TW201726854A - Adhesive layer with separator, optical film with adhesive layer with separator, image display device and method for manufacturing the same - Google Patents

Abstract

To provide an adhesive layer with a separator and an optical film with an adhesive layer with a separator, which can prevent problems of a liquid crystal panel such as uneven brightness due to bright spots by suppressing elution of oligomer included in a substrate film such as a polyester film used for a separator into the adhesive layer, and which can suppress white unevenness of a liquid crystal panel even when a RTP (roll-to-panel) bonding step is applied in manufacturing a liquid crystal display device. An adhesive layer with a separator has an adhesive layer on a separator, in which the separator has a release layer on a substrate film, and has an oligomer prevention layer and a conductive layer between the substrate film and the release layer, and the adhesive layer is disposed on the release layer of the separator. An optical film with the adhesive layer with the separator is also provided.

Description

Adhesive layer with spacer, optical film with adhesive layer attached to spacer, image display device and manufacturing method thereof

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive layer with a spacer and an optical film with a spacer layer attached to the spacer. The present invention relates to an optical film comprising the adhesive layer with a spacer attached thereto, and an image display device in which the adhesive layer side of the optical film with the adhesive layer in the state of the release spacer is bonded to the display panel and the manufacture thereof method.

As the optical film, a surface-treated film such as a polarizing film, a retardation film, an optical compensation film, a brightness enhancement film, or an antireflection film, and a laminate of these films can be used. The optical film with the adhesive layer obtained by peeling the spacer from the optical film with the adhesive layer of the spacer is used in an image display device such as a liquid crystal display device, an organic EL display device, a CRT, or a PDP.

Background Art An optical film such as a polarizing film is used in an image display device such as a liquid crystal display device. When the optical film is bonded to a display panel such as a liquid crystal panel, a binder is usually used. Since there is no need to perform a drying step for bonding the optical film, an optical film having an adhesive layer in which an adhesive is provided as an adhesive layer on the side of the optical film is usually used. In addition, the optical film with the adhesive layer is generally used for the purpose of protecting the adhesive layer before bonding, and is provided as a spacer (also referred to as a release film or a release liner) on the surface of the adhesive layer. Fabrication of an optical film with a layer of adhesive attached to the spacer.

The optical film having the adhesive layer with a spacer attached thereto is dissolved in the adhesive layer by the oligomer contained in the base film such as the polyester film in the spacer, and uneven brightness due to the bright spot is caused. In the case of a poor condition of the liquid crystal panel, Patent Document 1 proposes to provide an oligomer blocking layer on the spacer.

Further, in the production of the liquid crystal display device, when the spacer of the optical film having the adhesive layer with the spacer attached is peeled off, static electricity (peeling electrification) is generated in the optical film and the spacer to which the adhesive layer is attached. When an optical film having an electrostatic adhesive layer is attached to the liquid crystal panel, induction charging is generated in the liquid crystal panel. The inductively charged electric charge affects the alignment of the liquid crystal of the liquid crystal panel, which may result in uneven display of the image. In addition, static electricity may cause a problem such as product failure due to adhesion or introduction of foreign matter or the like at the manufacturing site.

In Patent Documents 2 to 4, in order to suppress the occurrence of static electricity, an adhesive sheet having an adhesive layer which imparts an antistatic interference function by blending an ionic compound or a conductive polymer into a binder layer has been proposed. Further, Patent Document 5 proposes a spacer which imparts an antistatic interference function to the release layer of the spacer. Advanced technical literature

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 5: JP-A-2014-141557

Disclosure of the Invention Problems to be Solved by the Invention However, when the spacer of Patent Document 5 or the optical film having the adhesive layer with a spacer attached thereto is used, the occurrence of static electricity at the time of peeling of the spacer cannot be sufficiently suppressed. In particular, it has been found that an optical film of an adhesive layer which is exposed after peeling off the spacer from the optical film having the adhesive layer with the spacer attached thereto (see FIG. 3) and simultaneously peeling off the spacer is used. When the adhesive layer layer is attached to the liquid crystal panel (Roll-To-Panel (RTP) bonding step), when the liquid crystal display device is manufactured, the optical layer having the adhesive layer with un-attenuated static electricity is attached to the liquid crystal panel. The film is inductively charged. In the subsequent manufacturing step, the inductively charged liquid crystal panel is brought into contact with a dielectric such as a manufacturing machine, whereby a current (magnetic field) is generated in the liquid crystal panel, and white unevenness (light leakage) of the liquid crystal panel is caused by poor alignment of the liquid crystal. ). When white unevenness is generated in the liquid crystal panel, white unevenness is continued until the liquid crystal alignment is restored to the original state, so that the quality inspection in the manufacturing step is delayed, resulting in a problem of deterioration in production efficiency.

An object of the present invention is to provide an adhesive layer with a spacer which can be prevented from being caused by a bright spot by suppressing dissolution of an oligomer contained in a base film such as a polyester film used in a spacer to a binder layer. A poor condition of the liquid crystal panel due to uneven brightness, and in the manufacture of the liquid crystal display device, even if the above-described RTP bonding step is applied, white unevenness of the liquid crystal panel can be suppressed, and a spacer attached thereto is also provided. An optical film of the adhesive layer.

Another object of the present invention is to provide an image display device in which an optical film from the adhesive layer with a spacer attached thereto is attached to at least one surface of the display panel, and the spacer is peeled off. The adhesive layer side of the optical film with the adhesive layer is provided, and a method of manufacturing the image display device is also provided. Means for solving problems

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found the following adhesive layer with a spacer, an optical film with an adhesive layer with a spacer attached thereto, an image display device, and a method for manufacturing the same, thereby completing the present invention. invention.

That is, the present invention relates to a pressure-sensitive adhesive layer with a spacer attached to a spacer having a spacer layer on a spacer, wherein the spacer has a release layer on the substrate film. And an oligomer blocking layer and a conductive layer between the substrate film and the release layer, wherein the adhesive layer is provided on the release layer of the spacer.

In the adhesive layer of the spacer of the present invention, it is preferable that the oligomer blocking layer is a layer formed of a composition containing a cerium oxide-based material and/or a polyvinyl alcohol-based resin.

In the adhesive layer of the spacer of the present invention, it is preferable that the conductive layer is a layer formed of a conductive composition containing a conductive polymer.

Preferably, the release layer of the spacer of the present invention has a surface resistance value of 1.0 × 10 ¹² Ω / □ or less.

Preferably, the adhesive layer of the spacer of the present invention is a layer formed of a binder composition containing a base polymer and a conductive compound.

Preferably, the adhesive layer of the spacer of the present invention has a surface resistance value of 1.0 × 10 ¹² Ω / □ or less.

The present invention relates to an optical film having an adhesive layer with a spacer attached thereto, wherein the adhesive layer side of the adhesive layer with the spacer is attached to at least one surface of the optical film.

The present invention relates to an image display device in which an optical film from the adhesive layer with a spacer attached thereto is attached to at least one surface of the display panel, and the adhesive layer in the state of the spacer is peeled off. The adhesive layer side of the optical film.

The present invention relates to a method of manufacturing an image display device, which is characterized in that it comprises a coil preparation step for preparing a long strip of an optical film with an adhesive layer attached to a spacer. a recording material transport preparation step of preparing the display panel to the adhesive position; and a bonding step of extracting the optical film with the adhesive layer attached to the spacer from the web, and The optical film with the adhesive layer with the spacer attached is peeled off by the release body, and the adhesive layer side of the optical film with the adhesive layer exposed after the spacer is peeled off is attached to the carrier. The adhesive position is on the display panel. Effect of the invention

The adhesive layer of the spacer of the present invention has a structure in which an oligomer blocking layer and a conductive layer are laminated between the base film of the separator and the release layer. The oligomer blocking layer can suppress the elution of the oligomer contained in the base film such as the polyester film of the separator to the adhesive layer, and is useful for preventing the unevenness of the liquid crystal panel due to uneven brightness caused by bright spots.

