JP2009197222A - Method of stripping pressure-sensitive adhesive optical film and pressure-sensitive adhesive optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of easily stripping a pressure-sensitive adhesive optical film from a glass substrate to which the pressure-sensitive adhesive optical film is attached without damaging the glass substrate and without leaving any adhesion residue on the glass substrate, and to provide a pressure-sensitive adhesive optical film used in the method of stripping pressure-sensitive adhesive optical film. <P>SOLUTION: In the method of stripping pressure-sensitive adhesive optical film of stripping the pressure-sensitive adhesive optical film from the glass substrate to which the pressure-sensitive adhesive optical film is pasted, a pressure-sensitive adhesive layer of the pressure-sensitive adhesive optical film is made of a water dispersion type pressure-sensitive adhesive, the glass substrate with the optical film is exposed in an environment having a temperature of 40°C or higher and a relative humidity of 80% or more, or a temperature of 50°C or higher and a relative humidity of 70% or more and, thereafter, the pressure-sensitive adhesive optical film is stripped from the glass substrate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive optical film peeling method for peeling an adhesive optical film from a glass substrate with an optical film, and an adhesive optical film used in the peeling method. Examples of the optical film include a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, a viewing angle widening film, and a laminate of these.

  In a liquid crystal display or the like, it is indispensable to dispose polarizing elements on both sides of a liquid crystal cell because of its image forming method, and generally a polarizing plate is attached. In addition to the polarizing plate, various optical elements are used for the liquid crystal panel in order to improve the display quality of the display. For example, a retardation plate for preventing coloring, a viewing angle widening film for improving the viewing angle of a liquid crystal display, and a brightness enhancement film for increasing the contrast of the display are used. These films are collectively called optical films.

  When sticking the optical film on a liquid crystal cell, an adhesive is usually used. In addition, the adhesive between the optical film and the liquid crystal cell and the optical film is usually in close contact with each other using an adhesive to reduce the loss of light. In such a case, since the adhesive has the merit that a drying step is not required to fix the optical film, the adhesive is an adhesive optical film provided in advance as an adhesive layer on one side of the optical film. Commonly used.

  Conventionally, when the adhesive optical film is pasted on the surface of a liquid crystal cell, if the bonding position is shifted or a foreign object is caught, a problem occurs in the liquid crystal display. A new adhesive optical film was again attached to the surface of the liquid crystal cell. However, it is becoming difficult to peel off the adhesive optical film due to the enlargement of the liquid crystal display and the thinning of the liquid crystal cell. Especially when the adhesive layer has a strong adhesive force, a large force is required to remove it. As a result, there are problems such as poor workability, a change in the cell gap of the liquid crystal cell to deteriorate display quality, and damage to the liquid crystal cell. In addition, in order to reduce the manufacturing cost, it is required to reuse the peeled adhesive optical film and to have reworkability that can be peeled without any adhesive residue.

  As a method for solving the above-mentioned problem, a method of softening or melting an adhesive while inserting a heated heating wire or a slicer between a liquid crystal panel and an optical film (Patent Documents 1 and 2), and on a liquid crystal panel There has been proposed a method (Patent Document 3) in which an optical film is cut and divided, and the divided pieces are peeled off.

  Moreover, after immersing the display material which stuck the transparent film through the adhesive in alkaline solution, the method of peeling a transparent film and an adhesive from this display material is proposed (patent document 4).

  In addition, a method for peeling an optical member together with the peeling sheet by bonding a peeling sheet to the optical member to be peeled (Patent Document 5), and a method for sticking a polarizing plate to an adhesive tape and peeling (Patent Document 6) Has been proposed.

  In addition, a method of removing a polarizing plate or the like contained in a glass substrate by immersing in concentrated sulfuric acid (Patent Document 7), and removing a polarizing plate by dissolving and removing the adhesive using a solvent such as acetone or trichloroethylene (Patent Document 8), a method of dissolving and removing with a solvent that is soluble in the polarizing plate (Patent Document 9), and a state in which a liquid exists at the peeling interface between the pressure-sensitive adhesive layer of the pressure-sensitive optical film and the substrate Has been proposed (Patent Document 10).

  However, the above method requires a difficult operation such as inserting a peeling jig between the liquid crystal panel and the optical film, or cutting only the optical film on the liquid crystal panel. In addition, there is a problem that a large amount of adhesive residue is generated on the liquid crystal panel or the liquid crystal panel is damaged by a solvent.

Japanese Patent Laid-Open No. 11-95210 JP 2002-350837 A JP 2001-242448 A JP 2001-328849 A Japanese Patent Laid-Open No. 2002-40259 JP 2002-159955 A JP 2001-305502 A JP 2001-337305 A JP 2005-224715 A JP 2005-148638 A

  The present invention relates to a method for easily peeling an adhesive optical film from a glass substrate to which an adhesive optical film is attached, without damaging the glass substrate, without causing adhesive residue on the glass substrate, and It aims at providing the adhesion type optical film used for a peeling method. In particular, the present invention provides a method for easily peeling an adhesive optical film without adhesive residue even when the adhesive optical film is bonded to a glass substrate for a long period of time, resulting in an increase in adhesive force and making rework work extremely difficult. Objective.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the following peeling method, and have completed the present invention.

That is, the present invention is an adhesive optical film peeling method for peeling an adhesive optical film from a glass substrate with an optical film in which an adhesive optical film is attached to a glass substrate.
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive optical film is formed from a water-dispersed pressure-sensitive adhesive,
The adhesive optical film is peeled from the glass substrate after the glass substrate with the optical film is exposed to an environment having a temperature of 40 ° C. or higher and a relative humidity of 80% or higher, or a temperature of 50 ° C. or higher and a relative humidity of 70% or higher. The present invention relates to a method for peeling an adhesive optical film.

  As described above, by exposing the glass substrate with an optical film to a predetermined environment (exposure treatment), the adhesive force of the pressure-sensitive adhesive layer of the pressure-sensitive optical film can be sufficiently reduced, and the glass substrate is damaged. Therefore, the adhesive optical film can be peeled from the glass substrate with no adhesive residue and good reworkability. According to the peeling method of the present invention, reworkability is good even when the size of the liquid crystal panel is large or the liquid crystal cell is thin. Moreover, according to the peeling method of this invention, even when an adhesive optical film is bonded to a glass substrate for a long time and the adhesive force becomes high, it can peel easily without adhesive residue.

  In addition, by forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive optical film from a water-dispersed pressure-sensitive adhesive, water absorption of the pressure-sensitive adhesive layer and penetration of moisture into the interface between the pressure-sensitive adhesive layer and the glass substrate proceed due to the exposure treatment. Since the adhesive force of the pressure-sensitive adhesive layer is sufficiently reduced, the reworkability is improved. Furthermore, even if it returns to room temperature after an exposure process, an adhesive force does not rise again, and it is preferable on the work process.

  The adhesive optical film preferably has an anchor layer between the optical film and the adhesive layer. By providing the anchor layer, the pressure-sensitive adhesive optical film can be stably adhered to the glass substrate, and when the pressure-sensitive adhesive optical film is peeled off, it can be easily peeled without any adhesive residue.

  Further, the present invention is an adhesive optical film having a pressure-sensitive adhesive layer formed from a water-dispersed adhesive on at least one surface of an optical film, which is used in the method for peeling the adhesive optical film, and is attached to a glass substrate. The adhesive strength after exposure for 100 hours in an environment of temperature 60 ° C. and relative humidity 30% is 20 N / 25 mm width or more, temperature 40 ° C. or more and relative humidity 80% or more, or temperature 50 ° C. or more and relative humidity 70 It is related with the adhesive optical film characterized by the adhesive force after being exposed to the environment of more than 10% of 10N / 25mm width or less.

