TWI716461B - Spacer-attached adhesive layer, optical film with spacer-attached adhesive layer, image display device and manufacturing method thereof - Google Patents

Abstract

The object of the present invention is to provide an adhesive layer with a spacer and an optical film with an adhesive layer with a spacer, which can prevent the oligomer contained in the base film such as polyester film used in the spacer from becoming The adhesive layer is eluted, which can prevent the poor condition of the liquid crystal panel caused by the uneven brightness caused by the bright spot, and in the manufacture of the liquid crystal display device, even if the RTP bonding step is applied, the white unevenness of the liquid crystal panel can be suppressed . The present invention is an adhesive layer with a spacer having an adhesive layer on the spacer, the spacer has a release layer on the base film, and between the base film and the release layer, there is an oligomer The object prevention layer and the conductive layer, and the adhesive layer is provided on the release layer of the spacer.

Description

Spacer-attached adhesive layer, optical film with spacer-attached adhesive layer, image display device and manufacturing method thereof

Technical Field The present invention relates to an adhesive layer with a spacer and an optical film with an adhesive layer with a spacer. The present invention relates to an image display device in which the adhesive layer side of the optical film with an adhesive layer in the state of peeling off the spacer is attached to a display panel from the optical film with an adhesive layer with spacers, and its manufacture method.

As the optical film, a polarizing film, a retardation film, an optical compensation film, a brightness enhancement film, a surface treatment film such as an anti-reflection film, and a laminate of these films can be used. The optical film with the adhesive layer obtained by peeling the optical film with the adhesive layer with the spacer is used in image display devices such as liquid crystal display devices, organic EL display devices, CRTs, and PDPs.

BACKGROUND ART In image display devices such as liquid crystal display devices, optical films such as polarizing films are used. When bonding the optical film to a display panel such as a liquid crystal panel, an adhesive is usually used. Since there is no need to perform a drying step for bonding the optical film, an optical film with an adhesive layer preliminarily provided with an adhesive as the adhesive layer on one side of the optical film is generally used. In addition, the optical film with the adhesive layer is usually used to protect the adhesive layer before lamination. It is used as the adhesive layer with spacers (also called release films or release liners) on the surface of the adhesive layer. Manufacture of optical film with adhesive layer with spacers.

This type of optical film with an adhesive layer with spacers is caused by the elution of oligomers contained in the base film such as polyester film used in the spacer to the adhesive layer, resulting in uneven brightness caused by bright spots. Due to the poor condition of the liquid crystal panel, Patent Document 1 proposed to provide an oligomer prevention layer on the spacer.

In addition, in the manufacture of liquid crystal display devices, when the spacer of the optical film with the adhesive layer with the spacer is peeled off, static electricity (peeling charge) is generated in the optical film with the adhesive layer and the spacer. Sticking an optical film with an electrostatic adhesive layer on a liquid crystal panel will cause induction charging in the liquid crystal panel. The inductively charged charge affects the alignment of the liquid crystal of the liquid crystal panel, and may cause the uneven display of the image. In addition, static electricity at the manufacturing site may cause product defects and other problems due to the adhesion or introduction of foreign objects.

In Patent Documents 2 to 4, in order to suppress the generation of static electricity, an adhesive sheet having an adhesive layer provided with an antistatic interference function by mixing an ionic compound or a conductive polymer into the adhesive layer has been proposed. In addition, Patent Document 5 proposes a spacer that imparts an antistatic interference function to the release layer of the spacer. Prior technical literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2006-113600 Patent Document 2: Japanese Patent Application Publication No. 6-128539 Patent Document 3: Japanese Patent Application Publication No. 2007-536427 Patent Document 4: Japanese Patent Application Publication No. 2003-246874 Patent Document 5: Japanese Patent Publication No. 2014-141557

SUMMARY OF THE INVENTION Problems to be Solved by the Invention However, even in the case of using the spacer of Patent Document 5 and the optical film with a spacer-attached adhesive layer, the generation of static electricity when the spacer is peeled cannot be sufficiently suppressed. In particular, it has been found that the optical film with the adhesive layer that is exposed after the spacer is peeled off while peeling the spacer (see FIG. 3) (simultaneously with the peeling) from the optical film with the adhesive layer with the spacer The adhesive layer side of the liquid crystal panel is attached to the liquid crystal panel (Roll-To-Panel (RTP) bonding step). When the liquid crystal display device is manufactured, the adhesive layer with non-attenuated static electricity is attached to the liquid crystal panel. Thin film, and induced electrification. In the subsequent manufacturing steps, the inductively charged liquid crystal panel comes into contact with a dielectric such as a manufacturing machine, thereby generating a current (magnetic field) in the liquid crystal panel, and the liquid crystal panel becomes white uneven due to poor alignment of the liquid crystal (light leakage). ). Once the white unevenness occurs in the liquid crystal panel, the white unevenness will continue until the liquid crystal alignment is restored to the original state. Therefore, the quality inspection in the manufacturing step is delayed and the production efficiency deteriorates.

The object of the present invention is to provide an adhesive layer with spacers, which can prevent elution of oligomers contained in base films such as polyester films used in the spacers to the adhesive layer, thereby preventing bright spots from being caused The poor condition of the liquid crystal panel caused by uneven brightness, and during the manufacture of the liquid crystal display device, even if the above-mentioned RTP bonding step is applied, the white unevenness of the liquid crystal panel can be suppressed. In addition, a spacer with a spacer is also provided. Optical film with adhesive layer.

In addition, an object of the present invention is to provide an image display device characterized in that at least one surface of the display panel is bonded with an optical film from the spacer-attached adhesive layer, and the spacer is peeled off. The adhesive layer side of the optical film attached with the adhesive layer also provides a manufacturing method of the image display device. Means to solve the problem

In order to solve the above-mentioned problems, the inventors of this case have conducted intensive studies and found the following adhesive layers with spacers, optical films with adhesive layers with spacers, image display devices, and manufacturing methods thereof, thereby completing the present invention invention.

That is, the present invention relates to a spacer-attached adhesive layer, which is a spacer-attached adhesive layer having an adhesive layer on the spacer, characterized in that the spacer has a release layer on a base film, And between the base film and the release layer, there is an oligomer prevention layer and a conductive layer, and the adhesive layer is provided on the release layer of the spacer.

The adhesive layer with a spacer of the present invention is preferably a layer formed of a composition containing a silica-based material and/or a polyvinyl alcohol-based resin.

It is preferable that the adhesive layer with a spacer of the present invention is a layer formed of a conductive composition containing a conductive polymer.

The adhesive layer with a spacer of the present invention preferably has a surface resistance value of the release layer of 1.0×10 ¹² Ω/□ or less.

The mixture layer with spacers of the present invention is preferably a layer formed of an adhesive composition containing a base polymer and a conductive compound.