In addition, the side of the adhesive layer of the adhesive layer of the spacer is adhered to the optical film, and the optical film with the adhesive layer attached to the spacer of the present invention has a conductive layer, so the spacer is peeled off. When the static electricity is generated less. On the other hand, when a conductive agent such as a conductive compound is added to the oligomer blocking layer or the release layer, the conductive agent in the oligomer blocking layer and the release layer may interact with the conductive adhesive to cause damage. In the case of the antistatic interference function, in the present invention, by laminating the oligomer blocking layer and the conductive layer, it is possible to impart sufficient conductivity to the surface of the spacer.

Further, the optical film of the present invention having the adhesive layer with a spacer attached to the liquid crystal display device, even when the following steps (RTP bonding step) are applied, that is, from the adhesive with the attached spacer The optical film of the layer is bonded to the liquid crystal panel by the release layer peeling spacer (simultaneously with the peeling), and the adhesive layer layer of the optical film with the adhesive layer exposed after peeling off the spacer, because the spacer has a conductive layer Therefore, it is also possible to suppress the generation of static electricity (peeling electrification), and further, even if static electricity is generated due to peeling of the spacer, the electrostatic charge generated in the optical film with the adhesive layer can be quickly moved to the spacer after peeling. Therefore, it is also possible to attenuate the electrostatic charge, which is useful for suppressing white unevenness of the liquid crystal panel.

Embodiments for Carrying Out the Invention Hereinafter, embodiments of the present invention will be described in detail.

<Overall Structure of Adhesive Layer Attached to Spacer and Optical Film Attached with Adhesive Layer with Spacer> A typical configuration example of the adhesive layer of the spacer of the present invention is schematically shown in Fig. 1(a) And (b). The adhesive layer 2 with a spacer is a form in which the adhesive layer 21 is provided on the release layer 12 of the spacer 1. Further, the spacer 1 is in a form in which the oligomer blocking layer 13 and the conductive layer 14 are provided between the base film 11 and the release layer 12. The order of laminating the oligomer blocking layer 13 and the conductive layer 14 is not limited. However, in the case of (a), since the oligomer blocking layer 13 is in contact with the base film 11, it is suppressed in a substrate such as a polyester film. The effect of dissolving the oligomer-containing polymer into the binder layer is high, and since the conductive layer 14 is in contact with the mold release layer 12, the effect of suppressing white unevenness of the liquid crystal panel is high. In the case of (b), the effect of suppressing the elution of the oligomer into the adhesive layer while maintaining the antistatic interference effect of the entire separator 1 is high. Further, the laminate of the oligomer blocking layer 13 and the conductive layer 14 may be a plurality of layers of the oligomer blocking layer 13 and the conductive layer 14.

A typical configuration example of an optical film to which the adhesive layer of the present invention is attached is shown in Fig. 2. The optical film 3 with the adhesive layer with a spacer attached is formed by bonding the optical film 31 to the adhesive layer 2 of the spacer. From the optical film 3 with the adhesive layer with the spacer attached thereto, the optical film 4 with the adhesive layer attached after peeling the spacer 1 is used by adhering the adhesive layer 21 to a display panel as an adherend.

<Adhesive Layer Attached to Spacer> The adhesive layer of the spacer of the present invention has a structure in which a binder layer is provided on the spacer. The spacer has an oligomer blocking layer and a conductive layer between the substrate film and the release layer.

<Base film> As the base film of the separator of the present invention, a plastic film can be used. Examples of the plastic film include a polyolefin film such as a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, or a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, or the like. Film; polyester film such as polyethylene terephthalate film, polybutylene terephthalate film, polybutylene terephthalate film; and polyurethane film, ethylene-vinyl acetate copolymer Film and the like. In the present invention, in order to prevent elution of the oligomer in the base film, it is preferred to use a polyester film among the base films.

The thickness of the base film is usually 5 to 200 μm, preferably 5 to 100 μm. When the oligomer blocking layer and the conductive layer are formed, the base film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

<Oligomer Prevention Layer> The oligomer blocking layer of the present invention can be formed by preventing an appropriate material from eluting the oligomer contained in the base film such as a polyester film to the adhesive layer. As a material for forming the oligomer blocking layer, an inorganic material, an organic material, or a composite material thereof or the like can be used. Examples of the inorganic material include a cerium oxide-based material or a metal containing an alloy such as gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt or tin, or the like, or an indium oxide. A metal oxide of a mixture of tin oxide, titanium oxide, cadmium oxide or the like, or another metal compound containing iodinated steel or the like. Examples of the organic substance include a polyvinyl alcohol resin, an acrylic resin, a urethane resin, a melamine resin, a UV curable resin, and an epoxy resin. Further, examples of the composite material include a mixture of the organic substance and inorganic particles such as alumina, ceria, and mica.

The oligomer blocking layer is preferably formed of a composition containing a cerium oxide-based material or a polyvinyl alcohol-based resin.

<The cerium oxide-based material> The organic cerium oxide represented by the following general formula (I) is exemplified as the cerium oxide-based material. [Chemical 1]

In the above formula (I), R ¹ and R ² are each independently an epoxy group-containing organic group such as a γ-glycidoxypropyl group or a 3,4-epoxycyclohexylethyl group. Or an alkoxy group such as a methoxy group or an ethoxy group, and R ³ is an alkoxy group such as a methoxy group or an ethoxy group, or a group represented by the following formula (II). n and m are integers from 0 to 10. [Chemical 2]

In the above formula (II), R4 is an epoxy group-containing organic group or alkoxy group which is the same as the R1 group or the R2 group.

Specific examples of the organic decane may, for example, be γ-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2- Monomers such as (3,4-epoxycyclohexyl)ethyltriethoxydecane, 5,6-epoxycyclohexyltriethoxydecane, tetraethoxydecane, and the like or the like A hydrolyzable product (oligomer) of a mixture of monomers.

Further, examples of the cerium oxide-based material include a decane compound having an amine group. The decane compound having an amine group is preferably an alkoxy decane represented by the following formula (III). Y-R-Si-(X) ₃ (III) In the above formula (III), Y represents an amine group, R represents an alkylene group such as a methylene group, an ethylene group or a propylene group, and X represents an A group. An alkoxy group such as an oxy group or an ethoxy group, an alkyl group, or an organic functional group having such a group is at least one or more alkoxy groups.

Specific examples of the decane compound having an amine group include N-β(aminoethyl)γ-aminopropyltrimethoxydecane and N-β(aminoethyl)γ-aminopropyl Triethoxy decane, N-β (aminoethyl) γ-aminopropyl methyl dimethoxy decane, γ-aminopropyl trimethoxy decane, N-phenyl-γ-amino group Propyltrimethoxydecane, and the like.

Further, examples of the cerium oxide-based material include (meth)acryl oxime such as 3-propenyl methoxypropyltrimethoxy decane and 3-methyl propylene oxypropyltriethoxy decane. A decane compound containing an isocyanate group such as a decane compound or a 3-isocyanate propyl triethoxy decane.

Specific examples of the cerium oxide-based material include KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, and KR-213 manufactured by Shin-Etsu Chemical Co., Ltd. KR-217, X-41-1053, X-40-1056, X-41-1805, X-41-1810, X-40-2651, X-40-2652B, X-40-2655A, X-40- 2761, X-40-2672, etc.

The cerium oxide-based material may be used alone or in combination of two or more.

In the oligomer blocking layer formed using the cerium oxide-based material, an organic compound (metal compound such as a metal chelate compound) having a metal element, a catalyst, or the like may be contained as needed. The metal organic compound having a metal element may be used alone or in combination of two or more.

