TW201235714A - Manufacturing method of polarizing plate - Google Patents

Abstract

In making a polarizing plate, wherein a protective film composed of cycloolefin resin is laminated through adhesives to a polarizing film on which dichroic dye has been adsorbed and aligned in the polyvinyl alcohol-based resin, given the thin film haze value is not more than 0.5%, the protective film is, after contacting a mixed organic solvent including a good solvent and a weak solvent and essentially containing no solute, wherein the good solvent refers to the organic solvent that would result in changing the resin due to the contact, and the weak solvent refers to the organic solvent that would not make substantial changes to the resin due to the contact, adhesively laminated to the polarizing film. The mixed organic solvent can be substituted by alicyclic hydrocarbon alone, but the alicyclic hydrocarbon is favorably mixed with the weak solvent.

Description

201235714 VI. [Technical Field] The present invention relates to a protective film made of a cycloolefin-based resin bonded to a surface of a polarizing film made of a polyvinyl alcohol-based resin via an adhesive to produce polarized light. The method of the board. [Prior Art] The polarizing plate is usually formed on one or both sides of a polarizing film made of a polyvinyl alcohol-based resin in which a dichroic dye has been adsorbed and aligned, and a transparent resin film is laminated via an adhesive, for example, triacetyl cellulose. It is composed of a representative cellulose acetate film. If necessary, an optical film such as an optical compensation film or a retardation film is bonded to the liquid crystal cell via an adhesive to form a component of the liquid crystal display device. The liquid crystal display device is rapidly expanding in use on a thin display screen such as a liquid crystal television, a liquid crystal monitor, or a personal computer. In particular, the market for LCD TVs has been significantly expanded, and the demand for cost reduction has been very strong. In the past, polarizers for liquid crystal televisions were laminated on both sides of a polarizing film made of a polyvinyl alcohol-based resin via a water-based adhesive. A film having a triacetyl cellulose film is mainly used, and a retardation film is laminated on one side of the polarizing plate via an adhesive. In the retardation film laminated on the polarizing plate, a stretched product of a polycarbonate resin film or a stretched product of a cycloolefin resin film is used, but in a liquid crystal television, a phase difference at a high temperature is often used. A retardation film made of a cycloolefin-based resin film having a very small unevenness. In the case of a laminate of a polarizing plate and a retardation film made of a stretched olefin-based resin film, 201235714, in order to improve the productivity or reduce the cost of the product, the number of components to be formed is reduced or the process is simplified. For example, JPH08-43 8 1 2-A discloses a laminated structure of a cycloolefin-based (norbornene-based) resin film/polarized film/triethylene cellulose film having a phase difference function. In JP 2005-70140-A, JP 2005-181817-A, and JP 2005-20845 6-A, a polyvinyl alcohol-based polarizing film and a cycloolefin-based resin film are bonded together with an aqueous urethane-based adhesive. On the other hand, JP2004-245 92 5-A is described on a polyvinyl alcohol-based polarizing film, and when a protective film having a low moisture permeability including a cycloolefin-based resin film is bonded, an active energy ray containing an epoxy compound is used. Hardenable adhesive. Further, it is disclosed in KR2 010-92265-A that it is selected from the group consisting of cyclohexanone, methyl isobutyl ketone, diethyl ether, ethylene oxide, tetrahydrofuran, tetrahydropyran, n-heptane, n-hexane, and At least one solution of a group consisting of phenol, toluene, xylene, dioctyl phthalate, and dimethylformamide, typically an aqueous solution of a compound selected from the group, used in a cyclic olefin A method of surface treatment in a resin film. Further, a method of producing a polarizing plate by bonding a cycloolefin-based resin film having such a surface treatment to a polyvinyl alcohol-based polarizing film by an adhesive is also disclosed. When a water-based adhesive is used for bonding a polyvinyl alcohol-based polarizing film and a cycloolefin-based resin film, the adhesion between the two is not sufficient. For example, peeling occurs at the interface between the polarizing film and the cycloolefin resin film. Therefore, after the polarizing plate is placed on the liquid crystal cell, it is necessary to reinstall the work (referred to as reworking) due to the defect of the polarizing plate, etc., and the layer of the polarizing plate is compared with the adhesive force of the adhesive of the polarizing plate and the liquid crystal cell. The adhesion in the structure (for example, the adhesion between the polarizing -6-201235714 film and the cycloolefin resin film) is relatively small, and only the cycloolefin resin remains on the glass unit from which the polarizing plate has been removed. The problem of liquid crystal cells can no longer be used. According to the method disclosed in the above-mentioned KR20 No. 10-92265-A, although the adhesion of the cycloolefin-based resin film to the polyvinyl alcohol-based polarizing film can be improved, when the surface treatment is carried out with an aqueous solution, it is necessary to maintain moisture after evaporation. The degree of temperature of the drying oven. On the other hand, in the organic compound specifically disclosed in the literature, it is considered that the cycloolefin-based resin film is directly used as a liquid at room temperature (organic solvent), but in this case, the cycloolefin resin film is excessively eroded. An object of the present invention is to provide a polarizing plate comprising a protective film made of a cycloolefin-based resin on a polarizing film made of a polyvinyl alcohol-based resin via an adhesive, wherein the polarizing film and the cycloolefin-based resin film are improved. Adhesion. Another object of the present invention is to adhere to a polyvinyl alcohol-based polarizing film via an adhesive without excessively eroding the cycloolefin-based resin film, thereby maintaining the high performance as a polarizing plate and improving the polarizing film and the ring. Adhesion between olefin-based resin films. As a result of the investigation of the present invention, it has been found that when the contact with the cycloolefin-based resin film is used, the organic solvent which changes the cycloolefin-based resin does not cause the cyclic olefin-based resin when it is brought into contact with the cycloolefin-based resin film. It is effective to contact the cycloolefin-based resin film so that the smog of the cycloolefin-based resin film does not exceed 0.5%. In addition, among the organic solvents which change the cyclic olefin resin by contact, if it is an alicyclic hydrocarbon, the contact treatment of the cycloolefin resin 201235714 film is effective and It is more effective to use a cyclic hydrocarbon together with an organic solvent which does not substantially change the cyclic olefin resin by contact. SUMMARY OF THE INVENTION That is, the present invention includes the following. [1] A method for producing a polarizing plate, wherein a protective film made of a cycloolefin-based resin is bonded to a polarizing film in which a dichroic dye has been adsorbed and attached to a polyvinyl alcohol-based resin, and an adhesive film is bonded thereto. A method of producing a polarizing plate comprising: contacting the protective film made of the cycloolefin-based resin with an organic haze of contact with the cycloolefin resin by contact with the haze of the protective film of not more than 0.5%; The mixture of the solvent and the organic solvent which does not substantially change the cyclic olefin-based resin by contact is substantially free of the solute mixed organic solvent, and then bonded to the polarizing film via the adhesive. [2] A method for producing a polarizing plate, wherein a surface of a polarizing film in which a dichroic dye has been adsorbed and attached to a polyvinyl alcohol-based resin is bonded to a first layer of a cycloolefin-based resin via an adhesive; A protective film, wherein a second protective film made of a thermoplastic resin is bonded to the other surface of the polarizing film via an adhesive to produce a polarizing plate, comprising: the first protection by the cycloolefin resin The film, in such a manner that the haze of the first protective film does not exceed 〇·5%, contacts the organic solvent which changes the cycloolefin resin by contact, and does not cause substantial change to the cycloolefin resin by contact. The mixture of the organic solvents contains substantially no solute mixed organic -8-201235714 solvent, and is then bonded to the polarizing film via the above-mentioned adhesive. [3] A method for producing a polarizing plate, wherein a protective film made of a cycloolefin-based resin is bonded to a polarizing film in which a dichroic dye has been adsorbed to a polyvinyl alcohol-based resin, and an adhesive film is bonded thereto. A method for producing a polarizing plate comprising: contacting a protective film made of the above cycloolefin-based resin with an organic material containing an alicyclic hydrocarbon and substantially containing no solute so that the haze of the protective film is not more than 0.5% After the solvent, the polarizing film is bonded to the polarizing film via the above adhesive. [4] A method for producing a polarizing plate, wherein the first surface of the polarizing film in which the dichroic dye has been adsorbed and applied to the polyvinyl alcohol resin is bonded to the first surface of the polarizing film via an adhesive. A protective film, a second protective film formed of a thermoplastic resin bonded to the other surface of the polarizing film via an adhesive to produce a polarizing plate, comprising: the first protection by the cycloolefin resin The film is bonded to the polarizing film via the above-mentioned adhesive by contacting the organic solvent containing the alicyclic hydrocarbon and containing substantially no solute so that the haze of the first protective film does not exceed 〇5 ° 〇. [5] The production method according to [3] or [4] wherein the alicyclic hydrocarbon is a compound represented by the following formula (I): (CH2)m IV〇CH2