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

The present invention relates to an optical film with a spacer-attached adhesive layer, characterized in that the adhesive layer side of the spacer-attached adhesive layer is attached to at least one surface of the optical film.

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

The present invention relates to a method of manufacturing an image display device. The method of manufacturing the image display device is characterized by comprising: a coil preparation step of preparing a strip of optical film with a spacer-attached adhesive layer As a coil; the display panel transport preparation step is prepared by transporting the display panel to the pasting position; and the laminating step is to extract the optical film with the spacer-attached adhesive layer from the coil and remove it from The optical film with the adhesive layer with spacer is peeled off the spacer by the release body, and the adhesive layer side of the optical film with the adhesive layer exposed after the spacer is peeled is bonded to the On the display panel at the sticking position. Invention effect

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

In addition, the adhesive layer side of the adhesive layer with the spacer is stuck on the optical film to obtain the optical film with the adhesive layer with the spacer of the present invention. Since the spacer has a conductive layer, the spacer is peeled off The generation of static electricity is small. On the other hand, if a conductive agent such as a conductive compound is added to the oligomer prevention layer and mold release layer, the conductive agent in the oligomer prevention layer and mold release layer interacts with the conductive adhesive, which will cause damage In the case of the anti-static interference function, however, in the present invention, by laminating the oligomer preventing layer and the conductive layer, sufficient conductive performance can be provided to the surface of the spacer.

In addition, the optical film with a spacer-attached adhesive layer of the present invention is used in the manufacture of a liquid crystal display device, even when the following steps (RTP bonding step) are applied, that is, the spacer-attached adhesive layer The optical film of the layer is peeled off the spacer (simultaneously with the peeling), and the adhesive layer side of the optical film with the adhesive layer exposed after the spacer is peeled off is attached to the liquid crystal panel, because the spacer has a conductive layer Therefore, it is possible to suppress the generation of static electricity (peeling charge). In addition, even if static electricity is generated due to the peeling of the spacer, the electrostatic charge generated in the optical film with the adhesive layer can be quickly transferred to the peeled spacer Therefore, it can also attenuate the electrostatic charge, which is useful for suppressing the white unevenness of the liquid crystal panel.

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

<The overall structure of the adhesive layer with spacer and the optical film with the adhesive layer with spacer> A typical configuration example of the adhesive layer with spacer of the present invention is schematically shown in FIG. 1(a) And (b). The spacer-attached adhesive layer 2 is a form in which an adhesive layer 21 is provided on the release layer 12 of the spacer 1. In addition, the spacer 1 has a form in which the oligomer prevention layer 13 and the conductive layer 14 are provided between the base film 11 and the release layer 12. There is no restriction on the stacking order of the oligomer preventing layer 13 and the conductive layer 14. However, in the case of (a), since the oligomer preventing layer 13 contacts the base film 11, it suppresses the damage in the base material such as polyester film. The effect of the oligomer-containing elution into the adhesive layer is high, and since the conductive layer 14 is in contact with the 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 is high while maintaining the antistatic effect of the entire spacer 1. In addition, the laminated layer of the oligomer prevention layer 13 and the conductive layer 14 may be a multilayer of the oligomer prevention layer 13 and the conductive layer 14.

A typical configuration example of the optical film with a spacer-attached adhesive layer of the present invention is schematically shown in FIG. 2. The optical film 3 with a spacer-attached adhesive layer is formed by bonding the optical film 31 to the spacer-attached adhesive layer 2. From the optical film 3 with the adhesive layer with spacers to the optical film 4 with the adhesive layer after the spacer 1 is peeled off, the adhesive layer 21 is used to stick the adhesive layer 21 on the display panel as an adherend.

<Adhesive layer with spacer> The adhesive layer with spacer of the present invention has a structure having an adhesive layer on the spacer. The spacer has an oligomer prevention layer and a conductive layer between the base film and the release layer.

<Base film> As the base film of the spacer of the present invention, a plastic film can be used. Examples of plastic films include polyolefin films such as polyethylene films, polypropylene films, polybutene films, polybutadiene films, and polymethylpentene films, and vinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films. Series films; polyester films such as polyethylene terephthalate film, polybutylene terephthalate film, polynaphthalene terephthalate film, etc.; and polyurethane film, ethylene-vinyl acetate copolymer Film etc. In the present invention, for the purpose of preventing the elution of oligomers in the base film, among the base films, a polyester film is preferably used.

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

<Oligomer Prevention Layer> As the oligomer prevention layer of the present invention, it can be formed using an appropriate material that prevents oligomers contained in base films such as polyester films from eluting into the adhesive layer. As a material for forming the oligomer prevention layer, inorganic substances, organic substances, or composite materials thereof can be used. Examples of inorganic substances include silicon dioxide-based materials, metals containing gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, or alloys thereof, or metals containing indium oxide , Tin oxide, titanium oxide, cadmium oxide, or a mixture of metal oxides, and other metal compounds including steel iodide. Examples of organic substances include polyvinyl alcohol resins, acrylic resins, urethane resins, melamine resins, UV curable resins, and epoxy resins. In addition, as a composite material, a mixture of the organic substance and inorganic particles such as alumina, silica, mica, etc. can be cited.

The oligomer prevention layer is preferably formed of a composition containing a silica-based material and a polyvinyl alcohol-based resin.

<Silicon dioxide-based material> As the above-mentioned silicon dioxide-based material, for example, an organosiloxane represented by the following general formula (I) can be cited. [化1]

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

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

As specific examples of the organosiloxane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2- (3,4-Epoxycyclohexyl) ethyltriethoxysilane, 5,6-epoxycyclohexyltriethoxysilane, tetraethoxysilane and other monomers, and these monomers or this Hydrolyzable product (oligomer) of a mixture of other monomers.

In addition, as the silica-based material, a silane compound having an amine group can be cited. The silane compound having an amino group is preferably an alkoxysilane represented by the following general formula (III). Y-R-Si-(X) ₃ ……(III) In the general formula (III), Y represents an amino group, R represents an alkylene group such as methylene, ethylene, and propylene, and X represents methyl At least one of an alkoxy group such as an oxy group and an ethoxy group, an alkyl group, or an organic functional group having these groups is an alkoxy group.

Specific examples of the silane compound having an amino group include N-β (aminoethyl)γ-aminopropyl trimethoxysilane, and N-β (aminoethyl)γ-aminopropyl Triethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Propyl trimethoxysilane, etc.

In addition, examples of the silica-based materials include 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. containing (meth)acrylic acid Silane compounds containing isocyanate groups, 3-isocyanate propyl triethoxysilane, etc.

As specific products of the silicon dioxide-based materials, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, 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 above-mentioned silicon dioxide-based materials may use only one type or two or more types.

