 W JP 2007053900W WO 2007102393 A1 WO2007102393 A1 WO 2007102393A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- electromagnetic wave
- wave shielding
- shielding film
- coating
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0086—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single discontinuous metallic layer on an electrically insulating supporting structure, e.g. metal grid, perforated metal foil, film, aggregated flakes, sintering
Definitions
- the present invention relates to a method for producing an electromagnetic wave shielding film that shields electromagnetic waves generated from electronic equipment such as a mobile phone, a microwave oven, a CRT, and a flat panel display, and an electromagnetic wave shielding film obtained by the production method.
- a plasma display panel generates electromagnetic waves in principle because it is based on the principle that a rare gas is made into a plasma state to emit ultraviolet rays and phosphors emit light with this light beam.
- a rare gas is made into a plasma state to emit ultraviolet rays and phosphors emit light with this light beam.
- near infrared rays are also emitted at this time, so that malfunction of operation elements such as a remote controller is caused.
- the electromagnetic wave shielding ability can be simply expressed by the surface resistance value, and the translucent electromagnetic wave shielding film for PDP is required to be 10 ⁇ or less.
- the conductivity is extremely high, preferably 0.2 ⁇ or less.
- a layer containing silver halide grains needs to have a high ratio of silver to a binder in order to increase the conductivity of the formed mesh pattern, so that there are large restrictions on coating conditions.
- the antireflection layer can be applied using a non-aqueous organic solvent, and the near-infrared shielding layer has been tried to be dispersed in a hydrophobic plasticizer (see, for example, Patent Document 2). In other words, it is difficult to make it close to the layers it contains, which is a factor that reduces productivity.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2004-221564
- Patent Document 2 JP 2005-099820 A
- An object of the present invention is to provide an electromagnetic shielding film having high productivity, a method for producing an electromagnetic shielding film, a high electromagnetic shielding function produced by the production method, an excellent antireflection function, and a high near infrared absorption function.
- a film is provided.
- An anti-reflective function is obtained after forming a mesh-like metal part by exposing and developing an original plate for an electromagnetic wave shielding film in which a layer containing photosensitive halogen silver halide particles is provided on a support.
- a method for producing an electromagnetic wave shielding film comprising coating and forming a layer having the same.
- the electromagnetic wave shielding film having high electromagnetic wave shielding properties and high near-infrared ray absorption properties and further having an excellent antireflection function.
- the electromagnetic wave shielding film having high electromagnetic wave shielding properties and high near-infrared ray absorption properties and further having an excellent antireflection function.
- a mesh-shaped metal part is formed by exposing and developing an original plate for an electromagnetic wave shielding film in which a layer containing photosensitive silver halide particles is provided on a support. After the formation, a layer having an antireflection function is formed by coating.
- a layer containing silver halide grains (halogenated silver grain containing layer) is provided on the support.
- the halogen-containing silver particle-containing layer can contain a binder, an activator and the like in addition to the halogen-containing silver particles.
- halogen silver halide grains used in the present invention include inorganic silver halide grains such as halogen silver and organic halogen silver grains such as silver behenate, but it is easy to obtain conductive metal silver. It is preferable to use inorganic halogen silver.
- silver halide preferably used in the present invention for example, silver halide mainly composed of AgCl, AgBr, and Agl is preferably used, and fine particles with high sensitivity are preferable in order to obtain highly conductive metal silver.
- Silver halides mainly composed of AgBr containing iodine or AgCl containing bromine are preferably used.
- the average grain size of the silver halide is preferably 1 to 1000 nm (l ⁇ m) in terms of a sphere equivalent diameter 1 to 1 and more preferably LOOnm.
- the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.
- the size of the halogenated silver particles is the temperature, pAg, particle size control agent, for example, 1-Ferru 5 mercaptotetrazole, 2 mercaptobenzimidazole, benztriazole, tetrazaindene compounds, at the time of preparing the halogenated silver particles.
- nucleic acid derivatives, thioether compounds, and the like can be used in appropriate combinations.
- the shape of the silver halide grains is not particularly limited.
- the shape is spherical, cubic, or flat (6 (Square plate, triangle plate, quadrilateral plate, etc.), octahedron, and tetrahedron.
- tabular grains having an aspect ratio of 2 or more, 4 or more, 8 or more, and 16 or less can be preferably used.
- the particle size distribution may be wide or narrow, but a narrow distribution is preferable in order to obtain high conductivity and increase the aperture ratio.
- the monodispersity known in the photographic industry is preferably 100 or less, and more preferably 30 or less. From the viewpoint of facilitating the flow of electricity, the larger the contact area between the generated particles, the better the shape of the particles.The flatter and the larger the aspect ratio, the better, but the larger the aspect ratio, the better the concentration. Aspect ratio exists.
- the halogenated silver used in the present invention may further contain other elements.
- metal ions such as rhodium ions, ruthenium ions, and iridium ions are preferably used because the difference between the exposed portion and the unexposed portion tends to occur clearly when a metallic silver image is formed.
- Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands.
- ligands examples include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, and hydroxide ions.
- Specific examples of the compound include potassium bromate rhodate and potassium iridate.
- the content of rhodium compound and Z or iridium compound contained in halogenated silver is 10- ⁇ to ⁇ — 2 moles relative to the number of moles of silver in the silver halide.
- Z mode it is preferable
- Lumpur is Ag tool 10- 9 ⁇ :! LO- and even more preferably is 3 mol / mol Ag / ,.
- silver halides containing Pd ions, Pt ions, Pd metals, and Z or Pt metals can also be preferably used.
- Pd and Pt are uniformly distributed in the silver halide grains, but it is preferable that they are contained in the vicinity of the surface layer of the silver halide grains.
- Te, content of Pd ion and / or Pd metal contained in the silver halide is a 10- 6 to 0.1 mol Z mol Ag with respect to the number of moles of silver in the silver halide More preferably, it is 0.01 to 0.3 mol Z mol Ag.
- chemical sensitization performed on a photographic emulsion can be performed to further improve sensitivity.
- chemical sensitization for example, noble metal sensitization such as gold, palladium, platinum sensitization, Chalcogen sensitization such as io sensitization by inorganic thio or organic thio compounds, reduction sensitization such as sodium chloride, hydrazine and the like can be used.
- Chemically sensitized halogen silver halide grains can be spectrally sensitized.
- Preferred examples of the spectral sensitizing dye include cyanine, force nolevocyanin, dicanolevoyanine, complex cyanine, hemisyanine, styryl dye, merocyanine, complex merocyanine, and holopolar monochromator.
- the spectral sensitizing dyes used can be used alone or in combination.
- Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
- any of nuclei usually used in cyanine dyes can be used as the basic heterocyclic nuclei.
- nuclei may be substituted on carbon atoms.
- Merocyanine dyes or complex merocyanine dyes have pyrazoline mononuclear nuclei, thiohydantoin nuclei, 2 thoxazolidine 2,4 dione nuclei, thiazolidine 2,4 dione nuclei, rhodanine nuclei as nuclei having a ketomethylene structure. 5 to 6-membered heterocyclic nuclei such as thiobarbituric acid nuclei can be applied.
- near-infrared sensitizing dyes when using near-infrared lasers in the exposure of silver and silver particles.
- These dyes can be referred to JP-A-2000-347343, JP-A-2004-037711 and JP-A-2005-134710. Particularly preferred specific examples are shown below.
- sensitizing dyes may be used alone or in combination.
- sensitizing dyes is often used for the purpose of supersensitization.
- sensitizing dyes in a silver halide silver emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl mouthsolve, 2, 2, 3, It may be dissolved in a solvent such as 3-tetrafluoropropanol alone or in a mixed solvent and added to the L agent. Also, as described in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22 089, etc., an acid or base is allowed to coexist to form an aqueous solution, or US Pat. No. 3,822,135. No. 4, 4, 006, 025, etc.
- aqueous solution or a colloidal dispersion in the presence of a surfactant such as sodium zensulfonate may be added to the emulsion.
- a substantially non-miscible solvent such as phenoxyethanol
- water or a hydrophilic colloid dispersion may be added to the emulsion.
- the dispersion may be directly dispersed in an lyophilic colloid and the dispersion may be added to the emulsion.
- the electromagnetic wave shielding film has an antireflection layer on the same support.
- the antireflection layer may be formed on a layer having a mesh-like metal part formed by exposing and developing a layer containing silver halide grains, but an antireflection layer is provided on the back side of the support. It is preferable. It has been found that the adhesive strength of the antireflection layer is increased by the surface treatment on the back side, and that the antireflection layer cannot be sufficiently smooth when formed on a layer having a mesh-like metal part. It depends.
- the layer having an antireflection function preferably comprises a high refractive index layer, a medium refractive index layer, and a low refractive index containing inorganic fine particles that are preferably composed of a plurality of light transmissive layers having different refractive indexes. More preferably, the rate layer force is also configured.
- the layers having different refractive indexes are adjusted according to the kind of inorganic fine particles contained therein, the particle diameter, the amount added, the kind of resin binder, and the like.
- the refractive index of the high refractive index layer is preferably 1.55-2.30, more preferably 1.57-2.20.
- the refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the base film and the refractive index of the high refractive index layer.
- the refractive index of the medium refractive index layer is preferably 1.55 to L80.
- the refractive index of the low refractive index layer is preferably 1.46 or less, particularly 1.3 to 1.45.
- each layer is preferably 5 nm to 0.5 ⁇ m, more preferably 10 nm to 0.3 ⁇ m, and even more preferably 30 ⁇ ! Most preferred is ⁇ 0.2 m.
- the haze of the metal oxide layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less.
- the strength of the metal oxide layer is preferably 3H or more in terms of lead writing hardness of 1 kg load, and most preferably 4H or more.
- the metal oxide layer is formed by coating, it preferably contains inorganic fine particles and a binder polymer.
- the inorganic fine particles used in the metal oxide layer such as the medium refractive index layer or the high refractive index layer are bent. Fracture power i. 80-2. 80 power is preferred, 1. 90-2. 80 power ⁇ more preferred! /,.
- the mass average diameter of the primary particles of the inorganic fine particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm.
- the mass average diameter of the inorganic fine particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, and even more preferably 10 to 100 nm. 10 to 80 nm It is most preferable to be. If the average particle size of the inorganic fine particles is 20-30 nm or more, it is measured by a light scattering method, and if it is 20-30 nm or less, it is measured by an electron micrograph. The specific surface area of the inorganic fine particles, a measured value by the BET method, it is further preferable that a 10 to 400 m 2 / g is preferred instrument 2 0 ⁇ 200m 2 / g instrument 30 to 150 m 2 / g Most preferably.
- the inorganic fine particles are particles formed from a metal oxide.
- metal oxides or sulfates include titanium dioxide (eg, rutile, mixed crystals of rutile Z anatase, anatase, amorphous structure), tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide. 2um and so on. Of these, titanium dioxide, tin oxide and indium oxide are particularly preferred.
- the inorganic fine particles are mainly composed of oxides of these metals and can further contain other elements.
- the main component means the component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.
- the inorganic fine particles may be surface-treated!
- the surface treatment can be performed using an inorganic compound or an organic compound.
- inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable.
- organic compound used for the surface treatment include polyols, alcohols, stearic acid, silane coupling agents and titanate coupling agents. Of these, a silane coupling agent is most preferable. It may be processed by combining two or more kinds of surface treatments.
- the shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a layer shape, a spindle shape, or an indefinite shape. Two or more types of inorganic fine particles may be used in combination in the metal oxide layer.
- the proportion of inorganic fine particles in the metal oxide layer is preferably 5 to 90% by volume.
- the amount is preferably 10 to 65% by volume, more preferably 20 to 55% by volume.
- the inorganic fine particles are used in a coating solution for forming a metal oxide layer in a state of dispersion in a medium.
- the dispersion solvent for the inorganic fine particles it is preferable to use a liquid having a boiling point of 60 to 170 ° C.
- dispersion solvent examples include water, alcohol (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester ( For example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, propyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), aromatic hydrocarbons ( For example, benzene, toluene, xylene), amide (for example, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (for example, jetyl ether, dioxane, tetrahydrated furan), ether alcohol (for example,
- the inorganic fine particles can be dispersed in the medium using a disperser.
- the disperser include a sand grinder mill (for example, a bead mill with a pin), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill.
- a sand grinder mill and a high speed impeller mill are particularly preferred.
- preliminary dispersion processing may be performed.
- Examples of a disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an etastruder.
- the metal oxide layer preferably uses a polymer having a crosslinked structure (hereinafter also referred to as "crosslinked polymer”) as a binder polymer.
- crosslinked polymer include crosslinked polymers such as a polymer having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as “polyolefin”), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin.
- polyolefin crosslinked product which is preferably a crosslinked product of polyolefin, polyether, and polyurethane, and a crosslinked product of polyolefin, more preferably a crosslinked product of polyether, is most preferable.
- the crosslinked polymer has a ionic group.
- ionic group There are no key-on groups It has a function of maintaining the dispersed state of the fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film.
- the anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but may be bonded to the main chain as a side chain via the linking group. Is preferred.
- the refractive index of the low refractive index layer used in the present invention is preferably 1.46 or less, particularly 1.3 to 1.
- the low refractive index layer can be formed by a sol-gel method using silicon alkoxide as the coating composition.
- a low refractive index layer can be formed by using fluorine resin.
- it is preferably composed of a cured material of a thermosetting or ionizing radiation curable fluorine-containing resin and ultrafine particles of silicon oxide.
- Silicon oxide ultrafine particles are composite particles having porous particles described later and a coating layer provided on the surface of the porous particles, or hollow particles filled with a solvent, gas, or porous substance inside. It is preferable.
- the dynamic friction coefficient of the cured product is 0.02-0.2, and the pure water contact angle is preferably 90 to 130 °.
- the curable fluorine-containing resin include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), fluorine-containing copolymer. And a compound (having a monomer having a crosslinkable group and a fluorine-containing monomer as structural units).
- the fluorine-containing monomer unit include, for example, hexafluoroethylene, hexafluoropropylene, tetrafluoroethylene, fluoroolefins (for example, bi-lidene fluoride perfluoro-2, 2 —Dimethyl-1,3-diquinol, fluoroethylene, etc.), fluorinated alkyl ester derivatives of (meth) acrylic acid (eg, Biscote 6FM (Osaka Organic Chemical), M-2020 (Daikin), etc.), fluorinated butyl ether Etc.
- the monomer having a crosslinkable group has a carboxyl group, amino group, hydroxyl group, sulfonic acid group, etc. in addition to a (meth) atrelate monomer having a crosslinkable functional group in the molecule in advance, such as glycidyl methacrylate.
- (Meth) acrylate monomers for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.
- JP-A-10-25388 and JP-A-10-147739 describe that a crosslinked structure can be introduced after copolymerization.
- a copolymer with a monomer having no fluorine atom which is only a polymer having the above-mentioned fluorine-containing monomer as a structural unit.
- acrylic esters methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate
- methacrylate esters methyl methacrylate, methyl methacrylate
- the fluorine-containing resin used for forming the low refractive index layer is preferably added with silicon oxide fine particles in order to improve scratch resistance.
- the amount added is adjusted by the balance between refractive index and scratch resistance.
- Silica silicate fine particles can be added to the coating composition as it is silica sol dispersed in a commercially available organic solvent, and there are some! /, which can be used by dispersing various commercially available silica powders in an organic solvent. it can.
- a layer having an antireflection function is first formed on a support and then a layer containing photosensitive silver halide grains is provided on the support, a layer having an antireflection function is provided. It was found that some of the inorganic fine particles contained in the film fall off and contaminate the coating production process to form a layer containing photosensitive silver halide grains, which can cause spot failure in the coating stripe o
- a layer having an antireflection function is first formed on a support by coating, and then exposed to an electromagnetic wave shielding film master provided with a layer containing photosensitive silver halide grains. It has been found that when a mesh-like metal part is formed by development processing, the antireflection function is significantly reduced, the haze value is increased and the translucency is lowered, or spot-like defects are generated. . This is because the inorganic fine particles, particularly silicon oxide fine particles contained in the layer having an antireflection function are dissolved in the alkaline environment of the developing solution, or the dispersion stability of the inorganic fine particles is lowered to cause aggregation. This is presumed to occur.
- the antireflection layer is generally applied using a non-aqueous organic solvent for the constituent material, charging of the support must be avoided in the application process. I have to. For this reason, it is necessary not only to have grounding equipment and explosion-proof measures, but also to apply at low speed. If a layer having a mesh-like metal portion is provided in advance as in the present invention, the support can be prevented from being charged almost at all, so that high-speed coating is possible.
- the electromagnetic wave shielding film of the present invention it is preferable to enhance the photographic gradation of the layer containing the halogenated silver particles.
- a method of narrowing the particle size distribution of halogenated silver particles there is a method of narrowing the particle size distribution of halogenated silver particles, and it is known to use a hydrazine compound or a tetrazolium compound as a high contrast agent for plate making.
- a hydrazine compound is a compound having an NHNH- group, and a typical one is represented by the following general 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.
- a linear or branched alkyl group preferably having a carbon number of 1 To 20 methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.
- alkoxy group preferably methoxy group having 2 to 21 carbon atoms, ethoxy group etc.
- aliphatic isylamino group preferably 2 to 21 carbon atoms
- substituted or unsubstituted aromatic rings such as —CONH—, —O—, and the like, can be mentioned, such as acetylamino groups, heptylamino groups, and the like.
- V is a hydrogen atom or 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, pyro group) Group).
- the 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 halogenated silver particle layer, in the hydrophilic colloid layer adjacent to the halogenated silver particle layer, or in another hydrophilic colloid layer.
- Particularly preferred hydrazine compounds are listed below.
- the hydrazine compound is particularly preferably one in which a sulfonamidophenol group is substituted as the T group and a trifluoromethyl group is substituted as the V group.
- the oxalyl group bonded to hydrazine is particularly preferably a piperidylamino group, although it may be substituted. Specific examples of tetrazolium compounds are shown below.
- T-1) 2, 3 Di (p-methylphenol) 5 phenol tetrazolium chloride
- ⁇ --2 2, 3 -Di ( ⁇ --ethyl chloride)-1 5 tetratetrazolium chloride
- hydrazine When hydrazine is used as a thickening agent, an amine compound or a pyridine compound is used to enhance the reduction action of hydrazine.
- a representative amine compound can be represented by the following general formula containing at least one nitrogen atom.
- R, Q, Z, and W in the formula represent an alkyl group having 2 to 30 carbon atoms that may be substituted. Further, these alkyl group chains may be bonded by a heteroatom such as nitrogen, sulfur, or oxygen. R and Z, or Q and W may form a saturated and unsaturated ring with each other.
- L represents a divalent linking group. This linking group may contain a hetero atom such as sulfur, oxygen, and nitrogen. The linking group of L can have 1 to 200 carbon atoms, 1 to 30 sulfur atoms, 1 to 20 nitrogen atoms and 1 to 40 oxygen atoms. Flower ,. Specific examples of these amine compounds are shown below.
- the amine compound that promotes the reducing action of the hydrazine compound includes at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds in the molecule. Is particularly preferred.
- pyridinium compounds and phosphonium compounds are used in addition to amine compounds. Since the oum compound is positively charged, it adsorbs to the negatively charged silver halide particles and removes it from the developing agent during development. It is considered that high contrast is promoted by promoting electron injection.
- pyridinium compounds reference can be made to the bispyridium compounds described in JP-A-5-53231 and JP-A-6-242534. Particularly preferred pyridinium compounds are those that are linked at the 1- or 4-position of the pyridinium to form a bispyridium! To salt!
- the hydrazine compound acts on the high-concentration contrast, the contrast of the legs is insufficient, and as an attempt to improve this, an oxidized form of the developing agent produced during development is used. You can use this technique.
- the presence of a redox compound that reacts with the oxidized oxidant of the developing agent increases the sharpness of the image by releasing an inhibitor that suppresses the strength of the compound. Oxidation of the developing agent is generated by the progress of development and is related to the reduction rate of the particles. It is preferable to use a good chemical sensitizer because this effect can be enhanced by forming a development nucleus having a high reduction rate with a chemical sensitizer. Using redox compounds sharpens the edges of the image, reducing the grain spacing and reducing the resistance of silver metal lines.
- Redox compounds have hydroquinones, catechols, naphthohydroquinones, aminophenols, virazolidones, hydrazines, reductones, etc. as redox groups.
- Preferred redox compounds are compounds having an NHNH group as a redox group, and those represented by the following general formula are typical.
- T and V represent a group having the same meaning as the hydrazine compound.
- PUG represents a photographically useful group, for example, 5-troindazole, 4-troindazole, 1-phenoltetrazole, 1- (3-sulfophenol) tetrazole, 5-trobenztriazole, 4 --- trobenzotriazole , 5--troimidazole, 4--troimidazole and the like. What are these development-inhibiting compounds? ⁇ 1?
- a heteroatom such as 3 at the 0 site, or further through an alkylene, phenylene, aralkylene, or aryl group represented by (Time) It can be connected through N or S heteroatoms.
- a hydroquinone compound having a ballast group into which development inhibitory groups such as triazole, indazole, imidazole, thiazole and thiadiaol are introduced can be used.
- Hidorajini ⁇ thereof, Amini ⁇ thereof, pyrid - ⁇ beam compounds, Tetorazoriumu compound and TOLEDO box compound Shi preferred is to 1 X 10- 6 ⁇ 5 X 10- 2 molar content per mole of silver halide ingredients particularly 1 X 10- 4 ⁇ 2 X 10- 2 mol is preferred. It is easy to increase the degree of contrast ⁇ to 6 or more by adjusting the amount of applied force of these compounds. ⁇ can be further adjusted by the monodispersity of the emulsion, the amount of rhodium used, chemical sensitization, and the like. Here, ⁇ is the density difference with respect to the difference between the exposure amounts giving the densities of 0.1 and 3.0.
- These compounds are used by being added to a layer containing halogenated particles or another hydrophilic colloid layer. If it is water-soluble, add it to an aqueous solution, and if it is water-insoluble, add it as a solution of an organic solvent that is miscible with water, such as alcohols, esters, and ketones, to a halogenated silver particle solution or a hydrophilic colloid solution. do it. Further, when it is not soluble in these organic solvents, it can be added as fine particles having a size of 0.01 to 10 m by a ball mill, sand mill, jet mill or the like. As the fine particle dispersion method, a solid dispersion technique of a dye as a photographic additive can be preferably applied.
- a desired particle size can be obtained by using a disperser such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill.
- a disperser such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill.
- a surfactant is used during dispersion, stability after dispersion can be improved.
- the silver halide grains are uniformly dispersed and the silver halide grains are supported on the support, and the silver halide grain-containing layer and the support are supported.
- a binder can be 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 the water-insoluble polymer is not limited.
- it is advantageous to use gelatin as a binder but if necessary, gelatin derivatives, gelatin and other high molecular weight graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, single or A hydrophilic colloid such as a synthetic hydrophilic polymer such as a copolymer can also be used.
- the amount of the binder in the layer containing the silver halide silver particles is not particularly limited, and an optimum value can be used from the viewpoints of coating properties, film properties, electromagnetic wave shielding performance, and the like.
- the AgZ binder volume ratio is set higher than that of a normal photographic silver halide silver photographic material.
- the binder content in the particle-containing layer is preferably 0.2 to: LOO in terms of AgZ binder volume ratio, more preferably 0.3 to 30, and 0.3. It is more preferable to be ⁇ 10! / ⁇ .
- a layer containing a near-infrared absorbing dye is provided for the purpose of shielding near-infrared rays.
- This near-infrared absorbing dye is used together with fine particles of water-dispersible thermoplastic resin or phosphate ester, in order to increase its near-infrared shielding effect, increase dispersion or dissolution stability, and increase stability over time.
- the water-dispersible thermoplastic resin used in the present invention is a thermoplastic resin coated at a drying temperature so that a film can be formed by heating and drying on a support.
- the drying temperature is usually between room temperature and about 100 ° C, and drying is performed at a temperature in this range.
- the water-dispersible thermoplastic resin used in the present invention is treated as a synonym for latex because it handles a resin that is stably dispersed in an aqueous medium.
- Latex refers to a white milky liquid that can also be used to absorb forces such as rubber wrinkles, but since the advent of emulsion polymers, polymeric substances, including aqueous dispersions of synthetic polymers, have been incorporated into aqueous media. Those that are stably dispersed are now called latus status, so this designation is used!
- water-dispersible thermoplastic resin examples include polysalt-vinylidene, salt-syl-vinylidene-acrylic acid copolymer, salt-syl-vinylidene-taconic acid copolymer, sodium polyacrylate, polyethylene Oxide, acrylic acid amide-acrylic acid ester copolymer, styrene Water maleic acid copolymer, acrylonitrile butadiene copolymer, vinyl chloride-vinyl acetate copolymer, and monomers containing carboxylic acid groups such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, or dimethylacrylamide Examples thereof include a styrene butadiene copolymer and a styrene monoisoprene copolymer using a small amount of one or a plurality of monomers having a sulfonic acid group such as propane sulfonic acid and styrene sul
- the above latex is widely used as a binder for aqueous coating, and among them, a latex that improves water resistance is preferable as a binder.
- the amount of latus used for the purpose of obtaining water resistance as a binder is a power determined in consideration of applicability.
- the point of moisture resistance The amount used is preferably as high as possible. 50% or more to the total binder mass 100% 80% or more and 100% or less are more preferred. Such a rosin can also be marketed.
- styrene resin is an industry standard product number of styrene-butadiene copolymer
- the styrene-butadiene copolymer preferably has a styrene / butadiene copolymer ratio (mass) force of S10Z90 to 90Z10, more preferably 20Z80 to 60Z40.
- a high styrene latex having a ratio of 60 to 40 to 90 to 10 is preferably used in combination with a low styrene content and (10 to 90 to 70) resin in order to increase the scratch resistance and physical strength of the photosensitive layer.
- the mixing ratio (mass) is preferably in the range of 20-80-80-20.
- Examples of high styrene latex include JSR0051 and 0061 (Nippon Synthetic Rubber Co., Ltd.) and Nipol 2001, 2057, 2007 (Nippon Zeon Co., Ltd.). It can be used. Latexes with a low styrene content include those commonly used other than those listed above as the high styrene latex, and include JSR # 1500, # 1502, # 1507, # 1712, and # 1778.
- acrylic latex generally known as acrylic resin, such as Nipol AR31, AR32 or Hycar 4021 (V, trade name of Nippon Zeon Co., Ltd.) can be used.
- acrylic resin a polymer or copolymer using the following acrylate monomer as a raw material can also be used.
- the (meth) atalyloyl group is used in the meaning of an atalyloyl group or a methallyloyl group.
- Monomers having one (meth) atallyloyl group in the molecule include methacrylic acid esters of methyl alcohol, methyl acrylate, ethyl acrylate, ethyl acrylate, Acrylate esters of aliphatic alcohols such as acrylate, butyl acrylate and octyl acrylate, acrylate esters of alicyclic alcohol such as cyclohexyl acrylate and cyclohexyl methyl acrylate, cyclohexyl methacrylate Acrylates containing aromatic groups such as methacrylic acid esters of alicyclic alcohols such as acrylate, cyclohexylmethyl methacrylate, phenol acrylate, 4-propyl acrylate, benzyl acrylate, benzyl methacrylate Acid ester, phenol methacrylate, 4-chloro Methacrylic acid esters containing aromatic groups such as ethyl metatalylate and benzyl me
- Monomers having two or more (meth) atalyloyl groups in the molecule include ethylene glycol diatalate, propylene glycol diatalate, diethylene glycol diatalate, 1,3 diacryloxy-2-propanol polyethylene glycol diatalate.
- Acrylic acid diesters such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 dimethacryloxy-2-propanol and other methacrylic acid diesters, glycerin tritalylate, trimethylol Acrylic acid triesters such as propane tritalylate, methacrylic acid such as glycerin trimetatalylate, trimethylolpropane trimetatalylate There are acid triesterol.
- styrene resin As styrene resin, styrene monomers such as methyl styrene, ethyl styrene, propylene styrene, butyl styrene, hexyl styrene, heptyl styrene, otachinol styrene, dimethyl styrene, trimethyl styrene, jetyl styrene, triethyl styrene Halogenostyrene monomers such as styrene styrene monomer, fluorostyrene, chlorostyrene, bromostyrene, styrene styrene, dibutyl styrene, Using monomers, acetyl styrene monomers, methoxy styrene monomers, etc., alone or copolymerized with
- bur resin examples include butyl pyridine, butyl pyrrolidone, bulur rubazole, butyl acetate, acrylonitrile, butyl chloride, butyl bromide, salt vinylidene, odorous vinylidene, and the like as monomers.
- it contains berylene or the like as a structural unit.
- a monomer having two or more vinyl groups in the molecule may be included as a structural unit.
- conjugated genomers such as dibutylbenzene, butadiene, and black-opened plane, isoprene adipate divininole, divinyl sulfone, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol dibule ether, and the like.
- these monomers can be emulsion-polymerized as described above.
- the water-soluble polymerization initiator used in this emulsion polymerization any one can be selected. Examples thereof include 2, 2′-azobis (2 methylpropionamidine) dihydrochloride, 4, 4 ′ azobis (4 Shianoyoshi). Herbic acid), 2, 2'-azobis [2- (2-imidazoline-2-yl) propane] dihydrochloride, 2,2'-azobis [2-(5-methyl-2-imidazoline-2-yl) propane] 2 And hydrochloride, 2,2′-azobisisobutyramide dihydrate, and the like.
- the amount of the water-soluble polymerization initiator is from 001 to 0.5 mole 0/0 preferably 0. for all the monomers.
- the dispersant used in the emulsion polymerization is appropriately used to stabilize the system.
- the dispersion stabilizer or dispersant include polybulal alcohol, polybulurpyrrolidone, polyacrylamide, polymethacrylamide, hydroxyalkyl acrylate polymer, hydroxyalkyl methacrylate polymer, polyacrylic acid or a salt thereof, polymethacrylic acid or Its salt, ethylene acrylic acid copolymer or its salt, ethylene-methacrylic acid copolymer or its salt, ethylene maleic acid copolymer or its salt, styrene attalic acid copolymer or its salt, styrene-methacrylic acid copolymer Polymer or salt thereof, polyethyleneimine, polyalkylene glycol, polyalkylene oxide, methylolated polyamide, water-soluble melamine resin, water-soluble phenol resin, water-soluble urea resin, casein, gelatin, canoleboximethylol Norerozu
- the dispersant is preferably used in an amount of 0.01 to 20% by mass based on the total amount of monomers to be used or the total amount of rosin to be dispersed.
- the surfactant used in the emulsion polymerization is not particularly limited as long as it does not adversely affect the polymerization reaction, and is a cation surfactant, cationic surfactant, zwitterionic surfactant or nonionic surfactant. Any surfactant can be used.
- the surfactant is based on the total amount of the monomers used or the total amount of the resin to be dispersed.
- the water-dispersible thermoplastic resin according to the present invention is preferably used together with gelatin at a mixing mass ratio of 1: 2 to 10: 1.
- gelatin When used in combination with gelatin, it becomes possible to simultaneously coat the halogen-containing silver particle-containing layer, and the productivity is remarkably improved. If the mass ratio of gelatin used is large, the deterioration of moisture resistance will be large and the coating will not be uniform.