• R (I) (wherein, m is an integer of 2 to 6, and r is a hydrogen atom or a group having a carbon number of i to 5). [6] Manufactured according to any one of [3] to [5] In the above method, the solvent of the above-mentioned -9-201235714 is further contained, in addition to the alicyclic hydrocarbon, a mixed solvent of an organic solvent which does not substantially change the aforementioned cyclic olefin-based resin by contact. [7] The production method according to the above [6], wherein the alkyl olefin-based resin does not substantially change the alkyl ester of the organic solvent-based organic acid. [8] The production method according to [7], wherein the alkyl ester of an organic acid is acetate. [9] The production method according to [8], wherein the acetate is ethyl acetate, isopropyl acetate or propyl acetate. [10] The production method according to any one of [1] to [9] wherein the protective film formed of the cycloolefin-based resin has an in-plane phase difference of 30 nm or more before contact with the organic solvent. The in-plane phase difference 値 of the protective film after the contact is made more than 3 nm but not less than the in-plane phase difference 接触 before the contact. The production method according to any one of the above aspects, wherein the protective film formed of the cycloolefin-based resin is brought into contact with the organic solvent, and the operation of drying the organic solvent is simultaneously performed. [12] The method according to any one of [1], wherein the adhesive is a water-based adhesive, and the adhesive is a polyvinyl alcohol-based method. Resin. According to the present invention, the polarizing film and the cycloolefin resin can be improved by bonding a polarizing film made of a cycloolefin resin to a polarizing film made of a polyvinyl alcohol-based resin via an adhesive. The adhesion of the film. In particular, a polarizing plate can be produced which suppresses the erosion of the cycloolefin-based resin film <10-201235714, and maintains the adhesion between the olefin-based resin film as a high performance of the polarizing plate. [Embodiment] In the present invention, a polarizing film is formed on a polarizing film in a dichroic dye-based resin via a protective film made of an adhesive. When the cycloolefin-based resin film is bonded to one surface of the polarizing film, the protective film formed of the other thermoplastic resin and the cycloolefin-based resin may be bonded via an adhesive, and A protective film of a thermoplastic resin." First, the constituent members will be described. [Polarizing film] The polarizing film used in the present invention is specifically conjugated to the polyethylene polyvinyl alcohol-based resin film before, during or after adsorption, and the polychromatic dye can be borrowed from the extended resin by stretching. In addition to vinyl acetate, a vinyl acetate-based resin vinyl ester-based resin may be mentioned, and vinyl acetate may be used in combination with the vinyl chloride-based resin to improve the alignment of the polarizing film and the ring. The olefin-based resin film of the resin may be attached to one side. When the polarizing film is preferably formed on the opposite side of the protective film. The following film is also referred to as "the protective film of the first protective thin film". The dichroic dye of the polarizing plate produced by the first invention is adsorbed. The axial direction of the vinyl alcohol resin film of the dichroic dye is one axial direction. Medium-aligned. Polyvinyl alcohol-based saponification. Copolymer -11 - 201235714 as a monomer for the polymerization of polyvinyl acetate homopolymer of polyacetic acid homopolymer. For example, ethylene-vinyl acetate copolymer, etc. Examples of the other monomer copolymerizable with vinegar include unsaturated carboxylic acids, unsaturated base acids, olefins such as ethylene, vinyl ethers, and acrylamides having an ammonium group. The degree of saponification of the resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, for example, a polyvinyl formal modified by an aldehyde, or a poly Ethylene acetal, polyvinyl butyral, etc. Further, the degree of polymerization of the polyvinyl alcohol-based resin is usually in the range of 1,000 to 10,000, preferably in the range of 1,5 to 5,000. A vinyl alcohol resin film is used as a film. The raw material film of the polarizing film is not particularly limited as a method of forming a film of a polyvinyl alcohol-based resin. The film can be formed by a suitable method. A film of a raw material film made of a polyvinyl alcohol-based resin The thickness is not particularly limited, and is, for example, about 10 to 150 μm. The polarizing film is usually produced by dyeing a polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye. Step (dyeing step), a step of treating a polyvinyl alcohol-based resin film having a dichroic dye adsorbed thereto with a boric acid aqueous solution (boric acid treatment step), and a step of washing with water after the treatment with the aqueous boric acid solution (water washing treatment step) Further, in the production of a polarizing film, the polyvinyl alcohol-based resin film is stretched by one axis, and the one-axis extension may be performed before the dyeing step, or in the dyeing step, or after the dyeing step. -12- 201235714 When a shaft extension is performed after the dyeing step, the one-axis extension is performed before the boric acid treatment step, or In the acid treatment step, it is also possible to perform one-axis extension in the plurality of stages. The one-axis system can be carried out by passing between the rolls having different circumferential speeds, or by heat holding. The dry extension in which the stretching is carried out may be a wet stretching in which the stretching is carried out in a solvent. The magnification is usually about 3 to 8 times. The polyvinyl alcohol-based resin film is dyed by a dichroic dye by using The polyvinyl alcohol-based resin film is immersed in a liquid containing a dichroic dye. Specifically, iodine or a dichroic dye is used as the dichroic dye. The dichroic organic dye includes CI DIRECT 39 or the like. a dichroic direct dye formed by a bisazo compound, a dichroic direct dye formed from a compound such as triazolyl, etc. Further, the polyethylene resin film is preferably preliminarily administered in water before the dyeing treatment. deal with. When iodine is used as the dichroic dye, the iodine content in the aqueous solution is usually immersed in an aqueous solution containing iodine and potassium, and the amount of iodine in the aqueous solution is usually ~1 per 100 parts by weight of water. The content of potassium iodide is 0.5 to 20 parts by weight per 100 parts by weight of water. When iodine is used as the dichroic dye, the temperature of the dye solution is usually 20 to 40 ° C, and the immersion time (dyeing time) in the aqueous solution is usually 2 0 to 1,800 seconds. On the other hand, the use of a dichroic organic dye as a dichroic dye is usually employed in an aqueous solution containing a water-soluble dichroic organic dye. When the extension rolls are stretched, extensions such as water-soluble organic RED and tetraol-based iodination are used. 0.0 1 Frequent water stains, Dip-13-201235714 stained polyvinyl alcohol resin film and dyed method" The content of this water-soluble organic dye is usually 10 parts by weight per 1 part by weight of water. Preferably, it is 0_3~1 parts by weight, more preferably lxl (Γ2 parts by weight. The aqueous solution also contains a colorless auxiliary agent such as sodium sulfate. The temperature of the dye aqueous solution using the dichroic organic dye as the dichroic dye is usually 20 to 80. °c, and the immersion time (dyeing time) is usually 10 to 1, and the 800-second boric acid treatment step is carried out by immersing the dichromatic dye-enol resin film in an aqueous boric acid solution. The content is usually in a portion per 100 parts by weight of water, preferably 5 > 12 parts by weight. When iodine is used as the dichroic dye in the above dyed, the aqueous boric acid solution used in this step is potassium iodide. The potassium iodide content is usually 0.1 to 15 parts by weight, preferably 5 to 30%, and the immersion time in the aqueous boric acid solution is usually 60 to 1,200 to 600 seconds, more preferably 200 to 400 seconds. Often 50 1 or more, preferably 50 to 85 ° C, more preferably 60 to 50. Next, in the water washing treatment step, the temperature of the water in the water washing treatment by immersing the above-described vinyl borate vinyl resin film in water, for example, is usually 5~40 ° C, immersion time 120 seconds. After the water washing treatment, it is usually applied to dry treatment, and the drying treatment can be carried out, for example, by a hot air dryer or far infrared ray. The drying treatment temperature is usually 30 to 1 〇〇 ° C. , ® 80 ° C. The drying time is usually 60~600 seconds, compared with 1 X10·4~ in the liquid. 1 X 1 0·3~ Machine salt is used for dyeing. The dyed polydiborate aqueous solution 2~1 5 weight treatment step preferably comprises a system containing 12 parts by weight per 100 parts. Second, preferably the temperature of the liquid is 80 ° C. The treatment after the treatment. Washing Usually 1~ to polarized film heater, etc. Μ 为 为 5 5 120 120 120 120 120~ -14- 201235714 6 0 0 〇 以上 以上 , 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 二 二 二 二 二 二a polarizing film in a resin film. The thickness of the polarizing film can be In the present invention, the first protective film provided on at least one surface of the polarizing film is formed of a cycloolefin-based resin film, and the cycloolefin-based resin film is attached via an adhesive. The cycloolefin film is a thermoplastic resin having a unit of a monomer such as a cyclic olefin (cycloolefin) such as norbornene or a polycyclic norbornene monomer, and is also called a cycloolefin film. It is a thermoplastic cycloolefin resin. The cycloolefin resin may be a ring-opening polymer of the above cycloolefin or a hydrogenated product of a ring-opening copolymer of two or more kinds of cyclic olefins, or a cyclic olefin and a chain olefin or An addition polymer having an aromatic compound such as a polymerizable double bond of a vinyl group. In the cycloolefin resin, a polar group may also be introduced. When a first protective film is formed by using a copolymer of a cyclic olefin and a chain olefin and/or an aromatic compound having a vinyl group, examples of the chain olefin include ethylene, propylene, and the like, and an aromatic compound having a vinyl group. 'Styrene, α-methylstyrene, a core alkyl-substituted styrene, etc. are mentioned. The unit of the monomer formed from the cyclic olefin in such a copolymer may be 50 mol% or less, preferably about 15 to 50 mol%. In particular, when a first protective film is formed using a terpolymer of a cyclic olefin and a chain olefin and an aromatic compound having a vinyl group, the unit cell of the monomer formed by the cyclic olefin is -15-201235714 as described above. Become a relatively small amount. In the terpolymer, the unit of the monomer formed from the chain olefin is usually 5 to 80 mol%, and the unit of the monomer formed from the aromatic compound having a vinyl group is usually 5 to 80 m. For the 〇 〇 olefin resin film, a commercially available product can be used, and for example, TOPAS, squirrel, squirrel, squirrel, squirrel, squirrel, squirrel, squirrel, squirrel, squirrel "ARTON" sold, "ZEONOR" and "Rayon 臬 司" (ΖΕΟΝΕΧ) sold by Japan ΖΕΟΝ (shares), "APEL" sold by Mitsui Chemicals (shares) In order to form a film of such a cycloolefin-based resin into a film, a well-known method such as a solvent casting method or a melt extrusion method can be suitably used. For example, it can also be sold by Sekisui Chemical Industry Co., Ltd. “ESENNA” and “SCA40”, a “ZENOR film” sold by Sakamoto Co., Ltd., and a pre-formed cycloolefin resin film such as “ARTON film or more” sold by JSR (share) Commercial product as the first guarantee Film. The cycloolefin-based resin film used for the first protective film may be extended by one axis or biaxially. The stretching ratio at this time is usually 1.1 to 5 times, preferably 1. 1 to 3 times. By giving the phase difference by this extension, it becomes a phase difference film. The in-plane phase difference 适宜 can be suitably set in accordance with the type of liquid crystal cell to be applied, but is generally preferably 3 Onm or more. The upper limit of the in-plane phase difference 値 is not particularly limited, and is, for example, sufficient to be about 300 nm. The thinner cycloolefin resin film used for the first protective film is preferably thinner. However, if it is too thin, the strength is lowered, and the workability tends to be deteriorated. On the other hand, if the thickness of -16 to 201235714 is too thick, the transparency is lowered, or The weight of the polarizing plate tends to increase. From such a viewpoint, the thickness of the protective film made of the cycloolefin resin is usually 5 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm, and is formed of a cycloolefin resin. The protective film is bonded to the polarizing film using an adhesive as described in detail below. In order to improve the adhesion, the adhesion surface of the polarizing film and/or the protective film attached thereto may be suitably subjected to plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame). ) Surface treatment such as treatment, saponification treatment, and the like. Hereinafter, an adhesive used for bonding the polarizing film and the cycloolefin resin film will be described. [Adhesive] An adhesive is used for bonding the polarizing film and the cycloolefin resin film. The adhesive to be used for this purpose may be any one that exhibits adhesion to both, and examples thereof include a water-based adhesive in which an adhesive component is dissolved or dispersed in water, or a curable property containing an active energy ray-curable compound. Adhesive. When the surface of the polarizing film is considered to be hydrophilic, it is preferably a water-based adhesive obtained by dissolving or dispersing an adhesive component in water. A water-based adhesive is also preferable from the viewpoint of reducing the thickness of the hardened adhesive layer. Among the adhesive components of the main component of the aqueous adhesive, there are a polyvinyl alcohol resin or an urethane resin. When a polyvinyl alcohol-based resin is used as a main component of a water-based adhesive, the polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. -17-201235714 The polyvinyl acetate-based resin may, for example, be a polyvinyl acetate of a homopolymer of vinyl acetate, or a copolymer of vinyl acetate and another monomer copolymerizable therewith. Examples of the other monomer copolymerized with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group. The polyvinyl alcohol-based resin used for the adhesive preferably has a moderate degree of polymerization. For example, when it is a 4% by weight aqueous solution, the viscosity is in the range of 4 to 50 mPa·sec, more preferably in the range of 6 to 30 mPa·sec. Inside. The degree of saponification of the polyvinyl alcohol-based resin used in the adhesive is not particularly limited, and is generally preferably 80 mol% or more, and more preferably 90 mol% or more. When the degree of saponification of the polyvinyl alcohol-based resin used for the adhesive is low, the water resistance of the obtained adhesive layer tends to be insufficient. It is preferred to use a modified polyvinyl alcohol-based resin in the adhesive. Examples of a suitable modified polyvinyl alcohol-based resin include a polyvinyl alcohol-based resin modified with an acetamidine group, an anion-modified polyvinyl alcohol-based resin, and a cationically modified polyvinyl alcohol-based resin. Wait. When the thus-modified polyvinyl alcohol-based resin is used, the effect of improving the water resistance of the pressure-sensitive adhesive layer can be easily obtained. The polyvinyl alcohol-based resin modified with an acetamidine group may have an ethyl acetyl group (CH3COCH2CO-) in addition to the hydroxyl group constituting the polyvinyl alcohol skeleton, and may have another group such as an acetamidine group. This ethyl oxime group is typically present in a state of substituting a hydrogen atom constituting a hydroxyl group of polyvinyl alcohol. The polyvinyl alcohol-based resin modified with an ethyl hydrazine group can be produced, for example, by a method of reacting polyethylene glycol with diethyl ketone. The polyethyl acrylate ester -18-201235714 resin modified with acetamidine is preferred because of the durability of the highly reactive functional base adhesive layer. The content of the polyvinyl alcohol modified by the ethyl acetonitrile group is 〇. 1 mol% or more, and the content of the ethyl ruthenium group which is not solid is the hydroxyl group in the phase, and the ethyl hydrazide group. And other ester groups (in terms of %, the degree of oximation of ethyl oxime) is 0.1%, and 0.1 mol% of the polyvinyl alcohol-based resin does not necessarily sufficiently obtain an adhesive effect.