JP2009206117A - Production method of filter for display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method of a filter for a display which can attain price reduction while exhibiting high productivity. <P>SOLUTION: The production method of the filter for a display having a conductive mesh and a black resist layer formed thereon in register continuously in the longitudinal direction of a long base comprises a step for forming a metal thin film on the long base, a step for laminating a photosensitive black resist layer on the metal thin film, a step for exposing the photosensitive black resist layer by laser in the shape of a mesh pattern, a step for developing the photosensitive black resist layer, and a step for etching the metal thin film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a display filter useful for realizing a reduction in price.

  A display such as a liquid crystal display (hereinafter referred to as LCD) or a plasma display (hereinafter referred to as PDP) is a display device capable of clear full color display. A display is usually provided with a front filter (hereinafter simply referred to as a display filter) on the viewing side of the display for the purpose of preventing reflection of external light, shielding electromagnetic waves generated from the display, and protecting the display. . In particular, PDP generates strong electromagnetic waves due to its structure and principle of operation, so there are concerns about the effects on human bodies and other devices. Filters for displays with optical functions such as electromagnetic shielding and antireflection Is usually used.

  As the conductive layer used in the above-described display filter, a conductive mesh is preferably used from the viewpoint of electromagnetic wave shielding performance, manufacturing cost, and the like.

  Conventionally known methods for producing conductive meshes include the following: (a) A metal foil such as a copper foil is laminated on a base material via an adhesive, a resist layer is laminated, and a desired pattern is formed. A method using a photolithographic method of developing, etching, and resist stripping after exposure through a photomask (e.g., Patent Document 1), b) A method of plating after printing on a mesh pattern with an ink containing a catalyst core for plating (For example, Patent Document 2), c) Method of plating after forming a mesh pattern using photosensitive silver salt (Patent Document 3), d) After printing a dot pattern with a resin soluble in a solvent such as PVA A method of removing PVA after forming a metal thin film by plating or vapor deposition (Patent Document 4), e) Forming a metal thin film such as copper on a substrate by vacuum vapor deposition or the like, and laminating a resist layer on the metal thin film Shi After the b) and a method of making a conductive mesh by using a photolithographic method in the same manner (Patent Document 5), and the like.

Among the above production methods, the methods using the photolithographic methods (i) and (e) have the advantage that a high-definition conductive mesh having high conductivity and a relatively small line width can be produced. A high-definition conductive mesh is effective in suppressing the occurrence of moire and a decrease in transmittance. On the other hand, the method using the photolithographic method has a problem that the number of steps is large and various problems due to pattern exposure being performed through a photomask.
Various problems due to the above pattern exposure being performed through a photomask include: 1) the need for a photomask, 2) specifications for conductive meshes such as line width and line pitch, or display filters If the size of the photomask is changed, the photomask to be used must also be changed (not versatile). 3) One serious defect exists in one unit of conductive mesh obtained using the photomask. The entire conductive mesh of one unit becomes a defective product and is extremely inefficient. 4) Since the exposure is performed in units of photomasks, the mesh pattern of the conductive mesh in the longitudinal direction of the long base material. There is a problem that it cannot be formed continuously without being interrupted (a continuous mesh cannot be formed).
4) The mesh pattern of the conductive mesh is continuously formed in the longitudinal direction of the long base material without interruption, that is, the technical significance of forming the continuous mesh is as follows: 1) There is a serious defect in the conductive mesh. Even if it occurs, only the defective part can be removed, 2) it can easily cope with display filters of various sizes, and 3) a functional layer such as a hard coat layer or an antireflection layer is directly formed on the conductive mesh. Since the mesh pattern is continuously formed without interruption in the longitudinal direction of the long base material (coating direction of the functional layer), it is advantageous for continuous coating of the functional layer. (The conductive mesh produced using a photomask usually has a solid metal part formed on the four sides of the conductive mesh in order to secure a ground electrode. The continuous coating of the functional layer to emission portion and the metal solid portion are mixed include disadvantage in a), or the like.
As described above, the photolithographic method using a photomask has various problems on the other hand, although a high-definition conductive mesh can be obtained.
In addition, metals such as copper, silver, nickel, and aluminum are generally used for the conductive mesh, but the surface of the conductive mesh formed of these metals has a metallic luster, which makes it possible to There arises a problem that the contrast is lowered. In particular, in the case of a display filter in which only a functional layer such as a hard coat layer or an antireflection layer is present on the conductive mesh, the influence of the metallic gloss of the conductive mesh is more serious.
In order to suppress the metallic luster of the conductive mesh, the surface of the conductive mesh is usually blackened.
However, the blackened layer formed by blackening the conductive mesh has a characteristic that it is brittle and easily falls off. Such a characteristic is that the conductive mesh is formed when a functional layer such as an antireflection layer or a hard coat layer is applied and formed on the conductive mesh in a subsequent step when manufacturing the display filter targeted by the present invention. A problem arises in that a part of the blackening treatment layer comes into contact with a transport roll or the like of the production line, and the production line such as the transport roll is contaminated.

Further, blackening the conductive mesh means that the number of processing steps is increased by at least one (usually having a step of peeling and removing the resist layer before the blackening treatment, In total, this is an increase in two steps), which is not preferable from the viewpoint of productivity.
Instead of the above blackening treatment, it has been proposed to form a metal mesh pattern using a black resist layer, leave the black resist layer without peeling off, and use the black resist layer instead of the blackening treatment layer. (Patent Document 6).
However, the above-mentioned Patent Document 6 does not disclose exposing with a laser and forming a continuous mesh. Further, this document does not disclose that a functional layer such as an antireflection layer or a hard coat layer is formed on a black resist.
On the other hand, a display filter intended for shielding electromagnetic waves usually has at least a conductive mesh when the display filter is mounted on a display and assembled into a display housing in order to effectively shield electromagnetic waves generated from the display. An electrode (grounding electrode) for electrically connecting a part to the external electrode of the housing is provided on the periphery of the display filter (outside the image display area of the display).

Conventionally used display filters comprising two substrates, that is, an optical functional film in which a functional layer such as an antireflection function is laminated on a plastic film, and a conductive layer on the plastic film In the case of a filter in which an electromagnetic wave shielding film provided with an (electromagnetic wave shielding layer) is bonded via an adhesive layer, when the optical functional film and the electromagnetic wave shielding film are bonded together, the electromagnetic wave shielding film By designing the size of the optical functional film sheet to be smaller than the sheet, the conductive layer of the electromagnetic wave shielding film sheet is exposed on the four sides of the filter sheet for display obtained by bonding both sheets. The part is formed. A portion where the conductive layer is exposed is used as an electrode of a display filter.
In recent years, with the reduction in the price of displays, the price of filters for displays has been inevitably reduced. By using only one substrate (for example, a plastic film) for the display filter composed of two substrates as described above, the price can be reduced. As one means for realizing such a display filter comprising a single substrate, an antireflection layer, an antiglare layer, and a hard coat are formed on a conductive layer (conductive mesh) provided on the substrate. It is known to directly form a functional layer such as a layer (for example, Patent Document 7).

  However, the display filter composed of one substrate as described above cannot form a bare electrode of a conductive mesh (conductive layer) at the time of bonding as the filter composed of two substrates described above.

  Therefore, it has been proposed to use a laser for electrode formation of a filter for display (Patent Document 8). This method using a laser is a method in which a functional layer such as an antireflection layer on the conductive mesh is removed to expose a part of the conductive mesh.

However, Patent Document 8 does not disclose the advantage of using a black resist layer in place of the conductive mesh blackening process in electrode formation using a laser.
Japanese Patent No. 3388682 JP 2006-173189 A JP 2004-221564 A JP 2007-14080 A JP 2005-268688 A Japanese Patent Laid-Open No. 9-293989 JP 2007-140282 A WO2007 / 023828

  Accordingly, an object of the present invention is to provide a manufacturing method of a display filter that is high in productivity and can realize a reduction in cost in view of the above-described conventional technology. Another object of the present invention is to provide a method for manufacturing a display filter, in which an electrode that is electrically connected to a display housing (external electrode) can be easily formed on the display filter with good productivity.

The above object of the present invention has been basically achieved by the following invention.
1) A method for manufacturing a filter for a display, in which a conductive mesh and a black resist layer registered on the conductive mesh are continuously formed in the longitudinal direction of the long substrate. Forming a metal thin film, laminating a photosensitive black resist layer on the metal thin film, exposing the photosensitive black resist layer to a mesh pattern with a laser, developing the photosensitive black resist layer A method for producing a filter for display, comprising a step of etching the metal thin film.
2) The manufacturing method of the filter for displays as described in said 1) whose thickness of the said electroconductive mesh is 0.3-5 micrometers.
3) The production of the display filter according to 1) or 2), wherein the step of forming a metal thin film on the substrate is a step of forming a metal thin film on the substrate using a vapor deposition method. Method.
4) The manufacturing method of the filter for a display of any one of said 1) -3) whose optical density of the said photosensitive black resist layer is 0.5-8.
5) The manufacturing method of the filter for a display of any one of said 1) -4) whose thickness of the said photosensitive black resist layer is 0.5-3 micrometers.
6) Furthermore, the manufacturing method of the filter for a display of any one of said 1) -5) which has the process of coating-forming a functional surface layer so that a black resist layer may be coat | covered.
7) The display filter according to 6), wherein the functional surface layer is a functional layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, and an antifouling function. Production method.
8) Of the functional surface layer covering the black resist layer, the thickness (L) of the functional surface layer formed on the thin line portion of the black resist layer is 0.5 to 5 μm, 6) or The manufacturing method of the filter for displays as described in 7).
9) Further, any one of the above 6) to 8), further comprising a step of irradiating a laser from the functional surface layer side to remove the functional layer and the black resist layer to form an exposed portion of the conductive mesh. The manufacturing method of the filter for displays as described in a term.

  According to the present invention, the productivity can be improved and the price can be greatly reduced as compared with the conventional method for manufacturing a display filter. Further, according to the present invention, there is no contamination of the production line (functional layer coating line) by the conventional conductive mesh blackening layer, and the functional layer coating property is improved. Moreover, according to the preferable aspect of this invention, the electrode formation to the filter for a display becomes easy.

  The display filter according to the present invention is formed by continuously forming a conductive mesh and a black resist layer in register on the conductive mesh in the longitudinal direction of the long base material. The manufacturing method includes a step of forming a metal thin film on a long substrate, a step of laminating a photosensitive black resist layer on the metal thin film, a step of exposing the photosensitive black resist layer to a mesh pattern with a laser, A step of developing the photosensitive black resist layer, and a step of etching the metal thin film.

  Here, the conductive mesh and the black resist layer that coincides with the conductive mesh are continuously formed in the longitudinal direction of the long substrate. The conductive mesh is formed in the longitudinal direction of the long substrate. This means that the mesh pattern composed of the black resist layer is continuously formed without interruption. Similarly, the mesh pattern of the conductive mesh and the black resist layer is continuously formed in the width direction of the long base material. Hereinafter, the continuously formed mesh pattern is referred to as a continuous mesh.

Further, in the present invention, the conductive mesh and the black resist layer are arranged in register with each other. In the method for manufacturing a display filter of the present invention, a photosensitive black resist layer is laminated on a metal thin film, The black resist layer of the mesh pattern is formed on the metal thin film by exposing the photosensitive black resist layer to a mesh pattern with a laser and developing, and then the metal thin film in a portion not covered with the black resist layer is etched. Is a state in which a conductive mesh made of a metal thin film is formed, and a black resist is disposed on the conductive mesh.
(Long base material)
The long base material according to the present invention means a base material having a length such that at least 10 sheets of a single display filter as a final product can be taken in the longitudinal direction. For example, the length in the direction is preferably 10 m or more, more preferably 30 m or more, and particularly preferably 50 m or more. The upper limit of the length of the long base material is about 3000 m from the viewpoints of weight, handleability, load on the manufacturing apparatus, and the like. The length of the long base material in the width direction is preferably not less than the length of the short side (usually 550 to 560 mm) of a display filter applied to a 42-inch display (display screen size 520 mm × 930 mm). Therefore, it is more preferable that it is 600 mm or more.

  In order to obtain higher production efficiency, it is preferable that the display filter as a final product can be multi-chamfered (2 to 4 chamfers) in the width direction of the long substrate. For example, a long substrate having a width of about 1200 mm is used. By using it, the short side of the 42-inch display filter can be chamfered.

  The upper limit of the length of the long base material in the width direction is suitably about 2000 mm in consideration of the allowable width of the conductive mesh manufacturing facility and the functional layer coating facility.

  Since the long substrate is usually supplied and processed in a roll form, a plastic film is preferable from the viewpoint that it is suitable for handling and production in a roll form.

  Examples of the resin constituting the plastic film include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as triacetyl cellulose, polyolefin resins such as polyethylene, polypropylene, and polybutylene, acrylic resins, polycarbonate resins, arton resins, and epoxy resins. , Polyimide resin, polyetherimide resin, polyamide resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, and the like. Among these, polyester resins, polyolefin resins, and cellulose resins are preferable, and polyester resins are particularly preferably used. As the thickness of the plastic film, a range of 50 to 300 μm is appropriate, but a range of 90 to 250 μm is particularly preferable from the viewpoint of cost and ensuring the rigidity of the display laminate.

