TW201231589A - Polarizing plate and liquid crystal display comprising the same - Google Patents

Abstract

Disclosed are a polarizing plate and a liquid crystal display comprising the same, more particularly, a polarizing plate having a polarizer, an adhesive layer laminated on at least one side of the polarizer and a cellulose or polyolefin protective film laminated on the adhesive layer, as well as a liquid crystal display having the same; wherein the adhesive layer is formed of an adhesive composition having 1 to 100 wt. parts (in terms of solid content) of an acetoacetyl group-modified polyvinylacohol resin in relation to 100 wt. parts of an aqueous polyamide epoxy resin and, has a pH value ranging from 7 to 13, so as to increase bonding between a functional group of the adhesive composition in the adhesive layer and functional groups of a cellulose or polyolefin protective film and a polarizer and maintain adhesiveness to the polarizer and the protective film, thereby improving durability and reliability while enhancing optical properties by regulating alkalinity.

Description

201231589 VI. Description of the Invention: [Technical Field] The present invention relates to a polarizing plate having an adhesive layer and a liquid crystal display comprising a polarizing plate, and exhibiting excellent properties for a polarizer and/or a cellulose or polyolefin-based protective film. Viscosity to improve its optical properties as well as durability and reliability. [Prior Art] A liquid crystal display having low power consumption, low operating voltage, light and thin characteristics is used for various display devices. The liquid crystal display is composed of various materials such as a liquid crystal cell, a polarizing plate, a phase difference film, a light collecting sheet, a diffusion sheet, a light guiding panel, a light reflecting sheet, and the like. Extensive research has been made to improve the liquid crystal display by reducing the number of films or sheets used in liquid crystal displays or to reduce the thickness of the film or sheet, thereby reducing the weight and/or productivity or measurement of the liquid crystal display. 15 20 LCD monitors need to be able to withstand extreme conditions for different purposes. For example, compared to conventional television or personal computer monitors, liquid crystal displays for car navigation systems use extreme temperature and humidity conditions due to the sometimes elevated temperature and/or humidity in the car. In this regard, the polarizing plate of the above liquid crystal display also requires high durability (that is, temperature resistance and moisture resistance). The polarizing plate has a laminated structure of a polarizing plate (including a polyvinyl alcohol tree, in which a dichroic dye is adsorbed and oriented) and a transparent protective film (stacked on either or both sides of the 丨切片). The polarizer is a product obtained by extracting and dyeing a polyfluorene-resin film uniaxial P11IDRA006TW 4 201231589 using a dichroic dye, performing a crosslinking reaction via boric acid treatment, and then washing and drying. The dichroic dye may comprise iodine or a dichroic organic dye. After the protective film is stacked on either or both sides of the polarizer to produce a polarizing plate, the polarizing plate is placed in the liquid crystal display. 5 A typical cellulose acetate resin such as cellulose triacetate is widely used as a protective film, and the thickness of the protective film is usually from 3 to 120 eggs. Adhesives including a polyvinyl alcohol resin solution are commonly used to stack protective films. If a cellulose protective film made of cellulose triacetate is stacked on both sides or either side of a polarizer for adsorbing a dichroic dye, an adhesive comprising a solution of a polyethylene sterol resin is placed therebetween. When the polarizing plate is used under hydrothermal conditions for a long time, the polarization property may be deteriorated, or the protective film may be easily peeled off from the polarizer. Further, since the cellulose protective film has low heat resistance, the polarizing plate having the protective film is The disadvantage of poor performance such as polarization, color, etc. 15 is caused under high temperature and humidity conditions. Thus, it was attempted to produce a protective film on at least one side of the polarizing plate using various resins other than the cellulose acetate resin. For example, Japanese Laid-Open Patent Publication No. H8-438 No. 12 discloses a polarizing plate in which protective films are stacked on both sides of a polarizer, at least one of which is composed of a heat 20 plastic norbornene resin as a phase difference film. The polarizing plate on which the protective film is laminated is disclosed in the Japanese Patent Publication No. 2002-174729, in which a protective film composed of an amorphous poly thin resin is laminated on the side of a polarizer including a polyvinyl alcohol resin film, and iodine is adsorbed and oriented thereon. Or a dichroic organic dye, other than an amorphous polyolefin resin such as cellulose acetate resin

Another protective film composed of P11IDRA006TW 5 201231589 is laminated on the other side of the polarizer. Japanese Laid-Open Patent Publication No. 2004-334i68 discloses a polarizing plate having a protective enamel composed of a ring-like smoky base resin, in which an occlusive adhesive and a polyvinyl alcohol resin containing an adhesive are placed. 5 However: In recent years, amorphous polyolefin resins (or cyclic olefin resins) such as norbornene resin have been used, which are usually expensive. Further, the amorphous polystyrene resin is etched by an organic solvent such as acetone, toluene, ethyl acetate or the like. Since the organic solvent is used to produce the adhesive, the organic solvent remains in the adhesive. Furthermore, the viscosity of the polarizer and/or the protective film is reduced under high temperature and humidity conditions 10, failing to meet the requirements of durability and reliability. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polarizing plate having an adhesive layer which continuously maintains excellent adhesion between a polarizing film of a cellulose or a dense smoke-based protective film under conditions of high temperature and humidity. Therefore, there are improved optical properties and better durability and reliability. Another object of the present invention is to provide a liquid crystal display having the above polarizing plate. * In order to attain the object of the present invention, there is provided a polarizing plate having a polarizing plate, an adhesive layer stacked on either or both sides of the polarizing plate, and a cellulose or polyolefin-based protective film laminated on the adhesive layer, wherein the adhesive layer includes an adhesive The component has an i to 1 part by weight (solid content) of an ethyl hydrazide-modified polyvinyl alcohol resin with a pH of 7 to 13 25 100 with respect to 100 parts by weight of the aqueous polyamine epoxy resin.

