JP6208728B2 - Pressure-sensitive adhesive layer with separator, optical film with pressure-sensitive adhesive layer with separator, image display device, and manufacturing method thereof - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive layer with a separator and an optical film with a pressure-sensitive adhesive layer with a separator. The present invention relates to an image display device in which the pressure-sensitive adhesive layer side of an optical film with a pressure-sensitive adhesive layer in a state where a separator is peeled off from the optical film with a pressure-sensitive adhesive layer with a separator is bonded to a display panel, and a method for manufacturing the same. .

  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 antireflection film, and a laminate of these films can be used. The optical film with the pressure-sensitive adhesive layer in which the separator is peeled from the optical film with the pressure-sensitive adhesive layer with separator is used for image display devices such as liquid crystal display devices, organic EL display devices, CRTs, and PDPs.

  An optical film such as a polarizing film is used for an image display device such as a liquid crystal display device. When the optical film is attached to a display panel such as a liquid crystal panel, an adhesive is usually used. In general, since it has the merit that a drying step is not required for attaching an optical film, an optical film with an adhesive layer in which an adhesive is provided in advance as an adhesive layer on one side of the optical film. Is used. The optical film with the pressure-sensitive adhesive layer is usually a separator provided with a separator (also referred to as a release film or a release liner) on the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive layer before sticking. Manufactured as an optical film with an adhesive layer.

  Such an optical film with a pressure-sensitive adhesive layer with a separator is a liquid crystal panel due to luminance unevenness due to bright spots, etc., by eluting oligomers contained in a base film such as a polyester film used in the separator into the pressure-sensitive adhesive layer. Since defects may occur, Patent Document 1 proposes to provide an oligomer prevention layer on the separator.

  Further, in the manufacture of a liquid crystal display device, when the separator of the optical film with the pressure-sensitive adhesive layer with a separator is peeled off, static electricity (peeling charging) occurs in the optical film with the pressure-sensitive adhesive layer and the separator. When the optical film with an adhesive layer having static electricity is bonded to the liquid crystal panel, induction charging occurs in the liquid crystal panel. The charge of induction charging affects the alignment of the liquid crystal of the liquid crystal panel and causes defects such as image display unevenness. Furthermore, static electricity may cause problems such as the occurrence of product defects due to the attachment or entrainment of foreign substances or the like at the manufacturing site.

  Patent Documents 2 to 4 propose a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer imparted with an antistatic function by blending an ionic compound or a conductive polymer in the pressure-sensitive adhesive layer in order to suppress the generation of static electricity. Yes. Patent Document 5 proposes a separator in which an antistatic function is added to the release layer of the separator.

JP 2006-113600 A JP-A-6-128539 Special table 2007-536427 gazette JP 2003-246874 A JP 2014-141557 A

  However, even when an optical film with a pressure-sensitive adhesive layer with a separator using the separator of Patent Document 5 is used, generation of static electricity at the time of separation of the separator cannot be sufficiently suppressed. In particular, an optical film with a pressure-sensitive adhesive layer exposed after peeling of the separator while the separator is peeled off from the optical film with the pressure-sensitive adhesive layer with a separator (see FIG. 3) with a release body (see FIG. 3). When manufacturing in the process of bonding the adhesive layer side of the liquid crystal panel to a liquid crystal panel (roll-to-panel (RTP) bonding process), the liquid crystal panel has an optical film with an adhesive layer that has static electricity that is not attenuated. It has been found that induction charging is caused by bonding. In the subsequent manufacturing process, the inductively charged liquid crystal panel comes into contact with a dielectric such as a manufacturing device, so that a current (magnetic field) is generated in the liquid crystal panel and the liquid crystal panel becomes white due to poor alignment of the liquid crystal. (Light leakage) occurs. Once white unevenness occurs in the liquid crystal panel, the white unevenness continues until the liquid crystal alignment returns to the original state. This causes a problem that the quality inspection in the manufacturing process is delayed and the production efficiency is deteriorated.

  The present invention is able to prevent problems in the liquid crystal panel due to luminance unevenness due to bright spots, etc. by suppressing the oligomer contained in the base film such as polyester film used in the separator from eluting into the adhesive layer, and An object of the present invention is to provide a pressure-sensitive adhesive layer with a separator and an optical film with a pressure-sensitive adhesive layer with a separator that can suppress white unevenness of a liquid crystal panel even when the above RTP bonding step is applied during the production of a liquid crystal display device. To do.

  In the present invention, the pressure-sensitive adhesive layer side of the optical film with the pressure-sensitive adhesive layer in a state where the separator is peeled off is bonded to at least one surface of the display panel from the optical film with the pressure-sensitive adhesive layer with separator. An object of the present invention is to provide an image display device characterized by the above and a method for manufacturing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found the following pressure-sensitive adhesive layer with a separator, an optical film with a pressure-sensitive adhesive layer with a separator, an image display device and a method for producing the same, and completed the present invention. It came to do.

  That is, the present invention is a pressure-sensitive adhesive layer with a separator having a pressure-sensitive adhesive layer on a separator, the separator having a release layer on a base film, and the base film and the release layer The pressure-sensitive adhesive layer has a separator-preventing pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is provided in a release layer of the separator.

  In the pressure-sensitive adhesive layer with a separator of the present invention, the oligomer prevention layer is preferably a layer formed of a composition containing a silica-based material and / or a polyvinyl alcohol-based resin.

  In the pressure-sensitive adhesive layer with a separator of the present invention, the conductive layer is preferably a layer formed of a conductive composition containing a conductive polymer.

In the pressure-sensitive adhesive layer with a separator of the present invention, the release layer preferably has a surface resistance value of 1.0 × 10 ¹² Ω / □ or less.

  In the pressure-sensitive adhesive layer with a separator of the present invention, the pressure-sensitive adhesive layer is preferably a layer formed from a pressure-sensitive adhesive composition containing a base polymer and a conductive compound.

In the pressure-sensitive adhesive layer with a separator of the present invention, the surface resistance value of the pressure-sensitive adhesive layer is preferably 1.0 × 10 ¹² Ω / □ or less.

  The present invention relates to an optical film with a pressure-sensitive adhesive layer with a separator, wherein the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive layer with a separator is bonded to at least one surface of the optical film.

