TW201013240A - Polarizing plate and its production method, and liquid crystal display - Google Patents

Abstract

The present invention provides a polarizing plate and its production method, and a liquid crystal display using the same. The polarizing plate comprising a polarizing film 51 in which a dichromatic dyestuff is adsorbed and oriented on a polyvinyl alcohol based resin film, a first protective layer 52 which is laminated on one face of the polarizing film 51 and made of a cured material of a curable composition comprising an active-energy-ray-curable-compound, and a second protective layer 53 which comprises a thermoplastic resin film and laminated on the other face of the polarizing film 51 through a bond layer 54.

Description

201013240 VI. Description of the Invention: [Technical Field] The present invention relates to a polarizing plate, and more particularly to a polarizing plate suitable for a liquid crystal display device of a bridge 0 (IPS) mode and a method of manufacturing the same, and the polarizing plate is used A liquid crystal display device driven by a transverse electric field mode. [Previous Technology] In recent years, due to the low power consumption of the liquid crystal display device (LCD), & his electric action, lightweight, thin and other advantages, it is in the mobile digital assistant (Personal Digital Assistant: The use of information display devices such as PDAs, personal computers, and televisions has rapidly increased. With the development of liquid helium display technology, there are proposals for various types of liquid crystal display devices, ... gradually solve the problem of LCD speed such as response speed or contrast, narrow viewing angle. As one of countermeasures for compensating the viewing angle, a liquid crystal cell having an essentially expandable viewing angle has been proposed. For example, an Optically Compensated Bend (0CB) mode, a Vertical Aligature (VA) mode, and an in-plane switching (IPS) mode can be cited. The ips mode is a transverse electric field applied to a voltage parallel to the substrate surface to change the alignment state of the liquid crystal molecules. In the IPS weight formula, when the liquid crystal molecules are aligned in parallel with the substrate surface, the liquid crystal molecules are not aligned as in the TN type, but the alignment is almost in the same direction. The principle of the ips mode will be described in accordance with FIGS. 1 and 2. Fig. 1 is a schematic cross-sectional view showing a configuration example of a liquid crystal display device of an IPS mode, and Fig. 2 is a normal black for explaining the principle of the IPS mode (n〇rmally 3 321399 201013240)

Mack) is a schematic oblique view of an example, (4) indicates no applied state, and (8) indicates a state when power is applied. Moreover, in Fig. 2, the layers are separated to be easily understood. Meanwhile, in Fig. 2 (8), only the parts which are in a different state from (4) are referred to the reference symbols, and in the part which is in the same state as (4), the reference is omitted in order to avoid the complexity of the drawing. The liquid crystal cell 1 at the center of the liquid crystal display device of the mode is composed of the upper and lower unit substrates u and 12 and the liquid layer 14 held between the unit substrates. The liquid crystal molecules 15 constituting the liquid crystal layer 14 are aligned substantially in parallel with the faces of the respective unit substrates 1b. Further, in the upper and lower sides of the liquid crystal cell, the front side polarized light is disposed opposite to the rear side, and the rear side polarizing plate 3 is disposed, and only the liquid is supplied from the back side of the outer side (back side) of the liquid crystal. The linear polarized light that penetrates the axis of the back side polarizing plate 3 between the day unit 10 and the backlight 40 is incident on the liquid crystal cell 10. The polarizing plate is usually composed of a polarizing film and a protective film. In the state where no applied voltage is shown in Fig. 2(A), the liquid crystal molecules 15 are aligned in the same direction with respect to the unit substrate surface. In this example, the liquid crystal molecules 15 are aligned in a direction substantially parallel to the transmission axis 32 of the back side polarizing plate 30. On the other side of the unit substrate (in this example, the lower substrate) 12, the electrodes 13 and 13 are arranged in a comb shape. In this state, the linearly polarized light 16 that has penetrated the back side polarizing plate 3〇 passes through the liquid crystal layer 14 without changing the polarization state, and passes through the upper unit substrate u in a state of the linearly polarized light 17 in the same direction as the incident state. . As long as the transmission axis 22 of the front side polarizing plate 20 disposed thereon is offset from the back side side 321399 4 201013240, and the transmission axis 32 of the light plate 30 is perpendicular, the linearly polarized light 17 passing through the upper unit substrate η - cannot pass through the front. The side polarizing plate 20 is in a dark state. On the other hand, as shown in FIG. 2(B), when an electric field 18 indicated by a broken line is externally disposed between the electrodes 13 and 13 arranged in parallel on the unit substrate, the liquid crystal molecules The long axis of 15 is aligned as the electric field 18, and is deflected from the transmission axis 32 of the polarizing plate 30 on the back side. As a result, the linearly polarized light 16 incident on the liquid crystal cell 10 changes the polarization state when passing through the liquid crystal layer 14, passes through the liquid crystal layer 14, and becomes the circularly polarized light 17, thereby generating the transmission axis 22 which can pass through the front side polarizing plate 20. The composition, in turn, shows a bright state. In the second embodiment, the transmission axis 32 of the back side polarizing plate 3 is disposed almost parallel to the long axis of the liquid crystal molecules 15, and the front side polarizing plate 20 and the back side polarizing plate 3 are arranged. It is disposed in a vertical direction, but even if the transmission axis 22 of the front side polarizing plate 2 is disposed almost in parallel with the long axis of the liquid crystal molecules 15, and the front side polarizing plate 20 and the back side polarizing plate 30 are worn. The same result can be obtained by arranging the shaft as the 吉吉^ v Tian Shen as far as the summer. The important point is that as long as 傕汸S^ c , tc , and the long axis of the knives 15 of the day are arranged relative to the transmission axis of either of the polarizers, a few f _... long: = at this time 'not required to be strictly Parallel, the plate's transmission axis must be rotated to a certain square & field 8 to make the liquid crystal molecules 15 within the angle. ° „A certain degree of angle, for example, in the “20 and the rear side polarizer 3〇*2 half system, when the front side polarizing plate is applied with a voltage, the black 庐 1 tooth % is vertically arranged, and the When the voltage is applied, the bright state is 321399 5 201013240, that is, the so-called normal black, but as long as the front side polarizing plate 20 and the back side polarizing plate 30 are parallel to the transmission axis, It can become a bright state when no voltage is applied, and it exhibits a dark state when a voltage is applied, that is, a so-called normal whHe. Therefore, in the IPS mode, since the liquid crystal molecules are parallel to the substrate surface and When it is arranged in the same direction, it has excellent viewing angle characteristics when compared with other modes. However, the triacetyl cellulose film used as a protective film for a polarizing plate has a retardation in the in-plane. The retardation Rth of 5 nm and the film thickness direction is approximately 50 ηπι, so in the liquid crystal display device using the film as a protective film between the liquid crystal unit and the polarizing film, there is a birefringence of the transmitted light. In order to solve such a problem, in order to solve such a problem, for example, a transparent film having a retardation Re in the in-plane and a retardation Rth in the film thickness direction is disclosed, as disclosed in Japanese Laid-Open Patent Publication No. 2006-18245. In order to make the protective film of the polarizing plate thin, on the other hand, in order to make the protective film of the polarizing plate thin, for example, the patent document 2 (JP-A-2004-245924) discloses a polyvinyl alcohol-based resin. A technique in which an uncured epoxy composition is applied to at least one surface of a polarizing film on which a film is adsorbed to form a dichroic dye, and then the composition is cured to form a δ-protected film. In the polarizing plate of the epoxy composition, the durability of the polarizing plate is insufficient, for example, the shrinkage of the polarizing film under high temperature conditions is not sufficiently suppressed, and the size of the polarizing film is broken by more than 15 inches. [Problem of the Invention] 6 321399 201013240 An object of the present invention is to provide a polarizing plate and a method of manufacturing the same, wherein the polarizing plate has a retardation Re and a surface disposed on a surface of a protective layer on a liquid crystal cell side A polarizing plate having a small retardation Rth in the film thickness direction, and a polarizing plate excellent in thinness, lightness, and durability, and particularly a polarizing plate to which a liquid crystal display device of a transverse electric field (Ips) mode is applied. Further, the object of the present invention Provided is a liquid crystal display device using the polarizing plate, particularly a liquid crystal display device driven by a transverse electric field mode. The present invention provides a polarizing plate comprising: a polarizing film for adsorbing two colors of a vinyl alcohol resin film a pigment-aligned one; a first protective layer laminated on one surface of the polarizing film, which is composed of a cured product of a curable composition containing an active energy ray-curable compound; and an adhesive layer Further, a second protective layer laminated on the other surface of the polarizing film is composed of a thermoplastic resin film. In the polarizing plate of the present invention, the post-hardening composition used in forming the first protective layer preferably contains a cyclic fluorene compound having at least one epoxy group in the molecule as an active energy ray-curable compound. Epoxy epoxidation: The ruthenium is preferably one having at least one epoxy group bonded to a kinematic ring. The human sclerosing composition can also be used as a reactive energy ray hardening compound. Further, the curable composition may contain, as a hetero energy ray-curable compound, a (methane) (tetra) acid compound having at least one (meth) propylene oxide in the molecule. The first protective layer formed by the hard (four) of the intended product has a thickness of from 0 to 1 to 10 β ju. 321399 7 201013240 The second protective layer should be composed of cellulose acetate-based tree. The layer of the agent should be composed of active energy stone #彳^4曰臊. Further, the curable composition of the I-line curable compound of the cured product of the present invention may further comprise an adhesive layer which is laminated on the side of the polarizing film of the first protective layer. Sun, Takada μ ^ 々 恻 恻 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 本= light = on both sides of the unit - for the polarizing plate, and the - 7 彳 is the polarizing plate of the present invention provided with the above adhesive layer and bonded to the liquid crystal single-system Wei Qian through the adhesive layer The device is provided with a liquid crystal cell and a pair of polarizing plates disposed on both sides of the ancient single sheet, and the pair of polarizing plates are the polarizing plates of the present invention provided with the adhesive layer, and the adhesive is interposed therebetween. The layer is bonded to the liquid crystal cell. The liquid crystal cell in the liquid crystal display device of the present invention preferably has two sheets.

