TW200806719A - Polyvinyl alcohol-based film for optical use and polarizing film, polarizing plate - Google Patents

Abstract

To provide a polyvinyl alcohol-based film for optical use for producing polarizing film with high polarizing performance over the whole visible light region, especially near wavelength 460 mn. The polyvinyl alcohol-based film for optical use comprises a polyvinyl alcohol-based resin(A) containing 1,2-glycol linkages on the side chain and another polyvinyl alcohol-based resin(B) and meets the following relationship(1):0.01 ≤ A*G/(A+B) ≤ 6 ( wherein, A is the proportion(weight ratio) of the resin A to the total (weight ratio) of the resins A and B; B is the proportion (weight ratio) of the resin B; and G is the amount(mol%) of the 1,2-glycol linkages on the side chain).

Description

200806719 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a polyethylene-based film for optical use, and more specifically, a polyvinyl alcohol-based film which is excellent in the properties of light-off, and is in the entire visible light region. The optical polyvinyl alcohol-based film for the production of a polarizing film having excellent polarizing performance in the vicinity of a wavelength of 46 Gnm. [Preparation of the Invention] The conventional 'polyethylene-based film is prepared by dissolving a polyhexenol-based resin in a solvent of water to prepare a stock solution, and then forming a film by a solution casting method (washing method). It is produced by drying using a metal heating newspaper or the like. The polyvinyl alcohol-based film thus obtained is a film excellent in transparency and is used in many applications, and it is useful for use, for example, as a polarizing film. Such a polarizing film is used as a basic component of a liquid crystal display, and its use is expanding in recent years in a machine requiring high quality and high quality. Among them, a polarizing film having higher optical characteristics than conventional ones is required in accordance with the high luminance and high definition of the surface of a liquid crystal television or the like. In order to achieve the improvement of the polyvinyl alcohol-based resin and to obtain a polarizing film, for example, a polyvinyl alcohol having a 12-to-Ethylene T-binding amount of 1.8 mol% or more directly bonded to the main chain is proposed. A uniaxially stretched film composed of a polymer as a polarizing film of a substrate (for example, refer to Patent Document 1), and a silane containing a cationic unit of ~1 to 2%, and a stone inverse of 4 or less A polarizing film made of a polyvinyl alcohol film composed of a polymer of a polyetheranol-based polymer of 5 to 24 mol% (for example, refer to Patent Document 2). In addition, as a means of improving the polarizing performance of the 312XP/invention specification (supplement)/95-11/95127673 5 200806719 near the wavelength of 400 to 500 nm, it is proposed to have a cleaning step in the manufacturing process of the polarizing film = 0.8 in the life of the J. More than % of the deuterated aqueous solution is washed (for example, refer to Patent Document 3). [Patent Document] [Patent Document] [Patent Document] [Patent Document 2] [Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-341503 (Patent Document) However, in the technique disclosed in Patent Document 1 and Patent Document 2, the polarizing film composed of the polyvinyl alcohol-based film obtained by t is insufficient in the polarizing performance in the vicinity of the visible light line f and the length J domain (10), and therefore has a liquid crystal. It shows that the performance of the color tone display and the improvement of the contrast are not improved, and we hope to further improve. In addition, although the technique disclosed in Patent Reading 3 can mention 4::, the polarizing performance in the vicinity, but there is still a problem of foreign matter (optical defects) on the film due to the use of the mixed coffee/cleaning film. The invention is based on the provision of the optical polyethylene crucible (4), which is a polyvinyl alcohol-based film excellent in extensibility, and can be used for manufacturing even in a manufacturing condition towel. In order to solve the above problem*, the inventors of the present invention have repeatedly studied the polarized light in the vicinity of the entire visible light region, particularly in the vicinity of the wavelength of 46 Gnm (the means for solving the problem). -Glycol-bonded polyethylene 312XP/Invention Manual (Repair you seven/(6)· 6 200806719 Alcohol resin (A) as a polyvinyl alcohol-based resin, preferably used in side chains