Among the metal organic compounds having a metal element, in particular, from the viewpoint of good dissolution prevention performance of the oligomer, an organic compound having an aluminum element having a chelate structure, an organic compound having a titanium element, and zirconium are preferable. The organic compound of the element. This compound is specifically described in the Handbook of Crosslinking Agents (Mr. Yamashita, Kim Jong-soo, Daisuke Co., Ltd., Dacheng Society, Heisei 2nd Edition).

The formation of the oligomer blocking layer formed using the cerium oxide-based material can be carried out by dissolving the cerium oxide-based material in a solvent such as an alcohol, and applying the resulting solution to a substrate. Film or conductive layer and dry. The concentration of the solution in which the cerium oxide-based material is dissolved is not particularly limited, but is preferably about 0.1 to 40% by weight. The drying temperature after coating is not particularly limited, but is preferably about 100 to 150 °C. Further, the drying time after coating is not particularly limited, but is preferably from about 30 seconds to 30 minutes.

<Composition Containing Polyvinyl Alcohol Resin> The polyvinyl alcohol-based resin may, for example, be polyvinyl alcohol or a derivative thereof. Examples of the derivative of polyvinyl alcohol include polyvinyl formal and polyvinyl acetal, and examples thereof include an olefin such as ethylene or propylene, and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid. And a modified resin such as an alkyl ester or acrylamide. The polyvinyl alcohol-based resin may be used alone or in combination of two or more.

The degree of polymerization of the polyvinyl alcohol-based resin is not particularly limited, but a resin of 100 or more, preferably 300 to 40,000 is usually suitably used. On the other hand, the degree of saponification of the polyvinyl alcohol-based resin is not particularly limited, and a resin of 70 mol% or more, preferably 80 mol% or more, and 99.9 mol% or less is preferably used.

The composition containing the polyvinyl alcohol-based resin may contain a binder polymer. Examples of the binder polymer include polypropylene decylamine, polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starch, polyurethane, polyester, polyacrylate, and chlorine. Polymer (polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyolefin, and the like. In the case where the oligomer blocking layer is applied by a coating stretching method, an organic polymer which can be used as a nonionic, cationic or amphoteric aqueous solution or aqueous dispersion can be mentioned, and Among them, in the case of using a polyurethane, a polyester, or a polyacrylate, the adhesiveness becomes good. By copolymerizing a nonionic, cationic or amphoteric hydrophilic component as a component of the monomer of these polymers, it is possible to impart hydrophilicity and disperse it in water.

The composition containing the polyvinyl alcohol-based resin may contain a crosslinking agent. Examples of the crosslinking agent include a methylolated or hydroxyalkylated urea-based, melamine-based, guanamine-based, acrylamide-based, polyamidamine-based compound, an epoxy compound, an aziridine compound, and a blocked product. Polyisocyanate, decane coupling agent, titanium coupling agent, aluminum zirconium coupling agent, and the like. These cross-linking components can also be pre-bonded to the binder polymer.

In the composition containing the polyvinyl alcohol-based resin, inorganic particles may be contained for the purpose of improving the fixing property and slidability of the oligomer blocking layer. Examples of the inorganic particles include ceria, alumina, kaolin, calcium carbonate, titanium oxide, and barium salts.

The formation of the oligomer blocking layer can be carried out by dissolving the composition containing the polyvinyl alcohol-based resin in a solvent such as water or alcohol, and applying the resulting solution to a substrate film or After the oligomer is prevented from being on the layer, it is dried. In addition, it can also be stretched during drying. The concentration of the solution in which the composition containing the polyvinyl alcohol-based resin is dissolved is not particularly limited, but is preferably about 0.1 to 40% by weight. The drying temperature after coating is not particularly limited, but is preferably about 60 to 200 °C. Further, the drying time after application is not particularly limited, but is preferably about 3 to 60 seconds. Active energy ray irradiation such as heat treatment or ultraviolet irradiation may be used in combination as needed.

The content of the polyvinyl alcohol-based resin in the oligomer-preventing layer is not particularly limited, but is preferably from 10 to 100% by weight, more preferably from 20 to 90% by weight, most preferably from 30 to 80% by weight.

The method for forming the oligomer blocking layer is not particularly limited, and may be appropriately selected depending on the material to be formed, and a coating method, a spray method, a spin coating method, a wire coating method, or the like can be used. Further, a vacuum deposition method, a sputtering method, an ion plating method, a spray pyrolysis method, an electroless plating method, a plating method, or the like can also be used.

The thickness of the oligomer blocking layer is preferably set in the range of 5 to 100 nm, more preferably 10 to 70 nm.

<Conductive Layer> The conductive layer of the present invention can suppress generation of static electricity caused by peeling of the spacer, and even if static electricity is generated due to peeling of the spacer, the electrostatic charge generated in the optical film attached to the adhesive layer can be quickly Since the ground is moved to the peeled spacer, white unevenness of the liquid crystal panel can also be prevented. The conductive layer is not particularly limited as long as it is a conductive layer. However, a conductive composition containing a conductive polymer and an ionic surfactant such as an anionic surfactant or a cationic surfactant may be used. A composition comprising a conductive composition containing a metal oxide such as tin oxide, antimony oxide, indium oxide or zinc oxide. From the viewpoint of easily obtaining a spacer having a desired surface resistance value of the release layer, the conductive layer is preferably a layer formed using a conductive composition containing a conductive polymer.

Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, poly(ethylenedioxythiophene) (abbreviated as PEDOT), and poly(ethylenedioxythiophene)/polystyrenesulfonic acid. (referred to as PEDOT/PSS) and so on. From the viewpoint of antistatic interference and transparency, poly(ethylenedioxythiophene)/polystyrenesulfonic acid (abbreviated as PEDOT/PSS) is particularly preferred. The conductive polymer may be used alone or in combination of two or more.

The conductive composition containing the conductive polymer may contain a binder resin. Examples of the binder resin include a polyvinyl alcohol resin, a polyester resin, a polyurethane resin, an acrylic resin, a vinyl resin, an epoxy resin, and a guanamine resin.

The weight ratio of the conductive polymer to the binder resin (conductive polymer: binder resin) is preferably from 50:1 to 1:1, more preferably from 20:1 to 2:1, still more preferably 15 :1~5:1.

The formation of the conductive layer can be carried out by dissolving the conductive composition containing the conductive polymer in a solvent such as water or alcohol, and applying the resulting solution to a substrate film or oligomerization. After the layer is prevented from being on the layer, it is dried. The concentration of the solution in which the conductive composition containing the conductive polymer is dissolved is not particularly limited, but is preferably about 0.1 to 40% by weight. The drying temperature after coating is not particularly limited, but is preferably about 100 to 150 °C. Further, the drying time after application is not particularly limited, but is preferably about 1 to 60 minutes.

The method for forming the conductive layer is not particularly limited, and a coating method, a spray method, a spin coating method, a wire coating method, or the like can be used.

The thickness of the conductive layer is preferably from 1 nm to 500 nm, more preferably from 10 nm to 200 nm, still more preferably from 20 nm to 100 nm.

<Release Layer> Then, a release layer is provided on the oligomer blocking layer and the conductive layer of the present invention. The release layer is provided to improve the peelability from the adhesive layer. The material for forming the release layer is not particularly limited, and examples thereof include an anthrone-based, fluorine-based, long-chain alkyl-based or fatty acid-amine-based release agent. Among them, an anthrone-based release agent is preferred. The release layer can be formed as a coating layer on the oligomer blocking layer and the conductive layer. Further, the release layer can also be formed by transfer.

The fluorenone-based release agent may, for example, be an addition reaction type fluorenone resin. Examples of the addition reaction type fluorene ketone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T, and Toshiba Silicone TPR-6700, TPR manufactured by Shin-Etsu Chemical Co., Ltd. -6710, TPR-6721, SD7220, SD7226, etc. manufactured by Dow Corning Toray.