醯 醯 醯 醯 ° ° ° ° ° 系 , , , , , , , 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系 系The hydroxyl group of the alcohol-based resin skeleton further contains an anionic group, or a salt thereof, and may contain a group other than the group, for example, a modified polyvinyl alcohol-based resin, for example, an unsaturated monomer which is typically carboxyl group- It is produced by a method of saponification of ethyl acetate. On the other hand, the alcohol-based resin typically contains a tertiary amino group or a quaternary ammonium group, such as an ethenyl group, in addition to the group constituting the polyvinyl alcohol skeleton. The cation modification is, for example, an ethyl acetyl group which is copolymerized with an unsaturated monomer having a cationic group (typical group) and vinyl acetate. Therefore, the ethyl oxime group in the resin is particularly limited. Here, the total amount of the polyvinyl alcohol-based resin, such as acetonitrile, etc., is also referred to as "the degree of deterioration of the water resistance of the agent layer is preferably 0.1 to 40. It is preferably 2 to 7 mol%. The effect of water-based improvement is small, except for the formation of a polyvinyl alcohol-type carboxyl group (-COOH), an oxime group, etc. The anion has an anionic group (the olefin ester copolymerization, followed by the cation modification) The polyvinyl hydroxy group further contains a cationic group, and may also be produced by using a polyvinyl alcohol-based resin other than a polyvinyl alcohol-based resin, a tertiary amino group or a quaternary ammonium salt, followed by a saponification method of -19 to 201235714. The adhesive may of course contain two or more kinds of the above-mentioned modified polyvinyl alcohol-based resins, and may also contain an unmodified polyvinyl alcohol-based resin (specifically, a wholly or partial saponified product of polyvinyl acetate) and the above. The polyvinyl alcohol-based resin constituting the adhesive of both of the modified polyvinyl alcohol-based resins can be suitably selected from commercially available products. Specifically, for example, polyvinyl alcohol having a high degree of saponification can be mentioned. By (share) KURARAY "PVA-117H" sold, or "Gohsenol NH-20," modified by the Japanese synthetic chemical industry (shares), polyvinyl alcohol modified by acetamidine, by the Japanese synthetic chemical industry ( "Gohsefimer Z" series sold by the company, anion-modified polyvinyl alcohol, "KL-318" and "KM-118" sold by KURARAY, or by the Japanese synthetic chemical industry "Gohsenol T-330" sold, cationically modified polyvinyl alcohol, "CM-318" sold by KURARAY, or sold by Japan Synthetic Chemical Industry Co., Ltd. G〇hsefimer K-210", etc. The concentration of the polyvinyl alcohol-based resin in the adhesive is not particularly limited 'because it is used in the form of an aqueous solution, 'polyethyl alcohol' relative to 1 part by weight of water The resin is preferably in the range of 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, particularly preferably 1 to 10 parts by weight, particularly preferably 2 to 10 parts by weight. Polyethylene in an aqueous solution. If the concentration of the alcohol resin is too small, the adhesion tends to be lowered, and if the concentration is too small, the concentration is The optical characteristics of the polarizing plate obtained by the large one tend to be lowered. The water used for the adhesive may be pure water, ultrapure water, tap water, etc., and there is no other limitation, but from the holding place. From the viewpoint of uniformity and transparency of the formed adhesive layer, it is preferably pure water or ultrapure water. Further, an alcohol such as methanol or ethanol may be added to the aqueous solution of the adhesive. The water-based adhesive containing the resin as a main component may contain a crosslinking agent. The crosslinking agent may be a compound having a functional group reactive with a polyvinyl alcohol-based resin, and the conventional polyvinyl alcohol may be used without particular limitation. Used in the adhesive. If a compound capable of forming a crosslinking agent is additionally disclosed by a functional group, there is an isocyanate compound having at least 2 isocyanate groups (-NCO) in the molecule; and having at least 2 epoxy groups in the molecule (bridged-0-) Epoxide compound; mono or dialdehyde; organotitanium compound; inorganic salt of divalent or trivalent metal such as magnesium, calcium, iron, nickel, zinc and aluminum; metal salt of glyoxylic acid: methylol honey Amines, etc. Specific examples of the isocyanate compound as the crosslinking agent include toluene diisocyanate, hydrogenated toluene diisocyanate, an adduct of trimethylolpropane and toluene diisocyanate, diphenylmethane diisocyanate, and triphenylmethane triisocyanate. Isophorone diisocyanate, such ketoxime blocks or phenolic blocks, and the like. Specific examples of the epoxy compound as the crosslinking agent include ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, and di- or tri-epoxypropyl ether of glycerol 1 ,6-hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, diepoxypropyl aniline, diepoxypropylamine, polyalkylene polyamine and dicarboxylic acid A water-soluble polyamine epoxy resin obtained by reacting a polyamine transamine and epichlorohydrin. Specific examples of the monoaldehydes as the crosslinking agent include formaldehyde, acetaldehyde, -21 - 201235714 propionaldehyde, butyraldehyde, and the like, and specific examples of the dialdehydes include glyoxal and malondialdehyde. Succinic aldehyde, glutaraldehyde, maleic aldehyde, phthalaldehyde, and the like. The organic titanium compound as a crosslinking agent is sold by various companies by MATSUMOTO Fine Chemicals Co., Ltd. A web page related to the company's organic titanium compound (Internet [URL: http://www.m-chem.co.jp/products/productl.html], retrieved from November 18, 2005), if The water-soluble organotitanium compound to be used in the present invention is disclosed in the order of the chemical formula and the trade name of the company, and the following are the following. [(CH3)2CHO]2Ti[OCH2CH2N(CH2CH2OH)2]2: the chemical name "titanium diisopropoxy bis(triethanolamine)" by the company, and the trade name "Orgatix TC-400" of the same company, (HO)2Ti[OCH(CH3)COO_]2(NH4 + )2 : The chemical name of the company is "titanium lactate, the trade name of the company "Orgatix TC_3 00", (HO)2Ti[OCH(CH3 )COOH]2 : The chemical name "Titanium lactate", the company's trade name "Orgatix TC-310" and "〇rgatix TC · 3 1 5," are the same as the company's chemical name. Examples of the alkali metal salt or the alkaline earth metal salt include sodium glyoxylate, potassium glyoxylate, magnesium glyoxylate, calcium glyoxylate, and the like. Among these crosslinking agents, 'the above water-soluble polyfluorene An epoxy compound such as an amine epoxy resin, or an aldehyde, methylol melamine or an alkali metal or alkaline earth metal salt of glyoxylic acid is used. The crosslinking agent is preferably dissolved together with a polyvinyl alcohol resin. The amount of the crosslinking agent in the aqueous solution may be a little bit, as long as it has at least 0.1% by weight, as described below. The solubility in the left and right can be used as a crosslinking agent. Of course, a compound having a solubility in water which is generally called water solubility is suitable as a crosslinking agent used in the present invention. It is suitably designed according to the type of the polyvinyl alcohol-based resin, etc., but it is usually about 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyvinyl alcohol-based resin. The cross-linking agent gives good adhesion. As described above, in order to improve the durability of the adhesive layer, it is preferred to use a polyvinyl alcohol-based resin modified with an acetamidine group, but in this case, relative to the poly-polymer The 100 parts by weight of the vinyl alcohol-based resin is preferably a crosslinking agent blended in a proportion of 5 to 60 parts by weight, more preferably 10 to 50 parts by weight. If the amount of the crosslinking agent is too large, Then, the reaction of the crosslinking agent proceeds in a short period of time, and the adhesive tends to gel at an early stage, and as a result, the pot life becomes extremely short, and industrial use becomes difficult. In the adhesive, it does not hinder the effects of the present invention. For example, you can also take A suitable additive such as a decane coupling agent, a plasticizer, an antistatic agent, or a fine particle. When a urethane resin is used as a main component of a water-based adhesive, an example of a suitable adhesive is a polyester system. a mixture of an ionic polymer type urethane resin and a compound having a glycidoxy group. The polyester-based ionic polymer type urethane resin as described herein is an aminocarboxylic acid having a polyester skeleton. An ester resin into which a small amount of an ionic component (hydrophilic component) is introduced. The ionic polymer type urethane resin is directly emulsified in water to form an emulsion without using an emulsifier of -23 to 201235714, and is therefore suitable for use in an emulsion. Water adhesive. An adhesive for using a polyester-based ionic polymer type urethane resin in a polarizing film and a protective film is, for example, JP2005-070140-A, JP2005-1 8 1 8 1 7-A, and JP2005-208456-A. The records are well known. In the adhesion between the polarizing film and the cycloolefin resin film, a curable adhesive containing an active energy ray-curable compound can also be used. The "active energy ray-curable compound" means a compound which is hardenable by irradiation with an active energy ray. The active energy ray-curable compound may be a cationic polymerizable one or a radical polymerizable one. Examples of the cationically polymerizable compound include an epoxy compound having at least one epoxy group in the molecule, and an oxetane compound having at least one oxetane ring in the molecule. Further, examples of the radically polymerizable compound include a (meth)acrylic compound having at least one (meth)acryloxy group in the molecule. Further, the term "(meth)acryloxy" means "methacryloxy" or acryloxy. The active energy ray-curable compound to be bonded is preferably at least an epoxy compound, and therefore exhibits better adhesion between the polarizing film and the cycloolefin resin film. From the viewpoints of weather resistance, refractive index, cationic polymerizability and the like, the epoxy compound is preferably used as a main component in an epoxy compound which does not contain an aromatic ring in the molecule. The epoxy compound which does not contain an aromatic ring in the molecule can be exemplified by a glycidyl ether, an aliphatic epoxide, an alicyclic epoxy compound or the like of a polyhydric alcohol having an alicyclic ring. The epoxy compound thus suitable for the curable adhesive is described in detail in, for example, JP2004-245 925-A. -24-201235714 The strategy is also described herein. A epoxidized propyl ether of a polyhydric alcohol having an alicyclic ring, which is a nuclear hydrogenated polyhydroxy compound obtained by hydrogenating an aromatic ring in the presence of a catalyst under pressure and optionally under pressure. To be epoxy propyl etherified. Examples of the aromatic polyol include bisphenol type compounds such as bisphenol A, bisphenol F, and bisphenol S; and novolacs such as phenol novolak resin, cresol novolak resin, and hydroxybenzaldehyde phenol novolak resin; a resin; a polyfunctional compound such as tetrahydroxydiphenylmethane, tetrahydroxydiphenyl ketone, and polyvinyl phenol. The alicyclic polyol obtained by hydrogenating the aromatic ring of the aromatic polyol is reacted with epichlorohydrin to form a glycidyl propyl ether. Among the epoxidized propyl ethers of the polyol having such an alicyclic ring, hydrogenated diglycidyl ether of bisphenol A is preferred. The aliphatic epoxy compound may be a polyepoxypropyl ether of an aliphatic polyol or an alkylene oxide compound thereof. More specifically, it may be exemplified by di-epoxypropyl ether of 1,4-butanediol; diepoxypropyl ether of 1,6-hexanediol; triepoxypropyl ether of glycerol; trimethylol a tri-epoxypropyl ether of propane; a di-epoxypropyl ether of polyethylene glycol; a di-epoxypropyl ether of propylene glycol; and one or more aliphatic aliphatic alcohols of ethylene glycol, propylene glycol or glycerin A polyepoxy propyl ether of a polyether polyol derived from an alkylene oxide (ethylene oxide or propylene oxide). The alicyclic epoxy compound is a compound having at least one epoxy group bonded to an alicyclic ring in the molecule. Here, the "epoxy group bonded to the alicyclic ring" means a bridged oxygen atom - 〇- in the structure represented by the following formula (II), wherein η is an integer of 2 to 5. -25- 201235714 【化1】