The substrate and the liquid crystal layer in the transverse electric field mode of the liquid crystal layer held between the substrates are in the state of no applied voltage, and the liquid crystal layer is aligned slightly parallel to the substrate. Further, according to the present invention, a method for producing a polarizing plate can be provided, wherein the β-polarized plate is provided with a polarizing film which adsorbs a dichroic dye and is aligned with the poly-square plate, and the layer is deposited on the surface of the light-consuming surface. The first protective layer composed of the cured product of the curable composition of the active month b and the wire-cured material 5, and the layer formed on the other surface of the polarizing film via the adhesive layer and composed of a thermoplastic tree The second protective layer, the method includes: 321399 8 201013240. The step of forming a coating layer of the coating layer of the curable composition on the surface of the substrate, and coating the curable composition provided on the surface of the substrate a coating layer bonding step of laminating a layer on one surface of the polarizing film, a film bonding step of bonding the first protective layer to the other surface of the polarizing film via an adhesive, and hardening the coating layer and the adhesive The hardening step and the substrate removal step of removing the substrate. The hardening of the coating and the adhesive in the hardening step is preferably performed by simultaneously irradiating the active energy ray from the side of the substrate while hardening the both. The polarizing plate of the present invention has an in-plane retardation Re and 祺. Thick direction delay

The smaller - protective layer of Rth. Therefore, when the polarizing plate of the present invention is applied to a liquid crystal display device having the first protective layer on the liquid crystal cell side, light leakage can be effectively prevented. At the same time, since the first protective layer is composed of a cured product of the hardened composition, when compared with the conventional triacetyl cellulose (TAC) film or the like, the thickness of the protective layer can be reduced, so that the polarizing plate can be obtained. Thin and lightweight. Further, according to the method for producing a polarizing plate of the present invention, the polarizing plate of the present invention can be obtained without a drying step, so that the process can be simplified. [Embodiment] <Polarizing Plate> Fig. 3 is a view showing a polarizing plate of the polarizing plate of the present invention. The polarizing plate shown in Fig. 3 has a polarizing film 51 and a layer laminated on one side of the polarizing film 51. The upper transparent protective layer 52 and the second protective layer 53 laminated on the other surface. The first protective layer 52 is a cured composition of a hardenable composition having an amphoteric energy ray curable compound, 321399 9 201013240 The second protective layer 53 is composed of a thermoplastic resin film, and is passed through an adhesive layer. 54 is attached to the polarizing film 51. Further, the polarizing plate 50 is provided on the outer side of the first protective layer 52, that is, on the surface opposite to the polarizing film 51 of the first protective layer 52, and has an adhesive layer 55 for bonding a liquid crystal cell or the like. Further, the polarizing plate of the present invention may not have an adhesive layer. The polarizing plate of the present invention will be described in detail below. (Polarizing film) The polarizing film which exhibits the function of the polarizing plate is formed by causing the polyvinyl alcohol-based resin film to adsorb and disperse the dichroic dye. The polyvinyl alcohol constituting the polarizing film may be obtained by saponifying a polyvinyl acetate-based resin. The polyvinyl acetate-based resin may, for example, be a polyvinyl acetate which is a homopolymer of vinyl acetate, and a copolymer such as vinyl acetate and another monomer copolymerizable therewith. The other monomer copolymerizable with vinyl acetate may, for example, be an unsaturated carboxylic acid, an unsaturated sulfonic acid, an olefin or a vinyl ether. The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, and preferably 98 to 100 mol%. It is also possible to modify the poly-vinyl alcohol-based resin, for example, it is also possible to use an aldehyde-modified polyethylene condensate (?〇17¥丨1^1; ^1'111&amp;1) or polyethylene condensate Acid (vinyl acetate) and the like. Meanwhile, the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, and preferably about 1,500 to 10,000. As the film made of the polyvinyl alcohol-based resin, an original film as a polarizing film can be used. The method of forming the polyvinyl alcohol-based resin into a film is not particularly limited, and a film can be formed by a known method. 10321399 201013240 _ The thickness of the original film is not particularly limited, and is, for example, about 10 // m to 15 0 // m. The polarizing film is usually produced by the following steps: a step of uniaxially stretching an original film composed of the above polyvinyl alcohol-based resin, dyeing a polyvinyl alcohol-based resin film with a dichroic dye, and adsorbing a dichroic dye The step of treating the polyvinyl alcohol-based resin film which has adsorbed the dichroic dye with a boric acid aqueous solution, and the step of washing with a boric acid aqueous solution and then washing with water. * Uniaxial stretching can be carried out before dyeing with a dichroic dye, or simultaneously with the dyeing, or after the dyeing. When uniaxially stretching after dyeing with a dichroic dye, the uniaxial stretching can be carried out before the boric acid treatment or in the boric acid treatment. In addition, uniaxial stretching can also be performed in these several stages. When uniaxially extending, it can be extended to a single axis between rollers of different peripheral speeds (ro 11), or it can be extended to a single axis using a hot roller. At the same time, it may be a dry stretching such as stretching in the atmosphere, or a wet stretching in which the stretching is carried out in a state of swelling with a solvent. The stretching ratio is usually about 4 to 6 times. When the polyvinyl alcohol-based resin film is dyed with a dichroic dye, for example, the polyvinyl alcohol-based resin film may be impregnated into an aqueous solution containing a dichroic dye. As the dichroic dye, iodine, a dichroic dye or the like can be used. Further, the polyethylene glycol resin film is preferably subjected to a dipping treatment in water before the dyeing treatment. When iodine is used as the dichroic dye, the dyeing method is usually carried out by impregnating a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide. The content of the potassium iodide is usually about 0.5 parts per 100 parts by weight of water, and is usually about 0.5 parts by weight. Up to 10 parts by weight. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C, and the time (dyeing time) of being immersed in the aqueous solution is usually about 30 to 300 seconds. On the other hand, when a dichroic dye is used as the dichroic dye, the dyeing method is usually a method in which a polyvinyl alcohol-based resin film is impregnated into an aqueous dye solution containing a water-soluble dichroic dye. When the amount is 100 parts by weight relative to water, the content of the dichroic dye in the aqueous dye solution is usually about 1X '1 (Γ3 to 1χ10_2 parts by weight. The dye aqueous solution may also contain a non-tantalum salt such as sodium sulfate as a dyeing auxiliary. The temperature of the aqueous solution of the dye is usually about 20 to 80 ° C, and the time (dyeing time) of the aqueous solution of the dye is usually about 30 to 300 seconds. The treatment with boric acid after dyeing with the dichroic dye is The dyed polyvinyl alcohol-based resin film is treated by being impregnated in an aqueous solution containing boric acid. The content of boric acid in the aqueous solution containing boric acid is usually about 2 to 15 parts by weight with respect to 100 parts by weight of water, and is 5 The amount of the boric acid-containing aqueous solution preferably contains potassium iodide. When the iodine is used as the dichroic dye, the potassium iodide content in the aqueous solution containing boric acid is usually about 2 to 20 by weight relative to 100 parts by weight of water. And preferably from 5 to 15 parts by weight. The time of impregnation in the aqueous solution containing boric acid is usually about 100 to 1,200 seconds, preferably 150 to 600 seconds, and preferably 200 to 400 seconds. Water soluble boric acid The temperature of the liquid is usually about 50 ° C or higher, and preferably 50 to 80 ° C. The boric acid-treated polyvinyl alcohol resin film is usually washed with water 12 321399 201013240 treatment system, for example, by acid-treated polymerization The ethoxylated resin is carried out in water. The temperature of the water treated with water is usually about 5 to 12 sec. The water is washed and dried to obtain a polarizing film. The drying process can use a hot air dryer. Or a far-infrared heater. The drying temperature is usually about 40 to lorc. The drying treatment time is usually about 120 to 600 seconds. Through the above treatment, a uniaxially stretched polyethylene glycol ruthenium resin film can be produced. a polarizing film obtained by adsorbing a dichroic dye. The thickness of the polarizing film is about 5 to 40/zm. (Protective layer) In the invention, the first protective layer provided on one surface of the polarizing film as described above is It is composed of a cured product of a curable composition containing an active energy ray-curable compound. Further, a second protective layer 设 provided on the other surface of the polarizing film is composed of a thermoplastic resin film, and the thermoplastic resin is molded. The resin film is bonded to the other surface of the polarizing film via an adhesive layer. Hereinafter, the first protective layer and the second protective layer will be sequentially described. Further, the curable composition may also be referred to as curability. (1) (First protective layer) As described above, the first protective layer provided on one surface of the polarizing film is composed of a cured product of a curable composition containing an active energy ray-curable compound. The active energy ray-curable compound is a compound which can be cured by irradiation with an active energy ray (for example, ultraviolet light, visible light, electron beam, x-ray, etc.) The active energy ray-curable compound may be a cationically polymerizable compound or may be A radical polymerizable compound. Examples of the cationically polymerizable compound 13 321399 201013240 include an epoxy compound having at least one epoxy group in the molecule (3) and an epoxide in the molecule. A ring oxetane compound (hereinafter, simply referred to as "oxetan compound"). Further, examples of the radically polymerizable compound include a (meth)acrylic compound having at least one (meth)acryloxy group in the knives (hereinafter, simply referred to as "(meth)acrylic compound"). The term "(?)-propanyloxy" means methyl propyloxy or acryloxy. The hardened material obtained by applying the curable composition of the curable composition of the active energy ray-curable compound to f 3 is excellent in transparency, mechanical strength, stability, and the like, and can be provided by the following formula (1). The retardation value Re in the in-plane of the film-first protective layer and the protective layer in which the retardation value Rth of the film thickness defined by the formula (2) is almost zero. Here, in the case of H, what is called :: zero means that it is within the range of 0亀2〇, and preferably, and more preferably. In addition, it is within the range of the zero-named I P I ^, and the |R seven 1 soil, and the Μ I Rth | $20 is better. also

Re= (nx-ny) Xd R "=[(nx + ny)/2 - nJ Xd where, the direction of the vertical direction) m. The refractive index of the slow axis direction in the plane of the film 仏. The in-plane fast axis direction of the film (Refractive index nz in the direction of the slow axis Zn. Refractive index in the thickness direction of the film: thickness of the film 321399 14 201013240 The cured composition of the curable composition by the retardation value Re in the in-plane and the retardation in the film thickness direction The first protective layer, that is, when the first protective layer side is attached to the liquid crystal cell, is effective = the light leakage in the black display when the liquid crystal display device is applied. Further, the method = thickness Therefore, it is possible to achieve a polarizing plate and a liquid crystal display device: thinner, since the protective layer laminated on the polarizing film is preferably optical, the haze value of the first protective layer is preferably 5% or less, and preferably ❹ or less. 'And 〇. Add better. Such as haze value; light scattering causes the penetration rate to become lower... The above hardenable composition is preferably at least the above-mentioned active energy ray-curable compound. Thereby, the phase = a protective layer which exhibits good adhesion as a film can be obtained. (4) For the polarized light, the above epoxy compound From the viewpoint of sub-polymerization and the like, it is preferred to use a compound of the cation type 0 as a main component. Such a molecule does not contain a ring gas compound, and examples thereof include a hydrogenated epoxy compound, and a hydrogen peroxide ring. Epoxy compound, etc. D g alkane compound, in the presence of a catalyst, under the addition, so that the aromatic "optional hydrogenation reaction, then, can be selected Examples of the oxygen compound include a two-year-old milk compound, an aromatic (called ice coffee ether), a two-shot two-shrinking water _ diglycidyl surface, and the like, and a double-twisted epoxy tree wax, such as #/由_, two years old s cholesteric lac) epoxy resin, A__Oxygen _ (Phen〇1 epoxime, hydroxybenzaldehyde phenol 321399 201013240 epoxy resin and other (novo 1 ac) epoxy; A glycidyl ether of tetraphenyldiphenylmethane, a glycidyl ether of tetrahydrobenzophenone, a polyfunctional epoxy resin such as epoxidized polyethylene glycol, etc. Among them, bisphenol A hydrogenation is preferred. The glycidyl ether of the substance is used as a hydrogenated epoxy compound. The aliphatic epoxy compound may, for example, be aliphatic. A polyglycidol mystery of an alcohol or an alkylene oxide adduct thereof, more specifically, a diglycidyl ether of 1, 4-butanediol or 1,6-hexanediol Diglycidyl ether, triglycidyl ether of glycerol, trishydroxylated glycerol triglyceride ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol; for ethylene glycol or propylene glycol, An aliphatic polyhydric alcohol such as glycerin is added to one or more types of polyglycidyl polycondensate of polyhydric alcohol obtained by epoxy burning (epoxy Ethylene or epoxy propylene). In addition, the so-called alicyclic epoxy type The compound means an epoxy compound having at least one epoxy group bonded to an alicyclic ring. The "epoxy group bonded to the alicyclic ring" means a structure represented by the following formula, and wherein m ^ is an integer of 2 to 5.

