TW201839475A - Polarizing film with optical functional layer, and liquid crystal display device - Google Patents

Abstract

This polarizing film with an optical functional layer comprises an optical functional layer A containing a pigment and a polyvinyl alcohol-base polarizer P, and is characterized in that the distance x between the optical functional layer A and the polyvinyl alcohol-base polarizer P is less than or equal to 45 [mu]m. This polarizing film with an optical functional layer has an optical functional layer that has excellent stability over time, and contains a pigment such that the broadening of the color gamut by the pigment can be maintained.

Description

Polarized film with optical functional layer and liquid crystal display device

The present invention relates to a polarizing film having an optical functional layer having a photofunctional optical layer and a polarizing film having a polyvinyl alcohol-based polarizing member. The polarizing film with the optical function layer described above may be used as an optical film to form an image display device such as a liquid crystal display (LCD) or an organic EL display device.

BACKGROUND OF THE INVENTION Image display devices and the like are indispensable for arranging polarizing elements on both sides of a liquid crystal cell, and generally have a polarizing film attached thereto. When the polarizing film is attached to a liquid crystal cell, an adhesive is usually used. Further, in order to reduce the loss of light, in general, the polarizing film and the liquid crystal cell are adhered to each other using an adhesive. In this case, a polarizing film in which an adhesive is previously provided in the form of an adhesive layer on one side of the polarizing film with an adhesive layer is generally used, since it does not have to undergo a drying step when the polarizing film is fixed. advantage.

Further, it has been proposed to impart a color tone to a polarizing film by adding a dye or a pigment to the color of the pressure-sensitive adhesive layer to obtain a liquid crystal display having a high contrast (Patent Document 1). In recent years, the image display device has required brightness and vividness (i.e., wide color gamut), and the organic EL display device (OLED) has attracted attention, and the liquid crystal display device has also sought wide color gamut. As a method of broadening the color gamut of the liquid crystal display device, for example, a method of laminating a polarizing film by absorbing an adhesive layer containing a dye which absorbs a maximum wavelength in a range of a specific wavelength (560 to 610 nm) has been proposed. One side or both sides of the liquid crystal cell (Patent Documents 2 and 3).

CITATION LIST PATENT DOCUMENT Patent Document 1: Japanese Patent Publication No. 3052812. Patent Document 2: Japanese Patent Laid-Open No. 2011-039093. Patent Document 3: JP-A-2014-092611

SUMMARY OF THE INVENTION Problems to be Solved by the Invention The dye as described above may be contained in a film layer applied to an optical member in addition to the adhesive layer. In this manner, the optical layer containing the dye can be formed by including a pigment in the film layer or the resin layer such as the adhesive layer. However, in order to contain a dye in the optical functional layer, the optical functional layer in the optical functional layer deteriorates with time from the viewpoint of moisture permeability of the resin layer as the base of the optical functional layer, and the optical functional layer gradually fades. In particular, when the optical functional layer is a pigment-containing adhesive layer, the durability of the adhesive layer is insufficient from the viewpoint of moisture permeability, so that the adhesive layer dyed even by the initial pigmentation gradually fades. . Therefore, when the pigment in the optical functional layer (especially the adhesive layer) deteriorates with time, it is difficult to maintain a wide color gamut by the pigment.

An object of the present invention is to provide an optical functional layer-attached polarizing film having an optical functional layer containing a dye, which has excellent stability over time and maintains a wide color gamut by a pigment.

MEANS FOR SOLVING THE PROBLEMS The present inventors have found a polarizing film with an adhesive layer described below in order to solve the above problems, and have completed the present invention.

That is, the present invention relates to a polarizing film having an optical function layer, which is an optical functional layer containing a dye on at least one side of a polarizing film having a polyvinyl alcohol-based polarizing member, and a polarizing film with an optical functional layer The distance between the polyvinyl alcohol-based polarizer and the optical functional layer containing the dye is 45 μm or less. The distance between the polyvinyl alcohol-based polarizer and the optical functional layer is preferably 25 μm or less.

The polarizing film with the optical functional layer described above can be directly laminated with the above-mentioned adhesive layer using the polyvinyl alcohol-based polarizer.

In the polarizing film having the optical function layer, the polyvinyl alcohol-based polarizer and the pressure-sensitive adhesive layer may have at least one layer having a thickness of 45 μm or less and no dye.

In the polarizing film having the optical function layer, the polyvinyl alcohol-based polarizer preferably has an oxygen permeability of 1 {cm ³ /(m ^2. 24h·atm)} or less.

In the polarizing film having the optical function layer, the dye may be used for at least one of a wavelength region of 470 to 510 nm and a wavelength region of 570 to 610 nm having a maximum absorption wavelength.

In the polarizing film having the optical functional layer, a tetraazaporphyrin-based dye can be used as the dye.

The polarizing film with the optical functional layer is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the base polymer of the resin layer forming the optical functional layer.

In the polarizing film having the optical function layer, the thickness of the adhesive layer containing the dye is preferably 25 μm or less.

Further, the present invention relates to an image display device having the above-described polarizing film with an optical function layer.

Advantageous Effects of Invention The polarizing film with an optical function layer of the present invention has an optical functional layer containing a dye. The optical functional layer can absorb light of a part of the wavelength by the dye, thereby adjusting the overall hue of the liquid crystal display device, and can improve the vividness by using a wide color gamut. In particular, a dye having a maximum absorption wavelength in at least one of a wavelength region of 470 to 510 nm and a wavelength region of 570 to 610 nm can be absorbed in a wavelength region other than RGB (wavelength region 470 to 510 nm and/or wavelength region 570 to 610 nm). The unnecessary color luminescence in the color expression suppresses the aforementioned unnecessary light emission, and is particularly effective for wide color gamuting.

The dye fading of the optical functional layer containing the dye is known to be caused by the intrusion of oxygen in the atmosphere or in the resin into the optical functional layer, and is activated by heat to attack the dye. We believe that oxygen enters from the upper, lower, left and right sides of the adhesive layer.

In the polarizing film with an optical function layer of the present invention, the optical functional layer containing the dye can be applied to a polarizing film using a polyvinyl alcohol-based polarizing member. The polyvinyl alcohol-based polarizer has a low oxygen permeability and prevents oxygen from entering the optical functional layer from above or below the optical functional layer containing the dye. In addition, the polarizing film with the optical function layer of the present invention can be used with a separator having a low oxygen permeability on the other surface of the optical function layer during the period until the specific use, and on the other hand, the glass is used in a specific use. The adherend having a low oxygen content prevents oxygen from intruding into the optical functional layer and suppresses discoloration (decomposition) of the dye, thereby providing an optical functional layer which is stable over time and can maintain a wide color gamut.