- phosphate ester compound is used instead of water-dispersible thermoplastic resin
- the product can be used by dispersing fine particles in gelatin.
- the average particle size of the phosphoric acid ester compound is ⁇ ! Dispersing the phosphoric acid ester compound in an ester organic solvent such as ethyl acetate, adding a nonionic or ionic surfactant, and dispersing it in gelatin. can do.
- a non-ionic or ionic surfactant used here a surfactant of the type used for emulsion polymerization of water-dispersible thermoplastic resin can be applied.
- a highly efficient homogenizer, ultrasonic dispersion, supersonic jet dispersion, etc. can be used to disperse as fine particles.
- Examples of the phosphoric acid ester compound include those obtained by esterifying phosphoric acid with an aliphatic alcohol, aromatic alcohol, or mixed alcohol thereof, and condensed esters obtained by condensing two or more dialkyl or diaryl phosphoric acid esters. be able to. Specific examples include trioctyl phosphate ester, tridodecyl phosphate ester, triphenyl phosphate ester, tricresyl phosphate ester, tri p-methylphenyl phosphate ester, and the like.
- near-infrared absorbing dyes include polymethine series, phthalocyanine series, naphthalocyanine series, metal complex series, aminium series, imonium series, dimonium series, anthraquinone series, dithiol metal complex series, naphthoquinone series, indole phenol , Azo and triarylmethane compounds.
- Near-infrared absorptivity is required for optical filters for PDP mainly for heat ray absorption and noise prevention of electronic devices.
- a metal complex-based, amino-based, phthalocyanine-based, naphthalocyanine-based, dimethyl-containing pigment having a maximum absorption wavelength of 750-: LlOOnm is preferred.
- a sulfur system and a smutium compound system are particularly preferable.
- the absorption maximum of a conventionally known nickel dithiol complex compound or fluorinated phthalocyanine compound is 700 to 900 nm, and in practical use, it usually absorbs in a longer wavelength region than the above compound.
- An effective near-infrared absorption effect can be obtained by using in combination with an aminium-based compound having a maximum, particularly a diimonium-based compound.
- dimo-um compounds are IRG-022, IRG-040 (these are trade names manufactured by Nippon Gyaku Co., Ltd.), nickel dithiol complex compounds, SIR—128, SIR—130, SIR—132, SIR—159, SIR—152, SIR—162 (these are trade names manufactured by Mitsui Engineering Co., Ltd.), phthalocyanine compounds are IR-10, IR — Commercially available products such as 12 (above, Nippon Shokubai Co., Ltd. trade name) can be used.
- the near-infrared absorbing dyes are alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl ether and toluene. It is preferable to use it as a fine particle having an average particle size of 0.01 to 10; ⁇ ⁇ by using a micronizing machine described later.
- the optical density is a maximum wavelength from 0.05 to 3. It is preferably used in the range of 0 concentration.
- any one of the above dyes may be contained, or two or more kinds may be contained. It is preferable to use UV absorbers to avoid deterioration of near-infrared absorbing dyes by UV rays.
- ultraviolet absorber known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S triazine compounds, and cyclic imino ester compounds 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.
- the method for producing an electromagnetic wave shielding film of the present invention it is preferable to provide a layer containing photosensitive halogen silver halide grains after providing a layer having a near infrared absorption function on a support. Or it is preferable to provide simultaneously the layer which has a near-infrared absorption function, and the layer containing a photosensitive halogenated silver particle on a support body.
- the silver Z binder volume ratio of the layer containing photosensitive halogen-silver particles is considerably high. Moreover, it is also the force which discovered that high-speed application
- a cellulose ester film for example, a polyester film, a polycarbonate film, a polyarylate film, a polysulfonate (including polyethersulfone) film, polyethylene terephthalate, polyethylene Polyester film such as phthalate, polyethylene film, polypropylene film, cellophane, cenorelose diacetate vinylome, cenorelose acetate butyrate film, poly (vinylidene chloride) film, polyvulcoalcohol film, ethylene vulcoal film, syndicate Otactic polystyrene film, polycarbonate film, norbornene resin film, polymethylpentene film, polyetherketone film It is possible to use a film, a polyether ketone imide film, a polyamide film, a fluorine resin film, a nylon film, a polymethyl methacrylate film or an acrylic film.
- cellulose triacetate film polycarbonate film, polysulfone (including polyethersulfone) and polyethylene terephthalate film are preferably used.
- a cellulose ester film as the support from the viewpoints of transparency, isotropicity, adhesiveness, and the like.
- the electromagnetic wave shielding film of the present invention is used for a display screen of a display, high transparency is required. Therefore, it is desirable that the support itself has high transparency.
- the average transmittance of the plastic film or glass plate in the entire visible light region is preferably 85 to: LOO%, more preferably 90 to: LOO%.
- the color tone regulator a plastic film or glass plate colored to such an extent that the object of the present invention is not hindered can be used.
- the average transmittance in the visible light region is obtained by integrating the transmittances of the visible light castle obtained by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm. Defined as the average value.
- an embodiment in which the average transmittance in the visible light region is 85% or more is preferable, more preferably 88% or more, and still more preferably 90% or more.
- the thickness of the support used in the present invention is not particularly limited. From the viewpoint of sex, it is preferably 5 to 200 m, more preferably 30 to 150 / ⁇ ⁇ .
- the support used in the present invention may be subjected to a hydrophilic treatment on the surface, or an undercoat layer or the like may be applied to various supports before applying a halogenated silver layer or the like, if necessary. I prefer that.
- Various methods are conventionally known as a method for applying a halogenated silver particle layer, a near infrared absorbing dye layer, and an antireflection layer in the present invention.
- dip coating method, blade coating method, air knife coating method, wire bar coating method, gravure coating method, reverse roll coating method, slot type coating method, slide hopper coating method, slot type curtain coating method, slide type curtain coating method Laws are known.
- these coating methods in order to obtain a uniform dry film thickness with high accuracy in the width direction of the substrate, pay attention to the coating film thickness accuracy and uniformity during coating (after coating and before drying), Applying.
- a coating apparatus having a flow rate regulation die is particularly capable of high-speed, thin-film, high-precision, multi-layer simultaneous coating, and photographic photosensitive material, ink jet recording material, It is widely used as a coating device for magnetic recording materials.
- the slide hopper type coating device and the slide type curtain coating device can be used for simultaneous multi-layer coating, and the productivity can be significantly improved by simultaneously coating the layers containing halogen silver and silver particles and the layer containing near-infrared absorbing dye. It becomes possible.
- the slot-type coating device is also a coating device having a die, and high-precision coating can be performed by using this method.
- the coating liquid sent to the die from the liquid feeding pump enters a liquid pool called a pocket extending in the width direction, and this force also has a uniform thickness in the coating width direction.
- the liquid is pushed out of the narrow slit, flows down the slide surface, forms a coating liquid reservoir called a bead between the slide surface tip and the continuously running support, and the coating is performed through this bead.
- a pressure reducing chamber is provided at the bottom of the bead for bead stabilization. The negative pressure is maintained so as to be formed constantly.
- the coating liquid force slit force extruded with a uniform film thickness in the width direction is pushed out, and a bead is formed directly with the traveling support, and the coating is performed via this bead. Is done.
- a decompression chamber is installed below the bead as needed to stabilize the bead.
- the coating solution may be dried by various drying methods and then wound up, or may be directly transported to the next step.
- the silver halide grain-containing layer provided on the support is exposed in order to form a conductive pattern by the development / reinforcement process described later.
- the light source used for the exposure for example, an embodiment using a strong ultraviolet ray or near infrared ray, which includes light such as visible light and ultraviolet light, and radiation such as electron beam and X-ray, is preferable. Further, a light source having a wavelength distribution may be used for the exposure, or a light source having a narrow wavelength distribution may be used.
- the visible light various light emitters that emit light in the spectral region are used as necessary.
- a red light emitter, a green light emitter, or a blue light emitter may be used alone or in combination.
- the spectral region is not limited to the above-mentioned red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used.
- mercury lamp g-line and mercury lamp i-line are also used.
- the exposure in the present invention includes 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 monochromatic high-density light can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F laser, or the like can also be used.
- 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.
- SHG second harmonic generation light source
- exposure is preferably performed using a semiconductor laser.
- the laser light source specifically, an ultraviolet semiconductor, a blue semiconductor laser, a green semiconductor laser, a red semiconductor laser, a near infrared laser, and the like are preferably used.
- the method of exposing the silver halide grain-containing layer to an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam.
- exposure methods such as surface contact exposure, near field exposure, reduced projection exposure, and reflection projection exposure may be used, such as condensing exposure using a lens or reflection exposure using a reflecting mirror.
- the output of the laser may be about several tens of ⁇ W to 5 W, as long as it is an amount suitable for sensitizing the silver halide.
- hydroquinones such as hydroquinone, sodium hydroquinone sulfonate, chlorohydroquinone, etc.
- 1-phenol 3-virazolidone 1-phenyl-1,4-dimethyl-1,3-virazolidone as developing agents. It can be used in combination with bisazolidone such as 1-phenyl-4-methyl-4-hydroxymethyl-3 virazolidone, 1-phenyl-4-methyl-3 virazolidone, and superadditive developing agents such as N-methylparaaminophenol sulfate.
- a reductone compound such as ascorbic acid or isoascorbic acid in combination with the superadditive developing agent without using hydroquinone.
- sodium sulfite salt or potassium sulfite salt as a preservative sodium carbonate salt or potassium carbonate salt as a buffering agent, diethanolamine, triethanolamine, or jetylamino as a development accelerator in a development processing solution.
- Propanediol or the like can be used as appropriate.
- the development processing solution used in the development processing according to the present invention may contain an image quality improving agent for the purpose of improving the image quality.
- the image quality improver include nitrogen-containing heterocyclic compounds such as 1-phenol-15-mercaptotetrazole and 5-methylbenzotriazole.
- the development processing performed after exposure may include physical development before fixing!
- the pre-fixing physical development is a process for reinforcing developed silver by supplying silver ions other than the inside of the halogen-containing silver particles having a latent image by exposure before the fixing process described later. Indicates.
- a specific method for supplying silver ions from the developing solution for example, a method in which silver ion-silver complex ion silver nitrate is previously dissolved in the developing solution as described in the physical development described later, Alternatively, a halogenated silver solvent such as sodium thiosulfate or ammonium thiocyanate is dissolved in the developing solution, and the unexposed portion of the halogenated silver is dissolved during development, so that a halogenated silver particle having a latent image is obtained. The method of supplementing the development of this.
- a fixing treatment is performed for the purpose of removing and stabilizing the unexposed portions of the silver halide grains.
- the fixing solution used in a photographic film or photographic paper using halogen silver halide grains can be used.
- the fixing solution used in the fixing process according to the present invention is a fixing agent.
- sodium thiosulfate potassium thiosulfate, ammonium thiosulfate, or the like can be used.
- As a hardening agent for fixing aluminum sulfate, chromium sulfate, or the like can be used.
- sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing solution can be used, and in addition, citrate, oxalic acid and the like can be used.
- N-methyl-isothiazole-3-one N-methyl-isothiazol-5-chloro-3-one, N-methyl-isothiazole- 4,5-Dichloro-3-one, 2-Nitroe 2-Bromue 3-hydroxypropanol, 2-Methyl-4-chlorophenol, hydrogen peroxide, etc. can be used.
- the intensifying process it is preferable to perform the intensifying process in order to assist the contact between the developed silvers formed by the above-described developing process and increase the conductivity.
- the auxiliary treatment The term ⁇ process '' refers to a process of increasing the conductivity by supplying a conductive material source not contained in the silver halide photosensitive material from the outside during the development process or after the process.
- a specific method For example, physical development or plating treatment can be exemplified.
- the case where the developed silver where the development start point of physical development is only the latent image nucleus becomes the physical development start point is also defined as physical development, and this can be preferably used.
- various conventionally known plating methods can be used for the plating treatment used as the intensifying treatment.
- electrolytic plating and electroless plating are carried out singly or in combination. Can do.
- electrolytic plating with excellent selectivity for plating metal, adjustment of plating speed, and plating strength can be preferably used in the present invention.
- a metal that can be used for plating for example, copper, nickel, conoleto, tin, silver, gold, platinum, and other various alloys can be used. It is particularly preferable to use a copper electrolytic plating from the viewpoint of relatively easy plating and high conductivity.
- the intensifying process can be performed at any time during development, after development, before fixing, or after fixing process. However, from the viewpoint of maintaining high transparency of the film, after the fixing process. Preferred is the mode of implementation.
- Oxidation treatment allows unnecessary metal components to be ionized and dissolved and removed, and the transmittance of the film can be further increased.
- a lattice-like fine line pattern is drawn by exposure, and then subjected to development processing or the like to conduct electricity.
- An embodiment in which a sex mesh pattern is formed is preferable.
- the conductive metal portion preferably has a line width of 20 m or less and a line interval of 50 m or more. Conductive metal parts such as earth connections For purposes, the line width may have a portion wider than 20 m. From the viewpoint of making the image inconspicuous, it is preferable that the line width of the conductive metal portion is less than 18 m.
- the thickness of the wire is preferably from 0.05 to 30 111, more preferably from 0.1 to 20 111, and more preferably from 0.1 to LO / z m force S.
- the visible light transmittance of a portion without a fine line in the lattice-like mesh pattern is 70% or more in order to impart high transparency and high! Electromagnetic wave shielding performance. 80% or more is more preferable, and 90% or more is particularly preferable. In measurement, it is necessary to make the measurement parameter sufficiently larger than the mesh pattern pitch described above, and it is preferable to measure at least 100 times larger than the mesh area of the mesh.
- the conductive metal part of the present invention has an aperture ratio of preferably 85% or higher, more preferably 90% or higher, and more preferably 95% or higher from the viewpoint of visible light transmittance. Is most preferred.
- the aperture ratio is the percentage of the mesh without fine lines. For example, the aperture ratio of a square mesh with a line width of 10 ⁇ m and a pitch of 200 ⁇ m is 90%.
- the visible light transmittance of the opening is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.
- the sample 101 was obtained using a laser beam with an oscillation wavelength of 440 nm (manufactured by Nichia Corporation). After performing mesh exposure using a blue semiconductor laser diode), development is performed at 25 ° C for 60 seconds using the following developer, and fixing treatment is further performed at 25 ° C for 120 seconds using the following fixer. And then washed with water. In the obtained sample 101, a mesh-like lattice pattern as a metallic silver image was formed.
- Titanium dioxide (primary particle mass average particle size: 50 nm, refractive index: 2.70) 30 parts by mass, cation diatalate monomer (PM21, Nippon Kayaku Co., Ltd.) 4.5 parts by mass, Cationic methacrylate monomer (DMAEA, manufactured by Kojin Co., Ltd.) 0.3 parts by mass and 65.2 parts by mass of methyl ethyl ketone were dispersed by a sand grinder to prepare a titanium dioxide diacid dispersion.
- cation diatalate monomer PM21, Nippon Kayaku Co., Ltd.
- Cationic methacrylate monomer (DMAEA, manufactured by Kojin Co., Ltd.) 0.3 parts by mass and 65.2 parts by mass of methyl ethyl ketone
- the ratio of the above titanium dioxide dispersion and the mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate D PHA, Nippon Kayaku Co., Ltd.
- D PHA dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate
- the amount was adjusted so as to be the refractive index of the refractive index layer, stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter having a pore diameter of 0.4 m to prepare a coating solution for a high refractive index layer.
- silica dispersion of silica fine particles with an average particle size of 15nm (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.) 3g silane coupling agent (KBM-503, Shin-Etsu Silicone Co., Ltd.) 3g and 0.1MZL hydrochloric acid 2g
- silane coupling agent KBM-503, Shin-Etsu Silicone Co., Ltd.
- 0.1MZL hydrochloric acid 2g 200g silica dispersion of silica fine particles with an average particle size of 15nm
- silane coupling agent KBM-503, Shin-Etsu Silicone Co., Ltd.
- photopolymerization initiator (Irgacure 907, manufactured by Ciba-Gaigi Co., Ltd.) 1.02 g and photosensitizer (Cacure 1 DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.51 g were dissolved in 772.85 g of isopropyl alcohol. Further, 25.6 g of a mixture of dipentaerythritol pentaatarylate and dipentaerythritol hexatatalylate (DPHA, Nippon Kayaku Co., Ltd.) was added and dissolved. 67.23 g of the resulting solution was added to the above dispersion, a mixture of isopropyl alcohol and diacetone alcohol. The mixture was stirred for 20 minutes at room temperature and filtered through a polypropylene filter having a pore size of 0.4 m to prepare a coating solution for a low refractive index layer.
- photopolymerization initiator (Irgacure 907
- a sample 102 was manufactured in the order of application opposite to that of the sample 101. That is, on the polyethylene terephthalate (PET) film that has been subjected to undercoating, the antireflection layer is successively applied by a slot type coating apparatus and dried, and then the silver halide grain-containing layer is slid to the opposite side of the support. Coating was performed using a hopper type coating apparatus, and exposure and development processes were performed to form an electromagnetic wave shielding layer having a mesh-like metal lattice pattern. in this way Thus, an electromagnetic wave shielding film sample 102 having an antireflection layer was produced.
- PET polyethylene terephthalate
- Each sample prepared by the above method was evaluated for electromagnetic wave attenuation effect, transparency, and spot failure on the film surface by the following method.
- the silver image area was heated with an infrared pulsed semiconductor laser (Frankfurt, pulse width 10 msec) with a wavelength of 800 to 870 nm and an output of 50 W.
- the electromagnetic wave attenuation effect was measured by the Kansai Electronics Industry Promotion Center (KEC method). ), The electromagnetic wave attenuation effect was measured, and the electromagnetic wave attenuation effect (dB) at 100 MHz was compared.
- the transparency was evaluated by a visual relative evaluation, which was evaluated according to three levels: good, slightly cloudy, and clear cloudy.
- the number of spot failures on the film surface as a product was evaluated by the number of visual observations per 10 cm2. Evaluation criteria were as follows.
- the antireflection layer is excellent in transparency, is highly resistant to spot failures, has high antireflection properties, and does not generate cracks. Recognize.
- sample 101 Compared to sample 102, sample 101 had a smaller charge and grounding was found to be effective. It turns out that it is the outstanding manufacturing method which can reduce the load to a production process.
- a 5 L three-necked flask was charged with 300 g of deionized water, 25 g of methyl methacrylate (MMA), 25 g of styrene, 45 g of ethyl acrylate (EA), 5 g of hydroxyethyl methacrylate HHEMA, and 250 mg of ammonium persulfate.
- the mixture was stirred at 100 ° C for 3 hours while bubbling with nitrogen to obtain an acrylic resin (AC) aqueous dispersion.
- AC acrylic resin
- lOOmg of hydroquinone was added to obtain a thermoplastic resin aqueous dispersion.
- an immonium-based near-infrared absorbing dye (I 2) in a fine solid state dispersion of lOOnm or less was added, and after stirring for 1 hour, a 2% by weight aqueous solution of gelatin was further added, and a near-infrared absorbing dye.
- the coating solution was 1.
- a near-infrared absorbing dye coating liquid 2 was prepared by adding a solid near-infrared absorbing dye (1-2) in a fine particle solid dispersion of lOOnm or less.
- the near-infrared absorbing dye was dispersed in the same manner as in the preparation of the near-infrared absorbing dye coating solution 1.
- Example 2 As the support, the same undercoated polyethylene terephthalate film as in Example 1 was used, and the amount of the immo-based near-infrared dye (1-2) was 0. Thus, near-infrared absorbing dye coating solutions 1 and 2 were applied using a slide hopper type coating device, respectively, to obtain samples 201 and 202.
- the near-infrared absorbing dye coating solutions 1 and 2 and the same silver halide particle-containing coating solution as in Example 1 were used, using a slide hopper type coating device, and the lower layer was a near-infrared absorbing dye layer, Samples 203 and 204 were prepared by simultaneous multilayer coating so that the upper layer was a layer containing a silver halide silver particle.
- Example 1 Samples 201 to 204 were exposed and developed in the same manner as in Example 1 to form a mesh-like metal lattice pattern. Then, a coating solution for the antireflection layer was prepared in the same manner as in Example 1, and applied to the back side of the support in the same amount as in Example 1. [0193] On the same undercoated polyethylene terephthalate film as in Example 1, the same halogen-silver particle-containing coating solution as in Example 1 was made to have a silver coating amount force S 10g Zm 2 (gelatin coating amount lg Zm 2 ).
- Example 2 After applying to the sample and exposing and developing in the same manner as in Example 1 to form a mesh-like metal lattice pattern, the above-mentioned near-infrared absorbing dye coating solutions 1 and 2 are applied to the sample, respectively. 205 and 206 were produced. Then, a coating solution for the antireflection layer was prepared in the same manner as in Example 1, and coated on the back side of the support in the same amount as in Example 1.
- Evaluation of stability over time was expressed as the percentage of deterioration of the absorption maximum after standing for 200 hours at a temperature of 70 ° C and a relative humidity of 90%.
- Table 2 shows the contents of the fabricated samples and the evaluated performance results.
- Light resistance deterioration test using Suga Test Instruments Co., Ltd. Super Xenon Weather Meter SX75, 50% relative humidity, and evaluated the rate of absorption degradation of irradiation intensity 50WZm 2, 100 hours after the test. The smaller the value, the higher the stability.
- aqueous gelatin solution was added to the coating solution containing the halogenated silver particles in Samples 203 and 204 of Example 2, and the silver coating amount was 1. Og / m 2 and the gelatin coating amount was 0.2 g / m 2 (silver / Samples 301 and 302 were prepared in the same manner except that the gelatin volume ratio was 0.64).
- the following physical development was performed continuously. The solution was subjected to physical development at 25 ° C. for 5 minutes and then washed with water. Then, the following copper plating solution was subjected to electrolytic plating at 2.5 AZcm 2 at 25 ° C. for 5 minutes and washed with water.
Landscapes
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Laminated Bodies (AREA)
Abstract
This invention provides a method for manufacturing an electromagnetic wave shielding film with high productivity, and an electromagnetic wave shielding film having a high electromagnetic wave shielding function, an excellent antireflection function, and a high near infrared light absorption function. The electromagnetic wave shielding film can be manufactured by a method characterized by comprising providing an original plate for an electromagnetic wave shielding film, comprising a layer containing photosensitive silver halide particles provided on a support, exposing and developing the original plate to form a meshy metal part, and then coating a layer having an antireflection function.
Description
明 細 書 Specification
電磁波遮蔽フィルムの製造方法、及び電磁波遮蔽フィルム Method for manufacturing electromagnetic shielding film, and electromagnetic shielding film
技術分野 Technical field
[0001] 本発明は、携帯電話、電子レンジ、 CRT及びフラットパネルディスプレイなどの電 子機器から発生する電磁波を遮蔽する電磁波遮蔽フィルムの製造方法、その製造 方法により得られる電磁波遮蔽フィルムに関する。 TECHNICAL FIELD [0001] The present invention relates to a method for producing an electromagnetic wave shielding film that shields electromagnetic waves generated from electronic equipment such as a mobile phone, a microwave oven, a CRT, and a flat panel display, and an electromagnetic wave shielding film obtained by the production method.
背景技術 Background art
[0002] 近年、電子機器の使用増大のために電磁波障害 (EMI)を低減する必要性が高ま つている。 EMIは電子、電気機器の誤動作、障害の原因になる他、人体に対しても 害を与えることが指摘されている。このため、電子機器では電磁波放出の強さを規格 または規制内に抑えることが要求されて 、る。 In recent years, there is an increasing need to reduce electromagnetic interference (EMI) due to increased use of electronic devices. It has been pointed out that EMI can cause malfunctions and failures of electronic and electrical equipment, as well as harm the human body. For this reason, electronic devices are required to keep the intensity of electromagnetic wave emission within the standards or regulations.
[0003] 特にプラズマ表示パネル (PDP)は、希ガスをプラズマ状態にして紫外線を放射さ せ、この光線で蛍光体を発光させる原理に基づくために原理的に電磁波を発生する 。また、このとき近赤外線も放射されるので、リモコン等の操作素子の誤動作を引き起 こすので電磁波遮蔽能と同時に近赤外線の遮蔽も求められている。 [0003] Particularly, a plasma display panel (PDP) generates electromagnetic waves in principle because it is based on the principle that a rare gas is made into a plasma state to emit ultraviolet rays and phosphors emit light with this light beam. In addition, near infrared rays are also emitted at this time, so that malfunction of operation elements such as a remote controller is caused.
[0004] 電磁波遮蔽能は簡便には表面抵抗値で表すことができ、 PDP用の透光性電磁波 遮蔽フィルムでは 10 ΩΖ口以下が要求され、 PDPを用いた民生用プラズマテレビに おいては 2 ΩΖ口以下とする必要性が高ぐより望ましくは 0. 2ΩΖ口以下という極 めて高 、導電性が要求されて 、る。 [0004] The electromagnetic wave shielding ability can be simply expressed by the surface resistance value, and the translucent electromagnetic wave shielding film for PDP is required to be 10 Ω or less. In consumer plasma televisions using PDP, 2 It is more necessary to set the impedance to Ω or less, and it is desirable that the conductivity is extremely high, preferably 0.2 Ω or less.
[0005] このような高い電磁波遮蔽性を達成するために、いくつかの方法がこれまで提案さ れている。例えば、開口率の高い金属メッシュを焼き付けた硝子板に赤外線吸収フィ ルムを貼付して作製すると!、う方法は金属メッシュの焼き付けの製造工程が煩雑、且 つ複雑で生産に熟練度が要求され、また工程時間が長くかかるという問題点があつ た。ハロゲンィ匕銀粒子カゝら得られる現像銀は金属銀であることから、写真現像を応用 した製法で金属銀のメッシュを作製することが考えられて 、る。ハロゲンィ匕銀粒子を 含む層を有する感光材料をメッシュ状に露光して現像処理すれば、銀粒子がメッシュ 状に集合した導電性金属銀部が形成される (例えば、特許文献 1参照。 ) o
[0006] また、 PDPに要求される他の機能として、外光の反射防止のための反射防止層、 近赤外線遮蔽のための近赤外線吸収層、色バランス補正のための色調補正層など があるが、従来はそれぞれの機能性フィルターを個別に生産し、貼り合わせる方式で 行われてきたため、製造工程が煩雑、且つ複雑で生産に熟練度が要求され、またェ 程時間が長くかかるなどの問題点があった。 In order to achieve such high electromagnetic shielding properties, several methods have been proposed so far. For example, when an infrared absorbing film is applied to a glass plate baked with a metal mesh having a high aperture ratio, the manufacturing method of the metal mesh baking is complicated and complicated, and skill is required for production. In addition, there is a problem that it takes a long process time. Since the developed silver obtained from the halogenated silver particles is metallic silver, it is conceivable to prepare a metallic silver mesh by a manufacturing method applying photographic development. When a photosensitive material having a layer containing silver halide silver particles is exposed in a mesh shape and developed, a conductive metal silver portion in which silver particles are gathered in a mesh shape is formed (see, for example, Patent Document 1). [0006] Other functions required for the PDP include an antireflection layer for preventing reflection of outside light, a near infrared absorption layer for shielding near infrared rays, and a color tone correcting layer for correcting color balance. However, since each functional filter has been produced separately and pasted together, the manufacturing process is complicated, complicated and requires skill in production, and takes a long time. There was a point.
[0007] 従って、単一の支持体上に上記の各機能層を統合することによって、この問題を解 決しようと 、う検討がされてきて 、る。 [0007] Therefore, studies have been made to solve this problem by integrating the above functional layers on a single support.
[0008] し力しながら、各機能層ごとに物理的化学的な性質や特性が異なるために、単純に 統合しょうとすると機能の低下を引き起こしてしまったり、製造工程に多大な負荷をか けてしまうことがわかった。 [0008] However, since the physical and chemical properties and characteristics of each functional layer are different, simple integration may cause functional degradation or a heavy load on the manufacturing process. I understood that.
[0009] 例えば、ハロゲン化銀粒子を含む層は形成されたメッシュ状パターンの導電性を高 くするためにバインダーに対する銀の比率を高くする必要があるために、塗布条件の 制約が大きいこと、反射防止層はその構成力も非水系有機溶剤を用いた塗布になる こと、近赤外線遮蔽層は疎水性可塑剤に分散させる試み (例えば、特許文献 2参照。 )があるが、ハロゲンィ匕銀粒子を含む層に近接させることが困難であることなど、却つ て生産性を低下させる要因となっている。 [0009] For example, a layer containing silver halide grains needs to have a high ratio of silver to a binder in order to increase the conductivity of the formed mesh pattern, so that there are large restrictions on coating conditions. The antireflection layer can be applied using a non-aqueous organic solvent, and the near-infrared shielding layer has been tried to be dispersed in a hydrophobic plasticizer (see, for example, Patent Document 2). In other words, it is difficult to make it close to the layers it contains, which is a factor that reduces productivity.
特許文献 1 :特開 2004— 221564号公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2004-221564
特許文献 2 :特開 2005— 099820号公報 Patent Document 2: JP 2005-099820 A
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0010] 本発明の目的は、生産性の高 、電磁波遮蔽フィルムの製造方法、該製造方法で 製造された高い電磁波遮蔽機能、優れた反射防止機能、そして高い近赤外線吸収 機能とを有する電磁波遮蔽フィルムを提供するものである。 An object of the present invention is to provide an electromagnetic shielding film having high productivity, a method for producing an electromagnetic shielding film, a high electromagnetic shielding function produced by the production method, an excellent antireflection function, and a high near infrared absorption function. A film is provided.
課題を解決するための手段 Means for solving the problem
[0011] 本発明の上記目的は、下記構成により達成される。 The above object of the present invention is achieved by the following configuration.
[0012] 1.支持体上に感光性ハロゲンィ匕銀粒子を含む層を設けた電磁波遮蔽フィルム用 原版に露光、現像処理することでメッシュ状の金属部を形成させた後、反射防止機 能を有する層を塗布形成することを特徴とする電磁波遮蔽フィルムの製造方法。
[0013] 2.前記反射防止機能を有する層が電磁波遮蔽機能を有する層の支持体裏面に 形成されることを特徴とする前記 1に記載の電磁波遮蔽フィルムの製造方法。 [0012] 1. An anti-reflective function is obtained after forming a mesh-like metal part by exposing and developing an original plate for an electromagnetic wave shielding film in which a layer containing photosensitive halogen silver halide particles is provided on a support. A method for producing an electromagnetic wave shielding film, comprising coating and forming a layer having the same. [0013] 2. The method for producing an electromagnetic wave shielding film as described in 1 above, wherein the layer having an antireflection function is formed on a back surface of a support having a layer having an electromagnetic wave shielding function.
[0014] 3.前記反射防止機能を有する層が無機微粒子を含有した屈折率の異なる複数の 光透過性層からなることを特徴とする前記 1または 2に記載の電磁波遮蔽フィルムの 製造方法。 [0014] 3. The method for producing an electromagnetic wave shielding film as described in 1 or 2 above, wherein the layer having an antireflection function comprises a plurality of light-transmitting layers containing inorganic fine particles and having different refractive indexes.