Therefore, the alicyclic epoxy compound means a compound having at least one structure represented by the above formula in the molecule. More specifically, a compound obtained by combining one or several hydrogens in the form of (CH2) m of the above formula with other chemical structures can be alicyclic epoxyated 16 321399 201013240 'Composition. The gas of one or several of (CH2) B_ may be appropriately substituted with a linear alkyl group such as Yin group or 'ethyl. In the above-mentioned filming compound, it is preferable to use an alicyclic epoxy compound, that is, a compound in which at least one epoxy group is bonded to the alicyclic ring, and it is particularly preferable to use an oxabicyclic ring. An epoxy compound having a burned ring (m=3 of the above formula) or an oxabicycloheptane ring (of the above formula (4)) has a high modulus of elasticity of the cured product and is easily obtained from the polarizing film. Excellent sex: Pauli layer. The following is specifically exemplified by the structure of the alicyclic epoxy compound to which the present invention is applied, but is not limited to these compounds. (a) Epoxy ring vinegar represented by the following formula (I) · 衣衣衣基基 methyl% Oxygen Cyclohexanol Rebellion °&lt;^ c-o-ch2 R1 R2

I) ❹ (wherein R1 and R2 each independently represent a cyclohexane cyclohexane carboxy chain alkyl group of an alkanediol). (b) Table of the following formula (Π): Hydrogen atom or a straight acid of 1 to 5 carbon atoms ^ ^ (^C-〇-(CH2)n~0-C R3 R4

(H) (wherein R 3 and R 4 each independently represent a hydrogen atom or a straight carbon number of 1 to 5 321 399 17 201013240 chain stimulus ' η represents an integer of 2 to 2 )). (6) Epoxycyclohexylmethicone of a dicarboxylic acid represented by the following formula (8)

(m) 0 〇(^ch2'〇-S-(ch2)p R5 (wherein R and R each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and p represents 2 to 2 Å. (4) Epoxycyclohexyl oxime ethers of polyethylene glycol represented by the following formula (iv): R7 CH2~(〇C2H4)q-〇-CH2 R8 (17) (wherein R and R8 are independent The direct bond-shaped alkyl group "q" representing a hydrogen atom or a carbon number i to 5 represents an integer of 2 to 1 Å. (e) Epoxycyclohexyl oxime ether of an alkanediol represented by the following formula (V): R9 CH2-〇-(CH2)r〇-CH2 (V)

R (wherein R and R each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and r represents an integer of 〇 to 18). (Ο Diepoxide trispiral compound represented by the following formula (VI): 321399 18 (VI) 201013240

°o°x°&gt;(S 〇«y \_〇R11 (wherein R11 and R12 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms). (g) The following formula ( The diepoxy single spiro compound represented by W): #1 R14 - R13 (wherein R13 and R14 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms). (h)乙烯基) indicates vinylcyclohexene diepoxides: Ο

(M) (wherein R15 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms). (i) Epoxycyclopentyl ethers represented by the following formula (IX):

(K) (wherein R16 and R17 each independently represent a hydrogen atom or a linear bond having 1 to 5 carbon atoms). 19 321399 201013240 (J) Diepylene tricyclodecane represented by the following formula (x)

(X) The acne-like epoxy compound is preferably used because it is relatively easy to obtain based on the existing cockroach or the like. (A) an ester of 7-oxabicyclo[4.1.0]heptane-3-carboxylic acid with (7-oxabicyclo[4.1.0]heptan-3-yl)methanol [in the above formula (1), r1 a compound of =r2=h], (B) 4-methyl-7-oxabicyclo[4.i 〇]heptane_3_carboxylic acid and (4_fluorenyl 7 oxabicyclo][4.ίο]g _3_yl) acetate acetate [R-4CH3, R=4-CH3 compound in the above formula (1)], (C) 7-oxabicyclo[4. 1. 〇]heptane_3_carboxylic acid And hydrazine, ester of 2_ethylene glycol [in the above formula (Π), R3=R4=H, n=2 compound], (D) (7-oxabicyclo[4. ι·〇]g 3-()) an esterified product of methanol and hexanediol [in the above formula (羾), R5=R6=H, p=4 compound], (E) (4-methyl-7-oxabicyclo[4. 1. 〇]g _3-yl) acetate and adipic acid acetate [in the above formula (melon), r5=4-CH3, R6=4-CH3, p=4 compound], (F) ( The mystery of 7-oxabicyclo[4. 1. 〇]heptan-3-yl) sterol and 1,2-ethanediol [in the above formula (V), ruler 9=1^°=11, r= 2 compounds]. In the present invention, only one epoxy compound may be used alone, or 321399 20 201013240

'In combination with two or more types of D, the content of the epoxy compound in the fully active energy ray-curable compound is preferably from 3 Å to 100% by weight in the curable composition used in forming the first protective layer, and It is preferably from 35 to 70% by weight, and more preferably from 40 to 60% by weight. When the content of the epoxy compound is too small, the adhesion between the polarizing film and the first protective layer may be lowered. Further, in addition to the above epoxy compound, the curable composition may contain an oxetane compound as a pure energy ray-curable compound, and an addition of an oxetane compound may cause a hardenable composition. The viscosity becomes lower, which in turn accelerates the hardening speed. - the oxaxanthene (tetra) compound is a compound having at least one oxetan ring (four-membered cyclic ether) in the molecule, and examples thereof include a 3-ethyl-3-yl group: a oxalate; ^一双(6)-Ethyloxetane)Methoxy sulfhydryl] stupid, 3-ethyl-3_(phenoxyindenyl)oxetane, bis[(^ethyl 3~ gas Heterocyclobutane)indenyl]ether, 3-ethyl-3-(2-ethylhexyloxyindenyl)oxetane, phenol novolac oxetane and the like. These oxetane compounds are readily available in commercial products such as "A···〆" Aronoxetane 0XT-121", "Aronoxetane" Aronoxetane OXT-221", "Aronoxetane defeat 1_212" (all East Asian synthesis) (share) system, etc. Although the compounding amount of the oxetane compound is not particularly limited, it is usually 30% by weight or less in the total active energy linear compound and is preferably 10 to 25% by weight in the formation of the first protective layer. When the curable composition to be used contains a cationically polymerizable compound 21 321399 201013240 such as an epoxy compound or an oxetane compound, a photocationic polymerization initiator can be usually formulated in the curable composition. When a photocationic polymerization initiator is used, since the protective layer can be formed at normal temperature, it is less necessary to consider the skew caused by the heat resistance or expansion of the polarizing film, and it is possible to form a good adhesion on the polarizing film. The first protective layer. Further, since the photocationic polymerization initiator acts as a catalyst by light, even if it is mixed in a curable composition, its storage stability and workability are excellent. The photocationic polymerization initiator is subjected to irradiation of an active energy ray such as visible light, ultraviolet light, X-ray, or electron beam to cause a cationic species or Lewis acid © to start an epoxy compound and/or an oxetane. Polymerization of the compound. Any type of photocationic polymerization initiator can be used in the present invention, and specific examples thereof include an onium salt such as an aromatic diazonium salt, an aromatic onium salt, and an aromatic onium salt, and iron. - Propadiene complex and the like. The aromatic diazonium salt may, for example, be a benzene diazonium hexafluoroantimonate salt, a hexahydrate benzene diazonium salt or a hexafluoroborate benzene diazonium salt. ^ The aromatic sulfonium salt may, for example, be diphenylphosphonium sulfonium (pentafluorophenyl)borate, diphenylsulfonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate or di(4-fluorenyl) hexafluorophosphate. Phenyl) phosphonium salt and the like. The aromatic onium salt may, for example, be a triphenylsulfonium hexafluorophosphate, a triphenylsulfonium hexafluoroantimonate, a triphenylsulfonium salt of iridium (pentafluorophenyl)borate, or a 4,4'-bis[diphenyl group. Thiol]diphenyl sulfide dihexafluorophosphate, 4,4'-bis[bis(/5-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluoroantimonate, 4, 4'-bis[bis(/S-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluorophosphate '22 321399 201013240 salt, 7-[di(p-phenyl) thiol]- 2_Isopropylthioxanthone hexafluoroantimonate, [bis(p-tolyl)indenyl]-2-isopropylthioxanthone oxime (pentafluorophenyl) borate, 4-phenylcarbonyl- 4'-diphenyldecyl-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)- 4,-diphenylfluorenyl-diphenyl sulfide hexafluoroantimonic acid Salt, 4-(p-t-butylphenylcarbonyl)-4'-(p-tolyl)indolyl-diphenyl sulfide quinone (pentafluorophenyl)borate, and the like. Further, the 'iron-propadiene complex compound may, for example, be xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, © Xylene-cyclopentadienyl iron (II)-tris(trifluoromethylsulfonyl)methyl anion (methanide) and the like. Such photocationic polymerization initiators are readily available on the market as commercially available products, for example, the respective trade names are "Kayarad PCI-220" and "Kayarad PCI-620" (the above are Japanese chemical products) "MPI-103 "BBI-103 "TPS-103 "DTS_102 "PI-2074 "UVI-6990" (Union Carbide), "Adeka Optoniier SP-150", "Adeka Optomer SP-170" (above) For the ADEKA q system, "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", "CIP-2048S", "CIP-2064S" (above is Japan Soda ( Stocks), "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-105", "BBI-101", "BTBI-102", "BBI- 105", "TPS-101", "TPS-102", "TPS-105", "MDS-103", "MDS-105", "DTS-103" (above is Midori Chemical Co., Ltd.), ( Rhodia company), "UVCURE 1590" (Daicel)

