JP2012041549A - Adhesive layer for optical member, its manufacturing method, and optical member with adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical member with an adhesive which can be easily released from a liquid crystal cell, particularly easily from a large size liquid crystal cell, hardly remains starch when releasing, has an excellent durability and relaxation to stress caused by size deformation of a polarizing plate or the like even after stored for a long period under severe conditions or at high temperature; and to provide its manufacturing method and an image display device using the same.SOLUTION: The optical member with an adhesive has an adhesive layer laminated on at least one side face of the optical member. The adhesive layer is composed of a first adhesive layer in contact with the optical member, an intermediate layer composed of a polymer film and a second adhesive layer.

Description

  The present invention relates to an optical member with pressure-sensitive adhesive in which a pressure-sensitive adhesive layer is laminated on at least one surface of an optical member, and a method for producing the same. Furthermore, the present invention relates to an image display device such as a liquid crystal display device, an organic EL display device, and a PDP using the optical member with an adhesive. Examples of the optical member include a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, and those in which these are laminated.

  An optical member used for a liquid crystal display device or the like, for example, a polarizing plate or a retardation plate is attached to a liquid crystal cell using an adhesive. Usually, an optical member with an adhesive in which an adhesive layer is laminated on an optical member is used. Since the material used for the optical member has a large expansion and contraction under a heating condition or a humidifying condition, it tends to be lifted or peeled off after being attached. For this reason, the pressure-sensitive adhesive for optical members is required to have durability that can cope with heating conditions and humidification conditions.

  In addition, when an optical member is attached, if the foreign material or dust is caught on the attachment surface or the attachment position is misaligned, the optical member is removed from the liquid crystal cell and reused. When such an optical member is peeled off from the liquid crystal cell, it is necessary not to have an adhesive state that changes or breaks the gap of the liquid crystal cell. The

  However, if a pressure-sensitive adhesive that simply emphasizes durability, such as a technique for increasing the adhesion state, is designed, the re-peelability is poor. On the other hand, if the stress caused by the dimensional change of the polarizing plate under heating conditions or humidification conditions cannot be alleviated uniformly, residual stress remains in the polarizing plate, resulting in defects such as uneven color and white spots. There is a problem.

  Up to now, as an attempt to improve the above-described problems, a technique for forming a pressure-sensitive adhesive in a layer structure has been proposed. For example, a polarizing plate (for example, refer to Patent Document 1) in which the gel fraction of the pressure-sensitive adhesive layer on the polarizing plate side is lower than the gel fraction of the other pressure-sensitive adhesive layer, the surface energy difference between the pressure-sensitive adhesive layers is 1 to 30 dyne. / Cm polarizing plate provided with a pressure-sensitive adhesive layer (for example, see Patent Document 2), optical film having two pressure-sensitive adhesive layers with different elastic moduli (for example, see Patent Document 3), 2 with different shear elastic moduli Pressure-sensitive adhesive sheet provided with a single pressure-sensitive adhesive layer (for example, see Patent Document 4), optical film laminated with pressure-sensitive adhesive layers having different stress relaxation times (for example, see Patent Document 5), two-layer pressure-sensitive adhesives having different adhesive forces An adhesive transfer tape provided with a layer (for example, see Patent Document 6) is disclosed.

  As described above, it is disclosed that by making the pressure-sensitive adhesive layer into a layer structure, effects such as improvement in durability, improvement in stress relaxation, and removability can be expressed. It is hard to say that each effect is sufficiently manifested.

  The main reason for this is that the pressure-sensitive adhesive layer has two layers. For example, as described above, the pressure-sensitive adhesive layer has a low gel fraction and the pressure-sensitive adhesive layer has a high gel fraction. The deformation mode at the time of peeling is presumed that the soft layer does not first deform, but deforms according to the elastic modulus of both layers, so that it is impossible to completely share the functions of each layer.

In addition, even when the pressure-sensitive adhesive layer is laminated in a layer structure as described above, the adhesive force at the interface between the two layers is very weak, and the optical member is adhered to the liquid crystal cell for a long time or stored under harsh conditions. In that case, the optical member may be peeled off between the pressure-sensitive adhesive layers when the optical member is peeled off from the liquid crystal cell.
Japanese Patent Laid-Open No. 7-294731 JP-A-8-43626 JP-A-8-336925 JP-A-9-33723 Japanese Patent Laid-Open No. 9-189906 Japanese Patent Laid-Open No. 2003-177241

  The present invention can be easily peeled off from a liquid crystal cell even when stored in a harsh state for a long period of time or when stored under a high temperature condition. An object of the present invention is to provide an optical member with a pressure-sensitive adhesive that hardly causes a residue, has excellent durability, and is excellent in relaxation of stress caused by dimensional change such as a polarizing plate. Moreover, an object of this invention is to provide the manufacturing method of the said optical member with an adhesive. Furthermore, this invention aims at providing the image display apparatus using the said optical member with an adhesive.

  In order to achieve the above object, the present inventors have made extensive studies on the layer structure and the like of the pressure-sensitive adhesive layer. As a result, the first pressure-sensitive adhesive layer in contact with the optical member, the intermediate layer made of a polymer film, and the second pressure-sensitive adhesive layer By using a pressure-sensitive adhesive layer consisting of a pressure-sensitive adhesive layer, there is no delamination between the layers within the pressure-sensitive adhesive layer, and the functions of each pressure-sensitive adhesive layer can be demonstrated, and excellent removability, durability, and stress relaxation properties are balanced. It has been found that an optical member with a pressure-sensitive adhesive that is well aligned can be obtained, and the present invention has been completed.

  That is, the optical member with the pressure-sensitive adhesive of the present invention is the first pressure-sensitive adhesive in which the pressure-sensitive adhesive layer is in contact with the optical member in the optical member with the pressure-sensitive adhesive in which the pressure-sensitive adhesive layer is laminated on at least one surface of the optical member. It is characterized by comprising a layer, an intermediate layer made of a polymer film, and a second pressure-sensitive adhesive layer.

  According to the optical member with pressure-sensitive adhesive of the present invention, as shown in the results of the examples, in the optical member with pressure-sensitive adhesive in which the pressure-sensitive adhesive layer is laminated on at least one surface of the optical member, the first member in contact with the optical member By using a pressure-sensitive adhesive layer, an intermediate layer made of a polymer film, and a pressure-sensitive adhesive layer made of a second pressure-sensitive adhesive layer, even when stored under harsh conditions for a long time or when stored under high-temperature conditions Can be easily peeled off from liquid crystal cells, especially in large liquid crystal cells, can be easily peeled off, has no adhesive residue when peeled off, has excellent durability, and has excellent relaxation of stress caused by dimensional changes such as polarizing plates It becomes. Although the details of the reason why the optical member with the adhesive expresses such properties are not clear, by using the adhesive layer having the above-described configuration, there is no separation between each adhesive layer and the intermediate layer, It is presumed that the functions of the pressure-sensitive adhesive layer can be exhibited, and thus excellent removability, durability, and stress relaxation properties can be provided side by side.

  The polymer film in the present invention is preferably a polymer film having an appropriate elongation and strength that is not sticky to the film after drying, is transparent and does not generate birefringence. More specifically, it refers to a polymer film having a transmittance at 800 nm of 85% or more and a birefringence at 800 nm of 30 nm or less, a transmittance at 800 nm of 90% or more, and a birefringence at 800 nm of 25 nm. The polymer film is preferably the following.

In the present invention, the preferably the tensile modulus of the intermediate layer is 5N / mm ² or more, more preferably 5~1000N / mm ^2, further preferably 10~500N / mm ^2. Further, the breaking strength of the pressure-sensitive adhesive layer is preferably 10 N / mm ² or more, and the breaking elongation of the pressure-sensitive adhesive layer is preferably 50% or more. If the tensile modulus is less than 5 N / mm ² , the movement of the optical member is directly transmitted to the liquid crystal cell, which may cause a phenomenon such as warpage. On the other hand, if it exceeds 1000 N / mm ² , cracks occur in each work process. There is a problem in the process such as entering, which is not preferable in any case. Further, if the elongation at break of the pressure-sensitive adhesive layer is less than 50%, the film layer cannot act as a support.

  In the present invention, the intermediate layer may be obtained from an aqueous dispersion (dispersion).

  Furthermore, in the present invention, the first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer can be obtained from an aqueous dispersion (dispersion).

  Many types of optical members swell or dissolve with an organic solvent, and by using an aqueous dispersion (dispersion) that does not use an organic solvent in an aqueous medium or a water-based mixed solvent system, such a problem can be solved. Furthermore, since no organic solvent is used, there is an advantage that the dry polymer film does not swell or dissolve even when applied on a normal dry polymer film. In addition, there is an advantage that disturbance of each layer is suppressed even after a step of drying after the formation of multiple layers. Furthermore, due to recent environmentally conscious movements, water dispersions (dispersions) that do not use organic solvents tend to be preferably used.