广^ CH (CH2)n I>0 (Π) In this formula (Π), one or a plurality of hydrogen atoms in (CH2)n are bonded to other chemically-structured compounds. Become an alicyclic epoxy compound. Further, one or a plurality of hydrogen atoms in the (CH2)n forming the alicyclic ring may be suitably substituted with a linear alkyl group such as a methyl group or an ethyl group. Among the above epoxy compounds, an alicyclic epoxy compound is preferred, and at least one epoxy group is bonded to the compound of the alicyclic ring, in particular, the modulus of elasticity from the cured product is high, and the polarized light is polarized. In view of imparting good adhesion between the film and the protective film, it is more preferable to use an oxacyclocyclohexane ring [n = 3 in the above formula (Π)] or an oxabicycloheptane ring [the above formula (II) An epoxy compound in which n = 4]. Specific examples of the alicyclic epoxy compound are disclosed below. Here, the compound name is first given, and then the corresponding chemical formula is shown, and the same symbol is attached to the compound name and the chemical formula corresponding thereto: 3A: 3,4-epoxycyclohexylmethyl 3,4- Epoxycyclohexanecarboxylate, B: 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, C: ethylene Bis(3,4-epoxycyclohexanecarboxylate), D: bis(3,4-epoxycyclohexylmethyl)adipate, E:bis(3,4-epoxy- 6-Methylcyclohexylmethyl) adipate ' -26- 201235714 F: diethylene glycol bis(3,4-epoxycyclohexylmethyl ether), G: ethylene glycol double (3,4 -Epoxycyclohexylmethyl ether), Η: 2,3,14,15-diepoxy-7,11,18,2,tetraoxaspiro[5.2.2.5.2.2] I: 3- (3,4-Epoxycyclohexyl)-8,9-epoxy-1,5-dioxaspiro[5.5]undecane, J: 4-vinylcyclohexene dioxide, Κ: Limonene dioxide, L: bis(2,3-epoxycyclopentyl)ether, hydrazine: dicyclopentadiene dioxide, and the like.