Cytec Co., Ltd., etc. 23 321399 201013240 These photocationic polymerization initiators may be used singly or in combination of two or more kinds. In the above-mentioned initial shots, especially aroma = suitable, since it has a purple-ray absorption characteristic even in a wavelength region of 300 nm or more, it can be imparted with excellent hardenability, good mechanical strength or with a polarizing film. Good adhesion hardened material. When the total amount of the cationically polymerizable compound such as the epoxy compound or the oxetane compound is 100 parts by weight, the amount of the photocationic polymerization initiator is usually from 0.5 to 2 parts by weight, and I to 6 heavy denier is preferred. When the amount of the photocationic polymerization initiator is too small, there is a tendency that the chemical strength is insufficient and the adhesion between the protective layer and the polarizing film is lowered. On the other hand, when the amount of the photocationic polymerization initiator is too large, the hygroscopicity of the cured product is increased by the increase in the ionic substance in the cured product, and the durability of the obtained polarizing plate may be lowered. Further, the curable composition used in forming the first protective layer preferably contains the above-mentioned epoxy compound, epoxy compound, and oxetane compound, and also contains radical polymerizable. (Methyl) acrylic acid compound. When a (meth)acrylic acid compound is used in combination, a protective layer having excellent hardness, excellent mechanical strength, and high durability can be obtained. Further, it is possible to more easily adjust the viscosity and the curing rate of the cured composition, the surface hardenability of the obtained protective layer, and the adhesion to the polarizing film. The (meth)acrylic compound may, for example, be a compound having a decyloxy group: a (meth) cyanoacrylate monomer having at least one (?) propylene group in the molecule, or two or more kinds thereof. The functional group-based compound is obtained by reacting at least two (meth) propylene 321399 24 201013240 - ethoxylated (meth) acetoacetate oligomers and the like. These compounds may be used in combination of two or more kinds. When two or more types are used in combination, two or more kinds of (mercapto)acrylic acid vinegar monomers may be used, or two or more kinds of methyl groups may be used as the acid vinegar polymer. Of course, one or more (meth) propylene women may be used in combination. An acid monomer and one or more (meth) acrylate oligomers. Further, "(meth)acrylate" means acrylate or methacrylate. The above (meth) acrylate monomer may, for example, be a monofunctional (meth)acrylic acid acrylate monomer having one (meth) acryloxy group in the molecule, and two (meth) propylene fibers in the molecular oxime. A difunctional (meth) acetoacetate monomer having an oxy group, and a polyfunctional (fluorenyl) acrylate monomer having three or more (meth) propylene-transalkyl groups in the molecule. Specific examples of the mono-g-(meth)acrylate monomer include (meth)acrylic acid tetrahydrofuran ester, (meth)acrylic acid 2-hydroxyethyl ester, and (meth)acrylic acid 2- or 3-hydroxypropyl ester. 2-Hydroxybutyl (meth)acrylate, 2-3⁄4-yl-3-phenoxypropyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl methacrylate , (methyl) ethyl hexyl ethyl acrylate, (meth) hexahexyl acrylate, dicyclopentanyl (meth) acrylate, benzyl methacrylate, (meth) propyl phthalate Borneol vinegar, phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethyl carbitol (A) Acrylate, trimethylolpropane mono(methyl) acrylate, pentaerythritol mono (meth) acrylate, phenoxy polyethylene glycol (mercapto) acrylate vinegar, and the like. Further, as the monofunctional (meth) acrylate monomer, a (meth) acrylate monomer having a carboxyl group can also be used. Monofunctional (meth)acrylic acid containing a carboxyl group 25 321399 201013240 The ester monomer may be exemplified by 2-(indenyl)acryloxyethylidene dicarboxylic acid and 2-(meth)acryloxyethyl hexahydro Dicarboxylic acid, carboxyethyl (meth) acrylate '2-(methyl) propylene methoxyethyl succinic acid, N-(methyl) propylene oxime-N, N'-didecyl fluorenyl Diamine, 4-(meth)acryloxyethylidene diisopropyl dicarboxylic acid, and the like. Although the difunctional (meth) acrylate monomer is a decanediol di(indenyl) acrylate, a polyoxyalkylene glycol di(meth)acrylic acid vinegar, a halogen-substituted alkanediol di(a) Di(meth) acrylates of acrylates, aliphatic polyols, di(methyl) acrylates of hydrogenated dicyclopentadiene or tricyclodecane dialkyl alcohol, diterpenoids Di(meth) acrylates of dioxane glycol or diterpene calcined alcohol, di(meth)acrylic acid vinegar of double-phase A or double-aged F, and biguanide A or The epoxy group of the epoxy group of the F is a representative, but it is not limited to these compounds, and various monomers can be used. More specific examples of the monofunctional (fluorenyl)acrylic acid S monomer include ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and ◎ 1 '4-Butanediol di(meth)acrylate, 1,6-hexanediol bis(indenyl)acrylic acid vinegar, 1,9-nonanediol di(meth)acrylate, neopentyl glycol Di(meth) acrylate, trishydroxypropyl propane di(meth) acrylate, pentaerythritol di(meth) acrylate, dimethylolpropane di(meth) acrylate, diethylene glycol di(a) Acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, poly Propylene glycol di(methyl)propionate, polytetramethylene glycol di(meth)acrylate, polyfluorene di(decyl)propene 321399 26 201013240 dilute acid vinegar, trisyl mercaptoacetate Pentyl glycol di(meth)acrylate, '2'2-bis[4_(methyl)acryloxyethoxyethoxyethoxyphenyl]propane, 2' 2-bis[4_(methyl Propylene methoxyethoxyethoxycyclohexyl]propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylic acid vinegar, 1,3-two D Alkanol-2,5-diylbis(indenyl)acrylate [alias. Dioxane glycol di(meth)acrylate], acetal compound of hydroxytrimethylacetaldehyde and dimethylolpropane [ Chemical name: di(meth) acrylate of 2 (2-hydroxyl-dimethylethyl)-5-ethyl-5-hydroxymethyl-indole, 3-dioxane], tris(hydroxyl) Base) isocyanurate di(meth)acrylate and the like. The difunctional or higher polyfunctional (meth) acrylate monomer is glycerol tri(meth) acrylate, trimethylolpropane tri (meth) acrylate, di (trimethylolpropane) tri (a) Acrylate, bis(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, one Poly(meth)acrylates of difunctional or higher aliphatic polyols such as pentaerythritol penta (meth)acrylic acid vinegar, dipentaerythritol hexa(methyl) propyl sulfonate, and the like are representative, but others are still Examples thereof include poly(meth)acrylates in which a trifunctional or higher (tetra)-substituted aldecan alcohol, an alkylene oxide adduct of glycerin, and an alkylene oxide adduct of trimethylolpropane. Three (methyl) propylene vinegar, 1,1, bis [(methyl) propylene oxide ethoxy ethoxy ethoxy] propane, tris (hydroxyethyl) isocyanurate three (a Base) acrylates and the like. On the other hand, among the (meth) acrylate oligomers, there are urethane (meth) acrylate oligomers, poly (meth) acrylate oligos, and epoxy (methyl) ) acrylate oligomers and the like. 321399 27 201013240 The urethane methacrylate (meth) acrylate oligomer refers to a compound having an amine acetal linkage and at least two (?) acryloxy groups in the molecule. Specifically, the acetalization reaction can be carried out with a polyisocyanate containing at least one (meth) acryloxy group and at least one thiol group in the molecule. Product generation, or by more

An amine T-acid vinegar compound containing an isocyanate group at the end of the sterols and polyisocyanate, and at least one (meth) propyloxy group and at least a chelating group in the molecule The base (meth)acrylic acid vinegar monomer is subjected to a product of a urethanization reaction or the like.

C The above-mentioned amine formic acid acetalization reaction uses a W-based acrylic acid vine monomer containing a radical (for example, (meth)acrylic acid 2 - ethyl acetoacetate, (m-methyl) acrylic acid 2- Base propyl vinegar, (meth)acrylic acid 2_ butyl vinegar, (meth) acrylic acid 2, yl-3- oxypropyl vinegar, glycerol di(W) acrylate vinegar, tribasic Propione di(meth)acrylic acid, pentaerythritol tris(methyl)-propyl acetoacetate, pentaerythritol penta (meth) acrylate, and the like. The polyisocyanate g which can be subjected to an amidoxime acid oximation reaction with such a hydroxyl group-containing (meth) acrylate monomer is exemplified by hexamethylene diisocyanate and lysine. Diisocyanate, isophorone diisocyanate, dicyclohexan-2-methane diisocyanate, methyl benzene diisocyanate, xylene diisocyanate vinegar, aromatics in these diisocyanates a diisocyanate obtained by hydrogenating isocyanic acid vinegar (such as hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, etc.), triphenyldecane triisocyanate, bis(benzyl)benzene triisocyanate, etc. The tri-isocyanate and the above-mentioned isocyanate are quantified to obtain a polyisocyanate or the like. 321399 28 201013240 In addition, the polyol used in the formation of an amine phthalate compound containing a thiocyanate group at the end by reaction with an isocyanate vinegar can be used in addition to aromatics, aliphatics and fats. In addition to the cyclic polyol, a polyester polyol, a polyether polyol, or the like can be used. Examples of the aliphatic and alicyclic polyols include 1'4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and trisole. Hydroxydecylethane, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, bis(trimethylolpentane), bis(trihydroxymethylpropionic acid), bis(trihydroxyl) Methyl butyric acid), glycerin, hydrogenated bisphenol oxime A, and the like. The polyester polyol can be obtained by a dehydration condensation reaction of the above polyol with a polycarboxylic acid or a hydrazine anhydride. Examples of the polybasic acid or anhydride thereof include succinic acid (anhydride), adipic acid, maleic acid (anhydride), isaconic acid (anhydride), phthalic acid (anhydride), and pyromellitic acid (anhydride). ), phthalic acid (anhydride), isophthalic acid, terephthalic acid, hexahydrophthalic acid (anhydride), and the like. The polyether polyol may be a polyalkylene glycol or a polyoxyalkylene-modified polyol obtained by the reaction of the above-mentioned hydrazine polyol or dihydroxybenzene with an alkylene oxide. The polyester (meth) acrylate oligomer refers to a compound having an ester bond and at least two (meth) acryloxy groups in the molecule. Specifically, it can be obtained by a dehydration condensation reaction of (meth)acrylic acid, a polyvalent carboxylic acid or an anhydride thereof, and a polyhydric alcohol. Examples of the polyvalent carboxylic acid or an anhydride thereof used in the dehydration condensation reaction include succinic acid (anhydride), adipic acid, maleic acid (anhydride), isaconic acid (anhydride), and trimellitic acid (anhydride). And pyromellitic acid (anhydride), hexahydroquinone oxime (anhydride), phthalic acid (anhydride), isophthalic acid, terephthalic acid, and the like. Further, 321399 29 201013240 The polyhydric alcohol used in the dehydration reaction may, for example, be butanediol", diol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neodecanediol, and tri-fies. Ethyl bromide, trihydroxyl-based propyl phenocyanate bis (trimethyl propyl propyl bromide), pentaerythritol, dipentaerythritol, di(tri-f-form), bis(trihydroxymethyl-propionic acid), bis (trishydroxyl) Butyric acid), glycerin, hydrogenated bisphenol 4, and the like. The earth epoxy (f-based) acrylic acid vinegar oligomer can be obtained by an addition reaction of polyglycidil scale (meth)acrylic acid having at least two (methionyl) acryloxy groups in the molecule. The more the polyglycidol used in the addition reflection, the ethylene glycol diglycidyl ether, the propylene glycol diglycidyl ether, the tripropylene glycol diglycidyl ether, the 1,6-hexanediol diglycidyl ether, the bisphenol oxime Diglycidyl ether and the like. &quot; Among the above (meth) acrylate compounds, a compound having a structure represented by the following ΟΠ) or (XII) is preferred because it can impart a high modulus of elasticity to the cured product while simultaneously polymerizing with the cation When a compound (particularly an alicyclic epoxy compound) is combined, an excellent adhesion layer with a polarizing film can be obtained.

