JP2010134436A - Filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filter for display, which comprises a pressure-sensitive adhesive layer having satisfactory adhesive strength for base material of a display panel or filter for display and having adequate shock resistance and, moreover, prevents decoloration of the pressure-sensitive adhesive layer due to the lapse of time. <P>SOLUTION: The filter for display comprises a conductive film having a conductive layer on a base material (A) and a pressure-sensitive adhesive layer (1). The pressure-sensitive adhesive layer (1) contains a resin having hydroxide group and/or carboxyl group, has a thickness of 100 μm or more and is arranged so as not to be brought into contact with the base material (A) and the conductive layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a display filter, and more particularly, to a display filter having an impact resistance and having an adhesive layer having an impact absorbing function.

  A display such as an organic EL display, a liquid crystal display, or a plasma display is a display device capable of clear full color display. The display is usually provided with a front filter (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, because plasma displays generate strong electromagnetic waves due to their structure and operating principle, they have been given anti-reflection and anti-glare functions to shield electromagnetic waves and prevent reflection and glare from outside light. Display filters are usually used.

  Conventional general display filters, particularly general display filters used in plasma displays, are conductive films (electromagnetic wave shielding films) in which a conductive layer (electromagnetic wave shielding layer) is laminated on a substrate such as a plastic film. ) And a functional film in which a functional layer such as an antireflection layer, an antiglare layer, or a hard coat layer is laminated on a base material such as a plastic film is bonded via an adhesive layer. And in order to affix this display filter to the display panel of a plasma display, it has the structure by which the adhesive layer was previously provided in the electromagnetic wave shielding film side of the display filter.

  The display filter described above is also required to have a function of protecting the display panel, and it has been proposed to impart an impact absorbing function to the adhesive layer (for example, Patent Documents 1 to 3).

JP 2006-171261 A JP 2007-182557 A JP 2007-254705 A

  In order to give sufficient impact resistance to the pressure-sensitive adhesive layer, the thickness of the pressure-sensitive adhesive layer is preferably 100 μm or more. Moreover, it is preferable to use resin which has a hydroxyl group or a carboxy group as resin which comprises an adhesive layer from a viewpoint of ensuring favorable adhesive strength with respect to the display panel of a display, or the base material of the filter for displays.

  As described above, when a resin having a hydroxyl group or a carboxy group is used for the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is directly or indirectly brought into contact with the conductive layer constituting the conductive film (electromagnetic wave shielding film). It has been found that the adhesive layer changes color with the passage of time. This discoloration of the pressure-sensitive adhesive layer becomes more conspicuous as the thickness of the pressure-sensitive adhesive layer is increased, which has been a hindrance when the thickness of the pressure-sensitive adhesive layer is increased in order to provide an impact absorbing function.

  Accordingly, in view of the above problems, an object of the present invention is to provide a display filter having a pressure-sensitive adhesive layer having good adhesion strength to a display panel or display filter substrate and having sufficient impact resistance. In this case, discoloration of the pressure-sensitive adhesive layer over time is prevented.

The above object of the present invention has been basically achieved by the following invention.
1) A conductive film having a conductive layer on a substrate (A), and a display filter having a pressure-sensitive adhesive layer (1),
The pressure-sensitive adhesive layer (1) contains a resin having a hydroxyl group and / or a carboxy group, and has a thickness of 100 μm or more.
The display-use filter, wherein the pressure-sensitive adhesive layer (1) is disposed so as not to contact the substrate (A) and the conductive layer.
2) The display filter has a laminate (B) in which the adhesive layer (1) is laminated on the substrate (B), and a laminate (AB) in which the conductive film is laminated.
The positional relationship between the laminate (B) and the conductive film in the laminate (AB) is characterized in that the adhesive layer (1), the substrate (B), the substrate (A), and the conductive layer are arranged in this order. The display filter as described in 1) above.
3) The display filter further includes a laminate (C) in which a pressure-sensitive adhesive layer (2) having a thickness of 5 μm or more and less than 100 μm is laminated on the substrate (C),
Laminate (C) and laminate (AB) are arranged in the order of pressure-sensitive adhesive layer (2), base material (C), pressure-sensitive adhesive layer (1), base material (B), base material (A), and conductive layer. The display filter as described in 2) above, wherein the display filter is laminated.
4) On the conductive layer side of the conductive film, a functional layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, and an antifouling function is directly or via a substrate. The display filter according to any one of 1) to 3), which is arranged.
5) The display filter as described in 1) to 4) above, wherein the pressure-sensitive adhesive layer (1) is obtained by curing the active energy ray-curable composition.
6) The display filter according to 5), wherein the active energy ray-curable composition is a solventless urethane-based ultraviolet curable composition.

  According to the present invention, in a display filter having a pressure-sensitive adhesive layer having good adhesion strength to a display panel or display filter substrate and having sufficient impact resistance, Discoloration over time can be prevented.

  The display filter according to the present invention is a display filter having a conductive film having a conductive layer on a substrate (A) and an adhesive layer (1).

  When the display filter of the present invention is applied to a display that emits an electromagnetic wave such as a plasma display, the conductive film constituting the display filter of the present invention preferably has sufficient electromagnetic wave shielding performance.

  The conductive film according to the present invention is obtained by forming a conductive layer on the substrate (A). In the following description of the conductive film, the base means the base (A) unless otherwise specified. A plastic film is preferably used as the base material (A) constituting the conductive film. 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, a polyester resin, a polyolefin resin, and a cellulose resin are preferable, and a polyester resin is particularly preferably used.

  The plastic film used as the substrate (A) may be a single layer film formed of the above-mentioned resin, or a composite film in which two or more layers of the above-described resin film are laminated. It may be.

  The thickness of the plastic film used as the substrate (A) is suitably in the range of 50 to 300 μm, but is particularly preferably in the range of 90 to 250 μm from the viewpoint of cost and ensuring the rigidity of the display filter.

  The plastic film used as the substrate (A) is an easy-adhesive layer (primer layer, lower layer) for strengthening the adhesion (adhesive strength) to the conductive layer or other functional layer formed on the substrate (A). A plastic film having a pulling layer) is preferred.

  A conventionally well-known conductive layer can be used for the conductive layer provided on a base material (A). For example, a conductive thin film, a conductive mesh, etc. are mentioned. The sheet resistance of the conductive layer is suitably 10Ω / □ or less, but from the viewpoint of electromagnetic wave shielding, it is preferably 5Ω / □ or less, more preferably 3Ω / □ or less, and particularly preferably 1Ω / □ or less. A lower sheet resistance is preferable because the electromagnetic wave shielding property is improved, but a practical lower limit is considered to be about 0.01Ω / □.

  Examples of the conductive thin film used for the conductive layer include a metal thin film, an oxide semiconductor film, and a laminate thereof. As a material for the metal thin film, a metal selected from silver, gold, palladium, copper, indium and tin, an alloy of silver and other metals, or the like is used. As a method for forming the metal thin film, a known method such as sputtering, ion plating, vacuum deposition, or plating can be used. As a material of the oxide semiconductor film, an oxide or sulfide of zinc, titanium, indium, tin, zirconium, bismuth, antimony, tantalum, cerium, neodymium, lanthanum, thorium, magnesium, gallium, or a mixture of these oxides Etc. are used. As a method for forming the oxide semiconductor, a known method such as sputtering, ion plating, ion beam assist, vacuum deposition, or wet coating can be used.

  Examples of the conductive mesh used for the conductive layer include a fiber mesh obtained by metal coating a synthetic fiber or metal fiber mesh, a metal mesh obtained by forming a metal mesh pattern, and the like.

  The conductive layer used in the display filter of the present invention is preferably a conductive layer containing a conductive mesh. The configuration of the conductive layer including the conductive mesh corresponds to, for example, an aspect in which the entire conductive layer is configured in a mesh pattern, or an image display region of the display when a display filter having the conductive layer is installed in the display. A mode in which the portion of the conductive layer is formed of a mesh pattern and the portion of the conductive layer corresponding to the outer periphery (non-image display region) is formed of a solid metal portion is exemplified.

  As a method for forming a conductive film by forming a conductive layer including a conductive mesh on the substrate (A), a known method can be used. For example, 1) A method of printing a conductive ink in a pattern on the substrate (A). 2) Method of performing plating after pattern printing with ink containing catalyst core of plating, 3) Method of using conductive fiber, 4) Method of patterning after bonding metal foil on base material (A) with adhesive 5) A method of patterning after forming a metal thin film on the substrate (A) by vapor deposition or plating, 6) a method using a photosensitive silver salt, and 7) a method of laser ablating the metal thin film. However, it is not limited to these.

  The manufacturing method of the electroconductive film which has an electroconductive layer containing said electroconductive mesh is demonstrated in detail.

  1) The method of printing conductive ink in a pattern on the substrate (A) is to print the conductive ink in a pattern on the substrate (A) by a known printing method such as screen printing or gravure printing. Is the method.

  2) The method of performing plating after pattern printing with ink containing catalyst nuclei for plating is, for example, printing on the substrate (A) in a pattern using a catalyst ink made of a palladium colloid-containing paste, In this method, electroless copper plating is performed by immersion in an electrolytic copper plating solution, followed by electrolytic copper plating, and further by electrolytic plating of a Ni-Sn alloy to form a conductive mesh pattern.

  3) The method using conductive fibers is a method in which a knitted fabric made of conductive fibers is bonded to the base material (A) via an adhesive or an adhesive.

  4) The method of patterning after bonding a metal foil on the base material (A) with an adhesive is the method of patterning the metal foil (copper, aluminum, nickel, etc.) on the base material (A) via an adhesive or an adhesive. Then, after the metal foil is bonded together, a resist pattern is produced using a photolithography method or a screen printing method, and then the metal foil is etched. As a method for forming the above resist pattern, a photolithography method is preferable, and the photolithography method is a method of applying a photosensitive resist on a metal foil or laminating a photosensitive resist film, adhering a pattern mask, and exposing, This is a method of forming an etching resist pattern by developing with a developing solution, and further eluting metals other than the pattern portion with an appropriate etching solution to form a desired conductive mesh.