  The pressure-sensitive adhesive optical film of the present invention is bonded to a glass substrate for a long time in a high-temperature environment and exposed to a predetermined environment (exposure treatment) even when the adhesive strength is higher than 20 N / 25 mm width. Adhesive strength of the agent layer can be sufficiently reduced, and the glass substrate can be peeled from the glass substrate with no adhesive residue and good rework without damaging the glass substrate. The pressure-sensitive adhesive optical film of the present invention can be peeled with good reworkability even when the size of the liquid crystal panel is large or the liquid crystal cell is thin.

  The glass substrate with an optical film of the present invention is obtained by adhering an adhesive optical film to a glass substrate, and the adhesive layer of the adhesive optical film is formed of a water-dispersed adhesive.

  Various water-dispersed pressure-sensitive adhesives such as rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives can be used as water-dispersible pressure-sensitive adhesives, but they are colorless and transparent, and have adhesion to liquid crystal cells (glass substrates). A preferable acrylic pressure-sensitive adhesive is preferable.

  The water-dispersed acrylic pressure-sensitive adhesive contains an acrylic polymer emulsion obtained by emulsion polymerization of alkyl (meth) acrylate in the presence of an emulsifier. (Meth) acrylate refers to acrylate and / or methacrylate, and (meth) has the same meaning. The alkyl group of the alkyl (meth) acrylate has about 1 to 14 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) Acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) ) Acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. ,these It can be used alone or in combination.

  In order to adjust the glass transition point of the acrylic polymer and the adhesive property of the adhesive layer, other polymerizable monomers may be used. In particular, in order to improve the adhesive force to the glass substrate, or to introduce a crosslinking point for post-crosslinking the resulting copolymer, and further to increase the cohesive force of the pressure-sensitive adhesive, a carboxyl group-containing monomer Is preferably used.

  Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Of these, acrylic acid and methacrylic acid are particularly preferably used.

  The addition amount of the carboxyl group-containing monomer is preferably 0.1 to 10% by weight, more preferably 1 to 7% by weight, based on the total amount of the monomer components forming the acrylic polymer.

  Other polymerizable monomers include, for example, a cohesive force / heat resistance improving component such as a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, and an acid anhydride. Adequate components with functional groups that act as crosslinking points, such as group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, N-acryloylmorpholine, vinyl ether monomers, etc. Can be used. These monomers may be used alone or in combination of two or more.

  Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth). Examples include acryloyloxynaphthalene sulfonic acid.

  Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacryloyl phosphate and mono [poly (propylene oxide) (meth) acrylate] phosphate.

  Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

  Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl laurate, and the like.

  Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethyl styrene, α-methyl styrene, and the like.

  Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, Examples include vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.

  Examples of the amide group-containing monomer include acrylamide and diethyl acrylamide.

  Examples of amino group-containing monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- (meth) acryloylmorpholine, and (meth) acrylic acid alkylaminoalkyl esters. Etc.

  Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.

  Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.

  Furthermore, examples of polymerizable monomers other than the above include silane monomers containing silicon atoms. Examples of the silane monomer include 3- (meth) acryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyl. Examples include trimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, and 10-acryloyloxydecyltriethoxysilane. It is done.

  The silane monomer may be used alone or in combination of two or more, but the total content is 0.01 to 3 parts per 100 parts by weight of the acrylic polymer. It is preferable that it is a weight part, and it is more preferable that it is 0.01-1 weight part. Copolymerization of a silane monomer is preferable for improving durability.

  It is desirable that the acrylic polymer has a solvent-soluble component having a weight average molecular weight of 500,000 or more, preferably 1,000,000 or more, and more preferably 1.8 million or more. When the weight average molecular weight is less than 500,000, the adhesive force tends to be generated due to the reduced cohesive force of the pressure-sensitive adhesive composition. A weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).

  The acrylic polymer is prepared by emulsion polymerization (emulsion polymerization). In addition, the obtained copolymer may be any of a random copolymer, a block copolymer, and the like.

  A polymerization initiator, an emulsifier, etc. are not specifically limited, It can select suitably and can be used.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2). -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), persulfates such as potassium persulfate and ammonium persulfate , Di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylper Oxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3 3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) Peroxides such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides and sodium bisulfite, peroxides and sodium ascorbate Examples include combined redox initiators, but are not limited to these No.

  The polymerization initiator may be used alone, or may be used in combination of two or more, but the total content is 0.002 to 0.5 weight with respect to 100 parts by weight of the monomer. Parts, preferably 0.005 to 0.2 parts by weight.

  Examples of the emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene sodium lauryl sulfate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, and polyoxyethylene alkyl phenyl ether sodium sulfate. Anionic emulsifiers such as sodium polyoxyethylene alkyl sulfosuccinate; Nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer It is done. These emulsifiers may be used alone or in combination of two or more.

  Furthermore, examples of reactive emulsifiers into which radically polymerizable functional groups such as propenyl groups and allyl ether groups are introduced include, for example, Aqualon HS-10, HS-20, HS-1025, KH-10, BC-05, BC- 10, BC-20 (Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE10N (Asahi Denka Co., Ltd.) and the like. Reactive emulsifiers are preferred because they are incorporated into the polymer chain by polymerization and thus have improved water resistance.

  The use amount of the emulsifier is preferably 0.5 to 5 parts by weight, and 1 to 4 parts by weight with respect to 100 parts by weight of the monomer from the viewpoints of polymerization stability, mechanical stability, adhesiveness, and the like. More preferred.

  A chain transfer agent may be used in the polymerization. By using a chain transfer agent, the molecular weight of the acrylic polymer can be appropriately adjusted.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, 1-dodecanethiol, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. .

  These chain transfer agents may be used alone or in admixture of two or more. However, the total content is 0.001 to 0.00 with respect to 100 parts by weight of the monomer. About 5 parts by weight.

  As an example of the polymerization operation, for example, the above-mentioned monomers and copolymerization monomers are first mixed, and after emulsifying and water are added thereto, the mixture is emulsified to prepare an emulsion. The monomer at this time may be blended in whole or in part with the total amount used, and the remainder may be dropped during the polymerization. Next, a polymerization initiator and, if necessary, water are added to this emulsion to carry out emulsion polymerization (emulsion polymerization).

  Water may be blended only at the time of preparing the emulsion, or may be blended further thereafter. Further, the amount of water is not particularly limited, but it is preferable to prepare so that the solid content concentration of the acrylic polymer after emulsion polymerization (emulsion polymerization) is 30 to 75% by weight, more preferably. 35 to 60% by weight.

  The method of emulsion polymerization (emulsion polymerization) is not particularly limited, and can be appropriately selected from a batch polymerization method, a total amount dropping method, a two-stage polymerization method combining these, and the like.

  In the batch polymerization method, for example, a monomer mixture, an emulsifier, and water are charged into a reaction vessel and emulsified by stirring and mixing to prepare an emulsion, and then a polymerization initiator and water as necessary are added to the reaction vessel to perform emulsion polymerization ( Emulsion polymerization).

  In addition, in the total amount dropping method, first, a monomer mixture, an emulsifier and water are added and emulsified by stirring and mixing to prepare a dropping solution, and a polymerization initiator and water are charged into a reaction vessel, and then the dropping solution is added to the reaction vessel. It is dripped in and emulsion polymerization (emulsion polymerization) is carried out.