(wherein 'Qi and Q2 each independently represent (indenyl) propylene oxime or (meth) propylene oxyalkyl) where the carbon number of the alkyl group is i to 1Q, &amp; represents nitrogen or charcoal a hydrocarbon number of 1 to 10). 321399 30 201013240 In the above formula (XI) or (XII), if 7 or & is (meth) propylene oxyalkyl, the alkyl group may be a straight chain or a branched chain, although the carbon number It can be from 1 to 10 ' but generally has a carbon number of about 1 to 6. Further, in the formula (XII), when Q3 is a smoky group, it may be a straight chain or a branched chain, and may be represented by a burning group. The alkyl group at this time is also generally a carbon number of about 1 to 6. The compound represented by the formula (XI) is a di(meth) acrylate derivative of hydrogenated dicyclopentadiene and a tricyclic terpene dialkyl alcohol. Specific examples thereof are exemplified above, but exemplified by Acrylic acid hydrogenated dicyclopentadienyl ester [in the formula (XI), Q! = Q2 = (meth) propylene oxime compound], tricyclodecane dimethanol mono (meth) acrylate [formula In (XJ), Q1 = Q2 = a compound of (meth) propylene methoxymethyl group]. Further, the compound represented by the formula (XII) is a di(meth) acrylate derivative of dioxane glycol or diterpene aryl alcohol, and specific examples thereof are exemplified above, but L3 may be mentioned. Dioxane 2,5-diyldi(meth)acrylic acid vinegar [alias: dioxane ethylene glycol di(meth)acrylate, and is in the formula (XII), Q1=Q2=(A Acryloxy group, compound of Q3=H], acetal compound of hydroxytrimethylacetaldehyde and trimethylolpropane [Chemical name: 2 (2 good base-1, 1-monomethylethyl)- Bis(methyl) acrylate of 5-ethyl-5-carbylmethyl-][,3-dioxane] [In the formula (χιι), Qi = (meth) propylene oxime, Q2 = 2-(Methyl) propylene oxime-1,1-dimethylethyl, Q3=ethyl compound] and the like. In the mellow composition used in forming the first protective layer, the content ratio of the (meth)acrylic compound in the fully active energy ray-curable compound is preferably 70% by weight or less, and is 35 to 70% by weight. The content of % is better than that of 321399 31 201013240, and the ratio of 40 to 6 重量% is more preferable. When the content of the (meth)acrylic compound exceeds 7% by weight, the adhesion to the polarizing film tends to decrease. When the curable composition contains a radically polymerizable compound such as the above (meth)acrylic compound, it is preferred to prepare a photoradical polymerization initiator. The photoradical polymerization initiator may be a polymerizable compound such as a (fluorenyl)acrylic compound to be polymerized by irradiation with an active energy ray, and a conventionally known initiator may be used. Specific examples of the photoradical polymerization initiator include acetophenone, 3-indolyl acetophenone, benzyl dimethyl ketal, i- y-isopropylphenyl) 2 -hydroxyl group. Methylpropan-1-one, 2-mercapto-1-[4-(fluorenylthio)phenyl-2-(n-morpholinyl)propan-1-one, 2-hydroxy-2-indenyl-笨-stupyl propane _ 丨 ketone-based acetophenone initiator; benzophenone, 4-dibenzophenone, 4, 4'-diamine and benzophenone-based diphenyl a ketone initiator; a benzoin ether initiator based on benzoin, anthraquinone ether; a thioxanthone initiator based on 4-isopropylthioxanthone; Ketone (xanthone), fluorenone, camphorquinone, benzaldehyde, hydrazine, and the like. When the amount of the radically polymerizable compound such as a (meth)acrylic compound is 100 parts by weight, the amount of the photoradical polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 6 parts by weight. If the amount of the photoradical polymerization initiator is too small, the hardening is insufficient, and there is a tendency to lower the mechanical strength or the adhesion between the protective layer and the polarizing film. Further, when the amount of the photoradical polymerization initiator is too large, it is possible to lower the durability of the obtained polarizing plate 321399 32 201013240. The curable composition may further contain a photosensitizer in accordance with requirements. By using a photosensitizer, the reactivity of cationic energy polymerization and/or radical polymerization of the active energy ray-curable compound can be improved, and the mechanical strength of the protective layer or the adhesion between the protective layer and the polarizing film can be further improved. The light-increasing (four) may, for example, be a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo or a diazo compound, a dentate compound or a photoreductive dye. Specific photo sensitizers include, for example, benzoin m-scented isopropyl test, «, a-dimethoxy-oxime: benzophenone and other benzoin derivatives; such as benzophenone, 2' 4- Dichlorobenzophenone, decyl-p-benzoylbenzoate, 4,4,-bis(monomethylamino)benzophenone, 4,4,_bis(diethylamino) a benzophenone derivative such as benzophenone; a xanthene steel derivative such as 2_gas thioxanthone or 2_isopropylthioxanthone; such as 2-chloroindole, 2-methylindole, etc. Anthracene derivatives; such as hydrazine-methyl. Acridone derivatives such as ketone and Ν-butylacridone; others such as α, diethoxydibenzophenone, benzil, ketone, ton Ketones, uranyl compounds, halogen compounds, and the like. These compounds may be used singly or in combination. When the active energy ray-curable compound is in parts by weight, the content of the photosensitizer is preferably in the range of from 0.1 to 20 parts by weight. Further, the curable composition may also contain an antistatic agent to impart antistatic properties to the polarizing plate. The antistatic agent is not particularly limited, and a well-known antistatic agent can be used. For example, 'cations such as acyl〇ylainide propyl dimethyl hydroxyethyl ammonium nitrate, decyl hydrazinyl propyl trimethyl sulphate, hexadecyl sulphate morpholine rust salts, etc. can be used. Surfactant; such as linear 33 321399 201013240 anionic surfactants such as potassium alkyl phosphate, polyoxyethyl methyl phosphate, alkane sulfonate; such as n, n-bis(hydroxyethyl)_N_ a nonionic surfactant such as an alkylamine, a fatty acid ester derivative or a polyol fatty acid partial ester. The blending ratio of these antistatic agents is appropriately determined depending on the desired properties, and is usually about 0.1 to 20 parts by weight based on 100 parts by weight of the active energy ray-curable compound. A well-known polymer additive which is usually used for a polymer material may be added to the curable composition. For example, primary antioxidants such as phenols or amines, secondary antioxidants for sulfur, hindered amine mosquitoes (HALS), 0, benzoic acid (tetra), benzotriene, benzene? (4) line absorbers such as acid lanthanum + In addition, cerium oxide microparticles may be added to the curable composition. The hardness and mechanical strength of the resulting protective layer can be further improved by the addition of oxidized 7 fine particles. / The cerium oxide fine particles can be blended in an organic solvent to form a liquid, for example, and then formulated in a curable composition. ❹

The surface of the cerium oxide microparticles may also have a reactive functional group such as a hydroxyl group, an epoxy group, a (mercapto)acrylinyl group or a vinyl group. Further, the particle size of the oxidized A is usually H) () nm or less, and preferably 5 to 5 Gmn. If the particle size of the fine particles exceeds iGGnm, there is a tendency that an optically transparent protective layer cannot be obtained. When the oxidized granules dispersed in the organic solvent are used, the oxygen concentration is not particularly limited, and for example, (9) to 40% by weight which can be obtained from commercially available products can be used. 321399 34 201013240 "Oxidized cerium granules" which are obtained by a commercially available product and which are dispersed in an organic solvent, for example, "methanol oxime" in which the organic solvent is decyl alcohol (manufactured by Suga Chemical Industries Co., Ltd.) To 15nm, solid content: 3〇% by weight), MA~ST—M” (manufactured by Nissan Chemical Industry Co., Ltd., cerium oxide particle size 2〇 to 25nm, solid content: 40% by weight), “0SCAL 1132” (touch Manufactured into a chemical system (manufactured by the company), the oxidized cerium particle size is 10 to 20 nm, and the solid content is 30 to 31% by weight. The organic solvent is ethanol "OSCAL 1232" (catalyzed into a chemical industry), C diameter 10 to 20 nm 'Solid form: 30 to 31% by weight); "OSCAL· 1332" which is dissolved in propanol (made by Catalyst Chemical Industry Co., Ltd.), 矽 particle size 10 to oxidized A-part · · 3G to 31 4 The amount of organic solvent is 1〇's order (manufactured by the Chemical Industry Co., Ltd., oxidized cerium particles 15nm 'solid content: 3〇% by weight), and “〇SCAL 1432” (touch: Industrial Co., Ltd.) Oxygen Q-catalyzed cerium oxide particle size 10 to 20 nm, solid content. Weight %); organic solvent is ^ * 30 ^ 31 system $ 4 is n-butanol "nb A-st" (Nissan Chemicals *(^)