Further, in the polarizing film with an optical function layer of the present invention, the optical functional layer containing the dye and the polyvinyl alcohol-based polarizer are laminated such that the distance is 45 μm or less. By setting the distance to 45 μm or less, it is possible to prevent oxygen from intruding from the end portion of the polarizing film with the optical function layer, and to suppress color fading (decomposition) of the end portion of the polarizing film with the optical function layer. The passage of time is still stable and maintains wide color gamuting.

(Embodiment for Carrying Out the Invention) Hereinafter, an embodiment of the polarizing film with an optical function layer of the present invention will be described in detail with reference to the drawings. However, the invention is not limited to the embodiments of the drawings.

As shown in Fig. 1, the polarizing film with an optical function layer of the present invention has a polyvinyl alcohol-based polarizer P and an optical functional layer A containing a pigment. The polyvinyl alcohol-based polarizer P and the optical functional layer A are laminated such that the distance x is 45 μm or less. The shorter the distance x, the more oxygen can be prevented from entering the end. The distance x is preferably 25 μm or less, more preferably 10 μm or less, and more preferably 5 μm or less and more preferably 1 μm or less.

Fig. 2 shows a state in which the polyvinyl alcohol-based polarizer P and the optical functional layer A are directly laminated (the aforementioned x = 0 μm). In addition, FIG. 2 exemplifies a case where a polarizing film (single-sided protective polarizing film) having a transparent protective film F is provided on one side of the polyvinyl alcohol-based polarizer P (on the side where the optical function layer A is not provided). In addition, FIG. 2 exemplifies a case where the optical layer A is provided with the substrate S, and the substrate S used for the period from the polarizing film with the optical function layer to the specific use may be a separator, a vapor deposited film, or the like. Specific examples of the use include glass, a transparent substrate on which a vapor deposited layer is laminated, and the like.

In the aspect of FIG. 2, the polyvinyl alcohol-based polarizer P and the optical functional layer A have a layer B having a thickness of 45 μm or less. In Fig. 3, the layer B is exemplified as one layer, but the layer B may be combined in multiple layers. The layer B may, for example, be an adhesive layer or a film layer. Further, the thickness of the layer B can be designed in accordance with the characteristics of each layer within a range of 45 μm or less.

In addition, in the aspect of FIG. 2, the polyvinyl alcohol-based polarizer P and the optical function layer A are directly laminated (the above-mentioned x=0 μm), and the optical functional layer A has a layer C. The layer C is exemplified as one layer, but the layer C may be combined in multiple layers. The layer C may, for example, be an adhesive layer, a surface treatment layer (a hard coat layer, an antiglare treatment layer, an antireflection layer, or the like). Further, the thickness of the layer C can be designed in accordance with the characteristics of each layer within a range of 45 μm or less. Layer C can also be combined with layer B for application.

The polarizing film with an optical function layer of the present invention has a polarizing film having a polyvinyl alcohol-based polarizing member and an optical functional layer containing a pigment. The following describes each component.

<Optical Functional Layer> The optical functional layer of the present invention is not particularly limited as long as it is a resin layer containing a dye. The resin layer may be a film layer, an adhesive layer or the like. The optical functional layer may be formed of a composition containing a base polymer and a pigment.

<Pigment> Various pigments can be used as the coloring matter contained in the optical functional layer of the present invention. Examples of the dye include a tetraazaporphyrin system, a porphyrin system, a cyanine system, an azo system, a pyrromethylene group, and a squaraine system. Various compounds such as a system, an oxaphthalocyanine system, and a squaraine system. From the viewpoint of broad color gamification, it is preferable to use a tetraazaporphyrin dye, a porphyrin dye, a cyanine dye, a squaraine dye, or a squaraine dye, and it is particularly preferable to use a tetraazaporphyrin. It is a pigment. The above-mentioned coloring matter is specifically disclosed in Japanese Laid-Open Patent Publication No. 2011-116818. These pigments may be used alone or in combination of two or more.

The dye is preferably one having a maximum absorption wavelength in at least one of a wavelength region of 470 to 510 nm and a wavelength region of 570 to 610 nm. A dye having a maximum absorption wavelength in the wavelength region can absorb unnecessary light emission in color expression, thereby suppressing the light emission, and is effective for wide color gamuting. A tetraazaporphyrin-based dye can be used as the dye having a maximum absorption wavelength in the wavelength region. The dye which exhibits a maximum absorption wavelength in the wavelength region of 570 to 610 nm, for example, a tetraazaporphyrin compound (trade name: PD-320, PD311) manufactured by Yamamoto Chemical Co., Ltd., and a porphyrazine compound (manufactured by Yamada Chemical Industry Co., Ltd.) Product name: FDG-007). In addition, the measurement of the maximum absorption wavelength of the dye was carried out by a spectrophotometer (V-570, manufactured by JASCO Corporation).

The pigment content of the optical functional layer of the present invention is adjusted according to the absorption wavelength region, the absorption coefficient and the type of the base polymer of the dye, but is usually 0.01 to 5 parts by weight, and 0.05 to 0.05 parts by weight relative to the base polymer. 3 parts by weight is preferred, and 0.1 to 1 part by weight is more preferred. In particular, when a tetraazaporphyrin dye is used, the above range is preferred.

<Adhesive Layer> The optical functional layer of the present invention may be an adhesive layer containing a pigment, and the adhesive layer may be formed of an adhesive composition containing an adhesive base polymer and a pigment. The type of the adhesive base polymer is not particularly limited, and examples thereof include a rubber-based polymer, a (meth)acrylic polymer, a polyoxymethylene polymer, an urethane polymer, and a vinyl alkyl ether. Various polymers such as a polymer, a polyvinyl alcohol polymer, a polyvinylpyrrolidone polymer, a polypropylene phthalamide polymer, and a cellulose polymer.

The adhesive composition of the present invention contains an adhesive base polymer as a main component. The main component refers to a component having the highest content ratio of the total solid content contained in the adhesive composition, and is, for example, a component which accounts for more than 50% by weight of the total solid content contained in the adhesive composition, and further refers to more than 70%. % by weight of ingredients.

Among these adhesive base polymers, those having excellent optical transparency, exhibiting suitable wettability, cohesiveness and adhesion properties, and excellent weather resistance and heat resistance are preferably used. A (meth)acrylic polymer can be suitably used for exhibiting the characteristics. Hereinafter, an acrylic adhesive which is a material for forming an adhesive layer, that is, a (meth)acrylic polymer containing a (meth)acrylic acid alkyl ester as a monomer unit, as a base polymer will be described.

<(Meth)Acrylic Polymer> The (meth)acrylic polymer usually contains a (meth)acrylic acid alkyl ester as a main component as a monomer unit. Further, (meth) acrylate means acrylate and/or methacrylate, and (meth) of the present invention is also agreed.

The (meth)acrylic acid alkyl ester constituting the main skeleton of the (meth)acrylic polymer may, for example, be a linear or branched alkyl group having 1 to 18 carbon atoms. These may be used alone or in combination. The average carbon number of the alkyl groups is preferably from 3 to 9.