Pill DRA006TW 201231589 Adhesive components can contain basic compounds. The test compound may be selected from a metal or alkaline earth metal hydroxide or a metal or soil metal carbonate. Such metal or alkaline earth metal hydroxides can be used to form an adhesive component having a pH of from 5 Torr to 13. Such metal or alkaline earth metal carbonates can be used to form an adhesive component having a pH of 7 to 1 Torr. The adhesive layer may comprise from 3 to 20 parts by weight of the adhesive component relative to 00 parts by weight of the solvent. 10 Adhesive layers may also include adhesive components of 2 to 25 mPa, sec (2 (TC). Ethylene-based modified polyvinyl alcohol resins may contain 10 to 5 parts by weight (solids content). The front side of the ruthenium or polyfluorene-based protective film can be treated by at least one of the following methods: corona discharge, plasma treatment, primer discharge. Use of adhesive layer, acryl, cellulose, polyolefin or polyester-based protection The film may be further laminated on the other side of the polarizer. A protective film based on acrylonitrile, cellulose, polyolefin or polyester may be applied to the other side of the polarizer via an adhesive laminate layer containing a water-like polyvinyl alcohol resin. A liquid crystal display having a polarizing plate is also provided. [Embodiment] The present invention provides a polarizing plate which has excellent adhesion to a polarizer and/or a cellulose or polyolefin-based protective film even under high temperature and humidity conditions.

ΪΜ1IDRA006TW 7 201231589 Improves optical properties as well as durability and reliability' and provides a liquid crystal display including a polarizing plate. The present invention is described in detail below with reference to the accompanying drawings. The invention provides a polarizing plate comprising a polarizer, an adhesive layer stacked on one side of the polarizer to 5, a cellulose or polyolefin-based protective film laminated on the adhesive layer, and an adhesive layer composed of an adhesive component, including water. Polyamine epoxy resin and ethyl ethoxylated modified polyvinyl alcohol resin, pH 7 to 13. The aqueous polyamine epoxy resin 10 contained in the adhesive component of the adhesive layer is not particularly limited, however, a polyalkylene polyamine such as diethylenetriamine or triethylenetriamine may be mixed with a polyalkylenepolyamine such as adipic acid. The dicarboxylic acid is reacted to prepare a polyamine polyamine, and then the prepared polyamine polyamine is reacted with epoxy propylene. Examples of the foregoing resin may include Sumirez resin 650 (Sumitomo Chemicals), Sumirez resin 675, (Sumitomo Chemicals), 15 WS-525 (Nippon PMC), and the like. The adhesive layer of the present invention exhibits excellent viscosity even if the above-mentioned cellulose protective film is not used, and a polyolefin-based protective film having a relatively low viscosity is used. Specifically, the epoxy functional group of the polyamine epoxy resin compound contained in the adhesive component reacts positively with the nucleophilic functional group on the surface of the protective film, and 20 exhibits excellent viscosity. Since the resin compound has many electrophilic functional groups and is activated by vaporized hydrogen, such a reaction between the epoxy functional group of the polyamide amine epoxy compound and the nucleophilic functional group on the surface of the protective film can be further increased. In this respect, if the adhesive component is under the conditions of the test, the nucleophilic functional group on the surface of the protective film is live.

PI11DRA006TVV 8 201231589 increased, further squeezing viscosity. The epoxy functional group of the polyamine epoxy resin compound of the 'adhesive component' is open-looped and generates a hydrophilic group, and the hydrophilic group is hydrogen-bonded to the hydroxyl group on the surface of the polarizer as if it is crosslinked in the adhesive layer. 5 Adhesive component Ethylene ethoxide-modified polyvinyl alcohol ('pVA,) tree ruthenium enhances the adhesion of the component to the pVA polarizer and a protective film such as a cellulose film. Compared with other modified PVA resins, such as carboxyl modified PVA resin, hydroxyindole modified PVA resin, amine modified pVA resin, etc., the ethyl acetate modified PVA resin contains higher reactive functional groups. In order to improve durability, the PVA resin is reacted with diketene according to a conventional method to obtain an ethyl acetonitrile-modified PVA resin. In particular, a process of pouring a PVA resin into a solvent such as acetic acid and adding diketene, a process of dissolving the pvA resin in a solvent such as monodecylamine or monohexacyclohexane and adding diethyl ketone, directly The process of contacting the PVA resin with diketene gas or liquid diethylene_, etc., can be used to produce an ethyl acetonitrile-modified PVA resin. The ethyl acetonitrile-modified PVA resin is not particularly limited as long as the ethyl sulfonate has a degree of modification of at least 0.1 mol%. The above-mentioned resin preferably has an ethylene sulfonate degree of 20 to 0.1 to 40 mol% '1 to 20 m〇l%, preferably 2 to 7 mol%. If the modification degree of the B-brewed base is less than 0.1 mol%, the adhesive layer is insufficient in water resistance. On the other hand, if the degree of modification of the acetamidine group exceeds 4 〇 m 〇 1%, only a slight increase in water resistance is obtained. Examples of the foregoing resin may include Ζ·1〇〇, Z-200, Z-200H, Z_21〇 11DRA006TW 9 201231589 , Z-220, Z-320 (Gohsefimer, Nippon Synthetic Chemical)