[0015] 4.前記感光性ハロゲン化銀粒子を含む層が支持体上に近赤外線吸収機能を有 する層を設けた後に、設けられることを特徴とする前記 1〜3のいずれか 1項に記載の 電磁波遮蔽フィルムの製造方法。 [0015] 4. The layer according to any one of the above items 1 to 3, wherein the layer containing the photosensitive silver halide grains is provided after providing a layer having a near-infrared absorbing function on a support. The manufacturing method of electromagnetic wave shielding film of description.
[0016] 5.前記感光性ハロゲン化銀粒子を含む層が支持体上に近赤外線吸収機能を有 する層と同時に設けられることを特徴とする前記 1〜4のいずれか 1項に記載の電磁 波遮蔽フィルムの製造方法。 [0016] 5. The electromagnetic wave according to any one of 1 to 4, wherein the layer containing the photosensitive silver halide grains is provided simultaneously with a layer having a near-infrared absorbing function on a support. A method for producing a wave shielding film.
[0017] 6.前記感光性ハロゲン化銀粒子を含む層及び近赤外線吸収機能を有する層がス ライドホッパー型塗布装置またはスライド型カーテン塗布装置による同時重層塗布で 形成されることを特徴とする前記 4または 5に記載の電磁波遮蔽フィルムの製造方法 [0017] 6. The above-mentioned layer characterized in that the layer containing photosensitive silver halide grains and the layer having a near infrared absorption function are formed by simultaneous multi-layer coating by a slide hopper type coating device or a slide type curtain coating device. Method for producing electromagnetic wave shielding film according to 4 or 5
[0018] 7.前記反射防止機能を有する層がスロット型塗布装置で逐次重層塗布で形成さ れることを特徴とする前記 1〜6のいずれか 1項に記載の電磁波遮蔽フィルムの製造 方法。 [0018] 7. The method for producing an electromagnetic wave shielding film as described in any one of 1 to 6, wherein the layer having an antireflection function is formed by successive multilayer coating using a slot type coating device.
[0019] 8.前記感光性ハロゲンィ匕銀粒子を含む層を設けた電磁波遮蔽フィルム用原版に 露光、現像処理を施した後、更に物理現像処理及び Zまたはめつき処理を施して、 メッシュ状の電磁波遮蔽機能を有する金属層を形成した後、反射防止機能を有する 層を塗布形成することを特徴とする前記 1〜7のいずれか 1項に記載の電磁波遮蔽フ イルムの製造方法。 [0019] 8. After exposing and developing the original plate for an electromagnetic wave shielding film provided with the layer containing the photosensitive halogen silver halide particles, the substrate is further subjected to physical development processing and Z or tacking treatment, 8. The method for producing an electromagnetic wave shielding film as described in any one of 1 to 7 above, wherein a metal layer having an electromagnetic wave shielding function is formed, and then a layer having an antireflection function is formed by coating.
[0020] 9.前記 1〜8のいずれか 1項に記載の電磁波遮蔽フィルムの製造方法により製造 されることを特徴とする電磁波遮蔽フィルム。 [0020] 9. An electromagnetic wave shielding film produced by the method for producing an electromagnetic wave shielding film as described in any one of 1 to 8 above.
発明の効果 The invention's effect
[0021] 本発明の電磁波遮蔽フィルムの製造方法によって、高い電磁波遮蔽性と高い近赤 外線吸収性とを同時に有し、更に優れた反射防止機能を有する電磁波遮蔽フィルム
を提供することができた。 [0021] By the method for producing an electromagnetic wave shielding film of the present invention, the electromagnetic wave shielding film having high electromagnetic wave shielding properties and high near-infrared ray absorption properties and further having an excellent antireflection function. Could be provided.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0022] 本発明の電磁波遮蔽フィルムの製造方法は、支持体上に感光性ハロゲン化銀粒 子を含む層を設けた電磁波遮蔽フィルム用原版に露光、現像処理することでメッシュ 状の金属部を形成させた後、反射防止機能を有する層を塗布形成することを特徴と する。 [0022] In the method for producing an electromagnetic wave shielding film of the present invention, a mesh-shaped metal part is formed by exposing and developing an original plate for an electromagnetic wave shielding film in which a layer containing photosensitive silver halide particles is provided on a support. After the formation, a layer having an antireflection function is formed by coating.
[0023] 本発明において、電磁波遮蔽機能を発現するために、ハロゲン化銀粒子を含有す る層 (ハロゲンィ匕銀粒子含有層)が支持体上に設けられる。ハロゲンィ匕銀粒子含有層 はハロゲンィ匕銀粒子の他、バインダー、活性剤等を含有することができる。 In the present invention, in order to exhibit an electromagnetic wave shielding function, a layer containing silver halide grains (halogenated silver grain containing layer) is provided on the support. The halogen-containing silver particle-containing layer can contain a binder, an activator and the like in addition to the halogen-containing silver particles.
[0024] 本発明で用いられるハロゲンィ匕銀粒子としては、ハロゲンィ匕銀などの無機ハロゲン 化銀粒子及びべヘン酸銀などの有機ハロゲンィ匕銀粒子が挙げられるが、導電性金 属銀を得やすい無機ハロゲンィ匕銀を用いることが好ましい。本発明で好ましく用いら れるハロゲン化銀は、例えば、 AgCl、 AgBr、 Aglを主体としたハロゲン化銀が好まし く用いられ、導電性のよい金属銀を得るためには感度の高い微粒子が好ましぐ沃素 を含む AgBr、あるいは臭素を含む AgClを主体としたハロゲン化銀が好ましく用いら れる。 [0024] Examples of the halogen silver halide grains used in the present invention include inorganic silver halide grains such as halogen silver and organic halogen silver grains such as silver behenate, but it is easy to obtain conductive metal silver. It is preferable to use inorganic halogen silver. As the silver halide preferably used in the present invention, for example, silver halide mainly composed of AgCl, AgBr, and Agl is preferably used, and fine particles with high sensitivity are preferable in order to obtain highly conductive metal silver. Silver halides mainly composed of AgBr containing iodine or AgCl containing bromine are preferably used.
[0025] ノ、ロゲン化銀粒子が現像され金属銀粒子になると、粒子から粒子へと電気が流れ て 、くには接触面積ができるだけ大きくなる必要がある。そのためには粒子サイズが 小さい程よいが、小さい粒子は凝集して大きな塊状になりやすぐ接触面積は逆に少 なくなってしまうので最適な粒子径が存在する。 [0025] When the silver halide grains are developed into metallic silver grains, electricity flows from the grains to the grains, and the contact area needs to be as large as possible. For that purpose, the smaller the particle size, the better. However, the small particles aggregate to form a large lump, and the contact area immediately decreases, so there is an optimum particle size.
[0026] ハロゲン化銀の平均粒子サイズは、球相当径で l〜1000nm (l μ m)であることが 好ましぐ 1〜: LOOnmであることがより好ましい。なお、ハロゲン化銀粒子の球相当径 とは、粒子形状が球形の同じ体積を有する粒子の直径である。ハロゲンィ匕銀粒子の 大きさは、ハロゲンィ匕銀粒子の調製時の温度、 pAg、粒子径コントロール剤、例えば 、 1 フエ-ルー 5メルカプトテトラゾール、 2 メルカプトべンズイミダゾール、ベンズト リアゾール、テトラザインデン化合物類、核酸誘導体類、チォエーテル化合物類等を 適宜組み合わせて使用することができる。 [0026] The average grain size of the silver halide is preferably 1 to 1000 nm (l μm) in terms of a sphere equivalent diameter 1 to 1 and more preferably LOOnm. In addition, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape. The size of the halogenated silver particles is the temperature, pAg, particle size control agent, for example, 1-Ferru 5 mercaptotetrazole, 2 mercaptobenzimidazole, benztriazole, tetrazaindene compounds, at the time of preparing the halogenated silver particles. In addition, nucleic acid derivatives, thioether compounds, and the like can be used in appropriate combinations.
[0027] ハロゲン化銀粒子の形状は特に限定されず、例えば、球状、立方体状、平板状 (6
角平板状、三角形平板状、 4角形平板状など)、八面体状、 14面体状など様々な形 状であることができる。感度を高くするために、アスペクト比が 2以上や 4以上、更に 8 以上であって 16以下であるような平板粒子も好ましく使用することができる。粒子サイ ズの分布は広くても狭くてもよいが、高い導電性を得て開口率を大きくするには狭い 分布が好ましい。写真業界で知られる単分散度で 100以下、更には 30以下が好まし い。粒子の形状は、電気が流れ易くするための観点からは生成した粒子間の接触面 積が大きい程よいので、扁平でアスペクト比が大きい程よいが、アスペクト比を大きく すると濃度が出に《なるので最適なアスペクト比が存在する。 [0027] The shape of the silver halide grains is not particularly limited. For example, the shape is spherical, cubic, or flat (6 (Square plate, triangle plate, quadrilateral plate, etc.), octahedron, and tetrahedron. In order to increase sensitivity, tabular grains having an aspect ratio of 2 or more, 4 or more, 8 or more, and 16 or less can be preferably used. The particle size distribution may be wide or narrow, but a narrow distribution is preferable in order to obtain high conductivity and increase the aperture ratio. The monodispersity known in the photographic industry is preferably 100 or less, and more preferably 30 or less. From the viewpoint of facilitating the flow of electricity, the larger the contact area between the generated particles, the better the shape of the particles.The flatter and the larger the aspect ratio, the better, but the larger the aspect ratio, the better the concentration. Aspect ratio exists.
[0028] 本発明で用いられるハロゲンィ匕銀は、更に他の元素を含有していてもよい。例えば 、写真乳剤において、硬調な乳剤を得るために用いられる金属イオンをドープするこ とも有用である。特に、ロジウムイオン、ルテニウムイオンやイリジウムイオンなどの遷 移金属イオンは、金属銀像の生成の際に露光部と未露光部の差が明確に生じやす くなるため好ましく用いられる。ロジウムイオン、イリジウムイオンに代表される遷移金 属イオンは、各種の配位子を有する化合物であることもできる。そのような配位子とし ては、例えば、シアン化物イオンやハロゲンイオン、チオシアナ一トイオン、ニトロシル イオン、水、水酸ィ匕物イオンなどを挙げることができる。具体的な化合物の例としては 、臭化ロジウム酸カリウムやイリジウム酸カリウムなどが挙げられる。 [0028] The halogenated silver 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 for obtaining a high-contrast emulsion. In particular, transition metal ions such as rhodium ions, ruthenium ions, and iridium ions are preferably used because the difference between the exposed portion and the unexposed portion tends to occur clearly when a metallic silver image is formed. Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, and hydroxide ions. Specific examples of the compound include potassium bromate rhodate and potassium iridate.
[0029] 本発明にお 、て、ハロゲンィ匕銀に含有されるロジウム化合物及び Zまたはイリジゥ ム化合物の含有率は、ハロゲン化銀中の銀のモル数に対して 10— ω〜ιο— 2モル Zモ ル Agであることが好ましぐ 10— 9〜: LO— 3モル/モル Agであることが更に好まし!/、。 In the present invention, the content of rhodium compound and Z or iridium compound contained in halogenated silver is 10- ω to ιο— 2 moles relative to the number of moles of silver in the silver halide. Z mode, it is preferable Lumpur is Ag tool 10- 9 ~:! LO- and even more preferably is 3 mol / mol Ag / ,.
[0030] その他、本発明では Pdイオン、 Ptイオン Pd金属及び Zまたは Pt金属を含有するハ ロゲン化銀も好ましく用いることができる。 Pdや Ptははハロゲン化銀粒子内に均一に 分布して 、てもよ 、が、ハロゲン化銀粒子の表層近傍に含有させることが好ま 、。 本発明にお 、て、ハロゲン化銀に含まれる Pdイオン及び/または Pd金属の含有率 は、ハロゲン化銀中の銀のモル数に対して 10— 6〜0. 1モル Zモル Agであることが好 ましく、 0. 01〜0. 3モル Zモル Agであることが更に好ましい。 [0030] In addition, in the present invention, silver halides containing Pd ions, Pt ions, Pd metals, and Z or Pt metals can also be preferably used. Pd and Pt are uniformly distributed in the silver halide grains, but it is preferable that they are contained in the vicinity of the surface layer of the silver halide grains. Contact to the present invention, Te, content of Pd ion and / or Pd metal contained in the silver halide is a 10- 6 to 0.1 mol Z mol Ag with respect to the number of moles of silver in the silver halide More preferably, it is 0.01 to 0.3 mol Z mol Ag.
[0031] 本発明では、更に感度を向上させるため写真乳剤で行われる化学増感を施すこと もできる。化学増感としては、例えば、金、パラジウム、白金増感などの貴金属増感、
無機ィォゥ、または有機ィォゥ化合物によるィォゥ増感などのカルコゲン増感、塩ィ匕 錫、ヒドラジン等還元増感等を利用することができる。 [0031] 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, platinum sensitization, Chalcogen sensitization such as io sensitization by inorganic thio or organic thio compounds, reduction sensitization such as sodium chloride, hydrazine and the like can be used.
[0032] 化学増感されたハロゲンィ匕銀粒子を分光増感することができる。好ま 、分光増感 色素としては、シァニン、力ノレボシァニン、ジカノレボシァニン、複合シァニン、へミシァ ニン、スチリール色素、メロシアニン、複合メロシアニン、ホロポーラ一色素等を挙げる ことができ、当業界で用いられている分光増感色素を単用、あるいは併用して使用す ることがでさる。 [0032] Chemically sensitized halogen silver halide grains can be spectrally sensitized. Preferred examples of the spectral sensitizing dye include cyanine, force nolevocyanin, dicanolevoyanine, complex cyanine, hemisyanine, styryl dye, merocyanine, complex merocyanine, and holopolar monochromator. The spectral sensitizing dyes used can be used alone or in combination.
[0033] 特に有用な色素は、シァニン色素、メロシアニン色素、及び複合メロシアニン色素 である。これらの色素類には、その塩基性異節環核としてシァニン色素類に通常利 用される核のいずれをも通用できる。即ち、ピロリン核、ォキサゾリン核、チアゾリン核 、ピロール核、ォキサゾール核、チアゾール核、セレナゾール核、イミダゾール核、テ トラゾール核、ピリジン核及びこれらの核に脂環式炭化水素環が融合した核;及びこ れらの核に芳香族炭化水素環が融合した核、即ちインドレニン核、ベンズインドレ- ン核、インドール核、ベンズォキサゾール核、ナフトォキサゾール核、ベンゾチアゾー ル核、ナフトチアゾール核、ベンゾセレナゾール核、ベンズイミダゾール核、キノリン 核などである。これらの核は、炭素原子上で置換されてもよい。メロシアニン色素また は複合メロシアニン色素には、ケトメチレン構造を有する核として、ピラゾリン一 5—ォ ン核、チォヒダントイン核、 2 チォォキサゾリジン 2, 4 ジオン核、チアゾリジン 2, 4 ジオン核、ローダニン核、チォバルビツール酸核などの 5から 6員異節環核を 適用することができる。 [0033] Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of nuclei usually used in cyanine dyes can be used as the basic heterocyclic nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, namely indolenine nucleus, benzindolene nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselena Such as sol nucleus, benzimidazole nucleus, quinoline nucleus. These nuclei may be substituted on carbon atoms. Merocyanine dyes or complex merocyanine dyes have pyrazoline mononuclear nuclei, thiohydantoin nuclei, 2 thoxazolidine 2,4 dione nuclei, thiazolidine 2,4 dione nuclei, rhodanine nuclei as nuclei having a ketomethylene structure. 5 to 6-membered heterocyclic nuclei such as thiobarbituric acid nuclei can be applied.
ノ、ロゲンィ匕銀粒子の露光において、近赤外線レーザーなどを適用する場合は近赤 外増感色素を用いることが好まし 、。これらの色素は特開 2000— 347343号公報、 特開 2004— 037711号公報及び特開 2005— 134710号公報を参考にすることが できる。特に好ましい具体例を下記に示す。 It is preferable to use near-infrared sensitizing dyes when using near-infrared lasers in the exposure of silver and silver particles. These dyes can be referred to JP-A-2000-347343, JP-A-2004-037711 and JP-A-2005-134710. Particularly preferred specific examples are shown below.
[0035] これらの増感色素は単独に用いてもよいが、それらの組み合わせを用いてもよい。 [0035] These sensitizing dyes may be used alone or in combination.
増感色素の組み合わせは、特に強色増感の目的でしばしば用いられる。 A combination of sensitizing dyes is often used for the purpose of supersensitization.
[0036] これらの増感色素をハロゲンィ匕銀乳剤中に含有せしめるには、それらを直接乳剤 中に分散してもよいし、あるいは水、メタノール、プロパノール、メチルセ口ソルブ、 2, 2, 3, 3—テトラフルォロプロパノール等の溶媒の単独もしくは混合溶媒に溶解して 孚 L剤へ添カロしてもよい。また、特公昭 44— 23389号、同 44— 27555号、同 57— 22 089号の各公報等に記載の様に酸または塩基を共存させて水溶液としたり、米国特 許第 3, 822, 135号、同 4, 006, 025号の各明糸田書等【こ記載のよう【こド、デシノレベン
ゼンスルホン酸ナトリウム等の界面活性剤を共存させて水溶液、あるいはコロイド分 散物としたものを乳剤へ添加してもよい。また、フエノキシエタノール等の実質上水と 非混和性の溶媒に溶解した後、水または親水性コロイド分散したものを乳剤に添カロ してもよい。特開昭 53— 102733号、同 58— 105141号の各公報に記載の様に親 水性コロイド中に直接分散させ、その分散物を乳剤に添加してもよい。 [0036] In order to incorporate these sensitizing dyes in a silver halide silver emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl mouthsolve, 2, 2, 3, It may be dissolved in a solvent such as 3-tetrafluoropropanol alone or in a mixed solvent and added to the L agent. Also, as described in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22 089, etc., an acid or base is allowed to coexist to form an aqueous solution, or US Pat. No. 3,822,135. No. 4, 4, 006, 025, etc. An aqueous solution or a colloidal dispersion in the presence of a surfactant such as sodium zensulfonate may be added to the emulsion. Further, after dissolving in a substantially non-miscible solvent such as phenoxyethanol, water or a hydrophilic colloid dispersion may be added to the emulsion. As described in JP-A-53-102733 and JP-A-58-105141, the dispersion may be directly dispersed in an lyophilic colloid and the dispersion may be added to the emulsion.
[0037] 本発明においては、電磁波遮蔽フィルムは同一支持体上に反射防止層を有する。 [0037] In the present invention, the electromagnetic wave shielding film has an antireflection layer on the same support.
反射防止層はハロゲン化銀粒子を含む層を露光、現像処理して形成されたメッシュ 状の金属部を有する層の上に形成されてもよいが、支持体の裏面側に反射防止層 を設けることが好ましい。裏面側の方が表面処理による反射防止層の接着強度が高 められること、メッシュ状の金属部を有する層の上に形成すると反射防止層の充分な 平滑性が得られな 、ことを見い出したことによる。 The antireflection layer may be formed on a layer having a mesh-like metal part formed by exposing and developing a layer containing silver halide grains, but an antireflection layer is provided on the back side of the support. It is preferable. It has been found that the adhesive strength of the antireflection layer is increased by the surface treatment on the back side, and that the antireflection layer cannot be sufficiently smooth when formed on a layer having a mesh-like metal part. It depends.
[0038] 本発明に係る反射防止機能を有する層は、屈折率の異なる複数の光透過性層か らなることが好ましぐ無機微粒子を含有した高屈折率層、中屈折率層、低屈折率層 力も構成されることがより好ましい。屈折率の異なる層はそれぞれに含有される無機 微粒子の種類、粒径、添加量、榭脂バインダーの種類などによって調整される。 [0038] The layer having an antireflection function according to the present invention preferably comprises a high refractive index layer, a medium refractive index layer, and a low refractive index containing inorganic fine particles that are preferably composed of a plurality of light transmissive layers having different refractive indexes. More preferably, the rate layer force is also configured. The layers having different refractive indexes are adjusted according to the kind of inorganic fine particles contained therein, the particle diameter, the amount added, the kind of resin binder, and the like.
[0039] 高屈折率層の屈折率は 1. 55-2. 30であることが好ましぐ 1. 57-2. 20である ことが更に好ましい。中屈折率層の屈折率は、基材フィルムの屈折率と高屈折率層 の屈折率との中間の値となるように調整する。中屈折率層の屈折率は 1. 55〜: L 80 であることが好ましい。低屈折率層の屈折率は 1. 46以下が好ましぐ特に 1. 3〜1. 45であることが望ましい。 [0039] The refractive index of the high refractive index layer is preferably 1.55-2.30, more preferably 1.57-2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the base film and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.55 to L80. The refractive index of the low refractive index layer is preferably 1.46 or less, particularly 1.3 to 1.45.
[0040] 各層の厚さは 5nm〜0. 5 μ mであることが好ましぐ 10nm〜0. 3 μ mであることが 更に好ましぐ 30ηπ!〜 0. 2 mであることが最も好ましい。 [0040] The thickness of each layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and even more preferably 30ηπ! Most preferred is ~ 0.2 m.
[0041] 金属酸ィ匕物層のヘイズは 5%以下であることが好ましぐ 3%以下であることが更に 好ましぐ 1%以下であることが最も好ましい。金属酸ィ匕物層の強度は lkg荷重の鉛 筆硬度で 3H以上であることが好ましぐ 4H以上であることが最も好ましい。金属酸化 物層を塗布により形成する場合は、無機微粒子とバインダーポリマーとを含むことが 好ましい。 [0041] The haze of the metal oxide layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the metal oxide layer is preferably 3H or more in terms of lead writing hardness of 1 kg load, and most preferably 4H or more. When the metal oxide layer is formed by coating, it preferably contains inorganic fine particles and a binder polymer.
[0042] 中屈折率層あるいは高屈折率層などの金属酸ィ匕物層に用いる無機微粒子は、屈
折率力 i. 80-2. 80であること力好ましく、 1. 90〜2. 80であること力 ^更に好まし!/、 。無機微粒子の 1次粒子の質量平均径は l〜150nmであることが好ましぐ 1〜100 nmであることが更に好ましぐ l〜80nmであることが最も好ましい。 [0042] The inorganic fine particles used in the metal oxide layer such as the medium refractive index layer or the high refractive index layer are bent. Fracture power i. 80-2. 80 power is preferred, 1. 90-2. 80 power ^ more preferred! /,. The mass average diameter of the primary particles of the inorganic fine particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm.
[0043] 層中での無機微粒子の質量平均径は l〜200nmであることが好ましぐ 5〜150n mであることがより好ましぐ 10〜100nmであることが更に好ましぐ 10〜80nmであ ることが最も好まし ヽ。無機微粒子の平均粒径は 20〜30nm以上であれば光散乱法 により、 20〜30nm以下であれば電子顕微鏡写真により測定される。無機微粒子の 比表面積は、 BET法で測定された値として、 10〜400m2/gであることが好ましぐ 2 0〜200m2/gであることが更に好ましぐ 30〜150m2/gであることが最も好ましい。 [0043] The mass average diameter of the inorganic fine particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, and even more preferably 10 to 100 nm. 10 to 80 nm It is most preferable to be. If the average particle size of the inorganic fine particles is 20-30 nm or more, it is measured by a light scattering method, and if it is 20-30 nm or less, it is measured by an electron micrograph. The specific surface area of the inorganic fine particles, a measured value by the BET method, it is further preferable that a 10 to 400 m 2 / g is preferred instrument 2 0~200m 2 / g instrument 30 to 150 m 2 / g Most preferably.
[0044] 無機微粒子は金属の酸ィ匕物カゝら形成された粒子である。金属の酸ィ匕物または硫ィ匕 物の例として、二酸化チタン (例えば、ルチル、ルチル Zアナターゼの混晶、アナタ ーゼ、アモルファス構造)、酸化錫、酸化インジウム、 ITO、酸化亜鉛、酸化ジルコ二 ゥム等が挙げられる。中でも、二酸化チタン、酸化錫及び酸化インジウムが特に好ま しい。無機微粒子は、これらの金属の酸化物を主成分とし、更に他の元素を含むこと ができる。主成分とは、粒子を構成する成分の中で最も含有量 (質量%)が多い成分 を意味する。他の元素の例としては、 Ti、 Zr、 Sn、 Sb、 Cu、 Fe、 Mn、 Pb、 Cd、 As、 Cr、 Hg、 Zn、 Al、 Mg、 Si、 P及び Sが挙げられる。 [0044] The inorganic fine particles are particles formed from a metal oxide. Examples of metal oxides or sulfates include titanium dioxide (eg, rutile, mixed crystals of rutile Z anatase, anatase, amorphous structure), tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide. 2um and so on. Of these, titanium dioxide, tin oxide and indium oxide are particularly preferred. The inorganic fine particles are mainly composed of oxides of these metals and can further contain other elements. The main component means the component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.
[0045] 無機微粒子は表面処理されて!ヽてもよ!/ヽ。表面処理は無機化合物または有機化合 物を用いて実施することができる。表面処理に用いる無機化合物の例としては、アル ミナ、シリカ、酸化ジルコニウム及び酸化鉄が挙げられる。中でもアルミナ及びシリカ が好ましい。表面処理に用いる有機化合物の例としては、ポリオール、アル力ノール ァミン、ステアリン酸、シランカップリング剤及びチタネートカップリング剤が挙げられる 。中でも、シランカップリング剤が最も好ましい。二種類以上の表面処理を組み合わ せて処理されて 、ても構わな 、。 [0045] The inorganic fine particles may be surface-treated! The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alcohols, stearic acid, silane coupling agents and titanate coupling agents. Of these, a silane coupling agent is most preferable. It may be processed by combining two or more kinds of surface treatments.
[0046] 無機微粒子の形状は米粒状、球形状、立方体状、層状、紡錘形状あるいは不定形 状であることが好ましい。二種類以上の無機微粒子を金属酸ィ匕物層に併用してもよ い。 [0046] The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a layer shape, a spindle shape, or an indefinite shape. Two or more types of inorganic fine particles may be used in combination in the metal oxide layer.
[0047] 金属酸ィ匕物層中の無機微粒子の割合は 5〜90体積%であることが好ましぐより好
ましくは 10〜65体積%であり、更に好ましくは 20〜55体積%である。 [0047] The proportion of inorganic fine particles in the metal oxide layer is preferably 5 to 90% by volume. The amount is preferably 10 to 65% by volume, more preferably 20 to 55% by volume.
[0048] 無機微粒子は媒体に分散した分散体の状態で、金属酸ィ匕物層を形成するための 塗布液に供される。無機微粒子の分散溶媒としては、沸点が 60〜170°Cの液体を 用いることが好ましい。 [0048] The inorganic fine particles are used in a coating solution for forming a metal oxide layer in a state of dispersion in a medium. As the dispersion solvent for the inorganic fine particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C.
[0049] 分散溶媒の具体例としては、水、アルコール (例えば、メタノール、エタノール、イソ プロパノール、ブタノール、ベンジルアルコール)、ケトン(例えば、アセトン、メチルェ チルケトン、メチルイソブチルケトン、シクロへキサノン)、エステル(例えば、酢酸メチ ル、酢酸ェチル、酢酸プロピル、酢酸ブチル、蟻酸メチル、蟻酸ェチル、蟻酸プロピ ル、蟻酸プチル)、脂肪族炭化水素 (例えば、へキサン、シクロへキサン)、芳香族炭 化水素(例えば、ベンゼン、トルエン、キシレン)、アミド(例えば、ジメチルホルムアミド 、ジメチルァセトアミド、 n—メチルピロリドン)、エーテル(例えば、ジェチルエーテル、 ジォキサン、テトラハイド口フラン)、エーテルアルコール(例えば、 1—メトキシ一 2— プロパノール)が挙げられる。中でも、トルエン、キシレン、メチルェチルケトン、メチル イソブチルケトン、シクロへキサノン及びブタノールが特に好まし!/、。 [0049] Specific examples of the dispersion solvent include water, alcohol (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester ( For example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, propyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), aromatic hydrocarbons ( For example, benzene, toluene, xylene), amide (for example, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (for example, jetyl ether, dioxane, tetrahydrated furan), ether alcohol (for example, 1- Methoxy-2-propanol) It is below. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred! /.
[0050] 無機微粒子は分散機を用いて媒体中に分散することができる。分散機の例として は、サンドグラインダーミル (例えば、ピン付きビーズミル)、高速インペラ一ミル、ぺッ ブルミル、ローラーミル、アトライター及びコロイドミルが挙げられる。サンドグラインダ 一ミル及び高速インペラ一ミルが特に好ましい。また、予備分散処理を実施してもよ い。予備分散処理に用いる分散機の例としては、ボールミル、三本ロールミル、ニー ダー及びエタストルーダーが挙げられる。 [0050] The inorganic fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with a pin), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high speed impeller mill are particularly preferred. In addition, preliminary dispersion processing may be performed. Examples of a disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an etastruder.
[0051] 金属酸ィ匕物層は、架橋構造を有するポリマー(以下、「架橋ポリマー」ともいう)をバ インダーポリマーとして用いることが好ましい。架橋ポリマーの例として、ポリオレフイン 等の飽和炭化水素鎖を有するポリマー(以下「ポリオレフイン」と総称する)、ポリエー テル、ポリウレア、ポリウレタン、ポリエステル、ポリアミン、ポリアミド及びメラミン榭脂等 の架橋物が挙げられる。中でも、ポリオレフイン、ポリエーテル及びポリウレタンの架橋 物が好ましぐポリオレフイン及びポリエーテルの架橋物が更に好ましぐポリオレフィ ンの架橋物が最も好ましい。 [0051] The metal oxide layer preferably uses a polymer having a crosslinked structure (hereinafter also referred to as "crosslinked polymer") as a binder polymer. Examples of the crosslinked polymer include crosslinked polymers such as a polymer having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as “polyolefin”), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. Among them, a polyolefin crosslinked product, which is preferably a crosslinked product of polyolefin, polyether, and polyurethane, and a crosslinked product of polyolefin, more preferably a crosslinked product of polyether, is most preferable.
[0052] また、架橋ポリマーがァ-オン性基を有することは更に好ま U、。ァ-オン性基は無
機微粒子の分散状態を維持する機能を有し、架橋構造はポリマーに皮膜形成能を 付与して皮膜を強化する機能を有する。上記ァニオン性基はポリマー鎖に直接結合 していてもよいし、連結基を介してポリマー鎖に結合していてもよいが、連結基を介し て側鎖として主鎖に結合して 、ることが好まし 、。 [0052] Further, it is more preferable that the crosslinked polymer has a ionic group. There are no key-on groups It has a function of maintaining the dispersed state of the fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but may be bonded to the main chain as a side chain via the linking group. Is preferred.
[0053] 本発明に用いられる低屈折率層の屈折率は 1. 46以下が好ましぐ特に 1. 3〜1. [0053] The refractive index of the low refractive index layer used in the present invention is preferably 1.46 or less, particularly 1.3 to 1.