Further, from the viewpoints of adhesion characteristics, durability, adjustment of phase difference, adjustment of refractive index, etc., it is possible to use an aromatic ring such as phenoxyethyl (meth)acrylate or benzyl (meth)acrylate. Alkyl acrylate.

In order to improve the adhesiveness and the heat resistance, one or more polymerizable functional groups having an unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group may be introduced into the (meth)acrylic polymer by copolymerization. Base comonomer. Specific examples of such comonomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate and (4-hydroxymethylcyclohexyl)- Hydroxy-containing monomer such as acrylate; carboxylated monomer such as (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid An acid anhydride group-containing monomer such as maleic anhydride or itaconic acid anhydride; a caprolactone adduct of acrylic acid; styrenesulfonic acid or allylsulfonic acid, 2-(methyl)acrylamido-2-methylpropane a sulfonic acid group-containing monomer such as sulfonic acid, (meth) acrylamide, propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid; 2-hydroxyethyl acrylonitrile A phosphate group-containing monomer or the like.

Further, examples of the monomer to be modified include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide or N. - (N-substituted) guanamine monomer such as hydroxymethyl (meth) acrylamide or N-hydroxymethylpropane (meth) acrylamide; amine ethyl (meth) acrylate, (meth) acrylate -N,N-dimethylaminoethyl ester, alkylaminoalkyl (meth)acrylate such as tributylbutyl (meth)acrylate; methoxyethyl (meth)acrylate An alkoxyalkyl (meth) acrylate monomer such as ethoxyethyl (meth) acrylate; N-(methyl) propylene oxymethylene succinimide or N-(methyl) Propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene decyl-8-oxy octamethyl succinimide, N-propylene fluorenyl Amber quinone imine monomer such as porphyrin; N-cyclohexylmaleimide or N-isopropylmaleimide, N-lauryl maleimide or N-phenylmaleimide And other maleic imine monomers; N-methyl Ikonium imine, N-ethyl Ikonium imine, N-butyl Ikonide, N-octylkonkine, An Ikonideimine monomer such as N-2-ethylhexyliconazole, N-cyclohexylkkonium imine, N-lauryl Icinoimine or the like.

Further, as the modifying monomer, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl may also be used. Piper Vinylpyr , vinyl pyrrole, vinyl imidazole, vinyl Azole, vinyl Vinyl, N-vinylcarboxylic acid decylamine, vinyl monomer such as styrene, α-methylstyrene, N-vinyl caprolactam; cyanoacrylate such as acrylonitrile or methacrylonitrile An epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (A) Glycol acrylate monomer such as acrylate or methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, fluoro (meth) acrylate, polyfluorene (methyl) An acrylate type monomer such as acrylate or 2-methoxyethyl acrylate or the like. Further, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.

Further, the copolymerizable monomer other than the above may be a decane-based monomer containing a ruthenium atom. Examples of the decane-based monomer include 3-propenylphosphonium propyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 4-vinyl butyl trimethoxy decane, and 4- Vinyl butyl triethoxy decane, 8-vinyloctyltrimethoxy decane, 8-vinyloctyltriethoxy decane, 10-methylpropenyl fluorenyltrimethoxydecane, 10-propene Anthracene trimethoxy decane, 10-methyl propylene fluorenyl decyl triethoxy decane, 10-propylene fluorenyl decyl triethoxy decane, and the like.

Further, as the comonomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A may also be used. Diepoxypropyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa a polyfunctional monomer having two or more unsaturated double bonds such as a (meth)acryl fluorenyl group or a vinyl group, such as an ester of a (meth)acrylic acid and a polyhydric alcohol, such as a methyl acrylate, or a polyester, a polyester (meth) acrylate having two or more unsaturated double bonds such as a (meth) acryl fluorenyl group or a vinyl group as a functional group similar to a monomer component, and a skeleton such as an epoxy group or a urethane group; Epoxy (meth) acrylate, urethane (meth) acrylate, and the like.

The weight ratio of the (meth)acrylic polymer in the total constituent monomer is based on the alkyl (meth)acrylate as a main component, and the ratio of the aforementioned comonomer in the (meth)acrylic polymer is The ratio of the comonomer is preferably from 0 to 20%, from 0.1 to 15%, more preferably from 0.1 to 10%, based on the total weight of the constituent monomers.

Among these comonomers, a hydroxyl group-containing monomer or a carboxyl group-containing monomer is preferably used from the viewpoints of adhesion, durability, and the like. A hydroxyl group-containing monomer and a carboxyl group-containing monomer may be used in combination. These comonomers become a reaction point with the crosslinking agent when the adhesive composition contains a crosslinking agent. Since the hydroxyl group-containing monomer, the carboxyl group-containing monomer, and the like have good reactivity with each other between the molecules and the crosslinking agent, it is preferred to use these monomers in order to enhance the cohesiveness and heat resistance of the obtained adhesive layer. From the viewpoint of reworkability, a hydroxyl group-containing monomer is preferred, and a carboxyl group-containing monomer is preferable from the viewpoint of both durability and reworkability.

When a monomer having a hydroxyl group is contained as the comonomer, the ratio is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, still more preferably 0.05 to 7% by weight. When a monomer having a carboxyl group is contained as the comonomer, the ratio is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, still more preferably 0.2 to 6% by weight.

The (meth)acrylic polymer of the present invention is usually one having a weight average molecular weight of from 500,000 to 3,000,000. In consideration of durability, particularly heat resistance, it is preferred to use a weight average molecular weight of 700,000 to 2.7 million. More than 800,000 to 2.5 million is appropriate. When the weight average molecular weight is less than 500,000, it is not preferable from the viewpoint of heat resistance. Further, if the weight average molecular weight becomes more than 3,000,000, a large amount of a diluting solvent is required to adjust the viscosity required for coating to increase the cost, which is not preferable. Further, the weight average molecular weight means a value measured by GPC (Gel Permeation Chromatography) and calculated in terms of polystyrene.

For the production of the (meth)acrylic polymer, a known production method such as radiation polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization such as solution polymerization or UV polymerization can be appropriately selected. Further, the obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

Further, in the solution polymerization, for example, ethyl acetate, toluene or the like can be used as the polymerization solvent. As a specific example of the solution polymerization, the reaction may be carried out by adding a polymerization initiator under an inert gas stream such as nitrogen, and usually carried out under the reaction conditions of about 50 to 70 ° C for about 5 to 30 hours.