  In the present invention, the pressure-sensitive adhesive layer side of the optical film with the pressure-sensitive adhesive layer in a state where the separator is peeled off is bonded to at least one surface of the display panel from the optical film with the pressure-sensitive adhesive layer with separator. The present invention relates to a characteristic image display device.

  The present invention is a method for manufacturing the image display device, comprising: a roll original fabric preparation step of preparing a long sheet of an optical film with a separator-attached adhesive layer as a roll original fabric; The display panel transport preparation step to be prepared, and the optical with adhesive layer exposed after peeling of the separator while peeling the separator from the optical film with adhesive layer with separator separated from the roll raw fabric. And a bonding step of bonding the adhesive layer side of the film to the display panel conveyed to the bonding position.

  The pressure-sensitive adhesive layer with a separator of the present invention has a configuration in which an oligomer prevention layer and a conductive layer are laminated between a separator base film and a release layer. The oligomer prevention layer can suppress the oligomer contained in the base film such as polyester film of the separator from eluting into the pressure-sensitive adhesive layer, and is useful for preventing defects in the liquid crystal panel such as luminance unevenness due to bright spots. It is.

  In addition, the optical film with the pressure-sensitive adhesive layer with a separator according to the present invention in which the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive layer with a separator is attached to the optical film, the separator has a conductive layer. There is little outbreak. On the other hand, when a conductive agent such as a conductive compound is added to the oligomer prevention layer or the release layer, the conductive agent in the oligomer prevention layer or the release layer interacts with the conductive adhesive, thereby preventing the antistatic function. Although it may be damaged, in the present invention, sufficient conductivity performance can be imparted to the separator surface by laminating the oligomer prevention layer and the conductive layer.

  Furthermore, the optical film with the pressure-sensitive adhesive layer with a separator of the present invention is separated from the optical film with the pressure-sensitive adhesive layer with a separator by a peeling body (at the same time as the peeling) while the liquid crystal display device is manufactured. Since the separator has a conductive layer even when applying the step of bonding the pressure-sensitive adhesive layer side of the optical film with the pressure-sensitive adhesive layer exposed after peeling to the liquid crystal panel (RTP bonding step), static electricity (peeling charging) In addition, even if static electricity is generated due to the separation of the separator, the static charge generated on the optical film with the adhesive layer can be quickly transferred to the separated separator, so that the static charge is attenuated. It is useful for suppressing white unevenness of the liquid crystal panel.

It is typical sectional drawing which shows the structural example of the adhesive layer with a separator. It is typical sectional drawing which shows the structural example of an optical film with an adhesive layer with a separator. It is a schematic diagram explaining the RTP bonding process in the manufacturing method of an image display apparatus.

  Hereinafter, embodiments of the present invention will be described in detail.

<Overall structure of optical film with pressure-sensitive adhesive layer with separator and pressure-sensitive adhesive layer with separator>
The typical structural example of the adhesive layer with a separator of this invention is typically shown to Fig.1 (a) and (b). The separator-attached pressure-sensitive adhesive layer 2 is a form in which a pressure-sensitive adhesive layer 21 is provided on the release layer 12 of the separator 1. Further, the separator 1 has a form in which an oligomer prevention layer 13 and a conductive layer 14 are provided between the base film 11 and the release layer 12. Although there is no restriction | limiting in the lamination | stacking order of the oligomer prevention layer 13 and the conductive layer 14, in the case of (a), since the oligomer prevention layer 13 is in contact with the base film 11, it is contained in base materials, such as a polyester film. The effect of suppressing the oligomer from eluting into the pressure-sensitive 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 dissolution of the oligomer into the pressure-sensitive adhesive layer is high while maintaining the antistatic effect of the entire separator 1. The lamination 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.

  The typical structural example of the optical film with an adhesive layer with a separator of this invention is typically shown in FIG. The optical film 3 with the separator-attached pressure-sensitive adhesive layer is formed by bonding the optical film 31 to the pressure-sensitive adhesive layer 2 with a separator. The optical film 4 with the pressure-sensitive adhesive layer obtained by peeling the separator 1 from the optical film 3 with the pressure-sensitive adhesive layer with a separator is used by attaching the pressure-sensitive adhesive layer 21 to a display panel as an adherend.

<Adhesive layer with separator>
The pressure-sensitive adhesive layer with a separator of the present invention has a structure having a pressure-sensitive adhesive layer on the separator. The separator 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 separator of the present invention, a plastic film can be used. Plastic films include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polyolefin film such as polymethylpentene film, vinyl chloride film such as polyvinyl chloride film and vinyl chloride copolymer film; polyethylene terephthalate film, polybutylene Polyester films such as terephthalate film and polynaphthylene terephthalate film; other examples include polyurethane film and ethylene-vinyl acetate copolymer film. In this invention, since it aims at the elution prevention of the oligomer in the said base film, it is suitable when a polyester film is used among the said base films.

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

<Oligomer prevention layer>
As an oligomer prevention layer of this invention, it can form with an appropriate material for preventing the oligomer contained in base film, such as a polyester film, eluting to an adhesive layer. As the material for forming the oligomer prevention layer, an inorganic material, an organic material, or a composite material thereof can be used. Examples of inorganic substances include silica-based materials, gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, and alloys thereof, or indium oxide, tin oxide, and titanium oxide. And metal oxides composed of cadmium oxide or a mixture thereof, other metal compounds composed of steel iodide and the like. Examples of organic substances include polyvinyl alcohol resins, acrylic resins, urethane resins, melamine resins, UV curable resins, and epoxy resins. Examples of the composite material include a mixture of the organic substance and inorganic particles such as alumina, silica, and mica.

  The oligomer prevention layer is preferably formed from a composition containing a silica material or a polyvinyl alcohol resin.

<Silica-based material>
Examples of the silica-based material include organosiloxanes represented by the following general formula (I).

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

In the general formula (II), R ⁴ is the same epoxy group-containing organic group or alkoxy group as the R ¹ group or R ² group.

  Specific examples of the organosiloxane include γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 5 , 6-epoxycyclohexyltriethoxysilane, tetraethoxysilane, and other monomers, and hydrolyzable organisms (oligomers) of these monomers or mixtures of these monomers.

Examples of the silica-based material include silane compounds having an amino group. As the silane compound having an amino group, an alkoxysilane represented by the following general formula (III) is preferable.
Y-R-Si- (X) ₃ (III)
(In the general formula (III), Y is an amino group, R is an alkylene group such as methylene, ethylene and propylene, X is an alkoxy group such as methoxy group and ethoxy group, an alkyl group, or an organic functional group having these groups) And at least one or more is an alkoxy group).