The plastic film used in the present invention is preferably provided with an undercoat layer (primer layer) for enhancing adhesion (adhesive strength) with a conductive mesh or a near-infrared shielding layer described later.
(Manufacturing method of display filter)
Hereinafter, the manufacturing method of the display filter of the present invention will be described step by step.

(Metal thin film formation process)
First, in a metal thin film forming step, a metal thin film is formed on a long base material (hereinafter simply referred to as a base material). As a method of forming a metal thin film on a base material, a method of laminating a metal foil such as a copper foil via an adhesive on a base material, a method of forming a metal thin film by a plating method on a base material, And a method of forming a metal thin film by vapor deposition. Among these metal thin film forming methods, a vapor phase film forming method capable of stably and uniformly forming a metal thin film having a relatively small thickness at low cost is preferably used. In addition, the vapor deposition method can form a metal thin film on the base material without interposing an adhesive layer, so that a uniform coating property is ensured in the functional layer coating process described later. Therefore, it is possible to produce a conductive mesh having high transparency (low haze value) for the above reason (no adhesive is interposed).

  Examples of the vapor deposition method include sputtering, ion plating, electron beam vapor deposition, vacuum vapor deposition, chemical vapor deposition, and the like, and one or more of these methods can be used in combination. In the present invention, sputtering, ion plating, and vacuum deposition are preferable, and sputtering and vacuum deposition are particularly preferable.

  As a metal for forming a metal thin film, an alloy or a combination of two or more of metals such as copper, aluminum, nickel, iron, gold, silver, stainless steel, chromium and titanium is used. it can. Among these, copper is preferably used from the viewpoints of obtaining good electromagnetic shielding properties, easy mesh pattern processing, and low cost.

  When copper is used as the metal thin film, it is preferable to form a copper layer as the main layer after forming a metal such as nickel, chromium or nichrome as the underlayer. The underlayer is a part of the metal thin film according to the present invention, and the thickness of the underlayer is preferably in the range of 5 to 100 nm, and more preferably in the range of 10 to 50 nm. By providing the base layer, adhesion between the base material and the copper layer is improved.

  As the thickness of the metal thin film formed on the substrate, the thickness of the metal thin film should be smaller from the viewpoint of uniformly coating the functional layer on the conductive mesh formed by etching the metal thin film. Therefore, it is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3.5 μm or less. The lower limit of the thickness of the metal thin film is preferably 0.3 μm or more, more preferably 1 μm or more, and particularly preferably 1.5 μm or more from the viewpoint of ensuring good electromagnetic wave shielding performance.

(Lamination process of photosensitive black resist layer)
After forming a metal thin film on a base material as described above, a photosensitive black resist layer is laminated on the metal thin film. As a method of laminating the photosensitive black resist layer on the metal thin film, a method of attaching a resist film or a method of applying a liquid resist can be used. As a method for applying a liquid resist, for example, a dip coating method, a spin coating method, a slit die coating method, a gravure coating method, a reversal coating method, a rod coating method, a bar coating method, a spray method, a roll coating method, and the like are known. A wet coating method can be used.

  The thickness (dry film thickness) of the photosensitive black resist layer laminated on the metal thin film is to ensure an optical density sufficient to suppress the metallic luster of the conductive mesh, and to apply a functional layer described later. From the viewpoint of ensuring coatability in the process, a range of 0.5 to 3 μm is preferable, and a range of 0.5 to 2 μm is more preferable. When the thickness of the photosensitive black resist layer is smaller than 0.5 μm, it becomes difficult to obtain a sufficient optical density, and when the thickness is larger than 3 μm, the coatability of the functional layer is lowered.

  The photosensitive black resist layer according to the present invention is exposed with a laser in the next step. Accordingly, as the photosensitive black resist layer used in the present invention, a negative resist in which a portion exposed by a laser is cured and an unexposed portion is dissolved by development, or a positive resist in which an exposed portion is dissolved by development is used. Can do. In view of environmental problems in the development process of the resist layer, an alkali development type resist is preferable.

  The photosensitive black resist layer according to the present invention (hereinafter simply referred to as a black resist layer) is prepared by containing a black pigment or a mixture of a red pigment, a blue pigment and a green pigment in a resin constituting the resist. can do.

  As the black pigment, Color Index No. Pigment black 7, carbon black, titanium black, metal oxide, and the like can be used. These pigments may be used alone or in combination of two or more. As a red pigment, Color Index No. Pigment Red (hereinafter abbreviated as PR) 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 254, and the like, and Color Index No. Pigment Green (hereinafter abbreviated as PG) 7, 36, and the like, as a blue pigment, Color Index No. Pigment blue (hereinafter abbreviated as PB) 15: 3, 15: 4, 15: 6, 21, 22, 60, 64, and the like.

  As the above-mentioned pigment for obtaining a black resist, titanium black and carbon black are preferable, and titanium black is particularly preferable because high photosensitive characteristics can be obtained.

  As the particle diameter of the pigment described above, the average primary particle diameter is preferably in the range of 5 to 400 nm, more preferably in the range of 10 to 200 nm in consideration of the dispersibility of the pigment and the coatability of the resist. The thing of the range of 10-100 nm is especially preferable.

  The content of the pigment described above is preferably in the range of 5 to 80% by mass and more preferably in the range of 10 to 70% by mass with respect to all the components of the black resist layer (total amount of non-volatile components excluding the organic solvent). If the pigment content is too small, the optical density (OD value) becomes low, and the metallic gloss of the conductive mesh cannot be sufficiently suppressed. On the other hand, if the content of the pigment is too large, the black resist layer is liable to be reduced in curability, adhesiveness to the metal thin film, and coating property.

  The black resist layer according to the present invention has an optical density of preferably 0.5 or more, more preferably 1.0 or more, and particularly preferably 1.5 or more. By setting the optical density of the black resist layer to 0.5 or more, preferably 1.0 or more, and further 1.5 or more, the metallic luster of the conductive mesh can be sufficiently suppressed.

  The upper limit of the optical density of the black resist layer is about 8.0. However, if the optical density of the black resist layer is increased, the sensitivity at the time of laser exposure decreases, so that the optical density is 5 from the viewpoint of securing a certain level of sensitivity. 0.0 or less is preferable, and 4.0 or less is more preferable.

  Here, the optical density (OD value) of the black resist layer can be obtained from the following relational expression using, for example, a microspectroscope (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

Optical density (OD value) = log ₁₀ (I ₀ / I)
Where I ₀ is the incident light intensity and I is the transmitted light intensity.

The black resist layer used in the present invention is a layer that is exposed to laser light to cause a chemical reaction such as curing, and includes the above-described pigment and resin component. The resin component is composed of a photosensitive component that reacts with laser light. The There are a positive type in which the resin irradiated with light increases the dissolution rate in the developer and a negative type in which the resin irradiated with light is cured and the dissolution rate in the developer decreases, both of which can be used. Negative type resins having high transparency of the photosensitive component with visible light are preferably used.
As the laser used for exposing the black resist layer in a mesh pattern, a laser light source that oscillates light in the ultraviolet to near infrared region can be used. For example, UV argon gas laser (364 nm), solid-state UV laser (350 to 380 nm), blue-violet semiconductor laser (390 to 430 nm), argon ion laser (488 nm), FD-YAG laser (532 nm), near infrared semiconductor laser (832 nm) ), YAG laser (1064 nm) and the like.

  Among these laser light sources, a UV laser or a blue-violet semiconductor laser that can work in a bright room environment such as yellow illumination and can easily obtain resist sensitivity is preferably used.

  As the resin component constituting the black resist layer according to the present invention, materials such as a polyimide resin, an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, and a polyolefin resin are preferably used.

  An acrylic resin will be described in detail as an example of the resin component described above. The photosensitive acrylic resin can be configured to contain at least an acrylic polymer, an acrylic polyfunctional monomer or oligomer, and a photopolymerization initiator in order to impart photosensitivity. Furthermore, so-called acrylic epoxy resin to which epoxy is added can also be used.

  The acrylic polymer that can be used is not particularly limited, but a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides.

  Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone having a methacryloyl group And the like, but not limited thereto.

Further, when an acrylic polymer having an ethylenically unsaturated group added to the side chain is used, it can be preferably used because the sensitivity during processing is improved. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, acrylic groups, and methacrylic groups. As a method of adding such a side chain to an acrylic (co) polymer, when the acrylic (co) polymer has a carboxyl group or a hydroxyl group, an ethylenically unsaturated compound having a glycidyl group therein In general, an addition reaction of acrylic acid or methacrylic acid chloride is used. In addition, a compound having an ethylenically unsaturated group can be added using isocyanate. Examples of the ethylenically unsaturated compound having glycidyl group and acrylic acid or methacrylic acid chloride include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, and glycidyl isocrotonate. Examples of polyfunctional monomers that include ether, acrylic acid chloride, and methacrylic acid chloride include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, and adipic acid 1 , 6-hexanediol (meth) acrylic ester, phthalic anhydride propylene oxide (meth) acrylic ester, trimellitic acid diethyleneglycol (Meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, oligomer such as alkyd modified (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A Diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Examples include penta (meth) acrylate. These can be used alone or in combination. In addition, the following monofunctional monomers can be used in combination, for example, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butyl methacrylate, glycidyl methacrylate, lauryl ( There are meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate and the like, and a mixture of two or more of these or a mixture with other compounds is used. By selecting and combining these polyfunctional and monofunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, a methacrylate compound is preferable to an acrylate compound for increasing the hardness, and a compound having 3 or more functional groups is preferable for increasing the sensitivity. Melamines and guanamines can also be preferably used in place of the acrylic monomers.

  There are no particular limitations on the photopolymerization initiator, and known ones can be used, such as benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2 , 2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, , 4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer Etc. In addition, other acetophenone compounds, imidazole compounds, hexaarylbiimidazole compounds, benzophenone compounds, thioxanthone compounds, phosphorus compounds, triazine compounds, halogenated hydrocarbon derivatives, organoboronate compounds, titanates, etc. Inorganic photopolymerization initiators can also be preferably used. Further, it is preferable to add a sensitizing aid such as p-dimethylaminobenzoic acid ester because the sensitivity can be further improved. Moreover, these photoinitiators can also be used in combination of 2 or more types.

  As content of a photoinitiator, the range of 1-25 mass% is suitable with respect to all the components of a black resist layer.

  The black resist layer can further contain a sensitizing dye that absorbs the oscillation wavelength of a laser light source used for exposure. For example, when using a blue-violet semiconductor laser, a dialkylaminobenzene compound, a triarylamine compound, an acridone compound, an imidazole / oxazole / thiazole compound, or the like can be used as a sensitizing dye.

  The content of the resin component constituting the black resist layer according to the present invention is preferably in the range of 20 to 90% by mass and more preferably in the range of 30 to 80% by mass with respect to all the components of the black resist layer. If the content of the resin component is too small, the black resist layer tends to be hardened and the adhesion to the metal thin film tends to decrease. If the amount of the resin component is too large, the optical density (OD value) of the black resist layer is increased. ) And the metallic gloss of the conductive mesh cannot be sufficiently suppressed.

  Moreover, the removal of the black resist layer by laser irradiation mentioned later can be made easy by containing 20 mass% or more of resin components with respect to all the components of a black resist layer.

  The black resist layer described above is an example using a so-called photopolymerizable negative photosensitive resin containing a photopolymerization initiator as a resin component. However, as other photosensitive resin, a chemically amplified negative photosensitive resin is used. Resin and chemically amplified positive photosensitive resin can be used.

  As said chemically amplified negative photosensitive resin, the composition containing alkali-soluble resin, the crosslinking agent which acts on alkali-soluble resin on acidic conditions, and an acid generator can be mentioned.

  The alkali-soluble resin is not particularly limited as long as the unexposed portion becomes alkali-soluble during development and can be eluted into an alkali developer, but is usually novolak resin, resol resin, polyvinylphenols, polyacrylic acid, Polyvinyl alcohol, styrene-maleic anhydride resin, polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, or derivatives thereof are used.

  The crosslinking agent that acts on the alkali-soluble resin under the acidic conditions is not particularly limited as long as it is a compound that undergoes a crosslinking reaction with the alkali-soluble resin under acidic conditions. For example, melamine, benzoguanamine, glycoluril, or urea is formalin. Or an alkyl-modified compound thereof, an epoxy compound, a resole compound, or the like.

  The acid generator is a compound that generates an acid when the photosensitive resin composition is irradiated with a laser, for example, halogen-containing compounds such as halogen-substituted alkanes and halomethylated s-triazine derivatives, Examples include onium salts and sulfone compounds.

  Examples of the chemically amplified positive photosensitive resin include a composition containing an acid-decomposable group-containing polymer and an acid generator.

  The acid-decomposable group-containing polymer is decomposed by an acid generated by an acid generator as an active compound when the photosensitive resin composition is subjected to laser irradiation, and imparts alkali solubility to the polymer itself. It is not particularly limited as long as it is a polymer containing such an acid-decomposable group. Specific examples of the acid-decomposable group include alkoxy groups having 1 to 15 carbon atoms such as methoxy group, i-propoxy group, and t-butoxy group, methoxymethoxy group, 1-methoxyethoxy group, and 1-ethoxyethoxy group. Alkoxy groups having 2 to 15 carbon atoms such as 1-cyclohexyloxyethoxy group, 2-15 alkoxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, i-propoxycarbonyloxy group and t-butoxycarbonyloxy group Examples thereof include an alkoxycarbonyloxyalkoxy group having 2 to 15 carbon atoms such as a carbonyloxy group, an ethoxycarbonyloxymethoxy group, an i-propoxycarbonyloxymethoxy group, and a t-butoxycarbonyloxymethoxy group.