The polymerization initiator, chain transfer agent, emulsifier and the like used for the radical polymerization are not particularly limited and may be appropriately selected. Further, the weight average molecular weight of the (meth)acrylic polymer can be controlled by the amount of the polymerization initiator, the chain transfer agent used, and the reaction conditions, and the amount thereof can be appropriately adjusted depending on the type thereof.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, and 2,2'-azobis. [2-(5-Methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'- Azobis(N,N'-dimethyleneisobutylphosphonium), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (and pure light) An azo initiator such as VA-057), a persulfate such as potassium persulfate or ammonium persulfate, a di(2-ethylhexyl)peroxydicarbonate, or a di-(4-tert-butyl) Cyclohexyl)peroxydicarbonate, di-secondary butylperoxydicarbonate, tertiary butyl peroxy neodecanoate, trihexyl peroxydiacetate, trimethylacetate peroxide Butyl butyl ester, dilaurinyl peroxide, di-n-octyl decyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di(4-methyl) Perphenylidene) peroxide, benzhydryl peroxide, tertiary butyl peroxybutyrate, 1,1-di(tri-hexylperoxy)cyclohexane, tert-butyl Hydrogen peroxide, hydrogen peroxide, etc. a redox initiator such as an oxide initiator, a combination of a persulfate and sodium hydrogen sulfite, a combination of a peroxide and sodium ascorbate, and a reducing agent, etc., but is not limited by the above. .

The above-mentioned radical polymerization initiator may be used singly or in combination of two or more kinds. The total content is preferably from 0.005 to 1 part by weight, more preferably from 0.02 to 0.5 part by weight, per 100 parts by weight of the monomer.

Examples of the chain transfer agent include lauryl mercaptan, epoxypropyl mercaptan, indole acetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-didecyl. -1-propanol and the like. The chain transfer agent may be used singly or in combination of two or more kinds, and the total content is about 0.1 part by weight or less based on 100 parts by weight of the total amount of the monomer components.

Further, examples of the emulsifier used in the emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene ethyl ether ether sulfate, and polyoxyethyl ether. An anionic emulsifier such as sodium alkylphenyl ether sulfate, polyoxyethylene ethyl ether, polyoxyethylene ethyl phenyl ether, polyoxyethyl alcohol ester, polyoxyethylene ethyl-poly A nonionic emulsifier such as an oxygen propyl block polymer. These emulsifiers may be used alone or in combination of two or more.

Further, as the reactive emulsifier, an emulsifier which introduces a radical polymerizable functional group such as an acryl group or an allyl ether group may, for example, be Aqualon HS-10, HS-20, KH-10 or BC. -05, BC-10, BC-20 (all of which are manufactured by First Industrial Pharmaceutical Co., Ltd.), ADEKA REASOAP SE10N (made by Asahi Chemical Co., Ltd.), and the like. Since the reactive emulsifier is incorporated into the polymer chain after polymerization, it is preferred that the water resistance is good. The amount of the emulsifier used is 0.3 to 5 parts by weight based on 100 parts by weight of the total of the monomer components, and is preferably 0.5 to 1 part by weight in terms of polymerization stability and mechanical stability.

<Crosslinking Agent> Further, in the present invention, a crosslinking agent may be contained in the adhesive composition for forming an adhesive layer having a pigment. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imide crosslinking agent. Polyfunctional metal chelates are those in which a polyvalent metal is covalently bonded or coordinately bonded to an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. The atom which may be covalently bonded or coordinately bonded to the organic compound may, for example, be an oxygen atom, and the organic compound may, for example, be an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound or a ketone compound.

Examples of the isocyanate crosslinking agent compound include isocyanate monomers such as toluene diisocyanate, chlorophenyl diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate. And an isocyanate compound, a trimeric isocyanate or a biuret-type compound obtained by adding such an isocyanate monomer to trimethylolpropane or the like, and a polyether polyol or a polyester polyol, an acrylic polyol, An urethane prepolymer type isocyanate obtained by addition reaction of a polybutadiene polyol, a polyisoprene polyol, or the like. More preferably, it is a polyisocyanate compound, and is a polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate, or a polyisocyanate compound derived therefrom. Here, the polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate or derived therefrom includes: hexamethylene di Isocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol modified hexamethylene diisocyanate, polyol modified hydrogenated xylylene diisocyanate, terpolymer hydrogenated xylylene diisocyanate and polyol Modified isophorone diisocyanate and the like. The reaction between the polyisocyanate compound and the hydroxyl group exemplified is particularly preferable because the acid or base contained in the polymer can be rapidly progressed as a catalyst.

The peroxide may be suitably used as long as it generates a radical active species by heating or light irradiation, and the base polymer of the adhesive composition is crosslinked. However, in consideration of workability and stability, a one-minute half-life temperature should be used. Peroxide at 80 ° C ~ 160 ° C, and preferably used at 90 ° C ~ 140 ° C peroxide.

The aforementioned peroxide may be bis(4-tert-butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), di- or di-butyl peroxydicarbonate (1 minute half-life temperature: 92.4) °C), peroxy neodecanoic acid tert-butyl ester (1 minute half-life temperature: 103.5 ° C), trimethyl hexyl peroxyacetate (1 minute half-life temperature: 109.1 ° C), trimethyl peracetate tertiary Butyl ester (1 minute half-life temperature: 110.3 ° C), dilauroyl peroxide (1 minute half-life temperature: 116.4 ° C), di-n-octyl peroxide (1 minute half-life temperature: 117.4 ° C), 1, 1, 3 , 3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), bis(4-methylbenzhydryl) peroxide (1 minute half-life temperature: 128.2 °C), benzoyl hydrazine peroxide (1 minute half-life temperature: 130.0 ° C), tertiary butyl peroxybutyrate (1 minute half-life temperature: 136.1 ° C), 1,1-di (tertiary hexyl peroxyl) Base) cyclohexane (1 minute half-life temperature: 149.2 ° C) and the like. Among them, in view of excellent cross-linking reaction efficiency, bis(4-tert-butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), dilauroyl peroxide (1) Minute half-life temperature: 116.4 ° C), benzoyl hydrazine peroxide (1 minute half-life temperature: 130.0 ° C), etc. are suitable for use.

Further, the half-life of the peroxide is an index indicating the decomposition rate of the peroxide, and means the time when the residual amount of the peroxide becomes half. The decomposition temperature for achieving the half-life at any time, and the half-life time at any temperature are described in the manufacturer's catalogue, etc., for example, in the "Organic peroxide catalogue" of Nippon Oil & Fat Co., Ltd. Edition (May 2003) and so on.

In the adhesive composition, the crosslinking agent is preferably used in an amount of 20 parts by weight or less, more preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the base polymer of the (meth)acrylic polymer or the like. It should be 0.03~10 parts by weight. On the other hand, when the amount of the crosslinking agent is more than 20 parts by weight, the moisture resistance is insufficient, and peeling easily occurs in a reliability test or the like.