The oligomer prevention layer formed using the silica-based material may contain an organic compound having a metal element (metal compound such as a metal chelate), a catalyst, and the like as necessary. Only 1 type may be used for the metal organic compound which has a metal element, and 2 or more types may be used for it.

Among the metal-organic compounds with metal elements, especially from the viewpoint of good oligomer elution prevention performance, organic compounds with aluminum element having chelate structure, organic compounds with titanium element, and zirconium are preferred. Organic compounds of the elements. The compound is specifically described in the "Crosslinking Agent Handbook" (edited by Shinzo Yamashita and Tosuke Kaneko (Co., Ltd.) Daseisha, Heisei 2).

The formation of the oligomer prevention layer formed by the silica-based material can be carried out by dissolving the silica-based material in a solvent such as alcohol, and coating the resulting solution on a substrate On the film or conductive layer, and dry. The concentration of the solution in which the silica-based material is dissolved should not be particularly limited, but is preferably about 0.1-40% by weight. The drying temperature after coating should not be particularly limited, but it is preferably about 100 to 150°C. In addition, the drying time after coating should not be particularly limited, but it is preferably about 30 seconds to 30 minutes.

<Composition containing polyvinyl alcohol-based resin> As the polyvinyl alcohol-based resin, polyvinyl alcohol or a derivative thereof can be given. Examples of derivatives of polyvinyl alcohol include polyvinyl formal, polyvinyl acetal, etc., in addition to olefins such as ethylene and propylene, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid. Its alkyl ester, acrylamide and other modified resins. Only one type of polyvinyl alcohol resin may be used, or two or more types may be used.

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

The composition containing the polyvinyl alcohol-based resin may contain a binder polymer. Examples of binder polymers include polyacrylamide, polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches, polyurethane, polyester, polyacrylate, and chlorine-based Polymers (polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyolefins, etc. Among them, when the oligomer preventing layer is applied by the coating stretching method, organic polymers that can be used as nonionic, cationic, and amphoteric aqueous solutions or dispersions can be cited. In addition, in Among them, in the case of using polyurethane, polyester, or 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 crosslinking agents include methylolated or hydroxyalkylated urea-based, melamine-based, guanamine-based, acrylamide-based, polyamide-based compounds, epoxy compounds, aziridine compounds, and blocked Polyisocyanate, silane coupling agent, titanium coupling agent, aluminum zirconium coupling agent, etc. These crosslinking components can also be pre-bonded with the binder polymer.

The composition containing the polyvinyl alcohol-based resin may contain inorganic particles for the purpose of improving the fixability and sliding properties of the oligomer prevention layer. Examples of inorganic particles include silica, alumina, kaolin, calcium carbonate, titanium oxide, and barium salts.

The formation of the oligomer preventing layer can be performed by dissolving the composition containing the polyvinyl alcohol-based resin in a solvent such as water and alcohol, and coating the resulting solution on a substrate film or After the oligomer prevention layer is applied, 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 resin is dissolved should not be particularly limited, but is preferably about 0.1 to 40% by weight. The drying temperature after coating should not be particularly limited, but it is preferably about 60 to 200°C. In addition, the drying time after coating should not be particularly limited, but it is preferably about 3 to 60 seconds. If necessary, active energy ray irradiation such as heat treatment and ultraviolet irradiation may be used in combination.

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

The method for forming the oligomer prevention layer is not particularly limited, as long as it is appropriately selected according to its forming material, and a coating method, a spray method, a spin coating method, an inline coating method, etc. can be used. In addition, a vacuum vapor deposition method, a sputtering method, an ion plating method, a spray thermal decomposition method, an electroless plating method, an electroplating method, etc. can also be used.

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

<Conductive layer> The conductive layer of the present invention can suppress the generation of static electricity caused by the peeling of the spacer, and even if static electricity is generated due to the peeling of the spacer, the charge of the static electricity generated in the optical film with the adhesive layer can be fast Since the ground moves to the spacer after peeling, the 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, it can be a conductive composition using a conductive composition containing a conductive polymer, an anionic surfactant, a cationic surfactant, and a plasma surfactant. A layer formed of a conductive composition, a conductive composition containing metal oxides such as tin oxide, antimony oxide, indium oxide, and 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 of a conductive composition containing a conductive polymer.

Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, poly(ethylenedioxythiophene) (referred to as PEDOT), poly(ethylenedioxythiophene)/polystyrene sulfonic acid (Referred to as PEDOT/PSS) etc. From the perspective of anti-static interference and transparency, poly(ethylenedioxythiophene)/polystyrene sulfonic acid (referred to as PEDOT/PSS) is particularly preferred. Only one type of conductive polymer may be used, or two or more types may be used.

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

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

The formation of the conductive layer can be performed by dissolving a conductive composition containing the conductive polymer in a solvent such as water, alcohol, and coating the resulting solution on a substrate film or oligomer. After the material prevention layer is on, 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. In addition, the drying time after coating is not particularly limited, but it is preferably about 1 to 60 minutes.

The method of forming the conductive layer is not particularly limited, and a coating method, spray method, spin coating method, in-line coating method, etc. can be used.

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

<Release layer> Then, a release layer is provided on the oligomer prevention layer and the conductive layer of the present invention. The release layer is provided to improve the releasability from the adhesive layer. The material for forming the release layer is not particularly limited, and examples include silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based mold release agents. Among them, a silicone-based mold release agent is preferred. The release layer can be formed as a coating layer on the oligomer prevention layer and the conductive layer. In addition, the release layer can also be formed by transfer.

As said silicone type mold release agent, addition reaction type silicone resin is mentioned, for example. As addition reaction type silicone resins, KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T, TPR-6700, TPR manufactured by Toshiba Silicone manufactured by Shin-Etsu Chemical Industry -6710, TPR-6721, SD7220, SD7226 manufactured by Dow Corning Toray, etc.

The coating amount (after drying) of the silicone-based mold release layer is preferably in the range of 0.01 to 2 g/m ² , more preferably 0.01 to 1 g/m ² , and still more preferably 0.01 to 0.5 g/m ² .

The formation of the release layer can be performed by the following operations, for example, the above-mentioned materials are coated on the functional layer by a conventionally known coating method such as reverse gravure coating, bar coating, and die coating, and then, Generally, the heat treatment is performed at about 120 to 200°C for 30 seconds to 30 minutes to cure it. In addition, it is also possible to combine active energy ray irradiation such as heat treatment and ultraviolet irradiation as necessary.

The thickness of the release layer is usually 10 to 2000 nm, preferably 10 to 1000 nm, more preferably 10 to 500 nm.

The surface resistance value of the mold 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 spacer and suppressing white unevenness of the liquid crystal panel /□ or less, more preferably 1.0×10 ¹⁰ Ω/□ or less.