  The average particle size of the emulsion particles is not particularly limited as long as the mechanical stability and the coating property are good, but is usually 0.07 to 3 μm, preferably 0.07 to 1 μm. When the average particle size is less than 0.07 μm, the viscosity of the pressure-sensitive adhesive tends to be too high, and when it exceeds 3 μm, the adhesion between emulsion particles tends to decrease and the cohesive force tends to decrease. .

  The water-dispersed acrylic pressure-sensitive adhesive can contain the above-mentioned acrylic polymer emulsion as a main ingredient component and, if necessary, a crosslinking agent. Examples of the crosslinking agent include carbodiimide compounds, oxazoline group-containing compounds, polyisocyanate compounds, polyamine compounds, melamine resins, urea resins, and epoxy resins. The addition amount of the crosslinking agent is not particularly limited as long as it does not interfere with the adhesive properties, and is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight in the solid content of the adhesive. is there. When the amount of the crosslinking agent added is large, the elastic modulus of the pressure-sensitive adhesive layer tends to be too high, and the adhesive force may be reduced. Furthermore, tackifying components and other various additives can be blended.

  Furthermore, other known additives may be added to the water-dispersed acrylic pressure-sensitive adhesive, such as tackifiers, plasticizers, fillers, antioxidants, ultraviolet absorbers, silane coupling agents, etc. It can be added as appropriate.

  The pressure-sensitive adhesive optical film is obtained by forming a pressure-sensitive adhesive layer on at least one surface of the optical film with the pressure-sensitive adhesive.

  As a method for forming the pressure-sensitive adhesive layer, for example, a method in which a water-dispersed pressure-sensitive adhesive is applied to a release-processed separator, and a polymerization solvent is dried and removed to form a pressure-sensitive adhesive layer, which is then transferred to an optical film, or Examples include a method of forming a pressure-sensitive adhesive layer by applying a water-dispersed pressure-sensitive adhesive to an optical film and drying and removing a polymerization solvent.

  Various methods are used as a method of forming the pressure-sensitive adhesive layer. For example, a method using a coater such as a comma coater, a fountain die coater, a lip coater, or a slot die coater can be mentioned.

  The thickness in particular of an adhesive layer is not restrict | limited, Usually, it is about 3-500 micrometers. Preferably it is 5-100 micrometers, More preferably, it is 5-40 micrometers.

  The adhesive optical film preferably has an anchor layer between the optical film and the adhesive layer.

  As a material for forming the anchor layer, a polymer having a functional group that reacts with the polymer of the pressure-sensitive adhesive layer is preferably used, and examples thereof include an oxazoline group-containing polymer and an amino group-containing polymer.

  The anchor layer can be formed by directly applying a solution or an aqueous dispersion containing the polymer onto one or both sides of the optical film and drying it.

  The thickness of the anchor layer after drying is usually 1 to 500 nm, preferably 10 to 450 nm, more preferably 15 to 400 nm. If it is the thickness of this range, the adhesive force of an optical film and an adhesive layer can fully be made high.

  Examples of the optical film used for the pressure-sensitive adhesive optical film include a polarizing plate. A polarizing plate having a transparent protective film on one or both sides of a polarizer is generally used.

  The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic 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. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances 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 material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be prepared, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.

  As a material constituting the transparent protective film, for example, 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. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

  Moreover, as a transparent protective film, the polymer film as described in Unexamined-Japanese-Patent No. 2001-343529 (WO01 / 37007), for example, (A) thermoplastic resin which has a substituted and / or unsubstituted imide group in a side chain, ( B) Resin compositions containing thermoplastic resins having substituted and / or unsubstituted phenyl and nitrile groups in the side chains. A specific example is a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing plate can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.

  Although the thickness of a transparent protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable. The transparent protective film is particularly suitable when the thickness is 5 to 150 μm.

  In addition, when providing a transparent protective film on both sides of a polarizer, the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used.

  As the transparent protective film, it is preferable to use at least one selected from cellulose resin, polycarbonate resin, cyclic polyolefin resin, and (meth) acrylic resin.

  Cellulose resin is an ester of cellulose and fatty acid. Specific examples of the cellulose ester resin include triacetyl cellulose, diacetyl cellulose, tripropionyl cellulose, dipropionyl cellulose and the like. Among these, triacetyl cellulose is particularly preferable. Many products of triacetylcellulose are commercially available, which is advantageous in terms of availability and cost. Examples of commercially available products of triacetyl cellulose include trade names “UV-50”, “UV-80”, “SH-80”, “TD-80U”, “TD-TAC”, and “UZ” manufactured by Fujifilm Corporation. -TAC "and" KC series "manufactured by Konica. In general, these triacetyl celluloses have an in-plane retardation (Re) of almost zero, but a thickness direction retardation (Rth) of about 60 nm.

  In addition, the cellulose resin film with a small thickness direction phase difference is obtained by processing the said cellulose resin, for example. For example, a base film such as polyethylene terephthalate, polypropylene, and stainless steel coated with a solvent such as cyclopentanone and methyl ethyl ketone is bonded to a general cellulose film and dried by heating (for example, at 80 to 150 ° C. for about 3 to 10 minutes). ) And then peeling the base film; a solution obtained by dissolving norbornene resin, (meth) acrylic resin, etc. in a solvent such as cyclopentanone, methyl ethyl ketone, etc. is applied to a general cellulose resin film and dried by heating ( For example, a method of peeling the coated film after 80 to 150 ° C. for about 3 to 10 minutes is mentioned.

  Moreover, as a cellulose resin film with a small thickness direction retardation, the fatty acid cellulose resin film which controlled the fat substitution degree can be used. Generally used triacetyl cellulose has an acetic acid substitution degree of about 2.8. Preferably, the Rth can be reduced by controlling the acetic acid substitution degree to 1.8 to 2.7. Rth can be controlled to be small by adding a plasticizer such as dibutyl phthalate, p-toluenesulfonanilide, acetyltriethyl citrate to the fatty acid-substituted cellulose resin. The addition amount of the plasticizer is preferably 40 parts by weight or less, more preferably 1 to 20 parts by weight, and still more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the fatty acid cellulose resin.

  Specific examples of the cyclic polyolefin resin are preferably norbornene resins. The cyclic olefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, cyclic olefins and α-olefins such as ethylene and propylene (typically random copolymers), And graft polymers obtained by modifying them with an unsaturated carboxylic acid or a derivative thereof, and hydrides thereof. Specific examples of the cyclic olefin include norbornene monomers.

  Various products are commercially available as the cyclic polyolefin resin. As specific examples, trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION, product names “ARTON” manufactured by JSR Corporation, “TOPAS” manufactured by TICONA, and product names manufactured by Mitsui Chemicals, Inc. “APEL”.

  The (meth) acrylic resin preferably has a Tg (glass transition temperature) of 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. When Tg is 115 ° C. or higher, the polarizing plate can be excellent in durability. Although the upper limit of Tg of the (meth) acrylic resin is not particularly limited, it is preferably 170 ° C. or lower from the viewpoint of moldability and the like. From the (meth) acrylic resin, a film having in-plane retardation (Re) and thickness direction retardation (Rth) of almost zero can be obtained.

  As the (meth) acrylic resin, any appropriate (meth) acrylic resin can be adopted as long as the effects of the present invention are not impaired. For example, poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (Meth) acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), a polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, Methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.). Preferably, poly (meth) acrylate C1-6 alkyl such as poly (meth) acrylate methyl is used. More preferred is a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).