Further, the adhesive composition for forming an adhesive layer having a pigment of the present invention may contain a decane coupling agent. Durability can be improved by using a decane coupling agent. Specific examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-epoxypropoxypropyl group. Epoxy-containing decane coupling agent such as 2-dimethoxydecane, 2-(3-4-epoxycyclohexyl)ethyltrimethoxydecane; 3-aminopropyltrimethoxydecane, N-2-( Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-γ-amine An amine group-containing decane coupling agent such as propyltrimethoxydecane; (meth)acryl oxime containing 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, etc. a decane coupling agent such as a decane coupling agent; an isocyanate group-containing decane coupling agent such as 3-isocyanate propyl triethoxy decane.

The decane coupling agent may be used alone or in combination of two or more. The total content of the decane coupling agent is preferably 0.001 to 5 by weight based on 100 parts by weight of the base polymer of the (meth)acrylic polymer or the like. The portion is preferably 0.01 to 1 part by weight, more preferably 0.02 to 1 part by weight, further preferably 0.05 to 0.6 part by weight. This is an amount which can improve the durability and appropriately maintain the adhesion force to the optical member such as the liquid crystal cell.

Further, in the adhesive composition for forming an adhesive layer having a pigment in the present invention, polyether-modified polyfluorene oxide may be blended. As the polyether-modified polyfluorene, for example, those disclosed in Japanese Laid-Open Patent Publication No. 2010-275522 can be used.

In the present invention, the adhesive composition for forming the adhesive layer having a pigment may further contain other known additives. For example, a powder such as a colorant or a pigment, a dye, a surfactant, and a plasticizer may be appropriately added depending on the intended use. , tackifier, surface lubricant, leveling agent, softener, anti-aging agent, antioxidant, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic or organic filler, metal powder, granular, foil Wait. Further, a redox system to which a reducing agent is added may be employed within a controllable range.

Although the adhesive composition is formed by using the above-described adhesive composition, it is preferable to adjust the amount of the crosslinking agent to be added in the formation of the adhesive layer, and to fully consider the influence of the crosslinking treatment temperature and the crosslinking treatment time.

The crosslinking treatment temperature and the crosslinking treatment time can be adjusted depending on the crosslinking agent used. The crosslinking treatment temperature is preferably 170 ° C or less.

Further, the crosslinking treatment may be carried out at a temperature at the drying step of the adhesive layer, or may be carried out by additionally providing a crosslinking treatment step after the drying step.

Further, the crosslinking treatment time can be set in consideration of productivity and workability, but it is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.

In the method of forming the adhesive layer having a pigment, for example, the adhesive composition may be applied to a release-treated separator or the like, and a polymerization solvent or the like may be dried to form an adhesive layer, and then transferred. a method of printing onto a polarizing film having a polyvinyl alcohol-based polarizing member; or applying the above-mentioned adhesive composition to a polarizing film having a polyvinyl alcohol-based polarizing member, and drying a polymerization solvent or the like to have polyvinyl alcohol It is produced by a method of forming an adhesive layer on a polarizing film of a polarizing material. Further, when the adhesive is applied, one or more solvents other than the polymerization solvent may be appropriately added.

The release treated release member is preferably a polyoxynitride release liner. In the step of applying the adhesive composition of the present invention to the lining material and drying it to form an adhesive layer, the method of drying the adhesive may be carried out in an appropriate and appropriate manner for the purpose. A method of subjecting the above coating film to superheat drying is preferably employed. The heating and drying temperature is preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 180 ° C, and particularly preferably from 70 ° C to 170 ° C. By setting the heating temperature to the above range, an adhesive having excellent adhesive properties can be obtained.

The drying time can be appropriately selected for a suitable period of time. The drying time is preferably from 5 seconds to 20 minutes, more preferably from 5 seconds to 10 minutes, and particularly preferably from 10 seconds to 5 minutes.

Further, an adhesive layer can be formed by forming an anchor layer (for example, a thickness of about 0.5 to 2 μm) on the surface of the polarizing film having a polyvinyl alcohol-based polarizing material, or performing various subsequent treatments such as corona treatment or plasma treatment. Further, the surface of the adhesive layer can be easily treated.

Various methods can be employed for the formation of the aforementioned adhesive layer. Specific examples thereof include roll coating, contact roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roller coating, bar coating, blade coating, and air knife coating. Curtain coating, lip coating, a method such as a die coating method using a die coater or the like.

The thickness of the above-mentioned adhesive layer is not particularly limited and is, for example, about 1 to 100 μm. It should be 2~50μm, preferably 2~40μm, more preferably 5~35μm. The thickness of the pigment-containing adhesive layer is preferably 25 μm or less from the viewpoint of preventing oxygen from entering from the end portion of the adhesive layer.

When the aforementioned adhesive layer is exposed, the release-treated sheet (separator) can also be used to protect the adhesive layer until it is ready for practical use.

<Thin film layer> Further, the optical functional layer of the present invention may be a film layer containing a dye, and the film layer may be formed of a composition containing a base polymer for forming a film and a coloring matter. The material of the base polymer used to form the film layer can be exemplified by the same materials as those described later for constituting the transparent protective film. In particular, a cellulose resin such as triacetyl cellulose, a polyester resin, a (meth)acrylic resin, a cyclic polyolefin resin (northene-based resin), or the like is preferably used. The film layer can be suitably applied to a polyvinyl alcohol-based polarizing member using an adhesive, an adhesive or the like.

Various methods can be employed for the method of forming the film layer containing the pigment. For example, when the resin material particles are dissolved in a solvent, the composition can be prepared by mixing a pigment, and then the composition can be cast or extruded to produce a film layer. At this time, the film layer can be formed into a suitable thickness. The additive may be suitably blended in the preparation of the aforementioned composition.

The thickness of the film layer is not particularly limited, and is, for example, about 1 to 100 μm, similarly to the pressure-sensitive adhesive layer. It should be 2~50μm, preferably 2~40μm, more preferably 5~35μm. The separator can also be applied to a film layer containing a pigment.

The constituent material of the separator may be, for example, a plastic film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film, a porous material such as paper, cloth or non-woven fabric, a mesh, a foamed sheet, or a metal. A suitable sheet such as a foil or the like, or the like, is preferably a plastic film from the viewpoint of excellent surface smoothness.

The plastic film is not particularly limited as long as it can protect the optical functional layer (especially the adhesive layer), and examples thereof include a polyvinyl alcohol film, a polyethylene film, a polypropylene film, a polybutene film, and a polypentadiene film. , polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-acetic acid B Ester copolymer film and the like.

The thickness of the separator is usually 5 to 200 μm, and preferably about 5 to 100 μm. The release member may be subjected to mold release and antifouling treatment using a polyfluorene-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, cerium oxide powder, etc., and a coating type, Antistatic treatment such as kneading type or vapor deposition type. In particular, by appropriately performing a release treatment such as polyfluorination treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator, the peeling property from the optical functional layer (especially the adhesive layer) can be further improved.