〇 1532" (catalytic Chenggong*; 〇sCAL

p war industry (stock) system, oxidized stone eve particle size 1 〇 to? n L ^: 30 to 31 by weight "EGn; 'solid = industry (8), gas pellet (4) to 15μ, Ε: Τ" (% by weight); organic solvent: 2 加"_T (8)9 alcohol ether (ethyl Cel1 coffee Ivek 2〇mn' solid content: 30 to 1 to 0〇~士: main 31% straight%), organic solvent propyl ether "NPC-STj (Nissan: B ~ Pian Magic 5nm, solid content: 3 () heavy ^ 2 shares of this 'oxidized stone Xi 勉 column weight%); organic solvent is two "DMAC-ST 丨 (日吝儿傲., .. ^基乙醯月 cmue) _ Chemical Cheng ## (share) system, oxygen cut J nm, solid content: 30 5 w - one,. School! 1〇$ alcohol single DMAC-ST" (曰产化化11/机,制',,,一T乙i to chemical industry (share) system, cerium oxide particle size 1〇3213% 35 201013240 15nm, solid content: 2 〇 weight (stock) system, oxidized hard grain and 7G, dirty Lu ZL" (Nissan Chemical Industry Machine solvent It is dimethyl stupid and positive 100·'solids: weight ^ industrial (stock), oxygen granules ί = compound "toe ST" (Nissan chemical organic solvent is methyl isobutyl _ 〇 Μ 5 Μ, solid Servings: 30-weight system, oxygen cut _ 1 () to 15 bribes - ST" ( Nissan Chemical Industry Co., Ltd. is methyl ethyl _ "_^, solid content: 30 suspicions"; organic lysine particle size 10 to ^, solid shape ji J (Nissan Chemical Industry Co., Ltd., oxidation chemical industry (stock) system, oxidized stone eve = ^ weight%), "heart 120" (Xiaoxi 10% by weight), "SP-6120" 2: to 2 〇 nm' solid fraction. 5 to diameter m, solid fraction. 5 West Chemical industry (stock) system, type or two or more types of oxidized stone granules. The other 5 to 1 〇 weight, etc., can use these traders "SNOWTEX 20" (Nissan can also use dispersant as water) Family nO, "S_m C" (made by Shiyeye Co., Ltd., Oxidized Oxide particle size 10 to 10 to 20 nm). Chemical industry (stock) system, the particle size of cerium oxide is relative to the hardening composition. When 100 parts by weight, the active energy ray is contained in a hardened weight fraction, and H) to (10) fossil granules are preferably added in an amount of 5 to 250. When the amount is too small, the damage may be caused by damage. For example, the addition of cerium oxide microparticles The hardness is insufficient. If the protective layer is further formed by cutting the fine particles, the addition amount of the microparticles may be excessive when the amount of the polarizing film and the protective layer is excessively increased. In addition, such as oxidized scorpion = female genital lowering, or hardening, the viscosity of the composition is excessively increased. 'And, the hardening composition can also contain solvents in accordance with requirements. Solvent 321399 36 201013240 - Depending on the solubility of the components constituting the hardenable composition - the solvent to be used is generally ok, k and selected. It is a hydrocarbon; for example, toluene or xylene oxime... such as hexane or per hexane Alcohols such as aliphatic alcohols, isopropanols, and n-butanol; such as acetone, methyl isobutyl ketone, cyclohexyl, etc.; such as acetonitrile, vinegar, etc.; , ethylene glycol acetamidine, diethylene glycol single coffee (10) lve); such as two: = work: and so on. The blending ratio of the solvent is a hardening property of the film forming property plus two = four (4) version _, (4) a suitable requirement. Further, the hard recording composition can be leveled with the requirement. When the curable composition is coated on the polarizing film or the substrate (4), the film or the substrate lacks wet impurities, or the surface of the cured product of the hardenable composition is not good, it can be improved by adding a leveling agent: leveling As the agent, various compounds such as silicones, gases, polyscales, acrylic copolymers, and titanates can be used. These leveling agents may be used alone or in combination of two or more. 5至份。 Preferably, the above-mentioned leveling agent is preferably added in an amount of from 0.1 to 丨. 7 parts by weight. And 〇. 2 to 〇· 5 weights are better. If the amount of the leveling agent added is too small, the improvement in wettability or surface properties may be insufficient. Further, if the amount of the leveling agent added is too large, the adhesion between the polarizing film and the protective layer may be lowered. The thickness of the first protective layer formed of the curable composition containing the active energy ray-curable compound described above is preferably 0.1 to 10/m, and 37 321399 201013240 is preferably 1 to 5/zm. If the thickness of the first protective layer is too thin, the durability is insufficient, and when it is too thick, the effect of reducing the thickness and weight of the polarizing plate is small. A method of forming a first protective layer using a hardenable composition will be described later. (2) Second protective layer The second protective layer composed of the thermoplastic resin film is laminated on the surface of the polarizing film opposite to the side on which the first protective layer is laminated via the adhesive layer. The second protective layer of the polarizing plate of the present invention may be, for example, a cellulose acetate resin, a cycloolefin resin, a polyolefin resin, an acrylic resin, a polyimide resin, or a polycarbonate resin. A polyester resin or the like is widely used in the field as a thermoplastic resin film which is a suitable material for a protective layer forming material, and is not particularly limited. From the viewpoint of mass productivity and adhesion, it is preferable to use a cellulose acetate resin film or a cycloolefin resin film as the second protective layer. Further, from the viewpoint of easiness and optical characteristics of the surface treatment layer, it is preferred to use a cellulose acetate based resin film as the second protective layer. The cycloolefin-based resin which is the second protective layer of the present invention is, for example, a unit of a monomer composed of a cyclic olefin (cyclonon hydrocarbon) such as a norbornene or a polycyclic norbornene monomer. Thermoplastic resin (also known as thermoplastic cyclic olefin resin). The cycloolefin resin may be a ring-opening polymer of the above cycloolefin, a hydrogenated product of a ring-opening copolymer using two or more kinds of cyclic olefins, or a cyclic olefin, a chain olefin, or an aromatic group having a vinyl group. An addition polymer of a compound or the like. In addition, it is also effective to introduce a polar base. When a second protective layer is formed by using a copolymer of a cyclic olefin, a chain olefin, and a vinyl compound having an aromatic compound 38 321399 201013240, the chain olefin may be a vinyl group. Examples of the aromatic compound include stupid ethylene-α-methylstyrene and a nuclear alkyl-substituted stupyl ethylene. In such a copolymer, the unit of the monomer composed of a cyclic olefin may also be 5 〇 mol% or less (preferably 15 to 50 mol%). In particular, when a second protective layer is formed using a ternary copolymer of a cyclic olefin and a chain-like diluted hydrocarbon and an aromatic compound having a vinyl group, the unit of the monomer composed of the cyclic olefin may be as described above. Less amount. In the ternary copolymer, the unit of the oxime monomer composed of the chain olefin is usually 5 to 80 mol%, and the unit of the monomer composed of the aromatic compound having a vinyl group is usually 5 to 8〇% of the ear. As the cycloolefin resin, a commercially available product such as "T〇pas" (manufactured by Ticorm Co., Ltd.), "ART0N" (manufactured by JSR Co., Ltd.), and "ze〇n〇r" (manufactured by Sakamoto Zeon Co., Ltd.) can be used. ), "ZE0NEX" (made by Japan ZeZn Co., Ltd.), "Ape丨" (Mitsui Chemical Co., Ltd.) (all of which are trade names). When the cycloolefin-based resin is formed into a film, a well-known method such as a solvent casting method or a melt extrusion method can be suitably used. At the same time, it is also possible to use, for example, rESSINA (made by Sekisui Chemical Co., Ltd.), "SCA40" (made by Sekisui Chemical Industry Co., Ltd.), "ze〇n〇r"

A commercially available product of a film of a cyclic sulfonated hydrocarbon resin which has been previously formed into a film, such as a film (manufactured by pts), is used as the second protective layer. The cycloolefin resin film used as the second protective layer may be a film which is uniaxially stretched or biaxially stretched. The stretching ratio at this time is usually from 1 to 5 times, and preferably from 1.1 to 3. Further, the cellulose acetate-based resin film which is applicable to the second protective layer of the present invention is a film of 321399 39 201013240 which is composed of a part or a complete acetic acid of cellulose, and may, for example, be a triacetyl cellulose film. , diethyl acetyl cellulose film, and the like. For the cellulose acetate-based resin constituting the cellulose acetate-based resin film, a commercially available product such as r Fu ji tac TD8 0" (Fuji Photo Film Co., Ltd.) and "Fujitac TD80 UF" (Fuji Photo Fiim) can be used. (share) system, "Fujitac TD80UZ" (Fuji Photo Fiim (share) system), "KC8UX2M" (Konica Minolta Opto (share) system), "KC8UY" (Konica Minolta)

A film made of a cellulose acetate resin such as Opto (manufactured by the company). The second protective layer used in the polarizing plate of the present invention has a thickness ❹ which is preferably smaller, but if it is too thin, the strength is lowered, and the workability is deteriorated, and if it is too thick, The transparency is lowered or the weight of the polarizing plate is made large. In view of the above, when the second protective layer in the polarizing plate of the present invention is a protective layer composed of a cycloolefin resin, the thickness thereof is usually 5 to 2 〇 0 / zm ' and is 1 〇 to i5. 〇/(Zm is preferred, and 2〇 to 1〇〇 is more preferable, and in the protective layer 4 composed of cellulose acetate-based resin, the thickness is usually 20 to 2 〇Mm, and is 30 to 150/ Preferably, zm is 40 to 1 〇〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Surface treatment, such as antistatic treatment, anti-reflection treatment, etc. X, in the surface of the second layer of the second layer opposite to the surface on which the polarizing film is adhered, a liquid crystal compound can be formed as a high molecular weight compound. The coating layer to be formed. &gt; The polarizing film and the second protective layer (thermoplastic resin film) can be used in the following manner. When the film is attached to the film, it is also possible to use 40 321399 201013240 in the polarizing film and / or on the subsequent surface of the second protective layer to which it is attached, apply appropriate electrical treatment, corona Surface treatment such as ultraviolet irradiation treatment, flame treatment, or saponification treatment to improve adhesion. The treatment may be carried out by impregnating an aqueous solution such as sodium hydroxide or hydrazine. An adhesive agent used when the polarizing film is bonded to the second protective layer. (Adhesive layer) The defect of the money is provided by the adhesive layer, which is an adhesive used when the polarizing film is adhered to the second protective layer. a layer composed of (adhesive composition) or a cured product thereof. The subsequent hybrid product of the present invention is particularly limited, and examples thereof include a hard, inert composition containing an active energy ray-curable compound. Or a water-based adhesive which is obtained by dissolving an adhesive component in water or dispersing an adhesive component in water. It is preferable to use a curable fine product containing an active energy ray-curable compound. The drying step is required. 硬化 纟 The curable composition of the above-mentioned adhesive composition is the same as the curable composition of the first protective layer. The hardenable composition of the first protective layer is formed. The active energy ray-hardening yttrium or the like contained therein may be the same as or different from the curable composition as the adhesive composition and/or the active energy ray-curable compound. In addition, a water-based adhesive which is obtained by dissolving an adhesive component in water or a binder into a water, and using a polyethyl alcohol resin or an amine 曱In order to use a polyvinyl alcohol-based resin as a main component of a water-based adhesive, the polyvinyl alcohol-based resin may be partially saponified polyvinyl alcohol or fully saponified polyvinyl alcohol. In addition, it can also be a modified polyethylene shaft resin such as modified polyvinyl alcohol, ethylene-modified ethylene glycol, methyl modified polyvinyl alcohol, and amine-modified polyethylene. When a polyethylene resin is used as the binder component, the binder is often prepared as an aqueous solution of a polyvinyl alcohol resin. When the amount is 100 parts by weight with respect to water, the concentration of the polyethylene tree in the adhesive agent is usually about i to 1 G by weight, and preferably 1 to 5 parts by weight.

In the adhesive containing a polyvinyl alcohol-based resin as a main component, t-ethyl or water-soluble epoxy curable component or a crosslinking agent is preferably added to improve the adhesion. The water-soluble epoxy resin may, for example, be obtained by reacting a poly(alkylene) such as diethylenetriamine or diethylenetetramine with a diremediate acid such as adipic acid to a polyamine polyamine. A polyamidamine polyamine epoxy resin obtained by reacting the polyamine polyamine with epichlorohydrin. This kind

Products such as "sumiraze resin 650" and "sumiraze resin 675" sold by PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 When the amount is 100 parts by weight based on the polyvinyl alcohol resin, the addition of such a curable component or a crosslinking agent is preferably from 1 to 100 parts by weight, and preferably from 5% to 5 parts by weight. If the amount of force is small, the effect of improving the adhesion is reduced. On the other hand, when the amount of the cerium is increased, the adhesive layer is made brittle. h When a urethane carboxylic acid resin is used as a main component of a water-based adhesive, an example of the adhesive composition of the * is a polyester-based ionic polymer-type amine 321399 42 201013240 Acid: the purpose of the tree and the glycidol A mixture of compounds of oxy groups. Here, the so-called polyester-based ionic polymer type uric acid has = and a small amount of ions (4) has been introduced therein (pro- 2 2 = day.) This ionic polymer type amine-based resin does not make it directly The emulsion is emulsified in water to form an emulsion. Therefore, it is suitable as a water system. The vinegar-based ionic polymer type urethane is a well-known ketone-free type described in JP-A-H07-975 (4). Aminic acid _ lipid is an example for dispersing a lye resin in an aqueous solvent dispersant, and in Japanese Patent Laid-Open (10) No. 0, No. 1817, The thickness of the second and second of the compound of the lyophilic acid and the glycidyloxy group is preferably 2. (4), and when it is thinner at 10 Å, it is preferably lower for the lower (10) or less. Thickness <The adhesive has less damage to the appearance of the polarizing film. 臈 Side = The hair (4) polarizer can also have an adhesive layer on the surface of the first protective layer and the polarizing agent such as the liquid. The layer can be used for the example: the bonding of the stickers. Using the adhesive layer, the polarizing plate and the liquid crystal == into a liquid crystal display In the case of the device, the polarizing film and the liquid crystal cell are formed, and the first step is to prevent the black phase from being formed by the hardened material of the curable composition and the phase difference in the thickness direction is almost zero. Light leakage. 321399 43 201013240 The formation of the adhesive layer can be carried out by, for example, ^^^(base polymer)#f^#j ^ Loosing or dispersing in the organic solvent of u or acetic acid to 40% by weight of the solution, 'the method of directly applying the solution to the (4)th repellent layer' or pre-existing on the protective film: then moving it onto the first protective layer to form an adhesive layer, etc. ^