  The second pressure-sensitive adhesive layer preferably contains a silane coupling agent. By containing the silane coupling agent in the second pressure-sensitive adhesive layer, an optical member with a pressure-sensitive adhesive having improved adhesion to glass used in a liquid crystal cell, heat resistance and moisture resistance can be obtained.

  On the other hand, the optical member with the pressure-sensitive adhesive of the present invention is formed, for example, by applying the second pressure-sensitive adhesive raw material liquid to at least one surface of the peeled film (sheet or belt) and drying the second pressure-sensitive adhesive layer. After forming and drying the polymer film raw material liquid on the second pressure-sensitive adhesive layer to form an intermediate layer, the first pressure-sensitive adhesive liquid material is applied and dried on the intermediate layer. 1 pressure-sensitive adhesive layer can be formed and further bonded to an optical member.

  In the optical member with an adhesive of the present invention, for example, the second adhesive material liquid is applied to at least one surface of a peeled film (sheet or belt), and the second adhesive is applied. After the polymer film raw material liquid is applied on the layer, the first pressure sensitive adhesive raw material liquid is applied on the polymer (intermediate) coating layer obtained by applying the polymer film raw material liquid. Obtaining the second pressure-sensitive adhesive coating layer, the polymer film (intermediate) coating layer, and the first pressure-sensitive adhesive layer by simultaneously drying the layers so that the layers do not cross each other, and further bonding them to an optical member Can do.

  Furthermore, the optical member with pressure-sensitive adhesive of the present invention has, for example, a raw material liquid for the second pressure-sensitive adhesive, a raw material liquid for the polymer film, and the first material on at least one surface of the peel-treated film (sheet or belt). The adhesive raw material liquid can be simultaneously applied so that the coating layers do not cross each other, dried simultaneously so that the coating layers do not cross each other, and further bonded to the optical member.

  The optical member with pressure-sensitive adhesive obtained by the above-described manufacturing method has no peeling between each pressure-sensitive adhesive layer and an intermediate layer, can exhibit the function of each pressure-sensitive adhesive layer, and has excellent removability and durability. , And stress relaxation properties are balanced.

  Further, the image display device of the present invention is a liquid crystal display device, an organic EL display device, a PDP or the like using the optical member with an adhesive, and does not cause peeling or foaming even when stored in a high temperature and high humidity state. Durability is developed, stress relaxation due to dimensional change such as polarizing plate is excellent, and even when the optical member is peeled off and the image display device is reused, no increase in adhesive force is seen, which adversely affects the device It has a function that can be easily peeled off.

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

  That is, the optical member with the pressure-sensitive adhesive of the present invention is the first pressure-sensitive adhesive in which the pressure-sensitive adhesive layer is in contact with the optical member in the optical member with the pressure-sensitive adhesive in which the pressure-sensitive adhesive layer is laminated on at least one surface of the optical member. It is characterized by comprising a layer, an intermediate layer made of a polymer film, and a second pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive forming the first pressure-sensitive adhesive layer of the optical member with pressure-sensitive adhesive of the present invention is a material used for bonding the optical member and the polymer film layer, and is not particularly limited. Various pressure-sensitive adhesives such as pressure-sensitive adhesives and silicone-based pressure-sensitive adhesives can be used. Among them, acrylic pressure-sensitive adhesives that are colorless and transparent and have good adhesion to optical members and the like are generally used.

  The acrylic pressure-sensitive adhesive uses, as a base polymer, a (meth) acrylic polymer having an alkyl (meth) acrylate monomer unit as a main skeleton. In addition, (meth) acrylate refers to acrylate and / or methacrylate, and (meth) acrylic polymer refers to acrylic polymer and / or methacrylic polymer.

  A (meth) acrylic monomer having an alkyl group having 4 or more carbon atoms in the present invention is preferred. For example, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, n-pentyl (meth) acrylate, isopentyl (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, isomyristyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate and the like. Of these, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and the like are preferably used. These acrylic monomers may be used alone or in combination of two or more.

  The (meth) acrylic polymer in the present invention is formed by using the above-mentioned (meth) acrylic monomer having an alkyl group having 4 or more carbon atoms, from 50 to 100% by weight of all monomer components. It is preferable to use 60 to 99% by weight. If the total monomer component is less than 50% by weight, the stress relaxation property of the polymer film layer is inferior.

  Other polymerizable monomers other than the (meth) acrylic monomer having an alkyl group having 4 or more carbon atoms are polymerizable monomers for adjusting the glass transition point and peelability of the (meth) acrylic polymer, etc. Can be used as long as the effects of the present invention are not impaired. These monomers may be used alone or in combination, but the total content is less than 50% by weight of the monomer component of the (meth) acrylic monomer.

  Other polymerizable monomers used in (meth) acrylic polymers include, for example, cohesion and heat resistance of sulfonic acid group-containing monomers, phosphate group-containing monomers, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, etc. It works as an adhesion-improving component, carboxyl group-containing monomer, acid anhydride group-containing monomer, amide group-containing monomer, amino group-containing monomer, epoxy group-containing monomer, N-acryloylmorpholine, vinyl ether monomer, etc. A component having a functional group can be appropriately used. These monomer compounds may be used alone or in admixture 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, (meth And acryloyloxynaphthalene sulfonic acid.

  Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacryloyl phosphate.

  Examples of the cyano group-containing monomer include acrylonitrile.

  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 carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Of these, it is preferable to use (meth) acrylic acid.

  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, and 8-hydroxyoctyl. (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2 -Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and the like.

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

  Examples of the amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.

  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.

  Especially, it is preferable that the (meth) acrylic-type polymer in this invention uses the said carboxyl group containing monomer for 0.2-10 weight% among all the monomer components, and 0.5-7. It is preferable to use 0% by weight. By using such a (meth) acrylic polymer, an optical member with a pressure-sensitive adhesive having better adhesive strength, removability and the like is obtained. When the total monomer component exceeds 10% by weight, an adverse effect on the optical member such as saponification occurs, and when it is less than 0.2% by weight, the durability is inferior.

  The (meth) acrylic polymer used in the present invention has a weight average molecular weight of 1,000,000 to 5,000,000, preferably 1,200,000 to 4,000,000, more preferably 1,400,000 to 3,500,000. preferable. When the weight average molecular weight is less than 1,000,000, the adhesive strength at the time of peeling increases due to the improvement of wettability to the polarizing plate, which may cause damage to the polarizing plate in the peeling process. There is a tendency for adhesive residue to occur due to the reduced cohesive force, and the durability is poor. On the other hand, when the weight average molecular weight exceeds 5,000,000, the fluidity of the polymer is lowered and the wetting to the polarizing plate becomes insufficient, which tends to cause blisters generated between the optical member and the pressure-sensitive adhesive composition layer. There is. A weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).

  Moreover, for the reason that it is easy to balance the adhesive performance, the glass transition temperature (Tg) of the (meth) acrylic polymer is −10 ° C. or lower (usually −100 ° C. or higher), preferably −25 ° C. or lower. . When the glass transition temperature is higher than 0 ° C., the polymer is difficult to flow and the wetting of the optical member is insufficient, and there is a tendency to cause blisters generated between the optical member and the pressure-sensitive adhesive composition layer. In addition, the glass transition temperature (Tg) of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.

  The polymerization method of the (meth) acrylic polymer used in the present invention is not particularly limited, and it can be polymerized by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization or the like. Further, the obtained copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

  As a specific example of solution polymerization, for example, 0.01 to 0.2 parts by weight of a polymerization initiator such as azobisisobutyronitrile is used for 100 parts by weight of all monomer components, and polymerization of ethyl acetate or the like is performed. It can carry out by making it react at 50-70 degreeC under nitrogen stream for 8 to 30 hours using a solvent.

  In particular, from the viewpoint of environmental measures in recent years, the use of a pressure-sensitive adhesive that does not use an organic solvent such as emulsion polymerization is preferred. In the present invention, an aqueous dispersion of a polymer obtained by emulsion polymerization is also used as a pressure-sensitive adhesive layer. It can use suitably for formation.

  In the present invention, the emulsifier, polymerization initiator and the like used for emulsion polymerization are not particularly limited and can be appropriately selected and used.

Examples of the emulsifier used in the present invention include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene alkyl ether. And nonionic emulsifiers such as polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer.
These emulsifiers may be used alone or in combination of two or more.

  Furthermore, as reactive emulsifiers, as emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE10N (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like. Reactive emulsifiers are preferred because, even if the rate of reaction addition during emulsion polymerization is low, they are incorporated into the polymer chain after polymerization, so that the water resistance is greatly improved by passing through a drying step. The amount of the emulsifier used is more preferably 0.3 to 5 parts by weight and 0.5 to 1 part by weight with respect to 100 parts by weight of the monomer in view of polymerization stability and mechanical stability.

  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 monomers at this time can be blended in whole or in part with the total amount used, and the remainder can be added dropwise during the polymerization. Next, a polymerization initiator and, if necessary, water are added to this emulsion to carry out emulsion polymerization (emulsion polymerization).