Industry Co, Ltd.) and more. The content of the modified PVA resin may vary depending on the type of protective film to be attached. In particular, the weight is 1 to 1 part by weight (parts by weight; the solid content is 5), relative to 100 parts by weight of water. The polyacetamide epoxy resin is preferably from 1Q to 5 parts by weight. If the content is less than i part by weight, the viscosity to the pvA polarizer is poor. On the other hand, when the content exceeds 1 part by weight, the adhesion to the acrylonitrile or acryl-based protective film is poor, and the durability is deteriorated and the polarizer is peeled off during rework. 10 The adhesive layer may include the adhesive component of pH 7 to 13. The higher the pH value, the greater the reaction between the adhesive component functional group and the protective film functional group, thereby improving the viscosity. However, if the pH is less than 7, the reaction between the protective film functional adhesive components is rather low, and thus the viscosity is deteriorated under high temperature and humidity conditions. On the other hand, when the pH exceeds 13, the polarizing plate loses its function due to problems such as the decolorization of the 15 polarizer. The pH of the adhesive component can be controlled using a basic compound. Examples of such a basic compound may include an alkali metal or alkaline earth metal hydroxide and/or a carbonate. The alkali metal or alkaline earth metal hydroxide may be a compound 20 represented by M〇H, and an alkali metal or alkaline earth metal carbonate. It may be a compound represented by (M)n(H)2-nC03 (wherein η is 1 or 2). The alkali metal or soil test metal used for the aforementioned compound may contain Li, Na, Mg, or the like. The pH of the adhesive component including the metal or soil metal hydroxide may be from 10 to 13, and includes an alkali metal or alkaline earth metal carbonate adhesive.

P11IDRA006TW 10 201231589 The pH of the components can range from 7 to 丨0. The type of the adhesive + component is not particularly limited, however, it is preferable to use a liquid type of the adhesive component to form an adhesive layer on the surface of the polarizer or the protective film to be attached. This liquid type of adhesive may contain a solution or various knife sprays/night. When considering the coating properties of the substrate, it is preferred to use a solution type adhesive. Chevalier & m, on the other hand, when considering stability, an adhesive of the type of dispersion in solution or water is suitable. In order to shorten the dry process, water prepared by adding an alcohol solvent (easy to be miscible with water and boiling 10 15 20 lower than fire) to the adhesive solution may be used, and the solvent may be mixed with alcohol. in

It is y alcoholic agent boiling point is not more than i 〇〇 it, 8 〇 it is better, the following is better. The above description of the adhesive component may further comprise a 4:5L additive which does not detract from the object of the present invention. In particular, the additive may contain an anti-foaming agent, logo: 1 colorant (dye, pigment), fluorescent bleach, UV absorber, anti-oxidant, plasticizer, antistatic agent, thermal stabilizer , surfactants, desiccants, deodorants, antibiotics, preservatives, etc. The adhesive layer may include 3 i 2 parts by weight relative to i00 parts by weight of the solvent: the adhesive component '3 to the weight of the solids is preferably a solid content. If the amount of solid s is less than 3 damages, the viscosity between the protective film and the polarizer is poor. When the solid content exceeds 20 parts by weight, the viscosity of the adhesive component increases, and the treatment and coating properties are deteriorated. The adhesive layer maintains a viscosity of 2 to 25 mPa sec (2 (rc) in the range of solid content of the adhesive component. A representative example of the resin used for the cellulose protective film may contain cellulose acetate.

ΡΠ I DRA006TVV 201231589 Vitamin resin. The resin obtained by partially or completely succinic acid acetate of the cellulose acetate tree may contain a triacetin or a resin. Vinyl resin, propylene crystalline polyolefin resin. The resin used for the polythene oxide protective film 5 may comprise a linear polyolefin resin such as a resin or a butene resin, or may be a grease which is not considered in the immediate vicinity of the polarizer and/or enhances durability. The amorphous polyolefin resin is a thermoplastic film group on a cyclic olefin resin, and its unit is derived from a cyclic olefin containing a monomer such as norbornene or a polycyclonorbornene. The cyclic olefin resin may be a ring-opening polymer of the above cyclic olefin, a hydrogenated product of a ring-opening polymer formed using at least two different cyclic olefins, or a cyclic olefin and a chain paraffin or an aromatic compound having a vinyl group. Polyaddition copolymer. Materials having polar groups can also be used. For the cycloaliphatic resin in the form of a copolymer of a ring-dense hydrocarbon and a chain sarcophagus or an aromatic compound having a vinyl group, examples of such a chain sarcophagus may include ethylene, propylene or the like. Examples of the aromatic compound having a vinyl group may include stupid ethylene, a-methylstyrene, and the like. The content of the monomer having a cyclic olefin in the copolymer may be 50 mole% or less, preferably 15 to 50 mole%. In particular, a terpolymer composed of a cyclic olefin and a chain paraffin and an aromatic compound having a vinyl group 20 may contain a relatively small amount of a monomer. The monomer content of the terpolymer containing chain paraffin may be usually from 5 to 80 mole%. Similarly, the aromatic compound having a vinyl group in the terpolymer may be from 5 to 80 mole%. The present invention can be made using a film made of the above cellulose or polyolefin resin.