  Specific examples of the silane compound having an amino group include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and N-β (aminoethyl). γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like can be mentioned.

  Other examples of the silica-based material include (meth) acryl group-containing silane compounds such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane, and isocyanate group-containing silanes such as 3-isocyanatopropyltriethoxysilane. Compounds and the like.

  Specific examples of the silica-based material include KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, KR-217, and X manufactured by Shin-Etsu Chemical Co., Ltd. -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. are mentioned.

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

  The oligomer prevention layer formed of the silica-based material can contain an organic compound having a metal element (metal compound such as a metal chelate), a catalyst, or the like, if 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 having the metal element, an organic compound having an aluminum element having a chelate structure, an organic compound having a titanium element, and an organic compound having a zirconium element are particularly preferable in that the oligomer elution prevention performance is good. Such compounds are specifically described in "Crosslinking Agent Handbook" (Yamashita Shinzo, Kaneko Tosuke Editor Co., Ltd. Taiseisha, 1990).

  The oligomer-preventing layer formed from the silica-based material can be formed by applying a solution obtained by dissolving the silica-based material in a solvent such as alcohol to a base film or a conductive layer and then drying it. The concentration of the solution in which the silica-based material is dissolved is not particularly limited, but is preferably about 0.1 to 40% by weight. Although the drying temperature after application | coating is not necessarily limited, It is preferable that it is about 100-150 degreeC. The drying time after coating is not particularly limited, but is preferably about 30 seconds to 30 minutes.

<Composition containing polyvinyl alcohol resin>
Examples of the polyvinyl alcohol resin include polyvinyl alcohol and derivatives thereof. Derivatives of polyvinyl alcohol include polyvinyl formal, polyvinyl acetal and the like, olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid and alkyl esters thereof, acrylamide and the like. Is mentioned. Only 1 type may be used for a polyvinyl alcohol-type resin, and 2 or more types may be used for it.

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

  The composition containing the polyvinyl alcohol resin may contain a binder polymer. Binder polymers include polyacrylamide, polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches, polyurethane, polyester, polyacrylate, chlorinated polymers (polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyolefins Etc. Among them, when coating the oligomer prevention layer by a coating stretching method, examples include organic polymers that can be used as nonionic, cationic, and amphoteric aqueous solutions or water dispersions. Among them, polyurethane, When polyester or polyacrylate is used, the adhesion is good. These polymers are imparted with hydrophilicity and can be dispersed in water by copolymerizing nonionic, cationic or amphoteric hydrophilic components as one component of the monomer.

  The composition containing the polyvinyl alcohol resin may contain a crosslinking agent. Cross-linking agents include methylolated or alkylolized urea, melamine, guanamine, acrylamide, polyamide, epoxy compound, aziridine compound, block polyisocyanate, silane coupling agent, titanium coupling agent, zircote. Examples include aluminate coupling agents. These crosslinking components may be previously bonded to the binder polymer.

  The composition containing the polyvinyl alcohol resin may contain inorganic particles for the purpose of improving the adhesion and slipping property of the oligomer prevention layer. Examples of inorganic particles include silica, alumina, kaolin, calcium carbonate, titanium oxide, barium salt and the like.

  The oligomer prevention layer can be formed by applying a solution obtained by dissolving the composition containing the polyvinyl alcohol resin in a solvent such as water or alcohol to the base film or the oligomer prevention layer and then drying it. . Moreover, you may extend | stretch in the case of drying. Although the density | concentration of the solution which melt | dissolved the composition containing the said polyvinyl alcohol-type resin is not necessarily restrict | limited, It is preferable that it is about 0.1 to 40 weight%. Although the drying temperature after application | coating is not necessarily limited, It is preferable that it is about 60-200 degreeC. The drying time after application is not particularly limited, but is preferably about 3 to 60 seconds. If necessary, heat treatment and active energy ray irradiation such as 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 30 to 80% by weight. Good.

  The method for forming the oligomer prevention layer is not particularly limited and may be appropriately selected depending on the forming material, and a coating method, a spray method, a spin coating method, an in-line coating method, or the like is used. Further, a vacuum deposition method, a sputtering method, an ion plating method, a spray pyrolysis method, a chemical plating method, an electroplating method, or the like 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 due to the separation of the separator, and even if static electricity is generated due to the separation of the separator, the static charge generated in the optical film with the adhesive layer is quickly separated. Therefore, it is possible to prevent white unevenness of the liquid crystal panel. The conductive layer is not particularly limited as long as it is a conductive layer. However, the conductive layer includes a conductive composition containing a conductive polymer, a conductive composition containing an ionic surfactant such as an anionic surfactant or a cationic surfactant. And a layer formed of a conductive composition containing a metal oxide such as a conductive composition, tin oxide, antimony oxide, indium oxide, and zinc oxide. The conductive layer is preferably a layer formed of a conductive composition containing a conductive polymer from the viewpoint of easily obtaining a separator having a desired surface resistance value of the release layer.

  Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, poly (ethylenedioxythiophene) (abbreviation PEDOT), poly (ethylenedioxythiophene) / polystyrene sulfonate (abbreviation PEDOT / PSS), and the like. In particular, poly (ethylenedioxythiophene) / polystyrene sulfonate (abbreviation PEDOT / PSS) is preferable in terms of antistatic properties and transparency. Only 1 type may be used for a conductive polymer, and 2 or more types may be used for it.

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

  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 15: 1 to 5: 1 is more preferable.

  The conductive layer is formed by applying a solution obtained by dissolving the conductive composition containing the conductive polymer in a solvent such as water or alcohol to the base film or the oligomer prevention layer and then drying the solution. it can. 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. Although the drying temperature after application | coating is not necessarily limited, It is preferable that it is about 100-150 degreeC. 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, an in-line coating method, or the like is 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>
Next, 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 peelability from the pressure-sensitive adhesive layer. The material for forming the release layer is not particularly limited, and examples thereof include silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents. Of these, silicone release agents are preferred. The release layer can be formed as a coating layer on the oligomer prevention layer and the conductive layer. The release layer can also be formed by transfer.