  In addition, water may be blended only at the time of preparing the emulsion, or may be further blended thereafter, and can be appropriately selected according to the polymerization method described later. The amount of water is not particularly limited, but the solid content concentration of the (meth) acrylic polymer after emulsion polymerization (emulsion polymerization) is 30 to 75% by weight, preferably 35 to 70% by weight. Prepare to be.

  The method of emulsion polymerization (emulsion polymerization) is not particularly limited, and can be appropriately selected from a batch polymerization method, a continuous dropping method, a 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. Then, a polymerization initiator and water as necessary are added to the reaction vessel to perform emulsion polymerization ( Emulsion polymerization).

  In the continuous 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 in 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.

  As the additive after emulsion polymerization, for example, known ones such as a pH buffer, a neutralizer, an antifoaming agent, and a stabilizer can be appropriately used.

In addition, the urethane-acrylic hybrid aqueous dispersion can be treated by introducing an acidic group into the urethane skeleton and using a urethane dispersion in which a urethane resin is dispersed as a seed without using an emulsifier in water. ) It can be obtained by seed polymerization of acrylic monomer.
Such a urethane-acrylic hybrid aqueous dispersion does not require the use of an emulsifier, and therefore has good adhesiveness with the pressure-sensitive adhesive layer and is preferably used.

  Examples of the polymerization initiator used in the present invention 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′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), azo initiators, potassium persulfate, ammonium persulfate Persulfate such as di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di- sec-butyl peroxydicarbonate, 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) peroxide initiators such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, Examples include redox initiators combined with reducing agents. The present invention is not limited to.

  The polymerization initiators may be used alone or in combination of two or more, but the total content is usually 0.01 to 0. About 2 parts by weight are used.

  In the present invention, a chain transfer agent may be used in the polymerization. By using a chain transfer agent, the molecular weight of the (meth) acrylic polymer and the gel fraction of the pressure-sensitive adhesive layer can be adjusted by using these chain transfer agents.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, 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, but the total content is 0.01 to 0. 0 with respect to 100 parts by weight of the monomer. About 5 parts by weight.

  As the pressure-sensitive adhesive that forms the second pressure-sensitive adhesive layer of the optical member with pressure-sensitive adhesive of the present invention, the same material as the first pressure-sensitive adhesive layer can be used as appropriate, and the liquid crystal cell or the like can be adhered to the polymer film layer. A material with excellent properties is selected. In particular, it is preferable to contain a silane coupling agent in order to improve adhesion to glass, heat resistance and moisture resistance.

  As the silane coupling agent, those conventionally known can be used without particular limitation. For example, epoxy such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Group-containing silane coupling agent, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyl Amino group-containing silane coupling agents such as amines, (meth) acryl group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane Insiane Such as preparative group-containing silane coupling agent.

  The silane coupling agent is blended in an amount of 0.01 to 1 part by weight, preferably 0.02 to 0.6 part by weight, based on 100 parts by weight of the solid content of the (meth) acrylic polymer. When the blending amount is increased, the adhesive strength to the liquid crystal cell may be increased and the removability may be decreased. On the other hand, when the content is too small, the durability may be decreased.

  In addition, the pressure-sensitive adhesive layer used in the present invention (hereinafter referred to as including both the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer) is more heat-resistant by appropriately crosslinking a (meth) acrylic polymer. It will be excellent in nature. As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, and the like are used. Among these, an isocyanate compound and an epoxy compound are particularly preferably used mainly from the viewpoint of obtaining an appropriate cohesive force. These compounds may be used alone or in combination of two or more.

  Examples of the isocyanate compound include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate and xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene Diisocyanate trimer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), isocyanurate of hexamethylene diisocyanate Body (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and isocyanate adducts and the like. These compounds may be used alone or in combination of two or more.

  Examples of the epoxy compound include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Company) and 1,3-bis (N, N-diglycidyl). Aminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Company, Inc.). These compounds may be used alone or in combination of two or more.

  Examples of the melamine resin include hexamethylol melamine. Examples of the aziridine derivative include a commercially available product name HDU (manufactured by Mutual Pharmaceutical Company), a product name TAZM (manufactured by Mutual Pharmaceutical Company), and a product name TAZO (manufactured by Mutual Pharmaceutical Company). These compounds may be used alone or in combination of two or more.

  Examples of the metal chelate compound include aluminum, iron, tin, titanium, and nickel as metal components, and acetylene, methyl acetoacetate, and ethyl lactate as chelate components. These compounds may be used alone or in combination of two or more.

  The content of the crosslinking agent used in the present invention is preferably 0.01 to 5 parts by weight, and 0.02 to 2 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer. It is more preferable. When the content is less than 0.01 parts by weight, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the pressure-sensitive adhesive layer becomes small, and sufficient heat resistance may not be obtained, and the adhesive residue There is a tendency to cause. On the other hand, when the content exceeds 5 parts by weight, the cohesive force of the polymer is large, the fluidity is lowered, and the wettability to the adherend becomes insufficient, and occurs between the optical member and the pressure-sensitive adhesive composition layer. There is a tendency to cause dandruff. These crosslinking agents may be used alone or in combination of two or more.

  In the present invention, a polyfunctional monomer having two or more radiation-reactive unsaturated bonds can be added as a crosslinking agent. In such a case, the pressure-sensitive adhesive is crosslinked by irradiating with radiation or the like. As a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule, for example, it can be crosslinked (cured) by irradiation with radiation such as vinyl group, acryloyl group, methacryloyl group and vinylbenzyl group. Examples thereof include polyfunctional monomers having two or more radiation reactivity of one kind or two or more kinds. As the polyfunctional monomer, generally, those having 10 or less radiation-reactive unsaturated bonds are preferably used. These compounds may be used alone or in combination of two or more.

  Specific examples of the polyfunctional monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6 hexane. Examples thereof include diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, N, N′-methylenebisacrylamide and the like.

  The amount of the polyfunctional monomer used is appropriately selected depending on the intended use depending on the balance with the (meth) acrylic polymer to be crosslinked. In general, in order to obtain sufficient heat resistance by the cohesive force of the acrylic pressure-sensitive adhesive, it is preferably blended in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Moreover, it is more preferable to mix | blend at 10 weight part or less with respect to 100 weight part of (meth) acrylic-type polymers from the point of a softness | flexibility and adhesiveness.

  Examples of the radiation include ultraviolet rays, laser rays, α rays, β rays, γ rays, X rays, electron rays, and the like, and ultraviolet rays are preferably used from the viewpoints of controllability, good handleability, and cost. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated using an appropriate light source such as a high-pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. In addition, when using an ultraviolet-ray as a radiation, a photoinitiator is added to an acrylic adhesive.

  The photopolymerization initiator may be any substance that generates radicals by irradiating ultraviolet rays having an appropriate wavelength that can trigger the polymerization reaction according to the type of the radiation-reactive component.

  As radical photopolymerization initiators, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, benzyldimethyl ketal, trichloro Acetophenones such as acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4′-isopropyl-2-methylpropiophenone, etc. Propiophenones, benzophenone, methylbenzophenone, p-chlorobenzophenone, benzophenones such as p-dimethylaminobenzophenone, 2-chlorothioxanthone, 2-ethylthio Thioxanthones such as xanthone and 2-isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)- Examples include acylphosphine oxides such as (ethoxy) -phenylphosphine oxide, benzyl, dibenzosuberone, α-acyloxime ester, and the like. These compounds may be used alone or in combination of two or more.

  In addition, a photoinitiator having a high hydrogen abstraction ability such as 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer is used without using a polyfunctional monomer. Photo-crosslinking can also be performed by adding about 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer.

  Furthermore, without adding a photoinitiator or a polyfunctional monomer, a crosslinking method by irradiation with an active energy ray such as an electron beam or γ ray (usually about 0.5 to 10 Mrad), a peroxide is added. A cross-linking method by generating radicals by heat treatment can also be used.

  In the present invention, the gel fraction of the pressure-sensitive adhesive layer after the crosslinking treatment is preferably 40 to 90%, and more preferably 45 to 85%. In the case of emulsion polymerization or the like, the gel fraction can be appropriately adjusted in the post-polymerization stage, and there is a case where the crosslinking treatment may not be performed.

  Furthermore, the pressure-sensitive adhesive layer used in the present invention may contain other known additives, such as powders such as colorants and pigments, antistatic agents, surfactants, plasticizers, and adhesive properties. Additives, low molecular weight polymers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, UV absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles It can be added as appropriate depending on the application in which the shape, foil or the like is used.

  The pressure-sensitive adhesive layer of the present invention is generally crosslinked after the application of the pressure-sensitive adhesive raw material liquid, but the pressure-sensitive adhesive layer comprising the crosslinked pressure-sensitive adhesive is transferred to an adherend such as an optical member. It is also possible.

  Examples of the solvent used in the raw material solution for the pressure-sensitive adhesive in the present invention include, for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, and isopropanol. And water. These solvents may be used alone or in combination of two or more, but it is preferable to use water.