  Examples of the polymer containing an acid-decomposable group include the above-mentioned acid decomposition by etherification or esterification of at least a part of a phenolic hydroxyl group of a phenolic hydroxyl group-containing resin such as a novolak resin, a resole resin, and a polyvinylphenol resin. Examples thereof include resins having a sex group introduced therein.

As the acid generator, the same acid generator as that constituting the chemically amplified negative photosensitive resin is used.
(Laser exposure process)
The photosensitive black resist layer laminated on the metal thin film is exposed to a mesh pattern with a laser. The laser light source used in the exposure process is as described above.

  In such a laser exposure process, as one method for obtaining a continuous mesh, a substrate on which a metal thin film and a photosensitive black resist layer are laminated is continuously conveyed on a curved exposure stage. A method of scanning exposure with a laser beam can be used.

As the laser beam scanning exposure apparatus, a capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 can be used. Further, in the capstan system, instead of beam scanning by rotation of a polygon mirror. In addition, a digital micromirror device (DMD) described in Japanese Patent Application Laid-Open No. 2004-1244 can be used for a light beam scanning system.
(Development process of photosensitive black resist layer)
The black resist layer is developed after laser exposure to become an etching resist pattern having a mesh pattern.
As the developer used in the developing step, an alkali developer is preferable. Examples of the alkali developer include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. Specifically, sodium carbonate, potassium carbonate, lithium carbonate An alkaline aqueous solution containing 0.5 to 5% by mass of a hydroxide such as carbonate such as sodium hydroxide, potassium hydroxide, or lithium hydroxide can be used. The development temperature is suitably about 10 to 50 ° C, and preferably 20 to 40 ° C.

(Metal thin film etching process)
As described above, after an etching resist pattern made of a black resist layer is formed on the metal thin film, the portion of the metal thin film not covered with the black resist layer is etched (the metal foil is dissolved and removed).
As an etching method used in the etching process, a chemical etching method can be given. Examples of the etching solution used in the etching method include ferric chloride aqueous solution, cupric chloride aqueous solution, and alkaline etching solution.
(Conductive mesh)
Through the above-described metal thin film forming process, photosensitive black resist layer laminating process, laser exposure process, development process, and etching process, a conductive mesh made of a metal thin film is formed on the substrate, and at the same time on the conductive mesh. A mesh pattern is formed in which a black resist that is in register with the conductive mesh is disposed.

  A method for producing a conductive mesh using a photolithographic method, which is generally used in the past, that is, a method of laminating a resist layer on a metal thin film and exposing through a photomask is the size of the photomask. Since this is a so-called single-wafer exposure method in which the exposure in the above range is repeated, it was possible to produce only those in which the mesh was interrupted in units of photomasks, and it was not possible to produce the continuous mesh aimed by the present invention.

  In contrast, the exposure method using the laser of the present invention can continuously expose in the longitudinal direction of the base material on which the metal thin film and the photosensitive black resist layer are laminated. It has become possible.

  The technical significance of forming a continuous mesh is 1) Even if a serious defect occurs in the conductive mesh, only the defective portion can be removed, so that the yield is greatly improved. 2) For displays of various sizes 3) When the functional layer is directly formed on the conductive mesh, the mesh pattern is continuous without interruption in the longitudinal direction of the base material (functional layer coating direction). Therefore, it is advantageous for continuous coating of the functional layer. (The conductive mesh produced using a photomask is usually a metal solid on the four sides around the conductive mesh in order to secure the ground. And the mesh pattern portion and the solid metal portion are mixed, which is disadvantageous for continuous coating of the functional layer).

  In the present invention, by using the black resist layer, the conductive mesh blackening process and the resist layer peeling process before the blackening process can be omitted, and the productivity is greatly improved. Also, when the conductive mesh is blackened, the blackened portion becomes less conductive, so the thickness of the conductive mesh needs to be set larger considering the thickness of the blackened layer, This results in a disadvantage that the raw material cost and the time required for forming the metal thin film increase.

  In addition, since the blackened layer formed by blackening the conductive mesh has the characteristics of being brittle and easy to drop off, a functional layer is applied and formed on the conductive mesh in a later step. In some cases, the conductive mesh comes into contact with the transport roll or the like of the production line, and a part of the blackening treatment layer is peeled off, resulting in the problem of contaminating the production line such as the transport roll. By using it, the above problem can be avoided.

  The conductive mesh according to the present invention is for shielding electromagnetic waves generated from a display. The surface resistance value of the conductive mesh is preferably lower, preferably 3Ω / □ or less, more preferably 1Ω / □ or less, and particularly preferably 0.5Ω / □ or less. The lower limit of the surface resistance is about 0.01Ω / □. The surface resistance value can be measured by a four-terminal method.

  The thickness of the conductive mesh is from the viewpoint of uniformly coating and forming a functional layer, which will be described later, and from the viewpoint of reducing the influence of the metallic luster from the side surface of the conductive mesh (the side surface of the fine wire constituting the conductive mesh). 5 μm or less is preferable, 4 μm or less is more preferable, and 3.5 μm or less is particularly preferable. The lower limit of the thickness of the conductive mesh is preferably 0.3 μm or more, more preferably 1 μm or more, and particularly preferably 1.5 μm or more from the viewpoint of ensuring good electromagnetic wave shielding performance.

  In the present invention, the blackening treatment of the conductive mesh can be omitted by using the black resist layer as described above. However, the black resist layer may be provided on the blackened conductive mesh. it can. Of course, in the present invention, it is most preferable that the blackening treatment is not performed at all. However, as described below, the blackening treatment and the black resist layer can be used in combination.

  When using a blackened conductive mesh, it is necessary to blacken the metal thin film before processing the metal thin film formed on the substrate into a mesh pattern. Here, the blackening treatment applied to the metal thin film can loosen the blackening treatment conditions as compared with the conventional blackening treatment sufficient to suppress the metallic luster. That is, since the total of the blackening treatment layer and the black resist layer suppresses the metallic gloss of the conductive mesh, the blackening concentration of the blackening treatment layer may be lower than that of the conventional one. The treatment conditions can be relaxed. As a result, the cost for the blackening process can be reduced. Further, by using the blackening treatment layer and the black resist layer in combination, the optical density of the black resist layer can be lowered as compared with the case where the blackening treatment layer is not provided. Further, by providing a black resist layer on the blackening treatment layer, it is possible to prevent the blackening treatment layer from falling off.

  The metallic luster of the conductive mesh may be influenced not only by the surface of the fine wire portion constituting the conductive mesh but also by the side surface of the fine wire portion, but the conductive mesh of the present invention using a black resist layer is a mesh. The metallic luster on the side surface of the thin wire cannot be suppressed. However, according to the present invention, as described above, by reducing the thickness of the conductive mesh, the influence of the metallic luster on the side surface of the thin wire portion of the conductive mesh can be reduced.

  As the shape of the mesh pattern of the conductive mesh, for example, a lattice mesh pattern composed of squares, rectangles, rhombuses, etc., a mesh pattern composed of triangles, pentagons or more polygons, a mesh pattern composed of circles, ellipses, The mesh pattern which consists of composite shapes, and a random mesh pattern are mentioned.

  The line width (W) and line pitch (P) of the conductive mesh effectively suppresses moire generated when a display filter is mounted on a display panel, and also suppresses a decrease in transmittance. The line width (W) is preferably less than 10 μm, more preferably 8 μm or less, and particularly preferably 7 μm or less. The lower limit of the line width is preferably 3 μm or more from the viewpoint of avoiding disconnection in the production process and securing a low surface resistance value.

The line pitch (P) is preferably 160 μm or less, more preferably 150 μm or less, and particularly preferably 130 μm or less from the viewpoint of suppressing moire. The lower limit of the line pitch is preferably 50 μm or more, and more preferably 70 μm or more, from the viewpoint of ensuring high transmittance.
(Functional surface layer coating process)
After a conductive mesh and a black resist layer that is in register with the conductive mesh are formed on the substrate, it is preferable to coat and form a functional surface layer so as to cover the black resist layer.

  The functional surface layer (hereinafter simply referred to as a functional layer) is a layer that becomes the outermost surface on the viewing side (viewer side) when the display filter of the present invention is mounted on the front surface of the display. The functional layer preferably has a protective function and / or an optical function, and examples of the function include an antireflection function, an antiglare function, a hard coat function, and an antifouling function. The functional layer is laminated so as to cover a black resist layer provided on the conductive mesh. The functional layer is preferably formed directly on the black resist layer.

  The functional layer according to the present invention is preferably a functional layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, and an antifouling function, and more preferably an antireflection function. A functional layer having at least one function selected from an antiglare function and a hard coat function. In particular, a functional layer having at least a hard coat function is preferable.

  The functional layer may be a single layer or a plurality of layers, or may be a layer having a plurality of functions. The layer which has a reflection prevention function, a glare-proof function, a hard-coat function, and an antifouling function which comprises a functional layer below is demonstrated concretely.

(Antireflection layer)
The layer having an antireflection function (antireflection layer) prevents reflection or reflection of external light such as a fluorescent lamp that affects the image display of the display. The antireflection layer preferably has a surface luminous reflectance of 5% or less, more preferably 4% or less, and particularly preferably 3% or less. Here, the luminous reflectance is a luminous reflectance (Y) calculated according to the CIE1931 system by measuring the reflectance in the visible region wavelength (380 to 780 nm) using a spectrophotometer or the like.

  As such an antireflection layer, a layer in which two or more layers of a high refractive index layer and a low refractive index layer are laminated so that the low refractive index layer is on the viewing side can be used. The refractive index of the high refractive index layer is preferably in the range of 1.5 to 1.7, particularly preferably in the range of 1.55 to 1.69. The refractive index of the low refractive index layer is preferably in the range of 1.25 to 1.49, particularly preferably in the range of 1.3 to 1.45.

Materials for forming the high refractive index layer include those obtained by polymerizing and curing urethane (meth) acrylate, polyester (meth) acrylate, etc., or those obtained by crosslinking and curing a silicone-based, melamine-based, or epoxy-based crosslinkable resin material. And organic materials such as those containing indium oxide as a main component and containing a small amount of titanium dioxide or the like, or inorganic materials such as Al ₂ O ₃ , MgO, and TiO ₂ . Among these, organic materials are preferably used. Hereinafter, preferred embodiments of the high refractive index layer of the present invention will be described.

  In the present invention, the high refractive index layer is a single or mixed resin component such as acrylic resin, urethane resin, melamine resin, organic silicate compound, silicone resin, phosphorus-containing resin, sulfide-containing resin, halogen-containing resin. Although it can be used in a system, it is particularly preferable to use a silicone resin or an acrylic resin from the viewpoint of hardness and durability. Furthermore, from the viewpoint of curability, flexibility, and productivity, an active energy ray-curable acrylic resin or a thermosetting acrylic resin is preferable. In particular, a (meth) acrylate-based resin is preferable because radical polymerization easily occurs upon irradiation with active energy rays and the solvent resistance and hardness of the formed film are improved.

  Examples of such (meth) acrylate resins include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ethylene-modified trimethylolpropane tri (meth) acrylate, and tris- (2- Trifunctional (meth) acrylate such as hydroxyethyl) -isocyanuric acid ester tri (meth) acrylate, tetrafunctional such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate The above (meth) acrylate etc. are mentioned.

  In the high refractive index layer, a (meth) acrylate compound (monomer) having an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group can be used. Specifically, as the acidic functional group-containing monomer, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, Examples thereof include phosphoric acid (meth) acrylic acid esters such as mono (2- (meth) acryloyloxyethyl) acid phosphate and diphenyl-2- (meth) acryloyloxyethyl phosphate, and 2-sulfoester (meth) acrylate. In addition, a (meth) acrylate compound having a polar bond such as an amide bond, a urethane bond, or an ether bond can be used.

  The high refractive index layer may contain an initiator in order to advance curing of the applied resin component. As the initiator, the applied resin component initiates or accelerates polymerization and / or crosslinking reaction by radical reaction, anion reaction, cation reaction, etc., and various conventionally known photopolymerization initiators can be used. is there.

  Specific examples of such photopolymerization initiators include sulfides such as sodium methyldithiocarbamate sulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide, thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, Thioxanthone derivatives such as 2,4-diethylthioxanthone, azo compounds such as hydrazone and azobisisobutyronitrile, diazo compounds such as benzenediazonium salt, benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, dimethylaminobenzophenone Michler's ketone, benzylanthraquinone, t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, Aromatic carbonyl compounds such as -chloroanthraquinone, dialkylaminobenzoic acid esters such as methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, butyl D-dimethylaminobenzoate, isopropyl p-diethylaminobenzoate, Peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, 9-phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine, benzacridine, etc. Acridine derivatives, phenazine derivatives such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine, 10-methoxybenzphenazine, and 6,4 ′, 4 ″ -trimethoxy-2,3-diphenylquinoxaline Quinoxaline derivatives, 2,4,5-triphenylimidazolyl dimer, 2-nitrofluorene, 2,4,6-triphenylpyrylium tetrafluoride boron salt, 2,4,6-tris (trichloromethyl) ) -1,3,5-triazine, 3,3′-carbonylbiscoumarin, thiomichler ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- ( 4- (1-methylvinyl) phenyl) propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, and the like.