  Examples of the silicone release agent include addition reaction type silicone resins. Examples of the addition reaction type silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T manufactured by Shin-Etsu Chemical Co., Ltd., TPR-6700, TPR-6710, TPR manufactured by Toshiba Silicone. -6721, SD7220, SD7226, manufactured by Toray Dow Corning.

The coating amount of the silicone-based release layer (after drying) is preferably 0.01 to 2 g / ^{m 2,} more preferably 0.01 to 1 g / ^{m 2,} more preferably of 0.01 to 0.5 g / ^{m 2} It is a range.

  The release layer is formed, for example, by applying the above material on the functional layer by a conventionally known coating method such as reverse gravure coating, bar coating, die coating, or the like, and usually at about 120 to 200 ° C., 30 It can be performed by curing by applying a heat treatment in seconds to 30 minutes. Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed.

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

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

<Adhesive layer>
The pressure-sensitive adhesive layer of the present invention is formed from a pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition includes a rubber-based pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive composition, a silicone-based pressure-sensitive adhesive composition, a urethane-based pressure-sensitive adhesive composition, a vinyl alkyl ether-based pressure-sensitive adhesive composition, and a polyvinyl alcohol-based pressure-sensitive adhesive composition. Products, polyvinylpyrrolidone-based pressure-sensitive adhesive compositions, polyacrylamide-based pressure-sensitive adhesive compositions, cellulose-based pressure-sensitive adhesive compositions, and the like. The pressure-sensitive adhesive composition preferably contains a base polymer.

<Base polymer>
As the base polymer, an adhesive base polymer is selected according to the type of the pressure-sensitive adhesive composition.

  Among the above-mentioned pressure-sensitive adhesive compositions, acrylic pressure-sensitive adhesive compositions are excellent in terms of excellent optical transparency, suitable wettability, cohesiveness, and adhesive pressure-sensitive properties, and excellent weather resistance, heat resistance, and the like. Are preferably used. The acrylic pressure-sensitive adhesive composition preferably contains a (meth) acrylic polymer as an adhesive base polymer. The (meth) acrylic polymer usually contains an alkyl (meth) acrylate as a main component as a monomer unit. Note that (meth) acrylate refers to acrylate and / or methacrylate, and (meth) of the present invention has the same meaning.

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

  In addition, as the alkyl (meth) acrylate, aromatic rings such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are used from the viewpoints of adhesive properties, durability, retardation adjustment, refractive index adjustment, and the like. The contained alkyl (meth) acrylate can be used.

  In the (meth) acrylic polymer, one or more having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group for the purpose of improving adhesiveness and heat resistance These copolymerizable monomers can be introduced by copolymerization. Specific examples of the copolymerization monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, ( Hydroxyl-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate; (meth) acryl Carboxyl group-containing monomers such as acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Acrylic acid caprolacto Adducts such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, etc. Sulfonic acid group-containing monomers; phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate.

  The (meth) acrylic polymer has an alkyl (meth) acrylate as a main component in the weight ratio of all constituent monomers, and the ratio of the copolymerizable monomer in the (meth) acrylic polymer is not particularly limited. The ratio of the polymerization monomer is preferably about 0 to 20%, about 0.1 to 15%, and more preferably about 0.1 to 10% in the weight ratio of all constituent monomers.

  As the (meth) acrylic polymer, those having a weight average molecular weight (Mw) in the range of 500,000 to 3,000,000 are usually used. In view of durability, particularly heat resistance, it is preferable to use a weight average molecular weight (Mw) of 700,000 to 2,700,000, and more preferably 800,000 to 2,500,000. If the weight average molecular weight (Mw) is smaller than 500,000, it is not preferable in terms of heat resistance. On the other hand, if the weight average molecular weight (Mw) is larger than 3 million, a large amount of diluent solvent is required to adjust the viscosity for coating, which is not preferable. 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. Further, the (meth) acrylic polymer obtained may be a random copolymer, a block copolymer, a graft copolymer or the like.

  The polymerization initiator, chain transfer agent, emulsifier and the like used for 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 polymerization initiator, the amount of chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types. The

  In the solution polymerization, ethyl acetate, toluene or the like is used as a polymerization solvent. As a specific example of solution polymerization, the reaction is performed under an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.

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

  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 or inorganic salt of an alkali metal can be used. The “organic cation-anion salt” in the present invention refers to an organic salt whose cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. There may be. “Organic cation-anion salt” is also called an 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 lithium, sodium, and potassium ions. Of 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. As an 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 general formula (1) 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 - ( where, m is an integer of from 1 to 10),
^{_{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by those such as are used. In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. The anion part constituting the inorganic salt includes 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 ⁻ , and the like are used. As the anion moiety, (perfluoroalkylsulfonyl) imide represented by the general formula (1) such as (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , and the like is preferable. (Trifluoromethanesulfonyl) imide represented by CF ₃ SO ₂ ) ₂ N ⁻ is preferable.

Specific examples of the alkali metal organic salt include sodium acetate, sodium alginate, sodium lignin sulfonate, 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 , and the like, among these _{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 and the like are preferable, 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} Fluorine-containing lithium imide salt is more preferably equal, particularly (perfluoroalkyl sulfonyl) imide lithium salts are preferred.

  Examples of the alkali metal inorganic salt 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. As the cation component, specifically, pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, Examples include pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, and tetraalkylphosphonium cation.

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 the following general formula (1) 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 - ( where, m is an integer of from 1 to 10),
_{^{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by those such as are used. Among these, an anion component containing a fluorine atom is particularly preferably used because an ionic compound having good ion dissociation properties can be obtained.

  Examples of the ionic compound include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate in addition to the alkali metal salt and organic cation-anion salt. It is done.

  Examples of the ionic surfactant include a cationic type (quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.), anionic type (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.), Zwitterionic type (sulfobetaine type, alkylbetaine type, alkylimidazolium betaine type, etc.) or nonionic type (polyhydric alcohol derivative, β-cyclodextrin inclusion compound, sorbitan fatty acid monoester / diester, polyalkylene oxide derivative, amine oxide) Etc.) of various surfactants. Only one type of ionic surfactant may be used, or two or more types may be used.

  Examples of the conductive polymer include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers. Among these, polyaniline, which easily becomes a water-soluble conductive polymer or a water-dispersible conductive polymer, Polythiophene and the like are preferably used. Polythiophene is particularly preferable. Only 1 type may be used for a conductive polymer and it may use 2 or more types.