  5) A method of patterning after forming a metal thin film on the substrate (A) by vapor deposition or plating is performed by using a metal thin film (copper, aluminum, silver, gold, palladium, indium on the substrate (A). , Tin, or a metal made of an alloy of silver and other metals) is formed by vapor deposition such as vapor deposition, sputtering, ion plating, or plating, and this metal thin film is formed by photolithography or screen. This is a method of etching a metal thin film after preparing a resist pattern using a printing method or the like. As a method of forming the above resist pattern, a photolithography method is preferable, and the photolithography method is a method of applying a photosensitive resist on a metal thin film or laminating a photosensitive resist film, adhering a pattern mask, and exposing, This is a method of forming an etching resist pattern by developing with a developing solution, and further eluting metals other than the pattern portion with an appropriate etching solution to form a desired conductive mesh. In this method, it is preferable to form a metal thin film on a transparent substrate without using an adhesive or a pressure-sensitive adhesive.

  6) In the method using a photosensitive silver salt, a silver salt emulsion layer such as silver halide is coated on the substrate (A), and after photomask exposure or laser exposure, development processing is performed to form a silver mesh. There is a way. The formed silver mesh is preferably further plated with a metal such as copper or nickel. This method is described in WO 2004/7810, JP-A 2004-221564, JP-A 2006-12935, and the like, and can be referred to.

  7) The method of laser ablating a metal thin film is a method of producing a metal thin film mesh pattern by laser ablation of a metal thin film formed on a substrate (A) in the same manner as in 5) above.

  Laser ablation means that when a solid surface that absorbs laser light is irradiated with laser light with a high energy density, the bonds between the irradiated parts are broken and evaporated, causing the solid surface of the irradiated part to break. It is a phenomenon that is cut away. By utilizing this phenomenon, the solid surface can be processed. Since laser light is highly straight and condensing, it is possible to selectively process a fine area about 3 times the wavelength of the laser light used for ablation, and high processing accuracy is obtained by the laser ablation method. I can do it.

  The laser used for such ablation can be any laser having a wavelength that is absorbed by the metal. For example, a gas laser, a semiconductor laser, an excimer laser, or a solid laser using a semiconductor laser as an excitation light source can be used. A second harmonic light source (SHG), a third harmonic light source (THG), or a fourth harmonic light source (FHG) obtained by combining these solid-state lasers and a nonlinear optical crystal can be used.

  Among such solid-state lasers, an ultraviolet laser having a wavelength of 254 nm to 533 nm is preferably used from the viewpoint of not processing a plastic film. Among them, it is preferable to use a solid-state laser SHG (wavelength 533 nm) such as Nd: YAG (neodymium: yttrium, aluminum, garnet), more preferably a solid laser THG (wavelength 355 nm) ultraviolet laser such as Nd: YAG. .

  As a laser oscillation method, any type of laser can be used. From the viewpoint of processing accuracy, a pulse laser is preferably used, and a Q-switch type pulse laser having a pulse width of ns or less is more preferable.

  It is preferable to laser ablate the metal thin film and the metal oxide layer after further forming a 0.01 to 0.1 μm metal oxide layer on the metal thin film (viewing side). As the metal oxide, metal oxides such as copper, aluminum, nickel, iron, gold, silver, stainless steel, chromium, titanium, and tin can be used. However, copper oxide is used from the viewpoint of price and film stability. preferable. As a method for forming the metal oxide, a vacuum deposition method, a sputtering method, an ion plate method, a chemical vapor deposition method, an electroless method, an electrolytic plating method, or the like can be used.

  Among the above-described methods for producing a conductive layer including a conductive mesh, a conductive mesh having a relatively small thickness (for example, a conductive mesh having a thickness of 8 μm or less) can be easily produced, and high electromagnetic shielding properties are ensured. From the viewpoint of being able to do so, the above production methods 2), 5), 6) and 7) are preferably used. Moreover, since the manufacturing cost of a conductive mesh is low, the manufacturing method of said 5) is used especially preferable.

  The production method 5) will be described in more detail.

  As a method for forming a metal thin film on the substrate (A), a vapor deposition method is preferred. Examples of the vapor deposition method include sputtering, ion plating, electron beam vapor deposition, vacuum vapor deposition, and chemical vapor deposition. Among these, sputtering and vacuum vapor deposition are preferable. As a metal for forming a metal thin film, an alloy or a multilayer of one or more of metals such as copper, aluminum, nickel, iron, gold, silver, stainless steel, chromium and titanium is used. can do. Among these, copper is preferably used from the viewpoints of obtaining good electromagnetic shielding properties, easy mesh pattern processing, and low cost.

  Moreover, when using copper as a metal of a metal thin film, it is preferable to further use a nickel thin film with a thickness of 5 to 100 nm between the base material (A) and the copper thin film. Thereby, the adhesiveness of the film which is a base material (A), and a copper thin film improves. In addition, the thickness of the electroconductive mesh in such an aspect shall mean the sum total thickness of a nickel thin film layer and a copper thin film layer.

  As a method for forming a resist pattern on the metal thin film, photolithography is preferably used. In such a photolithography method, a photosensitive resist layer is laminated on a metal thin film, the resist layer is exposed to a mesh pattern, developed to form a resist pattern, and then the metal thin film is etched to form a mesh pattern. In this method, the resist layer on the mesh is peeled and removed.

  As the photosensitive resist layer, a negative resist in which the exposed portion is cured or a positive resist in which the exposed portion is dissolved by development can be used. The photosensitive resist layer may be coated and laminated directly on the metal thin film, or a film made of a photoresist may be bonded. As a method for exposing the photoresist layer, there can be used a method of exposing with an ultraviolet ray or the like through a photomask, or a method of directly scanning and exposing using a laser.

  Etching methods include chemical etching methods. Chemical etching is a method in which a metal other than a metal portion protected by a resist pattern is dissolved and removed with an etching solution. Examples of the etching solution include a ferric chloride aqueous solution, a cupric chloride aqueous solution, and an alkaline etching solution.

  The conductive layer including the conductive mesh according to the present invention is preferably blackened. By applying a blackening treatment, reflection from the viewer side and reflection from the display side due to the metallic luster of the conductive mesh can be reduced, and further reduction in image visibility can be reduced. An excellent display filter can be obtained.

  The pitch of the conductive mesh in the conductive layer including the conductive mesh is preferably in the range of 50 to 500 μm, more preferably in the range of 75 to 450 nm, and still more preferably in the range of 100 to 350 μm. If the pitch of the conductive mesh is smaller than 50 μm, the transmittance tends to decrease. If the pitch is larger than 500 μm, the conductivity tends to decrease, which is not preferable. Here, the pitch of the conductive mesh is the interval between the portions where the conductive mesh does not exist (opening portions surrounded by the thin lines of the conductive mesh). Specifically, the center of gravity of one opening portion, The distance between the center of gravity of the opening and the center of gravity of the adjacent opening sharing one side.

  The line width of the conductive mesh in the conductive layer including the conductive mesh is preferably in the range of 3 to 30 μm, and more preferably in the range of 5 to 20 μm. When the line width of the conductive mesh is smaller than 3 μm, the electromagnetic shielding property tends to be lowered. On the other hand, when the line width is larger than 30 μm, the transmittance tends to be lowered.

  The shape of the mesh pattern of the conductive mesh (the shape of the opening) is, for example, a lattice mesh pattern formed of a quadrangle such as a square, a rectangle, or a rhombus, a triangle, a pentagon, a hexagon, an octagon, or a dodecagon. Examples thereof include a mesh pattern made of a polygon, a mesh pattern made of a circle and an ellipse, a mesh pattern made of the composite shape, and a random mesh pattern. Among these, a lattice mesh pattern made of a tetragon and a mesh pattern made of a hexagon are preferable, and a regular mesh pattern is more preferably used.

  The display filter of the present invention has the above-described conductive film and a specific pressure-sensitive adhesive layer (1). It is important that the specific pressure-sensitive adhesive layer (1) contains a resin having a hydroxyl group and / or a carboxy group. In the following description, unless otherwise noted, the pressure-sensitive adhesive layer means the pressure-sensitive adhesive layer (1).

  The display filter of the present invention includes a substrate (conductive) that constitutes a glass plate (display panel of display) or a filter for display by containing a resin having a hydroxyl group and / or a carboxy group in the adhesive layer (1). It is a base material different from the base material (A) in a film, for example, the adhesiveness of the base material (B) mentioned later, a base material (C)), and an adhesive layer (1) becomes favorable.

  The pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group according to the present invention is formed of a pressure-sensitive adhesive cured by irradiating an active energy ray-curable composition with active energy rays. preferable. Here, active energy rays refer to energy rays such as ultraviolet rays, visible rays, electromagnetic waves such as infrared rays, and radiations such as electron beams. Among these, ultraviolet rays are preferably used from the viewpoint of production equipment and production process. Moreover, an active energy ray hardening-type composition points out the composition which a chemical reaction occurs and hardens | cures by irradiating the said active energy ray.

  As the resin used for the active energy ray-curable composition, known resins are used. For example, acrylic resins, urethane resins, polyester resins, silicone resins, rubber resins and the like can be mentioned. Among these resins, acrylic resins and urethane resins are preferable, and urethane resins are particularly preferable.

  The resin constituting the pressure-sensitive adhesive layer (1) may have 1) a hydroxyl group and / or carboxy group in the molecule in advance, or 2) a hydroxyl group in the molecule in the curing process by irradiation with active energy rays. And / or a carboxy group introduced therein, or 3) a combination of the two. Preferably, as the resin constituting the pressure-sensitive adhesive layer (1), a resin having at least a hydroxyl group and / or a carboxy group in the molecule in the above 1) is used.