PillDRAOOeTVV 12 201231589 is a polarizer protective film. The film can be made transparent, with no coplanar retardation 'extrusion process using molten resin, and coated with organic grease on the plate (4), μ (four), (four), dissolved (four) cast =, etc., can be used for manufacturing Membrane without coplanar retardation. According to the present day (4), the polarizing plate can further have a protective film base on C (10), cellulose ene l or poly siloxane, and is laminated on the other side of the polarized light via the above adhesion. In detail, the protective film may comprise: an acryl resin such as polymethyl methacrylate, polyethyl acrylate, etc.; such as polyethylene to benzoic acid vinegar, polyethylene benzene A polyester resin such as dicarboxylic acid vinegar, polyethylene diacetate vinegar, polybutylene terephthalate or the like, and the like. In this regard, the resin type and protective film process for the cellulose and/or polyolefin-based protective film may be substantially the same as described above. It can be surface treated on the side of the protective film attached to the polarizer. Such a surface may include drying such as plasma treatment, corona discharge, etc., chemical treatment such as saponification (saponification), coating process for forming an adhesive layer for adhesion, and the like. The cellulose film is preferably alkalized, and the polyolefin film can be treated by corona discharge. After the surface treatment, the surface of the protective film has a large amount of negative (_) charge, and the epoxy group having a positive (+) charge of the polyamine epoxy resin exhibits an increase of 20, and thus has excellent viscosity. The alkalization is a treatment in which a resin film is immersed in an alkali solution containing sodium hydroxide or potassium hydroxide to activate the film. Corona discharge is a process in which high-voltage electric energy is applied to an electrode and energy is discharged to activate a resin film aligned between electrodes. The effect of corona discharge depends on the type of electrode, its spacing 'voltage, humidity, resin P|] IDRA006TW 13 201231589 and so on. For example, the electrode spacing can be from ... to ^, and the migration speed can be in the range of 3 to 20 m/min. The thickness is usually from 1 to 1 〇, from 5 to 5, and from 1 to 1 is best. The protective film of the non-stick polarizer can be hard coated, anti-reflective, anti-adhesive, diffused, or anti-glare. The poisoning method can be applied to the adhesive side of the polarizer or the protective film by a conventional one, for example, by adhesive treatment, Meyer bar coating, gravure coating, mold coating, dip coating, and spray coating. Stick the polarizer and protective film. The flexible treatment is a method of flowing the adhesive component on the adhesive side 10 15 20 while moving the polarizer or the protective film in a vertical or horizontal direction or in an oblique direction therebetween. After the adhesive component is applied, the polarizer or protective film is attached to the squeegee and re-adhered to the protective film. After the polarizer is stuck to the protective film, it can be dried. For example, spraying hot air at a drying temperature of 4 to 100 ° C '60 to 10 (rc is preferred. The drying time can be 20 to 1, 2 sec. After drying, the treated product can be at room temperature or slightly The temperature is vulcanized or hardened, for example, at 2 to 5 (rc for 12 to 6 hours). The thickness of the adhesive layer after drying is usually 〇〇〇1 to 5 泖, and 〇〇1 to 2/M is preferable. 〇.01 to i泖 is better. If the thickness of the adhesive layer exceeds 5 泖, the polarizing plate is susceptible to appearance damage. If necessary, surface treatment such as hard coat layer, antireflection layer, antiglare layer, antistatic layer, etc. The layer may be further laminated on the other side of the polarizer having the protective film attached thereto. Further, the 'optical functional film may be further laminated on the adhesive layer. Such an optical functional film may include: an optical compensation film 'where a liquid crystal compound or a polymer compound thereof is Alignment on the surface of the substrate; reflective polarizing separation film, which can transmit specific polarized light and reflect light of opposite nature through PJIIDRAOUMAV 14 201231589; phase difference film containing polycarbonate resin or ring-shaped polyolefin resin; anti-glare additive film with uneven surface; Addition of surface reflection processing Film; reflective film with surface reflection function; semi-transmissive reflective film with reflection and transmission function; etc. 5 Since the adhesive layer containing water-like pVA resin is coated on the other side of the polarizer, acryl, cellulose, and poly The olefin or polyester-based protective film may be laminated on the adhesive layer. The aqueous P VA resin is not particularly limited, however, it may comprise partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl modified polyvinyl alcohol, B 10醯 醯 改 modified polyvinyl alcohol, hydroxymethyl modified polyvinyl alcohol, amine modified polyvinyl alcohol, etc. The polarizer has an oriented polyvinyl alcohol film containing two colors adsorbed and aligned thereon Sex coloring agent 15 The PVA resin constituting the polarizer can be prepared by saponification of a polyvinyl acetate resin. The polyvinyl acetate resin may comprise a copolymer of vinyl acetate and a monomer copolymerizable therewith, without homopolymerization of vinyl acetate. Polyvinyl acetate. The monomer copolymerizable with vinyl acetate may comprise an unsaturated carboxylic acid, an unsaturated sulfonic acid, a paraffin or a vinyl ether based monomer, and an ammonium acrylamide monomer. Etc. PVA resin can be modified, for example, polyvinyl formal or polyvinyl acetal modified to aldehyde. The degree of saponification of pvA resin is usually 85 to 1 〇〇 m〇l%, at least % is preferred. The degree of polymerization of the pVA resin is usually 1'_ to ^(10)...丨, preferably up to 5, preferably

Dish-shaped film. PVA forms a film of PVA resin, which can be used as a polarizer

PjIIDRA006TW 15 201231589 The resin-forming film can be carried out by any conventional method, and the thickness of the crucible is not particularly limited, and for example, it can be from 1 Torr to 洳. ", the polarizer is usually manufactured as follows. · Uniaxial extraction of polyvinyl alcohol:., 5::Colorant: The film is dyed and adsorbed with a coloring agent, and the film is treated with an acid-cut solution and washed and dried. The uniaxial extraction of the ethyl alcohol film can be performed before and during the dyeing. If the uniaxial extraction is performed after the dyeing, the process can be performed in the middle or the other of the boric acid treatment. Of course, the 'single-axis extraction can be more The stage 10 can be used to extract drums and/or heat rollers of different rotor speeds. In addition, the single-axis extraction can be dry extraction in the atmosphere, or extraction of the film by the wet extraction. Usually, the extraction ratio can be 3 to 8 It is known that the PVA film dyeing using a dichroic coloring agent may include a process of immersing the PVA film in an aqueous solution containing a dichroic coloring agent. Such a dichroic coloring agent 15 may be a broken or dichroic dye. The film can be immersed in water before dyeing to properly swell. When 峨 is used as a dichroic colorant, the dyeing method is to immerse the PVA film in a dyeing solution containing cerium and potassium hydride. Usually, the cerium content of the dyeing solution is relatively At 100 parts by weight (Steaming water) can be 〇〇1 to t 20 injury weight, quantity 'and 峨 卸 卸 含量 相对 相对 相对 相对 相对 相对 〇 〇 〇 〇 〇 〇 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The dipping time can be from 2 〇 to 1,800 sec. The right organic-color dye is used as a dichroic coloring agent, and the dyeing method is ~VA film into the dyeing solution containing the aqueous organic dichroic dye.仃 dyeing. The organic dichroic dye content of the dye solution is relative to 100 parts