•ch3 h3cο

ο ο χ>°

CH2- d_0 - CH2 h3c -27- 201235714 F : G : H : O:

CH2-(OCH2CH2)2—O-CH:

O

CH2—0—(ch2)2~〇~ch2 x>°

0 〇rv

In the curable adhesive, the epoxy compound may be used singly or in combination of two or more. Further, the curable adhesive may contain an oxetane compound in addition to the above epoxy compound. By adding an oxetane compound, the viscosity of the curable adhesive can be lowered and the rate of hardening can be accelerated. The oxetane compound is a compound having at least one oxetane ring (4-membered cyclic ether) in the molecule, and examples thereof include 3-ethyl-3-hydroxymethyloxetane, and 1 , 4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, two [ (3- -28 · 201235714 ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac Varnish oxetane and the like. Such an oxetane compound can be easily obtained as a commercial product, and examples thereof include "Arone Oxetane OXT-101" and "Arone Oxetane OXT-121," which are sold under the trade name of East Asia Synthetic Co., Ltd. "AroneOxetane OXT-211", "Arone Oxetane OXT-221,," "Arone Oxetane OXT-2 12", and the like. The amount of the oxetane compound to be added is not particularly limited, and is usually 50% by weight or less, preferably 1% to 40% by weight based on the entire active energy ray-curable compound. When the curable adhesive contains a cationically polymerizable compound such as an epoxy compound or an oxetane compound, a photocationic polymerization initiator is usually used in the curable adhesive. When a photo-cationic polymerization initiator is used, since the pressure-sensitive adhesive layer can be formed at a normal temperature, the heat resistance of the polarizing film or the distortion due to expansion is reduced, and the polarizing film and the protective film can be bonded to each other with good adhesion. Further, since the photocationic polymerization initiator is catalyzed by light, even if it is mixed in a curable adhesive, the curable adhesive retains stability and workability. The photocationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with an active energy ray of visible light, ultraviolet rays, X-rays or electron beams, and initiates polymerization of a cationically polymerizable compound. The photocationic polymerization initiator may be of any type, and, as a specific example, an aromatic diazo salt, such as a key salt of an aromatic iodine salt or an aromatic onium salt, an iron-aromatic hydrocarbon complex or the like. Examples of the aromatic diazonium salt include the following compounds: -29- 201235714 Benzazinediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, and the like. Examples of the aromatic iodine salt include compounds such as diphenyl iodine tetrakis(pentafluorophenyl) borate, diphenyl iodine hexafluorophosphate, and diphenyl iodine hexafluoroantimonic acid. Salt, bis(4-mercaptophenyl) iodine hexafluorophosphate, and the like. Examples of the aromatic onium salt include the following compounds: triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and 4, 4'-bis[diphenylsulfanyl]diphenylthio-bis-hexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenylthio-bishexafluoroantimony Acid salt, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenylthio bishexafluorophosphate, 7-[bis(p-tolylhydrazyl)indenyl]-2 -isopropyl thioxanthone hexafluoroantimonate, 7-[bis(p-tolylhydrazyl)indenyl]-2_isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl -4'-diphenylfluorenyl-diphenylsulfanyl hexafluorophosphate, 4-(t-butylphenylcarbonyl)-4'-diphenylfluorenyl-diphenylthio hexafluoroantimonic acid Salt, -30- 201235714 4-(T-butylphenylcarbonyl)-4'-di(p-tolylhydrazyl)fluorenyl-diphenylthio-tetrakis(pentafluorophenyl)borate. Further, 'as an iron-aromatic complex', for example, the following compounds are mentioned: a methyl-cyclopentanyl iron (II) hexafluoroantimonate, cumene·cyclopentadienyl iron (II) β hexafluorophosphate, xylene-cyclopentadienyl iron (π) tris(trifluoromethylsulfonyl) methanide, etc. β such photocationic polymerization initiators are readily available in commercial products, for example, The trade name includes "Kayarad PCI-220" and "Kayarad PCI-620" sold by Nippon Kayaku Co., Ltd., "UVI-6990, sold by UNION CARBIDE," by DAICEL Science ( "UVACURE1590" sold by the company "Adecaoptomer SP-150" and "Adecaoptomer SP-170" sold by ADEKA, "CI-5102" sold by Japan's Soda Co., Ltd. "CIT-1370", "CIT-1682", "CIP-1866S", "CIP-2048S" and "CIP-2064S", "DPI-101" and "DPI-102" sold by MIDORI Chemicals , " DPI -1 0 3,', " D PI -1 0 5 ", "Μ PI -1 0 3,,," Μ ΡI -1 0 5,,, "ΒΒΙ-101", "Β Β I -1 0 2,', " Β Β I -1 0 3,,," Β Β I -1 0 5 ',, " TPS 1 0 1,, "TPS-102", "TPS-I03", "TPS-105", "MDS-103", "MDS-105", "DTS-102", and "DTS-103" are "Ρ1-2074" sold by ROHDIA Corporation. These photocationic polymerization initiators may be used alone or in combination of two or more. Among these, it is particularly preferable to use an aromatic sulfonium salt because it has ultraviolet absorbing properties in a wavelength region of 300 nm or more - 31 - 201235714, excellent in hardenability, imparts good mechanical strength, and can be imparted to a polarizing film. A cured product having good adhesion to the protective film. The compounding amount of the photo-cationic polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 6 parts by weight, based on 100 parts by weight of the total of the cationically polymerizable compound containing an epoxy compound or an oxetane compound. Share. When the amount of the photocationic polymerization initiator is small, the curing is insufficient, and the mechanical strength or the adhesion between the polarizing film and the protective film tends to be lowered. On the other hand, when the amount of the photocationic polymerization initiator is too large, the ionic substance in the cured product increases, and the hygroscopicity of the cured product increases, and the durability of the obtained adhesive layer may be lowered. Further, the curable adhesive may contain a radical polymerizable (meth)acrylic compound together with the above epoxy compound or together with an epoxy compound and an oxetane compound. By using a (meth)acrylic compound, the effect of improving the hardness or mechanical strength of the adhesive layer can be expected, and the viscosity of the curable adhesive, the curing rate, and the like can be more easily adjusted. The (meth)acrylic compound may be obtained by reacting a (meth) acrylate monomer having at least one (meth) acryloxy group in the molecule or a compound having a functional group in two or more kinds. A (meth) acrylate oligomer having at least two (meth) acryloxy groups in the molecule. These may be used alone or in combination of two or more. When two or more types are used, two or more kinds of (meth) acrylate monomers may be used, and two or more kinds of (meth) acrylate oligomers may be used. Of course, (meth) acrylate singles may be used. One or more kinds of the compound and one or more kinds of (meth) acrylate oligomer-32-201235714. Further, the term "(meth)acrylate" means acrylate or methacrylate. Among the above (meth) acrylate monomers, there is a monofunctional (meth) acrylate monomer having one (meth) propylene fluorenyloxy group in the molecule, and two (meth) propylene groups in the molecule. A fluorenyl bifunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer having three or more (meth) acryloxy groups in the molecule. Specific examples of the monofunctional (meth) acrylate monomer include (meth)acrylic acid tetrahydroanthracene vinegar, (meth)propionic acid 2 -acetic acid, (meth)acrylic acid 2- or 3-propyl ester, (meth)acrylic acid 2-butylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (meth)acrylic acid isobutyl vinegar, (Methyl)-acrylic acid, third vinegar, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Benzyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dimethyl (meth)acrylate Aminoethyl ester, ethyl carbitol (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, phenoxy polyethylene glycol (methyl) Acrylate and the like. As the monofunctional (meth) acrylate monomer, a hydroxyl group-containing (meth) acrylate monomer can also be used. Examples of the monofunctional (meth) acrylate monomer having a carboxyl group include 2-(meth) acryloxyethyl phthalic acid and 2-(methyl) propylene oxyethyl carbene-formic acid. , ketoethyl (meth) acrylate vinegar, -33- 201235714 2-(methyl) propylene methoxyethyl succinic acid, N-(methyl) propylene oxy-N', N'- Dicarboxymethyl-p-phenylenediamine, 4-(meth)acrylomethoxyethyl trimellitic acid, and the like. As the bifunctional (meth) acrylate monomer, alkanediol di(meth)acrylates, polyoxyalkylene glycol di(meth)acrylates, halogen-substituted alkanediols (represented) Methyl) acrylates, di(meth) acrylates of aliphatic polyols, di(meth) acrylates of hydrogenated dicyclopentadiene or tricyclodecane dialkyl alcohol, dioxane diol Or a di(meth) acrylate of dioxane dialtanol, a di(meth) acrylate of bisphenol A or an alkylene oxide adduct of bisphenol F, a ring of bisphenol A or bisphenol F Oxydi(meth)acrylates and the like. More specific examples of the bifunctional (meth) acrylate monomer include ethylene glycol di(meth) acrylate, 1,3-butylene glycol di(meth) acrylate, and 1,4-butylene. Diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylic acid Esters, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(methyl) Acrylate, polytetramethylene glycol di(meth)acrylate, polyoxydi(meth)acrylate, di(meth)acrylate of hydroxytrimethylacetate neopentyl glycol, 2 , 2-bis[4-(methyl)acryloxyethoxyethoxyethoxyphenyl]propane, 2,2-bis[4- -34- 201235714 (meth)propene醯 ethoxyethoxyethoxycyclohexyl] propyl compound 'hydrogenated 111 cyclopentadienyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,3-dioxane Alkanol-2,5-diyldi(methyl)propane acid vinegar [alias: dioxanediol di(meth)acrylate], acetal trimethylacetate and trimethylolpropane acetal compound [ Chemical name: di(meth) acrylate of 2-(2-transyl-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane, Tris(hydroxyethyl)isocyanate di(meth)acrylate or the like. The trifunctional or higher polyfunctional (meth) acrylate monomer is represented by tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tris(A). Acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol A poly(meth)acrylate of a trifunctional or higher aliphatic polyol such as (meth) acrylate or dipentaerythritol hexa (meth) acrylate, and more preferably a trifunctional or higher halogen-substituted polyol ( Methyl) acrylate, an alkylene oxide adduct of tris(meth)acrylate trimethylolpropane, an alkylene oxide adduct of tris(meth)acrylate, 1,1,1_three [(Meth) propylene methoxy ethoxy ethoxy] propane, tris(hydroxyethyl) isotrimeric phthalate tri(meth) acrylate, and the like. On the other hand, among the (meth) acrylate oligomers, there are urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers 'epoxy groups (methyl groups) ) acrylate oligomers and the like. -35- 201235714 The so-called urethane (meth) acrylate oligomer, which has a urethane bond (-NHCOO.) and at least two (meth) acryloxy groups in the molecule. Compound. Specifically, it may be a urethane-forming reaction product of a hydroxyl group-containing (meth) acrylate monomer and a polyisocyanate having at least one (meth) acryloxy group and at least one hydroxyl group in the molecule. a terminallyocyanate group-containing urethane compound obtained by reacting a polyhydric alcohol with a polyisocyanate, and a methyl group having at least one (meth)acryloxy group and at least one hydroxyl group in the molecule A ureidolation reaction product of an acrylate monomer or the like. The hydroxyl group-containing (meth) acrylate monomer used in the above urethanation reaction may, for example, be 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di(meth) acrylate, trimethylolpropane di(meth) acrylate, pentaerythritol Tris(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. Examples of the polyisocyanate to be used for the urethanization reaction of the hydroxyl group-containing (meth) acrylate monomer include hexamethylene diisocyanate, amide diisocyanate, and isophorone diisocyanate. Dicyclohexylmethane diisocyanate, toluene diisocyanate, benzodimethyl diisocyanate, and aromatic isocyanates in such isomeric acid esters to obtain diisocyanates (for example, hydrogenated toluene diisocyanate, hydrogenated phthalic acid) a di- or tri-isocyanate such as a bis-isocyanate or a triphenylmethane triisocyanate or a dibenzyl benzene triisocyanate; and a polyisocyanate obtained by multimerizing the above-mentioned diisocyanate. -36-201235714 Further, as a polyol for a urethane compound containing a terminal isocyanate group by reaction with a polyisocyanate, in addition to an aromatic, aliphatic or alicyclic polyol, A polyester polyol, a polyether polyol, or the like is used. Examples of the aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and neopentyl glycol. , trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, dimethylol heptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerol, hydrogenation Bisphenol A and the like. The polyester polyol is obtained by a dehydration condensation reaction of the above polyol with a polyvalent carboxylic acid or an anhydride thereof. Examples of the polycarboxylic acid or its anhydride include succinic acid (anhydride), adipic acid, maleic acid (anhydride), and itaconic acid (anhydride) when an acid anhydride is added. Trimellitic acid (anhydride), pyromellitic acid (anhydride), phthalic acid (anhydride), isophthalic acid, terephthalic acid, hexahydrophthalic acid (anhydride), and the like. The polyether polyol is a polyalkylene oxide-modified polyol obtained by the reaction of the above polyol or dihydroxybenzene with an alkylene oxide, in addition to the polyalkylene glycol. The polyester (meth) acrylate oligomer is a compound having an ester bond and at least two (meth) acryloxy groups in the molecule. Specifically, it can be obtained by a dehydration condensation reaction using (meth)acrylic acid, a polycarboxylic acid or an anhydride thereof and a polyhydric alcohol. Examples of the polycarboxylic acid or its anhydride used in the dehydration condensation reaction. If the "anhydride" is added, there may be succinic acid (anhydride), adipic acid, maleic acid (anhydride), and Ikon. Acid (anhydride), trimellitic acid (anhydride), pyromellitic acid (anhydride), hexahydrophthalic acid (anhydride), -37- 201235714 phthalic acid (anhydride), isophthalic acid, terephthalic acid Wait. Further, examples of the polyhydric alcohol used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and neopentyl glycol. , trimethylolethane, trimethylolpropane, bis. by methyl propane, pentaerythritol, dipentaerythritol, dimethylol heptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerol, Hydrogenated bisphenol A and the like. The epoxy (meth) acrylate oligomer can be obtained by an addition reaction of a polyepoxypropyl ether and (meth)acrylic acid, and has at least two (meth) acryloxy groups in the molecule. . Examples of the polyepoxypropyl ether used in the addition reaction include ethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, and 1,6-hexanediol. When a (meth)acrylic compound is blended into a curable adhesive such as di-epoxypropyl ether or bisphenol A diglycidyl ether, the amount is based on the total amount of the active energy ray-curable compound. It is preferably 20% by weight or less, more preferably 1% by weight or less. When the amount of the (meth)acrylic compound is too large, the adhesion between the polarizing film and the protective film tends to be lowered. When the curable adhesive contains a radically polymerizable compound such as the above (meth)acrylic compound, it is preferably a photoradical polymerization initiator. As the photo-radical polymerization initiator, a polymerizable of a radically polymerizable compound such as a (meth)acrylic compound can be used as long as it is irradiated with an active energy ray, and a conventional one can be used. Specific examples of the photoradical polymerization initiator include acetophenone, 3-methylacetophenone, benzyldimethylketal, and 1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropan-1-one-38- 201235714, 2-methyl-l-[4-(methylthio)phenyl-2-morpholinylpropan-1-one, 2-hydroxy-2-methyl Acetophenone-based initiator such as -1-phenylpropan-1-one; diphenyl group such as diphenyl ketone, 4-chlorodiphenyl ketone or 4,4'-diaminodiphenyl ketone a ketone initiator; a benzoin ether initiator such as benzoin propyl ether benzoin ethyl ether; a thioxanthone initiator such as 4-isopropylthioxanthone; , fluorenone, camphorquinone, benzaldehyde, hydrazine and the like. The amount of the photo-radical polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 6 parts by weight, based on 100 parts by weight of the radically polymerizable compound such as a (meth)acrylic acid compound. If the amount of the photoradical polymerization initiator is too small, the curing is insufficient, and the mechanical strength or the adhesion between the polarizing film and the protective film tends to be lowered. In addition, when the amount of the photo-radical polymerization initiator is too large, the active energy ray-curable compound in the curable adhesive (the cationically polymerizable curable compound containing an epoxy compound and the (meth)acrylic compound are free. The base polymerizable compound) is relatively small, and the durability of the obtained pressure-sensitive adhesive layer may be lowered. The curable adhesive may further contain a photosensitizer as needed. By aligning the photosensitizer, the reactivity of the cationic polymerization and/or radical polymerization can be improved, and the mechanical strength of the adhesive layer or the adhesion between the polarizing film and the protective film can be improved. Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo, a diazo compound, and a halogen compound 'photoreducible dye. If a more specific example of a photosensitizer is given, there are benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, and α,α-dimethoxy-α-phenylacetophenone. Such as diphenyl ketone, 2,4-39-201235714 dichlorodiphenyl ketone, methyl phthaloyl benzoate, 4·4'-bis(dimethylamino)diphenyl ketone and a diphenyl ketone derivative of 4,4'-bis(diethylamino)diphenyl ketone; a thioxanthone derivative such as 2-chlorothioxanthone or 2-isopropylthioxanthone; - anthracene derivatives of proguanil or 2-methylindole; acridinone derivatives such as N-methylacridone or N-butylacridone; additionally alpha, alpha-diethoxybenzene Ethyl ketone, benzyl, fluorenone, xanthone, uranium quinone compound, halogen compound, and the like. These photosensitizers may be used singly or in combination of two or more kinds. The total amount of the active energy ray-curable compound is 1 part by weight, and the photosensitizer is preferably used in an amount of 0.1 to 20 parts by weight. A well-known polymer additive which is usually used in a polymer may be added to the curable adhesive. For example, a primary antioxidant such as a phenol type or an amine type, a sulfur-based secondary antioxidant, a hindered amine light stabilizer (HALS), such as a diphenylketone type, a benzotriazole type or a benzoic acid may be mentioned. An ester-based ultraviolet absorber or the like. Further, the curable adhesive may contain a solvent as needed. The solvent is suitably selected in consideration of the solubility of the components constituting the curable adhesive. If a general solvent is exemplified, there are aliphatic hydrocarbons such as n-hexane or cyclohexane; aromatic hydrocarbons such as toluene or xylene; such as methanol, ethanol, propanol, isopropanol and n-butanol. Alcohols; such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone ketones; such as methyl acetate, ethyl acetate and butyl acetate esters; such as methyl cellosolve, B a cellosolve for a cellosolve agent and a butyl cellosolve; for example, a halogenated hydrocarbon such as dichloromethane or chloroform. The mixing ratio of the solvent is suitably determined from the viewpoint of viscosity adjustment for the purpose of processing such as film forming property. -40-201235714 [Second protective film] As described above, when a cycloolefin-based resin film is bonded to one surface of the polarizing film, the surface of the opposite side of the polarizing film can be bonded to another thermoplastic resin. Two protective film. The second protective film made of a thermoplastic resin is also bonded to the polarizing film via an adhesive. The second protective film may be, for example, a cellulose acetate resin, a polyolefin resin, an acrylic resin, a polyimide resin, a polycarbonate resin, a polyester resin, or the like as a material for forming a protective film in the field. It is composed of suitable materials that are widely used. From the viewpoint of mass productivity or adhesion, among these, a cellulose acetate-based resin film is preferably used as the second protective film. From the viewpoint of easiness of setting the surface treatment layer and optical characteristics, it is also preferred to use a cellulose acetate resin film as the second protective film. The cellulose acetate-based resin film is a film made of a part or a complete acetate of cellulose, and examples thereof include a triacetyl cellulose film and a diethylcellulose film. As such a cellulose acetate-based resin film, a commercially available product such as "Fujitec TD80", "Fujitec TD80UF", and "Fuj itec TD80UZ" sold by Fujifilm Co., Ltd., by Konica-Minolta Opto can be used. (KC8UX2M), "KC8UY", and "KC4UEW" (the above are all trade names) sold by the company. The adhesive to be used for bonding the second protective film and the polarizing film is not particularly limited, and various types of adhesives previously used as a bonding agent for a polarizing film and a cycloolefin resin film can be used in the same manner, but it is preferred. The same as the adhesive used for the above cycloolefin-based resin film. When the film is bonded to the film using -41 - 201235714, in order to improve the adhesion, the adhesion surface to the second protective film and/or the polarizing film bonded thereto may be suitably applied to the surface for improving the adhesion. deal with. When a second protective film is formed of a cellulose acetate-based resin film and bonded to a polarizing film using a water-based adhesive, 'one of the preferred surface treatments for the cellulose acetate-based resin film' can be saponified. . The saponification treatment is carried out by immersing the film in an aqueous solution of a base such as sodium hydroxide or potassium hydroxide. The second protective film is preferably thinner. However, if it is too thin, the strength is lowered and the workability tends to be deteriorated. On the other hand, if it is too thick, the transparency is lowered and the weight of the polarizing plate tends to be large. From such a viewpoint, the thickness of the second protective film is usually 10 to 200 μm, preferably 20 to 15 μm, more preferably 3 to 10 μm, when it is composed of a cellulose acetate resin. The second protective film is applied to the surface opposite to the surface to which the polarizing film is adhered, and can be subjected to surface treatment such as antiglare treatment, hard coating treatment, antistatic treatment, and antireflection treatment. [Method of Manufacturing Polarizing Plate] Next, a method of manufacturing the polarizing plate of the present invention will be described. As described above, in the present invention, a protective film made of a cycloolefin-based resin is bonded to a polarizing film via an adhesive to produce a polarizing plate. If necessary, a first protective film made of a cycloolefin-based resin may be bonded to one surface of the polarizing film as described above, and the other thermoplastic resin may be bonded to the other surface of the polarizing film via an adhesive. Second protective film. Further, the haze of the cycloolefin-based resin film does not exceed 0.5 °/ before the bonding of the polarizing film. -42 - 201235714 Scope 'The protective film made of the cycloolefin resin is brought into contact with a substantially solute organic solvent. This contact organic solvent is also referred to as "solvent treatment" in this specification. The organic solvent used for the solvent treatment is also referred to as a "good solvent" when the ring resin constituting the first protective film described above is separately contacted from one viewpoint. A mixture of an organic solvent which is not substantially changed in the cyclic olefin-based resin, which is also referred to as a "weak solvent", in the same manner as in the case of contacting the cycloolefin alone. When a certain organic solvent is equivalent to a cycloolefin-based resin film or a weak solvent, it can be determined by the following test, and the cycloolefin-based resin film of the protective film is cut to obtain about 1.0 g. Weigh to the third digit below the decimal point and weigh it to Fg. Further, the organic solvent was accurately weighed in units of grams to about 99.0 g of the third digit below the number of dots, and the mass was regarded as Sg. In the agent, the above precisely weighed resin film was completely impregnated and placed. After 24 hours, the shape or external change of the impregnated resin film was observed. Further, an organic solvent solution in which a resin film has been impregnated is still accurately weighed in grams units to the third digit below the decimal point, and its mass is regarded as Lg. The organic solvent is removed by drying, and the solid content is weighed, and the mass is regarded as Rg. Therefore, the amount of resin dissolved is obtained. When the resin film is completely dissolved, it becomes [F (= dry /{F + S (= about 100g) } xl00% by weight] (= about 1% by weight), so the solid content after drying should be left [L (= about L〇g) xF ( =| The above is not included in the agent, it is an olefin system (the following hydrocarbon system tree agent (for good solubility. First, it is treated as a single amount, to a small organic solution. So far, the residual film Jig) solution sentence 1 g) -43- 201235714