When the photopolymerization initiator as an optional component is added as described above, the adhesive raw material liquid is applied directly on the object to be protected, or applied to one or both sides of the support substrate The pressure-sensitive adhesive layer can be obtained by light irradiation. Usually, the pressure-sensitive adhesive layer is obtained by irradiating ultraviolet rays having an illuminance of 1 to 200 mW / cm ² at a wavelength of 300 to 400 nm and photopolymerizing them with a light amount of about 400 to 4000 mJ / cm ² .

  On the other hand, the polymer film forming the intermediate layer of the present invention can be appropriately used without particular limitation as long as it has the above-mentioned predetermined characteristics.

  Examples thereof include films having a base polymer of synthetic rubber such as polystyrene-polybutadiene polymer and polyacrylonitrile-polybutadiene polymer, polyurethane resin, polyepoxy resin, polyester resin, polyacrylic resin, polyolefin resin, and cellulose polymer.

  Also, by using these polymers dissolved in a solvent or using an aqueous dispersion of the polymer, the polymer film can be easily dried to form a uniform film. There is also no risk of occurrence.

  The polymerization method of the polymer for forming the polymer film used in the present invention is not particularly limited, and the polymerization can be performed by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization. In addition, the obtained copolymer may be any of a random copolymer, a block copolymer, and the like.

  Further, as in the case of the pressure-sensitive adhesive layer, an aqueous dispersion is preferably used from the viewpoint of the environment and processing steps, and in particular, an emulsion polymerization and a urethane-acrylic hybrid aqueous dispersion not using an emulsifier are preferably used.

  Regarding emulsion polymerization, the same polymerization method as that for the pressure-sensitive adhesive layer is appropriately used.

  Urethane-acrylic hybrid water dispersion is a (meth) acrylic resin that uses a urethane dispersion in which a urethane resin is dispersed as a seed without introducing an emulsifier in water by introducing an acidic group into the urethane skeleton. It can be obtained by seed polymerization of monomers. Such a urethane-acrylic hybrid aqueous dispersion does not require the use of an emulsifier, and therefore has good adhesiveness with the pressure-sensitive adhesive layer and is preferably used.

  Examples of the solvent used in the polymer film raw material liquid in the present invention include, for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, Examples include isopropanol and water. These solvents may be used alone or in combination of two or more, but it is preferable to use water.

  Furthermore, the intermediate layer used in the present invention may contain other known additives, such as powders such as colorants and pigments, antistatic agents, surfactants, plasticizers, and tackifiers. Agent, low molecular weight polymer, surface lubricant, leveling agent, antioxidant, corrosion inhibitor, light stabilizer, UV absorber, polymerization inhibitor, silane coupling agent, inorganic or organic filler, metal powder, particulate It can be added as appropriate depending on the use of the foil.

  The method for forming the pressure-sensitive adhesive layer (and the intermediate layer) on the optical member or the like is not particularly limited. For example, the raw material liquid of the pressure-sensitive adhesive (and the intermediate layer) is used as the optical member (or polymer coating layer or the like). It is produced by applying the coating material to the optical member (or the dried polymer coating layer, etc.) by drying and removing the polymerization solvent and the like. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction. When the pressure-sensitive adhesive (and the intermediate layer) is applied onto the optical member (or polymer coating layer) to produce the pressure-sensitive adhesive layer (and the intermediate layer), the optical member (or One or more solvents other than the polymerization solvent may be newly added to the composition so that it can be uniformly coated on a polymer coating layer or the like.

  Moreover, as a formation method of the adhesive layer of this invention, the well-known method used for manufacture of adhesive tapes etc. is used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.

  In the optical member with pressure-sensitive adhesive of the present invention, the thickness of each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is usually 5 to 50 μm, preferably about 10 to 40 μm. The thickness is adjusted as appropriate in consideration of the desired adhesive properties.

  Moreover, in the optical member with the pressure-sensitive adhesive of the present invention, the intermediate layer is usually prepared so that the thickness of the intermediate layer is usually about 5 to 15 μm, preferably about 7 to 12 μm. The thickness is adjusted appropriately.

  Furthermore, cushioning properties can be imparted to the intermediate layer by adding a foaming agent and foaming the intermediate layer within a range that does not adversely affect the optical properties. In such a case, the thickness of the intermediate layer is about 10 to 200 μm.

  Moreover, in order to improve the adhesiveness between each adhesive layer and an intermediate | middle layer or an optical member, you may perform easy attachment processes, such as a corona treatment, on the surface of each adhesive layer and an intermediate | middle layer.

  The present invention has the above-described configuration, and by appropriately adjusting the physical properties and thickness of each pressure-sensitive adhesive layer and intermediate layer, the range of property changes of the entire pressure-sensitive adhesive layer including the intermediate layer is widened, and can be used for various applications. And the optical member with an adhesive which has various thickness and a characteristic can be obtained easily.

  Further, the composition and physical properties of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are changed (for example, the elastic modulus of the second pressure-sensitive adhesive layer is made larger than the elastic modulus of the first pressure-sensitive adhesive layer). Then, the expansion and contraction of the optical member is absorbed by the first pressure-sensitive adhesive layer, and the influence of the stress is completely cut off by the intermediate layer, and the second pressure-sensitive adhesive layer has sufficient adhesion to the liquid crystal cell. It is also possible to demonstrate the durability exhibited.

  The optical member with pressure-sensitive adhesive of the present invention has the structure of the first pressure-sensitive adhesive layer, the intermediate layer, and the second pressure-sensitive adhesive layer as described above, and the specific production method thereof is as follows. An example is the technique.

  For example, (a) a film (sheet or belt) that has been subjected to a release treatment is formed by applying and drying the second pressure-sensitive adhesive raw material liquid to form a second pressure-sensitive adhesive layer; The raw material of the first pressure-sensitive adhesive is applied to the release-treated surface of the film (sheet or belt) formed by applying and drying the polymer film raw material liquid on the release-treated surface of the belt) and the peel-treated film (sheet or belt). It can be obtained by applying each of the liquids to form a first pressure-sensitive adhesive layer and laminating each of these layers on the optical member.

  In addition, (b) a second pressure-sensitive adhesive raw material liquid is applied to the release-treated surface of the peel-treated film (sheet or belt) to form a second pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer A polymer film raw material liquid is applied and dried to form an intermediate layer made of a polymer film, and then a first pressure sensitive adhesive raw material liquid is applied and dried on the intermediate layer made of the polymer film. It can be obtained by forming a pressure-sensitive adhesive layer and further bonding it to an optical member.

  Furthermore, (c) the second adhesive material solution is applied to the release-treated surface of the peeled film (sheet or belt), and the polymer film material solution is applied onto the second adhesive application layer. Then, the first adhesive material liquid is applied onto the polymer (intermediate) application layer obtained by applying the polymer film raw material liquid, and then the second adhesive application layer, the polymer ( The intermediate) coating layer and the first pressure-sensitive adhesive coating layer can be obtained by drying at the same time so that the layers do not cross each other and further bonding them to the optical member.

  Further, (d) the second adhesive material liquid, the polymer film raw material liquid, and the first adhesive raw material liquid are each applied to the release-treated surface of the release-treated film (sheet or belt). It can be obtained by applying simultaneously so that the layers do not cross each other, drying simultaneously so that each coating layer does not cross each other, and further adhering to the optical member.

  Further, (e) the second pressure sensitive adhesive raw material liquid and the polymer film raw material liquid are simultaneously applied to the peeled surface of the peeled film (sheet or belt) so that the two coating layers do not cross each other. The first pressure-sensitive adhesive is obtained by applying and drying the first pressure-sensitive adhesive raw material liquid on the peel-treated surface of the film (sheet or belt) that has been dried at the same time so that the two coating layers do not cross each other. Each of the layers can be prepared and the respective layers can be sequentially laminated on the optical member.

  In addition, (f) a film (sheet or belt) subjected to a release treatment, a second pressure-sensitive adhesive raw material liquid is applied and dried to form a second pressure-sensitive adhesive layer, and a release-treated film ( The raw material liquid of the first pressure-sensitive adhesive and the raw material liquid of the polymer film are simultaneously applied to the release treatment surface of the sheet or belt so that the coating layers do not cross each other, and the coating layers do not cross each other. Thus, it can obtain by drying each simultaneously, and laminating | stacking each of these each layer on an optical member sequentially.

  In addition, since the manufacturing method of (c)-(f) also includes the process of laminating each layer in a liquid state, it is necessary to appropriately devise and adjust the coating method so that each layer flows in a laminar flow state. A die coater having a plurality of manifolds that can be applied in a state or a die coater that can apply a certain amount such as to be placed on an applied lower layer (such as an application layer) is used. Further, at the time of drying, a method of heating from the inside such as heating from the peeled film side is used so that the surface is not dried first and becomes a skin burr state.

  In the above production method, the release-treated film (sheet or belt) can be used as it is as a release liner (release sheet, separator) of the optical member with an adhesive, and the process can be simplified. In particular, when an aqueous dispersion of polymer is used, since no organic solvent is used, the second pressure-sensitive adhesive coating layer and polymer (intermediate) coating layer previously applied and dried do not swell or dissolve. There is no restriction on the process, and an optical member with an adhesive can be easily obtained.