<Adhesive layer> The adhesive layer of the present invention is formed of an adhesive composition. Examples of the adhesive composition include rubber-based adhesive compositions, acrylic-based adhesive compositions, silicone-based adhesive compositions, urethane-based adhesive compositions, and vinyl alkyl ether-based adhesives. Composition, polyvinyl alcohol-based adhesive composition, polyvinylpyrrolidone-based adhesive composition, polyacrylamide-based adhesive composition, cellulose-based adhesive composition, etc. The adhesive composition preferably contains a base polymer.

<Base polymer> The base polymer can select an adhesive base polymer according to the type of the adhesive composition.

Among the adhesive compositions, from the viewpoints of excellent optical transparency, proper wettability, cohesiveness and adhesive properties, weather resistance and heat resistance, etc., it is preferable to use acrylic adhesive.剂组合物。 Agent composition. The acrylic adhesive composition preferably contains a (meth)acrylic polymer as an adhesive base polymer. The (meth)acrylic polymer is usually contained as a monomer unit with an alkyl (meth)acrylate as a main component. In addition, (meth)acrylate means acrylate and/or methacrylate, and the term (meth) in the present invention means the same.

As the (meth)acrylic acid alkyl ester constituting the main skeleton of the (meth)acrylic polymer, a linear or branched alkyl group having 1 to 18 carbon atoms (methyl) can be exemplified Alkyl acrylate. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, Nonyl, decyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. Alkyl (meth)acrylate may be used only 1 type or 2 or more types. The average number of carbon atoms of these alkyl groups is preferably 3-9.

In addition, as the alkyl (meth)acrylate, phenoxyethyl (meth)acrylate, (methyl) ) Alkyl (meth)acrylates containing aromatic rings such as benzyl acrylate.

In the (meth)acrylic polymer, for the purpose of improving adhesiveness and heat resistance, one or more kinds of unsaturated double bonds with (meth)acrylic groups or vinyl groups can be introduced by copolymerization. The comonomer of polymerizable functional groups. Specific examples of the comonomer include: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methacrylate Monomers containing hydroxyl groups such as (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. Body; maleic anhydride, itaconic anhydride and other acid anhydride group-containing monomers; acrylic acid caprolactone adducts; styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methyl Sulfonic acid group-containing monomers such as propanesulfonic acid, (meth)acrylamide propanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloxynaphthalenesulfonic acid; acrylic acid 2-hydroxyl phosphate Phosphoric acid group-containing monomers such as ethyl ester.

The (meth)acrylic polymer has an alkyl (meth)acrylate as the main component in the weight ratio of all constituent monomers, and the ratio of the comonomer in the (meth)acrylic polymer There is no particular limitation. However, the ratio of the comonomer is preferably about 0-20%, more preferably about 0.1-15%, and still more preferably about 0.1-10% in the weight ratio of all constituent monomers.

The (meth)acrylic polymer generally uses a polymer having a weight average molecular weight (Mw) in the range of 500,000 to 3 million. If durability is considered, especially heat resistance is considered, it is preferable to use a polymer having a weight average molecular weight (Mw) of 700,000 to 2.7 million, more preferably 800,000 to 2.5 million. If the weight average molecular weight (Mw) is less than 500,000, it is undesirable from the viewpoint of heat resistance. In addition, if the weight average molecular weight (Mw) is greater than 3 million, in order to adjust the viscosity for coating, a large amount of diluting solvent is required, which increases the cost, which is not desirable. In addition, the weight average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

For the production of the (meth)acrylic polymer, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. In addition, the obtained (meth)acrylic polymer may be any copolymer such as a random copolymer, a block copolymer, and a graft copolymer.

The polymerization initiator, chain transfer agent, emulsifier, etc. 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 usage amount of the polymerization initiator and the chain transfer agent, and the reaction conditions, and the usage amount can be appropriately adjusted according to the kind of the polymerization initiator and the chain transfer agent.

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

<Conductive compound> The adhesive composition of the present invention preferably contains a conductive compound in addition to the base polymer. Examples of conductive compounds include ionic compounds, ionic surfactants, conductive polymers, and metal oxides.

As the ionic compound, alkali metal salts and/or organic cation-anion salts can be preferably used. As the alkali metal salt, organic salts and inorganic salts of alkali metals can be used. Furthermore, the "organic cation-anion salt" in the present invention refers to an organic salt, and means a salt whose cation portion is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. "Organic cation-anion salt" is also called ionic liquid or ionic solid. Only one type of ionic compound may be used, or two or more types may be used.

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

The anion part of the alkali metal salt may be composed of an organic substance or an inorganic substance. As the anion part constituting the organic salt, 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 the following formula (1 ) an anionic portion and the like to _{(4): (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 ^- (wherein, 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, q is an integer of 1 to 10). In particular, the anion portion containing a fluorine atom is preferably used because an ionic compound with good ion dissociation properties can be obtained. Examples of the anionic portion constituting the inorganic salt may be used ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF ₆ ^－ , NbF ₆ ^－ , TaF ₆ ^－ , (CN) ₂ N ^－ etc. Examples of the anionic portion is preferably _{(CF 3 SO 2) 2 N} -, (C 2 F 5 SO 2) 2 N - etc. (perfluoroalkyl sulfonylurea) imide by the general formula (1), Particularly preferred is (trifluoromethanesulfonamide) imine represented by (CF ₃ SO ₂ ) ₂ N ^- .

As the organic salt of alkali metal, specifically, sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, 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 them, 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 ₄ F ₉ SO ₂ ) ₂ N and other fluorine-containing imide lithium salt, particularly preferably (perfluoroalkylsulfonyl) imide lithium salt.

In addition, examples of inorganic salts of alkali metals include lithium perchlorate and lithium iodide.

The organic cation-anion salt is composed of a cation component and an anion component, and the cation component is composed of an organic substance. Specific examples of the cationic component include: pyridinium cation, pyridinium cation, pyrrolidinium cation, pyrroline skeleton cation, pyrrole skeleton cation, imidazolium cation, tetrahydropyrimidinium cation, di Hydropyrimidinium cation, pyrazolium cation, pyrazolium cation, tetraalkylammonium cation, trialkylaluminium cation, tetraalkylphosphonium cation, etc.

Examples of the anion component include ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 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 according to the following general formula (1) to (4) the anion component represented _{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 ^- (wherein, 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 ) (where p and q are integers from 1 to 10). Among them, especially anion components containing fluorine atoms can obtain good ion dissociation Ionic compounds are therefore preferably used.

In addition, as the ionic compound, in addition to the alkali metal salt, organic cation-anion salt, ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, sulfuric acid Inorganic salts such as ammonium.

Examples of the ionic surfactant include cationic (quaternary ammonium salt type, phosphonium salt type, sulfonate type, etc.), anionic type (carboxylic acid type, sulfonate type, sulfate type, phosphate type, etc.) , Sulfite type, etc.), zwitterionic type (sulfobetaine type, alkyl betaine type, alkyl imidazolium betaine type, etc.) or non-ionic type (polyol derivatives, β-cyclodextrin inclusion compound , Sorbitan fatty acid monoesters and diesters, polyalkylene oxide derivatives, amine oxides, etc.) various surfactants. The ionic surfactant may be used alone or in two or more types.