Further, the release-treated sheet used in the production of the polarizing film with the above-mentioned adhesive layer can be directly used as a separator of the polarizing film of the optical function layer, and can be simplified in terms of process.

The separator is preferably one having an oxygen permeability of 1 [cm ³ /(m ^2. 24h·atm)] or less. The oxygen permeability is preferably 0.8 [cm ³ /(m ^2. 24h·atm)] or less, and preferably 0.6 [cm ³ /(m ^2. 24h·atm)] or less, 0.5 [cm ³ /(m ^{2 ). .} 24h・atm)] The following is better. The above oxygen permeability may depend on the material, thickness, and the like. The oxygen permeability of the optical member is specifically determined by the description of the examples.

The separator which satisfies the aforementioned low oxygen permeability is preferably a polyvinyl alcohol film, a polyethylene terephthalate film, a film which is subjected to vapor deposition of aluminum, polyacrylonitrile, ethylene vinyl alcohol or the like. Further, the thickness of the film is preferably from 10 to 100 μm, and more preferably from 25 to 75 μm.

<Polarizing Film> The polarizing film of the present invention has the above polyvinyl alcohol-based polarizing material. The polyvinyl alcohol-based polarizer has a low oxygen permeability and an oxygen permeability of 1 [cm ³ /(m ^2. 24h·atm)] or less.

The polarizing film is generally used in a case where a polyvinyl alcohol-based polarizing member has a transparent protective film on one side or both sides.

The polyvinyl alcohol-based polarizer is not particularly limited, and various types can be used. As the polarizing material, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer-based partially saponified film may be adsorbed by iodine or a dichroic dye. The coloring matter is uniaxially stretched, and a polyene-based alignment film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride is used. Among these, a polarizer comprising a polyvinyl alcohol-based film and a dichroic material such as iodine is preferred. The thickness of the polarizing members is not particularly limited, and is generally about 80 μm or less.

A polarizing member which is uniaxially stretched with a iodine-based film of a polyvinyl alcohol-based film can be dyed by, for example, immersing a polyvinyl alcohol-based film in an aqueous solution of iodine, and extending it to a length of 3 to 7 times. . It may also be immersed in an aqueous solution containing potassium iodide such as boric acid, zinc sulfate or zinc chloride as needed. Further, it is also possible to immerse the polyvinyl alcohol-based film in water for washing with water before dyeing. By washing the polyvinyl alcohol-based film with water, the dirt and the anti-caking agent on the surface of the polyvinyl alcohol-based film can be washed, and the polyvinyl alcohol-based film can be swollen to prevent unevenness such as uneven dyeing. The extension may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after extension. It is also possible to carry out the extension in an aqueous solution of boric acid or potassium iodide or in a water bath.

Further, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferred because it has less thickness variation, better visibility, less dimensional change, and excellent durability, and is also capable of being thinned as a thickness of a polarizing film.

The thin polarizer is representatively described in Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, WO2010/100917, and PCT/JP2010/001460, or Japanese. A thin polarizing film of the specification of Japanese Patent Application No. 2010-269692 or Japanese Patent Application No. 2010-263692. The thin polarizing film can be obtained by a method comprising the step of stretching a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a resin substrate for stretching in a layered body, and a step of dyeing. According to this production method, even if the PVA-based resin layer is thin, since it is supported by the resin substrate for stretching, it can be extended without causing problems such as breakage due to stretching.

As the thin polarizing film, in the method of the step of extending in the state of the laminated body and the step of dyeing, it is possible to increase the polarizing performance at a high magnification, and it is preferable to use, for example, WO2010/100917. Manufactured by a method of preparing a step of extending in an aqueous solution of boric acid as described in the specification of PCT/JP2010/001460, or the specification of Japanese Patent Application No. 2010-269002, or the specification of Japanese Patent Application No. 2010-263692. In particular, it is preferable to use a method for performing an auxiliary air extension step before extending in an aqueous boric acid solution as described in the specification of Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692. Producer.

As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture resistance, isotropy, and the like can be used. Specific examples of such a thermoplastic resin include cellulose resins such as triacetonitrile cellulose, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyimine. A mixture of a resin, a polyolefin resin, a (meth)acrylic resin, a cyclic polyolefin resin (northene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and the like. Further, on one side of the polarizer, the transparent protective film is bonded by the adhesive layer, and on the other side, the transparent protective film may be (meth)acrylic, urethane or urethane acrylate. A thermosetting resin such as an epoxy resin or a polysiloxane or an ultraviolet curable resin. The transparent protective film may contain one or more optional additives as appropriate. The additives may, for example, be ultraviolet absorbers, antioxidants, slip agents, plasticizers, mold release agents, anti-colorants, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the above thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, preferably from 50 to 99% by weight, more preferably from 60 to 98% by weight, particularly preferably from 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, the original high transparency of the thermoplastic resin or the like may not be sufficiently exhibited.

The thickness of the transparent protective film is not particularly limited and is, for example, about 10 to 90 μm. It should be 15~60μm, more preferably 20~50μm. When a transparent protective film is disposed between the polyvinyl alcohol-based polarizer and the pigment-containing adhesive layer, a transparent protective film having a thickness adjusted to be equal to or larger than the adhesive layer and having a total thickness of 45 μm or less can be used.

A functional layer (surface layer) such as a hard coat layer, an antireflection layer, an anti-adhesion layer, a diffusion layer or an anti-glare layer may be provided on the surface of the transparent protective film that is not attached to the polarizing member.

The adhesive used for bonding the polarizer and the transparent protective film may be any one of water, solvent, hot melt, radical hardening, and cationic hardening without any particular limitation. A form of an adhesive, but a water-based adhesive or a radical-curable adhesive is preferred. The thickness of the subsequent layer is usually about 0.01 to 3 μm, and preferably 0.3 to 2 μm, more preferably 0.5 to 1.5 μm.

The layer which does not have a pigment between the polyvinyl alcohol type polarizer and the said adhesive layer of the pigment (for example, the layer B of the aspect of FIG. 3) is mentioned, for example, the said anchor layer, and the transparent protection applied to a polarizer. a film, an adhesive layer (for bonding the transparent protective film to the polarizing member), an adhesive layer (without a pigment), a retardation layer (or a retardation film), a light scattering layer, a light-emitting layer, an undercoat layer, Liquid crystal layer, polarizing layer, and the like. The layer B may be used in a single layer or in combination. Further, when a layer B of a plurality of layers (for example, layer B1, layer B2) is used, for example, a polarizing member P/layer B1/adhesive layer (having no pigment)/layer B2/adhesive layer A (having a pigment) can be used. In this manner, the multilayered layer B is formed by laminating an adhesive layer having no pigment. The thickness of the layer B described above can be designed in accordance with the characteristics of each layer within a range of 45 μm or less. And the aforementioned layer B is preferably a low oxygen permeability.