  As a constituent material of the release liner (release sheet, separator), for example, a plastic film such as polyethylene, polypropylene, polyethylene terephthalate, and a polyester film, a porous material such as paper, cloth, and nonwoven fabric, a net, a foam sheet, a metal foil, In addition, suitable thin leaf bodies such as these laminates can be mentioned, and a plastic film is preferably used from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer. Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

  The thickness of the release liner (release sheet, separator) is usually about 5 to 200 μm, preferably about 5 to 100 μm. For the release liner (release sheet, separator), if necessary, release agent and antifouling treatment with silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, etc., coating type Further, antistatic treatment such as kneading type and vapor deposition type can also be performed. In particular, it is possible to further improve the releasability from the pressure-sensitive adhesive layer by appropriately subjecting the surface of the release liner (release sheet, separator) to a release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment.

  The optical member with pressure-sensitive adhesive obtained by such a production method has no peeling between the layers in the pressure-sensitive adhesive layer, can exhibit the function of each pressure-sensitive adhesive layer, and has excellent removability, durability, and stress relaxation properties Are aligned in a balanced manner.

  The optical member with pressure-sensitive adhesive obtained by such a production method has no peeling between each pressure-sensitive adhesive layer and the polymer film (intermediate) layer, can exhibit the function of each pressure-sensitive adhesive layer, and has excellent removability. Durability and stress relaxation properties are aligned in a balanced manner.

  Moreover, the optical member with an adhesive of this invention forms the adhesive layer which has said structure on the single side | surface or both surfaces of an optical member.

  As the optical member, those used for forming an image display device such as a liquid crystal display device are used, and the type thereof is not particularly limited. For example, examples of the optical member include a polarizing plate. As the polarizing plate, 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. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. Examples thereof include polyene-based oriented films such as those obtained by adsorbing volatile 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 produced, for example, by dyeing 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 and 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, or may be performed while dyeing, or may be performed with dyeing after iodine. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

  As a material for forming the transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) -Based polymer, polycarbonate-based polymer and the like. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Polymer blends and the like are also examples of polymers that form the transparent protective film. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

  Moreover, the polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, and (B) a substitution in the side chain And / or a resin composition containing an unsubstituted phenyl and a thermoplastic resin having a nitrile group. 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.

  Although the thickness of a 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.

  Moreover, it is preferable that a protective film has as little color as possible. Therefore, Rth = [(nx + ny) / 2−nz] · d (where nx and ny are the main refractive index in the plane of the film, nz is the refractive index in the film thickness direction, and d is the film thickness). A protective film having a retardation value in the film thickness direction 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 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.

  As the protective film, a cellulose polymer such as triacetyl cellulose is preferable from the viewpoints of polarization characteristics and durability. A triacetyl cellulose film is particularly preferable. In addition, when providing a protective film in the 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. The polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.

  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.

  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 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. Further, the anti-sticking treatment is performed for the purpose of preventing adhesion with an adjacent layer.

  Anti-glare treatment is applied for the purpose of preventing external light from being reflected on the surface of the polarizing plate and obstructing the visibility of light transmitted through the polarizing plate. For example, a roughening method using 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 a conductive material made of silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide or the like having an average particle diameter of 0.5 to 50 μm. Transparent fine particles such as inorganic fine particles, organic fine particles composed of a crosslinked or uncrosslinked polymer, etc. may be used. When forming a surface fine uneven structure, the amount of fine particles used is generally about 2 to 50 parts by weight, preferably 5 to 25 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.

  The optical member of the present invention includes, for example, a liquid crystal display device such as a reflecting plate, a semi-transmissive plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a viewing angle compensation film, and a brightness enhancement film. What becomes an optical layer which may be used for formation of this is mention | raise | lifted. These can be used alone as the optical member of the present invention, and can be laminated on the polarizing plate for practical use and used in one 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 viewing angle compensation film is further laminated on a plate, or a polarizing plate in which a brightness 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. Moreover, the transparent protective film contains fine particles so as to have 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. The transparent 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 having a fine concavo-convex structure reflecting the surface fine concavo-convex structure of the transparent protective film can be formed by, for example, depositing a metal 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 directly attaching to the surface of the transparent protective layer.

  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 or the like that displays an image using a built-in light 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 is useful for forming a liquid crystal display device of a type that can save energy of using a light source such as a backlight in a bright atmosphere and can be used with a built-in light source 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 the image is displayed in color, and also has an antireflection function.

  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, polyvinyl alcohol, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulose polymer, norbornene resin, or binary, ternary various copolymers, graft copolymers Examples thereof include polymers and blends. These polymer materials become oriented products (stretched films) by stretching or the like.

  Examples of the liquid crystalline 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. It is done. Specific examples of main-chain liquid crystalline polymers include nematic-oriented polyester-based liquid crystalline polymers, discotic polymers, and cholesteric polymers that have a structure in which a mesogenic group is bonded to a spacer portion that imparts flexibility. It is done. Specific examples of the side chain type liquid crystalline polymer include polysiloxane, polyacrylate, polymethacrylate, or polymalonate as a main chain skeleton, and a nematic alignment imparting paraffin through a spacer portion composed of a conjugated atomic group as a side chain. Examples thereof include those having a mesogen moiety composed of a substituted cyclic compound unit. These liquid crystalline polymers are prepared by, for example, applying a solution of a liquid crystalline polymer on an alignment surface such as those obtained by rubbing the surface of a thin film such as polyimide or polyvinyl alcohol formed on a glass plate, or by obliquely depositing 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 for the purpose of compensating for coloring or viewing angle due to birefringence of various wavelength plates and liquid crystal layers, for example. In this case, the retardation plate may be laminated to control optical characteristics such as retardation.

  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 member 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 viewing angle compensation film is a film for widening the viewing angle so that an 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. As such a viewing angle compensation phase difference plate, for example, a phase difference plate, an alignment film such as a liquid crystal polymer, or an alignment layer such as a liquid crystal polymer supported on a transparent substrate is used. A normal retardation plate uses a birefringent polymer film uniaxially stretched in the plane direction, whereas a retardation plate used as a viewing angle compensation film stretches biaxially 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 tilted 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, or a film obtained by obliquely aligning a liquid crystal polymer. Is mentioned. 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.

  Also, from the viewpoint of achieving a wide viewing angle with good visibility, an optically compensated phase difference in which a liquid crystal polymer alignment layer, in particular an optically anisotropic layer composed of a discotic liquid crystal polymer gradient alignment layer, is supported by a triacetylcellulose film. A 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 on the rear side thereof and re-incident on the brightness enhancement film, and a 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 the amount of light that can be used for liquid crystal image display or the like is reduced accordingly, resulting in a dark image. The brightness enhancement film allows light having a polarization direction that is absorbed by the polarizer to be reflected once by the brightness enhancement film without being incident on the polarizer, and further inverted through a reflective layer provided on the rear side thereof. Repeatedly re-enter the brightness enhancement film, and the brightness enhancement film transmits only polarized light whose polarization direction is such that the polarization direction of light reflected and inverted between the two can pass through the polarizer. Therefore, 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 diffuser plate returns the polarized light to the original natural light state. The light in the non-polarized state, that is, the natural light state is directed toward the reflection layer and the like, reflected through the reflection layer and the like, and again passes through the diffusion plate and reenters the brightness enhancement film. Thus, while maintaining the brightness of the display screen by providing a diffuser plate that returns polarized light to the original natural light state between the brightness enhancement film and the reflective layer, etc., the brightness unevenness of the display screen is reduced at the same time, A uniform and bright screen can be provided. 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.

  As the brightness enhancement film, for example, a dielectric multilayer thin film or a multilayer laminate of thin film films having different refractive index anisotropy, such as a characteristic that transmits linearly polarized light having a predetermined polarization axis and reflects other light. Such as a cholesteric liquid crystal polymer alignment film or a film substrate whose alignment liquid crystal layer is supported on a film substrate, which reflects either left-handed or right-handed circularly polarized light and transmits other light. Appropriate things such as those shown 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 incident on the polarizing plate with the polarization axis aligned as it is, 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 emits circularly polarized light such as a cholesteric liquid crystal layer, it can be directly incident on a polarizer, 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 in a wide wavelength range such as a visible light region has, for example, a retardation layer that functions as a quarter-wave plate for light-color light having a wavelength of 550 nm and other retardation characteristics. The phase difference layer shown, for example, the phase difference layer which functions as a half-wave plate, etc. can be obtained by the method of superimposing. 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, the cholesteric liquid crystal layer can also be obtained by reflecting circularly polarized light in a wide wavelength range such as the visible light region by combining two or more layers with different reflection wavelengths and having 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 three or more optical layers like 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-mentioned reflective polarizing plate or transflective polarizing plate and a retardation plate are combined may be used.

  The optical member in which the optical layer is laminated on the 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 a pressure-sensitive 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 the target phase difference characteristic.

  In addition, in each layer such as an optical member and an adhesive layer of the adhesive optical member of the present invention, for example, a salicylic acid ester compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex compound, etc. What gave the ultraviolet absorptivity by systems, such as a system processed with a ultraviolet absorber, etc. may be used.