Examples of the conductive polymer include polyaniline, polythiophene, polypyrrole, polyquinoxaline and other polymers. Among them, it is preferable to use a water-soluble conductive polymer or water. Disperse conductive polymer such as polyaniline and polythiophene. Particularly preferred is polythiophene. Only one type of conductive polymer may be used, or two or more types may be used.

As said metal oxide, tin oxide type, antimony oxide type, indium oxide type, zinc oxide type, etc. are mentioned. Among them, tin oxide is preferred. As tin oxide-based metal oxides, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide composites, Titanium oxide-tin oxide composites, etc. Only one type of metal oxide may be used, or two or more types may be used.

In addition, examples of conductive compounds other than those described above include acetylene black, Ketjen black, natural graphite, artificial graphite, titanium black, or cationic (quaternary ammonium salts, etc.), zwitterionic (betaine compounds, etc.) , Anionic (sulfonate, etc.) or non-ionic (glycerol, etc.) ionic conductive group monomer homopolymers or copolymers of this monomer and other monomers, with quaternary ammonium salt groups The acrylate or methacrylate part of the polymer and other polymers with ion conductivity; the type of alloying hydrophilic polymers such as polyethylene methacrylate copolymer with acrylic resins, etc. permanent anti-static interference Agent.

From the viewpoint of high conductivity, excellent dispersibility in the adhesive, and transparency, and the viewpoint of storage stability in the adhesive, it is preferable to use an ionic compound as the conductive compound.

The blending ratio of the conductive compound is preferably 0.0001 to 5 parts by weight with respect to 100 parts by weight of the base polymer. If the conductive compound is less than 0.0001 part by weight, the effect of improving the anti-static interference performance may be insufficient. On the other hand, if the conductive compound exceeds 5 parts by weight, the durability may be insufficient. The conductive compound is preferably 0.01 part by weight or more, more preferably 0.1 part by weight or more. In addition, the conductive compound is preferably 3 parts by weight or less, more preferably 2 parts by weight or less.

In addition, the adhesive composition of the present invention may contain a crosslinking agent. As the crosslinking agent, organic crosslinking agents and polyfunctional metal chelate compounds can be used. Examples of the organic crosslinking agent include isocyanate-based crosslinking agents, peroxide-based crosslinking agents, epoxy-based crosslinking agents, and imine-based crosslinking agents. Multifunctional metal chelate is a compound in which a multivalent metal and an organic compound form a covalent bond or a coordinate bond. Examples of multivalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti Wait. Examples of the atoms in the organic compound forming a covalent bond or coordination bond include an oxygen atom, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds. As the crosslinking agent, isocyanate-based crosslinking agents and peroxide-based crosslinking agents are preferred. As for the crosslinking agent, only 1 type may be used, and 2 or more types may be used.

The mixing ratio of the crosslinking agent is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight relative to 100 parts by weight of the base polymer. Moreover, if the crosslinking agent is less than 0.01 parts by weight, the cohesive force of the adhesive tends to be insufficient, and foaming may occur during heating. On the other hand, if the crosslinking agent is greater than 20 parts by weight, the moisture resistance is insufficient and the Peeling easily occurs during performance tests.

In addition, the adhesive composition of the present invention may contain a silane coupling agent. By using silane coupling agent, durability can be improved. Only one type of silane coupling agent may be used, or two or more types may be used.

The mixing ratio of the silane coupling agent is preferably 0.001 to 5 parts by weight relative to 100 parts by weight of the base polymer, more preferably 0.01 to 1 part by weight, and still more preferably 0.02 to 1 part by weight Parts, particularly preferably 0.05 to 0.6 parts by weight. In order to improve durability and appropriately maintain the adhesive force to optical members such as liquid crystal panels, it can be appropriately selected within this range.

In addition, the adhesive composition of the present invention may also contain other well-known additives, and powders such as colorants and pigments, dyes, surfactants, plasticizers, and tackifiers may be appropriately added according to the intended use. Agents, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. . In addition, a redox system with a reducing agent can also be used within a controllable range.

The adhesive layer with the spacer of the present invention can be produced by applying a solution containing the adhesive composition on the release layer of the spacer, and then drying to form an adhesive layer. In addition, at the time of applying the adhesive composition, one or more solvents other than the polymerization solvent may be newly added as appropriate.

As a coating method of the adhesive composition, various methods can be used. Specifically, the roller coating method, the roller lick coating method, the gravure coating method, the reverse coating method, the roller brush method, the spray method, the immersion roller coating method, the bar coating method, the blade coating method, the gas Knife coating method, curtain coating method, die lip coating method, extrusion coating method by die coater, etc.

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

From the viewpoint of imparting conductivity to the spacer-attached adhesive layer and suppressing white unevenness of the liquid crystal panel, the surface resistance value of the adhesive layer is preferably 1.0×10 ¹² Ω/□ or less, more preferably 1.0× 10 ¹¹ Ω/□ or less, more preferably 1.0×10 ¹⁰ Ω/□ or less.

<Optical film with spacer-attached adhesive layer> The optical film with spacer-attached adhesive layer of the present invention has the adhesive layer side of the spacer-attached adhesive layer bonded to at least one surface of the optical film.

As the optical film, optical films used in the formation of image display devices such as liquid crystal display devices can be used, and the type thereof is not particularly limited. Examples of the optical film include surface treatment films such as polarizing films, retardation films, optical compensation films, brightness enhancement films, or anti-reflection films, and laminates of these films.

The polarizing film generally uses a polarizing film having a transparent protective film on one or both sides of a polarizer. The polarizer is not particularly limited, and various polarizers can be used. Examples of polarizers include two hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films, which adsorb iodine or dichroic dyes. Materials obtained by uniaxially stretching coloring substances, polyolefin-based alignment films such as dehydrated polyvinyl alcohol or dehydrated polyvinyl chloride. Among them, a polarizer containing a dichroic substance such as a polyvinyl alcohol-based film and iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

In addition, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer has little unevenness in thickness, is excellent in observability, and has little dimensional change, so it is excellent in durability. In addition, the thickness of the polarizing film can also be reduced in thickness, which is preferable.

As a 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 thermoplastic resins include cellulosic resins such as triacetyl cellulose, polyester resins, polyether resins, polycarbonate resins, polycarbonate resins, polyamide resins, and polyimide resins. , Polyolefin resin, (meth)acrylic resin, cyclic polyolefin resin (norbornene resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof. Moreover, although the transparent protective film is attached to one side of the polarizer with an adhesive layer, on the other side, as a transparent protective film, (meth)acrylic, urethane, or acrylic amine can be used. Thermosetting resins or ultraviolet curing resins such as carbamic acid ester, epoxy, and silicone. One or more arbitrary suitable additives may be contained in the transparent protective film.