  Examples of the resin having a hydroxyl group and / or a carboxy group in the molecule in 1) above include a polymer having a hydroxyl group and / or a carboxy group at the terminal and / or side chain of the molecule. Preferred is a polymer having a hydroxyl group and / or a carboxy group at least at one or both ends of the molecule, and more preferred is a polymer having a hydroxyl group and / or a carboxy group at only one or both ends of the molecule. The polymer may be a polymerizable prepolymer (including an oligomer).

  In the case of introducing a hydroxyl group and / or a carboxy group into the resin molecule during the curing process by active energy ray irradiation in 2) above, a polymerizable prepolymer and a polymerizable monomer having a hydroxyl group and / or a carboxy group are used. What is necessary is just to make it contain in an active energy ray hardening-type composition.

  When combining the two aspects 1) and 2) of 3) above, (i) a polymer having a hydroxyl group and / or a carboxy group in the molecule in advance, and a hydroxyl group and / or carboxy in the molecule in advance. Active energy ray curing of at least one selected from the group consisting of a polymerizable prepolymer having a group, (ii) a polymerizable prepolymer, and (iii) a polymerizable monomer having a hydroxyl group and / or a carboxy group What is necessary is just to make it contain in a type | mold composition (that is, (i), (ii), and (iii) are contained in an active energy ray hardening-type composition).

  The above-mentioned polymerizable prepolymer having a hydroxyl group and / or a carboxy group is a polymer having a hydroxyl group and / or a carboxy group and further having an ethylenically unsaturated group in the molecule. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

  Examples of the active energy ray-curable composition using an acrylic resin include a composition containing an acrylic polymer having a hydroxyl group and / or a carboxy group in a molecule, a polymerizable monomer and / or a polymerizable oligomer, and a polymerization initiator. Can be mentioned. Hereinafter, each component suitable for the active energy ray-curable composition using an acrylic resin will be described.

  Examples of the acrylic polymer having a hydroxyl group and / or a carboxy group in the molecule include a monomer of (meth) acrylic acid ester (acrylic acid ester, methacrylic acid ester) and a monomer having a carboxyl group and / or a hydroxyl group. A polymerized acrylic polymer can be mentioned. The amount of the acrylic polymer having a hydroxyl group and / or a carboxy group in the molecule in the active energy ray curable composition is preferably in the range of 10 to 80% by mass with respect to 100% by mass of the active energy ray curable composition, The range of 20-60 mass% is more preferable.

  Furthermore, in addition to the acrylic polymer having a hydroxyl group and / or a carboxy group in the molecule, a polymerizable acrylic prepolymer having an ethylenically unsaturated group in the side chain can be used. The amount of the polymerizable acrylic prepolymer having an ethylenically unsaturated group in the side chain ranges from 5 to 500 parts by mass with respect to 100 parts by mass of the acrylic polymer having a hydroxyl group and / or a carboxy group in the molecule. The range of 10 to 300% by mass is more preferable.

  The weight average molecular weight of the acrylic polymer having a hydroxyl group and / or carboxy group in the molecule and the polymerizable acrylic prepolymer having an ethylenically unsaturated group in the side chain is preferably in the range of 10,000 to 500,000. The range of 10,000 to 400,000 is more preferable.

  The use amount of the acrylic polymer having a hydroxyl group and / or carboxy group in the molecule and the polymerizable acrylic prepolymer having an ethylenically unsaturated group in the side chain is an active energy ray curable type which is a raw material of the pressure-sensitive adhesive layer. The range of 30-95 mass% is preferable with respect to 100 mass% of compositions.

  Examples of the polymerizable monomer include 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl hexahydroisophthalic acid, 2- (meth) acryloyloxyethyl hexahydroterephthalic acid, 2 -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl isophthalic acid, 2- (meth) acryloyloxyethyl terephthalic acid, 2- (meth) acryloyloxyethyl succinic acid, (meth) Acrylate, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, 2- Hydroxyethyl (meth) a Modified caprolactone, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, glycidol di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl acid phosphate Fate, phenyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, cyclohexyl (meth) acrylate, cyclononyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclododecyl (meth) acrylate Rate, cyclostearyl (meth) acrylate, cyclolauryl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) Acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, tricyclodecal (meth) acrylate, cyclopropyl (meth) acrylate, cyclobutyl (meth) Acrylate, cyclopentyl (meth) acrylate, bisphenol A type ethylene oxide addition (meth) acrylate, water bisphenol A type Eth Examples include lenoxide added (meth) acrylate, divinylbenzene, vinyl adipate, and vinyl acrylate. Among these, monofunctional (meth) acrylate compounds are preferably used.

  Examples of the polymerizable oligomer include urethane oligomers, polyether oligomers, polyester oligomers, polycarbonate oligomers, and polybutadiene oligomers.

  The amount of the polymerizable monomer and / or polymerizable oligomer used (the total amount of both when the polymerizable monomer and the polymerizable oligomer are used together) is 100% by mass of the active energy ray-curable composition using an acrylic resin. And the range of 1-30 mass% is preferable, and the range of 2-20 mass% is more preferable.

  Examples of the polymerization initiator include acetophenones such as diethoxyacetophenone and benzyldimethyl ketal, benzoin ethers such as benzoin and benzoin methyl ether, benzophenones such as benzophenone and methyl o-benzoylbenzoate, and 1-hydroxy-cyclohexyl- Examples thereof include hydroxyalkylphenones such as phenyl-ketone, thioxanthones such as 2-isopropylthioxanthone and 2,4-dimethylthioxanthone, and amines such as triethanolamine and ethyl 4-dimethylbenzoate.

  The amount of the polymerization initiator used is suitably in the range of 0.05 to 5% by mass with respect to 100% by mass of the active energy ray-curable composition using an acrylic resin.

  As described above, an active energy ray-curable composition using a urethane resin is particularly preferably used as the pressure-sensitive adhesive layer. Hereinafter, the active energy ray-curable composition using a urethane resin will be described.

  As the urethane resin used in such a composition, a urethane polymer (A1) having a hydroxyl group and / or a carboxy group in the molecule or a urethane prepolymer (A2) having a hydroxyl group and / or a carboxy group in the molecule is preferable. Here, the urethane prepolymer (A2) means a polymerizable polymer, more specifically, a polymer having an ethylenically unsaturated group in the molecule. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

  Among the urethane polymers (A1), a urethane polymer having a hydroxyl group and / or a carboxy group at one or both ends of the molecule is preferable, and a urethane polymer having a hydroxyl group and / or a carboxy group at both ends of the molecule is more preferable. A urethane polymer having a hydroxyl group and / or a carboxy group only at both terminals is more preferred.

  Among the urethane prepolymers (A2), a urethane prepolymer having a hydroxyl group and / or a carboxy group at the molecular end is preferable, having a hydroxyl group and / or a carboxy group at one end of the molecule, and having no ethylenic group at the other end. A urethane prepolymer having a saturated group is more preferable, and a urethane prepolymer having a hydroxyl group and / or a carboxy group only at one end of the molecule and an ethylenically unsaturated group only at the other end is more preferable.

  The weight average molecular weight of the urethane polymer (A1) or urethane prepolymer (A2) having a hydroxyl group and / or a carboxy group at the molecular end is preferably in the range of 10,000 to 100,000, more preferably in the range of 2 to 80,000. The range of 2 to 50,000 is particularly preferable.

  The urethane polymer (A1) having a hydroxyl group and / or a carboxy group in the molecule and the urethane prepolymer (A2) having a hydroxyl group and / or a carboxy group in the molecule are collectively referred to as a urethane prepolymer (A) hereinafter. That's it.

  In the active energy ray-curable composition containing a urethane resin, a urethane prepolymer (B) having an ethylenically unsaturated group at the molecular end is used as another urethane resin in combination with the urethane prepolymer (A). It is preferable.

  Examples of the urethane prepolymer (B) include urethane prepolymers having an ethylenically unsaturated group at one or both ends of the molecule, but urethane prepolymers having an ethylenically unsaturated group at both ends of the molecule are preferred. Used. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group. The weight average molecular weight of the urethane prepolymer is preferably in the range of 10,000 to 100,000, more preferably in the range of 2 to 80,000, and particularly preferably in the range of 2 to 50,000.

  The use ratio of the urethane prepolymer (A) and the urethane prepolymer (B) is preferably in the range of 9: 1 to 1: 9, more preferably 8: 2 to 2: 8 in terms of mass ratio. As a result, it is possible to form a pressure-sensitive adhesive layer that has good adhesion to the substrate of the display panel or display filter and is excellent in impact resistance.

  The amount of the urethane resin used in the active energy ray-curable composition is preferably in the range of 30 to 95% by mass, more preferably in the range of 40 to 95% by mass, particularly 50 to 50% with respect to 100% by mass of the composition. A range of 95% by mass is preferred.

  The urethane prepolymer (A) can be obtained, for example, by reacting an isocyanate group of a urethane prepolymer having an isocyanate group at a molecular terminal with a polyvalent carboxylic acid, an oxycarboxylic acid, or a polyhydric alcohol.

  The urethane prepolymer (B) includes, for example, an isocyanate group of a urethane prepolymer having an isocyanate group at a molecular end and a functional group capable of reacting with the isocyanate group (for example, a hydroxyl group, a carboxyl group, an amino group, an amide). Group) and a compound having a (meth) acrylate group can be obtained.

  The urethane prepolymer having an isocyanate group at the molecular end can be synthesized by reacting a polyol and an isocyanate compound. Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol. Among these, polyester polyol, polyether polyol, and polycaprolactone polyol are preferable.

  The polyester polyol can be obtained by esterifying a polyvalent carboxylic acid and a polyhydric alcohol. Such polycarboxylic acids include adipic acid, sebacic acid, succinic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, fumaric acid, maleic acid, maleic anhydride, itacone Examples include acids, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, lactic acid, dimer acid, and the like. Of these, adipic acid, sebacic acid, pyrrolimetic acid, and dimer acid are preferable.

  Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, polyethylene glycol, polybutylene glycol, polypropylene glycol, 1,4-butanediol, 1,6 -Hexanediol, 3-methyl 1,5-pentanediol, ethylene oxide or propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc. can be used. Bifunctional alcohols such as 4-butanediol are preferred.