<Liquid Crystal Panel> The polarizing film with the optical function layer of the present invention described above can be suitably used when forming a liquid crystal panel. For example, when the optical functional layer of the polarizing film with an optical function layer of the present invention is a polarizing film with an adhesive layer of the adhesive layer, the polarizing film of the adhesive layer transmits the polarizing film through the adhesive layer. The adhesive layer of the film is bonded to at least one surface of the liquid crystal cell to form a liquid crystal panel. The polarizing film of the adhesive layer of the present invention is suitably used in the viewing side of the liquid crystal cell.

For the liquid crystal cell, for example, any type such as TN type, STN type, π type, VA type, and IPS type can be used. However, the liquid crystal panel of the present invention is preferably an IPS type liquid crystal cell.

In the formation of the liquid crystal panel, other optical layers may be applied in addition to the polarizing film described above. The optical layer is not particularly limited. For example, one or two or more layers such as a reflecting plate, a semi-transmissive plate, and a phase difference plate (including 1/2 and the like) may be used on the viewing side and/or the back side of the liquid crystal cell. A 1/4-wavelength plate), a viewing angle compensation film, a brightness enhancement film, and the like are used for the optical layer formed by the liquid crystal panel.

<Liquid Crystal Display Device> The liquid crystal display device is formed by using the above-described liquid crystal panel, and assembling a component such as an illumination system as necessary, and assembling it into a drive circuit or the like. Further, when forming a liquid crystal display device, one or more layers such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a tantalum array, a lens array sheet, a light diffusing plate, and the like may be disposed at appropriate positions. Suitable parts such as backlights. Further, a suitable liquid crystal display device such as a backlight or a reflector for use in an illumination system can be formed. Example

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. As for the weight and the percentage of each case, the weight basis. Hereinafter, the room temperature standing conditions which are not specifically defined are all 23 ° C and 65% RH.

<Measurement of Weight Average Molecular Weight of (Meth)Acrylic Polymer> The weight average molecular weight (Mw) of the (meth)acrylic polymer was measured by GPC (gel permeation chromatography). The measurement was also carried out for Mw/Mn.・Analytical device: manufactured by Tosoh (Tosoh Corporation), HLC-8120GPC ・Pipe column: manufactured by Tosoh, G7000H _XL +GMH _XL +GMH _XL . Column size: each 7.8mmφ×30cm 90cm ・Tub column temperature: 40°C . Flow rate: 0.8 mL/min ・Injection amount: 100 μL ・Solution solution: Tetrahydrofuran ・Detector: Differential refractometer (RI) ・Standard sample: Polystyrene

<Measurement of Oxygen Permeability> OX-TRAN, which is an oxygen permeability measuring apparatus manufactured by MOCON Corporation, was used in accordance with JIS K 7126-2 under the conditions of 23 ° C and 0% RH.

Example 1 <Preparation of Polarized Film> In order to produce a thin polarizing layer, a laminate of a PVA layer having a thickness of 9 μm was formed on an amorphous PET substrate, and an extended layered body was formed by an air-assisted extension at an extension temperature of 130 ° C. Then, the colored laminated body is formed by dyeing the extended laminated body, and then the colored laminated body and the amorphous PET substrate are integrally stretched by extension in boric acid water at an extension temperature of 65 degrees so that the total stretching ratio is 5.94 times. An optical film laminate including a PVA layer having a thickness of 4 μm was produced. Further, an optical thin film laminate including a PVA layer having a thickness of 4 μm for forming a highly functional polarizing layer which is formed by stretching the PVA molecules of the PVA layer of the amorphous PET substrate via the two stages can be formed. Highly aligned, and the iodine adsorbed by dyeing is highly aligned in one direction in the form of polyiodide complex. Further, a polyvinyl alcohol-based adhesive (the thickness of the formed adhesive layer is 1 μm) is applied to the surface of the polarizing layer of the optical film laminate, and the saponified first acrylic resin film having a thickness of 40 μm is bonded thereto. (Oxygen permeability is 5 [cm ³ /(m ^2. 24h・atm)]), and the amorphous PET substrate is peeled off to produce a thin polarizing member (the oxygen permeability is less than 0.02 [cm ³ /(m). ^2. 24h・atm)]) Single-sided protective polarizing film. It is called a thin single-sided protective polarizing film.

<Preparation of (meth)acrylic polymer> A monomer mixture containing 100 parts of butyl acrylate, 0.01 part of 2-hydroxyethyl acrylate, and 5 parts of acrylic acid is fed into a cooling tube, a nitrogen introduction tube, and a thermometer. And in the reaction vessel of the stirring device. Further, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was fed together with 100 parts of ethyl acetate with respect to 100 parts of the above monomer mixture, and nitrogen gas was slowly stirred while stirring. After introduction for nitrogen substitution, the liquid temperature in the flask was maintained at around 55 ° C for 8 hours to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.8 million and Mw/Mn = 4.1 (solid). The component concentration was 30% by weight).

(Preparation of the adhesive composition) The adhesive composition was prepared by blending the following with respect to 100 parts of the solid content of the acrylic polymer solution prepared above: 0.3 part of benzamidine peroxide (Japanese fat) NYPER BMT), one part isocyanate cross-linking agent (trade name Coronate L, manufactured by Tosoh Co., Ltd.), and 0.25 parts of porphyrazine-based pigment (trade name PD-320 manufactured by Yamamoto Kasei Co., Ltd.): It has a maximum absorption wavelength at a wavelength of 595 nm).

(Preparation of polarizing film with adhesive layer) The adhesive composition was uniformly applied to the surface of the polarizing member (PVA layer) of the thin single-sided protective polarizing film directly by a spreader, and air was passed at 155 ° C. After drying in a circulating constant temperature oven for 2 minutes, a pigmented adhesive layer having a thickness of 20 μm was formed on the surface of the polarizing member to prepare a single-sided protective polarizing film with an adhesive layer.

[Example 2] In the same manner as in Example 1, except that an adhesive layer having a thickness of 20 μm and a pigment-free adhesive layer was laminated on the surface of the polarizer to form a pigmented adhesive layer having a thickness of 20 μm. A single-sided protective polarizing film with an adhesive layer. Further, in the case of forming an adhesive layer having no pigment at a thickness of 20 μm, the same adhesive composition was used in addition to the dye composition for forming the above-mentioned adhesive layer having a pigment. The adhesive layer is formed by uniformly applying the above-mentioned adhesive composition to a release substrate of a polyethylene terephthalate film treated with a polyfluorene-based release agent by a spreader (manufactured by Mitsubishi Plastics Co., Ltd.). The surface of MRF38CK) was dried in an air circulating oven at 155 ° C for 2 minutes, and the adhesive layer was transferred to the above polarizer to laminate.