  Examples of the metal oxide include tin oxide, antimony oxide, indium oxide, and zinc oxide. Of these, tin oxide is preferable. Examples of the tin oxide-based material include, 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 composite, titanium oxide- Examples thereof include a composite of tin oxide. Only 1 type may be used for a metal oxide and 2 or more types may be used for it.

  Furthermore, as conductive compounds other than the above, acetylene black, ketjen black, natural graphite, artificial graphite, titanium black, cation type (quaternary ammonium salt etc.), amphoteric ion type (betaine compound etc.), anion type (sulfonic acid) Salt or the like) or nonionic type (glycerin etc.) monomer-containing homopolymer or copolymer of the monomer and other monomers, quaternary ammonium base acrylate or methacrylate Examples thereof include a polymer having ionic conductivity such as a polymer having a site derived from; a type of permanent antistatic agent in which a hydrophilic polymer such as a polyethylene methacrylate copolymer is alloyed with an acrylic resin or the like.

  The conductive compound is preferably an ionic compound from the viewpoints of high conductivity performance, excellent dispersibility and transparency in the pressure-sensitive adhesive, and storage stability in the pressure-sensitive adhesive.

  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. When the conductive compound is less than 0.0001 parts by weight, the effect of improving the antistatic performance may not be sufficient. On the other hand, if the conductive compound is more than 5 parts by weight, the durability may not be sufficient. The conductive compound is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more. Further, the conductive compound is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less.

  Furthermore, the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate can be used. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent. A polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned. Examples of the atom in the organic compound to be covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds. As a crosslinking agent, an isocyanate type crosslinking agent and a peroxide type crosslinking agent are preferable. Only 1 type may be used for a crosslinking agent and 2 or more types may be used for it.

  The blending ratio of the crosslinking agent is preferably 0.01 to 20 parts by weight and more preferably 0.03 to 10 parts by weight with respect to 100 parts by weight of the base polymer. If the crosslinking agent is less than 0.01 parts by weight, the cohesive force of the pressure-sensitive adhesive tends to be insufficient, and foaming may occur during heating. On the other hand, if it exceeds 20 parts by weight, the moisture resistance is not sufficient, Peeling easily occurs in reliability tests.

  Furthermore, the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent. The durability can be improved by using a silane coupling agent. A silane coupling agent may use only 1 type and may use 2 or more types.

  The blending ratio of the silane coupling agent is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, and 0.02 to 1 part by weight with respect to 100 parts by weight of the base polymer. Is more preferable, and 0.05 to 0.6 part by weight is particularly preferable. In order to improve the durability and appropriately maintain the adhesive force to an optical member such as a liquid crystal panel, it is appropriately selected within this range.

  Furthermore, the pressure-sensitive adhesive composition of the present invention may contain other known additives, such as powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubrication. For applications that use agents, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. It can be added as appropriate. Moreover, you may employ | adopt the redox system which added a reducing agent within the controllable range.

  The pressure-sensitive adhesive layer with a separator of the present invention can be produced by applying a solution containing the pressure-sensitive adhesive composition on the release layer of the separator and then drying to form a pressure-sensitive adhesive layer. In applying the pressure-sensitive adhesive composition, one or more solvents other than the polymerization solvent may be added as appropriate.

  Various methods are used as a method of applying the pressure-sensitive adhesive composition. Specifically, extrusion coating by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Methods such as law are listed.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is about 1 to 100 μm. Preferably, it is 2-50 micrometers, More preferably, it is 2-40 micrometers, More preferably, it is 5-35 micrometers.

The surface resistance value of the pressure-sensitive adhesive layer is preferably 1.0 × 10 ¹² Ω / □ or less from the viewpoint of imparting conductivity to the pressure-sensitive adhesive layer with a separator and suppressing white unevenness of the liquid crystal panel. It is more preferably 0.0 × 10 ¹¹ Ω / □ or less, and further preferably 1.0 × 10 ¹⁰ Ω / □ or less.

<Optical film with pressure-sensitive adhesive layer with separator>
As for the optical film with an adhesive layer with a separator of the present invention, the adhesive layer side of an adhesive layer with a separator is pasted on at least one side of an optical film.

  As said optical film, what is used for formation of image display apparatuses, such as a liquid crystal display device, can be used, The kind in particular is not restrict | limited. Examples of the optical film include a polarizing film, a retardation plate, an optical compensation film, a brightness enhancement film, a surface treatment film such as an antireflection film, and a laminate of these.

  As the polarizing film, one having a transparent protective film on one side or both sides of a polarizer is generally used. The polarizer is not particularly limited, and various types can be used. Polarizers include dichroic substances such as iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Polyene-based oriented films such as those adsorbed and uniaxially stretched, polyvinyl alcohol dehydrated products, and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

  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 is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.

  As a material constituting the transparent protective film, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic Examples thereof include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. A transparent protective film is bonded to one side of the polarizer by an adhesive layer. On the other side, as a transparent protective film, (meth) acrylic, urethane-based, acrylurethane-based, epoxy-based, silicone A thermosetting resin such as a system or an ultraviolet curable resin can be used. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film.

  The adhesive used for laminating the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent. However, water-based adhesives or radical curable adhesives are suitable.

<Image display device>
In the image display device of the present invention, the pressure-sensitive adhesive layer side of the optical film with the pressure-sensitive adhesive layer in a state where the separator is peeled off is bonded to at least one surface of the display panel from the optical film with the pressure-sensitive adhesive layer with separator. Yes. A liquid crystal panel etc. are mentioned as a display panel. As the liquid crystal panel, an arbitrary type such as an arbitrary type such as a TN type, an STN type, a π type, a VA type, or an IPS type can be used.

<Method for Manufacturing Image Display Device>
The manufacturing method of the image display device of the present invention includes a roll original fabric preparation step of preparing a long sheet of an optical film with a separator-attached adhesive layer as a roll original, and a display prepared by conveying the display panel to a pasting position. Adhesion of the optical film with the adhesive layer exposed after peeling of the separator while peeling the separator from the optical film with the pressure-sensitive adhesive layer with the separator fed out from the roll raw fabric with the release body. It is a manufacturing method including the bonding process (RTP bonding process) which bonds the agent layer side to the said display panel conveyed to the said bonding position.

<Roll roll preparation process>
The roll raw fabric preparation step is a step in which an optical film with a separator-attached pressure-sensitive adhesive layer is manufactured as a roll raw fabric of a long (band-shaped) sheet, and the roll raw fabric is not particularly limited and conforms to the prior art. Can be manufactured.