In the high refractive index layer, an amine compound may coexist in the photopolymerization initiator in order to prevent a decrease in sensitivity due to oxygen inhibition of the initiator. Such an amine compound is not particularly limited as long as it is a non-volatile compound such as an aliphatic amine compound or an aromatic amine compound. For example, triethanolamine, methyldiethanolamine and the like are preferable.
The high refractive index layer is preferably made of a resin or metal oxide fine particles containing molecules and atoms of a high refractive index component in order to increase the refractive index.

  Examples of the molecules and atoms contained in the resin that improves the refractive index include halogen atoms other than F, S, N, and P atoms, aromatic rings, and the like.

  The metal oxide fine particles preferably have a refractive index of about 1.6 to 2.7, for example, tin-containing antimony oxide particles (ATO), zinc-containing antimony oxide particles, tin-containing indium oxide particles (ITO). Zinc oxide / aluminum oxide particles, antimony oxide particles, and the like. Among these, tin-containing indium oxide particles (ITO) and tin-containing antimony oxide particles (ATO) are preferably used.

Such metal oxide particles have an average particle size (JIS Z8819-1: 1999 and Z8819) calculated from a sphere equivalent diameter distribution based on a non-surface area (JIS R1626: 1996) measured by a BET method. -2: 2001) is preferably 0.5 μm or less, more preferably 0.001-0.3 μm, and still more preferably 0.005-0.2 μm. If the average particle diameter exceeds 0.5 μm, the transparency of the high refractive index layer may be reduced, and if it is less than 0.001 μm, the particles are likely to aggregate and the haze value may increase. The content of the metal oxide particles in the refractive index layer is preferably in the range of 0.1 to 20% by mass with respect to 100% by mass of the resin component.
Furthermore, the high refractive index layer can contain various additives such as a polymerization inhibitor, a curing catalyst, an antioxidant, and a dispersant.

  The thickness of the high refractive index layer is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.05 to 0.5 μm.

The low refractive index layer constituting the antireflection layer is composed of a fluorine-containing polymer, a (meth) acrylic acid partial or fully fluorinated alkyl ester, an organic material such as fluorine-containing silicone, and an inorganic material such as MgF ₂ , CaF ₂ , and SiO _2. It can be composed of a system material. Hereinafter, preferred embodiments of the low refractive index layer will be exemplified.

As a preferred embodiment of the low refractive index layer, a method of forming a thin film such as MgF ₂ or SiO ₂ by a vapor deposition method such as vacuum deposition, sputtering, or plasma CVD, or a sol solution containing SiO ₂ sol from SiO ₂ Examples thereof include a method for forming a gel film.

  As another preferred embodiment of the low refractive index layer, a constitution mainly composed of a siloxane polymer bonded to silica-based fine particles can be employed. The term “bond” as used herein means a state in which the silica component of the silica-based fine particles and the siloxane polymer in the matrix are reacted and homogenized. A siloxane polymer formed by combining with silica-based fine particles once forms a silanol compound by a known hydrolysis reaction with a polyfunctional silane compound in a solvent and an acid catalyst in the presence of the silica-based fine particles. It can be obtained by utilizing the reaction.

  The polyfunctional silane compound preferably includes a polyfunctional fluorine-containing silane compound from the viewpoint of low refractive index and antifouling properties, and includes trifluoromethylmethoxysilane, trifluoromethylethoxysilane, and trifluoropropyltrimethoxy. Trifunctional fluorine-containing silane compounds such as silane, trifluoropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane, Examples include bifunctional fluorine-containing silane compounds such as heptadecafluorodecylmethyldimethoxysilane, all of which are preferably used. From the viewpoint of surface hardness, trifluoromethylmethoxysilane, trifluoro Chill silane, trifluoropropyl trimethoxy silane, trifluoropropyl triethoxy silane, more preferably.

  A polyfunctional fluorine-free silane compound can be used as the polyfunctional silane compound. Examples of such polyfunctional fluorine-free silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methyltrimethoxysilane, and methyltriethoxy. Silane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Trifunctional silanes such as silane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxysipropyltrimethoxysilane Compound, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-amino Propylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, 3-methacryloxypropyldimethoxy Bifunctional silane compounds such as silane and octadecylmethyldimethoxysilane, tetrafunctional silane compounds such as tetramethoxysilane and tetraethoxysilane, etc. All of these are preferably used. From the viewpoint of surface hardness, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable. More preferable.

  The silica-based fine particles are preferably silica-based fine particles having an average particle size of 1 nm to 200 nm, and particularly preferably an average particle size of 1 nm to 70 nm. When the average particle diameter is less than 1 nm, the bond with the matrix material becomes insufficient and the hardness may be lowered. On the other hand, if the average particle diameter exceeds 200 nm, the generation of voids between particles caused by introducing a large amount of particles is reduced, and the effect of lowering the refractive index may not be sufficiently exhibited. Further, among these silica-based fine particles, those having a structure having a cavity inside are particularly preferably used in order to lower the refractive index.

  Examples of such silica-based fine particles having cavities therein include silica-based fine particles having a hollow portion surrounded by an outer shell, porous silica-based fine particles having a large number of hollow portions, and the like. As such an example, for example, it can be produced by the method disclosed in Japanese Patent No. 3272111, and the volume occupied by the cavities inside the fine particles, that is, the porosity of the fine particles is preferably 5% or more, more preferably 30% or more. preferable. The porosity can be measured using, for example, a mercury porosimeter (trade name: Bore Sizer 9320-PC2, manufactured by Shimadzu Corporation). Further, the refractive index of the fine particles themselves is preferably 1.20 to 1.40, more preferably 1.20 to 1.35. Examples of such silica-based fine particles include those disclosed in Japanese Patent Application Laid-Open No. 2001-233611, and those commercially available such as Japanese Patent No. 3272111.

  The thickness of the low refractive index layer is preferably in the range of 0.01 to 0.4 μm, and more preferably in the range of 0.02 to 0.2 μm.

(Anti-glare layer)
The layer having an antiglare function (antiglare layer) prevents glare in the image, and a film having minute irregularities on the surface is preferably used. As the antiglare layer, for example, a thermosetting resin or a photocurable resin coated with a coating liquid in which particles are dispersed and applied, or a thermosetting resin or a photocurable resin is applied, For example, a mold having a desired surface state is pressed to form an unevenness and then cured. The antiglare layer preferably has a haze value (JIS K 7136; 2000) of 0.5 to 20%.

  In the present invention, since the functional layer is applied on the mesh pattern of the conductive mesh, the surface of the applied functional layer is provided with irregularities by utilizing the irregularities of the mesh pattern, thereby providing an anti-glare function. Can be expressed.

  In order to effectively exhibit the antiglare function, the center line average roughness Ra value on the surface of the antiglare layer is preferably in the range of 100 to 500 nm. Here, the centerline average roughness Ra value can be measured using a surface roughness measuring instrument SE-3400 (manufactured by Kosaka Laboratory) based on the provisions of JIS B0601-1982.

  As thickness of a glare-proof layer, the range of 0.5-10 micrometers is suitable, and the range of 1-8 micrometers is more preferable.

  It is one of preferred embodiments to use a layer having both an antireflection function and an antiglare function as the functional layer of the present invention.

(Hard coat layer)
A layer having a hard coat function (hard coat layer) is provided for preventing scratches. The hard coat layer preferably has high hardness, and the pencil hardness defined by JIS K5600-5-4 (1999) is preferably 1H or more, and more preferably 2H or more. The upper limit is about 9H.

  The hard coat layer can be composed of an acrylic resin, urethane resin, melamine resin, epoxy resin, organic silicate compound, silicone resin, or the like. In particular, silicone resins and acrylic resins are preferable in terms of hardness and durability. Further, in terms of curability, flexibility, and productivity, those made of an active energy ray-curable acrylic resin or a thermosetting acrylic resin are preferable.

  The active energy ray-curable acrylic resin or thermosetting acrylic resin is a composition containing a polyfunctional acrylate, an acrylic oligomer, or a reactive diluent as a polymerization curing component. In addition, you may use what contains a photoinitiator, a photosensitizer, a thermal-polymerization initiator, a modifier, etc. as needed.

  Acrylic oligomers include polyester acrylates, urethane acrylates, epoxy acrylates, polyether acrylates, etc., including those in which a reactive acrylic group is bonded to an acrylic resin skeleton, and rigid materials such as melamine and isocyanuric acid. A material in which an acrylic group is bonded to a simple skeleton can also be used.

  In addition, the reactive diluent serves as a solvent for the coating process as a coating medium, and has a group that itself reacts with a monofunctional or polyfunctional acrylic oligomer. It becomes a polymerization component.

  Also, commercially available polyfunctional acrylic cured paints include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam (registered trademark)” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol (registered trademark)”). Series, etc.), Shin-Nakamura Co., Ltd. (trade name “NK Ester” series, etc.), Dainippon Ink and Chemicals Co., Ltd. (trade name “UNIDIC (registered trademark)” series, etc.) (Product name "Aronix (registered trademark)" series, etc.), Nippon Oil & Fats Co., Ltd. (product name "Blenmer (registered trademark)" series, etc.), Nippon Kayaku Co., Ltd .; (product name "KAYARAD (registered trademark)" series, etc.) ), Kyoeisha Chemical Co., Ltd .; (Product name “Light Ester” series, “Light Acrylate” series, etc.) Can.

  When the typical thing of the acrylic compound which comprises a hard-coat layer formation composition is illustrated, it has 3 or more, More preferably 4 or more, More preferably 5 or more (meth) acryloyloxy group in 1 molecule An active energy ray comprising, as a main component, a mixture comprising at least one of a monomer and a prepolymer and at least one monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule A hard coat layer obtained by curing or thermosetting is preferably used in that it is excellent in hardness, wear resistance and flexibility. If there are too many (meth) acryloyloxy groups, the monomer will be highly viscous and difficult to handle, and will have to be of high molecular weight, making it difficult to use as a coating solution. The number of (meth) acryloyloxy groups is preferably 10 or less.

  As the monomer and prepolymer having 3 or more (meth) acryloyloxy groups in one molecule, the hydroxyl group of the polyhydric alcohol having 3 or more alcoholic hydroxyl groups in one molecule is 3 or more. Examples include compounds that are esterified products of (meth) acrylic acid. Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, etc. Can be used. These monomers and prepolymers can be used alone or in combination of two or more. Of these, polyfunctional acrylate compounds having at least one hydroxyl group are particularly preferred because they can improve the adhesion between the hard coat layer and the adjacent layer when used in combination with the isocyanate described below.

  The use ratio of the monomer and prepolymer having 3 or more (meth) acryloyloxy groups in one molecule is preferably 20 to 90% by mass, more preferably based on the total amount of the hard coat layer forming composition. It is 30-80 mass%, Most preferably, it is 30-70 mass%.

  When the use ratio of the monomer and prepolymer having 3 or more (meth) acryloyloxy groups in one molecule is less than 20% by mass relative to the total amount of the hard coat layer forming composition, sufficient resistance In some cases, it is insufficient in terms of obtaining a hardened film having wear properties. Moreover, when the usage rate of the monomer and prepolymer having 3 or more (meth) acryloyloxy groups in one molecule exceeds 90% by mass with respect to the total amount of the hard coat layer forming composition, In some cases, the shrinkage is large, and the cured film remains distorted, the flexibility of the film is lowered, or the curled side is greatly curled.

  Of these, the proportion of the polyfunctional acrylate compound having at least one hydroxyl group is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and most preferably the total amount of the hard coat layer forming composition. Is 30 to 60% by mass. When the proportion of the polyfunctional acrylate compound having at least one hydroxyl group is less than 10% by mass with respect to the total amount of the hard coat layer forming composition, the effect of improving the adhesion between the hard coat layer and its adjacent layer is obtained. It may be small. When the use ratio of the polyfunctional acrylate compound having at least one hydroxyl group exceeds 80% by mass with respect to the total amount of the hard coat layer forming composition, the crosslink density in the hard coat layer is lowered, and the hardness of the hard coat layer Tends to decrease.

  Next, the monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule can be used without particular limitation as long as it is a normal monomer having radical polymerizability.

  Moreover, as a compound which has two ethylenically unsaturated double bonds in a molecule | numerator, the following (a)-(f) (meth) acrylate etc. can be used.

(A) (meth) acrylic acid diesters of alkylene glycol having 2 to 12 carbon atoms: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc .;
(B) (Meth) acrylate diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc .;
(C) Polyhydric alcohol (meth) acrylic acid diesters: pentaerythritol di (meth) acrylate, etc .;
(D) (Meth) acrylic diesters of ethylene oxide and propylene oxide adducts of bisphenol A or bisphenol A hydride: 2,2′-bis (4-acryloxyethoxyphenyl) propane, 2,2′-bis ( 4-acryloxypropoxyphenyl) propane and the like;
(E) A terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound with two or more alcoholic hydroxyl group-containing compounds in advance, and further reacting an alcoholic hydroxyl group-containing (meth) acrylate with two molecules in the molecule. Urethane (meth) acrylates having a (meth) acryloyloxy group, and the like;
(F) Epoxy (meth) acrylates having two (meth) acryloyloxy groups in the molecule obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid.