  The pressure-sensitive adhesive optical member of the present invention can be preferably used for forming various image display devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, an adhesive optical member, and an illumination system as required, and incorporating a drive circuit. There is no limitation in particular except the point which uses the optical member by invention, It can apply to the former. As the liquid crystal cell, for example, an arbitrary type such as a TN type, an STN type, or a π type can be used.

  An appropriate liquid crystal display device such as a liquid crystal display device in which an adhesive optical member is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the optical member by this invention can be installed in the one side or both sides of a liquid crystal cell. When optical members are provided on both sides, they may be the same or different. Further, when forming a liquid crystal display device, for example, a single layer of appropriate parts such as a diffuser plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffuser plate, and a backlight at an appropriate position. Alternatively, two or more layers can be arranged.

  Next, an organic electroluminescence device (organic EL display device) will be described. Generally, in an organic EL display device, a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitter (organic electroluminescent light emitter). Here, the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Or a structure having various combinations such as a laminate of such a light-emitting layer and an electron injection layer made of a perylene derivative, or a stack of these hole injection layer, light-emitting layer, and electron injection layer. Are known.

  In organic EL display devices, holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the phosphor material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state. The mechanism of the recombination in the middle is the same as that of a general diode, and as can be expected from this, the current and the emission intensity show a strong non-linearity with rectification with respect to the applied voltage.

  In an organic EL display device, in order to extract light emitted from the organic light emitting layer, at least one of the electrodes must be transparent, and a transparent electrode usually formed of a transparent conductor such as indium tin oxide (ITO) is used as an anode. It is used as. On the other hand, in order to facilitate electron injection and increase luminous efficiency, it is important to use a material having a small work function for the cathode, and usually metal electrodes such as Mg—Ag and Al—Li are used.

  In the organic EL display device having such a configuration, the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate. The display surface of the organic EL display device looks like a mirror surface.

  In an organic EL display device comprising an organic electroluminescent light emitting device comprising a transparent electrode on the surface side of an organic light emitting layer that emits light upon application of a voltage and a metal electrode on the back side of the organic light emitting layer, the surface of the transparent electrode While providing a polarizing plate on the side, a retardation plate can be provided between the transparent electrode and the polarizing plate.

  Since the retardation plate and the polarizing plate have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action. In particular, the mirror surface of the metal electrode can be completely shielded by configuring the retardation plate with a quarter-wave plate and adjusting the angle formed by the polarization direction of the polarizing plate and the retardation plate to π / 4. .

  That is, only the linearly polarized light component of the external light incident on the organic EL display device is transmitted by the polarizing plate. This linearly polarized light becomes generally elliptically polarized light by the phase difference plate, but becomes circularly polarized light particularly when the phase difference plate is a quarter wavelength plate and the angle formed by the polarization direction of the polarizing plate and the phase difference plate is π / 4. .

  This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, is reflected by the metal electrode, is again transmitted through the organic thin film, the transparent electrode, and the transparent substrate, and becomes linearly polarized light again on the retardation plate. And since this linearly polarized light is orthogonal to the polarization direction of a polarizing plate, it cannot permeate | transmit a polarizing plate. As a result, the mirror surface of the metal electrode can be completely shielded.

  Hereinafter, examples and the like specifically showing the configuration and effects of the present invention will be described, but the present invention is not limited to these. In addition, the evaluation item in an Example etc. measured as follows.

<Tensile test: Measurement of tensile modulus, breaking strength, breaking elongation>
The raw material liquid for the polymer film was uniformly applied on the release liner, and after drying, the polymer film was sampled to have a cross-sectional area of about 2 mm ² to obtain a test sample.

This test sample was subjected to a tensile test using a tensile tester (manufactured by Shimadzu Corp., Autograph AGS-50D type) with a test sample length of 10 mm and a tensile speed of 300 mm / min, and a stress-strain curve at that time was obtained. Obtained. The tensile modulus (N / mm ² ) was calculated from the linear portion at the beginning of the stress-strain curve according to the following formula. Moreover, the strength at break and elongation at break were calculated.

Tensile modulus (N / mm ² ) = (F / A) / (ΔL / L0)
F: Tensile stress (N)
A: Cross-sectional area (1 / mm ² )
ΔL: Strain (elongation) change (mm)
L0: Initial length of sample (mm)

<Measurement of gel fraction>
An adhesive raw material solution is applied onto a polyethylene terephthalate (PET) film (thickness 38 μm) surface-treated with a release agent, and dried at 130 ° C. for 1 minute to remove the solvent and remove the adhesive layer (thickness 25 μm). ) Was formed. Thereafter, the pressure-sensitive adhesive layer was covered with a release film surface-treated with a release agent, and cured at room temperature (about 25 ° C.) for 3 days to obtain a sample for measuring gel fraction.

W ₁ g (about 0.1 g) of the prepared pressure-sensitive adhesive layer of the gel fraction measurement sample was taken out and immersed in ethyl acetate at room temperature (about 25 ° C.) for 1 week. Thereafter, the pressure-sensitive adhesive layer that has been soaked is taken out of the ethyl acetate, and the weight W ₂ g after drying at 130 ° C. for 2 hours is measured, and the value calculated as (W ₂ / W ₁ ) × 100 (% by weight) is obtained. The gel fraction (% by weight) was used.

<Measurement of molecular weight>
The molecular weight (number average molecular weight and weight part average molecular weight) was measured by GPC (gel permeation chromatography).

Device: HLC-8120GPC, manufactured by Tosoh Corporation
column:
When Mw is 500,000 or more;
G7000H _XL + GMH _XL + GMH _XL (3 stranded)
When Mw is less than 500,000;
GMH _HR -H + GMH _HR -H + G2000H _HR (3 linked)
Flow rate: 0.8ml / min
Injection volume: 100 μl
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: about 0.1% by weight
Detector: Refractive index (RI) meter The molecular weight was calculated in terms of polystyrene.

<Measurement of adhesive strength>
The produced optical member (width: 25 mm) was attached to a non-alkali glass plate (Corning Corp., 1737, size: 50 × 200 mm, thickness: 1.0 mm) (2 kg roll, one reciprocation), 50 ° C., 0 The autoclave treatment was performed at a pressure of 5 MPa for 30 minutes. Then, it preserve | saved for 3 hours at 23 degreeC x 60% RH, and obtained the sample (a) for evaluation.

  The adhesive strength when the sample for evaluation (a) was peeled off at a peeling speed of 300 mm / minute peeling angle of 90 ° was measured with a universal tensile tester. The measurement was performed in an environment of 23 ° C. × 50% RH.

  Further, after the autoclave treatment, the sample was continuously stored at 70 ° C. for 6 hours, and then stored at 23 ° C. × 60% RH for 3 hours to obtain an evaluation sample (b).

  The adhesive force after the heat treatment when the sample for evaluation (b) was peeled off at a peeling speed of 300 mm / minute peeling angle of 90 ° was measured with a universal tensile tester. The measurement was performed in an environment of 23 ° C. × 50% RH.

<Durability evaluation>
The produced optical member (12-inch size) was attached to a non-alkali glass plate (Corning Corporation, 1737, size: 210 × 300 mm, thickness: 0.5 mm), and 30 minutes at 50 ° C. and a pressure of 0.5 MPa. Autoclaving was performed. Thereafter, the sample was stored at 60 ° C. × 90% RH for 500 hours and then returned to room temperature (about 25 ° C.) to obtain a sample for evaluation.

  The adhesion state of the evaluation sample to the glass plate was observed and evaluated. The evaluation criteria are as follows.

The optical member did not float or peel off: ○
The optical member was lifted or peeled off: ×

<Evaluation of uneven color>
The prepared optical member (12-inch size) is pasted so that the absorption axis of the polarizing plate is perpendicular to both surfaces of an alkali-free glass plate (Corning Corp., 1737, size: 210 × 300 mm, thickness: 0.5 mm). The autoclave treatment was performed at 50 ° C. and a pressure of 0.5 MPa for 30 minutes. Then, after storing at 90 ° C. for 500 hours, the sample was returned to room temperature (about 25 ° C.) to obtain an evaluation sample.

  The state of color unevenness of the evaluation sample was visually observed and evaluated. The evaluation criteria are as follows.

If no color unevenness is found: ○
When color unevenness is observed: ×

<Evaluation of contamination>
On the non-alkali glass plate after measuring the adhesive strength of the evaluation sample (b) after being stored at 70 ° C. for 6 hours, the presence or absence of contamination due to the pressure-sensitive adhesive was visually observed and evaluated. The evaluation criteria are as follows.

If no contamination was observed: ○
If contamination is observed: ×

<Preparation of (meth) acrylic polymer>
[Acrylic polymer (A)]
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, isononyl acrylate 70 parts by weight, butyl acrylate 27 parts by weight, acrylic acid 3 parts by weight, 2-hydroxyethyl acrylate 0.1 parts by weight 1,2 parts of 2,2′-azobisisobutyronitrile and 200 parts by weight of ethyl acetate as a polymerization initiator were charged, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was adjusted to 55 ° C. The polymerization reaction was carried out for about 20 hours while maintaining the vicinity to prepare an acrylic polymer (A) solution. The acrylic polymer (A) had a weight average molecular weight of 1,370,000.