<Display panel transport preparation process>
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 transported according to the conventional method.

<RTP bonding process>
A typical schematic diagram of the RTP bonding step is shown in FIG. The long sheet of the optical film 3 with the separator-attached pressure-sensitive adhesive layer fed from the raw roll is separated from the optical film 3 with the separator-attached adhesive layer immediately before being conveyed to the attaching position 101. 100 peels off. The pressure-sensitive adhesive layer 21 of the optical film 4 with the pressure-sensitive adhesive layer exposed after the separation of the separator 1 is bonded to the display panel 5 guided to the predetermined bonding position 101 by the receiving roller 102 by the bonding roller 103, and the image display device is Manufactured.

  In the RTP bonding step, the optical film 3 with the pressure-sensitive adhesive layer with a separator is a long sheet that is not cut, so even after the separator 1 is peeled off, the optical film 4 with a pressure-sensitive adhesive layer in the form of a long sheet (or The pressure-sensitive adhesive layer 21) remains in contact with the separator 1 before peeling. Therefore, even if static electricity occurs in the long sheet-like optical film 4 with the pressure-sensitive adhesive layer (or the pressure-sensitive adhesive layer 21) due to the separation of the separator 1, the static charge is quickly transferred through the separator 1 before the separation. Since it can move to the separator 1 after peeling, the separator 1 after peeling serves as a ground, so that electrostatic charges are attenuated.

  In addition, the image display device is manufactured by combining the display panel and the optical film with the pressure-sensitive adhesive layer, and then appropriately assembling components such as an illumination system as necessary, and further incorporating a drive circuit. For example, a manufacturing method of a liquid crystal display device in which an optical film with an adhesive layer is disposed on one side or both sides of a display panel such as a liquid crystal panel, or a liquid crystal display device using a backlight or a reflector in an illumination system A manufacturing method etc. are mentioned. In that case, the optical film with an adhesive layer of this invention can be installed in the one side or both sides of display panels, such as a liquid crystal panel. When optical films are provided on both sides, they may be the same or different. Furthermore, in the method for manufacturing a liquid crystal display device, one or two layers of appropriate components such as a diffusion layer, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion sheet, and a backlight are disposed at appropriate positions. It is also possible to arrange more than one layer.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight.

Example 1
<Preparation of separator>
<< Formation of oligomer prevention layer >>
As a silica-based material, organosiloxane (ethyl silicate 48: Colcoat) was diluted with isopropyl alcohol to a solid content concentration of 1% to prepare a coating solution. The obtained coating solution was coated on a polyester film (thickness: 38 μm) as a base film with a gravure coater so that the thickness after drying was 50 nm, and then dried at 120 ° C. for 30 seconds to prevent oligomers. Layer (1) was formed.

<< Formation of conductive layer >>
A poly (ethylenedioxythiophene) / polystyrene sulfonate (PEDOT / PSS) was used as the conductive polymer, and a water / isopropyl alcohol (1/1: weight ratio) solution having a solid content concentration of 1% was prepared. The obtained solution was apply | coated so that the thickness after drying might be set to 100 nm on an oligomer prevention layer (1), and it dried at 80 degreeC for 2 minute (s), and formed the conductive layer (1).

<< Formation of Release Layer >>
Silicone resin (KS-847H: manufactured by Shin-Etsu Chemical Co., Ltd.): 20 parts and curing agent (PL-50T: manufactured by Shin-Etsu Chemical Co., Ltd.): 0.2 parts are diluted with 350 parts of methyl ethyl ketone / toluene mixed solvent (mixing ratio is 1: 1). Thus, a solution of a silicone release agent was prepared. The obtained silicone mold release agent solution was applied onto the conductive layer (1) by a gravure coater so that the thickness after drying was 100 nm, and then dried at 120 ° C. for 30 seconds to obtain a release layer. Thus, a separator of Example 1 having a configuration of polyester film / oligomer prevention layer (1) / conductive layer (1) / release layer was obtained.

Example 2
<Preparation of separator>
<< Formation of conductive layer >>
A poly (ethylenedioxythiophene) / polystyrene sulfonate (PEDOT / PSS) was used as the conductive polymer, and a water / isopropyl alcohol (1/1: weight ratio) solution having a solid content concentration of 1% was prepared. The obtained solution was applied onto 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 material, a silica sol having an average particle size of 0.05 μm was diluted with isopropyl alcohol to a solid content concentration of 1% to prepare a coating solution. The obtained coating solution was applied on the conductive layer (1) by a gravure coater so that the thickness after drying was 50 nm, and then dried at 120 ° C. for 30 seconds to form an oligomer prevention layer (2). .

<< Formation of Release Layer >>
In Example 1, in <<<< Formation of Release Layer >>, the polyester film / conductive layer (1) was prepared in the same manner as in Example 1 except that a release layer was formed on the oligomer prevention layer (2). The separator of Example 2 having the structure of / oligomer prevention layer (2) / release layer was obtained.

Example 3
<Preparation of separator>
<< Formation of conductive layer >>
Poly (ethylene dioxythiophene) / polystyrene sulfonate (PEDOT / PSS) is used as the conductive polymer, and polyurethane resin is used as the binder resin. The solid content concentration is 0.8% water / isopropyl alcohol (1/1: weight ratio). ) Was prepared. The weight ratio between the conductive polymer and the binder resin is 10: 1. The obtained solution was applied 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 Release Layer >>
In Example 2, in << Formation of oligomer prevention layer >> and << Formation of release layer >>, the oligomer prevention layer (2) was formed on the conductive layer (2), and the oligomer prevention layer ( 2) Separator of Example 3 having the structure of polyester film / conductive layer (2) / oligomer prevention layer (2) / release layer, except that a release layer was provided on 2) Got.