From the following formula (III /{F + S (= about l〇〇g) }g] (= about O.lg), the dissolution rate of the resin film was calculated. -xl 00 (wt%) [number 1] dissolution rate

R

LxF / (F + S) III) In this manner, the resin film after immersing in an organic solvent for 24 hours does not change the shape or appearance, and the dissolution rate is less than 1% by weight, and the organic solvent is a weak solvent. In the case other than the case where the shape or appearance is changed or the dissolution rate is 1% by weight or more, the organic solvent is a good solvent. Of course, when the shape or appearance is changed, and the solubility is 1% by weight or more, the organic solvent is also a good solvent. According to the experiment, in a state in which it does not dissolve but changes the shape or appearance of the film, there is a state in which the film is swollen without retaining the original state and the film is whitened. The stretched cyclic olefin-based resin film (trade name "ZENOR film", manufactured by Nippon Co., Ltd.) used in the examples described below was used as a sample, and after performing experiments in a plurality of organic solvents, the representative data was summarized as follows. in FIG. 1. In the table, "% j of solubility" is based on the above description. The column of "dissolution rate" is "-", which means that the appearance after immersion for 24 hours is observed only in the immersion test, but it is not performed. Until the measurement of the dissolution rate. Based on the observation of the appearance after 24 hours, the solubility was estimated to be about zero. -44- 201235714 [Table i] Solvent solubility After immersion change Good solvent toluene 6% Swelled xylene 14% Swelling cyclohexane 98% Dissolved methylcyclohexane 100% Dissolved ethylcyclohexane 99% Dissolved hexane Up to 1% Alkyd heptane is less than 1% Albino pentylene - Albino tetrahydrofuran is less than 1% Alkyd diethyl ether - Albino dichloromethane is less than 1% Albino chloroform 8% Swelling weak solvent methyl ethyl ketone is less than 1% No change, methyl isobutyl ketone, less than 1%, no change, cyclohexanone, less than 1%, no change, ethyl acetate, less than 1%, no change, isopropyl acetate, less than 1%, no change, propyl acetate, less than 1%. Change of butyl acetate is less than 1% No change of isopropyl alcohol is less than 1% No change of butanol is less than 1% No change Based on this result and the experience of the present inventors so far, cyclohexane, methylcyclohexane An alicyclic hydrocarbon such as ethylcyclohexane has a solubility ratio of a cycloolefin-based resin of approximately 1% by weight and is classified as a good solvent. Further, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; aliphatic ethers such as diethyl ether and tetrahydrofuran; and aliphatic groups such as pentane, hexane and heptane. The solubility rate of the hydrocarbon-based cycloolefin-based resin may be 1% -45 to 201235714 or more and less than 1%. However, since the shape or appearance are changed, it is classified as a good solvent. On the other hand, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aliphatic alcohols such as isopropyl alcohol and butanol, and ethyl acetate, propyl acetate, and isopropyl acetate. The aliphatic esters such as esters and butyl acetates have a solubility of less than 1% in the cycloolefin-based resin, and are classified as weak solvents since they do not change the shape or appearance of the film. In the organic solvent shown above, it has been found that an alicyclic hydrocarbon which is classified as a good solvent by dissolving a cycloolefin-based resin does not excessively erode the cycloolefin-based resin even when it is used alone, and is effective for improving the polarizing film. Adhesion. Therefore, from another viewpoint of the present invention, the organic solvent used for the solvent treatment described above contains an alicyclic hydrocarbon. The alicyclic hydrocarbon should typically be a compound of formula (I) as previously illustrated. When an alicyclic hydrocarbon is used, a mixed solvent containing a weak solvent in addition to the alicyclic hydrocarbon is advantageous. The weak solvent to be mixed in the alicyclic hydrocarbon is preferably an alkyl ester of an organic acid, which is also an acetate as exemplified above. In the present invention, it is important to carry out solvent treatment so as not to excessively erode the cycloolefin-based resin film, and to use a haze of the cycloolefin-based resin film after the solvent treatment as an index of no excessive erosion. When the surface of the cycloolefin-based resin film is eroded, the adhesion to the polarizing film is increased, but the optical properties of the cycloolefin-based resin film are impaired. Therefore, the solvent treatment is carried out so that the haze of the treated cycloolefin-based resin film does not exceed 0.5%. The haze at this time is preferably not more than 0.3%, more preferably not more than 0.2%. The smog is defined in JIS K 7 1 3 6:2000 "Haze for Plastics - Transparent Materials - 46-201235714", which is defined by (diffusion transmittance / total light transmittance) X1 00 (%) value. Further, when the etching is performed by the solvent treatment, the phase difference of the film is eliminated, and the in-plane phase difference tends to be lowered. Therefore, when the cycloolefin-based resin film is stretched to impart an in-plane retardation 値, the amount of change in the in-plane phase difference 环 of the cycloolefin-based resin film by the solvent treatment is effectively an index which does not excessively erode. Specifically, when the cycloolefin-based resin film has an in-plane retardation 3 of 3 Onm or more before the solvent treatment, the in-plane phase difference 以 after the solvent treatment is more than 3 nm than the in-plane phase difference before the solvent treatment, but Less than the mode, in other words, the amount of decrease in the in-plane phase difference 溶剂 after the solvent treatment with respect to the in-plane phase difference 溶剂 before the solvent treatment (in-plane phase difference before solvent treatment 値 - in-plane phase after solvent treatment) The ratio is 3 nm or less, and solvent treatment is preferred. The amount of decrease in the in-plane phase difference 溶剂 after the solvent treatment is more preferably 2.5 nm or less, and particularly preferably 2 nm or less, with respect to the in-plane phase difference 値 before the solvent treatment. If the amount of reduction is large, when the obtained polarizing plate is used in a liquid crystal display device, there is a possibility that display characteristics are affected. When the alicyclic hydrocarbon is used alone in the solvent treatment, the amount of decrease in the in-plane phase difference 稍 tends to be slightly large. Therefore, in view of this, the alicyclic hydrocarbon is preferably used in combination with a weak solvent. The in-plane phase difference 値Re of the film is such that the refractive index of the in-plane 遅 phase of the film is nx′ in the in-plane phase axis direction (the direction orthogonal to the 遅 phase axis in the plane) Ny, when the thickness is d, the enthalpy defined by the following formula (IV) can be measured using various commercially available phase difference meters.