  Specific examples of (meth) acrylic resins include (meth) acrylic resins having a ring structure in the molecule described in, for example, Acrypet VH and Acrypet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., and JP-A-2004-70296. And a high Tg (meth) acrylic resin system obtained by intramolecular crosslinking or intramolecular cyclization reaction.

  As the (meth) acrylic resin, a (meth) acrylic resin having a lactone ring structure can also be used. It is because it has high mechanical strength by high heat resistance, high transparency, and biaxial stretching.

  Examples of the (meth) acrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005. Examples thereof include (meth) acrylic resins having a lactone ring structure described in Japanese Patent No. 146084.

  The (meth) acrylic resin having a lactone ring structure preferably has a ring pseudo structure represented by the following general formula (Formula 1).

^Wherein, R 1, ^{R 2} and ^{R 3} each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.

  The content ratio of the lactone ring structure represented by the general formula (Formula 1) in the structure of the (meth) acrylic resin having a lactone ring structure is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, More preferably, it is 10 to 60% by weight, and particularly preferably 10 to 50% by weight. When the content of the lactone ring structure represented by the general formula (Chemical Formula 1) in the structure of the (meth) acrylic resin having a lactone ring structure is less than 5% by weight, the heat resistance, solvent resistance, and surface hardness are low. May be insufficient. If the content of the lactone ring structure represented by the general formula (Chemical Formula 1) in the structure of the (meth) acrylic resin having a lactone ring structure is more than 90% by weight, molding processability may be poor.

  The (meth) acrylic resin having a lactone ring structure has a mass average molecular weight (sometimes referred to as a weight average molecular weight) of preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, and particularly preferably. Is 50,000 to 500,000. If the mass average molecular weight is out of the above range, it is not preferable from the viewpoint of moldability.

  The (meth) acrylic resin having a lactone ring structure preferably has a Tg of 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. Since Tg is 115 ° C. or higher, for example, when incorporated into a polarizing plate as a transparent protective film, it has excellent durability. Although the upper limit of Tg of the (meth) acrylic resin having the lactone ring structure is not particularly limited, it is preferably 170 ° C. or less from the viewpoint of moldability and the like.

  The (meth) acrylic resin having a lactone ring structure is preferably as the total light transmittance of a molded product obtained by injection molding measured by a method according to ASTM-D-1003 is higher, preferably 85. % Or more, more preferably 88% or more, and still more preferably 90% or more. The total light transmittance is a measure of transparency. If the total light transmittance is less than 85%, the transparency may be lowered.

  As the transparent protective film, one having a front phase difference of less than 40 nm and a thickness direction retardation of less than 80 nm is usually used. The front phase difference Re is represented by Re = (nx−ny) × d. The thickness direction retardation Rth is represented by Rth = (nx−nz) × d. The Nz coefficient is represented by Nz = (nx−nz) / (nx−ny). [However, the refractive indexes in the slow axis direction, the fast axis direction, and the thickness direction of the film are nx, ny, and nz, respectively, and d (nm) is the thickness of the film. The slow axis direction is the direction that maximizes the refractive index in the film plane. ]. In addition, it is preferable that a transparent protective film has as little color as possible. A protective film having a thickness direction retardation value of −90 nm to +75 nm is preferably used. By using a film having a thickness direction retardation value (Rth) of −90 nm to +75 nm, the coloring (optical coloring) of the polarizing plate caused by the transparent protective film can be almost eliminated. The thickness direction retardation value (Rth) is more preferably −80 nm to +60 nm, and particularly preferably −70 nm to +45 nm.

  On the other hand, as the transparent protective film, a phase difference plate having a phase difference with a front phase difference of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used. The front phase difference is usually controlled in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 300 nm. When a retardation plate is used as the transparent protective film, the retardation plate functions also as a transparent protective film, so that the thickness can be reduced.

  Examples of the retardation plate include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, a liquid crystal polymer alignment film, and a liquid crystal polymer alignment layer supported by a film. The thickness of the retardation plate is not particularly limited, but is generally about 20 to 150 μm.

  Examples of the polymer material include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, polycarbonate, polyarylate, polysulfone, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, Polyphenylene sulfide, polyphenylene oxide, polyallylsulfone, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulose resin, cyclic polyolefin resin (norbornene resin), or any of these binary, ternary copolymers, graft copolymers Examples thereof include polymers and blends. These polymer materials become an oriented product (stretched film) by stretching or the like.

  Examples of the liquid crystal polymer include various main chain types and side chain types in which a conjugated linear atomic group (mesogen) imparting liquid crystal alignment is introduced into the main chain or side chain of the polymer. . Specific examples of the main chain type liquid crystal polymer include a nematic alignment polyester liquid crystal polymer, a discotic polymer, and a cholesteric polymer having a structure in which a mesogen group is bonded at a spacer portion that imparts flexibility. Specific examples of the side chain type liquid crystal polymer include polysiloxane, polyacrylate, polymethacrylate, or polymalonate as a main chain skeleton, and a nematic alignment-providing para-substitution through a spacer portion composed of a conjugated atomic group as a side chain. Examples thereof include those having a mesogenic part composed of a cyclic compound unit. These liquid crystal polymers can be prepared by, for example, applying a solution of a liquid crystalline polymer on an alignment surface such as a surface of a thin film such as polyimide or polyvinyl alcohol formed on a glass plate, or an oblique deposition of silicon oxide. This is done by developing and heat treatment.

  The retardation plate may have an appropriate retardation according to the purpose of use, such as those for the purpose of compensating for various wavelength plates or birefringence of liquid crystal layers and compensation of viewing angle, etc. It may be one in which retardation plates are stacked and optical characteristics such as retardation are controlled.

  The retardation plate has a relationship of nx = ny> nz, nx> ny> nz, nx> ny = nz, nx> nz> ny, nz = nx> ny, nz> nx> ny, nz> nx = ny. What is satisfactory is selected and used according to various applications. Note that ny = nz includes not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.

  For example, in a phase difference plate that satisfies nx> ny> nz, a surface plate having a front phase difference of 40 to 100 nm, a thickness direction phase difference of 100 to 320 nm, and an Nz coefficient of 1.8 to 4.5 is used. Is preferred. For example, for a retardation plate (positive A plate) that satisfies nx> ny = nz, it is preferable to use a retardation plate that satisfies a front phase difference of 100 to 200 nm. For example, for a retardation plate (negative A plate) that satisfies nz = nx> ny, it is preferable to use a retardation plate that satisfies a front phase difference of 100 to 200 nm. For example, in a retardation plate satisfying nx> nz> ny, it is preferable to use a retardation plate having a front phase difference of 150 to 300 nm and an Nz coefficient exceeding 0 to 0.7. As described above, for example, a material satisfying nx = ny> nz, nz> nx> ny, or nz> nx = ny can be used.

  The transparent protective film can be appropriately selected according to the applied liquid crystal display device. For example, in the case of VA (including Vertical Alignment, MVA, and PVA), it is desirable that at least one of the polarizing plates (cell side) has a retardation. As specific phase differences, it is desirable that Re = 0 to 240 nm and Rth = 0 to 500 nm. In terms of the three-dimensional refractive index, nx> ny = nz, nx> ny> nz, nx> nz> ny, nx = ny> nz (positive A plate, biaxial, negative C plate) are desirable. In the VA type, it is preferable to use a combination of a positive A plate and a negative C plate, or one biaxial film. When polarizing plates are used above and below the liquid crystal cell, both the upper and lower sides of the liquid crystal cell may have a phase difference, or any one of the upper and lower transparent protective films may have a phase difference.