The coating amount (after drying) of the anthrone-based release layer is preferably from 0.01 to 2 g/m ² , more preferably from 0.01 to 1 g/m ² , still more preferably from 0.01 to 0.5 g/m ² .

The formation of the release layer can be carried out by, for example, applying the above-mentioned material to the functional layer by a conventionally known coating method such as a reverse gravure coating method, a bar coating method, or a die coating method. The heat treatment is usually carried out at about 120 to 200 ° C for 30 seconds to 30 minutes to cure it. Further, active energy ray irradiation such as heat treatment or ultraviolet irradiation may be used in combination as needed.

The thickness of the release layer is usually from 10 to 2,000 nm, preferably from 10 to 1,000 nm, more preferably from 10 to 500 nm.

The surface resistance value of the release layer is preferably 1.0 × 10 ¹² Ω / □ or less, and more preferably 1.0 × 10 ¹¹ Ω from the viewpoint of imparting conductivity to the separator and suppressing white unevenness of the liquid crystal panel. /□ Below, further preferably 1.0 × 10 ¹⁰ Ω / □ or less.

<Binder Layer> The adhesive layer of the present invention is formed of a binder composition. Examples of the binder composition include a rubber-based pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive composition, an anthrone-based pressure-sensitive adhesive composition, an urethane-based pressure-sensitive adhesive composition, and a vinyl alkyl ether-based adhesive. The composition, the polyvinyl alcohol-based pressure-sensitive adhesive composition, the polyvinylpyrrolidone-based pressure-sensitive adhesive composition, the polypropylene amide-based pressure-sensitive adhesive composition, the cellulose-based pressure-sensitive adhesive composition, and the like. In the binder composition, it is preferred to contain a base polymer.

<Base Polymer> The base polymer can be selected from the binder base polymer depending on the kind of the binder composition.

Among the binder compositions, acrylic adhesion is preferred because it is excellent in optical transparency, exhibits appropriate wettability, cohesiveness and adhesiveness, and has excellent weather resistance and heat resistance. Composition. The acrylic adhesive composition preferably contains a (meth)acrylic polymer as a binder base polymer. The (meth)acrylic polymer is usually contained as a monomer unit and an alkyl (meth)acrylate as a main component. Further, the (meth) acrylate means an acrylate and/or a methacrylate, and the so-called (meth) of the present invention means the same meaning.

The (meth)acrylic acid alkyl ester constituting the main skeleton of the (meth)acrylic polymer may, for example, be a linear or branched alkyl group having 1 to 18 carbon atoms (methyl). Alkyl acrylate. The alkyl group may, for example, be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, Anthracenyl, fluorenyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like. The alkyl (meth)acrylate may be used alone or in combination of two or more. The average number of carbon atoms of these alkyl groups is preferably from 3 to 9.

In addition, as the alkyl (meth)acrylate, phenoxyethyl (meth)acrylate or (methyl) can be used from the viewpoints of adhesion characteristics, durability, adjustment of phase difference, adjustment of refractive index, and the like. An alkyl (meth) acrylate containing an aromatic ring such as benzyl acrylate.

In the (meth)acrylic polymer, one or more kinds of unsaturated double bonds having a (meth) acrylonitrile group or a vinyl group may be introduced by copolymerization for the purpose of improving the adhesiveness and heat resistance. A comonomer of a polymerizable functional group. Specific examples of the comonomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)acrylate a hydroxyl group-containing monomer such as a base ester; a carboxyl group such as (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. An acid anhydride group-containing monomer such as maleic anhydride or itaconic anhydride; a caprolactone adduct of acrylic acid; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2-methyl a sulfonic acid group-containing monomer such as propanesulfonic acid, (meth) acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid; A phosphate group-containing monomer or the like is used.

The ratio of the comonomer in the (meth)acrylic polymer in which the (meth)acrylic polymer has a (meth)acrylic acid alkyl ester as a main component in the weight ratio of all the constituent monomers. The proportion of the comonomer is preferably from 0 to 20%, more preferably from about 0.1 to 15%, still more preferably from about 0.1 to 10%, based on the total weight of the constituent monomers.

As the (meth)acrylic polymer, a polymer having a weight average molecular weight (Mw) of from 500,000 to 3,000,000 is usually used. When considering durability, particularly considering heat resistance, it is preferred to use a polymer having a weight average molecular weight (Mw) of 700,000 to 2.7 million, more preferably 800,000 to 2,500,000. If the weight average molecular weight (Mw) is less than 500,000, it is not desirable from the viewpoint of heat resistance. Further, if the weight average molecular weight (Mw) is more than 3,000,000, in order to adjust the viscosity for coating, a large amount of a diluent solvent is required, so that the cost is increased, and thus it is not desirable. In addition, the weight average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.

A known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected for the production of the (meth)acrylic polymer. Further, the obtained (meth)acrylic polymer may be any copolymer such as a random copolymer, a block copolymer or a graft copolymer.

The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. In addition, the weight average molecular weight (Mw) of the (meth)acrylic polymer can be controlled by the amount of use of the polymerization initiator, the chain transfer agent, and the reaction conditions, and the amount of use can be appropriately adjusted depending on the type thereof.

Further, in the solution polymerization, ethyl acetate, toluene or the like can be used as the polymerization solvent. As a specific example of solution polymerization, a polymerization initiator may be added under a flow of an inert gas such as nitrogen gas, and the reaction is usually carried out under a reaction condition of about 50 to 70 ° C for about 5 to 30 hours.

<Electrically Conductive Compound> The adhesive composition of the present invention preferably further contains a conductive compound in addition to the base polymer. Examples of the conductive compound include an ionic compound, an ionic surfactant, a conductive polymer, and a metal oxide.

As the ionic compound, an alkali metal salt and/or an organic cation-anion salt can be preferably used. As the alkali metal salt, an organic salt of an alkali metal and an inorganic salt can be used. Further, the "organic cation-anion salt" in the present invention is an organic salt, and means a salt in which the cation portion is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. "Organic cation-anion salts" are also referred to as ionic liquids, ionic solids. The ionic compound may be used alone or in combination of two or more.

Examples of the alkali metal ion constituting the cation portion of the alkali metal salt include ions of lithium, sodium, and potassium. Among these alkali metal ions, lithium ions are preferred.

The anion portion of the alkali metal salt may be composed of an organic material or an inorganic material. Examples of the anion portion constituting the organic salt may be used ^{_{CH 3 COO -, CF 3 COO}} -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- , PF ₆ ^- , CO ₃ ^{2 -} , or by the following formula (1) ) an anion portion or the like represented by (4): (1): (C _n F _{2n +1} SO ₂ ) ₂ N ^- (where n is an integer of 1 to 10), and (2): CF ₂ (C _m F _2m) SO ₂ ) ₂ N ^- (where m is an integer of 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (where l is an integer of 1 to 10), (4): (C _p F _{2p +1} SO ₂ )N ^- (C _q F _{2q +1} SO ₂ ) (wherein p and q are integers of 1 to 10). In particular, an anion moiety containing a fluorine atom is preferably used because it can obtain an ionic compound having excellent ion dissociation properties. As the anion portion constituting the inorganic salt, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , AsF ₆ ^- , SbF can be used. ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^-, etc. The anion moiety is preferably a (perfluoroalkylsulfonyl)imide represented by the above formula (1), such as (CF ₃ SO ₂ ) ₂ N ^- or (C ₂ F ₅ SO ₂ ) ₂ N ^- . Particularly preferred is (trifluoromethanesulfonyl)imide represented by (CF ₃ SO ₂ ) ₂ N ^- .