[Acrylic polymer (B)]
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser, 75 parts by weight of butyl acrylate, 20 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, 0.1 part by weight of 2-hydroxyethyl acrylate Then, 0.05 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of ethyl acetate were added as polymerization initiators, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was around 55 ° C. The polymerization reaction was carried out for about 20 hours to prepare an acrylic polymer (B) solution. The acrylic polymer (B) had a weight average molecular weight of 1,450,000.

[Acrylic polymer (C)]
A monomer mixture consisting of 97 parts by weight of butyl acrylate, 2 parts by weight of acrylic acid, and 1 part by weight of 6-hydroxyhexyl acrylate in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, and Charge 3 parts by weight of polyoxyethylene distyrenated phenyl ether ammonium sulfate as an emulsifier, emulsify in 122 parts by weight of water, and then add 0.05 part by weight of 2,2′-azobis (amidinopropane) dihydrochloride as a polymerization initiator. Then, nitrogen gas was introduced while gently stirring, the polymerization temperature was kept at around 50 ° C. for about 3 hours, then kept at around 65 ° C. for about 2 hours, and then ammonia water was added. Viscosity was adjusted using (concentration: 1.8%) to prepare an aqueous dispersion of acrylic polymer (C). When the acrylic polymer (C) aqueous dispersion was formed into a film, the gel fraction was 71%.

[Acrylic polymer (D)]
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 70 parts by weight of 2-ethylhexyl acrylate, 28 parts by weight of butyl acrylate, 1 part by weight of methacrylic acid, 6-hydroxyhexyl acrylate 1 1 part by weight and a monomer mixture comprising 0.05 part by weight of lauryl mercaptan, and 3 parts by weight of polyoxyethylene distyrenated phenyl ether ammonium sulfate as an emulsifier are added, emulsified in 122 parts by weight of water, and then 2,2 as a polymerization initiator '-Azobis (amidinopropane) dihydrochloride (0.05 parts by weight) was charged, nitrogen gas was introduced with gentle stirring, and the polymerization temperature was kept at around 50 ° C for about 3 hours. The polymerization reaction is carried out for about 2 hours while maintaining around 65 ° C., and then using aqueous ammonia (concentration: 1.8%) The viscosity was adjusted to prepare an aqueous dispersion of the acrylic polymer (D). The gel fraction when the aqueous dispersion of the acrylic polymer (D) was formed into a film was 53%.

[Acrylic polymer (E)]
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, diethylene glycol adipic acid ester 100 parts by weight (number average molecular weight 2500, hydroxyl value 41), N-methylpyrrolidone 31.0 parts by weight 12.4 parts by weight of dissolved dimethylol fupropionic acid was charged and heated to 80 ° C. to remove moisture. Next, 48.3 parts by weight of 4,4-dicyclohexylmethane diisocyanate was added, then 0.0298 parts by weight of dibutyltin dilaurate was added, and the temperature of the liquid in the flask was kept at about 60 ° C. for about 2 hours to carry out the isocyanate conversion. A prepolymer solution was obtained.

  To this urethane prepolymer solution, 9.3 parts by weight of triethylamine was added and stirred, and 224 parts by weight of distilled water (replaced with nitrogen for 1.5 hours) was added dropwise thereto. Next, after completion of the dropwise addition of the entire amount of distilled water, a mixed solution consisting of 4.0 parts by weight of ethylene diamine and 8.0 parts by weight of distilled water was added. Thereafter, the reaction was carried out for about 2 hours while maintaining the liquid temperature in the flask at around 60 ° C. to obtain an aqueous dispersion of urethane polymer (solid content: 39.5%).

  Distilled water (506 parts by weight) was added to 126.6 parts by weight of this urethane polymer aqueous dispersion, and a monomer mixture consisting of 60 parts by weight of butyl acrylate and 140 parts by weight of methyl methacrylate was added with stirring. After being absorbed in the aqueous dispersion, 0.5 part by weight of 2,2-azobis [2- (2-imidazolin-2-yl)] propane was used for polymerization reaction at 60 ° C. for 3 hours under a nitrogen stream. A urethane-acrylic aqueous dispersion without using an emulsifier was obtained.

From this urethane-acrylic aqueous dispersion as a seed, from 130 parts by weight of water, 50 parts by weight of butyl acrete, and 50 parts by weight of methyl methacrylate so that the solid content of the urethane-acrylic aqueous dispersion is 100 parts by weight. Then, 0.1 part by weight of 2,2azobis [N- (2-carboxyethyl) -2-methyl-propionamidine] is added, and nitrogen gas is introduced while gently stirring, The polymerization temperature was maintained at around 55 ° C. for about 5 hours to prepare an aqueous dispersion of urethane-acrylic polymer (E) (solid content: 30.2%). The tensile modulus of the dry film obtained by filming the urethane-acrylic polymer (E) aqueous dispersion was 96.5 N / mm ² , the breaking strength was 19.8 N / mm ² , and the breaking elongation was 700%.

[Acrylic polymer (F)]
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 50 parts by weight of butyl acrylate, 50 parts by weight of methyl methacrylate, and 2,2′-azobisisobutyronitrile 0 as a polymerization initiator .2 parts by weight and 200 parts by weight of ethyl acetate were charged, nitrogen gas was introduced while gently stirring, and the polymerization temperature was kept at around 55 ° C. for about 48 hours to carry out an acrylic polymer (F) A solution was prepared. The acrylic polymer (F) had a weight average molecular weight of 220,000. The tensile modulus of the dry film obtained by film-forming the acrylic polymer (F) solution was 136 N / mm ² , breaking strength 18.6 N / mm ² , and breaking elongation 870%.

[Acrylic polymer (G)]
100 parts by weight of butyl acrylate was charged into a four-necked flask equipped with a stirrer, thermometer, nitrogen gas introduction tube, rubber septum, and cooling tube, and the inside of the system was purged with nitrogen. Next, while introducing nitrogen gas into the system while gently stirring, 0.6 part by weight of copper bromide was added, the inside of the flask was heated and kept at around 100 ° C., and 2-bromo-2- Charge 0.8 parts by weight of 2-hydroxyethyl methylpropionate, introduce nitrogen gas while gently stirring, perform the polymerization reaction for about 12 hours while maintaining the liquid temperature in the flask at around 100 ° C., and polymer (G A solution of ₁ ) was obtained.

The polymerization rate of the polymer (G ₁ ) (value defined by a value obtained by dividing the polymer weight obtained by heating and removing the volatile component by the polymer weight of the polymerization solution before removing the volatile component) is 80% or more. After confirming this, 100 parts by weight of methyl methacrylate was added from a rubber septum to the polymer (G ₁ ) solution using a syringe, and the liquid temperature in the flask was kept at around 100 ° C. for about 8 hours. the reaction was carried out to obtain a solution of the polymer (G _2).

After confirming that the polymerization rate of the polymer (G ₂ ) is 80% or more, 6-hydroxyhexyl acrylate (6-HHA) 1 is used by using a syringe from a rubber septum into the solution of the polymer (G ₂ ). 0.0 part by weight was further added, and the polymerization temperature was kept at about 100 ° C. for about 3 hours to conduct polymerization reaction for about 3 hours, and both terminal hydroxyl group-containing AB type butyl acrylate-methyl methacrylate diblock polymer (G ) A solution was obtained. The number average molecular weight of the butyl acrylate-methyl methacrylate diblock polymer (G) was 48,000.

In addition, the butyl acrylate-methyl methacrylate diblock polymer (G) was formed into a film (after removing copper bromide as a catalyst and bipyridine as a cocatalyst, and then cast into an ethyl acetate solution to form a film). the tensile modulus of the dried film obtained Te is 350 N / mm ^2, the breaking strength of 17.5N / mm ^2, was breaking elongation 90%.

[Example 1]
(Preparation of adhesive solution)
100 parts by weight of the solid content of the acrylic polymer (B) solution, 0.1 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 0.8 parts by weight of trimethylolpropane / tolylene diisocyanate trimer adduct as a crosslinking agent Part was added and mixed and stirred uniformly to prepare an acrylic pressure-sensitive adhesive solution (1).

  Further, 0.2 part by weight of trimethylolpropane / tolylene diisocyanate trimer adduct as a crosslinking agent was added to 100 parts by weight of the solid content of the acrylic polymer (A) solution, and the mixture was uniformly mixed and stirred. An agent solution (2) was prepared.

(Preparation of optical member with adhesive)
The acrylic pressure-sensitive adhesive solution (1) is applied to one side of a silicone-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and dried to a second thickness of 15 μm. An adhesive layer was formed.

  Next, the acrylic polymer (F) solution is applied to one side of a polyethylene-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and dried to a thickness of 10 μm. An intermediate layer consisting of

  The acrylic pressure-sensitive adhesive solution (2) is applied to one side of a silicone-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and dried to a thickness of 15 μm. 1 pressure-sensitive adhesive layer was formed.