  For example, in the case of IPS (including In-Plane Switching, FFS), both cases where the transparent protective film on one side of the polarizing plate has a phase difference and does not have a phase difference can be used. For example, when there is no phase difference, it is desirable that the liquid crystal cell does not have a phase difference both above and below (cell side). In the case where the liquid crystal cell has a phase difference, it is desirable that the liquid crystal cell has a phase difference in the upper and lower sides, or the upper and lower sides have a phase difference (for example, nx> nz> ny on the upper side). Biaxial film satisfying the relationship, when there is no retardation on the lower side, positive A plate on the upper side, and positive C plate on the lower side). When it has a phase difference, it is desirable that Re = −500 to 500 nm and Rth = −500 to 500 nm. In terms of the three-dimensional refractive index, nx> ny = nz, nx> nz> ny, nz> nx = ny, nz> nx> ny (positive A plate, biaxial, positive C plate) are desirable.

  In addition, the film which has the said phase difference can be separately bonded to the transparent protective film which does not have a phase difference, and the said function can be provided.

  The transparent protective film may be subjected to surface modification treatment in order to improve adhesiveness with the polarizer before applying the adhesive. Specific examples of the treatment include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, saponification treatment, and treatment with a coupling agent. Further, an antistatic layer can be appropriately formed.

  The surface of the transparent protective film to which the polarizer is not adhered may be subjected to a hard coat layer, an antireflection treatment, an antisticking treatment, or a treatment for diffusion or antiglare.

  The hard coat treatment is applied for the purpose of preventing scratches on the surface of the polarizing plate. For example, a transparent protective film with a cured film excellent in hardness, sliding properties, etc. by an appropriate ultraviolet curable resin such as acrylic or silicone is used. It can be formed by a method of adding to the surface of the film. The antireflection treatment is performed for the purpose of preventing reflection of external light on the surface of the polarizing plate, and can be achieved by forming an antireflection film or the like according to the conventional art. In addition, the sticking prevention treatment is performed for the purpose of preventing adhesion with an adjacent layer (for example, a backlight-side diffusion plate).

  The anti-glare treatment is applied for the purpose of preventing the outside light from being reflected on the surface of the polarizing plate and obstructing the visibility of the light transmitted through the polarizing plate. For example, the surface is roughened by a sandblasting method or an embossing method. It can be formed by imparting a fine concavo-convex structure to the surface of the transparent protective film by an appropriate method such as a blending method of transparent fine particles. Examples of the fine particles to be included in the formation of the surface fine concavo-convex structure include conductive materials made of silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide, and the like having an average particle diameter of 0.5 to 20 μm. In some cases, transparent fine particles such as inorganic fine particles, organic fine particles composed of a crosslinked or uncrosslinked polymer, and the like are used. When forming the surface fine uneven structure, the amount of fine particles used is generally about 2 to 70 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the transparent resin forming the surface fine uneven structure. The antiglare layer may also serve as a diffusion layer (viewing angle expanding function or the like) for diffusing the light transmitted through the polarizing plate to expand the viewing angle.

  The antireflection layer, antisticking layer, diffusion layer, antiglare layer, and the like can be provided on the transparent protective film itself, or can be provided separately from the transparent protective film as an optical layer.

  An adhesive is used for the adhesion treatment between the polarizer and the transparent protective film. Examples of the adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, and water-based polyesters. The said adhesive agent is normally used as an adhesive agent which consists of aqueous solution, and contains 0.5 to 60 weight% of solid content normally. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing plate adhesive exhibits suitable adhesion to the various transparent protective films. The adhesive used in the present invention can contain a metal compound filler.

  In addition, as an optical film, for example, for formation of a liquid crystal display device such as a reflection plate, an anti-transmission plate, the retardation plate (including wavelength plates such as 1/2 and 1/4), a visual compensation film, and a brightness enhancement film. The optical layer which may be used is mentioned. These can be used alone as an optical film, or can be laminated on the polarizing plate for practical use and used as one layer or two or more layers.

  In particular, a reflective polarizing plate or a semi-transmissive polarizing plate in which a polarizing plate is further laminated with a reflecting plate or a semi-transmissive reflecting plate, an elliptical polarizing plate or a circular polarizing plate in which a retardation plate is further laminated on a polarizing plate, a polarizing plate A wide viewing angle polarizing plate in which a visual compensation film is further laminated on a plate, or a polarizing plate in which a luminance enhancement film is further laminated on a polarizing plate is preferable.

  A reflective polarizing plate is a polarizing plate provided with a reflective layer, and is used to form a liquid crystal display device or the like that reflects incident light from the viewing side (display side). Such a light source can be omitted, and the liquid crystal display device can be easily thinned. The reflective polarizing plate can be formed by an appropriate method such as a method in which a reflective layer made of metal or the like is attached to one surface of the polarizing plate via a transparent protective layer or the like as necessary.

  Specific examples of the reflective polarizing plate include those in which a reflective layer is formed by attaching a foil or a vapor deposition film made of a reflective metal such as aluminum on one side of a transparent protective film matted as necessary. In addition, the transparent protective film may contain fine particles to form a surface fine concavo-convex structure, and a reflective layer having a fine concavo-convex structure thereon. The reflective layer having the fine concavo-convex structure has an advantage that incident light is diffused by irregular reflection to prevent directivity and glaring appearance and to suppress unevenness in brightness and darkness. Moreover, the protective film containing fine particles also has an advantage that incident light and its reflected light are diffused when passing through it and light and dark unevenness can be further suppressed. The reflective layer of the fine concavo-convex structure reflecting the surface fine concavo-convex structure of the transparent protective film is formed by, for example, applying metal to the surface of the transparent protective layer by an appropriate method such as a vacuum deposition method, an ion plating method, a sputtering method, or a plating method. It can be performed by a method of attaching directly to the screen.

  Instead of the method of directly applying the reflecting plate to the transparent protective film of the polarizing plate, the reflecting plate can be used as a reflecting sheet provided with a reflecting layer on an appropriate film according to the transparent film. Since the reflective layer is usually made of metal, the usage form in which the reflective surface is covered with a transparent protective film, a polarizing plate or the like is used to prevent the reflectance from being lowered due to oxidation, and thus to maintain the initial reflectance for a long time. In addition, it is more preferable to avoid a separate attachment of the protective layer.

  The semi-transmissive polarizing plate can be obtained by using a semi-transmissive reflective layer such as a half mirror that reflects and transmits light with the reflective layer. A transflective polarizing plate is usually provided on the back side of a liquid crystal cell, and displays an image by reflecting incident light from the viewing side (display side) when a liquid crystal display device is used in a relatively bright atmosphere. In a relatively dark atmosphere, a liquid crystal display device of a type that displays an image using a built-in power source such as a backlight built in the back side of the transflective polarizing plate can be formed. In other words, the transflective polarizing plate can be used to form liquid crystal display devices that can save energy when using a light source such as a backlight in a bright atmosphere and can be used with a built-in power supply even in a relatively dark atmosphere. It is.