P"1DRA0%TNV 16 201231589 The amount of water may be from WO-4 to Η) part by weight of the weight of 1 〇 -3 to 份 parts by weight. The dyeing solution may further contain an inorganic salt such as sodium sulphate. The dyeing solution may have a degree of 20 to 80 ° C ′ and a dipping time (dyeing time) of 1,100 seconds. 10 15 20 The boric acid treatment of the dyed PVA film is to immerse the film in a solution containing boric acid. The boric acid-containing solution preferably has a boric acid content of from 2 to 15 parts by weight to 5 to 12 parts by weight per 1 part by weight of water. If iodine is used as a dichroic color; the boric acid-containing solution preferably contains potassium iodide in an amount of 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight of water. The temperature of the solution containing boric acid is at least 5 (rc, 5 〇 to 85. It is preferably '60 to 80 ° C: more preferably. The 'immersion time can be (9) to 12 sec., preferably 150 to 600 sec.' 200 to 400 seconds is better. After acid removal, the PVA film can be washed and dried. The cleaning is performed by immersing the PVA film obtained by the acid treatment in water. The water temperature for cleaning can be from $ to 40 ° C, soaking time. It can be from i to 12 sec. After drying after washing, a polarizer can be produced. Drying can be carried out by a hot air dryer or an & IR heater. The drying temperature can be 30 to 100 t, preferably 5 〇 to 8 〇, and The drying time may be 60 to 600 seconds, preferably 12 to 600 seconds. The thickness of the polarizer manufactured above may be 5 to 40 qing. According to an embodiment of the present invention, as shown in Fig. 1 (4), the polarizing plates may be sequentially stacked. Cellulose or polyolefin-based protective enamel; adhesive layer formed by the adhesive component' comprises a water-like polyamine epoxy resin and a styrene-based modified PVA resin; a polarizer; an adhesive formed by the adhesive component The layer comprises a water-like pvA resin and a protective film.

Pill DRA006TW 17 201231589 According to another embodiment, as shown in FIG. 1(b), the polarizing plates may be sequentially stacked: a cellulose or polyolefin-based protective film; an adhesive layer formed by an adhesive component, comprising a watery polyamine ring Oxygen resin and acetonitrile-based modified PVA resin; polarizer, adhesive layer formed by adhesive component, comprising water-like polyamidamine epoxy tree May and Ethylene-based modified PVA resin; protection membrane. According to still another embodiment, as shown in FIG. 1(c), the polarizing plates may be sequentially stacked: a cellulose or polyolefin-based protective film; an adhesive layer formed of an adhesive component, comprising a water-like polyamine epoxy resin and B A modified layer of pvA resin; a polarizer, an adhesive layer formed of an adhesive component, comprising a water-like polyamido epoxide 1 〇 resin and an acetonitrile-modified PVA resin; cellulose or polyolefin Base Protective Film 〇 Hereinafter, preferred embodiments of the present invention will be described with reference to the following examples. However, it will be apparent to those skilled in the art that various modifications and changes can be made without departing from the scope and spirit of the invention as defined by the appended claims. Preparation Example 1 - Polyvinyl alcohol (PVA) film having a thickness of polarizer 75, an average degree of polymerization of 2,400, and a degree of saponification of more than 9 m〇i% or more was immersed about 5 times in a dry mode uniaxially, and 20 was immersed in a state of 20 while maintaining the extraction state. . 〇 water (distilled water) for 1 minute. Then, the extracted membrane is immersed in person 28. (: 0.05/5/100 weight ratio of 峨 / 峨 钟 / steamed water solution for 60 seconds. Thereafter, the impregnated membrane was once again immersed in 72 of its 8.5 / 8.5 / 100 weight ratio of potassium iodide / boric acid / distilled water Another solution _ sec. The treated water is washed for 2G seconds, then in the dry

iMlIDRAOU^TW 18 201231589 Drying thus made a polarizer containing iodine adsorbed and aligned on the PVA film. Preparation Example 2 - Preparation of a protective film cellulose acetate diacetate film, KC8UX (manufactured by Konica Co., T), which was saponified by 5 lines, and Zeonoa (Nippon Zeon Co., Z) as a ring-shaped polyolefin resin, as propylene oxime The film I film (Nippon Zeon Co., P) and the polyethylene resin film were subjected to corona discharge on the adhesive surface at 〇3 to k5 kV, respectively. Example 1 1〇 (1) Preparation of an adhesive component 99.2 mol% of a degree of saponification of ethylene sulfonate-modified pVA resin (Kosenol Z200, Nippon Synthetic Chemical Industry Co,

Ltd.) Dissolved in water (distilled water) to prepare an aqueous solution of wt% solids 〇

15 30 parts by weight (solid content) of the prepared ethyl hydrazide-based modified pVA resin solution 'B' mixed with 1 part by weight of water-based polyamide resin

(SR-650, Sumitomo Chemicals, A). Then, 25 parts by weight of KOH 'C' was added to 1 part by weight (solid content) of aqueous polyamine epoxy resin (SR-650, Sumitomo Chemials, 30 wt.%) until the mixture pH reached 20 1 1 · 9 ' by which the adhesive component is prepared. Here, the adhesive component has a viscosity of 2.8 mPa·sec (20 ° C). The adhesive component was maintained to have a total solid content of 5 parts by weight relative to 1 part by weight of water (solvent). (2) Adhesion of polarizer and protective film (manufacturing of polarizing plate) The adhesive component was applied to both sides of the polarizer formed in Preparation Example 1.