Specific examples of the organic salt of the alkali metal include sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, and Li (CF). ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, KO ₃ S(CF ₂ ) ₃ SO ₃ K, LiO ₃ S(CF ₂ ) ₃ SO ₃ K, etc., among which are preferably LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, etc., more preferably Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C _A lithium salt of a fluorine-containing quinone imine such as ₄ F ₉ SO ₂ ) ₂ N, particularly preferably a lithium salt of (perfluoroalkylsulfonyl)imide.

Further, examples of the inorganic salt of an alkali metal include lithium perchlorate and lithium iodide.

The organic cation-anion salt is composed of a cationic component and an anionic component, and the cationic component is composed of an organic substance. Specific examples of the cation component include a pyridinium cation, an acridinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, and the like. A pyrimidine cation, a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or the like.

As the anion component, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF _{3 can be used.} COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , C _{4 ^{F 9 SO 3 -, C 3}} F 7 COO -, ((CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, or the following general formula (1) to (4) An anion component or the like: (1): (C _n F _{2n +1} SO ₂ ) ₂ N ^- (where n is an integer of 1 to 10), (2): CF ₂ (C _m F _2m SO _{2 2} N ^- (where m is an integer from 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (where l is an integer from 1 to 10), (4): (C _p F _{2p +1} SO ₂ )N ^- (C _q F _{2q +1} SO ₂ ) (wherein p and q are integers of 1 to 10). Among them, an anion component containing a fluorine atom in particular is excellent in ion dissociation property. Ionic compounds are therefore preferred for use.

Further, examples of the ionic compound include ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, iron chloride, and sulfuric acid in addition to the above-described alkali metal salt and organic cation-anion salt. An inorganic salt such as ammonium.

Examples of the ionic surfactant include a cationic system (quaternary ammonium salt type, sulfonium salt type, sulfonium salt type, etc.) and an anionic type (carboxylic acid type, sulfonate type, sulfate type, and phosphate type). , sulfite type, etc., zwitterionic (sulfobetaine type, alkylbetaine type, alkylimidazolium betaine type, etc.) or nonionic (polyol derivative, β-cyclodextrin enveloping compound) Various surfactants such as sorbitan fatty acid monoester/diester, polyalkylene oxide derivative, and amine oxide. The ionic surfactant may be used alone or in combination of two or more.

Examples of the conductive polymer include polymers such as polyaniline, polythiophene, polypyrrole, and polyquinoxaline. Among them, those which are preferably used as water-soluble conductive polymers or water are preferably used. A polyaniline or a polythiophene of a dispersible conductive polymer. Particularly preferred is polythiophene. The conductive polymer may be used alone or in combination of two or more.

Examples of the metal oxide include a tin oxide system, a lanthanum oxide system, an indium oxide system, and a zinc oxide system. Among them, tin oxide is preferred. Examples of the tin oxide-based metal oxide include, in addition to tin oxide, a composite of antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, and titanium oxide-yttria-tin oxide. A composite of titanium oxide-tin oxide. The metal oxide may be used alone or in combination of two or more.

Further, examples of the conductive compound other than the above include acetylene black, ketjen black, natural graphite, artificial graphite, titanium black, or a cationic type (quaternary ammonium salt or the like), and a zwitterionic type (betaine compound, etc.). a homopolymer of an ionically conductive group of an anionic (sulfonate or the like) or a nonionic (glycerol or the like) or a copolymer of the monomer with another monomer, having a quaternary ammonium salt group a polymer having ionic conductivity such as a polymer of a acrylate or methacrylate moiety; a permanent antistatic interference of a type in which a hydrophilic polymer such as a polyethylene methacrylate copolymer is alloyed with an acrylic resin or the like Agent.

The conductive compound is preferably an ionic compound from the viewpoint of high conductivity, excellent dispersibility in a binder, transparency, and storage stability in a binder.

The blending ratio of the conductive compound is preferably 0.0001 to 5 parts by weight based on 100 parts by weight of the base polymer. When the amount of the conductive compound is less than 0.0001 part by weight, the effect of improving the antistatic interference performance may be insufficient. On the other hand, if the conductive compound is more than 5 parts by weight, the durability may be insufficient. The conductive compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more. Further, the conductive compound is preferably 3 parts by weight or less, more preferably 2 parts by weight or less.

Further, a crosslinking agent may be contained in the adhesive composition of the present invention. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imide crosslinking agent. The polyfunctional metal chelate compound is a compound in which a polyvalent metal forms a covalent bond or a coordinate bond with an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Wait. Examples of the atom in the organic compound forming a covalent bond or a coordinate bond include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. As a crosslinking agent, an isocyanate type crosslinking agent and a peroxide type crosslinking agent are preferable. The crosslinking agent may be used alone or in combination of two or more.

The blending ratio of the crosslinking agent is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, per 100 parts by weight of the base polymer. Further, if the crosslinking agent is less than 0.01 part by weight, the cohesive force of the binder tends to be insufficient, and foaming may occur upon heating. On the other hand, if it is more than 20 parts by weight, the moisture resistance is insufficient and reliable. Peeling is likely to occur in sex tests and the like.

Further, a decane coupling agent may be contained in the binder composition of the present invention. Durability can be improved by using a decane coupling agent. The decane coupling agent may be used alone or in combination of two or more.

The compounding ratio of the decane coupling agent is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 1 part by weight based on 100 parts by weight of the base polymer. It is particularly preferably 0.05 to 0.6 parts by weight. In order to improve durability and moderately maintain the adhesive force to an optical member such as a liquid crystal panel, it can be appropriately selected within this range.

Further, in the adhesive composition of the present invention, other known additives may be further contained, and a powder such as a coloring agent or a pigment, a dye, a surfactant, a plasticizer, or a thickening agent may be appropriately added depending on the intended use. Agent, surface lubricant, leveling agent, softener, antioxidant, anti-aging agent, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic or organic filler, metal powder, granular, foil, etc. . Alternatively, a redox system to which a reducing agent is added may be employed within a controllable range.

The adhesive layer of the spacer of the present invention can be produced by applying a solution containing the binder composition to the release layer of the spacer, followed by drying to form a binder layer. Further, at the time of application of the binder composition, one or more solvents other than the polymerization solvent may be newly added as appropriate.

As the coating method of the binder composition, various methods can be used. Specific examples thereof include a roll coating method, a roll coating method, a gravure coating method, a reverse coating method, a roll coating method, a spray coating method, an immersion roller coating method, a bar coating method, a knife coating method, and a gas coating method. A knife coating method, a shower coating method, a lip coating method, an extrusion coating method such as a die coater, or the like.

The thickness of the adhesive layer is not particularly limited and is about 1 to 100 μm. It is preferably 2 to 50 μm, more preferably 2 to 40 μm, still more preferably 5 to 35 μm.

The surface resistivity of the adhesive layer is preferably 1.0 × 10 ¹² Ω / □ or less, more preferably 1.0 × from the viewpoint of imparting conductivity to the adhesive layer of the spacer and suppressing white unevenness of the liquid crystal panel. 10 ¹¹ Ω / □ or less, further preferably 1.0 × 10 ¹⁰ Ω / □ or less.

<Optical Film Attached with Adhesive Layer with Spacer> The optical film of the present invention having the adhesive layer with a spacer attached to the adhesive layer side of the adhesive layer with the spacer attached to at least one surface of the optical film.

As the optical film, an optical film used for forming an image display device such as a liquid crystal display device can be used, and the kind thereof is not particularly limited. Examples of the optical film include a polarizing film, a retardation film, an optical compensation film, a brightness enhancement film, and a surface treatment film such as an antireflection film, and the like.