45であることが望まし、、塗布組成物として珪素アルコキシドを用いてゾルゲル法に よって低屈折率層を形成することができる。あるいは、フッ素榭脂を用いて低屈折率 層とすることができる。特に、熱硬化性または電離放射線硬化型の含フッ素榭脂の硬 化物と珪素の酸化物超微粒子から構成されることが好ま ヽ。珪素の酸化物超微粒 子は後述する多孔質粒子と該多孔質粒子表面に設けられた被覆層を有する複合粒 子、あるいは内部に溶媒、気体、または多孔質物質で充填された空洞粒子であること が好ましい。 The low refractive index layer can be formed by a sol-gel method using silicon alkoxide as the coating composition. Alternatively, a low refractive index layer can be formed by using fluorine resin. In particular, it is preferably composed of a cured material of a thermosetting or ionizing radiation curable fluorine-containing resin and ultrafine particles of silicon oxide. Silicon oxide ultrafine particles are composite particles having porous particles described later and a coating layer provided on the surface of the porous particles, or hollow particles filled with a solvent, gas, or porous substance inside. It is preferable.
[0054] 該硬化物の動摩擦係数は 0. 02-0. 2であることが好ましぐ純水接触角は 90〜1 30° であることが好ましい。該硬化性の含フッ素榭脂としては、パーフルォロアルキ ル基含有シラン化合物(例えば、(ヘプタデカフルオロー 1, 1, 2, 2—テトラデシル)ト リエトキシシラン)や、含フッ素共重合体 (架橋性基を有するモノマーと含フッ素モノマ 一を構成単位とする)が挙げられる。含フッ素モノマー単位の具体例としては、例え ば、へキサフルォロエチレン、へキサフルォロプロピレン、テトラフルォロエチレン、フ ルォロォレフイン類(例えば、ビ-リデンフルオライドパーフルオロー 2, 2—ジメチル - 1, 3—ジォキノール、フルォロエチレン等)、(メタ)アクリル酸のフッ素化アルキル エステル誘導体 (例えば、ビスコート 6FM (大阪有機化学製)や M— 2020 (ダイキン 製)等)、フッ素化ビュルエーテル類等である。架橋性基を有するモノマーとしては、 グリシジルメタタリレートのように分子内に予め架橋性官能基を有する (メタ)アタリレー トモノマーの他、カルボキシル基ゃァミノ基、ヒドロキシル基、スルホン酸基等を有する [0054] It is preferable that the dynamic friction coefficient of the cured product is 0.02-0.2, and the pure water contact angle is preferably 90 to 130 °. Examples of the curable fluorine-containing resin include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), fluorine-containing copolymer. And a compound (having a monomer having a crosslinkable group and a fluorine-containing monomer as structural units). Specific examples of the fluorine-containing monomer unit include, for example, hexafluoroethylene, hexafluoropropylene, tetrafluoroethylene, fluoroolefins (for example, bi-lidene fluoride perfluoro-2, 2 —Dimethyl-1,3-diquinol, fluoroethylene, etc.), fluorinated alkyl ester derivatives of (meth) acrylic acid (eg, Biscote 6FM (Osaka Organic Chemical), M-2020 (Daikin), etc.), fluorinated butyl ether Etc. The monomer having a crosslinkable group has a carboxyl group, amino group, hydroxyl group, sulfonic acid group, etc. in addition to a (meth) atrelate monomer having a crosslinkable functional group in the molecule in advance, such as glycidyl methacrylate.
(メタ)アタリレートモノマー(例えば、(メタ)アクリル酸、メチロール (メタ)アタリレート、ヒ ドロキシアルキル (メタ)アタリレート、ァリルアタリレート等)が挙げられる。これらは共 重合の後から架橋構造を導入できることが、特開平 10— 25388号公報及び特開平 10— 147739号公報に記載されている。
[0055] また、上記含フッ素モノマーを構成単位とするポリマーだけでなぐフッ素原子を含 有しないモノマーとの共重合体を用いることができる。併用可能なモノマー単位には 特に限定はなぐ例えば、アクリル酸エステル類 (アクリル酸メチル、アクリル酸メチル 、アクリル酸ェチル、アクリル酸 2—ェチルへキシル)、メタクリル酸エステル類 (メタタリ ル酸メチル、メタクリル酸ェチル、メタクリル酸ブチル、エチレングリコールジメタクリレ ート等)、スチレン誘導体(スチレン、ジビュルベンゼン、 a—メチルスチレン、ビュルト ルェン等)、アクリルアミド類 (N— t—ブチルアクリルアミド、 N—シクロへキシルアタリ ルアミド等)、メタクリルアミド類、アクリロニトリル誘導体等、ォレフィン類 (エチレン、プ ロピレン、イソプレン、塩化ビ-リデン、塩化ビュル等)、ビュルエーテル類 (メチルビ ニルエーテル等)、ビニルエステル類(酢酸ビニル、プロピオン酸ビニル、桂皮酸ビニ ル等)を挙げることができる。 (Meth) acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). JP-A-10-25388 and JP-A-10-147739 describe that a crosslinked structure can be introduced after copolymerization. [0055] Further, it is possible to use a copolymer with a monomer having no fluorine atom, which is only a polymer having the above-mentioned fluorine-containing monomer as a structural unit. There are no particular limitations on the monomer units that can be used in combination, for example, acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylate esters (methyl methacrylate, methyl methacrylate). Acid ethyl, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, dibutylbenzene, a -methylstyrene, butruluene, etc.), acrylamides (N-t-butylacrylamide, N-cyclohexene) Xylatylamide, etc.), methacrylamides, acrylonitrile derivatives, etc., olefins (ethylene, propylene, isoprene, vinylidene chloride, butyl chloride, etc.), butyl ethers (methylvinyl ether, etc.), vinyl esters (vinyl acetate, propion) Vinyl acid It can be mentioned cinnamic acid vinyl Le etc.).
[0056] 低屈折率層の形成に用いる含フッ素榭脂には、耐傷性を改善するために酸ィ匕珪素 微粒子を添加して用いるのが好まし ヽ。添加量は屈折率と耐傷性との兼ね合 、で調 整される。酸ィ匕珪素微粒子は、市販の有機溶剤に分散されたシリカゾルをそのまま 塗布組成物に添加することができ、ある!/、は市販の各種シリカ紛体を有機溶剤に分 散して使用することもできる。 [0056] The fluorine-containing resin used for forming the low refractive index layer is preferably added with silicon oxide fine particles in order to improve scratch resistance. The amount added is adjusted by the balance between refractive index and scratch resistance. Silica silicate fine particles can be added to the coating composition as it is silica sol dispersed in a commercially available organic solvent, and there are some! /, Which can be used by dispersing various commercially available silica powders in an organic solvent. it can.
[0057] 本発明にお ヽては、感光性ハロゲンィ匕銀粒子を含む層を設けた電磁波遮蔽フィル ム用原版に露光、現像処理することでメッシュ状の金属部を形成させた後、反射防止 機能を有する層を塗布形成することを特徴とする。即ち、メッシュ状の金属部を有す る層と反射防止機能を有する層のどちらを先に形成すべきかについて、我々は重要 な因果関係を見出し、本発明に至ったものである。 [0057] In the present invention, after forming a mesh-like metal part by exposing and developing an original plate for electromagnetic wave shielding film provided with a layer containing photosensitive halogen silver halide grains, antireflection is performed. A layer having a function is formed by coating. That is, we have found an important causal relationship regarding which of the layer having the mesh-like metal portion and the layer having the antireflection function should be formed first, and have arrived at the present invention.
[0058] まず第 1に、本発明とは逆に支持体上に先に反射防止機能を有する層を塗布形成 した後、感光性ハロゲンィ匕銀粒子を含む層を設けると反射防止機能を有する層に含 有される無機微粒子の一部が脱落し、感光性ハロゲン化銀粒子を含む層を形成する ための塗布生産工程内を汚染し、塗布スジゃスポット故障の原因となりうることがわか つた o First, contrary to the present invention, when a layer having an antireflection function is first formed on a support and then a layer containing photosensitive silver halide grains is provided on the support, a layer having an antireflection function is provided. It was found that some of the inorganic fine particles contained in the film fall off and contaminate the coating production process to form a layer containing photosensitive silver halide grains, which can cause spot failure in the coating stripe o
また第 2に、本発明とは逆に支持体上に先に反射防止機能を有する層を塗布形成し た後、感光性ハロゲン化銀粒子を含む層を設けた電磁波遮蔽フィルム用原版に露光
、現像処理することでメッシュ状の金属部を形成させると反射防止機能が大幅に低下 したり、ヘイズ値が増加して透光性が低下したり、スポット状の欠陥が発生することを 見出した。これは、反射防止機能を有する層に含有される無機微粒子、特に珪素の 酸ィ匕物微粒子が現像処理液のアルカリ性環境下で溶解したり、あるいは無機微粒子 の分散安定性が低下して凝集が発生したりするためと推定される。 Second, contrary to the present invention, a layer having an antireflection function is first formed on a support by coating, and then exposed to an electromagnetic wave shielding film master provided with a layer containing photosensitive silver halide grains. It has been found that when a mesh-like metal part is formed by development processing, the antireflection function is significantly reduced, the haze value is increased and the translucency is lowered, or spot-like defects are generated. . This is because the inorganic fine particles, particularly silicon oxide fine particles contained in the layer having an antireflection function are dissolved in the alkaline environment of the developing solution, or the dispersion stability of the inorganic fine particles is lowered to cause aggregation. This is presumed to occur.
[0059] 第 3に、反射防止層は前述のように、その構成材料のために非水系有機溶剤を用 いて塗布することが一般的であるので、塗布工程内において支持体の帯電を避けな ければならない。そのために、接地設備や防爆対策などを完備する必要があるだけ でなく低速で塗布せざるを得な 、状況にある。本発明のように先にメッシュ状の金属 部を有する層を設けておけば、支持体の帯電をほとんど防ぐことができるので、高速 塗布が可能である。 [0059] Thirdly, as described above, since the antireflection layer is generally applied using a non-aqueous organic solvent for the constituent material, charging of the support must be avoided in the application process. I have to. For this reason, it is necessary not only to have grounding equipment and explosion-proof measures, but also to apply at low speed. If a layer having a mesh-like metal portion is provided in advance as in the present invention, the support can be prevented from being charged almost at all, so that high-speed coating is possible.
[0060] 本発明の電磁波遮蔽フィルムは、ハロゲンィ匕銀粒子を含有する層の写真階調を硬 調化することが好まし 、。その方法としてハロゲンィ匕銀粒子の粒径の分布を狭くする 方法等があるが、製版用ではヒドラジン化合物ゃテトラゾリゥム化合物を硬調化剤とし て使用することが知られて 、る。ヒドラジンィ匕合物は NHNH -基を有する化合物 であり、代表的なものを下記一般式で示す。 [0060] In the electromagnetic wave shielding film of the present invention, it is preferable to enhance the photographic gradation of the layer containing the halogenated silver particles. As such a method, there is a method of narrowing the particle size distribution of halogenated silver particles, and it is known to use a hydrazine compound or a tetrazolium compound as a high contrast agent for plate making. A hydrazine compound is a compound having an NHNH- group, and a typical one is represented by the following general formula.
[0061] T NHNHCO— V、 T NHNHCOCO— V [0061] T NHNHCO— V, T NHNHCOCO— V
式中、 Tは各々置換されてもよいァリール基、ヘテロ環基を表す。 Tで表されるァリ 一ル基はベンゼン環やナフタレン環を含むもので、この環は置換基を有してもよく、 好ましい置換基として直鎖、分岐のアルキル基 (好ましくは炭素数 1〜20のメチル基 、ェチル基、イソプロピル基、 n—ドデシル基等)、アルコキシ基 (好ましくは炭素数 2 〜21のメトキシ基、エトキシ基等)、脂肪族ァシルァミノ基 (好ましくは炭素数 2〜21の アルキル基を持つ、ァセチルァミノ基、ヘプチルァミノ基等)、芳香族ァシルァミノ基 等が挙げられ、これらの他に、例えば、上記の様な置換または未置換の芳香族環が — CONH―、— O—、 -SO NH―、— NHCONH―、— CH CHN―、等の連結 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 having a carbon number of 1 To 20 methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.), alkoxy group (preferably methoxy group having 2 to 21 carbon atoms, ethoxy group etc.), aliphatic isylamino group (preferably 2 to 21 carbon atoms) In addition to these, for example, substituted or unsubstituted aromatic rings such as —CONH—, —O—, and the like, can be mentioned, such as acetylamino groups, heptylamino groups, and the like. , -SO NH-,-NHCONH-,-CH CHN-, etc.
2 2 twenty two
基で結合しているものも含む。 Vは水素原子、置換されてもよいアルキル基 (メチル基 Including those bonded by a group. V is a hydrogen atom or an optionally substituted alkyl group (methyl group
、ェチル基、ブチル、トリフロロメチル基等)、ァリール基(フエ-ル基、ナフチル基)、 ヘテロ環基 (ピリジル基、ピペリジル基、ピロリジル基、フラニル基、チォフェン基、ピロ
ール基等)を表す。 Ethyl group, butyl, trifluoromethyl group, etc.), aryl group (phenyl group, naphthyl group), heterocyclic group (pyridyl group, piperidyl group, pyrrolidyl group, furanyl group, thiophene group, pyro group) Group).
[0062] ヒドラジンィ匕合物は、米国特許第 4, 269, 929号明細書の記載を参考にして合成 することができる。ヒドラジンィ匕合物はハロゲンィ匕銀粒子層中、またはハロゲンィ匕銀粒 子層に隣接する親水性コロイド層中、更には他の親水性コロイド層中に含有せしめる ことができる。特に好ましいヒドラジンの化合物を下記に挙げる。 [0062] The 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 halogenated silver particle layer, in the hydrophilic colloid layer adjacent to the halogenated silver particle layer, or in another hydrophilic colloid layer. Particularly preferred hydrazine compounds are listed below.
[0063] (H— 1) : 1—トリフロロメチルカルボ-ル— 2— {〔4— (3— n—ブチルウレイド)フエ -ル〕 }ヒドラジン [0063] (H— 1): 1-trifluoromethyl carbole— 2— {[4— (3-n-butylureido) phenol]} hydrazine
(H— 2) : 1—トリフロロメチルカルボ-ル 2— {4—〔2— (2, 4 ジ— tert -ペンチ ルフエノキシ)ブチルアミド〕フエ-ル}ヒドラジン (H-2): 1-trifluoromethyl carboyl 2— {4— [2— (2, 4 di-tert-pentylphenoxy) butyramide] phenol} hydrazine
(H— 3) : 1— (2, 2, 6, 6—テトラメチルピペリジル一 4 アミノーォキザリル)一 2— {4一〔2— (2, 4ージ—tert ペンチルフエノキシ)ブチルアミド〕フエ-ル}ヒドラジン (H— 3): 1— (2, 2, 6, 6-tetramethylpiperidyl mono 4-aminooxalyl) one 2— {4 one [2- (2, 4-di-tert pentylphenoxy) Butyramide] phenol} hydrazine
(H-4) : 1 - (2, 2, 6, 6—テトラメチルピベリジルー 4 アミノーォキザリル) 2— {4-〔2— (2, 4ージ t—ペンチルフエノキシ)ブチルアミド〕フエ-ルスルホンアミド フエ-ル}ヒドラジン (H-4): 1-(2, 2, 6, 6-tetramethylpiveridyl 4-aminooxalyl) 2— {4- [2— (2, 4-di-t-pentylphenoxy) Butylamide] Phenolsulfonamide Phenol} hydrazine
(H— 5) : 1— (2, 2, 6, 6—テトラメチルピペリジル一 4 アミノーォキザリル)一 2— (4— (3— (4—クロ口フエ-ルー 4—フエ-ルー 3—チア一ブタンアミド)ベンゼンスル ホンアミド)フエ-ル)ヒドラジン (H— 5): 1— (2, 2, 6, 6-tetramethylpiperidyl 4-aminooxalyl) 1 2-— (4-— (3-— (4--black mouth ferru) 4-- feu-lou 3-thiabutanamide) benzenesulfonamide) phenol) hydrazine
(H— 6) : 1— (2, 2, 6, 6—テトラメチルピペリジル一 4 アミノーォキザリル)一 2— (4— (3 チア一 6, 9, 12, 15—テトラオキサトリコサンアミド)ベンゼンスルホンアミド )フエ-ルヒドラジン (H-6): 1- (2, 2, 6, 6-tetramethylpiperidyl 1-amino-oxalyl) 1 2— (4— (3 thia 6, 9, 12, 15- tetraoxatricosane Amide) Benzenesulfonamide) Ferhydrazine
(11 7) : 1—(1ーメチレンカルボ-ルピリジ-ゥム)ー2—(4ー(3—チァー6, 9, 1 2, 15—テトラオキサトリコサンアミド)ベンゼンスルホンアミド)フエニルヒドラジンクロラ イド。 (11 7): 1— (1-Methylenecarborpyridium) -2- (4- (3-Chaer 6, 9, 1 2, 15-Tetraoxatricosanamide) benzenesulfonamide) phenylhydrazine chloride .
[0064] ヒドラジンィ匕合物は T基としてスルホンアミドフエ-ル基、 V基としてトリフロロメチル基 が置換されているものが特に好ましい。またヒドラジンに結合するォキザリル基には、 置換されてもょ 、ピペリジルァミノ基が特に好ま 、。テトラゾリゥム化合物の具体例 を下記に示す。 [0064] The hydrazine compound is particularly preferably one in which a sulfonamidophenol group is substituted as the T group and a trifluoromethyl group is substituted as the V group. The oxalyl group bonded to hydrazine is particularly preferably a piperidylamino group, although it may be substituted. Specific examples of tetrazolium compounds are shown below.
[0065] (T- 1) : 2, 3 ジ(p—メチルフエ-ル) 5 フエ-ルテトラゾリゥムクロリド
(τ- - 2) : 2, 3 -ジ (Ρ - -ェチルフエ-ル)一 5 フエ-ルテトラゾリゥムクロリド[0065] (T-1): 2, 3 Di (p-methylphenol) 5 phenol tetrazolium chloride (τ--2): 2, 3 -Di (Ρ--ethyl chloride)-1 5 tetratetrazolium chloride
(τ- -3) : 2, 3, 5 トリ —P メチルフエ-ルテトラゾリゥムクロリド (τ- -3): 2, 3, 5 Tri —P Methylphenol tetrazolium chloride
(τ- -4) : 2, 3ージフヱ-ニル 5— (p—メトキシフエ-ル)テトラゾリゥムクロリド (τ- -4): 2, 3-diphenyl-nyl 5- (p-methoxyphenyl) tetrazolium chloride
(τ- -5) : 2, 3 —ジ(ο—メチルフヱ-ル)一 5—フエ-ルテトラゾリゥムクロリド(τ- -5): 2, 3 — Di (ο—methylphenol) 1—Fuel tetrazolium chloride
(τ- -6) : 2, 3, 5 トリ —P—メトキシフエニルテトラゾリゥムクロリド (τ- -6): 2, 3, 5 Tri —P-methoxyphenyltetrazolium chloride
(τ- -7) : 2, 3 —ジ(0—メチルフヱ-ル)一 5—フエ-ルテトラゾリゥムクロリド (τ- -7): 2, 3 — Di (0-methylphenol) -5-phenoltetrazolium chloride
(τ- -8) : 2, 3 —ジ(m_ -メチルフヱ-ル)一 5—フエ-ルテトラゾリゥムクロリド(τ- -8): 2, 3 — Di (m_-methylphenol) 5-5-tetratetrazolium chloride
(τ- -9) : 2, 3, 5 トリ p エトキシメチルフエ-ルテトラゾリゥムクロリド。 (τ- -9): 2, 3, 5 Tri-p ethoxymethylphenol tetrazolium chloride.
[0066] これらは特公平 5— 58175号公報の記載を参考に使用することができ、場合によつ てはヒドラジンィ匕合物と併用することもできる。 [0066] These can be used with reference to the description in JP-B-5-58175, and in some cases, they can be used in combination with hydrazine compounds.
[0067] 硬調化剤としてヒドラジンを使用するときに、ヒドラジンの還元作用を強化するため にアミンィ匕合物またはピリジンィ匕合物が使用される。代表的なアミンィ匕合物は、少なく とも一つの窒素原子を含む下記一般式で表すことができる。 [0067] When hydrazine is used as a thickening agent, an amine compound or a pyridine compound is used to enhance the reduction action of hydrazine. A representative amine compound can be represented by the following general formula containing at least one nitrogen atom.
[0068] R—N (Z)—Q、R— N (Z)—L— N (W)—Q [0068] R—N (Z) —Q, R—N (Z) —L—N (W) —Q
式中の R、 Q、 Z、 Wは炭素数 2〜30の置換されてもよいアルキル基を表す。また、 これらのアルキル基鎖は窒素、硫黄、酸素等のへテロ原子で結合されてもよい。 Rと Z 、あるいは Qと Wは、互いに飽和及び不飽和の環を形成してもよい。 Lは 2価の連結 基を表す。この連結基の中には、硫黄、酸素、窒素等のへテロ原子が含まれてもよい 。 Lの連結基の中の炭素数は 1から 200まで可能であり、硫黄原子は 1から 30まで、 窒素原子は 1から 20まで、酸素原子は 1から 40までである力 特に限定されるもので はな 、。これらのアミンィ匕合物の具体例を下記に示す。 R, Q, Z, and W in the formula represent an alkyl group having 2 to 30 carbon atoms that may be substituted. Further, these alkyl group chains may be bonded by a heteroatom such as nitrogen, sulfur, or oxygen. R and Z, or Q and W may form a saturated and unsaturated ring with each other. L represents a divalent linking group. This linking group may contain a hetero atom such as sulfur, oxygen, and nitrogen. The linking group of L can have 1 to 200 carbon atoms, 1 to 30 sulfur atoms, 1 to 20 nitrogen atoms and 1 to 40 oxygen atoms. Flower ,. Specific examples of these amine compounds are shown below.
(A- 1) :ジェチルァミノエタノール (A- 1): Jetylaminoethanol
(A- 2) :ジメチルアミノー 1 (A- 2): Dimethylamino-1
(A- -3) : 2 プロパンジオール (A- -3): 2 Propanediol
(A- -4) : 5 アミノー 1 ペンタノ一 (A- -4): 5 Amino-1 pentano
(A- -5) :ジェチノレアミン (A- -5): Jetenoreamine
(A- -6) :メチルァミン (A- -6): Methylamine
(A— -7) :トリエチルァミン
(A- 8):ジプロピルァミン (A— -7): Triethylamine (A-8): Dipropylamine
(A- 9) : 3—ジメチノレアミノ- -プロノ ノ一ノレ (A-9): 3-Dimethyleno-amino-prono-no-nore
(A- 10 1 ジメチルァミノ 2—プロパノール (A-10 1 Dimethylamino 2-propanol
(A- 11 ビス(ジメチルアミノテトラエトキシ)チォエーテル (A-11 Bis (dimethylaminotetraethoxy) thioether
(A- 12 ビス(ジェチルァミノペンタエトキシ)チォエーテル (A-12 Bis (jetylaminopentaethoxy) thioether
(A- 13 ビス(ピペリジノテトラエトキシ)チォエーテル (A- 13 Bis (piperidinotetraethoxy) thioether
(A- 14 ビス(ピベリジノエトキシェチル)チォエーテル (A-14 Bis (piberidinoethoxyethyl) thioether
(A- 15 ビス(-ペコチンジエトキシ)チォエーテル (A-15 Bis (-pecotinediethoxy) thioether
(A- 16 ビス(ジシァノエチノレアミノジエトキシ)エーテノレ (A-16 Bis (disyanethinoleaminodiethoxy) etherole
(A- 17 ビス(ジエトキシェチルアミノテトラエトキシ)エーテル (A-17 Bis (diethoxyethylaminotetraethoxy) ether
(A- 18 5—ジブチルアミノエチルカルバモイルペンゾトリアゾール (A-18 5-Dibutylaminoethylcarbamoyl benzotriazole
(A- 19 5 モルホリノエチルカルバモイルベンゾトリァゾール (A- 19 5 Morpholinoethylcarbamoylbenzotriazole
(A- 20 5—(2 メチルイミダゾールー 2 エチレン)力ルバモイルベンゾトリァゾ 一ノレ (A-20 5— (2 Methylimidazole-2 Ethylene) Force Rubamoylbenzotriazo Inore
(A- 21): 5 ジメチルアミノエチルゥレイレンべンゾトリアゾール (A-21): 5 Dimethylaminoethylureylene benzotriazole
(A- 22): 5 ジェチルアミノエチルゥレイレンべンゾトリアゾール (A-22): 5 Jetylaminoethylureylene benzotriazole
(A- 23) : 1 -ジェチノレアミノ 2—(6 ァミノプリン)ェタン (A-23): 1-Getinoreamino 2- (6 aminopurine) ethane
(A- 24): 1 (ジメチルアミノエチル) 5 メルカプトテトラゾール (A-24): 1 (dimethylaminoethyl) 5 mercaptotetrazole
(A- 25): 1ーピベリジノエチル 5 メルカプトテトラゾール (A-25): 1-Piberidinoethyl 5 Mercaptotetrazole
(A- 26): 1ージメチルアミノー 5 メルカプトテトラゾール (A- 26): 1-Dimethylamino-5 Mercaptotetrazole
(A- 27): 2 メルカプト 5 ジメチルアミノエチルチオチアジアゾール (A- 28) : 1 メルカプト 2 モルホリノエタン。 (A-27): 2 mercapto-5 dimethylaminoethylthiothiadiazole (A-28): 1 mercapto-2 morpholinoethane.
[0070] ヒドラジンィ匕合物の還元作用を促進するアミンィ匕合物としては、分子中にピぺリジン 環またはピロリジン環が少なくとも 1個、チォエーテル結合が少なくとも 1個、エーテル 結合が少なくとも 2個あることが特に好ましい。 [0070] The amine compound that promotes the reducing action of the hydrazine compound includes at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds in the molecule. Is particularly preferred.
[0071] ヒドラジンの還元作用を促進する化合物として、ピリジニゥム化合物やホスホニゥム 化合物がアミンィ匕合物の他に使用される。ォ -ゥム化合物は正電荷を帯びているた め、負電荷に帯電しているハロゲンィ匕銀粒子に吸着して、現像時の現像主薬からの
電子注入を促進することにより硬調化を促進するものと考えられている。好ましいピリ ジ-ゥム化合物は、特開平 5— 53231号、同 6— 242534号の各公報のビスピリジ- ゥム化合物を参照することができる。特に好ましいピリジ-ゥム化合物は、ピリジ-ゥム の 1位または 4位で連結してビスピリジ-ゥム体を形成して!/、るものである。塩にお!ヽ ては、ハロゲンァ-オンとして塩素イオンや臭素イオン等が好ましぐ他に 4フッ化ホウ 素イオン、過塩素酸イオン等が挙げられるが、塩素イオンまたは 4フッ化ホウ素イオン が好まし!/、。下記に好ま U、ビスピリジ-ゥム化合物を示す。 [0071] As compounds that promote the reduction action of hydrazine, pyridinium compounds and phosphonium compounds are used in addition to amine compounds. Since the oum compound is positively charged, it adsorbs to the negatively charged silver halide particles and removes it from the developing agent during development. It is considered that high contrast is promoted by promoting electron injection. As preferred pyridinium compounds, reference can be made to the bispyridium compounds described in JP-A-5-53231 and JP-A-6-242534. Particularly preferred pyridinium compounds are those that are linked at the 1- or 4-position of the pyridinium to form a bispyridium! To salt! For example, in addition to chlorine ions and bromine ions as halogen ions, boron tetrafluoride ions and perchlorate ions are preferred, but chlorine ions or boron tetrafluoride ions are preferred! / ,. Preferred U and bispyridium compounds are shown below.
(B- 1) : 1, 1' ジメチルー 4, 4' - -ビビリジニゥムジクロライド (B- 1): 1, 1 'Dimethyl-4, 4'--Bibiridinum dichloride
(B- 2) : 1, 1' ージベンジルー 4, 4' ビビリジニゥムジクロライド (B-2): 1, 1'-dibenzyl-4,4 'bibilidinium dichloride
(B- 3) : 1, 1' ージへプチルー 4, 4' ビビリジニゥムジクロライド (B- 3): 1, 1 'Huge Petit Lou 4, 4' Bibilidinum Dichloride
(B- 4) : 1, 1' ージー η—ォクチルー 4, 4' ビビリジニゥムジクロライド (B- 4): 1, 1 'Zee η-octyl 4, 4' bibilidinum dichloride
(B- 5) :4, ' ジメチルー 1, 1' - -ビビリジニゥムジクロライド (B-5): 4, 'Dimethyl-1, 1'--Bibiridinum dichloride
(B- 6) :4, ' ージベンジルー 1, \' ビビリジニゥムジクロライド (B- 6): 4, '-Benzyl- 1, \' Bibilidinum dichloride
(B- 7) :4, ' ージヘプチノレー 1, \' ビビリジニゥムジクロライド (B- 7): 4, '--Geheptinolay 1, \' Bibilidinum dichloride
(B- 8) :4, ' ージー η—ォクチルー 1, 1' ビビリジニゥムジクロライド (B-8): 4, 'Zee η-octyl 1, 1' bibilidinum dichloride
(B- 9) :ビス(4, 4' ージァセトアミド- - 1, 1' ーテトラメチレンピリジ-ゥム)ジクロ ライド。 (B-9): Bis (4,4′-diacetamido--1,1′-tetramethylenepyridinum) dichloride.
[0073] ヒドラジンィ匕合物は高濃度部の硬調化に作用するが、脚部の硬調化が不十分であ るため、これを改良する試みとして、現像時に生成する現像主薬の酸化体を利用す る技術を使用してもよ ヽ。現像主薬の酸化体と反応するレドックス化合物を存在させ て、この化合物力 脚部を抑制する抑制剤を放出させることにより画像の鮮明性を高 めるのである。現像主薬の酸化体の発生は現像の進行により発生するので、粒子の 還元速度と関係がある。化学増感剤で還元速度の早い現像核を形成しておくと、こ の効果を高めることができるので、良い化学増感剤を使用するのが好ましい。レドック ス化合物を使用すると、画像のエッジを鋭くするので粒子間隔を狭め銀の金属線の 抵抗を下げることができる。 [0073] Although the hydrazine compound acts on the high-concentration contrast, the contrast of the legs is insufficient, and as an attempt to improve this, an oxidized form of the developing agent produced during development is used. You can use this technique. The presence of a redox compound that reacts with the oxidized oxidant of the developing agent increases the sharpness of the image by releasing an inhibitor that suppresses the strength of the compound. Oxidation of the developing agent is generated by the progress of development and is related to the reduction rate of the particles. It is preferable to use a good chemical sensitizer because this effect can be enhanced by forming a development nucleus having a high reduction rate with a chemical sensitizer. Using redox compounds sharpens the edges of the image, reducing the grain spacing and reducing the resistance of silver metal lines.
[0074] レドックス化合物は、レドックス基としてハイドロキノン類、カテコール類、ナフトハイド ロキノン類、ァミノフエノール類、ビラゾリドン類、ヒドラジン類、レダクトン類等を有する
。好ましいレドックス化合物は、レドックス基として NHNH 基を有する化合物であ り、次の一般式で示すものが代表的である。 [0074] Redox compounds have hydroquinones, catechols, naphthohydroquinones, aminophenols, virazolidones, hydrazines, reductones, etc. as redox groups. . Preferred redox compounds are compounds having an NHNH group as a redox group, and those represented by the following general formula are typical.