P11IDRA006TW 19 201231589 After having a dry film thickness of o.i, a cellulose triacetate-based film, for example, KC8UX (Konica Co., T) is adhered to the polarizer via a pinch. The adhered polarizer was dried in a hot air drier at 80 ° C for 5 minutes to produce a polarizing plate. Example 2 A polarizing plate was produced according to the same procedure as in Example 1, except that after the adhesive component was applied to one side of the polarizer, KC8UX (K〇nica Co., T) as a cellulose triacetate film was adhered to the polarizer. And a cyclic polyolefin resin, for example, 10 Zeonoa (NiPP〇n Zeon Co., Z)' adheres to the other side of the polarizer. Example 3

The polarizing plate was fabricated in accordance with the same procedure of Example 1, except that after the adhesive component was applied to one side of the polarizer, KC8UX 15 (Konica Co., Τ) as a cellulose triacetate film was adhered to the polarizer, and the poly The vinyl film Q is adhered to the other side of the polarizer. Example 4 A polarizing plate was produced according to the same procedure as in Example 1, except that after the adhesive agent component was applied to one side of the polarizer, KC8UX (Konica Co., T) as a cellulose triacetate film was adhered to the polarizer. On the other hand, an acryl resin film, for example, an I film (Nippon Zeon Co., P), is adhered to the other side of the polarizer. Example 5 PI1IDRA006TW 20 201231589 The same procedure as in Example 1 The adhesive group of pH 12.1 of KOH was used to manufacture a polarizing plate. The adhesive composition was applied to pH 13 of KOH having the same procedure as in Example 6 5 according to Example 1. Making a polarizing plate A polarizing plate was produced except that the same procedure as in Example 7 was carried out according to Example 1, except that the adhesive component of pH 7 of 10 NaHC03 was applied. Eight' Example 8 According to the same procedure of Example 1, a polarizing plate was fabricated, except that it was coated.

Adhesive component of NaHC03 pH 7.68. Eight 15 Example 9 According to the same procedure of Example 1, 水i^ ^ Water 1 made a polarizing plate, except that it was coated with

Adhesive component of pH 8.14 of NaHC03. VIII 20 Example 1 偏 A polarizing plate was produced according to the same procedure as in Example 1, except that water-soluble polyamide resin (SR_65〇, Sumit〇m〇) was applied with respect to 100 parts by weight.

Chemicals) An adhesive component having 5 parts by weight (solids content) of an ethylene sulfonate-modified PVA resin solution. PI1IDRA006TW 21 201231589 Example 11 A polarizing plate was produced according to the same procedure as in Example 1 except that it was coated with 100 parts by weight (solid content) relative to 100 parts by weight of a water-based polyamide resin (SR-650, Sumitomo Chemicals). The acetaminophen is modified to the adhesive component of the 5 PVA resin solution. Example 12 A polarizing plate was produced in accordance with the same procedure as in Example 1 except that 10 parts of the adhesive component having a solid content of 20 parts by weight relative to 100 parts by weight of water (solvent) was applied. Comparative Example 1 A polarizing plate was produced according to the same procedure as in Example 1, except that 200 parts by weight (solid content) of ethyl hydrazine was applied with respect to 100 parts by weight of a water-based polyamide resin (SR_650, Sumitom® 15 Chemicals). The adhesive component of the ethoxylated PVA resin solution. Comparative Example 2 A polarizing plate was produced according to the same procedure as in Example 1, except that an adhesive of an anhydrous phthalocyanine epoxy resin having a weight of 20 〇〇 part by weight (solid content) of an acetonitrile-modified PVA resin solution was applied. Agent component. Comparative Example 3 A polarizing plate was produced according to the same procedure as in Example 1, except that it was coated with

PII1DRA006TW 22 201231589 100 parts by weight of water-like polyamine ring gas resin without ethyl acetate-based modified P VA resin solution adhesive component. Comparative Example 4 5 A polarizing plate was produced in accordance with the same procedure as in Example 1, except that an adhesive component having a pH of 6.5 of KOH was applied. Comparative Example 5 A polarizing plate was produced in accordance with the same procedure as in Example 1, except that an adhesive component having a pH of 14 KOH was applied. Comparative Example 6 A polarizing plate was produced according to the same procedure as in Example 1, except that 30 parts by weight of glyoxal was added with respect to 100 parts by weight (solid content) of acetonitrile-modified PVA resin, and anhydrous. Adhesive component of polyamine epoxy resin. Comparative Example 7 A polarizing plate was produced according to the same procedure as in Example 1, except that an adhesive component containing a 20-carboxy modified PVA resin solution (Kuraray Co., KL-318) in place of an ethylene-based modified PVA resin solution was applied. . Table 1 below shows the constituent components and physical properties of the adhesive components prepared by the examples and comparative examples. PI1IDRA006TW 23 25 201231589 Table 1 Item Adhesive Component Α/Β Component Solid Content Α/Β Ratio CA/C Total Solids Content (Parts by Weight) PH Viscosity (mPa. sec) (20°C) Example 1 SR650/Z200 100/30 ΚΟΗ 100 /25 5 11.9 2.8 Example 2 SR650/Z200 100/30 ΚΟΗ 100 /25 5 11.9 2.8 Example 3 SR650/Z200 100/30 ΚΟΗ 100 /25 5 11.9 2.8 Example 4 SR650/Z200 100/30 ΚΟΗ 100 /25 5 11.9 2.8 Example 5 —----- SR650/Z200 100/30 ΚΟΗ 100 /30 5 12.1 2.7 Example 6 SR650/Z200 100/30 ΚΟΗ 100 /40 5 13.0 2.1 Example 7 SR650/Z200 100/30 NaH COi 100 /25 5 7.1 3.5 Example 8 SR650/Z200 100/30 NaH C03 100 /50 5 7.68 3.28 Example 9 SR650/Z200 100/30 NaH C03 100 /10 0 5 8.14 2.5 Example 1 0 SR650/Z200 100/5 KOH 100 /25 5 11.1 2.1 Example 11 SR650/Z200 100/100 KOH 100 /25 5 11.4 4.5 Example 1 2 SR650/Z200 100/30 KOH 100 /25 20 11.7 20.6 Comparative SR650/Z200 100/200 KOH 100 /25 5 10.8 2.8 Comparative SR650/Z200 0/100 KOH 100 /25 5 11.9 9.2 Comparative example 3 SR650/Z200 100/30 KOH 100 /25 5 11.9 1.6 fComparative SR650/Z200 100/30 KOH 100 /1 5 6.5 4.5 Comparative __ϋ_5 SR650/Z200 100/30 KOH 100 /50 5 14.0 1.5 Comparative Example 6 Ζ200/Glyoxal 100/30 KOH 100 /25 5 11.9 8.4 Comparatively-JH7 Δ ]-ΪΓ -.,." ZR650/KL3 1 8 100/30 KOH 100 /25 5 11.9 2.8 Ethylene oxime modified PVA resin L · Inorganic inorganic salt: gray il dog polyamide epoxy resin, Sumitomo Chemicals T VII 00: Ethyl hydrazine modified ρϋα resin, Nippon Synthetic Chemical industry Co., Ltd. 〒: Acting agent: carboxyl modified PVA resin, Kuraray Co._