  An elliptically polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on a polarizing plate will be described. A phase difference plate or the like is used when changing linearly polarized light to elliptically polarized light or circularly polarized light, changing elliptically polarized light or circularly polarized light to linearly polarized light, or changing the polarization direction of linearly polarized light. In particular, a so-called quarter-wave plate (also referred to as a λ / 4 plate) is used as a retardation plate that changes linearly polarized light into circularly polarized light or changes circularly polarized light into linearly polarized light. A half-wave plate (also referred to as a λ / 2 plate) is usually used when changing the polarization direction of linearly polarized light.

  The elliptically polarizing plate is effectively used for black and white display without the above color by compensating (preventing) the coloration (blue or yellow) generated by the birefringence of the liquid crystal layer of the super twist nematic (STN) type liquid crystal display device. It is done. Further, the one in which the three-dimensional refractive index is controlled is preferable because it can compensate (prevent) coloring that occurs when the screen of the liquid crystal display device is viewed from an oblique direction. The circularly polarizing plate is effectively used, for example, when adjusting the color tone of an image of a reflective liquid crystal display device in which an image is displayed in color, and also has an antireflection function.

  The elliptical polarizing plate and the reflective elliptical polarizing plate are obtained by laminating a polarizing plate or a reflective polarizing plate and a retardation plate in an appropriate combination. Such an elliptically polarizing plate or the like can also be formed by sequentially laminating them sequentially in the manufacturing process of the liquid crystal display device so as to be a combination of a (reflective) polarizing plate and a retardation plate. An optical film such as a polarizing plate has an advantage that it can improve the production efficiency of a liquid crystal display device and the like because of excellent quality stability and lamination workability.

  The visual compensation film is a film for widening the viewing angle so that the image can be seen relatively clearly even when the screen of the liquid crystal display device is viewed from a slightly oblique direction rather than perpendicular to the screen. Examples of such a visual compensation phase difference plate include a phase difference plate, an alignment film such as a liquid crystal polymer, and a film in which an alignment layer such as a liquid crystal polymer is supported on a transparent substrate. A normal retardation plate uses a birefringent polymer film that is uniaxially stretched in the plane direction, whereas a retardation plate used as a visual compensation film is biaxially stretched in the plane direction. Birefringent polymer film, biaxially stretched film such as polymer with birefringence with a controlled refractive index in the thickness direction that is uniaxially stretched in the plane direction and stretched in the thickness direction, etc. Used. Examples of the inclined alignment film include a film obtained by bonding a heat shrink film to a polymer film and stretching or / and shrinking the polymer film under the action of the contraction force by heating, and a film obtained by obliquely aligning a liquid crystal polymer. can give. The raw material polymer for the phase difference plate is the same as the polymer described in the previous phase difference plate, preventing coloration due to a change in the viewing angle based on the phase difference by the liquid crystal cell and expanding the viewing angle for good visual recognition. An appropriate one for the purpose can be used.

  In addition, from the viewpoint of achieving a wide viewing angle with good visibility, an optical compensation position in which an alignment layer of a liquid crystal polymer, particularly an optically anisotropic layer composed of a tilted alignment layer of a discotic liquid crystal polymer, is supported by a triacetyl cellulose film. A phase difference plate can be preferably used.

  A polarizing plate obtained by bonding a polarizing plate and a brightness enhancement film is usually provided on the back side of a liquid crystal cell. The brightness enhancement film reflects a linearly polarized light with a predetermined polarization axis or a circularly polarized light in a predetermined direction when natural light is incident due to a backlight such as a liquid crystal display device or reflection from the back side, and transmits other light. In addition, a polarizing plate in which a brightness enhancement film is laminated with a polarizing plate allows light from a light source such as a backlight to enter to obtain transmitted light in a predetermined polarization state, and reflects light without transmitting the light other than the predetermined polarization state. The The light reflected on the surface of the brightness enhancement film is further inverted through a reflective layer or the like provided behind the brightness enhancement film and re-incident on the brightness enhancement film, and part or all of the light is transmitted as light having a predetermined polarization state. Luminance can be improved by increasing the amount of light transmitted through the enhancement film and increasing the amount of light that can be used for liquid crystal display image display or the like by supplying polarized light that is difficult to be absorbed by the polarizer. That is, when light is incident through the polarizer from the back side of the liquid crystal cell without using a brightness enhancement film, light having a polarization direction that does not coincide with the polarization axis of the polarizer is almost polarized. It is absorbed by the polarizer and does not pass through the polarizer. That is, although depending on the characteristics of the polarizer used, approximately 50% of the light is absorbed by the polarizer, and accordingly, the amount of light that can be used for liquid crystal image display or the like is reduced and the image becomes dark. The brightness enhancement film reflects light that has a polarization direction that is absorbed by the polarizer without being incident on the polarizer, and is reflected by the brightness enhancement film, and then inverted through a reflective layer or the like provided behind the brightness enhancement film. The brightness enhancement film transmits only the polarized light in which the polarization direction of the light reflected and inverted between the two is allowed to pass through the polarizer. Since the light is supplied to the polarizer, light such as a backlight can be efficiently used for displaying an image on the liquid crystal display device, and the screen can be brightened.

  A diffusion plate may be provided between the brightness enhancement film and the reflective layer. The polarized light reflected by the brightness enhancement film is directed to the reflective layer or the like, but the installed diffuser plate uniformly diffuses the light passing therethrough and simultaneously cancels the polarized state and becomes a non-polarized state. That is, the light in the natural light state is directed toward the reflection layer or the like, reflected through the reflection layer or the like, and again passes through the diffusion plate and reenters the brightness enhancement film. In this way, by providing a diffuser plate that returns polarized light to the original natural light between the brightness enhancement film and the reflective layer, the brightness of the display screen is maintained, and at the same time, the brightness of the display screen is reduced and uniform. Can provide a bright screen. By providing such a diffuser plate, it is considered that the first incident light has a moderate increase in the number of repetitions of reflection, and in combination with the diffusion function of the diffuser plate, a uniform bright display screen can be provided.

  The brightness enhancement film has a characteristic of transmitting linearly polarized light having a predetermined polarization axis and reflecting other light, such as a multilayer thin film of dielectric material or a multilayer laminate of thin film films having different refractive index anisotropies. Such as an alignment film of a cholesteric liquid crystal polymer or an alignment liquid crystal layer supported on a film substrate, which reflects either left-handed or right-handed circularly polarized light and transmits other light. Appropriate things such as a thing can be used.

  Therefore, in the brightness enhancement film of the type that transmits linearly polarized light having the predetermined polarization axis as described above, the transmitted light is directly incident on the polarizing plate with the polarization axis aligned, thereby efficiently transmitting while suppressing absorption loss due to the polarizing plate. Can be made. On the other hand, in a brightness enhancement film of a type that transmits circularly polarized light such as a cholesteric liquid crystal layer, it can be incident on a polarizer as it is, but from the point of suppressing absorption loss, the circularly polarized light is converted into linearly polarized light through a retardation plate. It is preferably incident on the polarizing plate. Note that circularly polarized light can be converted to linearly polarized light by using a quarter wave plate as the retardation plate.

  A retardation plate that functions as a quarter-wave plate at a wide wavelength in the visible light region or the like exhibits, for example, a retardation plate that functions as a quarter-wave plate for light-colored light having a wavelength of 550 nm and other retardation characteristics. It can be obtained by a method in which a phase difference layer, for example, a phase difference layer that functions as a half-wave plate is superimposed. Therefore, the retardation plate disposed between the polarizing plate and the brightness enhancement film may be composed of one or more retardation layers.