  Compounds having one ethylenically unsaturated double bond in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n- and i-propyl (meth) acrylate, n-, sec-, and t. -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-hydroxyethyl (meth) acrylamide, N-vinylpyrrolidone N- vinyl-3-methylpyrrolidone, or the like can be used N- vinyl-5-methyl pyrrolidone. These monomers may be used alone or in combination of two or more.

  The use ratio of the monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule is preferably 10 to 50% by mass, more preferably 20%, based on the total amount of the hard coat layer forming composition. -40 mass%. When the proportion of the monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule exceeds 50% by mass with respect to the total amount of the hard coat layer forming composition, sufficient wear resistance is obtained. It may be difficult to obtain a cured film having a slag. In addition, when the use ratio of the monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule is less than 10% by mass with respect to the total amount of the hard coat layer forming composition, the film can be used. The flexibility may decrease or the adhesiveness with the laminated film provided on the base film may decrease.

  In the present invention, as a method of curing the hard coat forming composition, for example, a method of irradiating ultraviolet rays as active energy rays, a high temperature heating method, or the like can be used. When using these methods, it is desirable to add a photopolymerization initiator or a thermal polymerization initiator to the hard coat layer forming composition.

  Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoylformate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethyl Sulfur compounds such as thiuram disulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone can be used. These photopolymerization initiators may be used alone or in combination of two or more. Moreover, as a thermal polymerization initiator, a peroxide compound such as benzoyl peroxide or di-t-butyl peroxide can be used.

  The amount of the photopolymerization initiator or thermal polymerization initiator used is suitably 0.01 to 10% by mass with respect to the total amount of the hard coat layer forming composition. When an electron beam or gamma ray is used as a curing means, it is not always necessary to add a polymerization initiator. In addition, when thermosetting at a high temperature of 220 ° C. or higher, it is not always necessary to add a thermal polymerization initiator.

  The hard coat layer forming composition in the present invention preferably contains a polyisocyanate compound. Examples of the polyisocyanate compound include 2,4- and / or 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), polymeric MDI, 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1, 6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, hydrogenated MDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, etc. The thing more than a dimer is mentioned at least. These polyisocyanate compounds can be used alone or in admixture of two or more.

  These polyisocyanate compounds and / or derivatives thereof are mixed and applied to the hard coat layer forming composition described above. The blending amount of the polyisocyanate compound and / or derivative thereof is preferably 0.5 to 50% by mass with respect to the total amount of the hard coat layer-forming composition in terms of adhesion, surface hardness, heat and humidity resistance and reduction of iris pattern. More preferably, it is 1-30 mass%, More preferably, it is 3-20 mass%. When the blending amount of the polyisocyanate compound and / or derivative thereof is less than 0.5% by mass with respect to the total amount of the hard coat layer forming composition, the effect of improving the adhesiveness is insufficient or the reduction of the iris pattern is not possible. In some cases, if the amount of the polyisocyanate compound and / or derivative thereof exceeds 50% by mass with respect to the total amount of the hard coat layer-forming composition, the surface hardness may decrease.

  The hard coat layer-forming composition to which the polyisocyanate is added preferably contains an organometallic catalyst for the purpose of increasing its curing efficiency.

  The organometallic catalyst is not particularly limited, and includes an organic tin compound, an organoaluminum compound, an organic group 4A element (titanium, zirconium, or hafnium) compound. A metal catalyst selected from organic zirconium compounds, organic aluminum compounds, and organic titanium compounds is preferably applied. Examples of the organic tin compound include dibutyltin fatty acid salts such as tetrabutyltin, tetraoctyltin, dibutyltin dichloride, and dibutyltin dilaurate, and dioctyltin fatty acid salts such as dioctyltin dilaurate.

  Examples of organozirconium compounds, organoaluminum compounds, organohafnium compounds, and organotitanium compounds include reaction products of these metal orthoesters and β-ketoesters (β diketones), specifically zirconium tetra-n-propoxy. Zirconium tetraisopropoxide, zirconium tetra-n-butoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, aluminum tetra-n-propoxide, aluminum tetraisopropoxide, Metal orthoesters such as aluminum tetra-n-butoxide and acetylacetone, methyl acetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, t-butyl acetoacetate Mention may be made of reaction products with β-ketoesters (β-diketone) such as tate. The mixing molar ratio of the metal orthoester and β-diketoester (β-diketone) is preferably about 4: 1 to 1: 4, more preferably 2: 1 to 1: 4. When there are more metal orthoesters than 4: 1, the reactivity of a catalyst is too high and a pot life tends to become short, and when there are many beta-diketoesters more than 1: 4, since catalyst activity falls, it is not a preferable aspect. The compounding amount of the organometallic catalyst is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 2% by mass with respect to the total amount of the hard coat forming composition. It is. When the compounding amount of the organometallic catalyst is less than 0.001% by mass with respect to the total amount of the hard coat forming composition, the effect of adding the catalyst is low, and it is not preferable from an economic standpoint to make it more than 10% by mass.

  As a preferable aspect of the above-mentioned hard coat layer forming composition, the polyfunctional acrylate compound having at least one hydroxyl group is 10 to 80% by mass, the isocyanate compound is 1 to 30% by mass and necessary with respect to the total amount of the hard coat layer forming composition. It is desirable that the content be in the range of 0.001 to 10% by mass according to the organometallic catalyst. Furthermore, you may add the monomer which has 1-2 ethylenically unsaturated bonds as needed from 0 mass% or more and 50 mass% or less.

  In the present invention, various additives can be further blended in the hard coat layer as required, as long as the effects of the present invention are not impaired. For example, stabilizers such as antioxidants, light stabilizers, ultraviolet absorbers, surfactants, leveling agents, antistatic agents, and the like can be used.

As the silicone-based leveling agent, those having polydimethylsiloxane as a basic skeleton and having a polyoxyalkylene group added are preferable, and dimethylpolysiloxane-polyoxyalkylene copolymer (for example, SH190 manufactured by Toray Dow Corning Co., Ltd.) is preferable. It is.
Moreover, when providing a laminated film further on a hard-coat layer, it is preferable to apply the acrylic leveling agent which does not inhibit adhesiveness. As such a leveling agent, “ARUFON-UP1000 series, UH2000 series, UC3000 series (trade name): manufactured by Toa Gosei Chemical Co., Ltd.) and the like can be preferably used. The amount of the leveling agent added is a hard coat forming composition. It is desirable to set it as the range of 0.01-5 mass% with respect to the total amount.

  Examples of active energy rays used in the present invention include electromagnetic waves that polymerize acrylic vinyl groups such as ultraviolet rays, electron beams, and radiation (α rays, β rays, γ rays, etc.). It is preferable. As the ultraviolet ray source, an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like can be used. Moreover, when irradiating actinic radiation, if it irradiates under a low oxygen concentration, it can harden | cure efficiently. Furthermore, the electron beam method is advantageous in that the apparatus is expensive and requires operation under an inert gas, but it is not necessary to include a photopolymerization initiator or a photosensitizer in the coating layer. is there.

  As the heat necessary for the thermosetting used in the present invention, steam heater, electric heater, infrared heater or far-infrared heater is used. The heat given by spraying on the base material and the coating film using is used. Among them, the heat by air heated to 200 degrees or higher is preferable, and the heat by nitrogen heated to 200 degrees or higher is more preferable. It is preferable because the curing rate is high.

  The thickness of the hard coat layer is preferably 0.5 to 10 μm, more preferably 1 to 8 μm. When the thickness of the hard coat layer is less than 0.5 μm, even if it is sufficiently cured, it is too thin, so that the surface hardness is not sufficient and it tends to be easily scratched. On the other hand, when the thickness of the hard coat layer exceeds 10 μm, curling tends to occur due to polymerization shrinkage during curing.

  The hard coat layer can be given a function as a high refractive index layer constituting the antireflection layer described above. The high refractive index of the hard coat layer is obtained by replacing the resin or metal oxide fine particles containing molecules and atoms of the high refractive index component used in the above-described high refractive index layer in the resin composition for forming the hard coat layer. This is achieved by adding.

(Anti-fouling layer)
The antifouling layer (antifouling layer) prevents oily substances from adhering to the display filter when touched by a finger, and prevents dust and dirt in the atmosphere from adhering. Or a layer for facilitating the removal of these deposits. As such an antifouling layer, for example, a fluorine coating agent, a silicone coating agent, a silicon / fluorine coating agent, or the like is used. The thickness of the antifouling layer is preferably in the range of 1 to 10 nm.

(Example of functional layer configuration)
As described above, the functional layer of the present invention may be a single layer or a plurality of layers. The functional layer having a plurality of structures includes a) hard coat layer / high refractive index layer / low refractive index layer, b) high refractive index hard coat layer / low refractive index layer, c) hard coat layer / antiglare layer, d) Examples include a hard coat layer / antiglare antireflection layer and the like. In addition, in the structure of said a) -d), the layer as described on the right side is arrange | positioned at the visual recognition side. When providing an antifouling layer, it is preferable to provide it on the outermost surface on the viewing side.

  When the functional layer is a single layer, it is preferable to have a plurality of functions. Examples of such a single layer are e) antireflection hard coat layer (single layer having antireflection function and hard coat function), f) antiglare hard coat layer (single layer having antiglare function and hard coat function) G) Antiglare antireflection hard coat layer (single layer having antiglare function, antireflection function and hard coat function) h) Antiglare antireflection layer (single layer having antiglare function and antireflection function) I) An antifouling hard coat layer (a single layer having an antifouling function and a hard coat function) and the like are exemplified.

(Functional layer coating formation)
In the present invention, the functional layer is preferably formed by direct coating so as to cover the black resist layer formed on the conductive mesh. In this case, the functional layer has a certain thickness in order to fill the black resist layer by filling the fine line portion constituting the mesh pattern composed of the conductive mesh and the black resist layer and the opening surrounded by the fine line. is necessary. However, as described above, the thickness of the functional layer can be reduced by using a conductive mesh having a relatively small thickness (for example, a thickness of 5 μm or less) and a black resist layer having a relatively small thickness (for example, a thickness of 3 μm or less). It can be made smaller. By reducing the thickness of the functional layer, the raw material cost can be reduced, and the coating speed and drying speed of the functional layer can be increased, thereby greatly reducing the production cost. In particular, when a layer including a hard coat function is applied and formed as the functional layer, reducing the thickness of the functional layer has an advantage that curling of the display filter due to polymerization shrinkage of the hard coat layer can be suppressed.

  FIG. 1 is a schematic cross-sectional view of an example of a display filter according to the present invention. A mesh pattern (hereinafter referred to as a resist laminated conductive mesh) 3 comprising a conductive mesh and a black resist layer on a substrate 4. And the functional layer 2 is laminated on the resist laminated conductive mesh 3. Here, the functional layer 2 is formed by coating so as to fill the opening 3b surrounded by the fine wire portion 3a constituting the resist laminated conductive mesh 3 and to cover the fine wire portion 3a.

  In order to coat and form the functional layer 2 so that the functional layer 2 completely covers the resist laminated conductive mesh 3, the total thickness of the functional layer 2 (N in FIG. 1) Is preferably 130% or more, more preferably 150% or more with respect to the thickness (reference numeral A in FIG. 1). Here, the total thickness (N) of the functional layer 2 is such that, as described above, the functional layer is coated and formed so as to fill the opening of the resist laminated conductive mesh and cover the thin line portion. This is the sum of the thickness (A) of the mesh (corresponding to the thickness of the fine wire portion 3a) and the thickness (L) of the functional layer formed on the fine wire portion. As described above, by increasing the total thickness (N) of the functional layers with respect to the thickness (A) of the resist laminated conductive mesh, the uneven surface of the resist laminated conductive mesh can be sufficiently filled and made uniform. .

  From the above viewpoint, the thickness (A) of the resist laminated conductive mesh is preferably in the range of 0.8 to 8 μm, more preferably in the range of 1.5 to 6 μm, and particularly preferably in the range of 2 to 5 μm. Further, the total thickness (N) of the functional layer is preferably in the range of 2 to 10 μm, particularly preferably in the range of 3 to 8 μm. Further, the thickness (L) of the functional layer formed on the thin line portion of the resist laminated conductive mesh is preferably in the range of 0.5 to 5 μm, and more preferably in the range of 1 to 4 μm.

  The thicknesses of the conductive mesh, the black resist layer, the resist laminated conductive mesh, and the functional layer described above can be obtained from an enlarged cross-sectional photograph of a display filter using a scanning electron microscope.

  As a coating method for forming a functional layer on the resist laminated conductive mesh, a dip coating method, a spin coating method, a slit die coating method, a gravure coating method, a reversal coating method, a rod coating method, a bar coating method, A known wet coating method such as a spray method or a roll coating method can be used.

(Other functional layers)
The display filter of the present invention preferably further has a near infrared shielding function, a color tone adjusting function, or a visible light transmittance adjusting function.