Pi] IDRA0U6TVV 24 201231589 Experimental Examples Examples 1 to 12 and Comparative Examples 丨 to 7 were used to measure the physical properties of each of the adhesive components and the polarizing plate, and the measurement of the surname, '0' is shown in Table 2. (1) Viscosity (tool evaluation) After the manufactured polarizing plate was left at room temperature for 1 hour, the cutter blade was inserted between the respective films of the polarizing plate (between the polarizer and the polarizer protective film I). Evaluation and classification according to the following criteria: Insertion condition when the force piece is pushed between the membranes 0 ◎: The cutter blades are not inserted into the gap between the membranes. 10: Insert at least one film when the tool blade is pushed, stop at i to 2mm △. Insert at least one film when the tool blade is pushed, x: When the tool blade is pushed, it is easy to insert at least one (2) hot water resistance stop At 3 to 5mm 臈. The manufactured polarizing plate was left in the environment of 23 t Shoukou 55% humidity for 24 hours, and the hot water resistance was measured. First, the polarizing plate was cut into a rectangular shape of 5 cm x 2 cm to prepare a sample, and the absorption axis (extraction direction) corresponds to the long side of the polarizing plate to accurately measure the dimension in the longitudinal direction. Here, the sample exhibits a uniform and unique color across the entire surface due to the iodine adsorbed on the polarizer. As shown in Fig. 2, (A) shows that the short side of the sample/injection hot water sample is gripped by the gripper 5, and (B) about 80% of the sample 1 which is not caught by the gripper is immersed in the longitudinal direction at 60 °C. The shrinkage sample 4 obtained after the hot water bath was maintained for 4 hours. After the immersion is completed, the sample 4 is taken out from the bath, and after dehumidification, the polarizer is measured to shrink. In detail, the distance between the end of the protective film '1 a' in the middle of the short side of the sample and the end of the shrinkage polarizer 4 was measured as the shrinkage length. Figure 2 (B), located in the center of the polarizer

Pi 11 〇Ra〇〇6T\V 25 201231589 The polarizer 4 shrinks due to hot water immersion, so a region 2 is produced between the two protective films, in which the polarizer is omitted. Due to the immersion in hot water, iodine penetrates away from the periphery of the polarizing plate 4 which contacts the hot water, causing a fading (bleaching) portion 3 around the periphery of the sample. In order to determine the degree of bleaching, the measured value is determined as the iodine fading length by measuring the distance between the 4 - end of the shrinkage polarizer in the middle of the short side of the sample and the area of the unique color of the polarizing plate. The sum of the aforementioned shrinkage length and the iodine fading length represents the total length of the money Χβ, that is, the total rot length χ represents the media from the middle of the short side of the sample 1. t, the end of the sample T between the T'la, to maintain the polarization The distance of the area of the board's unique color. When shrinking length, iodine fading length, total 10 20

When the length X of the rot is reduced, the viscous (hot water resistance) of the worm 丨rj* U JJ column 疋 water increases. ◎: total corrosion length (X) < lmm 〇: lmm = total rot money length (x) < 2 mm △ : 2 mm = total corrosion length (x) < 5 mr X : 5 mm = total corrosion length (χ) (7) optics Properties (transmittance, degree of polarization) Μ UV_W "Spectrometer (V·,

Bunko Co. Ltd.) Central: __ 旦 H

Transmittance and polarization of polarizers made in /. After measuring the parallel transmittances H.,, 匕4 and the vertical transmittance ,, the calculation results are evaluated according to the following criteria according to the following formula 1: In this respect, the #b ° 耵 ratio is in accordance with JISZ 8701 (published in 1982) based on the spectral sensitivity of the 2 degree field (C source) flat a f ))