It is determined in accordance with the adhesion, etc., but usually, the I base polymer may, for example, be an acrylic polymer, a polyoxohydrate, a polyester, a polypethane, a poly bond or the like. . It is preferred that the acrylic acid-based polymer as a base polymer is excellent in optical transparency, and can maintain moderate wet turbidity or political cohesion between the first protective layer or the liquid crystal cell. It is excellent in subsequent properties, and has weather resistance, heat resistance, and the like, and does not cause peeling problems such as peeling or floating under heating or humidification conditions.丙烯酸 The acrylic base polymer contained in the acrylic acid-based adhesive may, for example, be a methyl group having a carbon number of 2, or less, such as a methyl group, an ethyl group or a butyl group. An acrylic acid-based copolymer of acrylic acid or (meth)acrylic acid via a functional acrylic monomer such as ethyl acetoacetate. The glass transition temperature of the acrylic copolymer is preferably below hunger and preferably 〇 C or less. Further, the acrylic copolymer preferably has a weight average molecular weight of 100,000 or more. In the adhesive layer, it can also be blended with inorganic powder such as glass fiber, glass bead, resin pellet or metal powder to form a filler, a pigment, a coloring agent, an antioxidant, and an ultraviolet ray. Absorbent, etc. Examples of the ultraviolet absorber include a salicylate polymer, a benzophenone compound, a benzotriazole compound, a cyanoacrylate compound, and a nickel complex compound. <Method for Producing Polarizing Plate> The polarizing plate of the present invention can be produced through the following steps. There is no particular restriction on the order of the following steps (i) and (ii). (i) a step of forming the first protective layer on one surface of the polarizing film; and (ii) a step of bonding the second protective layer to the other surface of the polarizing film via an adhesive. (In the above step (i), the method of forming the first protective layer may be exemplified by the following method. First, a curable composition containing an active energy ray-curable compound forming a first protective layer is applied to a substrate and matched It is required to perform drying, that is, a coating layer (coating layer forming step) in which a curable composition is provided on the surface of the substrate. Next, the coated surface is used as a bonding surface, and the polarizing film is bonded to the coating layer (coating layer is bonded) Step). Then, on the laminate composed of the polarizing film/coating layer/substrate (when the step is performed before the step (i), the laminate includes the adhesive layer and the second protective layer) For example, the substrate side is heated by irradiation with an active energy ray such as visible light, light, ultraviolet light, X, line, or electron beam, and the coating layer composed of the curable composition is hardened to form a first protective layer (hardening step). Finally, the substrate on the first protective layer is removed (substrate removal step). At this time, the substrate may be a metal strip (belt), a glass plate, a polyethylene terephthalate film, a polycarbon film. Triethyl cellulose Lowering; water women sheet film, polyester film, polyethylene film or stupid B women. 321399 45 201013240 The surface of the coated hardenable substrate of the substrate may be peeled off, for example. Further, the other method of the above step (1) may be a method in which the curable composition containing the active energy ray-curable compound forming the first protective layer is directly coated on the polarizing film, and irradiated or heated by the active energy ray. The coating layer composed of the curable composition is cured to form a first protective layer. At this point, the substrate may not be needed. The method of bonding the second protective layer in the above step (ii) may be exemplified by the following method. First, the adhesive composition is applied to the second protective layer (thermoplastic plastic resin film), and then dried as required. Next, the coated surface is used as a bonding surface, and the polarizing film is bonded to the second protective layer (film bonding step). Then, 'the laminate of the polarizing film/adhesive/second protective layer is formed (when step (1) is carried out before step (ii), the laminate further comprises a first protective layer (or a hardenable composition) The coating layer) and the substrate are dried, or the laminate is irradiated or heated by an active energy ray such as visible light, ultraviolet light, X-ray, or electron beam to harden the adhesive composition to make the polarizing film and the second protective material. The layer is then 'dried with the requirements. When a curable &amp;amplifier containing an active energy ray-curable compound is used as the adhesive composition, the production efficiency can be improved by omitting the ruthenium (4). Further, a method may be mentioned in which the adhesive composition is directly applied to the polarizing film to bond the second protective layer, and then dried, or by irradiation or heating of the active u-ray. The composition is hardened to cause the bias film to follow the second protective layer and to dry it as required. The first protective layer and the second protective layer may be simultaneously formed. For example, a 321399 46 201013240 curable adhesive composition (a curable composition containing an active energy ray-curable compound, a water-based adhesive containing a curable component or a crosslinking agent, or the like) is used as an adhesive to prepare a second After the laminate of the protective layer/adhesive/polarizing film/coating layer/substrate, the laminate is irradiated with an active energy ray or heated from the substrate side, and the adhesive and the coating layer are simultaneously cured. Polarizer. By this method, it is only necessary to perform the hardening step once, so that the manufacturing efficiency can be further improved. In the present invention, the method of applying the curable composition containing the active energy ray-curable cerium compound and the adhesive composition to form the protective layer of the ruthenium-based protective layer is not particularly limited. For example, a doctor blade or a wire rod can be used. Various coating methods such as wire-bar), die coater, comma coater, and gravure coater. Further, after the above-mentioned curable composition or the adhesive composition containing the active energy ray-curable compound is dropped between the polarizing film and the second protective layer or the substrate, the method of uniformly stretching the expansion by pressing with a roller or the like In the middle, metal or rubber rubber can be used as the material of the roller. Further, after the curable composition or the adhesive composition containing the active energy ray-curable compound is dropped between the polarizing film and the second protective layer or the substrate, it is passed between the roller and the roller, and pressurized. In the method of extending the expansion, the rollers may be of the same material or different materials. When the curable composition and/or the adhesive composition containing the active energy ray-curable compound forming the first protective layer is cured by irradiation with an active energy ray, the light source used is not particularly limited. However, for example, a low-pressure mercury 321399 47 201013240 lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a halogenated metal lamp, etc., having a light-emitting distribution at a wavelength of 400 nm or less can be used. . The light irradiation intensity of the composition of the curable composition or the adhesive agent may be a wavelength field effective for activation of the photoradical polymerization initiator and/or the cationic polymerization initiator, although it may vary depending on the composition. The irradiation intensity is preferably from 10 to 2500 mV/cm2. If the light irradiation intensity of the hardenable composition is less than 10 mV/cm2, the reaction time becomes too long, for example, when it exceeds 2500 mV/cm2, the heat emitted by the lamp and the hardenable constituents or The heat of the composition of the polymer is then polymerized, and yellowing of the curable composition or the composition of the adhesive or deterioration of the polarizing film may occur. The light irradiation time of the curable composition or the composition of the adhesive is not particularly limited as long as it is dominated by the composition, but it is preferably set such that the cumulative amount of light represented by the product of the irradiation intensity and the irradiation time is 10 to 2500 mJ. /cm2. If the cumulative amount of light for the hardened twin composition is less than 10 mJ / cm2, the production of the active species derived from the polymerization initiator is insufficient, and the hardening of the resulting protective layer or the subsequent layer may be insufficient. Further, when the accumulated light amount exceeds 2,500 mJ/cm 2 , the irradiation time becomes extremely long, which is disadvantageous for the improvement in productivity. The irradiation of the active energy ray is preferably carried out in such a range that the various properties such as the degree of polarization and the transmittance of the polarizing film are not lowered. &lt;Liquid Crystal Display Device&gt; The liquid crystal display device of the present invention includes the above-described polarizing plate of the present invention, and more specifically, a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell spoon, and The polarizing plate of one or both of them is the above-mentioned 48 321 399 201013240 liquid crystal display device of the polarizing plate of the present invention. In the liquid crystal display device of the present invention, the polarizing plate of the present invention is bonded to the liquid crystal cell such that the first protective layer is on the liquid crystal cell side. That is, when the above-mentioned adhesive layer is provided on the first protective layer, it is bonded to the liquid crystal cell via the adhesive layer. The liquid crystal display device of the present invention having such a configuration can effectively prevent light leakage during black display, and can also be thin and light. Although the liquid crystal cell used in the liquid crystal display device of the present invention can be in any mode, in the case of using the liquid crystal unit of the IPS mode driven in the transverse electric field mode, in particular, the effect of preventing light leakage during black display can be obtained. (Embodiment) Hereinafter, the present invention will be described more specifically by way of examples, but the invention is not limited thereto. In the example, "parts" and "%" indicating the amount or content of use are based on weight unless otherwise specified. (Production Example 1: Preparation of Polarizing Film) A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more and a thickness of @75/zm was immersed in pure water at 30 ° C, and then It was immersed in an aqueous solution of iodine/potassium iodide/water in a weight ratio of 0.02/2/100 at 30 °C. Then, it was immersed in an aqueous solution of potassium iodide/boric acid/water in a weight ratio of 12/5/100 at 56.5 °C. Then, it was washed with pure water at 8 ° C, and then dried at 65 ° C to obtain a polarizing film in which iodine was adsorbed on the polyvinyl alcohol film and aligned.倍倍。 The extension of the iodine dyeing and boric acid treatment step, the full extension ratio of 5.3 times. (Production Example 2: Preparation of Hardened Composition I) First, the following components were mixed to obtain a cured composition I. 49 321399 201013240 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (Delcel Chemical Co., Ltd., Cel loxide 2021P) 35 parts of bis(3-ethyl-3-oxo Heterocyclic butanemethyl)ether (manufactured by East Asia Synthetic Co., Ltd.)

Aronoxetane 0XT-221) 15 parts by weight of trimethyl ethane ketone and tri-methyl propyl acetonate di- acrylate (A-D0G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts 2 -transmethyl-2-methyl-1-phenylpropanone-1- _ (Ciba refined (Ciba)

Specialty Chemicals) DAR0CURE 1173, photoradical polymerization initiator) 2. Photocationic polymerization of 5 parts of 4,4'-bis[diphenylfluorenyl]diphenyl sulfide hexafluorophosphate Starting agent (made by Daicel Cytec Co., Ltd., UVCURE 1590) 2. 5 parts of polysulfide-type leveling agent (made by Toray Dow Corning Co., Ltd., SH 710) 〇· 2 parts and 'A-D0G above The diacrylate of the tris-methylacetic acid and the triacetin-activated acetal compound is a compound having the structure of the following formula. CH2 - 〇 bH2CH3 ch2 = chcoo - ch2 - c (Production Example 3: Preparation of Hardened Composition II) The following components were mixed to obtain a cured composition 11. 3, 4-epoxycyclohexyldecyl-3, 4-epoxycyclohexanecarboxylate (Daice; 1 chemical, Celloxide 2021P) 75 parts of bis(3-ethyl-3-oxocycle) Butyryl fluorenyl ether (manufactured by East Asia Synthetic Co., Ltd., 321399 50 201013240