The adhesive used for bonding the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various forms of water-based, solvent-based, hot-melt-based, radical-curing type, and cation-curing type can be used. However, water-based adhesives or radical curing adhesives are preferred.

<Image display device> The image display device of the present invention is attached to at least one surface of the display panel from the optical film with the adhesive layer with spacers, and peels off the optical film with the adhesive layer in the state of the spacers The adhesive layer side. As a display panel, a liquid crystal panel etc. are mentioned. Any type of liquid crystal panel such as TN type, STN type, π type, VA type, and IPS type can be used for the liquid crystal panel.

<The manufacturing method of the image display device> The manufacturing method of the image display device of the present invention is a manufacturing method including the following steps: a roll preparation step, preparing a long sheet of optical film with a spacer-attached adhesive layer as a roll The display panel transportation preparation step, the display panel is transported to the bonding position and prepared; and the bonding step (RTP bonding step), the optical film with the adhesive layer with spacers is extracted from the roll , And while peeling the spacer from the optical film with the spacer with the adhesive layer using the release body, the adhesive layer side of the optical film with the adhesive layer exposed after the spacer is peeled is bonded to Transported to the display panel at the pasting position.

<The coil preparation step> The coil preparation step is a step of manufacturing an optical film with a spacer-attached adhesive layer as a long (belt-shaped) sheet of the coil. The coil is not particularly limited and can be Manufactured in the past method.

<Display panel transportation preparation step> The display panel transportation preparation step is a step of transporting a display panel such as a liquid crystal panel to the pasting position. The transportation method is not particularly limited, and it can be transported in accordance with the conventional method.

<RTP bonding step> A typical schematic diagram of the RTP bonding step is shown in FIG. 3. Immediately before the long sheet of the optical film 3 with the adhesive layer with spacers drawn from the roll is transported to the sticking position 101, it is peeled from the optical film 3 with the adhesive layer with spacers The body 100 peels off the spacer 1. The adhesive layer 21 of the optical film 4 with the adhesive layer exposed after the spacer 1 is peeled off is bonded by the adhesive roller 103 to the display panel 5 guided by the receiving roller 102 to the predetermined position 101 to produce an image Display device.

In the RTP bonding step, since the optical film 3 with the spacer-attached adhesive layer is a long strip that has not been cut, after the spacer 1 is peeled off, the long sheet-like adhesive layer The optical film 4 (or the adhesive layer 21) is also in a state of continuing contact with the spacer 1 before peeling. Therefore, even if static electricity is generated on the long sheet-shaped optical film 4 (or adhesive layer 21) with the adhesive layer attached due to the peeling of the spacer 1, the static charge can be quickly peeled off via the spacer 1 before peeling. After the spacer 1 moves, the separated spacer 1 functions as a ground. As a result, the electrostatic charge is attenuated.

In addition, the manufacturing method of the image display device may also be manufactured by bonding the display panel and the optical film with the adhesive layer, appropriately assembling the components such as the lighting system used as needed, and then incorporating the driving circuit. For example, Examples include a method of manufacturing a liquid crystal display device in which an optical film with an adhesive layer is arranged on one or both sides of a display panel such as a liquid crystal panel, and a method of manufacturing a liquid crystal display device using a backlight or a reflector in an illumination system. In this case, the optical film with an adhesive layer of the present invention can be provided on one 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. In addition, in the method of manufacturing a liquid crystal display device, one or two or more diffusion layers, anti-glare layers, anti-reflection films, protective plates, prism arrays, lens array sheets, light diffusion sheets, Appropriate components such as backlights.

[Examples] Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited by these examples. In addition, parts and% in each example are based on weight.

Example 1 <Production of spacer> <<Formation of oligomer prevention layer>> As a silica-based material, organosiloxane (Ethyl Silicate 48: COLCOAT) was diluted with isopropanol to a solid content concentration of 1% to prepare a coating liquid. The resulting coating solution was coated on a polyester film (thickness: 38μm) as a base film using a gravure coater so that the thickness after drying was 50nm, and dried at 120°C for 30 seconds to form an oligomer prevention layer (1).

＜＜Formation of conductive layer＞＞ As a conductive polymer, poly(ethylenedioxythiophene)/polystyrene sulfonic acid (PEDOT/PSS) was used to prepare water/isopropyl group with a solid content of 1% Alcohol (1/1: weight ratio) solution. The obtained solution was coated on the oligomer prevention layer (1) so that the thickness after drying was 100 nm, and dried at 80° C. for 2 minutes to form the conductive layer (1).

＜＜Formation of the release layer＞＞ The silicone resin (KS-847H: manufactured by Shin-Etsu Chemical): 20 parts and curing agent (PL-50T: manufactured by Shin-Etsu Chemical): 0.2 parts are mixed with methyl ethyl ketone/toluene mixed solvent (mixing ratio is 1:1) Dilute 350 parts to prepare a silicone-based release agent solution. The obtained silicone-based mold release agent solution was coated on the conductive layer (1) with a gravure coater so that the thickness after drying was 100 nm, and then dried at 120°C for 30 seconds to form a mold release layer to obtain a poly The spacer of Example 1 with the composition of ester film/oligomer prevention layer (1)/conductive layer (1)/release layer.

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

<<Formation of oligomer prevention layer>> As a silica-based material, a silica sol with an average particle diameter of 0.05 μm was diluted with isopropanol to a solid content concentration of 1% to prepare a coating liquid. The obtained coating liquid was coated on the conductive layer (1) with a gravure coater so that the thickness after drying was 50 nm, and then dried at 120° C. for 30 seconds to form the oligomer prevention layer (2).

<<Formation of the release layer>> In Example 1, the same as in Example 1, except that the release layer was formed on the oligomer preventing layer (2) in the case of <<Formation of the release layer>> The spacer of Example 2 having a composition of polyester film/conductive layer (1)/oligomer prevention layer (2)/release layer was obtained.

Example 3 <Production of spacer> <<Formation of conductive layer>> As the conductive polymer, poly(ethylenedioxythiophene)/polystyrene sulfonic acid (PEDOT/PSS) was used as the binder resin, Using polyurethane resin, a water/isopropyl alcohol (1/1: weight ratio) solution with a solid content concentration of 0.8% was prepared. Furthermore, the weight ratio of the conductive polymer to the binder resin is 10:1. The obtained solution was coated on a polyester film (thickness: 38 μm) as a base film so that the thickness after drying was 100 nm, and dried at 80° C. for 2 minutes to form a conductive layer (2).