  The polyether polyol can be obtained by an etherification reaction of a polyhydric alcohol. As a polyhydric alcohol used here, the thing similar to the polyhydric alcohol used for manufacture of the said polyester polyol can be used.

  The polycaprolactone polyol is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, ethylene oxide of bisphenol A, or Examples include propylene oxide adducts, glycerin, trimethylolpropane, trimethylolethane, and ε-caprolactone adducts of known and commonly used polyhydric alcohols such as pentaerythritol.

  Examples of the polycarbonate polyol include a dehydrochlorination reaction between the polyhydric alcohol and phosgene used in the synthesis of the polyester polyol, or a transesterification reaction between the polyhydric alcohol and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What is obtained is mentioned.

  Isocyanate compounds used for the synthesis of urethane prepolymers having an isocyanate group at the molecular end include tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate. And diisocyanate compounds such as xylene diisocyanate and hydrogenated xylylene diisocyanate.

  As a urethane prepolymer which has an isocyanate group in the molecular terminal used for the synthesis | combination of a urethane prepolymer (A) and a urethane prepolymer (B), what has an isocyanate group in the both terminal of a molecule | numerator is preferable.

  As described above, the urethane prepolymer (A) can be obtained by reacting an isocyanate group of a urethane prepolymer having an isocyanate group at a molecular terminal with a polyvalent carboxylic acid, an oxycarboxylic acid, or a polyhydric alcohol. Examples of polycarboxylic acids, oxycarboxylic acids and polyhydric alcohols used here are as follows.

  Examples of the polyvalent carboxylic acid include adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, and fumaric acid. , Maleic acid, maleic anhydride, itaconic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, dimer acid, ethane-1,1,2-tricarboxylic acid, hexane-2,3,5 -Known and commonly used organic acids such as tricarboxylic acids are preferably used, but dicarboxylic acids are preferred from the standpoint of compatibility with other components.

  As said oxycarboxylic acid, well-known and usual organic acids, such as lactic acid, glycolic acid, trioxybutyric acid, trioxyvaleric acid, trioxyhexanoic acid, gluconic acid, are used suitably, for example.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, polyethylene glycol, polybutylene glycol, polypropylene glycol, and 1,3-butanediol. 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, bisphenol A ethylene oxide or propylene oxide adduct, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc. A polyhydric alcohol can be preferably used. Among them, diols such as 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol are preferable from the viewpoint of compatibility with other components and water absorption stability. Particularly preferred.

  As described above, the urethane prepolymer (B) includes an isocyanate group of a urethane prepolymer having an isocyanate group at a molecular end and a functional group capable of reacting with the isocyanate group (for example, a hydroxyl group, a carboxyl group, an amino group, an amide group). Etc.) and a compound having a (meth) acrylate group can be obtained by using a functional group capable of reacting with an isocyanate group used herein (for example, a hydroxyl group, a carboxyl group, an amino group, an amide). Examples of compounds having a group or the like) and a (meth) acrylate group are given below.

  Examples of the compound having a functional group capable of reacting with the isocyanate group and a (meth) acrylate group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and butanediol mono (meth) acrylate. , 2-hydroxyethyl (meth) acrylate modified with caprolactone, glycidol di (meth) acrylate, hydroxyl group-containing (meth) acrylate such as pentaerythritol tri (meth) acrylate, (meth) acrylic acid, carboxyethyl (meth) acrylate , Carboxyl group-containing (meth) acrylates such as carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, and amino group-containing (meta) such as N, N-diethylaminoethyl (meth) acrylate Amide group-containing (meth) acrylates such as acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide Etc. Among these, a hydroxyl group-containing (meth) acrylate compound is particularly preferably used.

  In the present invention, the urethane prepolymer (C) obtained by simultaneously synthesizing the urethane prepolymer (A) and the urethane prepolymer (B) in one synthesis process may be used as the urethane resin. preferable.

  For example, the urethane prepolymer (C) reacts with an isocyanate group with at least one selected from polycarboxylic acid, oxycarboxylic acid and polyhydric alcohol in the urethane prepolymer having an isocyanate group at the molecular end described above. It can be obtained by reacting a functional group that can be obtained and a compound having a (meth) acrylate group simultaneously. As the compound having a functional group capable of reacting with a polyvalent carboxylic acid, oxycarboxylic acid, polyhydric alcohol, or isocyanate group and a (meth) acrylate group, the same compounds as described above are used.

  In the urethane prepolymer (C), the urethane prepolymer (A2) having a hydroxyl group and / or a carboxy group at one end of the molecule and an ethylenically unsaturated group at the other end, and At least the urethane prepolymer (B) having an ethylenically unsaturated group at both ends of the molecule is included. The urethane polymer (A1) having a hydroxyl group and / or a carboxy group at both molecular ends can be included by adjusting the synthesis method.

  In the urethane prepolymer (C), the molecular terminal acrylate ratio is preferably 50 to 90% of all terminals of all urethane molecules. The molecular terminal acrylate ratio is a charge ratio of a compound having at least one selected from polyvalent carboxylic acid, oxycarboxylic acid, and polyhydric alcohol, a functional group capable of reacting with an isocyanate group, and a (meth) acrylate group. It can be prepared by adjusting, or by adjusting the charging sequence and charging time.

  The molecular terminal acrylate ratio can be calculated from the acid value or hydroxyl value and molecular weight obtained by determining the acid value or hydroxyl value of the urethane prepolymer (C) by a titration method or the like.

  In the active energy ray-curable composition using a urethane resin, it is preferable to use a (meth) acrylate compound or a vinyl compound as a polymerizable monomer.

  Examples of the polymerizable monomer include 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl hexahydroisophthalic acid, 2- (meth) acryloyloxyethyl hexahydroterephthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl isophthalic acid, 2- (meth) acryloyloxyethyl terephthalic acid, 2- (meth) acryloyloxyethyl succinic acid, (meta ) Acrylate, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, 2 -Hydroxyethyl (me ) Caprolactone modified product of acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, glycidol di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl acid Phosphate, phenyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, cyclononyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclododecyl (meth) Acrylate, cyclostearyl (meth) acrylate, cyclolauryl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) Acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, tricyclodecal (meth) acrylate, cyclopropyl (meth) acrylate, cyclobutyl (meth) Acrylate, cyclopentyl (meth) acrylate, bisphenol A type ethylene oxide addition (meth) acrylate, water bisphenol A Type ethylene oxide addition (meth) acrylate, divinylbenzene, vinyl adipate, vinyl acrylate and the like. Among these, monofunctional (meth) acrylate compounds are preferably used. In particular, a monofunctional (meth) acrylate compound having a hydroxyl group or a carboxy group is used from the viewpoint of introducing a hydroxyl group or a carboxy group into the urethane resin during the curing process of the active energy ray-curable composition using the urethane resin. Preferably used.

  The amount of the polymerizable monomer described above is preferably in the range of 1 to 50% by mass and preferably in the range of 2 to 30% by mass with respect to 100% by mass of the active energy ray-curable composition using a urethane resin.

  Moreover, the usage-amount of the monofunctional (meth) acrylate compound which has said hydroxyl group or carboxy group is 2-2 with respect to 100 mass parts of total amounts of the urethane prepolymer (A2) and urethane prepolymer (B) mentioned above. The range of 20 parts by mass is preferable, and the range of 3 to 15 parts by mass is particularly preferable.

  The active energy ray-curable composition using a urethane resin preferably further contains a polymerization initiator. Commercially available products can be widely used as such polymerization initiators, but the following polymerization initiators are preferably used. For example, acetophenone series such as diethoxyacetophenone and benzyldimethyl ketal, benzoin ether series such as benzoin and benzoin methyl ether, benzophenone series such as benzophenone and methyl o-benzoylbenzoate, and hydroxy such as 1-hydroxy-cyclohexyl-phenyl-ketone Examples include alkylphenones, thioxanthones such as 2-isopropylthioxanthone and 2,4-dimethylthioxanthone, and amines such as triethanolamine and ethyl 4-dimethylbenzoate.

  The amount of the polymerization initiator used is suitably in the range of 0.05 to 5% by mass with respect to 100% by mass of the active energy ray-curable composition using a urethane resin.

  The active energy ray-curable composition such as the active energy ray-curable composition using the urethane resin and the active energy ray-curable composition using the acrylic resin are substantially free of an organic solvent. The solvent-free type is preferable, and a solvent-free urethane-based ultraviolet curable composition is more preferable. Here, that the active energy ray-curable composition does not substantially contain an organic solvent means that the amount of the organic solvent contained in 100% by mass of the active energy ray-curable composition is 5% by mass or less. The amount of the organic solvent is preferably 3% by mass or less, more preferably the amount of the organic solvent is 1% by mass or less, and particularly preferably no organic solvent is contained.

  The organic solvent is a highly volatile organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene, butyl acetate, ethanol, and methanol, and particularly an organic solvent having a boiling point of 130 ° C. or less.

  The organic solvent does not include a liquid polymerizable monomer (for example, a low-molecular acrylate monomer used as a reactive diluent).

  By making the above-mentioned active energy ray-curable composition non-solvent type, safety and environmental performance in the production process are improved, and the residual solvent in the pressure-sensitive adhesive layer (1) can be greatly reduced.

  In order to prevent yellowing, the pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group of the present invention preferably contains an antioxidant or a light stabilizer.

  As the antioxidant, a hindered phenol antioxidant and a phosphorus antioxidant are preferably used. As the light stabilizer, a monomer having a sterically hindered piperidyl group and an ethylenically unsaturated group is preferably used.

  Examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene-bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], isooctyl-3- 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], N, N′-hexamethylenebis ( 3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, diethyl [(3 5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl] phosphate, 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate-diethyl ester, 3,3 ′, 3 ″ , 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, 1,1,3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 1,3,5- Tris (4-sec-butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 1,3,5-tris (4-neopentyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 2,2 ′ -Methylenebis (4 -Methyl-6-t-butylphenol), 4,4'-butylidenebis (4-methyl-6-t-butylphenol), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, polycondensate of p-chloromethylstyrene and p-cresol, polycondensate of p-chloromethylstyrene and divinylbenzene, p -An isobutylene reaction product of cresol and divinylbenzene polycondensate, and the like.