Re=(nx-ny)xd (IV) -47- 201235714 When a mixed organic solvent is used, the mixing ratio can be determined in consideration of the haze or in-plane phase difference 环 of the cycloolefin resin film after the solvent treatment. In the present invention, the polarizing plate can be produced through the following steps (i) to (i i i ). When the first protective film made of a cycloolefin resin is bonded to one surface of the polarizing film, and the second protective film made of another thermoplastic resin is bonded to the other surface of the polarizing film, the following (iv) is used. Step (i) a solvent treatment step of treating the surface of the cycloolefin resin film with an organic solvent substantially free of solute as described above, (ii) a drying step of drying the above organic solvent, (i ii ) organic In the solvent treatment, the dried cycloolefin resin film is subjected to a first bonding step of bonding a polarizing film via an adhesive so that the treated surface is a bonding surface, and (iv) a bonding film is bonded to the polarizing film. A second bonding step of bonding a second protective film made of a thermoplastic resin film to the surface on the opposite side of the surface of the olefin-based resin film by an adhesive. In the solvent treatment step (i), the cycloolefin resin film is brought into contact with the organic solvent described above. Specifically, a method of applying the organic solvent to the surface of the cycloolefin-based resin film is preferably used. Therefore, the coating method used may be a casting method, a meyer bar coating method, a gravure coating method, a comma coating method, a squeegee method, a die coating method, a dip coating method, a spray method, or the like. A well-known method. The treatment surface may be one or both sides of the cycloolefin-based resin film, but the treatment is applied to the surface of the polarizing film-48-201235714. Next, in the above drying step (ii), the treatment of the cycloolefin resin is carried out. The surface of the film is dried with an organic solvent. Although it can be naturally dried, it is preferably dried at a temperature lower than the glass transition point of the cycloolefin-based resin film from the viewpoint of preventing deformation of the film when it is dried by heating. This drying step (?) may also be carried out in parallel with the solvent treatment step (i), and it is preferred to carry out the operation of drying the organic solvent while treating the cycloolefin resin film in an organic solvent. Specifically, a method of applying an organic solvent while blowing a coated surface, etc., in the first bonding step (iii), treating a cycloolefin-based brand film treated with an organic solvent The method of bonding the surface is bonded to the polarizing film via an adhesive. The bonding method herein can be generally known, for example, by a casting method, a meyer bar coating method, a gravure coating method, a comma coating method, a doctor blade method, a die coating method, A method of applying an adhesive to a polarizing film and/or an adhesive surface bonded to a cycloolefin-based resin film by a dip coating method, a spray method, or the like, and superposing the two. In the casting method, the film of the object to be coated is moved in the direction perpendicular to the vertical direction, the horizontal direction, or the oblique direction between the two, and the adhesive is spread on the surface thereof to spread the film. The method. After the application of the pressure-sensitive adhesive, the polarizing film and the cycloolefin resin film are sandwiched by a nip or the like to bond them. Further, when the adhesive is dropped between the films and then expanded by a press or the like to be uniformly pressed, the material of the rolls to be used may be metal or rubber, and each of the two rolls may be used. The roller system can be the same material or a different material. When the cycloolefin resin film is bonded to the polarizing film via an adhesive, when the water-based adhesive is used, when the water-based adhesive is used, when the curable adhesive is used, the adhesive layer is irradiated by the active energy ray. hardening. The drying treatment can be carried out, for example, by blowing hot air. The temperature is usually in the range of from 40 to 1001, preferably in the range of from 60 to 100 °C. Further, the drying time is usually 20 to 1, 2.00 seconds. On the other hand, the active energy line used for the active energy ray irradiation may be ultraviolet rays, electron beams, X-rays, visible rays, etc., and ultraviolet rays are generally used. The active energy ray may be irradiated on the surface of the polarizing film opposite to the surface on which the cycloolefin-based resin film is bonded, as long as it is irradiated with the necessary strength and amount to cure the adhesive layer, and bonded by another thermoplastic resin. In the case of the second protective film, the second bonding step (iv) is further performed. In this step, the same method as in the above-mentioned first bonding step (iii) can be employed. The second bonding step (iv) is preferably carried out simultaneously with the first bonding step (iii). The thickness of the adhesive layer obtained after drying or hardening is usually about 0.01 to 5 μm, but when using a water-based adhesive, it may be ι μιη or less. On the other hand, when a curable adhesive is used, it is preferably 2 μm or less. If the adhesive layer is too thin, the adhesion may be insufficient. On the other hand, if the adhesive layer is too thick, the appearance of the polarizing plate may be poor. [Polarizing Plate] The polarizing plate thus obtained is a high adhesion between the polarizing film and the cycloolefin resin film. In other words, the protective film formed of a cycloolefin-based resin is bonded to the polarizing film in which the dichroic dye has been adsorbed to the polyvinyl alcohol-based resin, and the above-mentioned cycloolefin-based resin is used. - 201235714 Protective film is a polarizing plate with a polarizing film of -5N/25mm or more via the above-mentioned adhesive, in a state where the haze is not more than 0.5%, and the organic solvent is treated by the above-mentioned adhesive. . Further, an adhesive which adsorbs a polarizing film in a polyvinyl alcohol-based resin is bonded to the other surface of the first protective film made of a cycloolefin-based resin, and a thermoplastic protective film is bonded via an adhesive. The olefin has a haze of not more than 0.5%, and is bonded to the polarizing film via the adhesive in a state where the smog is not more than 0.5% in a state treated by the prior agent. A polarizer above the adhesion. In any of the polarizing plates, the polarizing agent is applied to the polarizing agent by a thickness of 0.7 N/25 mm or more, more preferably 0.8 N/25 mm or more. Here, the olefin-based resin film was measured for the polarizing film as follows. That is, the film of the cycloolefin-based resin is bonded to one surface as described so far, and the adhesion to the polarizing film formed on the other surface of the polarizing film via the adhesive-adhesive resin is higher than that of the above-mentioned ring film. The second protective film is also larger, and the polarizing plate is made to be adhered as needed. A polarizing plate with an adhesive attached thereto is provided on the side of the cycloolefin resin film, and a test piece having a width of 200 mm is cut, and the adhesive surface is bonded to the adhesion of the glass adhesive to the glass plate, and then used. In the tensile test, the adhesive force applied to the upper film by the previously described agent is one side of the dichroic dye, and the organic protective film described in the first protective film formed of the polarizing resin via the film is 0.5. The adhesion of the N/25mm resin is the adhesion, for example, the first protective layer formed on the polarizing film is dried or hardened by another thermoplastic olefin resin thinner. 25mmx length plate, fully improved machine, clamp test -51 - 201235714 The second protective film and polarizing film at one end of the length direction (the side with a width of 25mm), at a temperature of 23 ° C, relative humidity of 60%, 9 (Γ peeling test) in accordance with JIS K 6854-1:1 999 "Adhesive-Peeling Strength Test Method - Part 1: 90-degree peeling" at a crosshead speed of 200 mm/min (clamp moving speed). The average peeling force (unit: N/25 mm) at this time is regarded as the adhesion of the cycloolefin-based resin film to the polarizing film. If the adhesive force is too small, the interface between the polarizing film and the cycloolefin-based resin film peels off, as described above. When the polarizing plate is adhered to the liquid crystal cell, only the cycloolefin resin film remains on the liquid crystal cell when rework is necessary. On the other hand, the larger the adhesion, the better, but if the adhesive force is to be increased, The treatment (erosion) of the cycloolefin-based resin film by the organic solvent is excessive, and the haze of the cycloolefin-based resin film is improved to impair the optical properties. Therefore, it is important to maintain the cycloolefin-based resin film. Solvent treatment is carried out to improve the adhesion of the cycloolefin-based resin film to the polarizing film. The polarizing plate obtained by the present invention is a polarizing film which can be bonded to a cycloolefin-based resin film of a polarizing film. On the opposite side of the surface, an adhesive layer is provided. The adhesive layer can be used for the bonding of the polarizing plate to the liquid crystal cell, and to other functional films, for example, to the phase difference film, and to the other layers. Among the agents, those based on an acrylic polymer, a polyoxymethylene polymer, a polyester, a polyurethane, a polyether or the like can be used. Among them, an acrylic adhesive is preferably used. Excellent optical transparency, moderate wettability or cohesion, excellent adhesion, weather resistance -52-201235714, heat resistance, etc., no swelling or peeling under heating or humidification conditions In the acrylic adhesive, an alkyl ester of (meth)acrylic acid having an alkyl group having a carbon number of 20 or less, such as a methyl group, an ethyl group or a butyl group, and (meth)acrylic acid or (meth) Acrylic-based monomer having a functional group-containing acrylic monomer formed by hydroxyethyl acrylate or the like, preferably having a weight-average molecular weight of 100,000 or more, preferably having a glass transition temperature of 25 ° C or less. It is suitable as a base polymer. The formation of the adhesive layer can be adjusted, for example, by dissolving or dispersing the adhesive composition such as the above base polymer in an organic solvent such as toluene or ethyl acetate. The weight % solution is formed by forming an adhesive layer on the protective film, moving it to a polarizing plate to form an adhesive layer, etc. In the adhesive, in addition to the above-mentioned base polymer, a crosslinking agent is generally used. Further, it is intended to bond the liquid crystal cells, preferably with a decane coupling agent. The thickness of the adhesive layer can be determined according to the adhesion or the like, and is usually in the range of 1 to 5 Ο μηη. In the adhesive, a filler, a pigment, a coloring agent, an antioxidant, an ultraviolet absorber or the like which is formed by mixing inorganic powder such as glass fiber, glass beads, resin beads or metal powder may be blended as needed. Examples of the ultraviolet absorber include a salicylate-based compound, a diphenylketone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, and a nickel-salted salt-based compound. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the example, the parts and % of the amount or content used are based on the weight unless otherwise specified. Further, the in-plane phase difference 値 and the thickness direction phase difference 薄膜 of the film were obtained by using a phase difference measuring device "KOBRA-2 1 ADH" manufactured by Oji Scientific Instruments Co., Ltd. as a monochromatic light having a wavelength of 5 5 9 nm. The flaw detected by the rotation detection photon method. [Production Example 1] Preparation of a polarizing film A polyvinyl alcohol film having a thickness of about 75, and an average degree of polymerization of about 2,400 and a saponification degree of 99.9 mol% or more was immersed in pure water at 30 ° C, and the weight ratio of iodine/potassium iodide/water was used. It was impregnated and dyed at 30 ° C in an aqueous solution of 0.02/2/1 00. Then, the aqueous solution of potassium iodide/boric acid/water in a weight ratio of 12/5/100 was immersed at 5 6.5 ° C to carry out boric acid treatment. Subsequently, the mixture was washed with pure water at 8 ° C, and then dried at 65 ° C to obtain a polarizing film having a thickness of about 30 μm in which iodine was adsorbed and aligned in polyvinyl alcohol. The extension was mainly carried out by the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times. [Production Example 2] Preparation of Adhesive Composition Ethyl acetonitrile-modified polyvinyl alcohol [trade name "Gohsefimer Ζ-200", manufactured by Nippon Synthetic Chemical Industry Co., Ltd., viscosity of 4% aqueous solution = 12.4 mPa · Sesec, degree of saponification=99.1 mol%] dissolved in pure water to prepare an aqueous solution having a concentration of 1% by weight. The sodium acetalate of the aqueous solution of the modified polyvinyl alcohol modified polyvinyl alcohol and the crosslinking agent is mixed in such a manner that the weight ratio of the solid component of the latter is 1:0.1, and more preferably 100 parts by weight relative to water. In other words, the ethylene-modified vinyl alcohol was added in a manner of 2.5 parts, and the adhesive composition was prepared by diluting -54-201235714 with pure water. [Comparative Example] (A) Protective film for a stretched cyclic olefin-based resin film having a thickness of 25 μm [trade name "ZENOR film" manufactured by Nippon Co., Ltd., in-plane phase difference 値 = 90 nm, thickness direction phase difference 値 = 79 nm On one side, it is subjected to corona treatment to become a protective film on the side. Using a haze transmittance meter in accordance with JIS K 7361-1:1997 "Test Method for Total Light Transmittance of Plastic Transparent Materials - Part 1: Single Beam Method" [(share) Murakami Color Technology Research Institute" HRdOO "] to determine the smog of the film' shown in Table 2. Further, a side of a cellulose acetate-based resin film (trade name "KC4UEW" having a thickness of 40 μm, manufactured by Konica-Minolta Opto Co., Ltd.) was subjected to corona treatment to form a protective film on the other side. (B) Preparation of Polarizing Plate The adhesive composition prepared in Production Example 2 was applied to both surfaces of the polarizing film produced in Production Example 1 at 23 ° C, and an adhesive device [made by Fujipla Co., Ltd.] was used. LPA3 3 0 1 ′′], the corona-treated stretched olefin-based resin film is bonded to one surface of the adhesive-coated surface so that the corona-treated surface thereof is bonded to the polarizing film. The corona-treated cellulose acetate-based resin film was bonded to the other adhesive-coated surface. It was dried at 80 ° C for 5 minutes to prepare a polarizing plate. 201235714 (C) Evaluation of Adhesive Force The surface of the cycloolefin-based resin film of the polarizing plate produced above was subjected to corona treatment, and then an acrylic adhesive sheet was bonded to the corona-treated surface. The obtained polarizing plate with an adhesive was cut into a test piece having a width of 25 mm and a length of about 200 mm, and the adhesive surface was attached to the soda glass, and then subjected to an autoclave at a pressure of 5 kgf/cm 2 and a temperature of 50 ° C. The pressure treatment was carried out for one minute, and it was allowed to stand for one day in an environment of a temperature of 23 ° C and a relative humidity of 60%. In this state, a cellulose acetate-based resin film and a polarizing film of one end (one side having a width of 25 mm) in the longitudinal direction of the test piece were sandwiched by a universal tensile tester ("AG-1" manufactured by Shimadzu Corporation). , at a temperature of 23 ° C and a relative humidity of 60%, at a crosshead speed of 200 mm / min (clamp moving speed), a 90 ° peel test (according to JIS K 6854-1:1 999 "adhesive - peel adhesion" Strength Test Method - Part 1: 90 degree peeling j, and the adhesion between the cycloolefin-based resin film and the polarizing film was evaluated. The results are shown in Table 2. [Example 1] As the side of the above comparative example On one side of the stretched olefin-based resin film used for the protective film, a ruthenium coater [first physicochemical (rod) bar coater] was applied, and toluene: methyl ethyl ketone = 1:9 (volume ratio) was applied. The organic solvent to be mixed is applied to the coated surface by a blower. The haze of the treated cycloolefin-based resin film is measured by the method shown in (A) of the comparative example, and is shown in Table 2. Results. Further, visual observation of the solvent-treated cycloolefin system The surface of the grease film-56-201235714 was uneven, and although the results were not clearly observed, the state of the unevenness was carefully observed. Similarly, the in-plane phase difference 値 was measured for the solvent-treated ring-fired film.値 before the self-treatment (change (the phase difference 当作 is lower than that before the treatment) is 0.3 nm. In the following examples and comparative examples, the olefin-based resin film in the solvent is the same as in this example. The smog is measured and the in-plane phase difference 値 is measured. The smog system shows the “haze” column, and the surface unevenness is “uneven” in Table 2 by the following three stages. The results of the evaluation and the change in the phase difference 自 from the self-treatment surface show the "Re change" in Table 2 (Evaluation criteria for the surface unevenness of the film after the solvent treatment) None: No unevenness was observed at all. : It is not clearly seen, but if observed carefully, the shell IJ is in the state of Example 1. Strong: The unevenness can be clearly confirmed. The solvent-treated stretched cyclic olefin-based resin film is coated. After corona treatment, for one side of the polarizing film The other surface of the light-shielding film was bonded to a corona cellulose-based resin film which was the same as that of the comparative example, and the other layer was the same as the comparative example. The evaluation was carried out in the same manner as in the control example (C). The adhesion between the cycloolefin-based resin film of the plate and the polarizing film is not satisfactory. It is found to be 90 nm of the hydrocarbon-based resin. The difference is the ring after the treatment, and the surface is shown in the L column of Table 2. In the column of the former film, it can be confirmed that the solvent is not combined, and the polarized light is polarized in the vinegar which is subjected to partial treatment, and Table 2 -57-201235714 [Example 2] except that the mixed solvent is changed to toluene: methyl ethyl ketone A polarizing plate was produced and evaluated in the same manner as in Example 1 except that the ratio was 2:8 (volume ratio). In Table 2, the haze of the cycloolefin-based resin film after the solvent treatment, the observation of the surface unevenness, the change in the in-plane phase difference 値, and the adhesion between the cycloolefin-based resin film of the polarizing plate and the polarizing film are summarized. . [Comparative Example 1] A polarizing plate was produced and evaluated in the same manner as in Example 1 except that the mixed solvent was changed to toluene: methyl ethyl ketone = 3:7 (volume ratio). In Table 2, the haze of the cycloolefin-based resin film after the solvent treatment, the observation of the surface unevenness, the change in the in-plane phase difference 値, and the adhesion between the cycloolefin-based resin film of the polarizing plate and the polarizing film are summarized. . [Example 3] On one surface of the same stretched cycloolefin-based resin film used as the protective film on one side of Example 1, the same coater as in Example 1 was used to apply cyclohexane to carry out solvent treatment. . Here, after the completion of the coating, since the cyclohexane has evaporated and dried, it is not blown by the blower. Table 2 summarizes the observation results of the haze and surface unevenness of the cycloolefin-based resin film after the solvent treatment and the change in the in-plane phase difference 値. In addition, a polarizing plate was produced in the same manner as in Example 1 except that the solvent-treated surface of the stretched cycloolefin-based resin film treated with cyclohexane was subjected to corona treatment, and the polarizing film was bonded to one surface. The adhesion between the cycloolefin-based resin film of the polarizing plate of -58-201235714 and the polarizing film was evaluated by the same method as in Example 1: The results are shown in Table 2. [Example 4] Methylcyclohexane was applied to one surface of the same stretched cyclic olefin-based resin film used as the protective film of the first embodiment, using the same coater as in Example 1. Solvent treatment. In this example, the coated surface was blown with a blower. Table 2 summarizes the results of observation of haze, surface unevenness, and in-plane retardation 値 of the cycloolefin resin film after solvent treatment. In the same manner as in Example 1, except that the solvent-treated surface of the stretched cycloolefin-based resin film treated with methylcyclohexane was subjected to corona treatment, and the polarizing film was bonded to one surface, the polarizing film was produced in the same manner as in Example 1. board. The adhesion between the cycloolefin-based resin film of the obtained polarizing plate and the polarizing film was evaluated by the same method as in Example 1, and the results are shown in Table 2 [Example 5] except that the organic solvent was changed to ethylcyclohexane. The same experiment as in Example 4 was carried out for the alkane, and the results are summarized in Table 2. [Examples 6 to 13] A mixed solvent of methylcyclohexane or ethylcyclohexane in which an organic solvent is a good solvent and ethyl acetate, isopropyl acetate or propyl acetate of a weak solvent, and the respective combinations thereof The volume was as shown in Table 2, and the other experiments were carried out in the same manner as in Example 4. The results are summarized in Table 2. -59-201235714 [Examples 14 and 15] A mixed solvent of a heptane of a good solvent and a methyl ethyl ketone of a weak solvent in an organic solvent, and the volume of both was the same as that of Example 4, and the other system was the same as that of Example 4. The experimental results are summarized in Table 2. [Comparative Example 2] The organic solvent was changed to heptane, and the other experiments were carried out in the same manner as in Example 4, and the total results in Table 2 were obtained. [Table 2] Example No. Film adhesion after treatment liquid treatment (volume ratio in parentheses) Variation in haze unevenness Recontrol Example (not treated) 0.1% — — 0.22N/25mm Η Example 1 Toluene: Methyl Ethyl ketone (1:9) 0.1% weak -0.3 mm 0.82 N/25 mm ΪΪ Example 2 Toluene: methyl ethyl ketone (2:8) 0.1% weak -0.5 mm 1.91 N/25 mm Comparative Example 1 Toluene: A Base ethyl ketone (3:7) 0.6% strong-1.2mm can not be stripped a Example 3 cyclohexanone 0.1% Λττ -2.2mm 0.84N/25mm 苡 Example 4 methylcyclohexanone 0.1% no -5.6mm 1.83 N/25mm 苡Example 5 Ethylcyclohexanone 0.1% None•9.1mm 1.91N/25mm K Example 6 Methylcyclohexane: ethyl acetate (5:5) 0.1% None-0.3mm 1.40N/25mm 0 Example 7 Ethylcyclohexane: ethyl acetate (2:8) 0.1% ftyr pick-0.8mm can not be stripped β Example 8 Ethylcyclohexane: isopropyl acetate (1:9) 0.1% 4nt Μ -0.2 mm 0.61 N/25 mm 贲 Example 9 Ethylcyclohexane: isopropyl acetate (2:8) 0.1% None-0.4 mm 2.92 N/25 mm 贲 Example 1 〇ethylcyclohexane: isopropyl acetate Ester (3:7) 0.1% None-1.1mm No peeling Example 11 Ethylcyclohexane: Propyl acetate (2:8) 0.1% ifnr Μ -0 .4 mm 0.83 N/25 mm Example Ethylcyclohexane: Propyl acetate (3:7) 0.1% Μ -1.2 mm 3.74 N/25 mm Example 13 Ethylcyclohexane: propyl acetate (4:6) 0.1 % • fnr m -2.2 mm 3.75 N/25 mm Η Example 庚 Heptane: methyl ethyl ketone (8:2) 0.1% weak - 0.3 mm 0.65 N / 25 mm Example 15 Heptane: methyl ethyl ketone ( 9:1) 0.3% weak - 0.5 mm 0.69 N / 25 mm Comparative Example 2 Heptane 0.5% Strong - 0.8 mm 0.77 N / 25 mm - 60 - 201235714 As shown in Table 2, using a cycloolefin system which was not subjected to solvent treatment In the comparative example of the resin film, the adhesion between the polarizing film and the cycloolefin resin film was low. On the other hand, in Comparative Example 1 in which the ratio of toluene in the toluene/methyl ethyl ketone mixed solvent used for the solvent treatment was increased to easily erode the cycloolefin resin film, adhesion between the polarizing film and the cycloolefin resin film was observed. The force is high, but the haze of the cycloolefin-based resin film is as high as 0.6%, and the optical characteristics at the time of polarizing plate formation cannot be satisfied. The smog of the cycloolefin-based resin film can be obtained in Examples 1 and 2 in which the ratio of toluene in the toluene/methyl ethyl ketone mixed solvent used for the solvent treatment is 10% by volume or 20% by volume. Maintaining a low enthalpy of 0.1% while increasing the adhesion between the polarizing film and the cycloolefin-based resin film. Further, Example 3 in which a solvent was treated with cyclohexane, methylcyclohexane or ethylcyclohexane. In the same manner, the haze of the cycloolefin-based resin film can be kept low at 0.1%, and the adhesion between the polarizing film and the cycloolefin-based resin film can be improved. In this case, in particular, in Example 4 in which solvent treatment was carried out using methylcyclohexane and Example 5 in which ethylcyclohexane was used, the in-plane phase difference of the cycloolefin-based resin film was observed by solvent treatment. Decrease the tendency to become slightly larger. On the other hand, in Examples 6 to 13 in which the acetate of the weak solvent is mixed with the alicyclic hydrocarbon of the good solvent, the reduction in the in-plane phase difference 环 of the cycloolefin-based resin film can be suppressed. When the thickness is 3 nm or less, the adhesion between the polarizing film and the cycloolefin resin film is increased. In Examples 3 to 3 which use an alicyclic hydrocarbon, the occurrence of unevenness after solvent treatment is suppressed, and the favorable appearance and visibility of the cycloolefin resin film can be maintained, as compared with Examples 1 and 2 in which toluene is used. Improve adhesion to polarizing film -61 - 201235714. In Comparative Example 2 in which the solvent was treated with heptane in a good solvent, the adhesion between the polarizing film and the cycloolefin resin film was increased, but the haze of the cycloolefin resin film was increased to 0.5%. Since the surface unevenness was also observed after the treatment, the optical characteristics at the time of polarizing plate formation could not be satisfied. In Examples 14 and 15 in which methyl ethyl ketone of a weak solvent was mixed with heptane, surface unevenness was improved, and smog rise and in-plane retardation of the cycloolefin resin film were suppressed. In the state where the crucible is lowered, the adhesion between the polarizing film and the cycloolefin resin film is improved. -62-