The polarizing film generally uses a polarizing film having a transparent protective film on one or both sides of the polarizing member. The polarizer is not particularly limited, and various polarizers can be used. Examples of the polarizing material include a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene/vinyl acetate copolymer-based partially saponified film, which adsorbs iodine or a dichroic dye. A coloring material is a material obtained by uniaxially stretching, a dehydrated material of polyvinyl alcohol, or a polyolefin-based alignment film such as a dehydrochlorinated product of polyvinyl chloride. Among them, a polarizer having a polyvinyl alcohol-based film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

Further, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. The thickness is preferably from 1 to 7 μm from the viewpoint of thinning. Such a thin polarizer has a small thickness unevenness, is excellent in observation property, and has a small dimensional change. Therefore, it is excellent in durability, and the thickness of the polarizing film can be made thinner, which is preferable.

As the material constituting the transparent protective film, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, water resistance, isotropy, and the like can be used. Specific examples of such a thermoplastic resin include cellulose resins such as triacetonitrile cellulose, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyimide resins. A polyolefin resin, a (meth)acrylic resin, a cyclic polyolefin resin (norbornene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and the like. Further, although the transparent protective film is bonded to the side of the polarizer by the adhesive layer, on the other side, as the transparent protective film, (meth)acrylic, urethane-based or acrylamide can be used. A thermosetting resin such as a urethane type, an epoxy type or an anthrone type, or an ultraviolet curable resin. One or more optional additives may be contained in the transparent protective film.

The adhesive used in the bonding of the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various forms of water, solvent, hot melt, radical curing, and cationic curing can be used. The material, however, is preferably a water based adhesive or a free radical curable adhesive.

<Image Display Device> The image display device of the present invention has an optical film attached to the adhesive layer with the spacer attached to at least one surface of the display panel, and the optical film of the adhesive layer in the state of the spacer is peeled off. The side of the adhesive layer. As a display panel, a liquid crystal panel etc. are mentioned. As the liquid crystal panel, any type of liquid crystal panel such as a TN type, an STN type, a π type, a VA type, or an IPS type can be used.

<Manufacturing Method of Image Display Device> The method of manufacturing the image display device of the present invention is a manufacturing method including the following steps, that is, a coil preparing step of preparing a long strip of an optical film with a binder layer with a spacer as a roll a display panel transport preparation step of preparing the display panel to the pasting position; and a bonding step (RTP bonding step) for extracting the optical film with the adhesive layer attached to the spacer from the web And peeling the spacer from the optical film with the adhesive layer with the spacer attached thereto, and bonding the adhesive layer layer of the optical film with the adhesive layer exposed after peeling the spacer to the optical film The sheet is transported to the display panel at the pasting position.

<Reel Preparation Step> The web preparation step is a step of producing an optical film having a binder layer with a spacer as a web of a long strip (belt), which is not particularly limited and may be The previous method was used to manufacture.

<Display Panel Transfer Preparation Step> The display panel transport preparation step is a step of transporting a display panel such as a liquid crystal panel to a pasting position, and the transport method is not particularly limited, and can be carried in accordance with a conventional method.

<RTP bonding step> A typical schematic diagram of the RTP bonding step is shown in FIG. The strip of the optical film 3 with the spacer-attached adhesive layer drawn from the web is peeled off from the optical film 3 with the adhesive layer attached to the spacer immediately before being conveyed to the pasting position 101. The body 100 peels off the spacer 1. The adhesive layer 21 of the optical film 4 with the adhesive layer exposed after the separator 1 is peeled off is bonded to the display panel 5 guided by the receiving roller 102 to the bonding position 101 by the bonding roller 103 to produce an image. Display device.

In the RTP bonding step, since the optical film 3 with the adhesive layer attached to the spacer is a long piece which is not cut, after the peeling of the spacer 1, the long sheet-like adhesive layer is The optical film 4 (or the adhesive layer 21) is also in a state of continuing contact with the spacer 1 before peeling. Thereby, even if static electricity is generated in the optical film 4 (or the adhesive layer 21) of the long sheet-like adhesive layer due to the peeling of the spacer 1, the electrostatic charge can be quickly peeled off via the spacer 1 before peeling. The rear spacer 1 is moved, so that the peeled spacer 1 functions as a ground, and as a result, the electrostatic charge is attenuated.

Further, in the method of manufacturing the image display device, after the display panel and the optical film with the adhesive layer are bonded together, components such as an illumination system that are used as needed may be appropriately assembled and then mounted in a drive circuit, for example, A method of manufacturing a liquid crystal display device in which an optical film having an adhesive layer is disposed on one or both sides of a display panel such as a liquid crystal panel, a method of manufacturing a liquid crystal display device using a backlight or a reflector in an illumination system, and the like are exemplified. In this case, the optical film of the adhesive layer of the present invention may be provided on one side or both sides of a display panel such as a liquid crystal panel. When optical films are provided on both sides, they may be the same or different. Further, in the method of manufacturing a liquid crystal display device, one or two or more diffusion layers, an anti-glare layer, an anti-reflection film, a protective plate, a prism array, a lens array sheet, and a light diffusion sheet may be disposed at appropriate positions. Suitable components such as backlights.

[Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. Moreover, the parts and % in each case are based on weight.

Example 1 <Preparation of a spacer> <<Formation of an oligomer prevention layer>> As a cerium oxide-based material, an organic decane (Ethyl Silicate 48: COLCOAT) was diluted with isopropyl alcohol to have a solid concentration of A coating liquid was prepared at 1%. The obtained coating liquid was applied onto a polyester film (thickness: 38 μm) as a base film so as to have a thickness of 50 nm after drying, and dried at 120 ° C for 30 seconds to form an oligomer preventing layer. (1).

<<Formation of Conductive Layer>> As a conductive polymer, poly(ethylenedioxythiophene)/polystyrenesulfonic acid (PEDOT/PSS) was used to prepare a water/isopropyl group having a solid concentration of 1%. A solution of alcohol (1/1: weight ratio). The obtained solution was applied onto the oligomer-preventing layer (1) so as to have a thickness of 100 nm after drying, and dried at 80 ° C for 2 minutes to form a conductive layer (1).

<<Formation of release layer>> Anthrone resin (KS-847H: manufactured by Shin-Etsu Chemical Co., Ltd.): 20 parts and a curing agent (PL-50T: manufactured by Shin-Etsu Chemical Co., Ltd.): 0.2 part of a mixed solvent of methyl ethyl ketone/toluene (mixing ratio is 1:1) 350 parts dilution to prepare a solution of an anthrone-based release agent. The solution of the obtained anthrone-based release agent was applied onto the conductive layer (1) by a gravure coater so as to have a thickness of 100 nm after drying, and then dried at 120 ° C for 30 seconds to form a release layer, thereby obtaining a polycondensation layer. The separator of Example 1 in which the ester film/oligomer preventing layer (1)/conductive layer (1)/release layer was constituted.

Example 2 <Preparation of a spacer> <<Formation of a conductive layer>> As a conductive polymer, poly(ethylenedioxythiophene)/polystyrenesulfonic acid (PEDOT/PSS) was used to prepare a solid concentration. A solution of 1% water/isopropyl alcohol (1/1: weight ratio). The obtained solution was applied onto a polyester film (thickness: 38 μm) as a base film so as to have a thickness of 100 nm after drying, and dried at 80° C. for 2 minutes to form a conductive layer (1).

<<Formation of oligomer blocking layer>> As a ceria-based material, a cerium oxide sol having an average particle diameter of 0.05 μm was diluted with isopropyl alcohol to a solid content concentration of 1% to prepare a coating liquid. The obtained coating liquid was applied onto the conductive layer (1) so as to have a thickness of 50 nm after drying by a gravure coater, and then dried at 120 ° C for 30 seconds to form an oligomer blocking layer (2).

<<Formation of Release Layer>> In the same manner as in Example 1, except that the release layer was formed on the oligomer-preventing layer (2) in the formation of "release layer" in Example 1. A spacer of Example 2 having a polyester film/conductive layer (1)/oligomer preventing layer (2)/release layer was obtained.