  Among the above compounds, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene-bis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], isooctyl-3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate compounds such propionate are preferably used.

  Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyl octyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tetrakis (2, 4-di-t-butylphenyl) -4,4'-biphenylene phosphite, trisnonylphenyl phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphos Phyto, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4- Dicumylphenyl) pentaerythrito Ru-diphosphite, tetrakis (2,4-di-t-butylphenyl) (1,1-biphenyl) -4,4'-diylbisphosphonite, di-t-butyl-m-cresyl-phosphonite, distearyl penta Erythritol diphosphite, di (2,4-di-t-butylphenyl) -pentaerythryl diphosphite, di (2,6-di-t-butyl-4-methylphenyl) -pentaerythryl diphosphite 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-ditridecyl) phosphite, cyclic neopentanetetrayl (octadecyl phosphite), diisodecyl pentaerythritol diphosphite, 2,2-methylene bis (4,6-di-t-butylphenyl) octyl phosphite, bis (tridecyl ) Pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra ( Tridecyl) -4,4′-isopropylidene diphenyl diphosphite, tetraphenyl dipropylene glycol diphosphite and the like.

  Among these, triphenyl phosphites such as triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyl octyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and diphenyl alkyl phosphite. Phytes and monophenyl dialkyl phosphites are preferably used.

  A monomer having a sterically hindered piperidyl group and an ethylenically unsaturated group that can be used in the present invention will be described. The sterically hindered piperidyl group in such a monomer is one having 1 to 2 alkyl groups at the 2-position and 6-position of the piperidyl group, respectively. The ethylenically unsaturated group is an acryl group (acryloyl group), A methacryl group (methacryloyl group), a crotonoyl group, a vinyl group, an allyl group, etc., and an ethylenically unsaturated group is directly or directly at the 1-position and / or 4-position of a sterically hindered piperidyl group, or a linking group such as an oxygen atom or imino group It is a compound bound via

  Monomers having a sterically hindered piperidyl group and an ethylenically unsaturated group that are preferably used in the present invention can be represented by the following general formulas (1) and (2).

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{2 to} R ⁵ each independently represents an alkyl group having 1 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or a cyano group. R ⁷ and R ⁸ each independently represents a hydrogen atom or a methyl group, and X ¹ represents an oxygen atom or an imino group.)

(Wherein R ^{12 to} R ¹⁵ each independently represents an alkyl group having 1 to 4 carbon atoms, R ¹⁶ represents a hydrogen atom or a cyano group, and R ^{17 to} R ²⁰ each independently represents a hydrogen atom or methyl) And X ² represents an oxygen atom or an imino group.)
Examples of the compound represented by the general formula (1) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6. -Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4 -Cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2 , 6,6-tetramethylpiperidine and the like.

  Examples of the compound represented by the general formula (2) include 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4. -Cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like.

  Among the compounds described above, the compound represented by the general formula (1) is preferable, and 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1, 2,2,6,6-pentamethylpiperidine is preferably used.

  Resin having a hydroxyl group and / or a carboxy group in each content ratio of the hindered phenol antioxidant, the phosphorus antioxidant, and the monomer having a sterically hindered piperidyl group and an ethylenically unsaturated group The range of 0.05-5 mass% is preferable with respect to 100 mass% of all the components (an organic solvent is not included) of the adhesive layer (1) containing A, and each content ratio is 0.1-3 mass%. A range is more preferred.

  A plasticizer can be added to the pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group according to the present invention, if necessary. Such plasticizers include benzyl benzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, dibutyl benzyl phthalate, dioctyl phthalate Phthalic acid compounds such as butyl phthalyl butyl glycolate, diisobutyl adipate, diisononyl adipate, diisodecyl adipate, dibutoxyethyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, etc. Sebacic acid compounds such as triethylene phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresylphenyl phosphate, dioctyl sebacate, methylacetylricinolate Any fatty acid compound, epoxy compound such as diisodecyl-4,5-epoxytetrahydrophthalate, trimellit such as tributyl trimellitic acid, tri-2-ethylhexyl trimellitic acid, tri-n-octyl trimellitic acid, triisodecyl trimellitic acid Examples include acid compounds, butyl oleate, chlorinated paraffin, polyoxypropylene glycol, polyoxytetramethylene glycol, polybutene, and polyisobutylene.

  The amount of the plasticizer used is preferably in the range of 1 to 30% by mass with respect to 100% by mass of all components (not including the organic solvent) of the pressure-sensitive adhesive layer (1).

  Furthermore, various polymerization inhibitors can be added to the pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group according to the present invention, if necessary. As such a polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, 2,6-dibutyl-4-methylphenol and the like can be used.

  Moreover, various additives other than the above, for example, antioxidants, antifoaming agents, leveling agents, light stabilizers, ultraviolet absorbers, anti-coloring agents, pigments, and the like can be used as necessary.

  The thickness of the pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group according to the present invention is 100 μm or more. The thickness of the pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group of the present invention is preferably larger from the viewpoint of improving impact resistance, but the upper limit of the thickness of the pressure-sensitive adhesive layer (1). Is preferably 2000 μm or less, more preferably 1500 μm or less, in consideration of productivity such as application suitability, curing speed, and visibility of the display image on the display.

  In the display filter of the present invention, the pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group is disposed so as not to contact the substrate (A) and the conductive layer constituting the conductive film. The

  As described above, when a resin having a hydroxyl group and / or a carboxy group is used for the pressure-sensitive adhesive layer (1), the pressure-sensitive adhesive layer (1) is in direct contact with the conductive layer constituting the conductive film. As a result, the pressure-sensitive adhesive layer (1) changes color over time. Here, the indirect contact between the conductive layer and the pressure-sensitive adhesive layer (1) is a mode in which the pressure-sensitive adhesive layer (1) is in contact with a member that has been in contact with the conductive layer in advance. There are such aspects of 1), 2) and 3).

  1) In the production process of forming a conductive layer on a base material (A), after forming a conductive layer on one surface of the long base material (A), the base material (A ) And the conductive layer are in contact with each other, and the component of the conductive layer may be transferred to the opposite surface of the substrate (A). When the pressure-sensitive adhesive layer (1) is laminated on the opposite surface of the base material (A) in the subsequent process, the problem of discoloration as described above may occur.

  2) After laminating other layers (for example, an easy-adhesion layer, an intermediate layer, a near-infrared shielding layer, a color tone adjustment layer, etc.) in advance on one surface of the substrate (A) of the conductive film, the substrate (A) When the conductive layer is formed on the other side of the film, it may be wound into a roll shape, as in the case described above, the other layer and the conductive layer may be in contact with each other, and the component of the conductive layer may be transferred to the other layer. In the same manner as above, discoloration of the pressure-sensitive adhesive layer (1) may occur.

  3) Even when the other layer is laminated on the other surface of the conductive film having the conductive layer formed on one surface of the substrate (A), the same problem as described above also occurs when the film is wound into a roll. It can happen.

  As described above, in the present invention, it is important to dispose the pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group so as not to contact the conductive layer directly or indirectly. The agent layer (1) is disposed so as not to contact the base material (A) and the conductive layer. Here, the base material (A) includes those in which other layers are laminated on the base material (A) as in the above-described aspects 2) and 3).

  As one of the preferable embodiments of the display filter of the present invention, a laminate (AB) in which a laminate (B) in which an adhesive layer (1) is laminated on a substrate (B) and a conductive film are laminated. The aspect containing is mentioned. The positional relationship between the laminate (B) and the conductive film in the laminate (AB) is arranged in the order of the pressure-sensitive adhesive layer (1), the substrate (B), the substrate (A), and the conductive layer. The laminate (B) and the conductive film are laminated.

  In the laminated body (AB), the base material (B) and the base material (A), that is, the laminated body (B) and the conductive film are adhesive layers having a thickness of about 5 to 50 μm made of an adhesive or an adhesive. Can be stacked.

  In the laminate (AB), a functional layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, and an antifouling function is further provided on the conductive layer side of the conductive film. It is preferable that they are arranged directly or via a substrate such as a plastic film. The above-described one in which the functional layer is disposed on the conductive layer side of the conductive film is referred to as a laminate (A). That is, the laminate (A) is a configuration in which the substrate (A), the conductive layer, and the functional layer are arranged in this order.

  In the display filter in which the laminate (A) and the laminate (B) are bonded, the pressure-sensitive adhesive layer (1) provided in the laminate (B) is disposed in the outermost layer of the display filter. Thus, the display filter can be used as an adhesive layer for adhering to a display panel of a display.

  In the above aspect, when the pressure-sensitive adhesive layer (1) is disposed on the outermost layer of the display filter, and the display filter is directly attached to the display panel of the display via the pressure-sensitive adhesive layer (1). The adhesiveness with the display panel is preferably good.

  Further, as another preferred embodiment of the display filter of the present invention, a laminate (C) in which an adhesive layer (2) having a thickness of 5 μm or more and less than 100 μm is laminated on the substrate (AB) on the laminate (AB). ) Is further laminated.

  The laminate (C) and laminate (AB) in this embodiment are the pressure-sensitive adhesive layer (2), the base material (C), the pressure-sensitive adhesive layer (1), the base material (B), the base material (A), and the conductive layer. The stacked body (C) and the stacked body (AB) are stacked so as to be arranged in this order. Here, the pressure-sensitive adhesive layer (2) of the laminate (C) is for affixing the display filter to the display panel of the display.

  In the aspect in which the laminate (C) is laminated on the laminate (AB), the conductive film is further selected from the antireflection function, the antiglare function, the hard coat function, and the antifouling function on the conductive layer side of the conductive film. It is preferable to use a laminate (A) in which a functional layer having at least one function is laminated directly or via a substrate such as a plastic film. That is, the laminate (2), the base material (C), the pressure sensitive adhesive layer (1), the base material (B), the base material (A), the conductive layer, and the functional layer are arranged in this order. C) and an embodiment in which the laminate (AB) having the laminate (A) are laminated are preferable.