  The near-infrared shielding function is preferably adjusted so that the maximum value of light transmittance in the wavelength range of 800 to 1100 nm is 15% or less. The near-infrared shielding function may be imparted by kneading and dispersing a near-infrared absorber on the base material, the functional layer, or an adhesive layer described later, or a near-infrared shielding layer may be newly provided. The near-infrared shielding function can be imparted by using a near-infrared absorbing agent or by providing a layer that reflects near-infrared rays by metal free electrons such as a conductive thin film. In the present invention, a near-infrared shielding layer formed by applying and drying a paint in which a near-infrared absorber is dispersed or dissolved in a resin binder is used, or a mode in which the near-infrared absorber is contained in a functional layer or an adhesive layer Is preferably used. Near-infrared absorbers include organic near-infrared absorbers such as phthalocyanine compounds, anthraquinone compounds, dithiol compounds, diimonium compounds, or titanium oxide, zinc oxide, indium oxide, tin oxide, zinc sulfide, cesium-containing oxides An inorganic near infrared absorber such as tungsten can be used.

  When the above-described near-infrared shielding layer is newly provided, it can be provided by coating the base material between the base material and the conductive mesh or on the opposite surface of the base material from the conductive mesh. .

  In the case where the near infrared shielding function is imparted to the viewer side from the base material, it is preferable to use an inorganic near infrared absorber having excellent light resistance.

  The color tone adjustment function is a function for improving color purity and whiteness by absorbing light of a specific wavelength emitted from the display. In particular, it is preferable to shield orange light that reduces the color purity of red light emission, and it is preferable to include a dye having an absorption maximum in a wavelength range of 580 to 620 nm. Furthermore, it is preferable to contain a dye having an absorption maximum at a wavelength of 480 to 500 nm in order to improve whiteness. For the color tone adjustment function, a layer containing a dye that absorbs light having the above-described wavelength may be newly provided, or a dye may be contained in the above-described near-infrared shielding layer, functional layer, or adhesive layer.

  The visible light transmittance adjusting function is a function for adjusting the visible light transmittance, and can be adjusted by containing a dye or a pigment. The visible light transmittance adjusting function may be imparted to the substrate, the near-infrared shielding layer, the functional layer, or the adhesive layer, or a transmittance adjusting layer may be newly provided.

  When a layer having the above-described color tone adjusting function and a layer having a visible light transmittance adjusting function are newly provided, these layers are between the base material and the conductive mesh, or the conductive mesh with respect to the base material. It can be provided on the opposite side.

  The display filter of the present invention can be attached to the display directly or via a known high-rigidity substrate such as a glass plate, an acrylic plate, or a polycarbonate plate. The display filter of the present invention is preferably provided with an adhesive layer for adhering to a display or a highly rigid substrate. As the high-rigidity substrate, a glass plate having a thickness of about 1 to 3 mm is preferable.

  An adhesive layer is provided in the outermost surface on the opposite side to a conductive mesh with respect to a base material. As described above, the adhesive layer can be provided with a near-infrared shielding function, a color tone adjusting function, or a visible light transmittance adjusting function. Moreover, it is a preferable aspect to provide the adhesive layer with an impact relaxation function for protecting the display from impact. In order to impart an impact relaxation function to the adhesive layer, the thickness of the adhesive layer is preferably 50 μm or more, more preferably 100 μm or more, and the upper limit thickness is preferably 500 μm or less in consideration of the coating suitability of the adhesive layer.

  A well-known adhesive material or an adhesive material can be used for an adhesive layer. Examples of the adhesive material include acrylic, silicon, urethane, polyvinyl butyral, and ethylene-vinyl acetate. Adhesives include bisphenol A type epoxy resins, tetrahydroxyphenylmethane type epoxy resins, novolac type epoxy resins, resorcin type epoxy resins, polyolefin type epoxy resins and other epoxy resins, natural rubber, polyisoprene, poly-1, 2- (Di) enes such as butadiene, polyisobutene, polybutene, poly-2-heptyl-1,3-butadiene, poly-1,3-butadiene, polyoxyethylene, polyoxypropylene, polyvinyl ethyl ether, polyvinyl hexyl ether, etc. Polyesters such as polyethers, polyvinyl acetate, polyvinyl propionate, polyurethane, ethyl cellulose, polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile, polysulfone, phenoxy resin Etc.

(Example of display filter configuration)
The display filter according to the present invention is preferably composed of a plastic film having only one substrate. As a structure of the display filter, a structure having an adhesive layer / near infrared shielding layer / plastic film / conductive mesh (including a black resist layer) / functional layer in order is preferable. The near-infrared shielding layer preferably has a color tone adjusting function.

  FIG. 1 is a schematic cross-sectional view of a display filter having the above configuration. In FIG. 1, the display filter 1 has a resist laminated conductive mesh 3 formed on one surface of a substrate 4 made of a plastic film, and a functional layer 2 is directly laminated on the resist laminated conductive mesh 3. The near-infrared shielding layer 5 and the pressure-sensitive adhesive layer 6 are sequentially laminated on the other surface of the substrate 4.

(Electrode formation process)
In order to effectively shield electromagnetic waves generated from the display, the display filter targeted by the present invention is usually at least part of the conductive mesh when the display filter is mounted on the display and assembled to the display housing. An electrode for electrically connecting the external electrode and the external electrode of the housing is provided on the periphery of the display filter (outside the image display area of the display).

  Conventionally used display filters comprising two substrates, that is, an optical functional film in which a functional layer such as an antireflection function is laminated on a plastic film, and a conductive layer on the plastic film In the case of a filter in which an electromagnetic wave shielding film provided with an (electromagnetic wave shielding layer) is bonded via an adhesive layer, when the optical functional film and the electromagnetic wave shielding film are bonded together, the electromagnetic wave shielding film By designing the size of the optical functional film sheet to be smaller than the sheet, the conductive layer of the electromagnetic wave shielding film sheet is exposed on the four sides of the filter sheet for display obtained by bonding both sheets. The part is formed. A portion where the conductive layer is exposed is used as an electrode of a display filter.

  However, since the display filter targeted by the present invention is a preferred mode in which the functional layer is laminated without interposing a substrate so as to cover the black resist layer formed on the conductive mesh. The exposed electrode of the resist laminated conductive mesh (conductive layer) may not be formed at the time of pasting, as in the filter composed of the two base materials described above.

  Therefore, an electrode formation method that takes advantage of the characteristics of the display filter according to the present invention, that is, only the functional layer of the thin film exists on the resist laminated conductive mesh, was studied, and a resist was formed using a laser. It has been found that the method of removing the functional layer on the laminated conductive mesh by evaporation and combustion is optimal.

  Specifically, the electrode of the display filter according to the present invention is formed by irradiating a laser from the functional layer side surface of the display filter, removing the functional layer to form a void, and exposing the conductive mesh. The At this time, the black resist layer laminated on the conductive mesh together with the functional layer is also removed. The exposed portion of the conductive mesh formed as described above becomes an electrode. The electrodes formed on the display filter of the present invention will be described in detail below.

  In the present invention, the electrode is provided on at least a part of the peripheral part of the display filter. Here, the peripheral part of the display filter is an image display area of the display when the display filter is installed on the display. The area corresponding to the outer periphery of the display filter is preferably 1 mm or more inside from the end of the display filter and 1 mm or more outside the part corresponding to the image display area.

  The display filter to which the present invention is directed is usually rectangular, and even if used for it, it is rectangular. The electrodes are preferably provided at least at the edge portions of the two sides facing each other, and more preferably formed at the edge portions of the four sides of the display filter. The electrode is preferably formed in an elongated groove shape in a straight line substantially parallel to the side of the display filter. The width of the electrode is preferably 4 mm or less, more preferably 3 mm or less, and further preferably 2 mm or less. As a minimum of the width of an electrode, 0.3 mm or more is preferred and 0.4 mm or more is more preferred. When the width of the electrode exceeds 4 mm, the exposed surface of the conductive mesh becomes large and the conductive mesh is likely to be oxidized and deteriorated, the production efficiency decreases as described later, and the electrode as described later. When the conductive material is disposed on the conductive material, there may be a problem that the conductive material is easily peeled off. On the other hand, if the width of the electrode is smaller than 0.3 mm, the conduction with the display housing (external electrode) becomes insufficient, and a sufficient electromagnetic wave shielding effect may not be obtained.

  The length of the electrode on one side of the display filter is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more with respect to the length of the side. A higher ratio is preferable from the viewpoint of electromagnetic shielding performance. The electrode in the present invention is preferably an elongated groove shape as a planar shape when the display filter is viewed from above, and the shape may be a straight line or a broken line shape. It may be discontinuous. In the case of the latter discontinuous electrode, the total length is an object of the above ratio.

  Hereinafter, the electrodes formed on the display filter of the present invention will be described in detail with reference to the drawings. FIG. 2 is a plan view of an example of the display filter of the present invention, and FIG. 3 is a schematic cross-sectional view taken along the line AA of FIG. In the periphery of the display filter, elongated electrodes 7 are provided in a straight line substantially parallel to the four sides. This display filter has a resist laminated conductive mesh 3 composed of a conductive mesh 31 and a black resist layer 32 laminated thereon on a substrate 4, and functions on the resist laminated conductive mesh 3. Layer 2 is laminated. A near-infrared shielding layer 5 and an adhesive layer 6 are laminated on the opposite surface of the substrate 4. In FIG. 3, the electrode 7 is formed by irradiating a laser from the functional layer side surface to remove the functional layer 2 and providing a gap reaching the conductive mesh 3. At this time, the black resist layer 32 is removed together with the functional layer 2 by laser irradiation. The conductive mesh 3 is exposed inside the gap, and this exposed portion becomes the electrode 7.

  FIG. 4 is a plan view of a mode in which the electrodes 7 are provided in a linear discontinuity (broken line shape). In the peripheral part of the display filter, electrodes 7 are provided in a broken line shape substantially parallel to the four sides. When providing an electrode in the shape of a broken line, the number of electrode portions per side is preferably 3 to 50, and more preferably 5 to 40. The ratio (A / B) of the total length (A) of the electrode portions per side and the total length (B) of the distance (interval) between the electrode portions and the electrode portions is preferably in the range of 0.2 to 20. The range of 0.5 to 10 is more preferable.

  Next, a method for forming an electrode using a laser will be described. The electrode of the display filter according to the present invention is preferably formed by irradiating a laser from the functional layer side surface of the display filter, removing the functional layer to form a void, and exposing the conductive mesh. . By using a laser, the functional layer can be removed without contact with the functional layer, and the functional layer or the like can be removed without mechanical and physical peeling.

In addition, the laser irradiation method has an advantage that the functional layer can be removed with a substantially constant width and that the control in the depth direction of the air gap can be accurately performed. Examples of such laser output sources include iodine, YAG, and CO _{2. In} particular, the CO ₂ laser evaporates and burns the functional layer mainly composed of organic substances without destroying the conductive mesh made of metal. It is preferable in that it can be removed.

  As a method of removing the functional layer, there is a method of cutting from the surface of the laminate using a cutter blade such as a knife. In this method, an electrode of a preferred embodiment in the present invention, that is, an electrode having a width of 0.3 mm or more is formed. There is a problem that conduction cannot be obtained because it cannot be performed, and that the conductive mesh is cut and conduction is insufficient. As another method of removing the functional layer, there is a method of removing the functional layer using an ultrasonic soldering iron, but this method brings a high-temperature iron tip into contact with the laminated body, so that the plastic film of the laminated body undergoes thermal deformation. There is a problem that it may occur and it is difficult to completely and stably expose the conductive mesh. As another method, there is a method of dry etching. However, this method may increase the size of the apparatus, and may become high temperature during operation and the display filter may be deformed.

  In view of the above, it has been found that a method using a laser is extremely useful as a method for forming a void for removing an electrode having an exposed conductive mesh by removing a functional layer laminated on the conductive mesh. .

  When irradiating a laser from the functional layer side surface to remove the functional layer and the black resist layer to form a void reaching the conductive mesh, the width and depth of the void are determined by the laser focal position, laser output, and It can be controlled by adjusting the laser scanning speed (head speed). The width of the gap (corresponding to the width of the electrode described above) can be controlled by further adjusting the number of scans, but the gap desired by the present invention can be formed even by one scan. As described above, the width of the gap is preferably 4 mm or less, but in order to form a gap with a width exceeding 4 mm, it is necessary to increase the number of laser operations or shift the focal position of the laser. In the former case, the production efficiency is reduced, and in the latter case, the functional layer at the edge of the gap is not sufficiently removed, and the residue of decomposition product that cannot evaporate or burn out the functional layer adheres to the edge of the gap. May cause inconvenience.

  Also, the method of removing the functional layer and the black resist layer using a laser is to remove the functional mesh and the black resist layer by evaporating or burning, so that the conductive mesh in the portion irradiated with the laser is completely exposed. Is possible.

  In the present invention, as described above, the functional layer and the black resist layer are removed to form a void, and the exposed portion of the conductive mesh is used as an electrode, thereby sufficiently ensuring the ground efficiency. In the display filter of the present invention, since the plastic film and the adhesive layer do not exist on the conductive mesh, the distance from the conductive mesh surface to the outermost surface on the functional layer side of the filter is a conventional general display filter. Therefore, even when the electrode width (gap width) is 4 mm or less, preferably 3 mm or less, and further 2 mm or less, sufficient conduction with the external electrode can be obtained. That is, by sufficiently reducing the distance from the surface of the conductive mesh to the outermost surface, the width of the electrode, that is, the width of the gap can be reduced.