Claims (1)

201235714 VII. Patent application scope: 1. A method for producing a polarizing plate which is formed by a cycloolefin resin bonded to a polarizing film in which a dichroic dye has been adsorbed and oriented in a polyvinyl alcohol resin. A protective film for producing a polarizing plate, comprising: the protective film formed of the cycloolefin-based resin, wherein the contact olefin is contacted so that the haze of the protective film is not more than 0.5% The organic solvent which is changed by the resin and the organic solvent which does not substantially change the cyclic olefin resin by contact, and the organic solvent which does not substantially contain a solute, is attached to the polarizing film 〇2_ via the adhesive. A method for producing a polarizing plate in which a first protective film made of a cycloolefin-based resin is bonded to one surface of a polarizing film in which a dichroic dye has been adsorbed and attached to a polyvinyl alcohol-based resin, and an adhesive film is bonded thereto. The other side of the polarizing film is a method of manufacturing a polarizing plate by attaching a second protective film made of a thermoplastic resin via an adhesive. The first protective film formed of the cycloolefin-based resin is contacted with an organic solvent which changes the cycloolefin resin by contact so that the haze of the first protective film does not exceed 0.5%. The mixture of organic solvents which substantially changes the cycloolefin resin by contact is substantially free of a solute mixed organic solvent, and then bonded to the polarizing film via the adhesive. (3) A method for producing a polarizing plate which is formed by a cycloolefin resin in which a dichroic dye is adsorbed and aligned on a polarizing film of a polyvinyl alcohol-based resin, and bonded via an adhesive-63-201235714 A film for producing a polarizing plate, comprising: the protective film formed of the cycloolefin-based resin, wherein the protective film has a haze of not more than 0.5%, and is in contact with an alicyclic hydrocarbon substantially After the organic solvent which does not contain a solute, it adheres to the said polarizing film via the said adhesive agent. 4. A method of producing a polarizing plate, wherein a first protective film made of a cycloolefin-based resin is bonded to one surface of a polarizing film in which a dichroic dye has been adsorbed to a polyvinyl alcohol-based resin, via an adhesive; a method of producing a polarizing plate by bonding a second protective film made of a thermoplastic resin to the other surface of the polarizing film via an adhesive, comprising: forming the first protective film made of the cycloolefin-based resin; The organic solvent having an alicyclic hydrocarbon and substantially containing no solute is contacted so that the haze of the first protective film is not more than 0.5%, and then bonded to the polarizing film via the adhesive. 5. The production method according to claim 3, wherein the alicyclic hydrocarbon is a compound represented by the following formula (I): (wherein 'm is an integer of 2 to 6, and R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The manufacturing method according to any one of the items 3 to 5, wherein the organic solvent is in addition to the alicyclic hydrocarbon, and further comprises a cyclic olefin system which is not contacted by -64 - 201235714 A mixed solvent of an organic solvent in which the resin causes substantial changes. 7. The production method according to claim 6, wherein the alkyl ester-based organic acid is an alkyl ester of the organic solvent-free organic acid, which is a manufacturing method of the seventh aspect of the invention, wherein the organic acid is Alkyl ester acetate. 9. The production method according to claim 8, wherein the acetate is ethyl acetate, isopropyl acetate or propyl acetate. 10. The production method according to any one of the first to ninth aspects, wherein the protective film made of the cycloolefin-based resin has an in-plane retardation of 30 nm or more before contact with the organic solvent. The in-plane phase difference 値 of the protective film after the contact is made more than 3 nm but not less than the in-plane phase difference 接触 before the contact. 11. The production method according to any one of the first to tenth aspects of the invention, wherein the protective film formed of the cycloolefin-based resin is brought into contact with the organic solvent, and the operation of drying the organic solvent is simultaneously performed. . 1. The manufacturing method according to any one of the items of the present invention, wherein the adhesive is a water-based adhesive. 13. The production method according to claim 12, wherein the adhesive comprises a polyvinyl alcohol-based resin. -65- 201235714 Four designated representative maps: (1) The representative representative figure of this case is: None (2) The symbol of the representative figure is simple Explanation: None-3-201235714 If there is a chemical formula in the five cases, please reveal the characteristics that can best show the invention. Chemical formula: none