  As each base material (namely, base material (B), base material (C)) used for said laminated body (A), laminated body (B), and laminated body (C), the above-mentioned conductive film is used. The same substrate (A) is used.

  Said aspect WHEREIN: The adhesive layer (1) containing the resin which has a hydroxyl group and / or carboxy group of this invention is a base material (B) of a laminated body (B), and a base material (C) of a laminated body (C). The adhesion strength with the base material is preferably higher to some extent. Specifically, the adhesion strength (to the glass plate) is preferably 3 N / 25 mm or more, and more preferably 4 N / 25 mm or more. Particularly preferred is 5 N / 25 mm or more. The upper limit of the adhesion strength is preferably 30 N / 25 mm or less, and more preferably 25 N / mm or less, since the impact resistance decreases when the adhesion strength of the pressure-sensitive adhesive layer (1) is too high.

  Moreover, in the said aspect, it is preferable that the adhesive strength of the adhesive layer (2) used for a laminated body (C) has favorable adhesiveness with a display panel.

  The functional layer constituting the laminate (A) 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. Such a functional layer may be directly formed on the conductive layer of the conductive film, or a functional film base (D) in which the functional layer is previously laminated on a base (D) such as a plastic film. You may laminate | stack the side and the conductive layer side of an electroconductive film via the contact bonding layer which consists of an adhesive or an adhesive agent whose thickness is about 5-50 micrometers. Moreover, you may laminate | stack the near-infrared shielding layer or the color tone adjustment layer on the surface opposite to the electroconductive layer of the said base material (A) of the said electroconductive film, or the function of the base material (D) of a functional film. A near-infrared shielding layer or a color tone adjusting layer may be laminated on the surface opposite to the layer. In this case, it is preferable to provide a color tone adjusting function to the near-infrared shielding layer.

  Furthermore, instead of laminating a near-infrared shielding layer or a color tone adjusting layer on one surface of the conductive film or functional film, a near-infrared shielding layer or a color tone adjusting layer is formed on a substrate (E) such as a plastic film. The laminated near-infrared shielding film (color tone adjusting film) is disposed between the conductive film and the functional film, and laminated through an adhesive layer made of an adhesive or adhesive having a thickness of about 5 to 50 μm. May be. In this case, it is preferable to provide a color tone adjusting function to the near-infrared shielding layer of the near-infrared shielding film.

Below, some of the structural examples of the filter for display concerning this invention are illustrated.
a) Adhesive layer (1) / Substrate (B) / Adhesive layer / Near-infrared shielding layer / Conductive film (= Substrate (A) / Conductive layer) / Functional layer b) Adhesive layer (1) / Group Material (B) / Adhesive layer / Near-infrared shielding layer / Conductive film (= Substrate (A) / Conductive layer) / Adhesive layer / Functional film (= Substrate (D) / Functional layer)
c) Adhesive layer (1) / Substrate (B) / Adhesive layer / Conductive film (= Substrate (A) / Conductive layer) / Adhesive layer / Near-infrared shielding layer / Functional film (= Substrate (D) ) / Functional layer)
d) Adhesive layer (1) / Substrate (B) / Adhesive layer / Conductive film (= Substrate (A) / Conductive layer) / Adhesive layer / Near-infrared shielding film (= Near-infrared shielding layer / Substrate ( E)) / adhesive layer / functional film (= base material (D) / functional layer)
e) Adhesive layer (2) / Substrate (C) / Adhesive layer (1) / Substrate (B) / Adhesive layer / Near-infrared shielding layer / Conductive film (= Substrate (A) / Conductive layer) / Functional layer f) Adhesive layer (2) / Base material (C) / Adhesive layer (1) / Base material (B) / Adhesive layer / Near-infrared shielding layer / Conductive film (= Base material (A) / Conductive layer) / adhesive layer / functional film (= base material (D) / functional layer)
g) Adhesive layer (2) / Substrate (C) / Adhesive layer (1) / Substrate (B) / Adhesive layer / Conductive film (= Substrate (D) / Conductive layer) / Adhesive layer / Near Infrared shielding layer / functional film (= base material (D) / functional layer)
h) Adhesive layer (2) / Substrate (C) / Adhesive layer (1) / Substrate (B) / Adhesive layer / Conductive film (= Substrate (A) / Conductive layer) / Adhesive layer / Near Infrared shielding film (= near infrared shielding layer / base material (E) / adhesive layer / functional film (= base material (D) / functional layer)
In the above configuration example, the near-infrared shielding layer preferably has a color tone adjustment function. Among the above configuration examples, the configurations c), d), g), and h) are preferable. Furthermore, in the above configuration example, the thickness of the base material (D) on which the functional layer is formed is preferably 150 μm or more and 250 μm or less, and the thickness of all other base materials is preferably 50 μm or more and less than 150 μm.

  Hereinafter, the functional layer, the near-infrared shielding layer, and the color tone adjusting layer constituting the preferred embodiment of the display filter of the present invention will be described.

  As described above, the functional layer has at least one function selected from an antireflection function, an antiglare function, a hard coat function, and an antifouling function. This functional layer is preferably provided on the outermost surface on the viewing side (viewing side) when the display filter is attached to the display panel of the display. Such a functional layer may be a single layer or a plurality of layers, or may be a layer having a plurality of functions.

  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.

  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. Further, an organic material such as metal oxide fine particles having a refractive index of about 1.6 to 3 such as titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, Examples thereof include zinc antimonate, tin oxide-doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide, gallium-doped zinc oxide, and fluorine-doped tin oxide.

  The thickness of the high refractive index layer is preferably in the range of 0.01 to 20 μm, and more preferably in the range of 0.05 to 10 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, an inorganic material such as MgF ₂ , CaF ₂ , and SiO _2. It can be composed of a system material. The thickness of the low refractive index layer is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.02 to 0.5 μm.

  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, particles are dispersed in a thermosetting resin or a photocurable resin and applied and cured on a support, or a thermosetting resin or a photocurable resin is applied to the surface. For example, a mold having a desired surface state and pressed to form an unevenness and then cured can be used. The antiglare layer preferably has a haze value (JIS K 7136: 2000) of 0.5 to 20%. The thickness of the antiglare layer is preferably from 0.01 to 20 μm.

  The layer having a hard coat function (hard coat layer) is a layer provided for preventing scratches. The hard coat layer preferably has high hardness, and the surface hardness of the hard coat layer can be expressed by pencil hardness defined by JIS K5600-5-4 (1999), and the surface on the side where the hard coat layer is provided. The pencil hardness can be evaluated by scratching the surface of another functional layer (if another functional layer is provided on the hard coat layer) directly with a pencil. In the present invention, the pencil hardness of the surface on which the hard coat layer is provided is preferably 1H to 9H, and more preferably 2H to 9H.

  For the hard coat layer, acrylic resin, urethane resin, melamine resin, epoxy resin, organic silicate compound, silicone resin, or the like can be used. 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.

  As for the thickness of a hard-coat layer, 0.1-20 micrometers is preferable, More preferably, it is 1-10 micrometers. When the thickness of the hard coat layer is less than 0.1 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 20 μm, the cured film tends to be cracked due to stress such as bending.

  The hard coat layer can be given a function as a high refractive index layer constituting the antireflection layer described above. The refractive index of the hard coat layer can be increased by adding metal oxide fine particles having a high refractive index.

  The antifouling layer (antifouling layer) prevents or prevents the adhesion of greasy substances and dust and dirt from the environment due to human touching the surface of the display filter. It is a layer to do. As the antifouling layer, for example, a fluorine coating agent, a silicon 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.

When the functional layer is composed of a single layer, it preferably has a plurality of functions, which will be exemplified below.
a) Antireflection hard coat layer b) Antiglare hard coat layer c) Antiglare antireflection layer.

Moreover, it is also preferable that the functional layer is composed of a plurality of layers, and a plurality of functional layers are exemplified below. In the following plural configurations, the layers described on the right side are arranged on the viewing side (the layers described on the left side are arranged on the display panel side).
d) hard coat layer / high refractive index layer / low refractive index layer e) high refractive index hard coat layer / low refractive index layer f) hard coat layer / antiglare layer g) hard coat layer / antiglare antireflection layer h ) High refractive index hard coat layer / low refractive index layer / antifouling layer i) Hard coat layer / high refractive index layer / low refractive index layer / antifouling layer j) Antiglare high refractive index hard coat layer / low refractive index Layer k) Antiglare hard coat layer / high refractive index layer / low refractive index layer l) Antiglare hard coat layer / antifouling layer.

  The near-infrared shielding layer is a layer that shields near-infrared rays generated from the display. The near-infrared shielding layer can be formed by applying and drying a paint in which a near-infrared absorber is dispersed or dissolved in a resin binder. As a near-infrared absorber, known organic absorbers such as phthalocyanine compounds, anthraquinone compounds, dithiol compounds, diimonium compounds, or tungsten oxide fine particles or composite tungsten oxides described in JP-A No. 2006-154516 Known inorganic absorbents such as fine particles can be used.

  The color tone adjusting layer 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 a tetraazaporphyrin dye is preferably used as the dye that absorbs orange light.

  As the color tone adjusting layer, a layer containing a dye that absorbs light of the above-described wavelength may be provided, or the dye may be contained in the near infrared shielding layer.

  Examples will be specifically described below, but the present invention is not limited to these examples.

<Synthesis of polyurethane resin>
First, a urethane prepolymer (a) having an isocyanate group at the molecular end was synthesized as follows.

<Synthesis of urethane prepolymer (a) having an isocyanate group at the molecular terminal>
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, “EXENOL 3020” [polypropylene glycol (number average molecular weight 3200) manufactured by Asahi Glass Urethane Co., Ltd.] 97.98 parts by mass, dilauric acid 0.11 part by mass of dibutyltin was charged.