[0075] T-NHNHCO-V- (Time) PUG [0075] T-NHNHCO-V- (Time) PUG
T-NHNHCOCO-V- (Time) PUG T-NHNHCOCO-V- (Time) PUG
式中、 T及び Vは前記ヒドラジンィ匕合物と同義の基を表す。 PUGは写真有用性基 を表し、例えば、 5 -トロインダゾール、 4 -トロインダゾール、 1 フエ-ルテトラ ゾール、 1— (3—スルホフエ-ル)テトラゾール、 5 -トロべンズトリァゾール、 4— - トロべンゾトリァゾール、 5— -トロイミダゾール、 4— -トロイミダゾール等が挙げられる 。これらの現像抑制化合物は、丁ー?《1?«1—じ0—のじ0部位に?^ゃ3等のへテロ 原子を介して直接または (Time)で表される、アルキレン、フエ-レン、ァラルキレン、 ァリール基を介して更に Nや Sのへテロ原子を介して接続することができる。その他に 、バラスト基がついたハイドロキノン化合物にトリァゾール、インダゾール、イミダゾー ル、チアゾール、チアジアオールなどの現像抑制基を導入したものも使用できる。 In the formula, T and V represent a group having the same meaning as the hydrazine compound. PUG represents a photographically useful group, for example, 5-troindazole, 4-troindazole, 1-phenoltetrazole, 1- (3-sulfophenol) tetrazole, 5-trobenztriazole, 4 --- trobenzotriazole , 5--troimidazole, 4--troimidazole and the like. What are these development-inhibiting compounds? 《1? «1--0--directly through a heteroatom such as 3 at the 0 site, or further through an alkylene, phenylene, aralkylene, or aryl group represented by (Time) It can be connected through N or S heteroatoms. In addition, a hydroquinone compound having a ballast group into which development inhibitory groups such as triazole, indazole, imidazole, thiazole and thiadiaol are introduced can be used.
[0076] 例えば、 2- (ドデシルエチレンオキサイド)チォプロピオン酸アミドー 5—(5 -トロ インダゾールー 2—ィル)ハイドロキノン、 2— (ステアリルアミド) 5— (1—フエ-ルテ トラゾールー 5 チォ)ハイドロキノン、 2—(2, 4 ジ t—アミルフエノプロピオン酸 アミド)—5— (5 -トロトリァゾールー 2—ィル)ハイドロキノン、 2 ドデシルチオ— 5 一(2 メルカプトチォチアジアゾールー 5 チォ)ハイドロキノン等が挙げられる。な お、 nは 1または 0を表す。レドックス化合物は、米国特許第 4, 269, 929号明細書の 記載を参考にして合成することができる。 [0076] For example, 2- (dodecylethylene oxide) thiopropionic acid amide-5- (5-troindazole-2-yl) hydroquinone, 2- (stearylamide) 5-(1-fertetrazol-5thio) hydroquinone, 2— (2,4 di-t-amylphenopropionic acid amide) —5— (5-trotriazole-2-yl) hydroquinone, 2 dodecylthio—5 1 (2 mercaptothiadiazole-5 thio) hydroquinone, etc. Can be mentioned. N represents 1 or 0. The redox compound can be synthesized with reference to the description in US Pat. No. 4,269,929.
[0077] 特に好ま 、レドックス化合物を下記に挙げる。 [0077] Particularly preferred are the redox compounds listed below.
[0078] ー1) : 1ー(4ー-トロィンダゾールー2—ィルーカルボ-ル)ー2—{〔4ー(3—11 ブチルウレイド)フエ-ル〕 }ヒドラジン [0078] -1): 1- (4-Troindazole- 2-Lucal Ball)-2-{[4- (3-11 Butylureido) -Fail]} Hydrazine
(R- 2): 1 (5 -トロインダゾールー 2—ィルーカルボ-ル)ー2—{4ー〔2—(2 , 4—ジ— tertペンチルフエノキシ)ブチルアミド〕フエ-ル}ヒドラジン (R-2): 1 (5-troindazol-2-yllucol) -2-2- {4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenol} hydrazine
(R— 3): 1— (4 -トロトリァゾール— 2—ィル—カルボ-ル)—2— {4—〔2— (2, 4—ジ一 tert—ペンチルフエノキシ)ブチルアミド〕フエ-ル}ヒドラジン (R—3): 1— (4-trotriazole-2-yl-carbol) —2— {4- (2- (2, 4-di-tert-pentylphenoxy) butyramide] phenol } Hydrazine
(R— 4) : 1— (4 -トロイミダゾールー 2—ィルーカルボ-ル)ー2—{4一〔2— (2,
4—ジ— t—ペンチルフエノキシ)ブチルアミド〕フエ-ルスルホンアミドフエ-ル}ヒドラ ジン (R—4): 1— (4-Troimidazole 2- 2-Lucol Ball) -2— {4 1 [2— (2, 4-Di-t-pentylphenoxy) butyramide] phenolsulfonamidephenol} hydrazine
(R—5): 1—(1 スルホフエ-ルテトラゾールー 4ーメチルォキサゾール)ー2— {3 -〔1—フエ-ル一 / —p クロ口フエ-ルメタンチォグリシンアミドフエ-ル〕スルホ ンアミドフエ-ル}ヒドラジン (R-5): 1- (1 Sulphophenyltetrazole-4-Methyloxazole) -2-{3-[1-Fel //-p Chloroform methanethioglycinamide phenol] sulfo Namidephenol} hydrazine
(R—6): 1—(4 -トロインダゾールー 2—ィルーカルボ-ル)ー2—{〔4 (オタチ ルーテトラエチレンオキサイド) チォ グリシンアミドフエ-ル スルホンアミドフエ- ル〕 }ヒドラジン。 (R-6): 1- (4-troindazol-2-yllucol) -2-{[4 (Otachirutetraethylene oxide) thioglycinamide file sulfonamide file]} hydrazine.
[0079] ヒドラジンィ匕合物、アミンィ匕合物、ピリジ-ゥム化合物、テトラゾリゥム化合物及びレド ックス化合物はハロゲン化銀 1モル当たり 1 X 10— 6〜5 X 10— 2モル含有するのが好ま しぐ特に 1 X 10— 4〜2 X 10— 2モルが好ましい。これらの化合物の添力卩量を調節して、 硬調化度 γを 6以上にすることは容易である。 γは更に乳剤の単分散性、ロジウムの 使用量、化学増感等によって調節することができる。ここに、 γは濃度 0. 1と 3. 0を 与えるそれぞれの露光量の差に対する濃度差とする。 [0079] Hidorajini匕合thereof, Amini匕合thereof, pyrid - © beam compounds, Tetorazoriumu compound and TOLEDO box compound Shi preferred is to 1 X 10- 6 ~5 X 10- 2 molar content per mole of silver halide ingredients particularly 1 X 10- 4 ~2 X 10- 2 mol is preferred. It is easy to increase the degree of contrast γ to 6 or more by adjusting the amount of applied force of these compounds. γ can be further adjusted by the monodispersity of the emulsion, the amount of rhodium used, chemical sensitization, and the like. Here, γ is the density difference with respect to the difference between the exposure amounts giving the densities of 0.1 and 3.0.
[0080] これらの化合物はハロゲン化粒子を含む層、または他の親水性コロイド層に添加し て使用する。水溶性の場合には水溶液にして、水不溶性の場合にはアルコール類、 エステル類、ケトン類等の水に混和しうる有機溶媒の溶液としてハロゲンィ匕銀粒子溶 液、または親水性コロイド溶液に添加すればよい。また、これらの有機溶媒に溶けな いときには、ボールミル、サンドミル、ジェットミル等で 0. 01〜10 mの大きさの微粒 子にして添加することができる。微粒子分散の方法は、写真添加剤である染料の固 体分散の技術を好ましく応用することができる。例えば、ボールミル、遊星回転ボー ルミル、振動ボールミル、ジェットミル等の分散機を使用して所望の粒子径にすること ができる。分散時に界面活性剤を使用すると分散後の安定性を向上させることができ る。 [0080] These compounds are used by being added to a layer containing halogenated particles or another hydrophilic colloid layer. If it is water-soluble, add it to an aqueous solution, and if it is water-insoluble, add it as a solution of an organic solvent that is miscible with water, such as alcohols, esters, and ketones, to a halogenated silver particle solution or a hydrophilic colloid solution. do it. Further, when it is not soluble in these organic solvents, it can be added as fine particles having a size of 0.01 to 10 m by a ball mill, sand mill, jet mill or the like. As the fine particle dispersion method, a solid dispersion technique of a dye as a photographic additive can be preferably applied. For example, a desired particle size can be obtained by using a disperser such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill. When a surfactant is used during dispersion, stability after dispersion can be improved.
[0081] 本発明に係るハロゲン化銀粒子含有層にお ヽて、ハロゲン化銀粒子を均一に分散 させ、且つハロゲンィ匕銀粒子を支持体上に担持し、ハロゲン化銀粒子含有層と支持 体の接着性を確保する目的でバインダーを用いることができる。 [0081] In the silver halide grain-containing layer according to the present invention, the silver halide grains are uniformly dispersed and the silver halide grains are supported on the support, and the silver halide grain-containing layer and the support are supported. A binder can be used for the purpose of ensuring the adhesion of the resin.
[0082] 本発明にお ヽて用 、ることができるバインダーには特に制限がなく、非水溶性ポリ
マー及び水溶性ポリマーのいずれも用いることができる力 現像性向上の観点からは 水溶性ポリマーを用いることが好ましい。本発明においては、バインダーとしてゼラチ ンを用いることが有利であるが、必要に応じてゼラチン誘導体、ゼラチンと他の高分 子のグラフトポリマー、ゼラチン以外のタンパク質、糖誘導体、セルロース誘導体、単 一あるいは共重合体のごとき合成親水性高分子物質等の親水性コロイドも用いること ができる。ハロゲンィ匕銀粒子含有層中のバインダー量には特に制限はなぐ塗布性、 皮膜物性、及び電磁波遮蔽性能等から、最適な値を用いることができる。 [0082] The binder that can be used in the present invention is not particularly limited, and the water-insoluble polymer is not limited. The ability to use both a polymer and a water-soluble polymer From the viewpoint of improving developability, it is preferable to use a water-soluble polymer. In the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, gelatin and other high molecular weight graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, single or A hydrophilic colloid such as a synthetic hydrophilic polymer such as a copolymer can also be used. The amount of the binder in the layer containing the silver halide silver particles is not particularly limited, and an optimum value can be used from the viewpoints of coating properties, film properties, electromagnetic wave shielding performance, and the like.
[0083] 現像銀のネットワークを形成し、現像後の皮膜の導電性を高めるという観点から、本 発明においては、通常の撮影用ハロゲンィ匕銀写真感光材料より AgZバインダー体 積比を高く設定することが好ましぐ粒子含有層中のバインダーの含有量は AgZバ インダー体積比で 0. 2〜: LOOであることが好ましぐ 0. 3〜30であることがより好まし く、 0. 3〜10であること力更に好まし!/ヽ。 [0083] From the viewpoint of forming a developed silver network and increasing the conductivity of the film after development, in the present invention, the AgZ binder volume ratio is set higher than that of a normal photographic silver halide silver photographic material. The binder content in the particle-containing layer is preferably 0.2 to: LOO in terms of AgZ binder volume ratio, more preferably 0.3 to 30, and 0.3. It is more preferable to be ~ 10! / ヽ.
[0084] 本発明において、近赤外線遮蔽の目的で近赤外線吸収染料を含む層が設けられ る。この近赤外線吸収染料は、その近赤外線遮蔽効果を高めること、分散または溶 解安定性を高めること、経時安定性を高めることのために、特に水分散性熱可塑性 榭脂または燐酸エステルの微粒子と共にゼラチン水溶液中で分散することが好まし いことを見出した。 In the present invention, a layer containing a near-infrared absorbing dye is provided for the purpose of shielding near-infrared rays. This near-infrared absorbing dye is used together with fine particles of water-dispersible thermoplastic resin or phosphate ester, in order to increase its near-infrared shielding effect, increase dispersion or dissolution stability, and increase stability over time. We have found that it is preferable to disperse in an aqueous gelatin solution.
[0085] 本発明に用いられる水分散性熱可塑性榭脂は支持体上に塗布され、加熱乾燥に よって皮膜を形成しうるように乾燥温度で熱可塑性の榭脂である。乾燥温度は、通常 、室温から約 100°Cの間であり、この範囲の温度で乾燥が行われる。 [0085] The water-dispersible thermoplastic resin used in the present invention is a thermoplastic resin coated at a drying temperature so that a film can be formed by heating and drying on a support. The drying temperature is usually between room temperature and about 100 ° C, and drying is performed at a temperature in this range.
[0086] 本発明に用いられる水分散性熱可塑性榭脂は、特に水媒体中に安定して分散さ れる榭脂を扱うのでラテックスと同義語として扱う。ラテックスとはゴムの榭など力も採 取される白色乳状の榭液を指していたが、乳化重合物の出現以来、合成高分子の 水分散体も含めて、水性媒体の中に高分子物質が安定して分散してるものをラテツ タスと呼ぶようになったのでこの呼称が使用されて!、る。 [0086] The water-dispersible thermoplastic resin used in the present invention is treated as a synonym for latex because it handles a resin that is stably dispersed in an aqueous medium. Latex refers to a white milky liquid that can also be used to absorb forces such as rubber wrinkles, but since the advent of emulsion polymers, polymeric substances, including aqueous dispersions of synthetic polymers, have been incorporated into aqueous media. Those that are stably dispersed are now called latus status, so this designation is used!
[0087] 水分散性熱可塑性榭脂としては、例えば、ポリ塩ィ匕ビユリデン、塩ィ匕ビユリデン一ァ クリル酸共重合体、塩ィ匕ビ -リデンーィタコン酸共重合体、ポリアクリル酸ナトリウム、 ポリエチレンォキシド、アクリル酸アミドーアクリル酸エステル共重合体、スチレン 無
水マレイン酸共重合体、アクリロニトリル ブタジエン共重合体、塩化ビニルー酢酸ビ -ル共重合体、場合によってはアクリル酸、メタアクリル酸、ィタコン酸及びマレイン酸 等のカルボン酸基を含むモノマーあるいは、ジメチルアクリルアミドプロパンスルホン 酸、スチレンスルホン酸基等のスルホン酸基を持つモノマーを一つまたは複数組み 合わせて少量使用したスチレン ブタジエン系共重合体、スチレン一イソプレン系共 重合体等が挙げられる。 [0087] Examples of the water-dispersible thermoplastic resin include polysalt-vinylidene, salt-syl-vinylidene-acrylic acid copolymer, salt-syl-vinylidene-taconic acid copolymer, sodium polyacrylate, polyethylene Oxide, acrylic acid amide-acrylic acid ester copolymer, styrene Water maleic acid copolymer, acrylonitrile butadiene copolymer, vinyl chloride-vinyl acetate copolymer, and monomers containing carboxylic acid groups such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, or dimethylacrylamide Examples thereof include a styrene butadiene copolymer and a styrene monoisoprene copolymer using a small amount of one or a plurality of monomers having a sulfonic acid group such as propane sulfonic acid and styrene sulfonic acid group.
[0088] 上記ラテックスは水系塗布の結合剤として広く使用されているが、中でも結合剤とし て耐水性を向上させるラテックスが好ましい。結合剤として耐水性を得る目的のラテツ タスの使用量は、塗布性を勘案して決められる力 耐湿性の点力 使用量は多いほ ど好ましく、全結合剤質量に対して 50%以上 100%以下が好ましぐ 80%以上 100 %以下がより好ま 、。このような榭脂を市場力も入手することもできる。 [0088] The above latex is widely used as a binder for aqueous coating, and among them, a latex that improves water resistance is preferable as a binder. The amount of latus used for the purpose of obtaining water resistance as a binder is a power determined in consideration of applicability. The point of moisture resistance The amount used is preferably as high as possible. 50% or more to the total binder mass 100% 80% or more and 100% or less are more preferred. Such a rosin can also be marketed.
[0089] 例えば、スチレン榭脂としてはスチレン ブタジエンコポリマーの業界統一品番で、 [0089] For example, styrene resin is an industry standard product number of styrene-butadiene copolymer,
# 1500、 # 1502、 # 1507、 # 1712、 # 1778などの種々の銘柄の住友 SBRラテ ックス (住友化学 (株))や JSRラテックス(日本合成ゴム (株))や Nipolラテックス (日本 ゼオン (株))を用いることができる。スチレン一ブタジエンコポリマーは、スチレンとブ タジェンの共重合比(質量)力 S10Z90〜90Z10、より好ましくは 20Z80〜60Z40 が好ましい。ハイスチレンラテックスと呼ばれる 60Ζ40〜90Ζ10の比率のものは、ス チレン含率の低 、(10Ζ90〜30Ζ70)榭脂と混合して用いるのが、感光層の耐傷 性、物理的強度を高める上で好ましい。混合比率 (質量)は、 20Ζ80〜80Ζ20の 範囲内が好ましい。 Various brands such as # 1500, # 1502, # 1507, # 1712, # 1778, Sumitomo SBR Latex (Sumitomo Chemical Co., Ltd.), JSR Latex (Nippon Synthetic Rubber Co., Ltd.), Nipol Latex (Nippon Zeon Corporation) )) Can be used. The styrene-butadiene copolymer preferably has a styrene / butadiene copolymer ratio (mass) force of S10Z90 to 90Z10, more preferably 20Z80 to 60Z40. A high styrene latex having a ratio of 60 to 40 to 90 to 10 is preferably used in combination with a low styrene content and (10 to 90 to 70) resin in order to increase the scratch resistance and physical strength of the photosensitive layer. . The mixing ratio (mass) is preferably in the range of 20-80-80-20.
[0090] ハイスチレンラテックスとしては、 JSR0051や同 0061 (以上、日本合成ゴム (株)の 商品名)、及び Nipol 2001、 2057、 2007 (日本ゼオン (株)の商品名)などの巿販 品が使える。またスチレン含率の低いラテックスとしては、上記のハイスチレンラテック スとして列挙した以外の常用のものが挙げられ、 JSR# 1500、 # 1502、 # 1507、 # 1712、 # 1778等力ある。 [0090] Examples of high styrene latex include JSR0051 and 0061 (Nippon Synthetic Rubber Co., Ltd.) and Nipol 2001, 2057, 2007 (Nippon Zeon Co., Ltd.). It can be used. Latexes with a low styrene content include those commonly used other than those listed above as the high styrene latex, and include JSR # 1500, # 1502, # 1507, # 1712, and # 1778.
[0091] また、アクリル榭脂として一般に知られるアクリル系ラテックス、例えば、 Nipol AR3 1、 AR32あるいは Hycar 4021 (V、ずれも日本ゼオン (株)の商品名 )を用いること ができる。
[0092] 前記したアクリル榭脂は、次のアタリレートモノマーを原料とする重合体または共重 合体を用いることもできる。なお、以下において、 (メタ)アタリロイル基はアタリロイル 基またはメタアタリロイル基の意味で用いる。分子中に (メタ)アタリロイル基を 1個有す るモノマとしては、メチルメタタリレート、ェチルメタタリレート、ォクチルメタタリレート等 の脂肪族アルコールのメタクリル酸エステル、メチルアタリレート、ェチルアタリレート、 ブチルアタリレート、ォクチルアタリレート等の脂肪族アルコールのアクリル酸エステル 、シクロへキシルアタリレート、シクロへキシルメチルアタリレート等の脂環式アルコー ルのアクリル酸エステル、シクロへキシルメタタリレート、シクロへキシルメチルメタタリ レート等の脂環式アルコールのメタクリル酸エステル、フエ-ルアタリレート、 4 プロ モフエ-ルアタリレート、ベンジルアタリレート、ベンジルメタタリレート等の芳香族基を 含むアクリル酸エステル、フエ-ルメタタリレート、 4—クロルフエ-ルメタタリレート、ベ ンジルメタタリレート等の芳香族基を含むメタクリル酸エステル、 2—ヒドロキシェチル アタリレート、 2—ヒドロキシェチルメタタリレート等のアクリル酸またはメタクリル酸のヒ ドロキシアルキルエステル等がある。 [0091] In addition, acrylic latex generally known as acrylic resin, such as Nipol AR31, AR32 or Hycar 4021 (V, trade name of Nippon Zeon Co., Ltd.) can be used. [0092] As the above-described acrylic resin, a polymer or copolymer using the following acrylate monomer as a raw material can also be used. In the following, the (meth) atalyloyl group is used in the meaning of an atalyloyl group or a methallyloyl group. Monomers having one (meth) atallyloyl group in the molecule include methacrylic acid esters of methyl alcohol, methyl acrylate, ethyl acrylate, ethyl acrylate, Acrylate esters of aliphatic alcohols such as acrylate, butyl acrylate and octyl acrylate, acrylate esters of alicyclic alcohol such as cyclohexyl acrylate and cyclohexyl methyl acrylate, cyclohexyl methacrylate Acrylates containing aromatic groups such as methacrylic acid esters of alicyclic alcohols such as acrylate, cyclohexylmethyl methacrylate, phenol acrylate, 4-propyl acrylate, benzyl acrylate, benzyl methacrylate Acid ester, phenol methacrylate, 4-chloro Methacrylic acid esters containing aromatic groups such as ethyl metatalylate and benzyl metatalylate, acrylic acid or methacrylic acid hydroxy such as 2-hydroxyethyl atylate, 2-hydroxyethyl metatalylate There are alkyl esters and the like.
[0093] 分子中に (メタ)アタリロイル基を 2個以上有するモノマーとしては、エチレングリコー ルジアタリレート、プロピレングリコールジアタリレート、ジエチレングリコールジアタリレ ート、 1, 3 ジァクリロキシー2 プロパノールポリエチレングリコールジアタリレート等 のアクリル酸ジエステル、エチレングリコールジメタタリレート、プロピレングリコールジ メタタリレート、ジエチレングリコールジメタタリレート、ポリエチレングリコールジメタタリ レート、 1, 3 ジメタクリロキシー2 プロパノール等のメタクリル酸ジエステル、グリセ リントリアタリレート、トリメチロールプロパントリアタリレート等のアクリル酸トリエステル、 グリセリントリメタタリレート、トリメチロールプロパントリメタタリレート等のメタクリル酸トリ エステノレ等がある。 [0093] Monomers having two or more (meth) atalyloyl groups in the molecule include ethylene glycol diatalate, propylene glycol diatalate, diethylene glycol diatalate, 1,3 diacryloxy-2-propanol polyethylene glycol diatalate. Acrylic acid diesters such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 dimethacryloxy-2-propanol and other methacrylic acid diesters, glycerin tritalylate, trimethylol Acrylic acid triesters such as propane tritalylate, methacrylic acid such as glycerin trimetatalylate, trimethylolpropane trimetatalylate There are acid triesterol.
[0094] スチレン榭脂としては、スチレンモノマーとしてメチルスチレン、ェチルスチレン、プ 口ピノレスチレン、ブチルスチレン、へキシルスチレン、へプチルスチレン、オタチノレス チレン、ジメチルスチレン、トリメチルスチレン、ジェチルスチレン、トリェチノレスチレン などのァノレキノレスチレンモノマー、フロロスチレン、クロロスチレン、ブロモスチレン、ョ 一ドスチレン、ジブ口モスチレンなどのハロゲンィ匕スチレンモノマー、ニトロスチレンモ
ノマー、ァセチルスチレンモノマー、メトキシスチレンモノマー等を使用し、単独または 他のモノマーと共重合したものである。 [0094] As styrene resin, styrene monomers such as methyl styrene, ethyl styrene, propylene styrene, butyl styrene, hexyl styrene, heptyl styrene, otachinol styrene, dimethyl styrene, trimethyl styrene, jetyl styrene, triethyl styrene Halogenostyrene monomers such as styrene styrene monomer, fluorostyrene, chlorostyrene, bromostyrene, styrene styrene, dibutyl styrene, Using monomers, acetyl styrene monomers, methoxy styrene monomers, etc., alone or copolymerized with other monomers.
[0095] ビュル榭脂としては、モノマーとしてビュルピリジン、ビュルピロリドン、ビュル力ルバ ゾール、酢酸ビュル、アクリロニトリル、塩化ビュル、臭化ビュル、塩ィ匕ビユリデン、臭 化ビ-リデンなどのハロゲンィ匕ビュル、またはビ-リデン等を構成単位として含むもの である。また構成単位として分子中に 2つ以上のビニル基を有するモノマを含んでも よい。例えば、ジビュルベンゼン、ブタジエン、クロ口プレンなどの共役ジェンモノマ 一、イソプレンアジピン酸ジビニノレ、ジビニルスルホン、トリエチレングリコールジビニ ルエーテル、 1, 4ーシクロへキサンジメタノールジビュルエーテル等が挙げられる。 [0095] Examples of bur resin include butyl pyridine, butyl pyrrolidone, bulur rubazole, butyl acetate, acrylonitrile, butyl chloride, butyl bromide, salt vinylidene, odorous vinylidene, and the like as monomers. Alternatively, it contains berylene or the like as a structural unit. Moreover, a monomer having two or more vinyl groups in the molecule may be included as a structural unit. Examples thereof include conjugated genomers such as dibutylbenzene, butadiene, and black-opened plane, isoprene adipate divininole, divinyl sulfone, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol dibule ether, and the like.
[0096] これらのモノマーは前記したように乳化重合させることができる。この乳化重合に用 いる水溶性重合開始剤としては、任意のものが選択できるが例示すると、 2, 2' —ァ ゾビス(2 メチルプロピオンアミジン)二塩酸塩、 4, 4' ァゾビス(4 シァノ吉草 酸)、 2, 2' ーァゾビス [2—(2—イミダゾリン 2—ィル)プロパン]二塩酸塩、 2, 2' ーァゾビス [2— (5—メチルー 2—イミダゾリンー2—ィル)プロパン]二塩酸塩、 2, 2 ' ーァゾビスイソブチルアミドニ水和物等が挙げられる。水溶性重合開始剤の使用 量は、全モノマーに対して 0. 001〜0. 5モル0 /0が好ましい。 [0096] These monomers can be emulsion-polymerized as described above. As the water-soluble polymerization initiator used in this emulsion polymerization, any one can be selected. Examples thereof include 2, 2′-azobis (2 methylpropionamidine) dihydrochloride, 4, 4 ′ azobis (4 Shianoyoshi). Herbic acid), 2, 2'-azobis [2- (2-imidazoline-2-yl) propane] dihydrochloride, 2,2'-azobis [2-(5-methyl-2-imidazoline-2-yl) propane] 2 And hydrochloride, 2,2′-azobisisobutyramide dihydrate, and the like. The amount of the water-soluble polymerization initiator is from 001 to 0.5 mole 0/0 preferably 0. for all the monomers.
[0097] また、前記の乳化重合に用いる分散剤は、系を安定化させるために適宜使用され る。分散安定剤または分散剤としては、ポリビュルアルコール、ポリビュルピロリドン、 ポリアクリルアミド、ポリメタクリルアミド、ヒドロキシアルキルアタリレートポリマー、ヒドロ キシアルキルメタタリレートポリマー、ポリアクリル酸またはその塩、ポリメタクリル酸また はその塩、エチレン アクリル酸共重合体またはその塩、エチレンーメタクリル酸共重 合体またはその塩、エチレン マレイン酸共重合体またはその塩、スチレン アタリ ル酸共重合体またはその塩、スチレンーメタクリル酸共重合体またはその塩、ポリエ チレンィミン、ポリアルキレングリコール、ポリアルキレンォキシド、メチロール化ポリア ミド、水溶性メラミン榭脂、水溶性フエノール榭脂、水溶性尿素樹脂、カゼイン、ゼラ チン、カノレボキシメチノレセノレローズ、メチノレセノレローズ、ヒドロキシァノレキノレセノレロー ズ、カルボキシメチルデンプン、カチオン化デンプン、デキストリン、アルギン酸または その塩、カラギーナン、ジエランガム、ローカストビーンガム、アラビアガム、トラガント
ガム、ダルコマンナン、ザレップマンナン、グァーガム、植物粘液質等の単独または 2 種以上の混合物が用いられる。 [0097] The dispersant used in the emulsion polymerization is appropriately used to stabilize the system. Examples of the dispersion stabilizer or dispersant include polybulal alcohol, polybulurpyrrolidone, polyacrylamide, polymethacrylamide, hydroxyalkyl acrylate polymer, hydroxyalkyl methacrylate polymer, polyacrylic acid or a salt thereof, polymethacrylic acid or Its salt, ethylene acrylic acid copolymer or its salt, ethylene-methacrylic acid copolymer or its salt, ethylene maleic acid copolymer or its salt, styrene attalic acid copolymer or its salt, styrene-methacrylic acid copolymer Polymer or salt thereof, polyethyleneimine, polyalkylene glycol, polyalkylene oxide, methylolated polyamide, water-soluble melamine resin, water-soluble phenol resin, water-soluble urea resin, casein, gelatin, canoleboximethylol Norerozu, methylcarbamoyl Roh receptacle Honoré Rose, hydroxy § Honoré Kino receptacle Honoré low's, carboxymethyl starch, cationic starch, dextrin, alginic acid or a salt thereof, carrageenan, Jierangamu, locust bean gum, gum arabic, tragacanth Gum, dalcomannan, zalepmannan, guar gum, plant mucus, etc. are used alone or as a mixture of two or more.
[0098] 分散剤は使用するモノマーの全量または分散させる榭脂の全量に対して、 0. 01〜 20質量%使用することが好ましい。更に前記の乳化重合に用いる界面活性剤として は、重合反応に悪影響を及ぼさないものであれば特に限定されず、ァ-オン界面活 性剤、カチオン界面活性剤、両性イオン界面活性剤または非イオン界面活性剤のい ずれでも使用できる。 [0098] The dispersant is preferably used in an amount of 0.01 to 20% by mass based on the total amount of monomers to be used or the total amount of rosin to be dispersed. Furthermore, the surfactant used in the emulsion polymerization is not particularly limited as long as it does not adversely affect the polymerization reaction, and is a cation surfactant, cationic surfactant, zwitterionic surfactant or nonionic surfactant. Any surfactant can be used.