Example 4
<Preparation of separator>
<< Formation of oligomer prevention layer >>
As a composition containing a polyvinyl alcohol-based resin, 70 parts of a polyvinyl alcohol-based resin (polyvinyl alcohol having a saponification degree = 88 mol% and a polymerization degree = 500) and a binder polymer (aqueous polyester resin: isophthalic acid, ethylene glycol, diethylene glycol) are mainly used. 15 parts of water-based polyester obtained by neutralizing a polyester obtained by copolymerizing neopentyl glycol and a dicarboxylic acid derivative having an aliphatic dicarboxylic acid anhydride with an amine compound to form a water-based polyester, a cross-linking agent (hexamethoxymethylmelamine) 10 parts and 5 parts of inorganic particles (silica sol having an average particle diameter of 65 nm) were diluted with water to a solid content concentration of 2% to prepare a coating solution. After apply | coating the obtained coating liquid on the polyester film (thickness: 38 micrometers) as a base film with a gravure coater so that the thickness after drying may be set to 50 nm, after guiding a film to a tenter and extending | stretching at 100 degreeC Then, heat setting was performed at 230 ° C. to form an oligomer prevention layer (3).

<< Formation of conductive layer >>
<< Formation of Release Layer >>
In Example 1, << formation of conductive layer >><< formation of release layer >>, in the same manner as in Example 1, polyester film / oligomer prevention layer (3) / conductive layer (1) / release A separator of Example 4 having a layer structure was obtained.

Comparative Example 1
<Preparation of separator>
In Example 1, except that the conductive layer (1) was not formed, the separator of Comparative Example 1 having the structure of base film / oligomer prevention layer (1) / release layer was obtained in the same manner as in Example 1. Obtained.

Comparative Example 2
<Preparation of separator>
<< Formation of Conductive Agent-Containing Oligomer Prevention Layer >>
As a composition for forming a conductive agent-containing oligomer-preventing layer, 85 parts of a compound having a nitrogen element as a conductive material (compound having a pyrroldium ring in the main chain: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Charol DC-303P), a polyvinyl alcohol type A coating solution is prepared by diluting 10 parts of a resin (polyvinyl alcohol having a saponification degree = 88 mol% and a polymerization degree = 500) and 5 parts of inorganic particles (silica sol having an average particle diameter of 50 nm) to a solid content concentration of 2% with water. did. After apply | coating the obtained coating liquid on the polyester film (thickness: 38 micrometers) as a base film with a gravure coater so that the thickness after drying may be set to 50 nm, after guiding a film to a tenter and extending | stretching at 100 degreeC Then, heat setting was performed at 230 ° C. to form an oligomer-preventing layer containing a conductive agent.

<< Formation of Release Layer >>
In Example 1, << Formation of release layer >> In the same manner as in Example 1 except that a release layer was formed on the conductive agent-containing oligomer prevention layer, polyester film / conductive agent-containing oligomer prevention A separator of Comparative Example 2 having a layer / release layer configuration was obtained.

<Preparation of pressure-sensitive adhesive layer with separator>
<< Preparation of acrylic polymer >>
A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was charged into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device. Furthermore, 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged with ethyl acetate to 100 parts of the monomer mixture (solid content), and nitrogen gas was introduced while gently stirring. Then, the temperature of the liquid in the flask was kept at around 60 ° C., and a polymerization reaction was carried out for 7 hours. Thereafter, an acrylic polymer solution having a weight average molecular weight (Mw) of 1.6 million was prepared by adding ethyl acetate to the obtained reaction solution to adjust the solid content concentration to 30%.

<< Preparation of pressure-sensitive adhesive composition >>
For 100 parts of the solid content of the acrylic polymer (A) solution obtained above, 0.7 parts of 1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonylimide and lithium bis ( Trifluoromethanesulfonyl) imide (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) 1.0 part, 0.1 parts of trimethylolpropane xylylene diisocyanate (manufactured by Mitsui Chemicals: Takenate D110N) as a crosslinking agent, and dibenzoyl A solution of a pressure-sensitive adhesive composition was prepared by blending 0.3 part of peroxide and 0.2 part of γ-glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) as a silane coupling agent. Obtained.

<< Formation of pressure-sensitive adhesive layer >>
The solution of the pressure-sensitive adhesive composition prepared above was uniformly applied with a fountain coater onto the release layers of the separators obtained in Examples 1 to 4 and Comparative Examples 1 and 2 above, and then air circulation at 150 ° C. It dried for 60 second in a type | mold thermostat oven, the 20-micrometer-thick adhesive layer was formed in the surface of the said mold release layer, and the adhesive layer with a separator of Examples 1-4 and Comparative Examples 1-2 was obtained.

<Production of optical film with pressure-sensitive adhesive layer with separator>
<< Preparation of optical film >>
In order to produce a thin polarizer, first, a laminate in which a 9 μm-thick polyvinyl alcohol (PVA) layer was formed on an amorphous polyethylene terephthalate (PET) substrate was stretched and laminated by air-assisted stretching at a stretching temperature of 130 ° C. Next, a colored laminate is produced by dyeing the stretched laminate, and further, the colored laminate is amorphous so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees. An optical film laminate including a 4 μm thick PVA layer stretched integrally with the conductive PET substrate was produced. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 μm that constitutes a highly functional polarizer. Furthermore, after applying a saponified 80 μm-thick triacetyl cellulose film while applying a polyvinyl alcohol-based adhesive on the surface of the polarizer of the optical film laminate, the amorphous PET substrate is peeled off and thinned. A polarizing film using a polarizer was produced.

<Production of optical film with pressure-sensitive adhesive layer with separator>
Next, the pressure-sensitive adhesive layers with separators of Examples 1 to 4 and Comparative Examples 1 and 2 obtained above were bonded to the polarizing film using the thin polarizer obtained above, and the pressure-sensitive adhesive layer was transferred. And the optical film with an adhesive layer with a separator of Examples 1-4 and Comparative Examples 1-2 was obtained.

<Manufacture of image display device>
In order to manufacture an image display apparatus by the RTP bonding process shown in FIG. 3, the long sheet of the optical film with the adhesive layer with a separator of Examples 1-4 and Comparative Examples 1-2 obtained above was used. A liquid crystal panel was prepared as a raw roll and transported to a pasting position. Then, with the adhesive layer exposed after peeling of the separator while peeling the separator from the optical film with the pressure-sensitive adhesive layer with separator of Examples 1 to 4 and Comparative Examples 1 and 2 fed out from the raw roll. The adhesive layer side of the optical film was bonded to a liquid crystal panel conveyed to the affixing position, and image display devices (liquid crystal display devices) using the liquid crystal panels of Examples 1 to 4 and Comparative Examples 1 to 2 were manufactured. .