  Next, the temperature inside the system was raised to 70 ° C. while blowing nitrogen gas, and after uniformly dissolving, 8.65 parts by mass of isophorone diisocyanate was added, and the temperature was kept stirring for 3 hours. As a result of GPC measurement every 30 minutes, The ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) was confirmed to be constant at 1.5, and the reaction was terminated to obtain a urethane prepolymer (a) having an isocyanate group at the molecular end. It was.

<Synthesis of urethane polymer (A1) having a hydroxyl group at the molecular terminal>
200 parts by mass of the urethane prepolymer (a) above was charged into a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen introduction tube, and then the temperature of the system was raised to 70 ° C. while blowing nitrogen gas. Then, 2.6 parts by mass of 3-butanediol was added, and the mixture was kept warm (70 ° C.) with stirring, and the reaction was terminated after confirming that the isocyanate group had completely disappeared by IR measurement. The urethane prepolymer (A1) (Weight average molecular weight 24000) was obtained.

<Synthesis of urethane prepolymer (B) having an ethylenically unsaturated group at the molecular terminal>
200 parts by mass of the above urethane prepolymer (a) was charged into a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, and then the system was heated to 80 ° C. to give 2-hydroxyethyl acrylate 3 .69 parts by mass and 0.22 parts by mass of hydroquinone monomethyl ether were added, and the mixture was kept warm (80 ° C.) with stirring. After confirming that the isocyanate group had completely disappeared by IR measurement, the reaction was terminated and a urethane prepolymer ( B) (weight average molecular weight 24000) was obtained.

<Synthesis of urethane prepolymer (AB)>
In a flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, “Exenol 3020” [polypropylene glycol (number average molecular weight 3200) manufactured by Asahi Glass Urethane Co., Ltd.] 97.98 parts by mass, dibutyltin dilaurate 0.11 part by mass was charged. Next, the temperature inside the system was raised to 70 ° C. while blowing nitrogen gas, and after uniformly dissolving, 8.65 parts by mass of isophorone diisocyanate was added, and the temperature was kept while stirring for 3 hours. Thereafter, while blowing oxygen gas and nitrogen gas, 0.42 parts by mass of 1,3-butanediol and 1.27 parts by mass of 2-hydroxyethyl acrylate were added, and the mixture was kept warm for 3 hours while measuring the molecular weight every 30 minutes. As a result, the ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) was confirmed to be constant at 1.5, and the reaction was terminated, and the urethane prepolymer (AB) (weight average molecular weight 24000). Got. The acrylate end ratio was 70%. The urethane prepolymer (AB) includes a urethane polymer (A1) having a hydroxyl group at both molecular ends, a urethane prepolymer (A2) having a hydroxyl group at one end of the molecule and an ethylenically unsaturated group at the other end. And urethane prepolymer (B) having an ethylenically unsaturated group at both ends of the molecule.

<Measurement of weight average molecular weight>
The weight average molecular weights of the urethane polymer (A1), urethane prepolymer (B) and urethane prepolymer (AB) synthesized above were measured by GPC. For measurement, WALTERS GPC-150CPplus (manufactured by Japan WALTERS) was used under the following conditions.
Detector: WALTERS 2410
・ Solvent: Tetrahydrofuran ・ Column: 2 HR4, 1 HR4E (7.5 mm × 300 mm)
・ Temperature: 40 ℃
・ Concentration: 0.2%
・ Injection volume: 100 μl
Flow velocity: 1.0m / m
-N number: 3.

<Acrylate terminal ratio>
The acrylate terminal ratio of the urethane prepolymer (AB) is based on JISK-1557, the hydroxyl value is calculated by dissolving the resin in chloroform, adding acetic anhydride and titrating with KOH, and the hydroxyl value and the weight average molecular weight. From this, the acrylate end ratio was calculated.

Example 1
First, a pressure-sensitive adhesive layer (1) containing a resin having a hydroxyl group and / or a carboxy group of the present invention was formed on a substrate (B) (PET film) as follows.

<Preparation of UV curable composition>
35 parts by mass of the urethane polymer (A1), 55 parts by mass of the urethane prepolymer (B), 10 parts by mass of 4-hydroxybutyl acrylate as a reactive diluent (polymerizable monomer), and dibutyl phthalate as a plasticizer. UV curable composition by adding 2 parts by mass and 0.5 parts by mass of hydroxyalkylphenone photopolymerization initiator (Ciba Geigy, Irgacure 184, hereinafter referred to as IC184) as a polymerization initiator and mixing them uniformly. Was prepared.

<Preparation of pressure-sensitive adhesive layer (1a)>
As the base material (B), a PET film having a thickness of 100 μm (Lumirror manufactured by Toray Industries, Inc .; registered trademark) was used, and the UV curable composition was applied onto the base material with a slit die coater. (Metal halide lamp) was irradiated (irradiated with an integrated light amount of 1600 mJ / cm ² ) to form an adhesive layer having a thickness of 500 μm. Furthermore, on the surface of this pressure-sensitive adhesive layer, a release film having a thickness of 75 μm (Celape (registered trademark) MD manufactured by Toray Film Processing Co., Ltd.) was laminated, and the base material (B) / pressure-sensitive adhesive layer (1a) / A release film laminate (b1) was obtained.

<Production of functional film>
The following hard coat layer, high refractive index layer, and low refractive index layer are sequentially laminated on one side of the substrate (D) (PET film having a thickness of 188 μm (Lumirror manufactured by Toray Industries, Inc.)). A film was obtained. The dry thickness of each layer is 5 μm for the hard coat layer, 0.1 μm for the high refractive index layer, and 0.1 μm for the low refractive index layer.

<Hard coat layer>
A commercially available hard coat agent (Opstar (registered trademark) Z7534 manufactured by JSR Corporation; solid content concentration 60% by mass) is diluted with methyl ethyl ketone so that the solid content concentration is 45% by mass. It was. This coating solution was applied with a micro gravure coater, dried at 100 ° C., and then cured by irradiation with ultraviolet rays of 1.0 J / cm ² to form a hard coat layer.

<High refractive index layer>
A commercially available high refractive index / antistatic coating (Opstar (registered trademark) TU4005 manufactured by JSR Corporation) was diluted with isopropyl alcohol to a solid content concentration of 8% to obtain a coating solution for a high refractive index layer. This coating liquid is applied with a micro gravure coater, dried at 100 ° C., and then cured by irradiation with ultraviolet light 1.0 J / cm ² to form a high refractive index layer having a refractive index of 1.65 on the hard coat layer. Formed.

<Low refractive index layer>
A commercially available coating for a low refractive index layer (Opstar (registered trademark) TU2180, manufactured by JSR Corporation) was diluted with methyl isobutyl ketone so that the solid content concentration was 3% by mass to obtain a coating solution for a low refractive index layer. . This coating solution is applied with a micro gravure coater, dried at 100 ° C., and then cured by irradiation with ultraviolet light 1.0 J / cm ² to form a low refractive index layer having a refractive index of 1.37 on the high refractive index layer. Formed.

<Formation of near-infrared shielding layer>
The near-infrared shielding layer (near-infrared absorption) which has an orange light shielding function on the surface opposite to the functional layer of the base material (D) of the functional film obtained above (that is, the surface on the base material (D) side) A layer in which a paint obtained by mixing an acrylic resin with a phthalocyanine dye and a diimonium dye as an dye and a tetraazaporphyrin dye as an orange light absorbing dye in an acrylic resin is provided. The functional film provided with the near-infrared shielding layer was obtained.

<Preparation of conductive film>
On one side of the substrate (A) (100 μm-thick PET film (Lumirror manufactured by Toray Industries, Inc.)), a nickel layer (thickness) by vacuum deposition under a vacuum of 3 × 10 ⁻³ Pa at room temperature. 0.02 μm) was formed. Further, a copper layer (thickness: 2.5 μm) was formed thereon by a vacuum vapor deposition method at a room temperature and under a vacuum of 3 × 10 ⁻³ Pa. Thereafter, a photoresist layer is applied and formed on the surface of the copper layer, and the photoresist layer is exposed and developed through a mask having a lattice mesh pattern. Then, an etching process is performed, and the line width is 13 μm and the pitch is 300 μm. A conductive layer having a grid-like conductive mesh was produced. Further, the conductive layer was blackened (oxidized). Thus, after the conductive layer was formed on the base material (A), it was wound up in a roll shape.

<Preparation of display filter>
The laminate (b1) produced above, the functional film provided with the near infrared shielding layer, and the conductive film are cut into sheets of a predetermined size, and first, the near infrared of the functional film provided with the near infrared shielding layer. The laminate (a1) was obtained by pasting with a commercially available acrylic pressure-sensitive adhesive (thickness 25 μm) so that the surface of the shielding layer and the surface of the conductive layer of the conductive film face each other. Next, the substrate of the laminate (b1) having the pressure-sensitive adhesive layer (1a) of the present invention faces the conductive film side of the laminate (a1) (the substrate (A in the laminate (a1)). And a substrate (B) in the laminate (b1) face each other) and a commercially available acrylic pressure-sensitive adhesive (thickness 25 μm) to obtain a display filter of the present invention.

<Evaluation>
About the display filter produced above, discoloration of the pressure-sensitive adhesive layer (1a), impact resistance, and adhesion to a glass plate were evaluated as follows. The results are shown in Table 1.

<Discoloration of adhesive layer>
The display filter was allowed to stand in an environment of 60 ° C. to 90% (RH) for 7 days, and then the state of discoloration of the pressure-sensitive adhesive layer was visually observed and evaluated according to the following criteria.
○: No discoloration.
X: There is discoloration.

<Evaluation of impact resistance>
The release filter laminated | stacked on the adhesive layer (1a) was peeled, and the display filter was bonded on the 1.3-mm-thick soda glass. While changing the height from above vertically, a steel ball having a diameter of 38 mm and a weight of about 229 g was freely dropped, and the height at the time of glass breakage was evaluated according to the following criteria.
A: No breakage at a height of 45 cm.
○: No breakage at a height of 30 cm, and breakage at 45 cm.
X: It was damaged at a height of 30 cm.