  From the above viewpoint, the distance from the surface of the conductive mesh to the outermost surface of the functional layer, that is, the total of the thickness of the black resist layer laminated on (L) in FIG. 1 and the conductive mesh is preferably 8 μm or less, 7 μm The following is more preferable, further 6 μm or less is preferable, and 5 μm or less is particularly preferable. The lower limit thickness is about 2 μm.

  In order to reduce the distance from the conductive mesh surface to the functional layer side outermost surface, the thickness (A) of the resist laminated conductive mesh 3 is in the range of 0.8 to 8 μm, preferably 1.5 to 6 μm. The thickness (L) of the functional layer formed on the thin line portion of the resist laminated conductive mesh is in the range of 0.5 to 5 μm, and more preferably in the range of 1 to 4 μm. It is preferable.

  Also, from the viewpoint of forming voids by laser, reducing the distance from the surface of the conductive mesh to the outermost surface of the functional layer is to reduce the absolute amount of organic substances that are evaporated and burned by laser irradiation. Since the amount of the organic decomposition product residue generated when the voids are formed by laser irradiation is reduced, there is an advantage that contamination of the electrode portion of the display filter due to the decomposition product residue and contamination of peripheral devices can be reduced.

  In addition, one feature of the display filter of the present invention is that a black resist layer is used to suppress the metallic luster of the conductive mesh, which has the advantage that the conventional blackening treatment can be omitted. In addition to this, the use of a black resist layer in place of the blackening treatment layer is also beneficial from the viewpoint of electrode formation by laser irradiation as described above.

  The blackened layer formed on the surface of the conductive mesh by blackening the conductive mesh is usually a metal oxide that forms the conductive mesh, and this metal oxide has low conductivity. When forming the electrode with the conductive mesh exposed, the metal oxide must be removed. However, the metal oxide cannot be easily removed with a laser unlike the functional layer and the black resist layer containing the organic substance (resin) as a constituent component. In order to remove the metal oxide, it is necessary to strengthen the laser irradiation conditions, which may destroy the conductive mesh. Therefore, it is beneficial to use a black resist layer in place of the blackening treatment layer in order to stably and accurately form electrodes with a laser.

  In the electrode formation by the laser described above, the display layer with a cover film further having a cover film on the functional layer side surface of the display filter, the gap reaching the conductive mesh by irradiating the laser from the cover film surface. It is preferable to form an electrode with the conductive mesh exposed.

  The cover film is provided for the purpose of protecting the functional layer, and is finally peeled off. By forming a void by irradiating a laser from the surface of the cover film, there is an advantage that a residue of a decomposition product of organic matter generated at the time of void formation is prevented from reattaching to the display filter.

  In consideration of the amount of decomposition residue generated by laser processing, the low price of the laser irradiation device, and the accuracy of void formation, the thickness of the cover film (including the adhesive layer if an adhesive layer for lamination is required) ) Is preferably in the range of 20 to 80 μm.

  Various plastic films can be used as the cover film used in the present invention. For example, polyester films such as polyethylene terephthalate, polyolefin films such as polyethylene film, polypropylene film, polybutylene film, polyacetylcellulose film, polyacryl film, polycarbonate film, epoxy film, polyurethane film, etc. A film or a polyolefin film is preferably used.

  Since the cover film is finally peeled off from the display filter, a peelable pressure-sensitive adhesive or adhesive is used. Or when using the film which has adhesiveness as a cover film, an adhesive material etc. are unnecessary. The cover film is preferably peeled off before or after the display filter is attached to the display.

  FIG. 5 is a schematic cross-sectional view of an electrode portion of a display filter with a cover film having a cover film on the functional layer surface of the display filter. The electrode 7 is formed by forming a gap reaching the conductive mesh 31 from the cover film 8 by laser irradiation and exposing the conductive mesh 31.

  As described above, the display filter of the present invention can be sufficiently connected to the external electrode by the electrode formed by exposing the conductive mesh, but the conductive mesh is further exposed to the exposed portion of the conductive mesh. An electrode can be formed by disposing the material. In this case, an electrode is formed by the exposed portion of the conductive mesh and the conductive material.

  As described above, the width (electrode width) of the exposed portion of the conductive mesh for forming the electrode is preferably 4 mm or less, thereby suppressing deterioration of the conductive mesh due to air oxidation or the like. However, by arranging a conductive material, for example, a fluid conductive material such as a conductive paste or solder described later, or a conductive adhesive tape on the exposed portion of the conductive mesh, the air in the exposed portion of the conductive mesh is further removed. There is an advantage that deterioration due to oxidation or the like can be suppressed.

  As one aspect of disposing a conductive material on the exposed portion of the conductive mesh, a mode in which a fluid conductive material (hereinafter referred to as a conductive paste or the like) such as a conductive paste or solder is applied or filled in the exposed portion. There is. As the conductive paste, a metal paste containing silver, gold, palladium, copper, indium, tin, or an alloy of silver and other metals can be used.

  As another aspect of disposing the conductive material on the exposed portion of the conductive mesh, there is an aspect of disposing a conductive solid processed so as to be inserted into the exposed portion. As the conductive solid, a conductive metal or a non-conductive surface coated with a conductive metal is used.

  The method of forming the exposed portion of the conductive mesh with a laser can form a void reaching the lower layer of the conductive layer through the opening portion of the conductive mesh without destroying the conductive mesh. By applying or filling a fluid conductive material such as a conductive paste into this gap, the conductive paste enters the lower side of the conductive mesh. As a result, the conductive mesh and the conductive paste, etc. The contact area with the material is increased, and conduction between the conductive mesh and the external electrode can be more stably ensured.

  As still another aspect of disposing the conductive material on the exposed portion of the conductive mesh, there is an aspect in which a conductive adhesive tape is attached from above the exposed portion. It is preferable to heat and press the conductive adhesive tape with a heat sealer or the like after the conductive adhesive tape is applied. Since the filter for display of the present invention has a small distance from the surface of the conductive mesh to the outermost surface of the functional layer, the conductive adhesive tape can be brought into contact with the conductive mesh by heating and pressurizing the conductive adhesive tape. The conductive adhesive tape is provided with an adhesive layer in which conductive particles are dispersed on one surface of a metal foil. This adhesive layer has an acrylic, rubber-based, silicon-based adhesive, or epoxy-based adhesive. A compound obtained by blending a phenolic resin with a curing agent can be used. In particular, a post-crosslinking type containing a polymer mainly composed of an ethylene-vinyl acetate copolymer, which is a crosslinkable conductive adhesive, and the crosslinker. What is an adhesive layer is preferable.

FIG. 6 is a schematic cross-sectional view of a display filter in which a conductive material is disposed on an exposed portion of a conductive mesh. An electrode 7 is formed by applying a conductive material 9 made of a conductive paste or the like to the exposed portion of the conductive mesh 31.
It is preferable that the above-described step of disposing a fluid conductive material such as a conductive paste or solder on the exposed portion of the conductive mesh is performed in a state where a cover film is present.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.
Example 1
Display filter comprising adhesive layer / near infrared shielding layer / base material (PET film) / conductive mesh / black resist layer / functional layer (hard coat layer / high refractive index layer / low refractive index layer) in the following manner Was made.
<Base material>
As the substrate, a roll-shaped PET film (Lumirror (registered trademark) manufactured by Toray Industries, Inc.) having a thickness of 100 μm, a width of 1000 mm, and a length of 100 m was used.
<Formation of conductive mesh>
A nickel layer (thickness: 0.02 μm) is continuously formed on one surface of the substrate by a sputtering method over a width of 980 mm and a length of 90 m, and a copper layer having a thickness of 2.5 μm is further formed thereon. Was continuously formed by vacuum evaporation. Next, the following photosensitive black resist layer was applied and laminated on the surface of the copper layer so that the thickness (dry film thickness) was 1 μm. The optical density (OD value) of this photosensitive black resist layer was 2.2.

  Next, while continuously transporting the substrate on which the metal thin film and the photosensitive black resist layer were laminated, scanning exposure was performed on the lattice pattern using a 405 nm blue-violet semiconductor laser. Subsequently, development processing was performed using an alkali developer to form a black resist layer having a mesh pattern. Next, etching was performed with a ferric chloride solution to obtain a conductive mesh having a line width of 7 μm, a line pitch of 150 μm, and a thickness of 2.5 μm.

The total thickness of the mesh pattern (resist laminated conductive mesh) made of the conductive mesh and the black resist layer thus produced was 3.5 μm.
<Black resist layer>
21.1 parts by mass of titanium black 13M-T (titanium nitride) manufactured by Mitsubishi Materials Co., Ltd. 31.16 parts by mass of acid-treated carbon black 9930CF manufactured by Daido Kasei Co., Ltd. 31. Carbon black PRINTEX25 manufactured by Degussa Co., Ltd. 16 parts by mass, 1.68 parts by mass of “Solspers (registered trademark)” 12000 (manufactured by Abyssia) and 56.14 parts by mass of a 45% by mass 3-methyl-3-methoxybutanol solution of an acrylic polymer (see below), “Disperbyk (registered trademark)” 167 (dispersant) manufactured by Big Chemi Japan Co., Ltd. 24.29 parts by mass and 751.1 parts by mass of propylene glycol monomethyl ether acetate were weighed, and a mill type disperser filled with zirconia beads was measured. And dispersed at 2500 rpm for 3 hours to obtain a pigment dispersion having a pigment concentration of 16.843 mass%.

  To 57.74 parts by mass of this pigment dispersion, 0.63 parts by mass of a 45% by mass 3-methyl-3-methoxybutanol solution of an acrylic polymer (see below), a bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (see below) 3- Methyl-3-methoxy-butyl acetate 30 mass% 7.56 parts by mass, dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. DPHA) as a polyfunctional monomer 30 mass of 3-methyl-3-methoxy-butyl acetate % Solution 3.24 parts by weight, “Irgacure (registered trademark)” 379 0.24 parts by weight as photopolymerization initiator, Asahi Denka Kogyo Co., Ltd. “Adeka (registered trademark) Optomer” N-1919 1.47 parts by weight and N, N'-tetraethyl-4,4'-diaminobenzophenone 0.19 parts by mass, improved adhesion 0.14 parts by weight of vinyltrimethoxysilane as a chemical agent and 0.28 parts by weight of a 10% by weight solution of propylene glycol monomethyl ether acetate as a silicone surfactant are dissolved in 28.51 parts by weight of 3-methyl-3-methoxy-butyl acetate. The prepared solution was added and mixed to prepare a black resist layer coating solution.

The content ratio of the black pigment in the black resist layer coating solution is 28% by mass with respect to all components of the black resist layer excluding the organic solvent.
<Acrylic polymer>
After synthesizing methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 33/34/33) by the method described in Example 1 of Japanese Patent No. 3120476, 33 parts by weight of glycidyl methacrylate was added, and purified water was added. Then, an acrylic polymer (P1) powder having an average molecular weight (Mw) of 9,000 and an acid value of 70 (mg KOH / g: according to JIS K-5407) was obtained.
<Bisphenoxyethanol fluorene-based tetrafunctional acrylate compound>
First, 296 parts by mass of bisphenoxyethanol fluorenediglycidyl ether (epoxy equivalent 296 g / eq), 3.4 parts by mass of dimethylbenzylamine, 0.34 parts by mass of p-methoxyphenol, 72.06 parts by mass of acrylic acid (1 Mol) and the temperature was raised while blowing air at a flow rate of 20 ml / min, and the reaction was carried out at a temperature of 110 to 120 ° C. During this time, the acid value was measured, and heating and stirring were continued until it became less than 2.0 mgKOH / g. It took 10 hours for the acid value to reach the target. Thereby, bisphenoxyethanol fluorene type acrylate was obtained.