[0099] 例えば、アルキルベンゼンスルホン酸ナトリウム、高級アルコール硫酸エステルナト リウム塩、高級 α—才レフインスルホンィ匕物ナトリウム塩、高級脂肪酸塩、高級アルキ ルフエノールアルキレンォキシドスルホン酸ナトリウム、高級アルキルアミン塩、高級ァ ルキルトリメチルアンモ -ゥム塩、高級アルキルピリジ-ゥム塩、高級ァシルアミノメチ ルピリジ -ゥム塩、高級ァシロキシメチルピリジ-ゥム塩、 Ν, Ν—ジポリオキシェチレ ン— Ν—高級アルキルアミン塩、高級アルキルポリエチレンポリアミン塩、トリメチル高 級アルキルァ-リンサルフェート、トリメチル高級アルキルべンジルアンモ -ゥム塩、 高級アルコールエチレンォキシド付加物、高級アルキルフエノールエチレンォキシド 付加物、高級脂肪酸エチレンォキシド付加物、高級アルキルアミンエチレンォキシド 付加物、高級脂肪酸アミドエチレンォキシド付加物、グリセリン高級脂肪酸エステル、 ペンタエリスリトール高級脂肪酸エステル、ソルビトールゃソルビタンの高級脂肪酸ェ ステル (またはこれらのエチレンォキシド付加物)、ショ糖高級脂肪酸エステル、ポリオ ールの高級アルキルエーテル、アルカノールァミンの高級脂肪酸アミド、アミノ酸型両 性活性剤、ベタイン型両性活性剤等の単独または2種以上の混合物が挙げられる。 [0099] For example, sodium alkylbenzenesulfonate, sodium salt of higher alcohol sulfate ester, higher α-year-old lefine sulfone salt sodium salt, higher fatty acid salt, higher alkylphenol alkylene oxide sulfonate sodium salt, higher alkylamine salt, Higher alkyl trimethylammonium salts, higher alkyl pyridinium salts, higher acyl aminomethyl rupyridium salts, higher acyloxymethyl pyridinium salts, Ν, Ν—dipolyoxyethylene-Ν—higher grades Alkylamine salts, higher alkyl polyethylene polyamine salts, trimethyl higher alkyl alkyl phosphate salts, trimethyl higher alkyl benzylammodium salts, higher alcohol ethylene oxide adducts, higher alkyl phenol ethylene oxide adducts, higher fatty acid ethylene oxides Adducts, higher alkylamine ethylene oxide adducts, higher fatty acid amide ethylene oxide adducts, glycerin higher fatty acid esters, pentaerythritol higher fatty acid esters, higher fatty acid esters of sorbitol and sorbitan (or their ethylene oxide adducts) Sucrose higher fatty acid ester, higher alkyl ether of polyol, higher fatty acid amide of alkanolamine, amino acid type amphoteric activator, betaine type amphoteric activator, and the like, or a mixture of two or more thereof.
[0100] 界面活性剤は使用するモノマーの全量または分散させる榭脂の全量に対して、 0. [0100] The surfactant is based on the total amount of the monomers used or the total amount of the resin to be dispersed.
01〜20質量%使用することが好ましい。 It is preferable to use 01 to 20% by mass.
[0101] 本発明に係る水分散性熱可塑性榭脂は、ゼラチンと共にその混合質量比は 1: 2〜 10 : 1で使用することが好ましい。ゼラチンと併用することで前記ハロゲンィ匕銀粒子含 有層と同時重層塗布可能となり、生産性が著しく向上する。ゼラチンの使用質量比が 大きいと耐湿性の劣化が大きぐ少ないと塗布が均一となりにくい。 [0101] The water-dispersible thermoplastic resin according to the present invention is preferably used together with gelatin at a mixing mass ratio of 1: 2 to 10: 1. When used in combination with gelatin, it becomes possible to simultaneously coat the halogen-containing silver particle-containing layer, and the productivity is remarkably improved. If the mass ratio of gelatin used is large, the deterioration of moisture resistance will be large and the coating will not be uniform.
[0102] ゼラチンと使用する場合には、水分散性熱可塑性榭脂に代えて燐酸エステルイ匕合
物をゼラチン中に微粒子分散して使用することができる。 [0102] When used with gelatin, phosphate ester compound is used instead of water-dispersible thermoplastic resin The product can be used by dispersing fine particles in gelatin.
[0103] 燐酸エステルイ匕合物を平均粒子径 ΙΟηπ!〜 10 mの大きさに微粒子分散する方 法は、燐酸エステル化合物を酢酸ェチルのようなエステル有機溶媒に溶解し、ノ-ォ ン性またはァ-オン性界面活性剤を添加しゼラチン中に分散することができる。ここ で使用するノ-オン性またはァ-オン性界面活性剤は、水分散性熱可塑性榭脂の 乳化重合に使用する種類の界面活性剤を適用することができる。分散性を向上させ るには、高能率のホモジナイザー、超音波分散、超音速ジェット分散等を使用すると 微細化粒子として分散が可能である。 [0103] The average particle size of the phosphoric acid ester compound is ΙΟηπ! Dispersing the phosphoric acid ester compound in an ester organic solvent such as ethyl acetate, adding a nonionic or ionic surfactant, and dispersing it in gelatin. can do. As the non-ionic or ionic surfactant used here, a surfactant of the type used for emulsion polymerization of water-dispersible thermoplastic resin can be applied. In order to improve the dispersibility, a highly efficient homogenizer, ultrasonic dispersion, supersonic jet dispersion, etc. can be used to disperse as fine particles.
[0104] 燐酸エステルイ匕合物としては、燐酸と脂肪族アルコールまたは芳香族アルコールま たはこれらの混合アルコールとエステル化したものや、ジアルキルまたはジァリール 燐酸エステルを 2つ以上縮合させた縮合エステルを挙げることができる。具体的には 、トリオクチル燐酸エステル、トリドデシル燐酸エステル、トリフヱ-ル燐酸エステル、ト リクレジル燐酸エステル、トリ p—メチルフエニル燐酸エステル等を挙げることができる [0104] Examples of the phosphoric acid ester compound include those obtained by esterifying phosphoric acid with an aliphatic alcohol, aromatic alcohol, or mixed alcohol thereof, and condensed esters obtained by condensing two or more dialkyl or diaryl phosphoric acid esters. be able to. Specific examples include trioctyl phosphate ester, tridodecyl phosphate ester, triphenyl phosphate ester, tricresyl phosphate ester, tri p-methylphenyl phosphate ester, and the like.
[0105] 近赤外線吸収染料の具体例としては、ポリメチン系、フタロシアニン系、ナフタロシ ァニン系、金属錯体系、アミニゥム系、ィモニゥム系、ジィモニゥム系、アンスラキノン 系、ジチオール金属錯体系、ナフトキノン系、インドールフエノール系、ァゾ系、トリア リルメタン系の化合物などが挙げられる。 [0105] Specific examples of near-infrared absorbing dyes include polymethine series, phthalocyanine series, naphthalocyanine series, metal complex series, aminium series, imonium series, dimonium series, anthraquinone series, dithiol metal complex series, naphthoquinone series, indole phenol , Azo and triarylmethane compounds.
[0106] PDP用光学フィルターで近赤外線吸収能が要求されるのは、主として熱線吸収や 電子機器のノイズ防止である。このためには、最大吸収波長が 750〜: L lOOnmであ る近赤外線吸収能を有する色素が好ましぐ金属錯体系、アミ-ゥム系、フタロシア- ン系、ナフタロシアニン系、ジィモ -ゥム系、スクヮリウム化合物系が特に好ましい。 [0106] Near-infrared absorptivity is required for optical filters for PDP mainly for heat ray absorption and noise prevention of electronic devices. For this purpose, a metal complex-based, amino-based, phthalocyanine-based, naphthalocyanine-based, dimethyl-containing pigment having a maximum absorption wavelength of 750-: LlOOnm is preferred. Of these, a sulfur system and a smutium compound system are particularly preferable.
[0107] 従来知られているニッケルジチオール錯体系化合物、またはフッ素化フタロシア- ン系化合物の吸収極大は 700〜900nmであり、実用化するに当たっては、通常、上 記化合物よりも長波長域に吸収極大を有するアミ二ゥム系化合物、特にはジインモニ ゥム系化合物と組み合わせて用いることにより、有効な近赤外線吸収効果を得ること ができる。 [0107] The absorption maximum of a conventionally known nickel dithiol complex compound or fluorinated phthalocyanine compound is 700 to 900 nm, and in practical use, it usually absorbs in a longer wavelength region than the above compound. An effective near-infrared absorption effect can be obtained by using in combination with an aminium-based compound having a maximum, particularly a diimonium-based compound.
[0108] 本発明に使用できるィモニゥム化合物の具体例を下記に示す。
[0109] (1- 1): N, N, N' , N' —テトラキス(4 ジ一 n—ブチルァミノフエ-ル)一 1, 4 -ベンゾキノン ビス(ィモ -ゥム ·へキサフルォロアンチモン酸) Specific examples of imonium compounds that can be used in the present invention are shown below. [0109] (1- 1): N, N, N ′, N ′ —tetrakis (4 di-n-butylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimony) acid)
(1- 2): N, N, N' , N' —テトラキス(4 ジ一 n—ブチルァミノフエ-ル)一 1, 4 ベンゾキノン ビス(ィモ -ゥム ·過塩素酸) (1-2): N, N, N ', N' —tetrakis (4 di-n-butylaminophenol) -1,4 benzoquinone bis (imum-perchloric acid)
(1— 3): N, N, N' , N' —テトラキス(4 ジ—アミルァミノフエ-ル)— 1, 4 ベン ゾキノン ビス(ィモ -ゥム ·へキサフルォロアンチモン酸) (1-3): N, N, N ', N' — Tetrakis (4 di-amylaminophenol) — 1, 4 Benzoquinone bis (immo-hexafluoroantimonic acid)
(1-4): N, N, N' , N' —テトラキス(4 ジ一 n—プロピルアミノフエ-ル)一 1, 4 -ベンゾキノン ビス(ィモ -ゥム ·へキサフルォロアンチモン酸) (1-4): N, N, N ′, N ′ —tetrakis (4 di-n-propylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimonic acid) )
(1- 5): N, N, Ν' , N' —テトラキス(4 ジ一 η—へキシルァミノフエ-ル)一 1, 4 -ベンゾキノン ビス(ィモ -ゥム ·へキサフルォロアンチモン酸) (1-5): N, N, Ν ', N' —tetrakis (4 di-η-hexylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimonic acid)
(1-6): Ν, Ν, Ν' , N' —テトラキス(4 ジ一 iso プロピルアミノフエ-ル)一 1, 4 -ベンゾキノン ビス(ィモ -ゥム ·へキサフルォロアンチモン酸) (1-6): Ν, Ν, Ν ', N' —tetrakis (4 di-iso propylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimonic acid)
(1- 7): N, N, Ν' , N' —テトラキス(4 ジ一 η—ペンチルァミノフエ-ル)一 1, 4 -ベンゾキノン ビス(ィモ -ゥム ·へキサフルォロアンチモン酸) (1-7): N, N, Ν ', N' —tetrakis (4 di-η-pentylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimony) Acid)
(1-8): Ν, Ν, Ν' , N' —テトラキス(4 ジ一メチルァミノフエ-ル)一 1, 4 ベ ンゾキノン一ビス(ィモ -ゥム ·へキサフノレオ口アンチモン酸)。 (1-8): Ν, Ν, Ν ', N' —tetrakis (4 dimethylaminophenol) -1,4 benzoquinone monobis (imum hexafnoreo oral antimonic acid).
[0110] 本発明における近赤外線吸収染料としては、ジィモ -ゥム化合物は、 IRG— 022、 I RG-040 (これらは日本ィ匕薬株式会社製商品名である)、ニッケルジチオール錯体 化合物は、 SIR— 128、 SIR— 130、 SIR— 132、 SIR— 159、 SIR— 152、 SIR— 1 62 (これらは三井ィ匕学株式会社製商品名である)、フタロシアニン系化合物は、 IR- 10, IR— 12 (以上、 日本触媒株式会社製商品名)などの市販品を利用することがで きる。 [0110] As the near-infrared absorbing dye in the present invention, dimo-um compounds are IRG-022, IRG-040 (these are trade names manufactured by Nippon Gyaku Co., Ltd.), nickel dithiol complex compounds, SIR—128, SIR—130, SIR—132, SIR—159, SIR—152, SIR—162 (these are trade names manufactured by Mitsui Engineering Co., Ltd.), phthalocyanine compounds are IR-10, IR — Commercially available products such as 12 (above, Nippon Shokubai Co., Ltd. trade name) can be used.
[0111] 上記近赤外線吸収染料は、メタノール、エタノール及びイソプロパノール等のアル コール溶剤、アセトン、メチルェチルケトン及びメチルブチルケトン等のケトン溶媒、ジ メチルスルホオキサイド、ジメチルホルムアミド、ジメチルエーテル、トルエン等有機溶 解して使用するか、後述する微粒子化機械で平均粒子径 0. 01〜10 ;ζ ΐηの微粒子 にして塗布すること好ましぐ添加量としては光学濃度が極大波長で 0. 05から 3. 0 濃度の範囲で使用するのが好ましい。
[0112] なお、近赤外線吸収能を有する色素を色調補正層に含有させる場合、上記の色素 のうちいずれか 1種類を含有させてもよいし、 2種以上を含有させてもよい。近赤外線 吸収染料の紫外線による劣化を避けるために紫外線吸収剤を使用することが好まし い。 [0111] The near-infrared absorbing dyes are alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl ether and toluene. It is preferable to use it as a fine particle having an average particle size of 0.01 to 10; ζ ΐη by using a micronizing machine described later. The optical density is a maximum wavelength from 0.05 to 3. It is preferably used in the range of 0 concentration. [0112] When a colorant having near infrared absorption ability is contained in the color tone correction layer, any one of the above dyes may be contained, or two or more kinds may be contained. It is preferable to use UV absorbers to avoid deterioration of near-infrared absorbing dyes by UV rays.
[0113] 紫外線吸収剤としては公知の紫外線吸収剤、例えば、サリチル酸系化合物、ベン ゾフエノン系化合物、ベンゾトリアゾール系化合物、 S トリアジン系化合物、環状イミ ノエステル系化合物などを好ましく使用することができる。これらの中、ベンゾフエノン 系化合物、ベンゾトリアゾール系化合物、環状ィミノエステル系化合物が好ましい。ポ リエステルに配合するものとしては、特に環状イミノエステル系化合物が好ましい。 As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S triazine compounds, and cyclic imino ester compounds 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.
[0114] 好ましい具体例としては、 [0114] As a preferred specific example,
(U— 1) : 2—(2—ヒドロキシ —3, 5 ジ α クミノレ) 2Η べンゾトリァゾーノレ (U— 1): 2 -— (2-Hydroxy —3, 5 di α cuminole) 2Η Benzotriazonore
(U 2) : 5 クロロー 2—(2 -ヒドロキシ— 3— t ブチル— 5—メチルフエ-ル) 2H ベンゾトリァゾーノレ、 (U 2): 5 Chloro-2- (2-hydroxy-3-t-butyl-5-methylphenol) 2H benzotriazolene,
(U 3) : 5 クロロー 2—(2 —ヒドロキシ— 3, 5 ジ— t—ブチルフエニル) 2H— ベンゾトリァゾーノレ (U 3): 5 Chloro-2- (2 —hydroxy-3,5 di-t-butylphenyl) 2H—benzotriazolone
(U—4) : 5 クロロー 2—(2ーヒドロキシー 3, 5 ジー α クミノレフエ二ノレ) 2Η— ベンゾトリァゾーノレ (U—4): 5 Chloro-2- (2-hydroxy-3, 5 G α cumino lefenore) 2Η— Benzotriazolene
(U 5) : 5 クロロー 2—(2—ヒドロキシ一 3— a—クミノレ一 5— t—ォクチノレフエ- ノレ) 2H—べンゾトリァゾーノレ (U 5): 5 Chloro 2— (2-hydroxy 1 3-a-cumino 1-t-octino lefe- nore) 2H-benzotriazonore
(U- 6) : 2 - (3— t—ブチルー 2 ヒドロキシー5—(2 イソォクチルォキシカルボ -ルェチル)フエ-ル) 5 クロ口 2H ベンゾトリアゾール (U-6): 2-(3— t-Butyl-2 hydroxy-5- (2 isooctyloxycarbo-ruethyl) phenol) 5 black 2H benzotriazole
(U— 7) : 5 トリフルォロメチル一 2— (2 ヒドロキシ一 3— a—タミル一 5— t—ォ クチルフエ-ル) 2H—ベンゾトリアゾール (U-7): 5 Trifluoromethyl mono 2- (2-hydroxy mono 3-a-tamyl mono 5-t-octylphenol) 2H-benzotriazole
(U— 8) : 5 トリフルォロメチル一 2— (2 ヒドロキシ一 5— t—ォクチルフエ-ル) 2H—ベンゾトリァゾーノレ (U-8): 5 Trifluoromethyl 2- (2-hydroxy-1-5-t-octylphenol) 2H-benzotriazolole
(U— 9) : 5 トリフルォロメチル一 2— (2 ヒドロキシ一 3, 5 ジ一 t—ォクチルフエ 二ノレ) 2H—ベンゾトリァゾーノレ (U-9): 5 trifluoromethyl-1- (2-hydroxy-1,3,5-di-tert-octylphenol 2-nole) 2H-benzotriazonole
(U— 10) : 5 トリフルォロメチル一 2— (2 ヒドロキシ一 3— a—タミル一 5— t—ブ
チルフエ-ル)— 2H—ベンゾトリアゾール (U—10): 5 Trifluoromethyl 2- (2-Hydroxy 3-3-a-Tamil 5- 5-t Tilphenol) — 2H-benzotriazole
(U— 11) : 2, 4 ビス(4 ビフエ-ルイル) 6— (2 ヒドロキシ一 4—ォクチルォ キシカルボ-ルェチリデンォキシフエ-ル) s トリァジン (U— 11): 2, 4 Bis (4 biphenyl) 6— (2 Hydroxy 4-octyloxycarboxylethylideneoxyphenyl) s Triazine
(U- 12) : 2, 4 ビス(2, 4 ジメチノレフエ-ノレ)一 6— [2 ヒドロキシ一 4— (3—ノ 二ルォキシ※一 2 ヒドロキシプロピルォキシ) 5 α—タミルフエ二ル]— s トリア ジン、(※はォクチルォキシ基、ノニルォキシ基及びデシルォキシ基の混合物を示す ο ) (U-12): 2, 4 Bis (2, 4 Dimethinolephenol) 1 6- [2 Hydroxy 4- (3-Noxyloxy * 1 2 Hydroxypropyloxy) 5 α-Tamilphenyl] — s Triazine, (* indicates a mixture of octyloxy, nonyloxy and decyloxy groups)
(U- 13) : 2, 4, 6 トリス(2 ヒドロキシ一 4—イソォクチルォキシカルボ-ルイソ プロピリデンォキシフエ-ル)—s—トリァジン (U-13): 2, 4, 6 Tris (2-hydroxy-4-isooctyloxycarbo-isopropylideneoxyphenyl) —s-triazine
(U— 14):ヒドロキシフエ-ノレ一 2Η ベンゾトリァゾーノレ (U—14): Hydroxyphenolone 2 ァ Benzotriazolene
(U— 15) : 2— (2 ヒドロキシ一 5—メチルフエ-ル) 2Η ベンゾトリアゾール (U— 16) : 2— (3, 5 ジ— t—ブチル—2 ヒドロキシフエ-ル) 2H ベンゾトリ ァゾーノレ等である。 (U— 15): 2— (2 Hydroxy-5-methylphenol) 2Η Benzotriazole (U— 16): 2— (3,5 Di-tert-butyl-2-hydroxyphenol) 2H Benzotriazole is there.
[0115] 本発明の電磁波遮蔽フィルムの製造方法において、支持体上に近赤外線吸収機 能を有する層を設けた後に、感光性ハロゲンィ匕銀粒子を含む層を設けることが好まし い。あるいは、支持体上に近赤外線吸収機能を有する層と感光性ハロゲンィ匕銀粒子 を含む層とを同時に設けることが好ましい。 [0115] In the method for producing an electromagnetic wave shielding film of the present invention, it is preferable to provide a layer containing photosensitive halogen silver halide grains after providing a layer having a near infrared absorption function on a support. Or it is preferable to provide simultaneously the layer which has a near-infrared absorption function, and the layer containing a photosensitive halogenated silver particle on a support body.
[0116] これは、本発明の感光性ハロゲン化銀粒子を含む層の銀 Zバインダー体積比が高 いことにより、通常の方法では塗布安定性が低いので低速塗布を余儀なくされるが、 前述の近赤外線吸収機能を有する層の上であれば感光性ハロゲン化銀粒子を含む 層の塗布安定性が向上して、高速塗布が可能であることを見出した力もである。 [0116] This is because, since the silver Z binder volume ratio of the layer containing the photosensitive silver halide grains of the present invention is high, the coating stability is low in the usual method, and thus low speed coating is unavoidable. If it is on a layer having a near-infrared absorbing function, the coating stability of the layer containing the photosensitive silver halide grains is improved, and it has been found that high-speed coating is possible.
[0117] また、近赤外線吸収機能を有する層と感光性ハロゲンィ匕銀粒子を含む層とを同時 多層方式で積層すると、感光性ハロゲンィ匕銀粒子を含む層の銀 Zバインダー体積 比がかなり高くても、高速塗布が可能であることを見出した力もである。更には、支持 体と近赤外線吸収機能を有する層と感光性ハロゲンィ匕銀粒子を含む層とが相互に 近接または隣接して 、ると、露光を近赤外レーザー光線等で行う場合のハレーション ゃィラジェーシヨンを低減することができ、よりシャープな細線力もなるメッシュパター ンを形成することができるので、好ましい。
[0118] 本発明においては、支持体として、例えば、セルロースエステル系フィルム、ポリエ ステル系フィルム、ポリカーボネート系フィルム、ポリアリレート系フィルム、ポリスルホ ン(ポリエーテルスルホンも含む)系フィルム、ポリエチレンテレフタレート、ポリエチレ ンナフタレート等のポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィル ム、セロファン、セノレロースジアセテートフイノレム、セノレロースアセテートブチレートフィ ルム、ポリ塩化ビ-リデンフィルム、ポリビュルアルコールフィルム、エチレンビュルァ ルコールフィルム、シンジォタクティックポリスチレン系フィルム,ポリカーボネートフィ ルム、ノルボルネン榭脂系フィルム、ポリメチルペンテンフィルム、ポリエーテルケトン フィルム、ポリエーテルケトンイミドフィルム、ポリアミドフィルム、フッ素榭脂フィルム、 ナイロンフィルム、ポリメチルメタタリレートフィルムまたはアクリルフィルム等を用いるこ とがでさる。 [0117] When a layer having a near-infrared absorbing function and a layer containing photosensitive halogen-silver particles are simultaneously laminated in a multilayer system, the silver Z binder volume ratio of the layer containing photosensitive halogen-silver particles is considerably high. Moreover, it is also the force which discovered that high-speed application | coating was possible. Furthermore, when the support, the layer having a near infrared absorption function, and the layer containing the photosensitive halogen silver halide particles are close to or adjacent to each other, the halation irradiation in the case where the exposure is performed with a near infrared laser beam or the like. This is preferable because a mesh pattern having a sharper fine line force can be formed. [0118] In the present invention, as the support, for example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfonate (including polyethersulfone) film, polyethylene terephthalate, polyethylene Polyester film such as phthalate, polyethylene film, polypropylene film, cellophane, cenorelose diacetate vinylome, cenorelose acetate butyrate film, poly (vinylidene chloride) film, polyvulcoalcohol film, ethylene vulcoal film, syndicate Otactic polystyrene film, polycarbonate film, norbornene resin film, polymethylpentene film, polyetherketone film It is possible to use a film, a polyether ketone imide film, a polyamide film, a fluorine resin film, a nylon film, a polymethyl methacrylate film or an acrylic film.
[0119] 中でも、セルローストリアセテートフィルム、ポリカーボネートフィルム、ポリスルホン( ポリエーテルスルホンを含む)、ポリエチレンテレフタレートフィルムが好ましく用いら れる。 Of these, cellulose triacetate film, polycarbonate film, polysulfone (including polyethersulfone) and polyethylene terephthalate film are preferably used.
[0120] 本発明にお 、ては、透明性、等方性、接着性等の観点から、支持体としてはセル口 ースエステルフィルムを用いることが特に好まし 、。 [0120] In the present invention, it is particularly preferable to use a cellulose ester film as the support from the viewpoints of transparency, isotropicity, adhesiveness, and the like.
[0121] 本発明の電磁波遮蔽フィルムをディスプレイの表示画面に用いる場合には、高い 透明性が要求されるため、支持体自体の透明性も高いことが望ましい。この場合にお けるプラスチックフィルムまたはガラス板の全可視光域の平均透過率は、好ましくは 8 5〜: LOO%であり、より好ましくは 90〜: LOO%である。また、本発明では色気調節剤と して、前記プラスチックフィルムまたはガラス板を本発明の目的を妨げない程度に着 色したものを用いることもできる。 [0121] When the electromagnetic wave shielding film of the present invention is used for a display screen of a display, high transparency is required. Therefore, it is desirable that the support itself has high transparency. In this case, the average transmittance of the plastic film or glass plate in the entire visible light region is preferably 85 to: LOO%, more preferably 90 to: LOO%. In the present invention, as the color tone regulator, a plastic film or glass plate colored to such an extent that the object of the present invention is not hindered can be used.
[0122] 本発明において、可視光域の平均透過率とは 400〜700nmまでの可視光領域の 透過率を少なくとも 5nm毎に測定して求めた可視光城の各透過率を積算し、その平 均値として求めたものと定義する。 [0122] In the present invention, the average transmittance in the visible light region is obtained by integrating the transmittances of the visible light castle obtained by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm. Defined as the average value.
[0123] 本発明においては、可視光域による平均透過率が 85%以上である態様が好ましく 、より好ましくは 88%以上であり、更に好ましくは 90%以上である。 [0123] In the present invention, an embodiment in which the average transmittance in the visible light region is 85% or more is preferable, more preferably 88% or more, and still more preferably 90% or more.
[0124] 本発明に用いる支持体の厚さには特に制限はないが、透過率の維持及び取り扱い
性の観点から、 5〜200 mであることが好ましぐ 30〜150 /ζ πιであることが更に好 ましい。 [0124] The thickness of the support used in the present invention is not particularly limited. From the viewpoint of sex, it is preferably 5 to 200 m, more preferably 30 to 150 / ζ πι.
[0125] 本発明に用いる支持体には、必要に応じてハロゲンィ匕銀層等を塗布する前に、表 面の親水化処理を施したり、下引き層などを各種の支持体上に塗布することが好まし い。 [0125] The support used in the present invention may be subjected to a hydrophilic treatment on the surface, or an undercoat layer or the like may be applied to various supports before applying a halogenated silver layer or the like, if necessary. I prefer that.
[0126] 本発明におけるハロゲンィ匕銀粒子層、近赤外線吸収染料層、反射防止層を塗布 する方法としては、従来より種々の方法が知られている。例えば、ディップ塗布法、ブ レード塗布法、エアーナイフ塗布法、ワイヤーバー塗布法、グラビア塗布法、リバース ロール塗布法、スロット型塗布法、スライドホッパー塗布法、スロット型カーテン塗布法 、スライド型カーテン塗布法等が知られている。そして、これらの塗布方法において、 基体の幅方向に高精度に均一な乾燥膜厚を得るために、塗布時の (塗布後、乾燥 前の)塗布膜厚精度、均一性等に注意を払い、塗布を行っている。 [0126] Various methods are conventionally known as a method for applying a halogenated silver particle layer, a near infrared absorbing dye layer, and an antireflection layer in the present invention. For example, dip coating method, blade coating method, air knife coating method, wire bar coating method, gravure coating method, reverse roll coating method, slot type coating method, slide hopper coating method, slot type curtain coating method, slide type curtain coating method Laws are known. And in these coating methods, in order to obtain a uniform dry film thickness with high accuracy in the width direction of the substrate, pay attention to the coating film thickness accuracy and uniformity during coating (after coating and before drying), Applying.
[0127] これらの塗布方法の中で、特に流量規制型のダイスを有する塗布装置は、高速、 薄膜、高精度、多層同時塗布が可能であり、その特徴により写真感光材料、インクジ エツト記録材料、磁気記録材料等の塗布装置として広く用いられて 、る。 [0127] Among these coating methods, a coating apparatus having a flow rate regulation die is particularly capable of high-speed, thin-film, high-precision, multi-layer simultaneous coating, and photographic photosensitive material, ink jet recording material, It is widely used as a coating device for magnetic recording materials.
[0128] 本発明においては、流量規制型のダイスを有する塗布装置の使用が好ましい。特 にスライドホッパー型塗布装置、スライド型カーテン塗布装置は同時重層塗布が可能 であり、ハロゲンィ匕銀粒子含有層、近赤外線吸収染料含有層を同時重層塗布するこ とにより、著しく生産性を向上させることが可能となる。 [0128] In the present invention, it is preferable to use a coating apparatus having a flow rate regulating die. In particular, the slide hopper type coating device and the slide type curtain coating device can be used for simultaneous multi-layer coating, and the productivity can be significantly improved by simultaneously coating the layers containing halogen silver and silver particles and the layer containing near-infrared absorbing dye. It becomes possible.
[0129] 反射防止層については塗布液の構成として同時重層塗布が難しいため、スロット型 塗布装置が最も適して ヽる。スロット型塗布装置もまたダイスを有する塗布装置であり 、この方法を用いることにより高精度の塗布が可能となる。 [0129] For the antireflection layer, the simultaneous application of multiple layers is difficult as the composition of the coating solution, so the slot type coating apparatus is most suitable. The slot-type coating device is also a coating device having a die, and high-precision coating can be performed by using this method.
[0130] スライドホッパー塗布装置の場合、送液ポンプよりダイスに送られた塗布液は、巾方 向に広がるポケットと呼ばれる液溜り部に入り、ここ力も塗布巾方向に均一な厚さにな るように狭いスリットから押し出され、スライド面を流下し、スライド面先端と連続走行す る支持体との間にビードと称する塗布液溜まりを形成し、このビードを介して塗布が行 われる。スライド面上で異種の液を重ね合わせることにより、同時重層塗布が可能と なる。ビード安定ィ匕のためにビード下部には減圧チャンバ一が設けられ、ビードが安
定に形成されるように負圧に維持される。 [0130] In the case of a slide hopper coating apparatus, the coating liquid sent to the die from the liquid feeding pump enters a liquid pool called a pocket extending in the width direction, and this force also has a uniform thickness in the coating width direction. Thus, the liquid is pushed out of the narrow slit, flows down the slide surface, forms a coating liquid reservoir called a bead between the slide surface tip and the continuously running support, and the coating is performed through this bead. By overlaying different liquids on the slide surface, simultaneous multi-layer coating becomes possible. A pressure reducing chamber is provided at the bottom of the bead for bead stabilization. The negative pressure is maintained so as to be formed constantly.
[0131] スライド型カーテン塗布装置の場合は、同様に塗布巾方向に均一な厚さでスライド 面を流下し、スライド面先端の両端に設けられたエッジガイドの間でカーテン状液膜 を形成し、この自由落下するカーテン状液膜が連続走行する支持体と衝突して塗布 層が形成される。スライド型カーテン塗布装置の場合も、スライド面上で異種の液を 重ね合わせることで、同時重層塗布が可能となる。 [0131] In the case of a slide type curtain coating apparatus, similarly, the slide surface flows down with a uniform thickness in the coating width direction, and a curtain-like liquid film is formed between the edge guides provided at both ends of the slide surface. The free-falling curtain-like liquid film collides with a continuously running support to form a coating layer. In the case of a slide-type curtain coating device, simultaneous multi-layer coating can be performed by stacking different liquids on the slide surface.
[0132] スロット型塗布装置の場合は、巾方向に均一膜厚で押し出された塗布液力スリット 力 押し出され、走行する支持体との間で直接ビードを形成し、このビードを介して塗 布が行われる。スロット型塗布装置の場合も、必要に応じてビードの安定化のために ビード下部に減圧チャンバ一が設置される。 [0132] In the case of a slot-type coating device, the coating liquid force slit force extruded with a uniform film thickness in the width direction is pushed out, and a bead is formed directly with the traveling support, and the coating is performed via this bead. Is done. In the case of a slot-type coating device, a decompression chamber is installed below the bead as needed to stabilize the bead.