[Example 3] An adhesive layer having a pigment having a thickness of 20 μm used in Example 2 in Example 1 was formed on the surface of the polarizer surface layer 2 (total thickness: 40 μm) to form a 20 μm thick adhesive layer having a pigment. A one-side protective polarizing film with an adhesive layer was produced in the same manner as in Example 1. Further, the formation of the adhesive layer having no pigment was the same as that described in Example 2.

Example 4 <Preparation of Polarized Film> The surface of the polarizing member (PVA layer) of the thin single-sided protective polarizing film obtained in Example 1 was adhered and saponified through an adhesive (the thickness of the adhesive layer was 1 μm). A second acrylic protective film having a thickness of 40 μm (oxygen permeability: 5 [cm ³ /(m ^2. 24h·atm)]) was used to produce a double-sided protective polarizing film. It is called a thin double-sided protective polarizing film.

(Production of Polarizing Film with Adhesive Layer) The back surface of the second acrylic resin film (the surface opposite to the adhesive layer) of the double-sided protective polarizing film was directly coated with the adhesive of Example 1 by a spreader. The material was dried in an air circulating oven at 155 ° C for 2 minutes, and a pigmented adhesive layer having a thickness of 20 μm was formed on the back surface of the second acrylic resin film to prepare a single-sided protective polarizing film with an adhesive layer.

Comparative Example 1 An adhesive layer having a pigment having a thickness of 20 μm and a pigment layer having a thickness of 20 μm was formed in Example 1 except that the adhesive layer having a thickness of 20 μm which was used in Example 2 was not formed on the surface layer of the polarizer surface layer (total thickness: 60 μm). Further, a one-side protective polarizing film with an adhesive layer was produced in the same manner as in Example 1. Further, the formation of the adhesive layer having no pigment was the same as that described in Example 2.

Comparative Example 2 A saponified 40 μm thick acrylic resin film was formed by forming the above-mentioned adhesive composition on the surface of the polarizing member (PVA layer) of the above-mentioned thin single-sided protective polarizing film in Example 1 (oxygen permeability) An acrylic resin film with an adhesive layer was produced in the same manner as in Example 1 except that it was 5 [cm ³ /(m ^2. 24h·atm)]).

The single-sided protective or double-sided protective polarizing film of the adhesive layer prepared in the above Examples and Comparative Examples, or the acrylic resin film with the adhesive layer was used as a sample for the following evaluation. The evaluation results are shown in Table 1.

(Evaluation of fading) After cutting the sample into a test piece of 50 mm in length × 25 mm in width, photographs of the front and end state (initial) were taken and read using a scanner (specifically, the product name PIXUS MX923 manufactured by Canon Co., Ltd.). . Next, the sample was placed in a thermostat at 85 ° C for 24 hours, and the endurance test was taken out and returned to room temperature (23 ° C), and then the front and end of the sample were taken with the same scanner (24 hours later). ) and read the photo. The photographs before (initial) and after (24) hours after the introduction of the test were binarized, and the presence or absence of discoloration and the amount of end fade were measured by the following method.

<Coloring of the front side> Based on the binarized photograph before the durability test and the image of the binarized photograph after the test, the color was visually evaluated. The transmittance of the test piece before and after the durability test was also reported in Table 1. The measurement of the transmittance was carried out using a spectroscopic transmittance measuring instrument (Dot-3c of Murakami Color Research Institute) equipped with an integrating sphere at 23 ° C in the test piece. 〇 The color is no different than before the input. × The color is noticeably lighter than before the input.

<Color drop of the end portion> The distance from the peripheral end portion of the test piece to the center was measured at the longest point of the portion where the peripheral end portion was clearly discolored, and it was evaluated as discoloration (fading distance: mm).

[Table 1]

No coloration occurred on the front side of the examples and the amount of color loss at the ends was small. The color at the end (fading distance: mm) is preferably 3 mm or less, preferably 2 mm or less, more preferably 1 mm or less, and preferably 0 mm. On the other hand, in Comparative Example 1, since the polyvinyl alcohol-based polarizer was used, no discoloration was observed on the front surface, but the distance between the polyvinyl alcohol-based polarizer and the optical functional layer (adhesive layer) was more than 45 μm, so that observation was observed. There is a fade to the end (fading distance: mm). In Comparative Example 2, since the polyvinyl alcohol-based polarizer was not used, it was observed that the front surface was discolored and the end portion was discolored.

P‧‧‧polyethylene glycol polarizer

A‧‧‧Optical functional layer

F‧‧‧Transparent protective film

S‧‧‧Substrate

B, C‧‧‧ other layers

x‧‧‧The distance between the PEG-based polarizer and the adhesive layer

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a polarizing film of an optical functional layer of the present invention. Fig. 2 is a cross-sectional view schematically showing an embodiment of a polarizing film of the present invention with an optical function layer. Fig. 3 is a cross-sectional view schematically showing an embodiment of a polarizing film of the present invention with an optical function layer. Fig. 4 is a cross-sectional view schematically showing an embodiment of a polarizing film of the present invention with an optical function layer.

Claims (10)

A polarizing film having an optical functional layer having an optical functional layer containing a pigment on at least one side of a polarizing film having a polyvinyl alcohol-based polarizing member, wherein the polarizing film with an optical functional layer is characterized by: the polyethylene The distance between the alcohol-based polarizer and the optical functional layer containing the dye is 45 μm or less. The polarizing film of the optical function layer according to claim 1, wherein the distance between the polyvinyl alcohol-based polarizer and the adhesive layer is 25 μm or less. A polarizing film comprising an optical functional layer as claimed in claim 1 or 2, wherein the polyvinyl alcohol-based polarizing member and the adhesive layer are directly laminated. The polarizing film of the optical function layer according to claim 1 or 2, wherein the polyvinyl alcohol-based polarizer and the optical functional layer have at least one layer having a thickness of 45 μm or less and no dye. The polarizing film of the optical function layer according to any one of claims 1 to 4, wherein the polyvinyl alcohol-based polarizing member has an oxygen permeability of 1 [cm ³ /(m ^2. 24h·atm)] or less. The polarizing film of the optical function layer according to any one of claims 1 to 5, wherein the dye has a maximum absorption wavelength in at least any one of a wavelength region of 470 to 510 nm and a wavelength region of 570 to 610 nm. The polarizing film of the optical function layer according to any one of claims 1 to 6, wherein the dye is a porphyrazine-based dye. The polarizing film with an adhesive layer according to any one of claims 1 to 7, which contains 0.01 to 5 parts by weight of the above-mentioned coloring matter with respect to 100 parts by weight of the base polymer of the resin layer forming the optical functional layer. The polarizing film with an optical function layer according to any one of claims 1 to 8, wherein the optical function layer containing the dye has a thickness of 25 μm or less. An image display device having a polarizing film with an optical function layer as claimed in any one of claims 1 to 9.