PIIIDRA006TW 26 201231589 Equation 1 Degree of polarization (Py, %) = {(H〇— H90)/(H0 + H9.)}丨/2 χ 100 Table 2 Protective film (fibrous, vitamin or cellulose resistance) Hot water transmission polarization project olefin-based or polyene protection ratio degree film/carbon-protecting film (%) (%) film) Example 1 T/T 〇〇〇42.3 99.9 Example 2 T/Z 〇 〇〇 42.3 99.9 Example 3 T/Q 〇〇〇 42.3 99.9 Example 4 T/P 〇〇〇 42.3 99.9 Example 5 T/T ◎ ◎ ◎ 42.3 99.9 Example 6 T/T ◎ ◎ ◎ 42.3 99.9 Example 7 T/T 〇 〇〇 42.3 99.9 Example 8 T/T ◎ ◎ ◎ 42.3 99.9 Example 9 T/T ◎ ◎ ◎ 42.3 99.9 Example 1 0 T/T 〇〇〇 42.3 99.9 Example 11 T/T 〇〇〇 42.3 99.9 Example 1 2 T/ T 〇〇〇 42.3 99.9 Comparative Example 1 T/TXX 〇 42.3 99.9 Comparative Example 2 T/TXX Δ 42.3 99.9 Comparative Example 3 T/TXX Δ 42.3 99.9 Comparative Example 4 T/TXX Δ 42.0 99.9 Comparative Example 5 T/T Δ Δ Δ 42.3 99.9 Comparative product comparison example 6 T/TXX Δ 42.3 99.9 7 T/TX 〇Δ 42.3 99.9 T : Konica Co., KC8UX (trademark), cellulose triacetate film Z: Nippon Zeon Co·, Zeonoa (trademark), cyclic polyolefin resin film P: Nippon Zeon Co·, I film , propylene resin film Q: polyethylene resin film

Pi 11DRA006FVV 27 201231589 As shown in Table 2, it was found that the polarizing plate according to the present invention comprises a first adhesive layer stacked on one side of the polarizer (formed by a water-based polyimide resin and an ethylene-based modified PVA tree) and The cellulose triacetate film and the polyolefin protective film laminated on the adhesive layer exhibit excellent viscosity and resistance to hot water even under high temperature and humidity conditions. On the other hand, according to the adhesive composition of the comparative example, in detail: the adhesive component of Example 1 was compared (using an excess of ethylene-based modified p VA resin); the adhesive component of Comparative Example 2 was compared ( Non-water-based polyamine epoxy resin); Comparative Example 3 adhesive component (without acetonitrile modified pVA 10 resin); Comparative Example 6 adhesive component (using glyoxal instead of aqueous poly The amine component epoxy resin was compared with the adhesive component of Example 7 (replacement of the acetonitrile-modified PVA resin with a rebel-modified PVA resin), which did not have both good viscosity and hot water resistance. The adhesive component of Example 4 (low pH) exhibited a low penetration ratio and reduced viscous and hot water resistance, while destroying optical properties. Further, the adhesive component (high pH) of Comparative Example 5 caused product failure due to damage such as a discolored polarizer. As described above, the polarizing plate according to the present invention can have a good viscosity, and in particular, 'excellent adhesion to a polarizer and a cellulose or polyolefin-based 20 protective film under high temperature and humidity conditions' to enhance durability and Reliability. The polarizing plate of the present invention or its liquid crystal display device can be effectively utilized or used therein when it is transported through a tropical region, an offshore region, a high temperature and humidity region such as near the equator, and the like. Furthermore, the present invention for improving adhesion is effective for diverging a large amount of heat backlight

PIIIDRA〇a6TW 28 201231589 For high resolution or where the distance between the polarizer and the backlight decreases as the thickness of the LCD monitor decreases. Further, the polarizing plate of the present invention may include an adhesive component having a controlled alkalinity to enhance optical properties such as degree of polarization, transmittance, and the like. Although the present invention has been described with reference to the preferred embodiments thereof, it is to be understood that various modifications and changes may be made without departing from the scope of the invention as defined by the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a configuration of a polarizing plate according to an embodiment of the present invention. FIG. 2 is a view showing a test method for water resistance of a polarizing plate. [Main component symbol description] 1 : Sample 1 a : One end of protective film 2: Area where polarizer is omitted 3 : Faded part around sample 4 : Polarizer 5 : Grip IDRA006TW 29

Claims (1)

201231589 VII. Patent application scope: 1. A polarizing plate having a polarizing plate, an adhesive layer stacked on one side or both sides of the polarizing plate, and a cellulose or polyolefin-based protective film laminated on the adhesive layer, wherein the adhesive layer includes 00 parts by weight of the aqueous polyamidamine epoxy 5 resin having an adhesive component of from 1 to 100 parts by weight (solid content) of an ethylene glycol modified polyethylene (PVA) resin, the pH of which is 7 to 13. 2. The polarizing plate of claim 1 wherein the adhesive component contains an inspective compound. 3. A polarizing plate according to claim 2, wherein the basic compound is selected from the group consisting of a metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate. 4. The polarizing plate of claim 3, wherein the alkali metal or alkaline earth metal hydroxide is used to form an adhesive component having a pH of from 1 to 13. 5. The polarizing plate of claim 3, wherein the alkali metal or alkaline earth 15 metal carbonate is used to form an adhesive component having a pH of 7 to 10. 6. The polarizing plate of claim 1, wherein the adhesive layer comprises an adhesive component having a solid content of from 3 to 2 parts by weight relative to 100 parts by weight of the solvent. 7. The polarizing plate of claim 6, wherein the adhesive layer comprises an adhesive component having a viscosity of 2 to 25 mPa.sec (20 ° C). 8* A polarizing plate according to claim 1, wherein the ethyl acetate-based modified PVA resin has a content of 10 to 50 parts by weight (in terms of solid content). 9. The polarizing plate of claim i, wherein the front side of the cellulose or polysulfide-based protective film is treated by one of a method of corona discharge, plasma treatment, and primer discharge. PIIIDRA006TVV 30 201231589 10. The polarizing plate of claim 1, wherein another protective film based on acrylonitrile, cellulose, polyolefin or polyester is further laminated on the other side of the polarizer via an adhesive layer. 11. The polarizing plate of claim 1, wherein the other protective film based on acryl, bismuth, polyolefin or polyester is further laminated on the polarizer via an adhesive layer containing a water-like PVA resin. One side. A liquid crystal display having a polarizing plate according to any one of claims 1 to 11. PI 11DRA006 FW 31