＜＜Formation of oligomer prevention layer＞＞ ＜＜Formation of mold release layer＞＞ Except in Example 2, when ＜＜Formation of oligomer prevention layer＞＞, ＜＜Formation of release layer＞＞ , The oligomer prevention layer (2) is formed on the conductive layer (2), and the release layer is provided on the oligomer prevention layer (2), and the polyester film/conductive layer is obtained in the same manner as in Example 2 (2) The spacer of Example 3 of the structure of (2)/oligomer prevention layer (2)/release layer.

Example 4 <Production of spacer> <<Formation of oligomer prevention layer>> As a composition containing a polyvinyl alcohol resin, a polyvinyl alcohol resin (degree of saponification=88 mol%, degree of polymerization=500 Polyvinyl alcohol) 70 parts, binder polymer (water-based polyester resin: polyester copolymerized with isophthalic acid, ethylene glycol, and diethylene glycol, with aliphatic dicarboxylic anhydride The dicarboxylic acid derivative of the resulting polyester is neutralized and hydrated with an amine compound to obtain 15 parts of an aqueous polyester, 10 parts of a crosslinking agent (hexamethoxymethyl melamine), and inorganic particles (average particle size) 5 parts of silica sol with a diameter of 65 nm) was diluted with water to a solid content concentration of 2% to prepare a coating liquid. The obtained coating solution was applied to a polyester film (thickness: 38μm) as a base film using a gravure coater so that the thickness after drying was 50nm, and the film was introduced into a stenter and stretched at 100°C Then, heat fixation is performed at 230°C to form an oligomer prevention layer (3).

<<Formation of conductive layer>> <<Formation of release layer>> In Example 1, in the case of <<Formation of conductive layer>> and <<Formation of release layer>>, the same as in Example 1 The spacer of Example 4 having a composition of polyester film/oligomer prevention layer (3)/conductive layer (1)/release layer was obtained.

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

Comparative Example 2 <Production of spacer> <<Formation of oligomer prevention layer with conductive agent added>> As a composition for forming an oligomer prevention layer with conductive agent added, a compound having a nitrogen element as a conductive material ( Compound having a pyrrolium ring in the main chain: Daiichi Kogyo Pharmaceutical Co., Ltd.: Sharoll DC-303P) 85 parts, polyvinyl alcohol resin (polyvinyl alcohol with saponification degree = 88 mol%, polymerization degree = 500) 10 Part, 5 parts of inorganic particles (silica sol with an average particle diameter of 50 nm) were diluted with water to a solid content concentration of 2% to prepare a coating liquid. The obtained coating solution was applied to a polyester film (thickness: 38μm) as a base film using a gravure coater so that the thickness after drying was 50nm, and the film was introduced into a stenter and stretched at 100°C Then, heat fixation is performed at 230°C to form an oligomer prevention layer with conductive agent added.

<<Formation of the release layer>> In Example 1, the same as Example 1 except that in the case of <<Formation of the release layer>>, the release layer was formed on the oligomer prevention layer with the conductive agent added Thus, a separator of Comparative Example 2 having a configuration of a polyester film/conducting agent-added oligomer prevention layer/release layer was obtained.

<Preparation of adhesive layer with spacer> <<Preparation of acrylic polymer>> Into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, add 99 parts of butyl acrylate and acrylic 4- A monomer mixture of 1 part of hydroxybutyl ester. Next, with respect to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile and ethyl acetate were added as a polymerization initiator, and nitrogen was introduced while stirring slowly. After the nitrogen replacement, the liquid temperature in the flask was maintained at around 60°C to perform the polymerization reaction for 7 hours. Then, ethyl acetate was added to the obtained reaction liquid, and the solution of the acrylic polymer of 1.6 million weight average molecular weight (Mw) adjusted to 30% of solid content concentration was prepared.

<<Preparation of adhesive 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 is blended as an ionic compound. 0.7 part of trifluoromethanesulfonimide, and 1.0 part of lithium bis(trifluoromethanesulfonate)imide (manufactured by Mitsubishi Materials Electronics Co., Ltd.) as a crosslinking agent, combined with trimethylolpropane xylene diisocyanate (Mitsui Chemical Co., Ltd.: Takenate D110N) 0.1 part, and 0.3 part of diphenylmethyl peroxide, as a silane coupling agent, mixed with γ-glycidoxypropyl methoxysilane (Shin-Etsu Chemical Co., Ltd.: KBM -403) 0.2 parts to obtain a solution of the adhesive composition.

<<Formation of Adhesive Layer>> The solution of the adhesive 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 using a jet coater After the release layer on the release layer, it was dried in an air-circulating constant temperature oven at 150°C for 60 seconds to form an adhesive layer with a thickness of 20 μm on the surface of the release layer to obtain Examples 1 to 4 and Comparative Examples 1 to 2 Adhesive layer with spacers.

＜Production of optical film with adhesive layer with spacer＞ ＜＜Production of optical film＞＞ In order to produce a thin polarizer, first of all, use an amorphous polyethylene terephthalate (PET) base A laminate with a 9μm-thick polyvinyl alcohol (PVA) layer formed on the material is stretched by air-assisted stretching at a stretching temperature of 130°C to produce a stretched laminate, and then the stretched laminate is dyed to produce a colored laminate, and then The colored laminate was stretched in boric acid water at a stretching temperature of 65°C to produce an optical film laminate comprising a 4μm thick PVA layer stretched integrally with an amorphous PET substrate so that the total stretch ratio was 5.94 times . With this two-stage stretching, the PVA molecules of the PVA layer formed on the amorphous PET substrate are aligned to a high degree, and the following optical film laminate can be produced. The iodine adsorbed by dyeing is used as polymer A highly functional polarizer in which an iodide ion complex is aligned in one direction at a high order and includes a PVA layer with a thickness of 4 μm. In addition, a polyvinyl alcohol-based adhesive was applied to the surface of the polarizer of the optical film laminate, and a saponified 80 μm-thick triacetyl cellulose film was laminated, and then the amorphous PET substrate was peeled off. Manufactured polarizing films using thin polarizers.

<Preparation of optical film with adhesive layer with spacer> Then, on the polarizing film using the thin polarizer obtained by the above operation, the Examples 1 to 4 and the comparative example 1 obtained by the above operation were bonded together The adhesive layer with spacer of 2 was transferred to the adhesive layer, and the optical film with the adhesive layer with spacer of Examples 1-4 and Comparative Examples 1-2 was obtained.

<Production of image display device> In order to manufacture an image display device using the RTP bonding process shown in FIG. 3, the spacers of Examples 1 to 4 and Comparative Examples 1 to 2 obtained by the above operations were prepared as roll materials. The long strip of optical film of the adhesive layer is prepared for the liquid crystal panel to be transported to the sticking position. After that, the optical films with the adhesive layer with spacers of Examples 1 to 4 and Comparative Examples 1 to 2 were taken out from the roll, and the optical film with the adhesive layer with spacers was used as a release body While peeling the spacer, the adhesive layer side of the optical film with the adhesive layer exposed after the spacer was peeled was bonded to the liquid crystal panel that was transported to the bonding position to manufacture and use Examples 1 to 4 and Comparative Examples 1 to 2 LCD panel image display device (liquid crystal display device).