Next, in the container, 184.0 parts by mass of the bisphenoxyethanol fluorene acrylate synthesized above (hydroxyl equivalent: 368 g / eq, calculated value), 100 parts by mass of 3-methoxy-3-methyl-butyl acetate, 26.6 parts by mass of triethylamine (0.263 mol) was charged and dissolved and cooled in a water bath, and then 25.38 parts by mass of isophthal chloride (0.125 mol: an amount necessary for reacting half of the hydroxyl group with the acid chloride) was converted to 3-methoxy- A solution dissolved in 100 parts by mass of 3-methyl-butyl acetate was added dropwise. The mixture was further reacted at room temperature for 2 hours, diluted with 267.3 parts by mass of 3-methoxy-3-methyl-butyl acetate, and the resulting white precipitate was filtered under pressure to obtain 30% by mass of the bisphenoxyethanol fluorene-based tetrafunctional acrylate compound. A solution was obtained.
<Functional layer coating>
As described above, the following hard coat layer, high refractive index layer, and low refractive index are formed on the mesh pattern (resist laminated conductive mesh) composed of the conductive mesh and black resist layer formed on the PET film. The layers were applied sequentially.
<Hard coat layer>
A paint obtained by diluting a commercially available hard coat agent (“Desolite Z7528” manufactured by JSR) with isopropyl alcohol to a solid content concentration of 30% by mass is coated with a microgravure coater, dried at 80 ° C., and then irradiated with ultraviolet rays of 1.0 J / cm ^2. Was hardened by irradiation. The thickness (thickness after drying and curing) of the hard coat layer was adjusted so that the thickness (L) on the fine line portion of the resist laminated conductive mesh was 3 μm.
<High refractive index layer>
A mixture of 6 parts by mass of tin-containing indium oxide particles (ITO), 2 parts by mass of polyfunctional acrylate, 18 parts by mass of methanol, 54 parts by mass of polypropylene glycol monoethyl ether, and 20 parts by mass of isopropyl alcohol was stirred to give a coating film refractive index of 1. A 67 high refractive index paint was prepared. This paint is applied onto the hard coat layer using a micro gravure coater, dried at 80 ° C., and then irradiated with ultraviolet light 1.0 J / cm ² to cure the applied layer, and has a thickness of about 0.1 μm. A high refractive index layer was formed.
<Low refractive index layer>
A silica slurry comprising 144 parts by mass of hollow silica particles having an outer shell with a primary particle diameter of 50 nm (porosity 40%) and 560 parts by mass of isopropyl alcohol was prepared, 219 parts by mass of methyltrimethoxysilane, 3,3,3-tri 158 parts by mass of fluoropropyltrimethoxysilane, 704 parts by mass of the above silica slurry, and 713 parts by mass of polypropylene glycol monoethyl ether are mixed with stirring, 1 part by mass of phosphoric acid and 130 parts by mass of water are mixed, and the mixture is stirred at 30 ° C. ± 10 ° C. Then, the mixture was hydrolyzed for 60 minutes, and the temperature was raised to 80 ° C. ± 5 ° C., followed by polymerization while stirring for 60 minutes to obtain a silica particle-containing polymer.

  Next, 1200 parts by mass of this silica particle-containing polymer and 5244 parts by mass of isopropyl alcohol were stirred and mixed, then 15 parts by mass of acetoxyaluminum as a curing catalyst was added and stirred again to prepare a paint having a refractive index of 1.35. .

This paint was applied onto the high refractive index layer with a small-diameter gravure coater, dried and cured at 130 ° C. to form a low refractive index layer having a thickness of about 0.1 μm.
<Lamination of near-infrared shielding layer>
A near-infrared shielding layer having an orange light shielding function on the surface opposite to the surface on which the functional layer of the PET film is coated (as a phthalocyanine dye and a diimonium dye as near-infrared absorbing dyes, and an orange light absorbing dye) A layer obtained by coating a paint obtained by mixing a tetraazaporphyrin-based pigment with an acrylic resin so that the dry film thickness is 12 μm.
<Lamination of adhesive layer>
A UV curable urethane acrylate resin (Hibon (registered trademark) manufactured by Hitachi Chemical Co., Ltd.) is applied on a separate film with a slit die coater to a thickness of 300 μm, and then applied using a UV irradiation device. Then, a separate film was attached to obtain an adhesive layer sandwiched between the separate films. Next, the adhesive layer was laminated | stacked on the near-infrared shielding layer of the laminated body produced above, peeling one separate film.

(Example 2)
A display filter was produced in the same manner as in Example 1 except that the functional layer was replaced with a single layer of the following antiglare hard coat layer.

<Anti-glare hard coat layer>
A commercially available hard coat agent (Opstar (registered trademark) Z7534 manufactured by JSR) is diluted with methyl ethyl ketone so that the solid content concentration is 50% by mass, and acrylic fine particles having an average particle size of 1.5 μm (Chemisnow manufactured by Soken Chemical Co., Ltd.) (Registered trademark) MX series) was added in an amount of 1% by mass based on the solid content of the hard coat agent to prepare a paint for an antiglare hard coat layer.

(Comparative Example 1)
A display filter was produced in the same manner as in Example 1 except that the following conductive mesh forming method was used instead of the conductive mesh forming method of Example 1. In this display filter, the conductive mesh is blackened, and does not have a black resist layer on the conductive mesh.

<Formation of conductive mesh>
In the same manner as in Example 1, a nickel layer (thickness 0.02 μm) and a copper layer (4 μm) were formed on the substrate. Next, a resist layer (dry film thickness 1 μm) obtained by removing the black pigment from the black resist layer of Example 1 is laminated on the surface of the copper layer, and exposed, developed, and etched in the same manner as in Example 1. Then, the resist layer was peeled off by treatment with an alkali stripping solution to obtain a conductive mesh having a line width of 7 μm, a line pitch of 150 μm, and a thickness of 4 μm. Subsequently, the conductive mesh was blackened using an oxidation treatment agent (adjusted at a ratio of Enplate MB-438A / B / pure water = 8/13/79 manufactured by Meltex Co., Ltd.).

(Comparative Example 2)
Instead of the conductive mesh forming method of the first embodiment, a display filter is formed in the same manner as in the first embodiment except that the following conductive layer forming method (having metal solid portions on the four sides around the conductive mesh) is used. Was made. In this display filter, the conductive mesh is blackened, and does not have a black resist layer on the conductive mesh.

<Formation of conductive layer consisting of conductive mesh and solid metal part>
On the same substrate as in Example 1, a 10 μm thick copper foil was laminated using a two-component adhesive for dry lamination (main agent AD-76P1 / curing agent CAT-10L manufactured by Toyo Morton Co., Ltd.), and a copper foil laminate A film was obtained. Next, on the surface of this copper layer, a commercially available alkaline developing negative resist film (thickness of 10 μm and no black pigment) is laminated, and a photomask (opening of 15 mm width on each of the four sides of the rectangular mesh pattern region). UV exposure through the substrate. This exposure in units of photomasks was repeatedly performed in the longitudinal direction of the substrate at intervals of 5 mm.

  Subsequently, after developing with an alkali developer, etching was performed with a ferric chloride solution. Finally, the resist layer was peeled off by treatment with an alkali stripping solution to obtain a conductive layer having a conductive mesh having a line width of 10 μm, a line pitch of 250 μm, and a thickness of 10 μm, and a copper solid part.

  The conductive layer thus produced has a solid copper portion having a width of 15 mm on each of the four sides around the rectangular conductive mesh region. Next, the conductive mesh portion and the solid copper portion were blackened using an oxidation treatment agent (adjusted at a ratio of Enplate MB-438A / B / pure water = 8/13/79 manufactured by Meltex Co., Ltd.). .

<Evaluation of filters for each display>
1) Visual evaluation of the metallic gloss of the conductive mesh and the bright contrast when each display filter is mounted on the plasma display. Examples 1 and 2 in which the black resist layer of the present invention is laminated are conventional blackening treatments. The metallic luster was suppressed to be equal to or higher than those of Comparative Examples 1 and 2 to which the image was applied, and the image contrast in a bright place was good without deterioration.
2) Evaluation in coating process of functional layer In Examples 1 and 2 in which the black resist layer of the present invention was laminated, the coating property of the functional layer was satisfactory without any problem.

  In Comparative Examples 1 and 2 in which the conductive mesh was subjected to blackening treatment, a part of the blackening treatment layer was peeled off and adhered to the conveyance roller or the like in the functional layer coating process, and the conveyance roller or the like was contaminated. .

Moreover, the comparative example 2 using the conductive layer which consists of a conductive mesh and a metal solid part (copper solid part) formed by the conventional copper foil of 10 micrometers in thickness and a photomask exposure system is as large as 10 micrometers. Due to the presence of the copper solid part and the mask exposure interval of 5 mm, the surface of the conductive layer has large irregularities, and the adhesive layer is interposed between the base material and the conductive layer, The coatability of the functional layer was lowered, and coating unevenness occurred on the coated surface of the functional layer.
3) Productivity Examples 1 and 2 in which the black resist layer of the present invention was laminated were compared with Comparative Examples 1 and 2 in which the conductive mesh was subjected to blackening treatment, and the blackening treatment step and the resist layer peeling step. Is no longer necessary, and the production time of the conductive mesh has been greatly reduced.

  Further, in Comparative Example 1 in which the conductive mesh is blackened, it is necessary to increase the thickness of the metal thin film in order to compensate for the decrease in conductivity due to the blackening treatment. Increased and productivity decreased.

  Further, in Comparative Example 2 using the photomask exposure method, when even one serious defect occurs in the conductive layer produced in the photomask exposure unit, one unit of photomask exposure (corresponding to one final display filter) Is completely defective. In contrast, in Examples 1 and 2 of the present invention, since a continuous mesh is produced by laser exposure, the defective display can be removed and the final display filter unit can be cut out, greatly improving the production yield. did.

(Example 3)
<Formation of electrode>
A 42-inch size display filter as a final product was cut out from the display filter of Example 1 (display filter made of a long base material; long filter) prepared as described above. The sheet was cut into a sheet so that the long side (964 mm) of the 42-inch size display filter was arranged in the width direction of the long filter and the short side (554 mm) was arranged in the longitudinal direction of the long filter.

Next, this sheet-like display filter is fixed to a laser cutter (Comax CO ₂ laser cutter), and each of the four sides of the sheet-like display filter is 10 mm inside from the end, and straight from the functional layer side surface. Laser irradiation was performed to remove the functional layer and the black resist layer to expose the conductive mesh.

The width of the exposed portion of the conductive mesh was 0.8 mm, and the length of the exposed portion was 930 mm on the long side and 520 mm on the short side.
<Evaluation of earth performance>
A simple casing (external electrode) is manufactured by joining a gasket with a cloth woven with conductive fibers around a sponge on one side of an aluminum plate with a thickness of 1 mm and a width of 2 cm. did.

  Next, after installing the display filter produced above on an acrylic plate having a thickness of 3 mm, the above-described simple housing was placed at the ends of the four sides of the display filter and fixed to the acrylic plate with a clamp. The clamping of the clamp was adjusted so that the distance between the acrylic plate and the simple housing was constant.

  Next, using a resistance measuring instrument “Pocket Multimeter” manufactured by Multi Instrument Co., Ltd., the conductivity between two opposing electrodes was confirmed by applying an end needle to the aluminum plate of the simple housing.

As a result, it was confirmed that there was continuity and grounding was possible.
Example 4
<Application of conductive paste to electrode>
A conductive paste (a silver paste “Dotite” (registered trademark) manufactured by Fujikura Kasei Co., Ltd.) was applied to the electrode (exposed portion of the conductive mesh) formed in Example 3 with a dispenser.

  The ground performance was evaluated in the same manner as described above. As a result, it was confirmed that there was electrical continuity between the electrodes on the two opposing sides, and grounding was possible.

(Example 5)
<Attaching conductive adhesive tape to electrode>
A conductive adhesive tape was affixed to the electrode (exposed portion of the conductive mesh) formed in Example 3, and heated and pressurized with a heat sealer.

  The display performance thus produced was evaluated for the earth performance in the same manner as described above. As a result, it was confirmed that there was electrical continuity between the electrodes on the two opposing sides, and grounding was possible.

The schematic cross section of an example of the filter for displays of the present invention. The top view of an example of the filter for displays of this invention in which the electrode was formed. FIG. 4 is a schematic cross-sectional view taken along a line AA in FIG. 3. The top view of an example of the filter for displays of this invention in which the electrode was formed. The schematic cross section of an example of the filter for displays of this invention which has a cover film. The top view of an example of the filter for displays of this invention in which the electrode was formed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display filter of this invention 2 Functional layer 3 Resist laminated conductive mesh 4 Base material 5 Near-infrared shielding layer 6 Adhesive layer 7 Electrode 8 Cover film 9 Conductive material 31 Conductive mesh 32 Black resist layer P Conductive mesh line Pitch W Conductive mesh line width

Claims (9)

In the longitudinal direction of the long substrate, a conductive mesh and a method for manufacturing a display filter in which a black resist layer registered on the conductive mesh is continuously formed,
Forming a metal thin film on a long substrate, laminating a photosensitive black resist layer on the metal thin film, exposing the photosensitive black resist layer to a mesh pattern with a laser, the photosensitive black resist The manufacturing method of the filter for a display which has the process of developing a layer, and the process of etching this metal thin film.   The manufacturing method of the filter for a display of Claim 1 whose thickness of the said electroconductive mesh is 0.3-5 micrometers.   The manufacturing method of the filter for a display of Claim 1 or 2 whose process of forming a metal thin film on the said base material is a process of forming a metal thin film on a base material using a vapor-phase film-forming method.   The manufacturing method of the filter for a display of any one of Claims 1-3 whose optical density of the said photosensitive black resist layer is 0.5-8.   The manufacturing method of the filter for a display of any one of Claims 1-4 whose thickness of the said photosensitive black resist layer is 0.5-3 micrometers.   Furthermore, the manufacturing method of the filter for a display of any one of Claims 1-5 which has the process of coating-forming a functional surface layer so that a black resist layer may be coat | covered. The method for producing a display filter according to claim 6, wherein the functional surface layer is a functional layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, and an antifouling function. . The thickness (L) of the functional surface layer formed on the thin line portion of the black resist layer among the functional surface layers covering the black resist layer is 0.5 to 5 μm. The manufacturing method of the filter for displays as described.   Furthermore, it has a process of irradiating a laser from the said functional surface layer side, removing a functional layer and a black resist layer, and forming the exposed part of an electroconductive mesh. Manufacturing method for display filters.

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