  In addition, a cholesteric liquid crystal layer having a reflection structure that reflects circularly polarized light in a wide wavelength range such as a visible light range can be obtained by combining two or more layers with different reflection wavelengths to form an overlapping structure. Based on this, transmitted circularly polarized light in a wide wavelength range can be obtained.

  Further, the polarizing plate may be formed by laminating a polarizing plate and two or more optical layers as in the above-described polarization separation type polarizing plate. Therefore, a reflective elliptical polarizing plate or a semi-transmissive elliptical polarizing plate in which the above-described reflective polarizing plate or semi-transmissive polarizing plate and a retardation plate are combined may be used.

  An optical film in which the optical layer is laminated on a polarizing plate can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. There is an advantage that the manufacturing process of a liquid crystal display device or the like can be improved because of excellent stability and assembly work. For the lamination, an appropriate adhesive means such as an adhesive layer can be used. When adhering the polarizing plate and the other optical layer, their optical axes can be set at an appropriate arrangement angle in accordance with a target phase difference characteristic.

  The glass substrate with an optical film of the present invention is obtained by adhering an adhesive optical film to a glass substrate (liquid crystal cell). The pressure-sensitive adhesive layer of the pressure-sensitive adhesive optical film is formed from a water-dispersed pressure-sensitive adhesive containing an emulsifier. When bonded to a glass substrate, it exhibits high adhesiveness immediately after bonding, and is also in a high-temperature and high-humidity atmosphere. Excellent durability even under.

  The pressure-sensitive adhesive film peeling method according to the present invention is such that the glass substrate with an optical film has a temperature of 40 ° C. or higher and a relative humidity of 80% or higher (Condition 1), or a temperature of 50 ° C. or higher and a relative humidity of 70% or higher (Condition 2). The adhesive optical film is peeled off from the glass substrate after exposure to the environment.

  When the glass substrate with an optical film is exposed to the environment of Condition 1 or Condition 2, the adhesive strength is reduced at the interface between the pressure-sensitive adhesive layer and the glass substrate, and the adhesive optical film can be easily peeled off. Moreover, even if the adhesive strength becomes 20 N / 25 mm width or more by sticking the adhesive optical film to the glass substrate for a long time in a high temperature environment, the adhesive strength can be increased by exposing it to the environment of Condition 1 or Condition 2. The width can be reduced to 10 N / 25 mm width or less. Therefore, it can be easily peeled with good reworkability even on a large-sized glass substrate. Preferred conditions for the exposure treatment are a temperature of 80 ° C. or higher and a relative humidity of 80% or higher. Moreover, it is preferable that the temperature of an exposure process is 100 degrees C or less. If the temperature of the exposure treatment exceeds 100 ° C., the liquid crystal display as the adherend may be damaged.

  The exposure treatment time is preferably 1 hour or longer, more preferably 2 hours or longer. If it is less than 1 hour, the water absorption of the pressure-sensitive adhesive layer does not proceed sufficiently, and the adhesive force does not sufficiently decrease at the interface between the pressure-sensitive adhesive layer and the glass substrate. Occurs and reworkability decreases. On the other hand, the exposure treatment time is usually 48 hours or less. Even if it exceeds 48 hours, the effect is hardly changed, which is not preferable from the viewpoint of production efficiency.

  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.

Production Example 1
(Preparation of monomer pre-emulsion)
In a container, 88 parts of butyl acrylate, 5 parts of N-cyclohexyl methacrylate, 5 parts of acrylic acid, 2 parts of mono [poly (propylene oxide) methacrylate] phosphate (average degree of polymerization of propylene oxide of about 5.0), Then, 0.03 part of 3-methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503) was added and mixed to prepare a monomer mixture. Next, 20 g of reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., Aqualon HS-1025) and 446 g of ion-exchanged water are added to 500 g of the monomer mixture, and 5000 (rpm) is used using a homogenizer (Special Machine Co., Ltd.). And stirred for 5 minutes to prepare a monomer pre-emulsion.

(Preparation of water-dispersed acrylic adhesive)
To a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser, a monomer pre-emulsion 96 g, ion-exchanged water 275 g, and a reactive emulsifier Aqualon HS-1025 (40 g) were added, and the reaction vessel was purged with nitrogen. . Thereafter, 0.05 g of ammonium persulfate was added, and a polymerization reaction was performed at 65 ° C. for 1 hour. Next, the temperature in the reaction vessel was raised to 75 ° C., and 0.35 g of ammonium persulfate was added. Thereafter, 869 g of monomer pre-emulsion was dropped into the reaction vessel over 3 hours, and a polymerization reaction was performed for 3 hours after the dropping. Thereafter, a polymerization reaction was performed at 75 ° C. for 3 hours while purging with nitrogen to prepare an emulsion solution having a solid content of 40%. And the obtained emulsion solution was cooled to room temperature, 10% ammonia water was added, pH was adjusted to 8, and the water dispersion-type acrylic adhesive was prepared.

(Formation of adhesive layer)
The water-dispersed acrylic pressure-sensitive adhesive was applied to one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., Diafoil MRF38, PET film) so that the thickness of the pressure-sensitive adhesive layer after drying was 23 μm. The pressure-sensitive adhesive layer was formed by drying at 2 ° C. for 2 minutes.

(Preparation of polarizing plate)
A polyvinyl alcohol film having a thickness of 80 μm was stretched 5 times in an iodine solution at 40 ° C. Thereafter, the polyvinyl alcohol film was pulled up from the iodine solution and dried at 50 ° C. for 4 minutes to obtain a polarizer. A polarizing plate was prepared by laminating a triacetyl cellulose film on both surfaces of the polarizer using a polyvinyl alcohol-based adhesive.

(Preparation of adhesive polarizing plate A)
An anchor coating agent was prepared by diluting an oxazoline group-containing acrylic polymer (Nippon Shokubai Co., Ltd., Epocros WS-700) with a water / isopropyl alcohol (weight ratio 1/1) mixed solution to a solid content of 0.25%. . An anchor coating agent was coated on one side of the polarizing plate using a Mayer bar # 5 and dried at 40 ° C. for 2 minutes to form an anchor layer. Next, the said adhesive layer was transcribe | transferred on the anchor layer, and the adhesion type polarizing plate A was produced.

(Measurement of adhesive strength)
The initial adhesive strength of the adhesive polarizing plate A and the adhesive strength after 60 ° C./100 hours were measured by the following method. As a result, the initial adhesive strength was 7.8 (N / 25 mm), and the adhesive strength after 60 ° C./100 hours was 36.0 (N / 25 mm).
<Initial adhesive strength>
A sample obtained by cutting the adhesive polarizing plate A to a width of 25 mm is attached to a glass substrate (Corning Corp., Corning # 1737) by one reciprocating press with a 2 kg roller, and then 15 minutes in an autoclave at 50 ° C. and 5 atm. Allowed to cool, then cooled to 25 ° C. And the adhesive force (N / 25mm) at the time of peeling a sample from a glass substrate on the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min was measured using the tensile tester.
<Adhesive strength after 60 ° C./100 hours>
A sample obtained by cutting the adhesive polarizing plate A to a width of 25 mm is attached to a glass substrate (Corning Corp., Corning # 1737) by one reciprocating press with a 2 kg roller, and then 15 minutes in an autoclave at 50 ° C. and 5 atm. Then, it was left for 100 hours in an atmosphere of 60 ° C. and a relative humidity of 30%, and then cooled to 25 ° C. And the adhesive force (N / 25mm) at the time of peeling a sample from a glass substrate on the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min was measured using the tensile tester.