Aronoxetane 0XT-221) 25 parts of 4, 4' [diphenylfluorenyl] diphenyl sulfide hexafluorophosphate photocationic polymerization initiator (Daicel Cytec, UVCURE 1590) 5 parts poly Shiki Oxygen Leveling Agent (manufactured by Toray Dow Corning Co., Ltd., SH 710) 2. 2 parts (Production Example 4: Preparation of polyvinyl alcohol-based adhesive) After mixing the following components, the polyethylene is obtained. · Alcohol binders. 100 parts of pure water, carboxy modified polyvinyl alcohol ("Kuraray Poval KL318" by Kuraray) 1.8 parts of water-soluble polyamide resin (Sumiraze resin 650, manufactured by Chem Chemex Co., Ltd.) Solid solution (30% aqueous solution)) 0. 9 parts (Production Example 5: Preparation of polarizing plate A) The polyvinyl alcohol obtained by the production example 4 was applied to one surface of the polarizing film produced in Production Example 1. After the subsequent treatment, a saponified protective layer (manufactured by Konica Minolta Opto Co., Ltd., KC8UY 'thickness 80 #m) composed of triethyl fluorenyl cellulose was bonded. After drying in 6 〇t &gt; C for 6 minutes, a polarizing plate A having a protective layer on one side was produced. <Example 1> The curable composition 1 obtained in Production Example 2 was coated on a polyethylene terephthalate (PET) film by a coater (first physicochemical (bar) type bar coater) (Toyobo Co., Ltd.) (share) system, one side of vinegar film E5100). In addition, the protective layer 321399 5! 201013240 (Konica Minolta 〇pt〇, KC8UX, thickness 8Mm) composed of triethyl fluorenyl cellulose which has not been subjected to the treatment treatment is subjected to corona treatment. After that, the curable composition II was applied in the same manner on this surface. At this time, since the film thickness of the coating layer when the curable composition is applied varies depending on the viscosity, the film number can be adjusted by changing the line number of the bar coater. Next, the pET film having the coating layer of the curable composition I is bonded to one side of the polarizing film produced by the y-1, using a bonding apparatus (manufactured by Fujipla Co., Ltd., LpA33〇1), and has The protective layer of the coating layer of the curable composition is bonded to the other surface of the polarizing film produced in the production example, and the respective coating layer sides are bonded to the polarizing film. Ultraviolet light having a cumulative light amount of 1500 J/cm 2 was irradiated onto the laminate from the ρΕΤ film side by a D valve manufactured by Fusion UV Systems, and the hardened composition I and the coating layer disposed on both surfaces of the polarizing film were hardened. . Then, after peeling off the PET film, a transparent first protective layer (cured material of the curable composition I) is provided on one surface of the polarizing film, and a transparent second protective layer is provided on the other surface (three-stranded A polarizing plate of a cellulose film). Further, when the thickness of the polarizing plate was measured by a film thickness measuring device (manufactured by Nikon Co., Ltd., ZC-101), it was 116 / / ΙΠ. Further, the thickness of the first protective layer is 4#ιη. &lt;Example 2&gt; The curable composition I obtained in Production Example 2 was coated on a polyethylene terephthalate (PET) film by a coater (a bar coater manufactured by Konica Minolta Co., Ltd.). (One side of Toyobo Co., Ltd.'s t-film E5100). At this time, the film thickness of the coating layer when the curable composition is applied varies depending on the viscosity, so that the film thickness can be adjusted by changing the line number of the bar coater. Then, the above-mentioned hardenable composition is provided on the side opposite to the surface on which the protective layer is bonded by the polarizing plate A of the manufacturing method 5 (manufactured by Fujipla Co., Ltd., LPA3301). The PET layer of the coating layer of I was bonded, and the coating layer side was brought into contact with the polarizing film. By applying a D valve manufactured by Fusion UV Systems Co., Ltd., an external line having a cumulative light amount of 1500 J/cm 2 was irradiated onto the pET film side, and then the coating layer of the curable composition 配置 disposed on both surfaces of the polarizing film was cured. Then, after the PET film was peeled off, a polarizing plate was produced. The thickness of this polarizing plate is 114#m. Further, the thickness of the first protective layer (hardened material of the curable composition 4) was 4 / Z ID &lt;=. &lt;Comparative Example 1&gt; The polarizing plate A produced in Production Example 5 was used. The thickness of the polarizing plate A was 110 β m 0 <Comparative Example 2> The polyvinyl alcohol-based adhesive obtained in Production Example 4 was applied onto both surfaces of the polarizing film produced in Production Example 1, and saponified on one side. a protective layer composed of triethyl fluorenyl cellulose (Konica Minolta Opto 1#, KC8UY, thickness 80/nn), and laminated on the other side; A protective layer (Konica Minolta Opto manufactured by Konica Minolta Opto, KC4UEW, thickness 40/zm) having a retardation value Re in the plane and a retardation value Rth in the film thickness direction is almost zero. After drying at 60 ° C, a polarizing plate was prepared. This polarizing plate has a thickness of 150/zm. <Evaluation Test>, (1) Adhesion Durability Test After the adhesive layer was provided on the polarizing plates of the above Examples 1 to 2 53 321399 201013240 and Comparative Examples 1 to 2 by the following method, the following test method was followed. Evaluate the durability of the polarizing plate. [Formation of Adhesive Layer] An adhesive solution containing a copolymer of butyl acrylate and acrylic acid, an amine phthalate acrylate oligomer, an isocyanate crosslinking agent, and an organic solvent was applied to Examples 1 and 2. On the first protective layer of the polarizing plate, the polarizing film of the polarizing plate of Comparative Example 1, and the protective layer (KC4UEW) composed of triethyl fluorene cellulose of the polarizing plate of Comparative Example 2, and then dried. That is, an adhesive layer is formed on each of the polarizing plates. © [Test method] The polarizing plate with the above-mentioned adhesive layer was bonded to the glass through the adhesive layer, and then stored under a drying condition at a temperature of 80 ° C for 300 hours, and then visually observed. After the polarizing plate, the results are shown in Table 1. The evaluation criteria are as follows. 〇: There is almost no change in appearance such as lifting, peeling, and foaming. △: A slight change in appearance such as lifting, peeling, and foaming was observed. ^ X : Apparent changes in appearance such as lifting, peeling, and foaming were confirmed. (2) Measurement of retardation of the protective layer The first protective layer (cured product of the curable composition I) used in the polarizing plates of Examples 1 and 2, and the triacetate-based cellulose of the polarizing plate of Comparative Example 2 were measured. In the protective layer (KC4UEW), the in-plane retardation value Re and the retardation value Rth in the film thickness direction can be measured by the following method. The results are shown in Table 1. Further, the measurement results of the retardation values of the first protective layer used in the polarizing plates of Examples 1 and 2 were obtained by forming a hardened material of the chemical composition 1 on the PET film in the same manner as described above. A cured film (thickness 4 &quot; m) 祺 [in-plane retardation value Re) obtained by PET 利用 [E-deletion of the measuring machine manufactured by the prince measuring machine (stock), with a monochromatic light of wavelength 559 The in-plane retardation value 仏 was measured by a rotational analyzer method (_ating analyzer me^thod).

[The retardation value RthJ in the film thickness direction is measured by the "K-cut_21 thin" similar to the above, and the retardation value Rth in the film thickness direction is measured by the early-color light having a wavelength of 559. The measuring step of this measuring machine is =1. The retardation in the two faces is as follows: 6. The retardation value R4 = at the =40 degree, the thickness d of the film, and the film ratio η are measured with the slow axis as the tilt axis. According to the following formulas (3) to (5), the values are calculated to obtain mi and these values are substituted into the above formula (2), and the retardation value Rth in the film thickness direction is calculated.

Re=(nx-ny)xd (3) ❹ R4〇=(nx-ny,)xd/cos(0)(4) (Πχ+Πγ+Πζ)/3=π〇. (5), Here, 0=sin_1[ Sin(4O°)/n〇] ny =nyXn°/[ny2xsin2(0)+nz2XCQS2(0) Yan 321399 55 201013240 Table 1

The embodiments and examples disclosed in the present invention are illustrative, and should be considered as non-sexual. The scope of the present invention is not intended to be limited by the scope of the invention, but not the scope of the claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a configuration example of a liquid (four) display device of the IPS mode. Fig. 2 is a schematic perspective view showing a normal black as an example for explaining the principle of the IPS mode, wherein (A) shows a state when no applied voltage is present, and (B) shows a state when an applied voltage is applied. Fig. 3 is a schematic cross-sectional view showing a preferred example of the polarizing plate of the present invention. Brother [Main component symbol description] 10 Liquid crystal cell η, 12 unit substrate 13 Electrode 14 Liquid crystal layer 15 Liquid crystal molecules 16 Linear polarized light incident on the liquid crystal cell 321399 56 201013240 Zero

17 Linear polarized light passing through the liquid crystal cell 17' Rounded polarized light passing through the liquid crystal cell 18 Electric field 20 Front side polarizing plate 22 Front side polarizing plate penetration axis 30 Back side polarizing plate 32 Back side polarizing plate penetration axis 40 Backlight 50 polarizing plate 51 polarizing film 52 first protective layer 53 second protective layer 54 subsequent agent layer 55 adhesive layer ◎ 57 321399

Claims (1)

201013240 VII. Patent application scope: 1. A polarizing plate comprising: a polarizing film which adsorbs a dichroic dye by a polyvinyl alcohol resin film, and a first protective layer laminated on one surface of the polarizing film, It is composed of a cured product of a curable composition containing an active energy ray-curable compound, and The second protective layer laminated on the other surface of the polarizing film via an adhesive layer is composed of a thermoplastic resin film. For example, in the polarizing plate of the first aspect of the patent application, the compound (10) has a molecule (10) and is the active energy ray-curable compound. For example, the patent application is as follows: 1. The first epoxy resin has at least one ring bonded to the alicyclic ring. The polarizing plate of the second or third aspect of the patent application, the sexual composition The oxetane compound is contained in the following item 71. * For example, a polarizing plate of the present invention, the sclerosing composition of the above-mentioned sclerosing composition contains a (meth)acrylic compound having a small acryloxy group in the molecule. A hardening compound. The thickness of the first protective layer is 〇. 1 to in, ' '1 υ m m 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏 偏, the second layer of the above-mentioned 4th 321399 58 201013240' layer is composed of a cellulose acetate-based resin film, and the polarizing plate of any one of the above-mentioned claims, wherein The adhesive layer is composed of a cured product of a curable composition containing an active energy ray-curable compound, and a polarizing plate according to any one of claims 1 to 8, wherein the adhesive layer is The polarizing plate according to any one of the first to ninth aspects of the present invention, which is used for the liquid crystal driven in the transverse electric field mode. 11. A liquid crystal display device comprising: a liquid crystal cell; and a pair of polarizing plates disposed on both sides of the liquid crystal cell; wherein at least one of the pair of polarizing plates is a polarizing plate of claim 9 And bonding through the adhesive layer A liquid crystal display device comprising: a liquid crystal cell; and a pair of polarizing plates disposed on both sides of the liquid crystal cell; wherein the pair of polarizing plates are polarizers of the ninth item of U Patent Application No. And the liquid crystal display device of claim 11 or 12, wherein the liquid crystal cell has two substrates and is held between the substrates a liquid crystal layer which is slightly parallel with respect to the substrate in the state of no applied voltage. The alignment 'and' the liquid crystal is preceded by a liquid crystal plate driven by a transverse electric field plate. 14. A method of manufacturing a polarizing plate The polarizing plate includes: a polarizing film that adsorbs a dichroic dye film by a polyvinyl alcohol resin film and is aligned to form a polarizing film of 59 321399 201013240; and a first protective layer laminated on one surface of the polarizing film, which contains active energy a cured material of the curable composition of the wire-curable compound and a second layer deposited on the other side of the polarizing film via the adhesive layer The method is composed of a thermoplastic resin film; the method includes the steps of: forming a coating layer on the surface of the substrate with a coating layer of the curable composition; and ❿ providing one side of the polarizing film on one side of the polarizing film a coating layer bonding step of bonding the coating layer of the curable composition on the surface of the substrate, and a film bonding step of bonding the second protective layer via an adhesive to the other surface of the polarizing film, A method of producing a polarizing plate according to claim 14 of the invention, wherein the coating layer The curing of the adhesive is performed simultaneously by irradiating the active energy ray from the substrate side. 60 321399