The weight average molecular weight (Mw) of the (meth) acrylic polymer obtained above was measured by GPC (gel permeation chromatography) under the following conditions.
・ Analyzer: HLC-8120GPC manufactured by Tosoh Corporation
Column: G7000HXL + GMHXL + GMHXL, manufactured by Tosoh Corporation
Column size: 7.8mmφ x 30cm each
-Column temperature: 40 ° C
・ Flow rate: 0.8ml / min
・ Injection volume: 100 μl
・ Eluent: Tetrahydrofuran ・ Detector: Differential refractometer (RI)
Standard sample: polystyrene

  The following evaluation was performed about the optical film with the separator of Examples 1-4 obtained above and Comparative Examples 1-2, the adhesive layer with a separator, and the adhesive layer with a separator. The evaluation results are shown in Table 1.

<Method for measuring surface resistance value of release layer>
About the separator of Examples 1-4 obtained by the above and Comparative Examples 1-2, the surface resistance value (ohm / square) of the surface of a mold release layer was measured using Mitsubishi Chemical Analytech Co., Ltd. MCP-HT450.

<Measurement method of surface resistance value of adhesive layer>
About the adhesive layer with a separator of Examples 1-4 obtained by the above and Comparative Examples 1-2, the surface resistance value (ohm / square) of the surface of an adhesive layer was used for Mitsubishi Chemical Analytech Co., Ltd. MCP-HT450. Measured.

<Measurement method of elution amount of PET oligomer>
The optical films with adhesive layers with separators of Examples 1 to 4 and Comparative Examples 1 and 2 obtained above were allowed to stand at 60 ° C. and 90% RH for 500 hours, and then the separators were removed. About 0.025 g of the pressure-sensitive adhesive layer (sample) was collected from the polarizing film with the pressure-sensitive adhesive layer, added with 1 ml of chloroform, shaken at room temperature for 18 hours, extracted with 5 ml of acetonitrile, and shaken for 3 hours. The obtained solution was filtered through a 0.45 ml membrane filter to prepare a sample. A standard product of trimer PET oligomer was adjusted to a constant concentration, a calibration curve was prepared, and the amount of PET oligomer (ppm) contained in the adhesive was determined using the calibration curve. The calibration curve was prepared by measuring with HPLC using a sample whose PET oligomer concentration (ppm) was known.
HPLC device: 1200 series manufactured by Agilent Technologies Measurement conditions Column: ZORBAX SB-C18 manufactured by Agilent Technologies
Column temperature: 40 ° C
Column flow rate: 0.8 ml / min
Eluent composition: water / acetonitrile reverse phase gradient injection volume: 5 μl
Detector: PDA
Quantitative method: A standard sample of a PET oligomer trimer was dissolved in chloroform, diluted with acetonitrile, and a preparation was prepared at a constant concentration. A calibration curve was created from the HPLC area and the adjusted concentration, and the elution amount of the sample PET oligomer was determined.
In addition, the elution amount of the PET oligomer is preferably 30 ppm or less, more preferably 20 ppm or less, and further preferably 10 ppm or less.

The following evaluation was performed about the liquid crystal display device of Examples 1-4 and Comparative Examples 1-2 obtained above. 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 above were installed on a backlight. The hand was brought into contact with the edge of the installed liquid crystal display device, and white unevenness was generated on the liquid crystal panel. The time for this white unevenness to disappear was measured. The disappearance time is preferably 200 seconds or less, more preferably 100 seconds or less, further preferably 50 seconds or less, and particularly preferably 20 seconds or less.

  As shown in Table 1, regarding Examples 1 to 4 of the present invention, good results were obtained in any evaluation items. On the other hand, about Comparative Examples 1-2, the result inferior compared with Examples 1-4 in any evaluation item was obtained. From this result, according to the present invention, by suppressing the oligomer contained in the base film such as the polyester film used in the separator from eluting into the pressure-sensitive adhesive layer, there is a problem with the liquid crystal panel due to luminance unevenness due to bright spots. Providing a pressure-sensitive adhesive layer with a separator and an optical film with a pressure-sensitive adhesive layer with a separator that can prevent white unevenness of a liquid crystal panel even when the above RTP bonding step is applied during the manufacture of a liquid crystal display device I knew it was possible.

1: Separator 2: Adhesive layer with separator 3: Optical film with adhesive layer with separator 4: Optical film with adhesive layer 5: Display panel 11: Base film 12: Release layer 13: Oligomer prevention layer 14: Conductive layer 21: Adhesive layer 31: Optical film 100: Release body 101: Pasting position 102: Receiving roller 103: Pasting roller

Claims (7)

A pressure-sensitive adhesive layer with a separator having a pressure-sensitive adhesive layer on the separator,
The separator has a release layer on a base film, and an oligomer prevention layer and a conductive layer between the base film and the release layer,
The pressure-sensitive adhesive layer is provided on the release layer of the separator ,
The pressure-sensitive adhesive layer with a separator , wherein the pressure-sensitive adhesive layer is a layer formed from a pressure-sensitive adhesive composition containing a base polymer and a conductive compound .   The pressure-sensitive adhesive layer with a separator according to claim 1, wherein the oligomer prevention layer is a layer formed of a composition containing a silica-based material and / or a polyvinyl alcohol-based resin.   The pressure-sensitive adhesive layer with a separator according to claim 1 or 2, wherein the conductive layer is a layer formed of a conductive composition containing a conductive polymer. The pressure-sensitive adhesive layer with a separator according to claim 1, wherein the release layer has a surface resistance value of 1.0 × 10 ¹² Ω / □ or less. 5. The pressure-sensitive adhesive layer with a separator according to claim 1 , wherein the pressure-sensitive adhesive layer has a surface resistance value of 1.0 × 10 ¹² Ω / □ or less. On at least one side of the optical film,
The optical film with an adhesive layer with a separator, wherein the adhesive layer side of the separator with an adhesive layer according to any one of claims 1 to 5 is bonded. A method for manufacturing an image display device , comprising:
A roll original fabric preparation step of preparing a long sheet of an optical film with an adhesive layer with a separator according to claim 6 as a roll original fabric,
A display panel transport preparation process for transporting and preparing the display panel to the pasting position;
While peeling the separator from the optical film with the pressure-sensitive adhesive layer with the separator fed from the roll raw fabric, the pressure-sensitive adhesive layer side of the optical film with the pressure-sensitive adhesive layer exposed after the separation of the separator, A bonding step of bonding to the display panel conveyed to the bonding position.

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