Production Example 2
(Preparation of acrylic polymer solution)
To a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 100 parts of butyl acrylate, 5 parts of acrylic acid, 0.1 part of benzoyl peroxide, and ethyl acetate were added, and the monomer concentration was 80%. A monomer solution was prepared. Nitrogen gas was introduced for 1 hour while stirring to replace the nitrogen, and then the polymerization temperature was kept at around 60 ° C. for 6 hours to prepare an acrylic polymer solution. The weight average molecular weight of the acrylic polymer was 1,600,000.

(Preparation of acrylic adhesive)
An acrylic pressure-sensitive adhesive was prepared by adding 0.8 part of a polyfunctional isocyanate compound (Nippon Polyurethane, Coronate L) to 100 parts (solid content) of the acrylic polymer solution.

(Formation of adhesive layer)
The acrylic pressure-sensitive adhesive was applied to one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., Diafoil MRF38, PET film) so that the thickness of the pressure-sensitive adhesive layer after drying was 21 μm, The adhesive layer was formed by drying for minutes.

(Preparation of adhesive polarizing plate B)
The pressure-sensitive adhesive layer was transferred onto a polarizing plate to prepare a pressure-sensitive adhesive polarizing plate B.

(Measurement of adhesive strength)
The initial adhesive strength of the adhesive polarizing plate B and the adhesive strength after 60 ° C./100 hours were measured by the same method as described above. As a result, the initial adhesive strength was 14.8 (N / 25 mm), and the adhesive strength after 60 ° C./100 hours was 31.0 (N / 25 mm).

Production Example 3
(Formation of adhesive layer)
A carbodiimide compound (Nisshinbo Co., Ltd., Carbodilite E-04) as a crosslinking agent was added to the water-dispersed acrylic pressure-sensitive adhesive of Production Example 1 to obtain a pressure-sensitive adhesive composition. In addition, the addition amount of a crosslinking agent is 0.4 weight% in solid content of a water dispersion-type acrylic adhesive. And it apply | coated so that the thickness of the adhesive layer after drying might be set to 23 micrometers on one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., Diafoil MRF38, PET film), and it dried at 120 degreeC for 2 minutes. An adhesive layer was formed.

(Preparation of adhesive polarizing plate C)
An adhesive polarizing plate C was produced in the same manner as in Production Example 1 except that the adhesive layer was used.

(Measurement of adhesive strength)
The initial adhesive strength of the adhesive polarizing plate C and the adhesive strength after 60 ° C./100 hours were measured by the same method as described above. As a result, the initial adhesive strength was 2.3 (N / 25 mm), and the adhesive strength after 60 ° C./100 hours was 30 (N / 25 mm) or more.

Production Example 4
(Formation of adhesive layer)
A carbodiimide compound (Nisshinbo Co., Ltd., Carbodilite E-04) as a crosslinking agent was added to the water-dispersed acrylic pressure-sensitive adhesive of Production Example 1 to obtain a pressure-sensitive adhesive composition. In addition, the addition amount of a crosslinking agent is 1.0 weight% in solid content of a water dispersion-type acrylic adhesive. And it apply | coated so that the thickness of the adhesive layer after drying might be set to 23 micrometers on one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., Diafoil MRF38, PET film), and it dried at 120 degreeC for 2 minutes. An adhesive layer was formed.

(Preparation of adhesive polarizing plate D)
An adhesive polarizing plate D was produced in the same manner as in Production Example 1 except that the adhesive layer was used.

(Measurement of adhesive strength)
The initial adhesive strength of the adhesive polarizing plate D and the adhesive strength after 60 ° C./100 hours were measured by the same method as described above. As a result, the initial adhesive strength was 2.1 (N / 25 mm), and the adhesive strength after 60 ° C./100 hours was 30 (N / 25 mm) or more.

Production Example 5
(Formation of adhesive layer)
A carbodiimide compound (Nisshinbo Co., Ltd., Carbodilite E-04) as a crosslinking agent was added to the water-dispersed acrylic pressure-sensitive adhesive of Production Example 1 to obtain a pressure-sensitive adhesive composition. In addition, the addition amount of a crosslinking agent is 1.0 weight% in solid content of a water dispersion-type acrylic adhesive. Then, it was applied to one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., Diafoil MRF38, PET film) so that the thickness of the pressure-sensitive adhesive layer after drying was 30 μm, and dried at 120 ° C. for 2 minutes. An adhesive layer was formed.

(Preparation of adhesive polarizing plate E)
An adhesive polarizing plate E was produced in the same manner as in Production Example 1 except that the adhesive layer was used.

(Measurement of adhesive strength)
The initial adhesive strength of the adhesive polarizing plate E and the adhesive strength after 60 ° C./100 hours were measured by the same method as described above. As a result, the initial adhesive strength was 2.6 (N / 25 mm), and the adhesive strength after 60 ° C./100 hours was 30 (N / 25 mm) or more.

Examples 1-12, Comparative Examples 1-3
A sample obtained by cutting the adhesive polarizing plate A to a width of 25 mm is attached to a glass substrate (Corning Corp., Corning # 1737) by one reciprocating press with a 2 kg roller, and then 15 minutes in an autoclave at 50 ° C. and 5 atm. Then, it was left for 100 hours in an atmosphere of 60 ° C. and a relative humidity of 30%, and then cooled to 25 ° C. Then, the exposure process was performed on each condition of Table 1, and it cooled to 25 degreeC. And the adhesive force (N / 25mm) at the time of peeling a sample from a glass substrate on the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min was measured using the tension tester, respectively.

Comparative Examples 4 and 5
The adhesive strength (N / 25 mm) was measured in the same manner as described above except that the adhesive polarizing plate B was used.

Examples 13 and 14
The adhesive strength (N / 25 mm) was measured in the same manner as described above except that the adhesive polarizing plate C was used.

Examples 15 and 16
The adhesive strength (N / 25 mm) was measured in the same manner as described above except that the adhesive polarizing plate D was used.

Examples 17 and 18
The adhesive strength (N / 25 mm) was measured in the same manner as described above except that the adhesive polarizing plate E was used.

Claims (3)

In the peeling method of the pressure-sensitive adhesive optical film that peels the pressure-sensitive adhesive optical film from the glass substrate with an optical film on which the pressure-sensitive adhesive optical film is attached to the glass substrate,
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive optical film is formed from a water-dispersed pressure-sensitive adhesive,
The adhesive type optical film is peeled off from the glass substrate after the glass substrate with the optical film is exposed to an environment having a temperature of 40 ° C. or higher and a relative humidity of 80% or higher, or a temperature of 50 ° C. or higher and a relative humidity of 70% or higher. To peel off the pressure-sensitive adhesive optical film.   The adhesive optical film peeling method according to claim 1, wherein the adhesive optical film has an anchor layer between the optical film and the adhesive layer.   A pressure-sensitive adhesive optical film having a pressure-sensitive adhesive layer formed from a water-dispersed pressure-sensitive adhesive on at least one side of an optical film, which is used in the method for peeling a pressure-sensitive adhesive optical film according to claim 1 or 2, and is attached to a glass substrate. The adhesive strength after exposure for 100 hours in an environment of temperature 60 ° C. and relative humidity 30% is 20 N / 25 mm width or more, temperature 40 ° C. or more and relative humidity 80% or more, or temperature 50 ° C. or more and relative humidity 70 A pressure-sensitive adhesive optical film having an adhesive strength of 10 N / 25 mm width or less after exposure to an environment of at least%.