Example 3 <Preparation of a spacer> <<Formation of a conductive layer>> As a conductive polymer, poly(ethylenedioxythiophene)/polystyrenesulfonic acid (PEDOT/PSS) was used as a binder resin. A solution of water/isopropyl alcohol (1/1: weight ratio) having a solid concentration of 0.8% was prepared using a polyurethane resin. Further, the weight ratio of the conductive polymer to the binder resin was 10:1. The obtained solution was applied onto a polyester film (thickness: 38 μm) as a base film so as to have a thickness of 100 nm after drying, and dried at 80 ° C for 2 minutes to form a conductive layer (2).

<<Formation of oligomer blocking layer>> <<Formation of release layer>> In addition to the formation of "the formation of the oligomer preventing layer" and "the formation of the release layer" in Example 2 An oligomer-preventing layer (2) was formed on the conductive layer (2), and a polyester film/conductive layer was obtained in the same manner as in Example 2 except that a release layer was provided on the oligomer-preventing layer (2). (2) The spacer of Example 3 in which the oligomer preventing layer (2)/release layer is constituted.

Example 4 <Preparation of a separator> <<Formation of oligomer blocking layer>> As a composition containing a polyvinyl alcohol-based resin, a polyvinyl alcohol-based resin (saponification degree = 88 mol %, polymerization degree = 500) Polyvinyl alcohol) 70 parts, binder polymer (water-based polyester resin: copolymerized with isophthalic acid, ethylene glycol, diethylene glycol-based polyester neopentyl glycol, with aliphatic dicarboxylic anhydride 15 parts of an aqueous polyester obtained by neutralizing and hydrolyzing the obtained polyester with an amine compound, 10 parts of a crosslinking agent (hexamethoxymethyl melamine), and inorganic particles (average particle) A coating liquid was prepared by diluting 5 parts of a cerium oxide sol having a diameter of 65 nm to a solid concentration of 2%. The obtained coating liquid was applied onto a polyester film (thickness: 38 μm) as a base film by a gravure coater so as to have a thickness of 50 nm after drying, and then the film was introduced into a tenter and stretched at 100 ° C. Then, heat fixation was performed at 230 ° C to form an oligomer blocking layer (3).

<<Formation of Conductive Layer>> <<Formation of Release Layer>> In the first embodiment, in the same manner as in the first embodiment, the formation of the conductive layer and the formation of the release layer are the same as in the first embodiment. A spacer of Example 4 having a polyester film/oligomer preventing layer (3)/conductive layer (1)/release layer was obtained.

Comparative Example 1 <Preparation of a spacer> A substrate film/oligomer preventing layer (1)/release layer was obtained in the same manner as in Example 1 except that the conductive layer (1) was not formed in Example 1. The spacer of Comparative Example 1 was constructed.

Comparative Example 2 <Preparation of a spacer> <<Formation of an oligomer preventing layer to which a conductive agent is added>> As a composition for forming an oligomer blocking layer to which a conductive agent is added, a compound having a nitrogen element as a conductive material ( Compound having a pyrrolidinium ring in the main chain: 85 parts of Sharoll DC-303P, manufactured by Dai-ichi Pharmaceutical Co., Ltd., polyvinyl alcohol-based resin (saponification degree = 88 mol%, polyvinyl alcohol having a polymerization degree = 500) 10 Parts and inorganic particles (cerium oxide sol having an average particle diameter of 50 nm) were diluted with water to a solid concentration of 2% to prepare a coating liquid. The obtained coating liquid was applied onto a polyester film (thickness: 38 μm) as a base film by a gravure coater so as to have a thickness of 50 nm after drying, and then the film was introduced into a tenter and stretched at 100 ° C. Then, heat setting was performed at 230 ° C to form an oligomer blocking layer to which a conductive agent was added.

<<Formation of Release Layer>> Except that in Example 1, the formation of the release layer was the same as in Example 1 except that a release layer was formed on the oligomer-preventing layer to which the conductive agent was added. A separator of Comparative Example 2 having a polyester film/an oligomer preventing layer/release layer to which a conductive agent was added was obtained.

<Preparation of Adhesive Layer Attached to Spacer> <<Preparation of Acrylic Polymer>> To a reaction vessel equipped with a cooling pipe, a nitrogen gas introduction pipe, a thermometer, and a stirring device, 99 parts of butyl acrylate and acrylic acid 4- were added. A monomer mixture of 1 part of hydroxybutyl ester. Then, 0.1 part of 2,2'-azobisisobutyronitrile was added together with ethyl acetate as a polymerization initiator, and the nitrogen gas was introduced while stirring slowly while stirring with respect to 100 parts of the monomer mixture (solid content). After the nitrogen gas was replaced, the liquid temperature in the flask was maintained at around 60 ° C to carry out a polymerization reaction for 7 hours. Thereafter, ethyl acetate was added to the obtained reaction liquid to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.6 million in which the solid content concentration was adjusted to 30%.

<<Preparation of a binder composition>> With respect to 100 parts of the solid content of the acrylic polymer (A) solution obtained by the above operation, 1-ethyl-1-methylpyrrolidinium was added as an ionic compound. 0.7 parts of trifluoromethanesulfonimide and 1.0 part of lithium bis(trifluoromethanesulfonate) imide (manufactured by Mitsubishi Materials, Inc.), and a trimethylolpropane xylene diisocyanate as a crosslinking agent (Mitsui Chemical Co., Ltd.: Takenate D110N) 0.1 parts, and 0.3 parts of diphenylguanidinium peroxide, as a decane coupling agent, combined with γ-glycidoxypropyl methoxy decane (Shin-Etsu Chemical Co., Ltd.: KBM) -403) 0.2 parts to obtain a solution of the binder composition.

<<Formation of Binder Layer>> The solution of the binder composition prepared by the above operation was uniformly applied to the spacers of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation by a spray coater. After being released from the mold release layer, the film was dried in an air loop type constant temperature oven at 150 ° C for 60 seconds, and a pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the release layer to obtain Examples 1 to 4 and Comparative Examples 1 and 2. The adhesive layer with the spacer.

<Preparation of optical film with adhesive layer with spacer> <<Production of optical film>> In order to produce a thin polarizer, first, it will be based on amorphous polyethylene terephthalate (PET). A laminate having a 9 μm-thick polyvinyl alcohol (PVA) layer formed on the material is formed into a stretched laminate by air-assisted stretching at a stretching temperature of 130° C., and then a colored laminate is formed by dyeing the stretched laminate, and then The colored laminate was formed by stretching in a boric acid water having a stretching temperature of 65 degrees to form a 4 μm-thick PVA layer integrally stretched with the amorphous PET substrate so as to have a total stretching ratio of 5.94 times. . By such a two-stage stretching, the PVA molecules of the PVA layer formed on the amorphous PET substrate are aligned at a high degree, and an optical thin film laminate which forms the iodine adsorbed by the dyeing can be formed as a polymer. A highly functional polarizer in which the iodide complex is aligned in a high order in a direction, comprising a PVA layer having a thickness of 4 μm. In addition, a polyvinyl alcohol-based adhesive is applied to the surface of the polarizing material of the optical film laminate, and a 80 μm-thick triethylenesulfide cellulose film which is subjected to saponification treatment is attached, and then the amorphous PET substrate is peeled off. A polarizing film using a thin polarizer was produced.

<Preparation of optical film with adhesive layer with spacers> Then, in the polarizing film using the thin polarizer obtained by the above operation, Examples 1 to 4 and Comparative Example 1 obtained by the above operation were bonded. The adhesive layer of the spacer with 2 was transferred to the adhesive layer, and the optical films of the adhesive layers with the spacers of Examples 1 to 4 and Comparative Examples 1 and 2 were obtained.