<Adhesion>
The laminate (b1) is cut to a width of 25 mm, the release film is peeled off, and a 5 kg rubber roller is reciprocated once on the glass plate, followed by pressure bonding. A 180 ° peel test was conducted at 25 ° C. at a peel rate of 300 mm / min, and the adhesion strength between the glass plate and the pressure-sensitive adhesive layer (1a) was measured.
A: Good adhesion strength and good.
X: Adhesive strength is low and peels easily.

(Example 2)
In preparation of the pressure-sensitive adhesive layer (1a) of Example 1, 90 parts by mass of the urethane prepolymer (AB) was used instead of the urethane polymer (A1) and the urethane prepolymer (B) used for the preparation of the ultraviolet curable composition. A UV curable composition was prepared in the same manner as in Example 1 except that it was used, and the pressure-sensitive adhesive layer (1b) was placed on the substrate (B) in the same manner as in Example 1 except that this UV curable composition was used. And a laminate (b2) was produced in the same manner as in Example 1.
<Preparation of display filter>
A display filter was produced in the same manner as in Example 1 except that the laminate (b2) was used in place of the laminate (b1) in Example 1.

(Example 3)
In the production of the pressure-sensitive adhesive layer (1a) of Example 1, the pressure-sensitive adhesive layer (1c) was formed on the substrate (B) in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed to 400 μm. Further, a laminate (b3) was produced in the same manner as in Example 1.
<Preparation of display filter>
A display filter was produced in the same manner as in Example 1 except that the laminate (b3) was used in place of the laminate (b1) in Example 1.

Example 4
In the production of the pressure-sensitive adhesive layer (1a) of Example 1, the pressure-sensitive adhesive layer (1d) was formed on the substrate (B) in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed to 250 μm. Further, a laminate (b4) was produced in the same manner as in Example 1.
<Preparation of display filter>
A display filter was produced in the same manner as in Example 1 except that the laminate (b4) was used in place of the laminate (b1) in Example 1.

(Example 5)
In the production of the pressure-sensitive adhesive layer (1a) of Example 1, the pressure-sensitive adhesive layer (1e) was formed on the substrate (B) in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed to 1000 μm. Further, a laminate (b5) was produced in the same manner as in Example 1.
<Preparation of display filter>
A display filter was produced in the same manner as in Example 1 except that the laminate (b5) was used in place of the laminate (b1) in Example 1.

(Comparative Example 1)
In the production of the pressure-sensitive adhesive layer (1a) of Example 1, it was carried out except that a release film having a thickness of 75 μm (Cerape (registered trademark) MD manufactured by Toray Film Processing Co., Ltd.) was used instead of the base material (B). A pressure-sensitive adhesive layer (1f) was formed in the same manner as in Example 1, and a release film / pressure-sensitive adhesive layer (1f) / release film laminate (b6) was obtained in the same manner as in Example 1.
<Preparation of display filter>
In the same manner as in Example 1, on the conductive film side of the laminate (a1) prepared by laminating a functional film having a near-infrared shielding layer and a conductive film, one of the laminates (b6) above The release film was peeled off and the pressure-sensitive adhesive layer (1f) was bonded to produce a display filter.

(Comparative Example 2)
In the same manner as in Example 1, a functional film and a conductive film provided with a near-infrared shielding layer were produced. A commercially available acrylic pressure-sensitive adhesive so that the surface of the near-infrared shielding layer of the functional film provided with the near-infrared shielding layer faces the surface opposite to the conductive layer of the conductive film (that is, the substrate (A) surface). The laminated body (a2) was obtained by pasting with (thickness 25 μm). Next, one release film of the laminate (b6) produced in the same manner as in Comparative Example 1 is peeled off from the surface of the conductive layer on the conductive film side of the laminate (a2), and the pressure-sensitive adhesive layer (1f ) Surfaces were bonded together to obtain a display filter.

(Comparative Example 3)
In the production of the pressure-sensitive adhesive layer (1a) of Example 1, the pressure-sensitive adhesive layer (1 g) was formed on the substrate in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed to 75 μm, and further implementation was performed. A laminate (b7) was produced in the same manner as in Example 1.
<Preparation of display filter>
A display filter was produced in the same manner as in Example 1 except that the laminate (b7) was used in place of the laminate (b1) in Example 1.

(Comparative Example 4)
In preparation of the pressure-sensitive adhesive layer (1a) of Example 1, 90 parts by mass of the urethane prepolymer (B) was used instead of the urethane polymer (A1) and the urethane prepolymer (B) used for the preparation of the ultraviolet curable composition. In addition, an ultraviolet curable composition was prepared in the same manner as in Example 1 except that 10 parts by mass of 2-ethylhexyl (meth) acrylate was used instead of 10 parts by mass of 4-hydroxybutyl acrylate. A pressure-sensitive adhesive layer (1h) was formed on the substrate (B) in the same manner as in Example 1 except that the composition was used, and a laminate (b8) was produced in the same manner as in Example 1.
<Preparation of display filter>
A display filter was produced in the same manner as in Example 1 except that the laminate (b8) was used in place of the laminate (b1) in Example 1.

(Comparative Example 5)
In the production of the pressure-sensitive adhesive layer (1h) of Comparative Example 4, instead of the base material (B), a release film having a thickness of 75 μm (Toray Film Processing Co., Ltd., Cerapeel (registered trademark) MD) was used. A pressure-sensitive adhesive layer was formed in the same manner as in Example 4, and a release film / pressure-sensitive adhesive layer (1h) / release film laminate (b9) was obtained in the same manner as in Comparative Example 4.
<Preparation of display filter>
In the same manner as in Example 1, on the conductive film side of the laminate (a1) prepared by laminating the functional film provided with the near-infrared shielding layer and the conductive film, one of the laminate (b9) above. The release film was peeled off and the pressure-sensitive adhesive layer (1h) was bonded to produce a display filter.

(Example 6)
In the same manner as in Example 1, the laminate (a1) and the laminate (b1) were bonded to obtain a laminate (ab). On the other hand, a laminate in which an adhesive layer (2a) (an acrylic adhesive having a thickness of 25 μm) is laminated on a substrate (C) (a PET film having a thickness of 100 μm (Lumirror manufactured by Toray Industries, Inc.)). (C1) was produced.

  The pressure-sensitive adhesive layer (2a with respect to the pressure-sensitive adhesive layer (1a) side of the laminate (ab) and the substrate (C) surface of the laminate (c1) (the substrate (C) of the laminate (c1)) ) Was bonded so that the surface opposite to the surface on the side having) faced to produce a display filter.

<Evaluation>
About the display filter of Example 2-6 and Comparative Example 1-5, in the same manner as in Example 1, discoloration, impact resistance, and adhesion of the pressure-sensitive adhesive layer were evaluated. The results are shown in Table 1. Table 2 shows configurations of Examples and Comparative Examples.

  From the result of Table 1, since the Example of this invention uses the adhesive layer (1) containing resin (urethane-type resin) which has a hydroxyl group and / or a carboxy group in a molecule | numerator, it is a glass surface (display panel). And the adhesiveness of the display filter to the base material is good and the thickness of the pressure-sensitive adhesive layer (1) is 100 μm or more, the impact resistance is good. Since it arrange | positions so that a material and an adhesive layer (1) may not contact, it turns out that discoloration has not arisen in the adhesive layer (1).

  On the other hand, the comparative example 1 is arrange | positioned so that the base material of an electroconductive film and an adhesive layer (1) may contact, and discoloration has arisen in the adhesive layer (1).

  The comparative example 2 is arrange | positioned so that the conductive layer of an electroconductive film and an adhesive layer (1) may contact, and discoloration has arisen in the adhesive layer (1).

  Since the thickness of the adhesive layer (1) is less than 100 micrometers (75 micrometers), the comparative example 3 is inferior in impact resistance.

  Since Comparative Example 4 does not use a resin having a hydroxyl group and / or a carboxy group as the resin for the pressure-sensitive adhesive layer, the adhesion to the display panel (glass plate) is poor.

  Although the comparative example 5 is arrange | positioned so that it may contact with the base material of an electroconductive film, since the resin which has a hydroxyl group and / or a carboxy group is not used as resin of an adhesive layer, discoloration arises in an adhesive layer. Not. However, the adhesion with the display panel (glass plate) is poor.

Claims (6)

A conductive film having a conductive layer on a substrate (A), and a display filter having a pressure-sensitive adhesive layer (1),
The pressure-sensitive adhesive layer (1) contains a resin having a hydroxyl group and / or a carboxy group, and has a thickness of 100 μm or more.
The display-use filter, wherein the pressure-sensitive adhesive layer (1) is disposed so as not to contact the substrate (A) and the conductive layer. The display filter has a laminate (B) in which a pressure-sensitive adhesive layer (1) is laminated on a substrate (B), and a laminate (AB) in which a conductive film is laminated,
The positional relationship between the laminate (B) and the conductive film in the laminate (AB) is characterized in that the adhesive layer (1), the substrate (B), the substrate (A), and the conductive layer are arranged in this order. The display filter according to claim 1. The display filter further includes a laminate (C) in which a pressure-sensitive adhesive layer (2) having a thickness of 5 μm or more and less than 100 μm is laminated on the substrate (C),
Laminate (C) and laminate (AB) are arranged in the order of pressure-sensitive adhesive layer (2), base material (C), pressure-sensitive adhesive layer (1), base material (B), base material (A), and conductive layer. The display filter according to claim 2, wherein the display filter is laminated.   On the conductive layer side of the conductive film, a functional layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, and an antifouling function is disposed directly or via a substrate. The display filter according to any one of claims 1 to 3.   The display-use filter according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive layer (1) is obtained by curing the active energy ray-curable composition.   The display-use filter according to claim 5, wherein the active energy ray-curable composition is a solventless urethane-based ultraviolet curable composition.