  Next, on the surface of the polarizing film, the first pressure-sensitive adhesive layer, the intermediate layer composed of the polymer film, and the second pressure-sensitive adhesive layer were laminated in this order to produce an optical member with a pressure-sensitive adhesive.

[Example 2]
(Preparation of optical member with adhesive)
An optical member with a pressure-sensitive adhesive was produced in the same manner as in Example 1 except that the acrylic polymer (G) solution was used instead of the acrylic polymer (F) solution.

Example 3
(Preparation of adhesive solution)
To 100 parts by weight of the solid content of the aqueous dispersion of the acrylic polymer (C), 0.2 part by weight of 3-glycidoxypropyltriethoxysilane is added and mixed and stirred uniformly. (3) was prepared.

(Preparation of optical member with adhesive)
The acrylic adhesive aqueous dispersion (3) is applied to one side of a silicone-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and a second adhesive having a thickness of 15 μm. An agent layer was formed.

  Next, an aqueous dispersion of the urethane-acrylic polymer (E) is applied onto the second pressure-sensitive adhesive layer, heated at 110 ° C. for 5 minutes, and composed of a polymer film having a thickness of 10 μm after drying. An intermediate layer was formed.

  Furthermore, the first pressure-sensitive adhesive having a thickness of 15 μm after drying by applying the aqueous dispersion of the acrylic polymer (D) onto the intermediate layer made of the polymer film and heating at 110 ° C. for 5 minutes. A layer was formed.

  Subsequently, the said 1st adhesive layer was bonded together on the surface of the polarizing film, and the optical member with an adhesive was produced.

  In this way, even when the second pressure-sensitive adhesive layer, the intermediate layer made of a polymer film, and the first pressure-sensitive adhesive layer are sequentially applied onto the dried film layer, Since the polymer was an aqueous dispersion, the lower layer could be laminated without dissolving.

Example 4
(Preparation of optical member with adhesive)
Polyethylene terephthalate film subjected to silicone treatment using an aqueous dispersion of acrylic adhesive (3), an aqueous dispersion of urethane-acrylic polymer (E), and an aqueous dispersion of acrylic polymer (D). 3 layers (from the polyethylene terephthalate film side, the second pressure-sensitive adhesive layer, the intermediate layer made of polymer film, and the first pressure-sensitive adhesive layer are laminated in this order by a die coater having a three-layer manifold on one side (thickness 38 μm). The pressure-sensitive adhesive layer) was simultaneously applied and heated at 90 ° C. for 5 minutes and then at 120 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 15 μm.

  Subsequently, the said 1st adhesive layer was bonded together on the surface of the polarizing film, and the optical member with an adhesive was produced.

[Comparative Example 1]
(Preparation of adhesive solution)
100 parts by weight of the solid content of the acrylic polymer (B) solution, 0.1 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 0.8 parts by weight of trimethylolpropane / tolylene diisocyanate trimer adduct as a crosslinking agent Part was added and mixed and stirred uniformly to prepare an acrylic pressure-sensitive adhesive solution (4).

(Preparation of optical member with adhesive)
The acrylic pressure-sensitive adhesive solution (4) is applied to one side of a silicone-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and dried to a thickness of 40 μm. Formed.

  Subsequently, the said adhesive layer was bonded together on the surface of the polarizing film, and the optical member with an adhesive was produced. The pressure-sensitive adhesive layer had a gel fraction of 72%.

[Comparative Example 2]
(Preparation of adhesive solution)
To 100 parts by weight of the solid content of the acrylic polymer (A) solution, 0.2 parts by weight of trimethylolpropane / tolylene diisocyanate trimer adduct is added as a cross-linking agent, and the mixture is uniformly mixed and stirred to obtain an acrylic adhesive solution (5) was prepared.

(Preparation of optical member with adhesive)
The acrylic pressure-sensitive adhesive solution (5) is applied to one side of a polyethylene-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and dried to a thickness of 40 μm. Formed.

  Subsequently, the said adhesive layer was bonded together on the surface of the polarizing film, and the optical member with an adhesive was produced. The gel fraction of the pressure-sensitive adhesive layer was 52%.

[Comparative Example 3]
(Preparation of adhesive solution)
To 100 parts by weight of the solid content of the aqueous dispersion of the acrylic polymer (C), 0.2 part by weight of 3-glycidoxypropyltriethoxysilane is added and mixed and stirred uniformly. (6) was prepared.

(Preparation of optical member with adhesive)
The acrylic adhesive aqueous dispersion (6) is applied to one side of a polyethylene-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and dried to a thickness of 40 μm. An adhesive layer was formed.

  Subsequently, the said adhesive layer was bonded together on the surface of the polarizing film, and the optical member with an adhesive was produced.

[Comparative Example 4]
(Preparation of optical member with adhesive)
The acrylic polymer (D) aqueous dispersion is applied to one side of a silicone-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and dried to a thickness of 40 μm. An agent layer was formed.

  Subsequently, the said adhesive layer was bonded together on the surface of the polarizing film, and the optical member with an adhesive was produced.

[Comparative Example 5]
(Preparation of optical member with adhesive)
The acrylic adhesive aqueous dispersion (3) is applied to one side of a silicone-treated polyethylene terephthalate film (thickness 38 μm), heated at 110 ° C. for 5 minutes, and a second adhesive having a thickness of 15 μm. An agent layer was formed.

  Next, an aqueous dispersion of the acrylic polymer (D) is applied onto the second pressure-sensitive adhesive layer, heated at 110 ° C. for 5 minutes, and the first pressure-sensitive adhesive having a dried thickness of 15 μm. A layer was formed.

  Subsequently, the said 1st adhesive layer was bonded together on the surface of the polarizing film, and the optical member with an adhesive was produced.

  According to the above method, the produced optical member with pressure-sensitive adhesive was subjected to a tensile test (measurement of tensile elastic modulus, breaking strength, breaking elongation), adhesion force, and durability, color unevenness, and contamination were evaluated. The obtained results are shown in Table 1.

上記表１の結果より、本発明によって作製された粘着剤付光学部材を用いた場合（実施例１〜４）、いずれの実施例においても、高温高湿処理後であっても、耐久性（剥がれや発泡が発生しない）に優れるとともに、色ムラの発生もなく、汚染性にも優れたものとなることが明らかとなった。

From the results of Table 1 above, when the optical member with pressure-sensitive adhesive produced according to the present invention was used (Examples 1 to 4), in any Example, even after high-temperature and high-humidity treatment, durability ( It was revealed that the film is excellent in that it does not cause peeling or foaming, has no color unevenness, and has excellent contamination.

On the other hand, when an optical member with an adhesive that does not satisfy the configuration of the present invention is used (Comparative Examples 1 to 5), in any Comparative Example, durability after high-temperature and high-humidity treatment, occurrence of color unevenness, As a result, it was found that the contamination of the pressure-sensitive adhesive layer cannot be controlled side by side, and it is not suitable for an optical member with a pressure-sensitive adhesive.

Claims (8)

  An optical member pressure-sensitive adhesive layer formed on at least one surface of the optical member, wherein the pressure-sensitive adhesive layer is a first pressure-sensitive adhesive layer in contact with the optical member, an intermediate layer made of a polymer film, and a second pressure-sensitive adhesive layer An adhesive layer for optical members, comprising an adhesive layer. The pressure-sensitive adhesive layer for an optical member according to claim 1, wherein the intermediate layer has a tensile elastic modulus of 5 N / mm ² or more.   The pressure-sensitive adhesive layer for an optical member according to claim 1, wherein the intermediate layer is obtained from an aqueous dispersion of a polymer.   The optical member according to any one of claims 1 to 3, wherein the first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer is obtained from an aqueous dispersion of a polymer. Adhesive layer.   The pressure-sensitive adhesive layer for an optical member according to claim 1, wherein the second pressure-sensitive adhesive layer contains a silane coupling agent. A step of forming a second pressure-sensitive adhesive layer by applying and drying the second pressure-sensitive adhesive raw material liquid on at least one surface of the peel-treated film;
A step of coating and drying a polymer film raw material liquid on the second pressure-sensitive adhesive layer to form an intermediate layer; and
A step of forming a first pressure-sensitive adhesive layer by applying and drying a first pressure-sensitive adhesive raw material liquid on the intermediate layer;
The manufacturing method of the adhesive layer for optical members characterized by having. A step of simultaneously or sequentially applying the second adhesive raw material liquid, the polymer film raw material liquid, and the first adhesive raw material liquid to at least one surface of the release-treated film, A step of simultaneously drying the pressure-sensitive adhesive coating layer comprising the first pressure-sensitive adhesive coating layer, the polymer coating layer, and the second pressure-sensitive adhesive coating layer;
The manufacturing method of the adhesive layer for optical members characterized by having. An optical member with a pressure-sensitive adhesive in which the pressure-sensitive adhesive layer for an optical member according to claim 1 is laminated on at least one surface of the optical member.