<Manufacturing of Image Display Device> In order to manufacture the image display device by the RTP bonding step shown in FIG. 3, the spacers of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation were prepared as a web. A long strip of the optical film of the adhesive layer and prepared for the liquid crystal panel to be transported to the pasting position. Thereafter, the optical films with the spacer-attached adhesive layers of Examples 1 to 4 and Comparative Examples 1 and 2 were taken out from the web, and the optical film using the adhesive layer with the spacer was used. While the separator was peeled off, the adhesive layer side of the optical film with the adhesive layer exposed after the separator was peeled off was bonded to the liquid crystal panel which was conveyed to the adhesive position, and Examples 1 to 4 and Comparative Example 1 were used. 2 image display device (liquid crystal display device) of liquid crystal panel.

The weight average molecular weight (Mw) of the (meth)acrylic polymer obtained by the above operation was measured by GPC (gel permeation chromatography) based on the following conditions.・Analytical device: manufactured by Tosoh Corporation, HLC-8120GPC ・Column column: manufactured by Tosoh Corporation, G7000HXL+GMHXL+ GMHXL ・Column size: 7.8mmφ×30cm ・Cylinder temperature: 40°C ・Flow rate: 0.8ml/min ・Injection amount : 100 μl • Eluent: Tetrahydrofuran • Detector: Differential Refractometer (RI) • Standard Sample: Polystyrene

The spacers of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation, the adhesive layer with a spacer, and the optical film with the adhesive layer with a spacer attached were evaluated as follows. The evaluation results are shown in Table 1.

<Method for Measuring Surface Resistance Value of Release Layer> The surface of the release layer was measured using MCP-HT450 manufactured by Mitsubishi Chemical Corporation, Inc., using the separators of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation. Surface resistance value (Ω/□).

<Method for Measuring Surface Resistance Value of Adhesive Layer> The adhesive layer of the separators of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation was measured for bonding using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd. The surface resistance value (Ω/□) of the surface of the agent layer.

<Method for Measuring the Dissolution Amount of PET Oligomer> The optical films having the adhesive layer with spacers of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation were at 60 ° C and 90% RH. After leaving for 500 hours under conditions, the spacers were removed. About 0.025 g of the adhesive layer (sample) was taken from the polarizing film with the adhesive layer, 1 ml of chloroform was added and shaken at room temperature for 18 hours, and then 5 ml of acetonitrile was added for extraction, and shaken for 3 hours. The resulting solution was filtered using a 0.45 ml membrane filter, and the sample was adjusted. The standard of the trimer PET oligomer was adjusted to a certain concentration to prepare a calibration curve, and the calibration curve was used to determine the amount of PET oligomer (ppm) contained in the binder. The calibration curve was prepared by using a sample having a known PET oligomer concentration (ppm) and measuring by HPLC. HPLC apparatus: Agilent Technologies 1200 series measurement condition chromatography column: ZORBAX SB-C18 manufactured by Agilent Technologies Column temperature: 40 ° C Column flow rate: 0.8 ml / min Eluent composition: water / acetonitrile reverse gradient condition Injection amount: 5 μl detector : PDA Quantitative method: After dissolving the standard sample of the PET oligomer trimer with chloroform, it is diluted with acetonitrile to prepare a standard at a certain concentration. A calibration curve was prepared from the HPLC area and the prepared concentration, and the elution amount of the PET oligomer of the sample was determined. Further, the amount of elution of the PET oligomer is preferably 30 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less.

The liquid crystal display devices of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation were subjected to the following evaluations. The evaluation results are shown in Table 1. <Evaluation of White Unevenness> The liquid crystal display devices of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation were placed on a backlight. The hand is brought into contact with the end portion of the liquid crystal display device provided, and white unevenness is generated in the liquid crystal panel. The time at which the white unevenness disappeared was measured. The disappearing time is preferably 200 seconds or less, more preferably 100 seconds or less, still more preferably 50 seconds or less, and particularly preferably 20 seconds or less.

[Table 1]

As shown in Table 1, in Examples 1 to 4 of the present invention, good results were obtained in any of the evaluation items. On the other hand, in Comparative Examples 1 and 2, the results which were inferior to Examples 1 to 4 were obtained in any of the evaluation items. From the results, according to the present invention, it is possible to provide an adhesive layer with a spacer which can be prevented from being eluted into the adhesive layer by suppressing the oligomer contained in the base film such as the polyester film used in the spacer. The poor condition of the liquid crystal panel due to uneven brightness caused by the bright spots, and the white unevenness of the liquid crystal panel can be suppressed even when the above-described RTP bonding step is applied at the time of manufacture of the liquid crystal display device, and An optical film having a layer of adhesive with a spacer.

1‧‧‧ spacers
2‧‧‧Binder layer with spacer
3‧‧‧Optical film with adhesive layer with spacers
4‧‧‧Optical film with adhesive layer
5‧‧‧ display panel
11‧‧‧Substrate film
12‧‧‧ release layer
13‧‧‧ oligomer barrier layer
14‧‧‧ Conductive layer
21‧‧‧Binder layer
31‧‧‧Optical film
100‧‧‧Exfoliation
101‧‧‧adhesive position
102‧‧‧Receiving roller
103‧‧‧Adhesive roller

1(a) and 1(b) are schematic cross-sectional views showing a configuration example of an adhesive layer with a spacer. 2 is a schematic cross-sectional view showing a configuration example of an optical film with an adhesive layer with a spacer attached thereto. 3 is a schematic view illustrating an RTP bonding step in a method of manufacturing a video display device.

1‧‧‧ spacers

2‧‧‧Binder layer with spacer

11‧‧‧Substrate film

12‧‧‧ release layer

13‧‧‧ oligomer barrier layer

14‧‧‧ Conductive layer

21‧‧‧Binder layer

Claims (9)

An adhesive layer with a spacer attached to a spacer layer having a spacer layer on a spacer, wherein the spacer has a release layer on the substrate film, and the substrate film An oligomer blocking layer and a conductive layer are provided between the release layer and the adhesive layer are provided on the release layer of the spacer. The adhesive layer of the spacer according to claim 1, wherein the oligomer blocking layer is a layer formed of a composition containing a cerium oxide-based material and/or a polyvinyl alcohol-based resin. The adhesive layer of the spacer according to claim 1 or 2, wherein the conductive layer is a layer formed of a conductive composition containing a conductive polymer. The adhesive layer of the spacer according to any one of claims 1 to 3, wherein the release layer has a surface resistance value of 1.0 × 10 ¹² Ω/□ or less. The adhesive layer of the spacer according to any one of claims 1 to 4, wherein the adhesive layer is a layer formed of a binder composition containing a base polymer and a conductive compound. The adhesive layer of the spacer according to any one of claims 1 to 5, wherein the surface resistivity of the adhesive layer is 1.0 × 10 ¹² Ω / □ or less. An optical film having a binder layer with a spacer attached thereto, wherein an adhesive layer side of the adhesive layer of the spacer according to any one of claims 1 to 6 is attached to at least one surface of the optical film. An image display device characterized in that an optical film from an adhesive layer with a spacer attached thereto as claimed in claim 7 is attached to at least one surface of the display panel, and the optical layer of the adhesive layer in the state of the spacer is peeled off. The adhesive layer side of the film. A method of manufacturing an image display device, such as the method of manufacturing the image display device of claim 8, characterized by comprising: a web preparation step of preparing an optical layer having an adhesive layer with a spacer as claimed in claim 7 a long strip of the film is used as a coil; a display panel transport preparation step is prepared by transporting the display panel to the pasting position; and a bonding step of extracting the optical film with the adhesive layer attached to the spacer from the coil And peeling the spacer from the optical film with the adhesive layer with the spacer attached thereto, and bonding the adhesive layer layer of the optical film with the adhesive layer exposed after peeling the spacer to the transfer To the aforementioned display panel of the aforementioned pasting position.