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.・Analysis device: Tosoh Corporation, HLC-8120GPC ・Column: Tosoh Corporation, G7000HXL+GMHXL+GMHXL ・Column size: 7.8mmφ×30cm each ・Column temperature: 40°C ・Flow rate: 0.8ml/min ・Injection volume : 100μl ・Eluent: Tetrahydrofuran ・Detector: Differential Refractometer (RI) ・Standard sample: Polystyrene

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

<Method for measuring the surface resistance of the release layer> The spacers of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation were measured using MCP-HT450 manufactured by Mitsubishi Chemical Analytech. Surface resistance value (Ω/□).

<Method for measuring the surface resistance of the adhesive layer> The adhesive layers with spacers of Examples 1 to 4 and Comparative Examples 1 to 2 obtained by the above operation were measured for adhesion using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd. The surface resistance value of the surface of the agent layer (Ω/□).

<Method for measuring the elution amount of PET oligomer> The optical films with spacer-attached adhesive layers of Examples 1 to 4 and Comparative Examples 1 to 2 obtained by the above operation were heated at 60°C and 90%RH After standing for 500 hours under the conditions, the spacer was removed. Collect about 0.025 g of the adhesive layer (sample) from the polarized film with the adhesive layer, add 1 ml of chloroform and shake at room temperature for 18 hours, then add 5 ml of acetonitrile for extraction and shake for 3 hours. The resulting solution was filtered using a 0.45ml membrane filter to adjust the sample. The trimer PET oligomer standard was adjusted to a certain concentration to create 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 created by using a sample with a known PET oligomer concentration (ppm) and measuring by HPLC. HPLC device: 1200 series manufactured by Agilent Technologies Chromatographic column: ZORBAX SB-C18 manufactured by Agilent Technologies Column temperature: 40°C Column flow: 0.8ml/min Eluent composition: Water/acetonitrile reversed phase gradient conditions Injection volume: 5μl detector : PDA Quantitative method: After dissolving a standard sample of PET oligomer trimer in chloroform, dilute it with acetonitrile to prepare a standard sample at a certain concentration. A calibration curve was prepared from the HPLC area and preparation concentration, and the elution amount of the PET oligomer of the sample was obtained. Furthermore, the elution amount of the PET oligomer is preferably 30 ppm or less, more preferably 20 ppm or less, and still more preferably 10 ppm or less.

The following evaluations were performed on the liquid crystal display devices of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by the above operation. 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 installed on a backlight. When the hand touches the end of the installed liquid crystal display device, white unevenness occurs in the liquid crystal panel. The time until the white unevenness disappeared was measured. The disappearance 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, for Examples 1 to 4 of the present invention, good results were obtained in any evaluation items. On the other hand, in Comparative Examples 1-2, results inferior to Examples 1-4 were obtained in any evaluation item. From this result, according to the present invention, it is possible to provide a spacer-attached adhesive layer, which can prevent elution of oligomers contained in a base film such as a polyester film used in the spacer to the adhesive layer. The poor condition of the liquid crystal panel caused by the uneven brightness caused by the bright spot, and in the manufacture of the liquid crystal display device, even if the above-mentioned RTP bonding step is applied, the white unevenness of the liquid crystal panel can be suppressed. In addition, additional accessories can be provided. Optical film with adhesive layer with spacers.

1‧‧‧Spacer 2‧‧‧Adhesive layer with spacer 3‧‧‧Optical film with adhesive layer with spacer 4‧‧‧Optical film with adhesive layer 5‧‧‧Display Panel 11‧‧‧Substrate film 12‧‧‧Release layer 13‧‧‧Oligomer prevention layer 14‧‧‧Conductive layer 21‧‧‧Adhesive layer 31‧‧‧Optical Film 100‧‧‧Peeling body 101‧‧‧Paste position 102‧‧‧Receiving roller 103‧‧‧Adhesive roller

Fig. 1 (a), (b) is a schematic cross-sectional view showing a configuration example of an adhesive layer with a spacer. Fig. 2 is a schematic cross-sectional view showing a configuration example of an optical film with a spacer-attached adhesive layer. 3 is a schematic diagram illustrating the RTP bonding step in the manufacturing method of the image display device.

1‧‧‧Spacer

2‧‧‧Adhesive layer with spacer

11‧‧‧Substrate film

12‧‧‧Release layer

13‧‧‧Oligomer prevention layer

14‧‧‧Conductive layer

21‧‧‧Adhesive layer

Claims (8)

A spacer-attached adhesive layer is a spacer-attached adhesive layer with an adhesive layer on the spacer, characterized in that the spacer has a release layer on the base film, and the base film is There is an oligomer prevention layer and a conductive layer between the mold release layer and the mold release layer; the adhesive layer is provided on the mold release layer of the spacer; and the adhesive layer is made of an adhesive containing a base polymer and a conductive compound The layer formed by the agent composition. According to the adhesive layer with spacer of claim 1, wherein the oligomer preventing layer is a layer formed of a composition containing a silica-based material and/or a polyvinyl alcohol-based resin. The adhesive layer with spacer of claim 1 or 2, wherein the conductive layer is a layer formed of a conductive composition containing a conductive polymer. For example, the adhesive layer with spacer of claim 1 or 2, wherein the surface resistance of the release layer is 1.0×10 ¹² Ω/□ or less. For example, the adhesive layer with spacer of claim 1 or 2, wherein the surface resistance of the adhesive layer is 1.0×10 ¹² Ω/□ or less. An optical film with a spacer-attached adhesive layer, characterized in that at least one side of the optical film is laminated with: the spacer-attached adhesive layer of any one of claims 1 to 5 side. An image display device, characterized in that at least one surface of the display panel is attached with: from the attached item of claim 6 For the optical film with the adhesive layer with the spacer, peel off the adhesive layer side of the optical film with the adhesive layer in the spacer state. A method for manufacturing an image display device is the method for manufacturing an image display device according to claim 7, which is characterized in that it comprises: a coil preparation step, which prepares an adhesive layer with spacers as described in claim 6. The long piece of film is used as a roll; the display panel transport preparation step is prepared by transporting the display panel to the bonding position; and the bonding step is to extract the optical film with the adhesive layer with spacers from the roll , And while peeling the spacer from the aforementioned optical film with the spacer with the adhesive layer by the release body, the adhesive layer side of the optical film with the adhesive layer exposed after the aforementioned spacer is peeled is pasted on the transport To the aforementioned display panel at the aforementioned pasting position.

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