[0133] これらの塗布装置により塗布された後、塗布液は種々の乾燥方法により乾燥され、 その後巻き取られてもよ 、し、そのまま次工程に搬送されてもょ 、。 [0133] After being coated by these coating apparatuses, the coating solution may be dried by various drying methods and then wound up, or may be directly transported to the next step.
[0134] 本発明では、後述する現像'補力処理により、導電性パターンを形成するために支 持体上に設けられたハロゲン化銀粒子含有層の露光を行う。露光に用いられる光源 としては、例えば、可視光線、紫外線などの光、電子線、 X線などの放射線等が挙げ られる力 紫外線または近赤外線を用いる態様が好ましい。更に露光には波長分布 を有する光源を利用してもよく、波長分布の狭 、光源を用 、てもよ 、。 In the present invention, the silver halide grain-containing layer provided on the support is exposed in order to form a conductive pattern by the development / reinforcement process described later. As the light source used for the exposure, for example, an embodiment using a strong ultraviolet ray or near infrared ray, which includes light such as visible light and ultraviolet light, and radiation such as electron beam and X-ray, is preferable. Further, a light source having a wavelength distribution may be used for the exposure, or a light source having a narrow wavelength distribution may be used.
[0135] 可視光線は、必要に応じてスペクトル領域に発光を示す各種発光体が用いられる 。例えば、赤色発光体、緑色発光体、青色発光体のいずれ力 1種または 2種以上が 混合されて用いられる。スペクトル領域は上記の赤色、緑色及び青色に限定されず、 黄色、橙色、紫色あるいは赤外領域に発光する蛍光体も用いられる。また紫外線ラン プも好ましぐ水銀ランプの g線、水銀ランプの i線等も利用される。 [0135] As the visible light, various light emitters that emit light in the spectral region are used as necessary. For example, a red light emitter, a green light emitter, or a blue light emitter may be used alone or in combination. The spectral region is not limited to the above-mentioned red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. In addition, mercury lamp g-line and mercury lamp i-line are also used.
[0136] また本発明では、露光は種々のレーザービームを用いて行うことができる。例えば、 本発明における露光は、ガスレーザー、発光ダイオード、半導体レーザー、半導体レ 一ザ一または半導体レーザーを励起光源に用いた固体レーザーと非線形光学結晶 を組み合わせた第二高調波発光光源 (SHG)等の単色高密度光を用いた走査露光 方式を好ましく用いることができ、更に KrFエキシマレーザー、 ArFエキシマレーザ 一、 Fレーザー等も用いることができる。
[0137] システムをコンパクトで迅速なものにするために、露光は半導体レーザー、半導体 レーザーあるいは固体レーザーと非線形光学結晶を組み合わせた第二高調波発生 光源(SHG)を用いて行うことが好ましい。特にコンパクトで迅速、更に寿命が長ぐ 安定性が高 、装置を設計するためには、露光は半導体レーザーを用いて行うことが 好ましい。 [0136] In the present invention, exposure can be performed using various laser beams. For example, the exposure in the present invention includes 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 monochromatic high-density light can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F laser, or the like can also be used. In order to make the system compact and rapid, 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 and quick, has a long life, and is highly stable, exposure is preferably performed using a semiconductor laser.
[0138] レーザー光源としては、具体的には紫外半導体、青色半導体レーザー、緑色半導 体レーザー、赤色半導体レーザー、近赤外レーザなどが好ましく用いられる。 [0138] As the laser light source, specifically, an ultraviolet semiconductor, a blue semiconductor laser, a green semiconductor laser, a red semiconductor laser, a near infrared laser, and the like are preferably used.
[0139] ハロゲン化銀粒子含有層を画像状に露光する方法は、フォトマスクを利用した面露 光で行ってもよいし、レーザービームによる走査露光で行ってもよい。この際、レンズ を用いた集光式露光でも反射鏡を用いた反射式露光でもよぐ面々接触露光、近接 場露光、縮小投影露光、反射投影露光などの露光方式を用いることができる。レー ザ一の出力は、ハロゲン化銀を感光させるのに適した量であればよいので数十 μ W 〜5W程度でよい。 [0139] The method of exposing the silver halide grain-containing layer to an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. In this case, exposure methods such as surface contact exposure, near field exposure, reduced projection exposure, and reflection projection exposure may be used, such as condensing exposure using a lens or reflection exposure using a reflecting mirror. The output of the laser may be about several tens of μW to 5 W, as long as it is an amount suitable for sensitizing the silver halide.
[0140] 本発明では、ハロゲンィ匕銀粒子含有層を露光した後、現像処理が行われる。現像 処理液としては、現像主薬としてハイドロキノン、ハイド口キノンスルホン酸ナトリウム、 クロルハイドロキノン等のハイドロキノン類の他に、 1—フエ-ルー 3—ビラゾリドン、 1 —フエニル一 4, 4 ジメチル一 3—ビラゾリドン、 1—フエニル一 4—メチル 4 ヒド ロキシメチル 3 ビラゾリドン、 1 フエニル 4 メチル 3 ビラゾリドン等のビラ ゾリドン類及び N—メチルパラアミノフエノール硫酸塩等の超加成性現像主薬と併用 することができる。また、ハイドロキノンを使用しないでァスコルビン酸やイソァスコルビ ン酸などレダクトン類ィ匕合物を上記超加成性現像主薬と併用することが好ましい。 [0140] In the present invention, after the halogenated silver particle-containing layer is exposed, development processing is performed. In addition to hydroquinones such as hydroquinone, sodium hydroquinone sulfonate, chlorohydroquinone, etc. as developing agents, there are 1-phenol 3-virazolidone, 1-phenyl-1,4-dimethyl-1,3-virazolidone as developing agents. It can be used in combination with bisazolidone such as 1-phenyl-4-methyl-4-hydroxymethyl-3 virazolidone, 1-phenyl-4-methyl-3 virazolidone, and superadditive developing agents such as N-methylparaaminophenol sulfate. Further, 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.
[0141] また、現像処理液には保恒剤として亜硫酸ナトリウム塩や亜硫酸カリウム塩、緩衝 剤として炭酸ナトリウム塩や炭酸カリウム塩、現像促進剤としてジエタノールァミン、トリ エタノールァミン、ジェチルァミノプロパンジオールなどを適宜使用できる。 [0141] In addition, sodium sulfite salt or potassium sulfite salt as a preservative, sodium carbonate salt or potassium carbonate salt as a buffering agent, diethanolamine, triethanolamine, or jetylamino as a development accelerator in a development processing solution. Propanediol or the like can be used as appropriate.
[0142] 本発明に係る現像処理で用いられる現像処理液は、画質を向上させる目的で画質 向上剤を含有することができる。画質向上剤としては、例えば、 1—フエ-ル一 5—メ ルカプトテトラゾール、 5—メチルベンゾトリアゾールなどの含窒素へテロ環化合物を 挙げることができる。
[0143] 本発明にお 、ては、露光後に行われる現像処理が定着前物理現像を含んで!/、る 態様であってもよい。ここで言う定着前物理現像とは、後述の定着処理を行う前に露 光により潜像を有したハロゲンィ匕銀粒子の内部以外力ゝら銀イオンを供給し、現像銀を 補強するプロセスのことを示す。現像処理液から銀イオンを供給するための具体的な 方法としては、例えば、後述の物理現像の記載のように予め現像処理液中に銀ィォ ンゃ銀錯イオン硝酸銀を溶かしておく方法、あるいは現像液中に、チォ硫酸ナトリウ ム、チォシアン酸アンモニゥムなどのようなハロゲンィ匕銀溶剤を溶解しておき、現像時 に未露光部のハロゲンィ匕銀を溶解させ、潜像を有するハロゲンィ匕銀粒子の現像を補 力する方法などが挙げられる。 [0142] The development processing solution used in the development processing according to the present invention may 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-phenol-15-mercaptotetrazole and 5-methylbenzotriazole. [0143] In the present invention, the development processing performed after exposure may include physical development before fixing! The pre-fixing physical development is a process for reinforcing developed silver by supplying silver ions other than the inside of the halogen-containing silver particles having a latent image by exposure before the fixing process described later. Indicates. As a specific method for supplying silver ions from the developing solution, for example, a method in which silver ion-silver complex ion silver nitrate is previously dissolved in the developing solution as described in the physical development described later, Alternatively, a halogenated silver solvent such as sodium thiosulfate or ammonium thiocyanate is dissolved in the developing solution, and the unexposed portion of the halogenated silver is dissolved during development, so that a halogenated silver particle having a latent image is obtained. The method of supplementing the development of this.
[0144] 本発明においては、現像液中に予めハロゲン化銀溶剤を溶解しておく処方を用い た方力 未露光部でのカプリ発生によるフィルムの透過率低下を抑制できるため好ま しい。 [0144] In the present invention, it is preferable to use a formulation in which a silver halide solvent is preliminarily dissolved in a developing solution because a reduction in film transmittance due to the occurrence of capri in an unexposed area can be suppressed.
[0145] 本発明における現像処理においては、露光されたハロゲンィ匕銀粒子の黒白現像終 了後に、未露光部分のハロゲンィ匕銀粒子を除去して安定化させる目的で行われる定 着処理を行う。 [0145] In the development processing in the present invention, after the black and white development of the exposed silver halide grains, a fixing treatment is performed for the purpose of removing and stabilizing the unexposed portions of the silver halide grains.
[0146] 本発明における定着処理は、ハロゲンィ匕銀粒子を用いた写真フィルムや印画紙な どで用いられる定着液処方を用いることができる本発明に係る定着処理で使用する 定着液は、定着剤としてチォ硫酸ナトリウム、チォ硫酸カリウム、チォ硫酸アンモ-ゥ ム等を使用することができる。定着時の硬膜剤として、硫酸アルミゥム、硫酸クロミゥム 等を使用することができる。定着剤の保恒剤としては、現像処理液で述べた亜硫酸 ナトリウム、亜硫酸カリウム、ァスコルビン酸、エリソルビン酸等を使用することができ、 その他にクェン酸、蓚酸等を使用することができる。 [0146] In the fixing process of the present invention, the fixing solution used in a photographic film or photographic paper using halogen silver halide grains can be used. The fixing solution used in the fixing process according to the present invention is a fixing agent. As sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, or the like can be used. As a hardening agent for fixing, aluminum sulfate, chromium sulfate, or the like can be used. As the preservative for the fixing agent, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing solution can be used, and in addition, citrate, oxalic acid and the like can be used.
[0147] 本発明に使用する水洗水には、防黴剤として N—メチルーイソチアゾールー 3—ォ ン、 N—メチルーイソチアゾールー 5—クロロー 3—オン、 N—メチルーイソチアゾール -4, 5—ジクロロー 3—オン、 2—二トロー 2—ブロムー3—ヒドロキシプロパノール, 2 —メチルー 4—クロ口フエノール、過酸ィ匕水素等を使用することができる。 [0147] In the washing water used in the present invention, N-methyl-isothiazole-3-one, N-methyl-isothiazol-5-chloro-3-one, N-methyl-isothiazole- 4,5-Dichloro-3-one, 2-Nitroe 2-Bromue 3-hydroxypropanol, 2-Methyl-4-chlorophenol, hydrogen peroxide, etc. can be used.
[0148] 本発明においては、上述の現像処理によって形成された現像銀同士の接触を補 助し、導電性を高めるために補力処理を行うことが好ましい。本発明において補カ処
理とは、現像処理中、あるいは処理後に予めハロゲン化銀感光材料中に含有されて いない導電性物質源を外部から供給し、導電性を高める処理のことを指し、具体的 な方法としては、例えば、物理現像、あるいはめっき処理などを挙げることができる。 [0148] In the present invention, it is preferable to perform the intensifying process in order to assist the contact between the developed silvers formed by the above-described developing process and increase the conductivity. In the present invention, the auxiliary treatment The term `` process '' refers to a process of increasing the conductivity by supplying a conductive material source not contained in the silver halide photosensitive material from the outside during the development process or after the process. As a specific method, For example, physical development or plating treatment can be exemplified.
[0149] 物理現像は、写真技術分野で周知のように潜像を有するハロゲン化銀乳剤を含有 する感光材料を、銀イオンあるいは銀錯イオンと還元剤を含有する処理液に浸漬す ることでこれを施すことがでさる。 [0149] Physical development is 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, as is well known in the photographic art. You can do this.
[0150] 本発明においては、物理現像の現像開始点が潜像核だけでなぐ現像銀が物理 現像開始点となった場合についても物理現像と定義し、これを好ましく用いることが できる。 [0150] In the present invention, the case where the developed silver where the development start point of physical development is only the latent image nucleus becomes the physical development start point is also defined as physical development, and this can be preferably used.
[0151] 本発明において、補力処理として用いられるめっき処理には従来公知の種々のめ つき方法を用いることができ、例えば、電解めつき及び無電解めつきを単独、あるいは 組み合わせて実施することができる。中でも、めっき金属の選択性、めっき速度の調 整、めっき強度に優れた電解めつきを本発明では好ましく用いることができる。無電 解めつきの場合は、電流分布ムラによるめつき ムラが発生しないという長所を有する 。めっきに用いることができる金属としては、例えば、銅、ニッケル、コノ レト、すず、 銀、金、白金、その他各種合金を用いることができる。めっき処理が比較的容易であ り、且つ高 、導電性を得やす 、と 、う観点から銅電解めつきを用いることが特に好ま しい。 [0151] In the present invention, various conventionally known plating methods can be used for the plating treatment used as the intensifying treatment. For example, electrolytic plating and electroless plating are carried out singly or in combination. Can do. Among these, electrolytic plating with excellent selectivity for plating metal, adjustment of plating speed, and plating strength can be preferably used in the present invention. In the case of non-wireless contact, there is an advantage that uneven contact due to current distribution unevenness does not occur. As a metal that can be used for plating, for example, copper, nickel, conoleto, tin, silver, gold, platinum, and other various alloys can be used. It is particularly preferable to use a copper electrolytic plating from the viewpoint of relatively easy plating and high conductivity.
[0152] なお、補力処理は現像中、現像後定着前、定着処理後のいずれのタイミングにお いても実施可能であるが、フィルムの透明性を高く維持するという観点から、定着処 理後に実施する態様が好ま 、。 [0152] The intensifying process can be performed at any time during development, after development, before fixing, or after fixing process. However, from the viewpoint of maintaining high transparency of the film, after the fixing process. Preferred is the mode of implementation.
[0153] 本発明においては、現像処理あるいは補力処理後に酸化処理を行うことが好まし い。酸化処理により、不要な金属成分をイオンィ匕して溶解除去することが可能となり、 フィルムの透過率をより高めることが可能となる。 [0153] In the present invention, it is preferable to carry out the oxidation treatment after the development treatment or the intensification treatment. Oxidation treatment allows unnecessary metal components to be ionized and dissolved and removed, and the transmittance of the film can be further increased.
[0154] 本発明にお ヽては、高 ヽ透光性と高!、電磁波遮蔽性能を付与するために格子状 の細線パターンを露光により描画し、次 、で現像処理等を行うことで導電性のメッシ ュパターンを形成する態様が好ましい。上記導電性金属部の線幅は 20 m以下、線 間隔は 50 m以上であることが好ましい。また、導電性金属部はアース接続などの
目的においては、線幅は 20 mより広い部分を有していてもよい。また画像を目立た せなくする観点からは、導電性金属部の線幅は 18 m未満であることが好ましぐ 15[0154] In the present invention, in order to impart high translucency, high !, and electromagnetic wave shielding performance, a lattice-like fine line pattern is drawn by exposure, and then subjected to development processing or the like to conduct electricity. An embodiment in which a sex mesh pattern is formed is preferable. The conductive metal portion preferably has a line width of 20 m or less and a line interval of 50 m or more. Conductive metal parts such as earth connections For purposes, the line width may have a portion wider than 20 m. From the viewpoint of making the image inconspicuous, it is preferable that the line width of the conductive metal portion is less than 18 m.
/z m未満であることがより好ましぐ 14 m未満であることが更に好ましぐ 10 /z m未 満であることが更により好ましぐ 7 m未満であることが最も好ましい。また、線の厚さ ίま、 0. 05〜30 111カ好ましく、0. 1〜20 111カょり好ましく、0. 1〜: LO /z m力 S特に 好ましい。 More preferably less than 14 m, more preferably less than 14 m, even more preferably less than 7 m, most preferably less than 7 m. Further, the thickness of the wire is preferably from 0.05 to 30 111, more preferably from 0.1 to 20 111, and more preferably from 0.1 to LO / z m force S.
[0155] 本発明にお ヽては、高 ヽ透光性と高!、電磁波遮蔽性能を付与するために格子状 のメッシュパターンの細線のない部分の可視光透過率は 70%以上が好ましぐ 80% 以上がより好ましぐ 90%以上が特に好ましい。測定においては、測定ァパチヤ一を 前述のメッシュパターンピッチより十分大きくとっておく必要があり、少なくともメッシュ の格子面積より 100倍以上大きな面積で測定して求めることが好ま 、。 [0155] In the present invention, it is preferable that the visible light transmittance of a portion without a fine line in the lattice-like mesh pattern is 70% or more in order to impart high transparency and high! Electromagnetic wave shielding performance. 80% or more is more preferable, and 90% or more is particularly preferable. In measurement, it is necessary to make the measurement parameter sufficiently larger than the mesh pattern pitch described above, and it is preferable to measure at least 100 times larger than the mesh area of the mesh.
[0156] 本発明における導電性金属部は、可視光透過率の点から開口率は 85%以上であ ることが好ましぐ 90%以上であることが更に好ましぐ 95%以上であることが最も好 ましい。開口率とはメッシュをなす細線のない部分が全体に占める割合であり、例え ば、線幅 10 μ m、ピッチ 200 μ mの正方形の格子状メッシュの開口率は 90%である 。また、開口部(細線のない部分)の可視光透過率は 80%以上であることが好ましぐ 90%以上であることがより好ましぐ 95%以上であることが特に好ましい。 [0156] The conductive metal part of the present invention has an aperture ratio of preferably 85% or higher, more preferably 90% or higher, and more preferably 95% or higher from the viewpoint of visible light transmittance. Is most preferred. The aperture ratio is the percentage of the mesh without fine lines. For example, the aperture ratio of a square mesh with a line width of 10 μm and a pitch of 200 μm is 90%. In addition, the visible light transmittance of the opening (the portion without the thin line) is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.
実施例 Example
[0157] 以下に、本発明の実施例を挙げて本発明を更に具体的に説明する。なお、以下の 実施例に示される材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を 逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体 例により限定的に解釈されるべきものではない。 [0157] Hereinafter, the present invention will be described in more detail with reference to examples of the present invention. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
[0158] 実施例 1 [0158] Example 1
《ハロゲン化銀粒子含有液の調製》 << Preparation of a solution containing silver halide grains >>
水媒体中の銀 100gに対してゼラチン 10gを含む、球相当径平均 0. 044 /z mの沃 臭化銀粒子 (1 = 2. 5モル%)を含有する乳剤を調製した。この際、銀 Zゼラチン質量 比は 10Z1 (銀 Zゼラチン体積比 1. 3)とし、ゼラチン種としては平均分子量 4万のァ ルカリ処理低分子量ゼラチンを用いた。
[0159] また、この乳剤中には臭化ロジウム酸カリウム及び塩化イリジウム酸カリウムを濃度 力 S 10— 7 (モル/モル銀)になるように添加し、臭化銀粒子に Rhイオンと Irイオンをドー プした。この乳剤に塩化パラジウム酸ナトリウムを添加し、更に塩化金酸とチォ硫酸ナ トリウムを用いて金硫黄増感を行った後、下記増感色素 SD— 1をハロゲンィ匕銀 1モル 当たり 10— 4モル添加し、分光増感をした後、硬調化剤としてヒドラジン (H— 2)、促進 剤のアミンィ匕合物 (A— 10)を加えた。 An emulsion containing 10 g of gelatin per 100 g of silver in an aqueous medium and containing silver iodobromide grains (1 = 2.5 mol%) having an average equivalent sphere diameter of 0.044 / zm was prepared. At this time, the mass ratio of silver Z gelatin was 10Z1 (silver Z gelatin volume ratio 1.3), and a gelatin-treated low molecular weight gelatin having an average molecular weight of 40,000 was used. [0159] Further, bromide rhodium potassium and potassium chloride iridium acid This emulsion was added to a concentration force S 10- 7 (mol / mol Ag), Rh and Ir ions bromide grains Doped. Adding sodium palladium chloride acid to the emulsion, further Harogeni匕銀per mole 10- 4 moles after gold-sulfur sensitization, the following sensitizing dye SD- 1 using chloroauric acid and Chio sodium sulfate After addition and spectral sensitization, hydrazine (H-2) and an accelerator amine compound (A-10) were added as a thickening agent.
[0160] 銀の塗布量が 10g/m2 (ゼラチン塗布量 lg/m2)となるように、両面下塗り処理済 みのポリエチレンテレフタレート(PET)フィルム上にスライドホッパー型塗布装置を用 いて塗布した。 [0160] Using a slide hopper type coating device on a polyethylene terephthalate (PET) film that had been primed on both sides so that the silver coating amount would be 10 g / m 2 (gelatin coating amount lg / m 2 ) .
[0161] [化 2] [0161] [Chemical 2]
[0162] 《露光 Z現像処理》 [0162] 《Exposure Z development processing》
得られた試料 101に対して、ライン Zスペース = 10 μ m/195 μ mの格子状のメッシ ュパターンを与えるイメージセッタを使用して、発振波長 440nmのレーザー光(日亜 化学 (株)製の青色半導体レーザーダイオード)を用いて、メッシュ露光を行った後、 下記の現像液を用いて 25°Cで 60秒間現像し、更に下記定着液を用いて 25°Cで 12 0秒間の定着処理を行い、次いで水洗処理を行った。得られた試料 101には金属銀 画像であるメッシュ状の格子パターンが形成された。 Using an image setter that gives a lattice-like mesh pattern with a line Z space of 10 μm / 195 μm, the sample 101 was obtained using a laser beam with an oscillation wavelength of 440 nm (manufactured by Nichia Corporation). After performing mesh exposure using a blue semiconductor laser diode), development is performed at 25 ° C for 60 seconds using the following developer, and fixing treatment is further performed at 25 ° C for 120 seconds using the following fixer. And then washed with water. In the obtained sample 101, a mesh-like lattice pattern as a metallic silver image was formed.
[0163] (現像液組成) [0163] (Developer composition)
ハイドロキノン 30g Hydroquinone 30g
1—フエニル一 3, 3—ジメチルピラゾリドン 1. 5g 1-phenyl 1,3,3-dimethylpyrazolidone 1.5 g
臭化カリウム 3. Og Potassium bromide 3. Og
亜硫酸ナトリウム 50g Sodium sulfite 50g
水酸化カリウム 30g Potassium hydroxide 30g
硼酸 10g
N—n—ブチルジェタノールァミン 15g 水を加えて 1Lとし、 pHは 10. 20に調節した。 Boric acid 10g N-n-Butyljetanolamine 15g Water was added to 1L, and the pH was adjusted to 10.20.
[0164] (定着液組成) [0164] (Fixing solution composition)
チォ硫酸アンモ-ゥム 72. 5%水溶液 240ml Ammonium thiosulfate 72.5% aqueous solution 240ml
亜流酸ナトリウム 17g Sodium sulfite 17g
酢酸ナトリウム · 3水塩 6. 5g Sodium acetate trihydrate 6.5 g
硼酸 6. Og Boric acid 6. Og
クェン酸ナトリウム · 2水塩 2. Og Sodium citrate dihydrate 2. Og
酢酸 90%水溶液 13. 6ml Acetic acid 90% aqueous solution 13.6ml
硫酸 50%水溶液 4. 7g Sulfuric acid 50% aqueous solution 4.7 g
硫酸アルミニウム (AI O換算含量が 8. 1%WZVの水溶液) 26. 5g Aluminum sulfate (AI O equivalent content 8.1% WZV aqueous solution) 26.5g
2 3 twenty three
水を加えて 1Lとし、 pHを 5. 0に調節した。 Water was added to 1L and the pH was adjusted to 5.0.
[0165] 現像処理済みのメッシュ状の金属格子パターンが形成された試料 101の裏面側に 、下記組成の液を中屈折層、高屈折層、低屈折層の順にスロット型塗布装置で逐次 重層塗布した。各層の乾燥後の塗布膜厚は、順に 80nm、 70nm、 95nmとなるよう に調整した。このようにして反射防止層を有する電磁波遮蔽フィルム試料 101を作製 した。 [0165] On the back side of the sample 101 on which the developed mesh-like metal lattice pattern was formed, a solution having the following composition was sequentially applied in a multilayer manner using a slot-type coating device in the order of the middle refractive layer, the high refractive layer, and the low refractive layer. did. The coating thickness after drying of each layer was adjusted to 80 nm, 70 nm, and 95 nm in order. In this way, an electromagnetic wave shielding film sample 101 having an antireflection layer was produced.
[0166] 《反射防止層の調製 Z塗布》 [0166] <Preparation of antireflection layer Z coating>
〈二酸ィヒチタン分散物の調製〉 <Preparation of titanium diacid titanium dispersion>
二酸化チタン(1次粒子質量平均粒径: 50nm、屈折率: 2. 70) 30質量部、ァ-ォ ン性ジアタリレートモノマー(PM21、 日本化薬 (株)製) 4. 5質量部、カチオン性メタ タリレートモノマー(DMAEA、興人(株)製) 0. 3質量部及びメチルェチルケトン 65. 2質量部をサンドグラインダーにより分散し、二酸ィ匕チタン分散物を調製した。 Titanium dioxide (primary particle mass average particle size: 50 nm, refractive index: 2.70) 30 parts by mass, cation diatalate monomer (PM21, Nippon Kayaku Co., Ltd.) 4.5 parts by mass, Cationic methacrylate monomer (DMAEA, manufactured by Kojin Co., Ltd.) 0.3 parts by mass and 65.2 parts by mass of methyl ethyl ketone were dispersed by a sand grinder to prepare a titanium dioxide diacid dispersion.
[0167] (中屈折率層用塗布液の調製) [0167] (Preparation of coating solution for medium refractive index layer)
シクロへキサノン 151. 9g及びメチルェチルケトン 37. Ogに、光重合開始剤(ィルガ キュア 907、チバガイギ一社製) 0. 14g及び光増感剤(カャキュア一 DETX、 日本ィ匕 薬 (株)製) 0. 04gを溶解した。更に、上記の二酸化チタン分散物 6. lg及びジペン タエリスリトールペンタアタリレートとジペンタエリスリトールへキサアタリレートの混合物
(DPHA、 日本化薬 (株)製) 2. 4gを加え、室温で 30分間攪拌した後、孔径 0. 4 μ mのポリプロピレン製フィルターで濾過して、中屈折率層用塗布液を調製した。 Cyclohexanone 151. 9 g and methyl ethyl ketone 37. Og, photopolymerization initiator (Irgacure 907, manufactured by Ciba-Gaigi Co., Ltd.) 0.14 g and photosensitizer (Cacure 1 DETX, Nippon Yakuhin Co., Ltd.) (Made) 0.04g was melt | dissolved. In addition, the above titanium dioxide dispersion 6. lg and a mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate (DPHA, Nippon Kayaku Co., Ltd.) 2.Add 4 g, stir at room temperature for 30 minutes, and then filter through a polypropylene filter with a pore size of 0.4 μm to prepare a coating solution for the medium refractive index layer .
[0168] (高屈折率層用塗布液の調製) [0168] (Preparation of coating solution for high refractive index layer)
シクロへキサノン 1152. 8g及びメチルェチルケトン 37. 2gに、光重合開始剤(ィル ガキュア 907、チバガイギ一社製) 0. 06g及び光増感剤(カャキュア一 DETX、 日本 化薬 (株)製) 0. 02gを溶解した。更に、上記の二酸化チタン分散物及びジペンタエ リスリトールペンタアタリレートとジペンタエリスリトールへキサアタリレートの混合物(D PHA、 日本化薬 (株)製)の二酸化チタン分散物の比率を増加させ、高屈折率層の 屈折率となるように量を調節して、室温で 30分間攪拌した後、孔径 0. 4 mのポリプ ロピレン製フィルターで濾過して、高屈折率層用塗布液を調製した。 Cyclohexanone 1152. 8g and methyl ethyl ketone 37.2g, photopolymerization initiator (ILGACURE 907, manufactured by Ciba-Gaigi Co., Ltd.) 0.06g and photosensitizer (CACURE I DETX, Nippon Kayaku Co., Ltd.) (Made) 0.02g was melt | dissolved. In addition, the ratio of the above titanium dioxide dispersion and the mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate (D PHA, Nippon Kayaku Co., Ltd.) increased the ratio of titanium dioxide dispersion to increase the refractive index. The amount was adjusted so as to be the refractive index of the refractive index layer, stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter having a pore diameter of 0.4 m to prepare a coating solution for a high refractive index layer.
[0169] (低屈折率層用塗布液の調製) [0169] (Preparation of coating solution for low refractive index layer)
平均粒径 15nmのシリカ微粒子のメタノール分散液 (メタノールシリカゾル、 日産化 学 (株)製) 200gにシランカップリング剤 (KBM— 503、信越シリコーン (株)製) 3g及 び 0. 1MZL塩酸 2gを加え、室温で 5時間攪拌した後、 3日間室温で放置して、シラ ンカップリング処理したシリカ微粒子の分散物を調製した。分散物 35. 04gに、イソプ 口ピルアルコール 58. 35g及びジアセトンアルコール 39. 34gを加えた。また、光重 合開始剤 (ィルガキュア 907、チバガイギ一社製) 1. 02g及び光増感剤 (カャキュア 一 DETX、 日本化薬 (株)製) 0. 51gを 772. 85gのイソプロピルアルコールに溶解し た溶液を加え、更にジペンタエリスリトールペンタアタリレートとジペンタエリスリトール へキサアタリレートの混合物(DPHA、 日本化薬 (株)製) 25. 6gを加えて溶解した。 得られた溶液 67. 23gを上記分散液、イソプロピルアルコール及びジアセトンアルコ ールの混合液に添加した。混合物を 20分間室温で攪拌し、孔径 0. 4 mのポリプロ ピレン製フィルターで濾過して、低屈折率層用塗布液を調製した。 200g silica dispersion of silica fine particles with an average particle size of 15nm (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.) 3g silane coupling agent (KBM-503, Shin-Etsu Silicone Co., Ltd.) 3g and 0.1MZL hydrochloric acid 2g In addition, the mixture was stirred at room temperature for 5 hours and then allowed to stand at room temperature for 3 days to prepare a dispersion of silica-coupled silica fine particles. To 35.04 g of the dispersion, 58.35 g of isopropyl alcohol and 39.34 g of diacetone alcohol were added. In addition, photopolymerization initiator (Irgacure 907, manufactured by Ciba-Gaigi Co., Ltd.) 1.02 g and photosensitizer (Cacure 1 DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.51 g were dissolved in 772.85 g of isopropyl alcohol. Further, 25.6 g of a mixture of dipentaerythritol pentaatarylate and dipentaerythritol hexatatalylate (DPHA, Nippon Kayaku Co., Ltd.) was added and dissolved. 67.23 g of the resulting solution was added to the above dispersion, a mixture of isopropyl alcohol and diacetone alcohol. The mixture was stirred for 20 minutes at room temperature and filtered through a polypropylene filter having a pore size of 0.4 m to prepare a coating solution for a low refractive index layer.
[0170] 次に比較例として、試料 101とは逆の塗布順にして試料 102を作製した。即ち、下 塗り処理済みのポリエチレンテレフタレート(PET)フィルム上に、前記反射防止層を スロット型塗布装置で逐次重層塗布して乾燥後、前記ハロゲン化銀粒子含有層を、 支持体の反対側にスライドホッパー型塗布装置を用いて塗布し、露光、現像処理を 施して、メッシュ状の金属格子パターンを有する電磁波遮蔽層を形成した。このように
して反射防止層を有する電磁波遮蔽フィルム試料 102を作製した。 [0170] Next, as a comparative example, a sample 102 was manufactured in the order of application opposite to that of the sample 101. That is, on the polyethylene terephthalate (PET) film that has been subjected to undercoating, the antireflection layer is successively applied by a slot type coating apparatus and dried, and then the silver halide grain-containing layer is slid to the opposite side of the support. Coating was performed using a hopper type coating apparatus, and exposure and development processes were performed to form an electromagnetic wave shielding layer having a mesh-like metal lattice pattern. in this way Thus, an electromagnetic wave shielding film sample 102 having an antireflection layer was produced.
[0171] 《評価》 [0171] << Evaluation >>
上記方法により作製した各試料に対し、電磁波減衰効果、透明性、膜面のスポット 故障の評価を以下の方法で実施した。 Each sample prepared by the above method was evaluated for electromagnetic wave attenuation effect, transparency, and spot failure on the film surface by the following method.
[0172] (電磁波減衰効果) [0172] (Electromagnetic wave attenuation effect)
現像後に波長 800〜870nm、出力 50Wの赤外パルス半導体レーザ(フランクフル ト社、パルス波幅 10msec)で銀画像部を加熱し、電磁波減衰効果は関西電子工業 振興センターによる電磁波遮蔽測定法 (KEC法)により、電磁波減衰効果を測定し、 100MHzにおける電磁波減衰効果 (dB)を比較した。 After development, the silver image area was heated with an infrared pulsed semiconductor laser (Frankfurt, pulse width 10 msec) with a wavelength of 800 to 870 nm and an output of 50 W. The electromagnetic wave attenuation effect was measured by the Kansai Electronics Industry Promotion Center (KEC method). ), The electromagnetic wave attenuation effect was measured, and the electromagnetic wave attenuation effect (dB) at 100 MHz was compared.
[0173] (透明'性) [0173] (Transparency)
透明性については、目視の相対評価で、良好である、やや曇りが認められる、明ら 力に曇りが認められる、の 3段階評価を行った。 The transparency was evaluated by a visual relative evaluation, which was evaluated according to three levels: good, slightly cloudy, and clear cloudy.
[0174] (スポット故障) [0174] (Spot failure)
製品としての膜面のスポット故障の数を 10cm2当たりの目視個数で評価した。評価 基準は下記で行った。 The number of spot failures on the film surface as a product was evaluated by the number of visual observations per 10 cm2. Evaluation criteria were as follows.
[0175] ◎:極めて良好 0個 [0175] ◎: Very good 0
〇:良好 1〜2個 Y: Good 1-2
△:実用上許容レベル 3〜4個 Δ: Practically acceptable level 3-4
X:実用不可レべノレ 5〜8個。 X: 5-8 pieces that are impractical.
[0176] (反射防止性の評価) [0176] (Evaluation of antireflection properties)
試料を机上に水平に配置し、 3mの高さの天井にパルック蛍光灯(3波長域発光形 )松下電器産業 (株)製 FL40SS .ELWZ37型 37WX 2本を 1セットとして、 lm間 隔で 8セット配置した。評価者は机の椅子に座り、机上の試料に反射して写る蛍光灯 の状況を、下記のように相対的にランク評価した。 Place a sample horizontally on a desk, and set a parok fluorescent lamp (3-wavelength emission type) FL40SS .ELWZ37 type 37WX 2 sets on a 3m-high ceiling as one set. A set was placed. The evaluator sat on a desk chair and evaluated the relative rank of the fluorescent lamps reflected on the sample on the desk as follows.
[0177] 〇:近くの蛍光灯の写りこみはやや気になる力 遠くは気にならない [0177] ○: Reflection of a nearby fluorescent lamp is a little worrisome.
△:遠くの蛍光灯の写りこみも気になる △: I'm worried about the reflection of distant fluorescent lights
X:蛍光灯の写りこみがかなり気になる。 X: I'm worried about the reflection of fluorescent lights.
[0178] (塗布速度限界)
ノ、ロゲン化銀粒子含有層塗布液の塗布に際して、塗布速度を変化させて、塗布ム ラ (主に段ムラ)が発生して塗布面の均一性が損なわれる上限速度 (mZ分)を調べ た。 [0178] (Application speed limit) When coating the coating solution containing silver halide particles, change the coating speed to determine the upper limit speed (mZ) at which coating unevenness (mainly unevenness) occurs and the uniformity of the coated surface is impaired. It was.
[0179] (その他) [0179] (Other)
その他、試料作成の上で認められた知見を示した。 In addition, the findings found in the preparation of the sample are shown.
[0180] [表 1] [0180] [Table 1]
[0181] なお、試料 102の反射防止層にわずかにひび割れが発生しているのが認められた [0181] A slight crack was observed in the antireflection layer of Sample 102.
[0182] 上記結果から、電磁波遮蔽フィルムの製造にぉ 、て、メッシュ状の金属部を形成さ せ [0182] From the above results, a mesh metal part was formed in the production of the electromagnetic shielding film.
後に反射防止機能を有する層を塗布形成する順とすることによって、反射防止層の 透明性に優れ、スポット故障も問題なぐ反射防止性が高ぐひび割れの発生もない 優れた製造方法であることがわかる。 Later, by applying the coating layer in the order of antireflection function, the antireflection layer is excellent in transparency, is highly resistant to spot failures, has high antireflection properties, and does not generate cracks. Recognize.
[0183] また、反射防止層を塗布する直前の搬送状態での支持体の帯電量を測定した結 果、 [0183] Further, as a result of measuring the charge amount of the support in the transport state immediately before applying the antireflection layer,
試料 102に比べて試料 101は帯電量が小さ アースが有効に作用していることが わかった。生産工程への負荷を低減できる優れた製造方法であることがわかる。 Compared to sample 102, sample 101 had a smaller charge and grounding was found to be effective. It turns out that it is the outstanding manufacturing method which can reduce the load to a production process.
[0184] 実施例 2 [0184] Example 2
《近赤外線吸収染料塗布液 1の調製》 《Preparation of near-infrared absorbing dye coating solution 1》
0. 5Lの三つ口フラスコに脱イオン水 300g、メタクリル酸メチル(MMA) 25g、スチ レン 25g、アクリル酸ェチル (EA) 45g、ヒドロキシェチルメタクリレー HHEMA) 5g、 過硫酸アンモニゥム 250mgをカ卩え、窒素でバブリングさせながら 100°Cで 3時間攪 拌し、アクリル榭脂 (AC)水分散液を得た。反応終了後、 lOOmgのハイドロキノンを 添加して熱可塑性榭脂水分散液とした。
[0185] この分散液にィモニゥム系近赤外線吸収染料 (I 2)を lOOnm以下に微粒子固体 分散したものを投入して、 1時間撹拌後、更にゼラチン 2質量%水溶液を追加し、近 赤外線吸収染料塗布液 1とした。 0. A 5 L three-necked flask was charged with 300 g of deionized water, 25 g of methyl methacrylate (MMA), 25 g of styrene, 45 g of ethyl acrylate (EA), 5 g of hydroxyethyl methacrylate HHEMA, and 250 mg of ammonium persulfate. The mixture was stirred at 100 ° C for 3 hours while bubbling with nitrogen to obtain an acrylic resin (AC) aqueous dispersion. After completion of the reaction, lOOmg of hydroquinone was added to obtain a thermoplastic resin aqueous dispersion. [0185] To this dispersion, an immonium-based near-infrared absorbing dye (I 2) in a fine solid state dispersion of lOOnm or less was added, and after stirring for 1 hour, a 2% by weight aqueous solution of gelatin was further added, and a near-infrared absorbing dye. The coating solution was 1.
[0186] 前記近赤外線吸収染料の分散は、伊藤製作製の遊星ボールミル (部分安定化ジ ルコニァ製)で分散した。容器 200ml中に 100mlの水、 10gの近赤外線吸収染料 (I 2)、ビーズ(5mm径)を 30mlで室温下で稼動させ、平均粒子径として lOOnmの 分散液を作製した。 [0186] The near-infrared absorbing dye was dispersed with a planetary ball mill (partially stabilized zirconium) manufactured by Ito. 100 ml of water, 10 g of near-infrared absorbing dye (I 2), and beads (5 mm diameter) were operated in 30 ml at room temperature in a 200 ml container to prepare a dispersion with an average particle diameter of lOOnm.
[0187] 《近赤外線吸収染料塗布液 2の調製》 [0187] << Preparation of near-infrared absorbing dye coating liquid 2 >>
燐酸エステル—ゼラチン分散は、 50mlのゼラチン水溶液中(4質量0 /0)に 4gのトリ クレジル燐酸エステル、 50mlの酢酸ェチル、界面活性剤(ラウリルアルコールと重合 度 10のポリエチレングリコールの縮合物)を 0. 2g添加し、超音波分散した。この分散 液に、ィモ-ゥム系近赤外線吸収染料 (1— 2)を lOOnm以下に微粒子固体分散した ものを投入して、近赤外線吸収染料塗布液 2とした。 Phosphate - gelatin dispersion, tri cresyl phosphate ester 4g in gelatin aqueous solution (4 wt 0/0) of 50 ml, 50 ml of acetic acid Echiru, surfactant (condensate of polyethylene glycol lauryl alcohol polymerization degree 10) 0.2 g was added and ultrasonically dispersed. To this dispersion, a near-infrared absorbing dye coating liquid 2 was prepared by adding a solid near-infrared absorbing dye (1-2) in a fine particle solid dispersion of lOOnm or less.
[0188] 前記近赤外線吸収染料の分散は、近赤外線吸収染料塗布液 1の調製と同様に 行った。 [0188] The near-infrared absorbing dye was dispersed in the same manner as in the preparation of the near-infrared absorbing dye coating solution 1.
[0189] 支持体として、実施例 1と同じ下塗り処理済みのポリエチレンテレフタレートフィルム を使用し、ィモ-ゥム系近赤外線染料 (1— 2)の付量が 0.
となるように、近 赤外線吸収染料塗布液ー1、 2をスライドホッパー型塗布装置を用いてそれぞれ塗 布して、試料 201、 202を得た。 [0189] As the support, the same undercoated polyethylene terephthalate film as in Example 1 was used, and the amount of the immo-based near-infrared dye (1-2) was 0. Thus, near-infrared absorbing dye coating solutions 1 and 2 were applied using a slide hopper type coating device, respectively, to obtain samples 201 and 202.
[0190] 試料 201、 202の近赤外線吸収層の上に、実施例 1と同じハロゲンィ匕銀粒子含有 塗布液を銀の塗布量が lOgZm2 (ゼラチン塗布量 lgZm2)となるように塗布した。 [0190] On the near-infrared absorbing layers of Samples 201 and 202, the same halogen-silver particle-containing coating solution as in Example 1 was applied so that the silver coating amount was lOgZm 2 (gelatin coating amount lgZm 2 ).
[0191] 次に、前記近赤外線吸収染料塗布液 1、 2と実施例 1と同じハロゲン化銀粒子含 有塗布液とを、スライドホッパー型塗布装置を用いて、下層が近赤外線吸収染料層、 上層がハロゲンィ匕銀粒子含有層となるように同時重層塗布を行って、試料 203、 204 を作製した。 [0191] Next, the near-infrared absorbing dye coating solutions 1 and 2 and the same silver halide particle-containing coating solution as in Example 1 were used, using a slide hopper type coating device, and the lower layer was a near-infrared absorbing dye layer, Samples 203 and 204 were prepared by simultaneous multilayer coating so that the upper layer was a layer containing a silver halide silver particle.
[0192] 試料 201〜204に対して、実施例 1と同じ方法で露光、現像処理を行って、メッシュ 状の金属格子パターンを形成した。そして、実施例 1と同じ方法で反射防止層の塗 布液を調製し、支持体の裏面側に実施例 1と同じ付量で塗布した。
[0193] 実施例 1と同じ下塗り処理済みのポリエチレンテレフタレートフィルム上に、実施例 1 と同じハロゲンィ匕銀粒子含有塗布液を銀の塗布量力 S10gZm2 (ゼラチン塗布量 lg Zm2)となるように塗布し、実施例 1と同様に露光、現像処理してメッシュ状の金属格 子パターンを形成した後、その上に前記近赤外線吸収染料塗布液 1、 2をそれぞ れ塗布して、試料 205、 206を作製した。そして、実施例 1と同じ方法で反射防止層 の塗布液を調製し、支持体の裏面側に実施例 1と同じ付量で塗布した。 [0192] Samples 201 to 204 were exposed and developed in the same manner as in Example 1 to form a mesh-like metal lattice pattern. Then, a coating solution for the antireflection layer was prepared in the same manner as in Example 1, and applied to the back side of the support in the same amount as in Example 1. [0193] On the same undercoated polyethylene terephthalate film as in Example 1, the same halogen-silver particle-containing coating solution as in Example 1 was made to have a silver coating amount force S 10g Zm 2 (gelatin coating amount lg Zm 2 ). After applying to the sample and exposing and developing in the same manner as in Example 1 to form a mesh-like metal lattice pattern, the above-mentioned near-infrared absorbing dye coating solutions 1 and 2 are applied to the sample, respectively. 205 and 206 were produced. Then, a coating solution for the antireflection layer was prepared in the same manner as in Example 1, and coated on the back side of the support in the same amount as in Example 1.
[0194] 《評価》 [0194] << Evaluation >>
上記方法により作製した各試料に対し、実施例 1と同様に評価を実施した。 Each sample produced by the above method was evaluated in the same manner as in Example 1.
[0195] (近赤外染料層の経時安定性) [0195] (Near-infrared dye layer stability over time)
経時安定性についての評価は温度 70°C相対湿度 90%の条件下 200時間放置し 、吸収極大の劣化割合%で表示した。作製試料の内容及び評価した性能結果を表 2に示す。耐光性劣化試験はスガ試験機株式会社製スーパーキセノンウエザーメー ター SX75を使用し、相対湿度 50%、照射強度 50WZm2、 100時間試験後の吸収 劣化の割合を評価した。数値が小さいほど安定性が高ぐ好ましい。 Evaluation of stability over time was expressed as the percentage of deterioration of the absorption maximum after standing for 200 hours at a temperature of 70 ° C and a relative humidity of 90%. Table 2 shows the contents of the fabricated samples and the evaluated performance results. Light resistance deterioration test using Suga Test Instruments Co., Ltd. Super Xenon Weather Meter SX75, 50% relative humidity, and evaluated the rate of absorption degradation of irradiation intensity 50WZm 2, 100 hours after the test. The smaller the value, the higher the stability.
[0196] (その他) [0196] (Others)
その他、試料作成の上で認められた知見を示した。 In addition, the findings found in the preparation of the sample are shown.
[0197] [表 2] [0197] [Table 2]
[0198] なお、試料 205、 206において、近赤外線吸収染料含有層の塗布ムラがわずかに 発生した。下層のメッシュパターンの凹凸に起因しているものと推察される。 [0198] In Samples 205 and 206, coating unevenness of the near-infrared absorbing dye-containing layer slightly occurred. It is inferred that this is due to the unevenness of the mesh pattern in the lower layer.
[0199] 上記結果から、電磁波遮蔽フィルムの製造にぉレ、て、近赤外線吸収機能を有する 層を設けた後に、感光性ハロゲンィ匕銀粒子を含む層を設けるカゝ、または近赤外線吸
収機能を有する層と感光性ハロゲンィ匕銀粒子を含む層とを同時重層塗布によって設 けることによって、電磁波減衰効果や反射防止層の透明性やスポット故障は言うに及 ばず、更に高速塗布が可能で、近赤外染料層の経時安定性も高ぐ近赤外染料層 の塗布性に問題がない、優れた製造方法であることがわ力る。 [0199] From the above results, in the production of the electromagnetic wave shielding film, after providing a layer having a near-infrared absorption function, a layer provided with a layer containing photosensitive silver halide particles, or near-infrared absorption. By providing a layer having a light-absorbing function and a layer containing photosensitive silver halide silver particles by simultaneous multi-layer coating, not only the electromagnetic wave attenuation effect, transparency of the antireflection layer and spot failure, but also high-speed coating can be achieved. This is an excellent manufacturing method that is possible and has no problems in applicability of the near-infrared dye layer.
[0200] 実施例 3 [0200] Example 3
実施例 2の試料 203、 204におけるハロゲンィ匕銀粒子含有塗布液にゼラチン水溶 液を添加して、銀の塗布量が 1. Og/m2、ゼラチン塗布量が 0. 2g/m2 (銀/ゼラチ ン体積比 0. 64)となるように塗布した以外は同様にして、試料 301、 302を作製した 実施例 1と同様に露光、現像処理を行った後、連続して、下記の物理現像液にて 2 5°C5分間の物理現像を行い、次いで水洗処理を行った。その後、下記銅メツキ液に て、 2. 5AZcm2で 25°C5分間の電解めつきを行って、水洗した。 An aqueous gelatin solution was added to the coating solution containing the halogenated silver particles in Samples 203 and 204 of Example 2, and the silver coating amount was 1. Og / m 2 and the gelatin coating amount was 0.2 g / m 2 (silver / Samples 301 and 302 were prepared in the same manner except that the gelatin volume ratio was 0.64). After the exposure and development processes were performed in the same manner as in Example 1, the following physical development was performed continuously. The solution was subjected to physical development at 25 ° C. for 5 minutes and then washed with water. Then, the following copper plating solution was subjected to electrolytic plating at 2.5 AZcm 2 at 25 ° C. for 5 minutes and washed with water.
[0202] (物理現像液) [0202] (Physical developer)
純水 800ml 800ml pure water
クェン酸 5g Quenic acid 5g
ハイドロキノン 7g Hydroquinone 7g
硝酸銀 3g Silver nitrate 3g
水を加えて全量を 1リットルとする。 Add water to bring the total volume to 1 liter.
[0203] (銅めつき液) [0203] (Copper plating solution)
硫酸銅 125g 125 g of copper sulfate
硫酸 85g 85g sulfuric acid
ポリエチレングリコール 0. lg Polyethylene glycol 0.lg
1M塩酸 2. Oml 1M hydrochloric acid 2.Oml
水を加えて全量を 1リットルとする。 Add water to bring the total volume to 1 liter.
[0204] 乾燥後、実施例 1と同じ方法で、反射防止層を支持体の裏面側に実施例 1と同じ付 量で塗布した。 [0204] After drying, in the same manner as in Example 1, an antireflection layer was applied to the back side of the support in the same amount as in Example 1.
[0205] 実施例 2と同様の評価を行った結果、物理現像やめつきなどの補力処理を施し た試料 301、 302は、評価項目のすべてを満足する優れた電磁波遮蔽フィルムであ
り、本発明の製造方法が優れていることがわかる。 [0205] As a result of performing the same evaluation as in Example 2, samples 301 and 302 subjected to intensifying treatment such as physical development and tacking are excellent electromagnetic shielding films satisfying all the evaluation items. This shows that the production method of the present invention is excellent.
[0206] 実施例 4 [0206] Example 4
実施例 1の試料 101と実施例 3の試料 301におけるハロゲンィ匕銀粒子中の増感色 素(SD— 1)を近赤外増感色素(S— 1)に置き換えた以外は同様にして、試料 401、 402を作成した。露光においては、発振波長 8 lOnmの近赤外半導体レーザー光を 用いた以外は同様の操作を行!、、電磁波遮蔽フィルムを作製した。 In the same manner except that the sensitizing dye (SD-1) in the halogen silver halide grains in Sample 101 of Example 1 and Sample 301 of Example 3 was replaced with a near-infrared sensitizing dye (S-1), Samples 401 and 402 were prepared. In the exposure, the same operation was performed except that near-infrared semiconductor laser light having an oscillation wavelength of 8 lOnm was used to produce an electromagnetic wave shielding film.
[0207] 金属メッシュを電子顕微鏡で調べたところ、試料 402の方がシャープな細線が再現 されて 、た。このことからハロゲンィ匕銀粒子が近赤外増感されて 、て近赤外感光性を 示し、近接層に近赤外吸収染料層を有する電磁波遮蔽フィルム原版を近赤外レー ザ一光にてメッシュパターンを露光した場合は、特に優れた電磁波遮蔽フィルムを製 造できることがわ力つた。
[0207] When the metal mesh was examined with an electron microscope, sharp thin lines were reproduced in the sample 402. As a result, the silver halide grains were sensitized in the near-infrared, showed near-infrared photosensitivity, and an electromagnetic wave shielding film master having a near-infrared absorbing dye layer in the near layer was irradiated with near-infrared laser light. When the mesh pattern was exposed, it was found that a particularly excellent electromagnetic shielding film could be produced.
Claims
[1] 支持体上に感光性ハロゲン化銀粒子を含む層を設けた電磁波遮蔽フィルム用原版 に露光、現像処理することでメッシュ状の金属部を形成させた後、反射防止機能を有 する層を塗布形成することを特徴とする電磁波遮蔽フィルムの製造方法。 [1] A layer having an antireflection function after forming a mesh-like metal part by exposing and developing an original plate for an electromagnetic wave shielding film provided with a layer containing photosensitive silver halide grains on a support. A method for producing an electromagnetic wave shielding film, characterized by coating and forming.
[2] 前記反射防止機能を有する層がメッシュ状の金属部を有する層の支持体裏面側に 塗布形成されることを特徴とする請求の範囲第 1項に記載の電磁波遮蔽フィルムの 製造方法。 [2] The method for producing an electromagnetic wave shielding film according to [1], wherein the layer having an antireflection function is applied and formed on the back side of a support having a layer having a mesh-like metal part.
[3] 前記反射防止機能を有する層が無機微粒子を含有した屈折率の異なる複数の光透 過性層からなることを特徴とする請求の範囲第 1項または第 2項に記載の電磁波遮 蔽フィルムの製造方法。 [3] The electromagnetic wave shielding according to claim 1 or 2, wherein the layer having an antireflection function is composed of a plurality of light-transmitting layers containing inorganic fine particles and having different refractive indexes. A method for producing a film.
[4] 前記感光性ハロゲンィ匕銀粒子を含む層が支持体上に近赤外線吸収機能を有する層 を設けた後に、設けられることを特徴とする請求の範囲第 1項乃至第 3項のいずれか [4] The method according to any one of claims 1 to 3, wherein the layer containing the photosensitive halogen silver halide grains is provided after providing a layer having a near infrared absorption function on a support.
1項に記載の電磁波遮蔽フィルムの製造方法。 2. A method for producing an electromagnetic wave shielding film according to item 1.
[5] 前記感光性ハロゲンィ匕銀粒子を含む層が支持体上に近赤外線吸収機能を有する層 と同時に設けられることを特徴とする請求の範囲第 1項乃至第 4項のいずれか 1項に 記載の電磁波遮蔽フィルムの製造方法。 [5] The method according to any one of claims 1 to 4, wherein the layer containing the photosensitive halogen silver halide grains is provided on the support simultaneously with the layer having a near infrared absorption function. The manufacturing method of the electromagnetic wave shielding film of description.
[6] 前記感光性ハロゲンィ匕銀粒子を含む層及び近赤外線吸収機能を有する層がスライ ドホッパー型塗布装置またはスライド型カーテン塗布装置による同時重層塗布で形 成されることを特徴とする請求の範囲第 4項または第 5項に記載の電磁波遮蔽フィル ムの製造方法。 [6] The layer including the photosensitive halogen silver halide particles and the layer having a near-infrared absorption function are formed by simultaneous multi-layer coating by a slide hopper type coating device or a slide type curtain coating device. 6. A method for producing an electromagnetic wave shielding film according to item 4 or 5.
[7] 前記反射防止機能を有する層がスロット型塗布装置で逐次重層塗布で形成されるこ とを特徴とする請求の範囲第 1項乃至第 6項のいずれか 1項に記載の電磁波遮蔽フ イルムの製造方法。 [7] The electromagnetic wave shielding film according to any one of [1] to [6], wherein the layer having an antireflection function is formed by successive multilayer coating using a slot type coating device. Irum manufacturing method.
[8] 前記感光性ハロゲンィ匕銀粒子を含む層を設けた電磁波遮蔽フィルム用原版に露光 、現像処理を施した後、更に物理現像処理及び Zまたはめつき処理を施して、メッシ ュ状の電磁波遮蔽機能を有する金属層を形成した後、反射防止機能を有する層を 塗布形成することを特徴とする請求の範囲第 1項乃至第 7項のいずれか 1項に記載 の電磁波遮蔽フィルムの製造方法。
請求の範囲第 1項乃至第 8項のいずれか 1項に記載の電磁波遮蔽フィルムの製造方 法により製造されることを特徴とする電磁波遮蔽フィルム。
[8] After exposing and developing the original plate for an electromagnetic wave shielding film provided with a layer containing the photosensitive halogen silver halide particles, the substrate is further subjected to physical development processing and Z or staking processing to form a mesh-shaped electromagnetic wave. The method for producing an electromagnetic wave shielding film according to any one of claims 1 to 7, wherein a metal layer having a shielding function is formed and then a layer having an antireflection function is applied and formed. . An electromagnetic wave shielding film produced by the method for producing an electromagnetic wave shielding film according to any one of claims 1 to 8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008503808A JPWO2007102393A1 (en) | 2006-03-06 | 2007-03-01 | Method for manufacturing electromagnetic shielding film, and electromagnetic shielding film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006059164 | 2006-03-06 | ||
JP2006-059164 | 2006-03-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007102393A1 true WO2007102393A1 (en) | 2007-09-13 |
Family
ID=38474824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/053900 WO2007102393A1 (en) | 2006-03-06 | 2007-03-01 | Method for manufacturing electromagnetic wave shielding film and electromagnetic wave shielding film |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPWO2007102393A1 (en) |
WO (1) | WO2007102393A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013000667A (en) * | 2011-06-17 | 2013-01-07 | Konica Minolta Holdings Inc | Manufacturing method for infrared shielding film |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11340681A (en) * | 1998-05-22 | 1999-12-10 | Dainippon Printing Co Ltd | Electromagnetic wave shielding member, manufacture thereof and display device |
JP2004221564A (en) * | 2002-12-27 | 2004-08-05 | Fuji Photo Film Co Ltd | Translucent electromagnetic wave shielding film and manufacturing method therefor |
JP2004221565A (en) * | 2002-12-27 | 2004-08-05 | Fuji Photo Film Co Ltd | Translucent electromagnetic wave shielding film and manufacturing method therefor |
JP2007096107A (en) * | 2005-09-29 | 2007-04-12 | Fujimori Kogyo Co Ltd | Electromagnetic wave shielding material roll body and its production method |
-
2007
- 2007-03-01 JP JP2008503808A patent/JPWO2007102393A1/en active Pending
- 2007-03-01 WO PCT/JP2007/053900 patent/WO2007102393A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11340681A (en) * | 1998-05-22 | 1999-12-10 | Dainippon Printing Co Ltd | Electromagnetic wave shielding member, manufacture thereof and display device |
JP2004221564A (en) * | 2002-12-27 | 2004-08-05 | Fuji Photo Film Co Ltd | Translucent electromagnetic wave shielding film and manufacturing method therefor |
JP2004221565A (en) * | 2002-12-27 | 2004-08-05 | Fuji Photo Film Co Ltd | Translucent electromagnetic wave shielding film and manufacturing method therefor |
JP2007096107A (en) * | 2005-09-29 | 2007-04-12 | Fujimori Kogyo Co Ltd | Electromagnetic wave shielding material roll body and its production method |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013000667A (en) * | 2011-06-17 | 2013-01-07 | Konica Minolta Holdings Inc | Manufacturing method for infrared shielding film |
Also Published As
Publication number | Publication date |
---|---|
JPWO2007102393A1 (en) | 2009-07-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2007007698A1 (en) | Electromagnetic wave shielding material, process for producing the same, and electromagnetic wave shielding material for plasma display panel | |
US7404915B2 (en) | Electromagnetic wave shielding material, method of manufacturing the same and electromagnetic wave shielding material for plasma display panel | |
JP2009188360A (en) | Electronic circuit and method of manufacturing the same | |
WO2006129886A1 (en) | Plating method, electrically conductive film and light-transmitting electromagnetic wave shielding film | |
JP2008300720A (en) | Light transmissive conductive film and electromagnetic wave shielding filter | |
WO2007102393A1 (en) | Method for manufacturing electromagnetic wave shielding film and electromagnetic wave shielding film | |
US8314986B2 (en) | Transparent electromagnetic wave-shielding filter and method of producing thereof, and conductive film | |
JP2009016526A (en) | Transparent electromagnetic wave shielding film and its manufacturing method | |
JP2009038078A (en) | Electromagnetic wave shield film, and plasma display panel | |
JP2012146548A (en) | Method for producing transparent conductive film and transparent conductive film | |
JP2008282840A (en) | Forming method of translucent conductive thin film, forming apparatus thereof and translucent conductive thin film obtained by the apparatus | |
JP2008218784A (en) | Photosensitive material for electromagnetic wave shielding material and manufacturing method of the electromagnetic wave shielding material | |
JP5131268B2 (en) | Transparent film having conductive metal pattern and method for producing the same | |
JP2006276208A (en) | Optical filter for display | |
JP2009021334A (en) | Transparent electromagnetic wave shielding film, and manufacturing method thereof | |
JP2009010001A (en) | Electromagnetic wave shielding film manufacturing method, and electromagnetic wave shielding film | |
JP2009004213A (en) | Light-transmitting conductive film, manufacturing method therefore, and light-transmitting electromagnetic wave shielding film | |
JP2008270405A (en) | Transparent electromagnetic wave shielding film, its manufacturing method, and plasma display panel using film | |
JP2009117277A (en) | Translucent conductive thin film, its manufacturing method, and transparent electromagnetic wave shielding film | |
JP2009059998A (en) | Translucent conductive film, its manufacturing method, and translucent electromagnetic wave shielding filter using translucent conductive film | |
JP2007287960A (en) | Electromagnetic wave shielding material and method for fabricating electromagnetic wave shielding material | |
JP2009088372A (en) | Method of manufacturing translucent conductive membrane | |
JP2009064654A (en) | Forming method of translucent conductive thin film | |
JP2009076358A (en) | Manufacturing method of translucent conductive thin film, and translucent conductive thin film | |
US20070176153A1 (en) | Electromagnetic wave shielding film, method of manufacturing the same, electromagnetic wave shielding film for plasma display panel, and optical film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2008503808 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07737580 Country of ref document: EP Kind code of ref document: A1 |