containing 1,2 - Polyethylene glycol-bonded polyvinyl alcohol-based resin (A) and polyvinyl alcohol-based resin (B) other than the above-mentioned polyethylene-based or enol-based resin (A), which can be obtained with excellent elongation and used for production. Polyvinyl alcohol based on polarizing film with excellent polarization performance near wavelength 〇nm The present invention relates to a polyvinyl alcohol-based thin T for optical use, which comprises a polyvinyl alcohol-based resin, wherein the polyvinyl alcohol-based tree is only due to The side chain contains ruthenium, 2_glycol-bonded polyvinyl alcohol tree _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the case of the polyvinyl alcohol-based resin for optical use, the polyvinyl alcohol-based resin is a polyvinyl alcohol-based resin (A) having a side chain containing an L2-ethylene glycol bond, and the polyvinyl alcohol-based resin (A). The polyvinyl alcohol-based resin (B) is composed and satisfies the following formula (丨). 〇· 0lSAxG/(A+B)S6 (1) Here, A is a polyethylene which is a total amount of the polyvinyl alcohol-based resin (A) and the polyvinyl alcohol-based resin (B). The content ratio (weight ratio) of the alcohol resin (A); B is the content ratio (weight ratio) of the polyvinyl alcohol resin (B) based on the total amount; and G is a side chain of 1,2-ethane. The amount of alcohol linkage (% by mole). Further, in the present invention, the polyvinyl alcohol-based resin (A) having a 1,2-glycol bond with respect to the side chain and the polyvinyl alcohol-based resin other than the polyvinyl alcohol-based resin (A) The total amount of the (B), the content of the polyvinyl alcohol-based resin (A) is preferably 50% by weight or less. In the present invention, it is preferable to further contain a plasticizer (〇 and/or a surfactant (D). 312XP/Invention Manual (Supplement)/95·11/95127673 7 200806719 Moreover, in the present invention, the film width is 2ηι or more. Preferably, the thickness of the film is preferably from 30 to 70 // m. Further, the present invention provides a polarizing film comprising the above-mentioned optical polyvinyl alcohol film, and further provided on at least one side of the polarizing film. (Polarizing effect of the protective film) The polyvinyl alcohol-based film for optical use of the present invention is a polyvinyl alcohol-based film excellent in stretchability, and has a polarizing film which is excellent in polarization performance near a wavelength of 460 Å. It is effective as an original film of a polarizing film used for a liquid crystal display device such as a polarized sunshade glass or a liquid crystal television, an original film used for a 1⁄2 wavelength plate and a 1⁄4 wavelength plate, and used for liquid crystal display. The original film of the phase difference film of the apparatus. [Embodiment] The polyethylene resin used in the optical polyethylene film of the present invention is a polyvinyl alcohol containing only U-glycol bonds in the side chain. Tether tree (A) a film in which the amount of ethylene glycol bonds in the side chain is 〇. 〇 £ 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫A film composed of a polyvinyl alcohol resin (B) other than the alcohol resin (A) and satisfying the above formula (1). Right is a polyvinyl alcohol-based wax (A) used in the present invention, and is a side A polyvinyl alcohol-based resin having a 2-glycol bond, that is, a compound represented by the formula (1), a 2-ethylene glycol structure J, an alcohol resin, and a G-cloth. ) 312XP / invention manual (supplement) / 95 seven / 95127673 200806719

OH OH (wherein, R1, R2, and R3 are each independently hydrogen or an alkyl group.) The polyvinyl alcohol-based resin (A) can be, for example, a (meth)vinyl ester monomer and 3, 4 to 2 A copolymer of decyloxy-indene-butene is produced by saponification. Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl acetonate, vinyl thioglycolate, vinyl decanoate, Vinyl laurate, vinyl vinegar stearate, vinyl benzoate, vinyl pentoxide, etc., of which vinyl acetate is preferred. 3, 4-diethoxycarbonyl-1-butene which is copolymerized with a vinyl ester monomer is represented by the following chemical formula (2). (2) ch2=ch-ch-CH2 f f Ο ο ^ I (2) ο-c c=o

I I R R 1 (wherein R is an alkyl group, preferably a fluorenyl group.) 312XP/Invention Manual (Supplement)/95-11/95127673 9 200806719

Further, the compound represented by the above formula (2), ring ΓΗΡΜΤγλι , ν η ^ was purified by using an intermediate obtained from the market of EASTMAN CHEMICAL Co., Ltd. and ACROSS's fj u. Or in the production of the taudiol, in the present invention, it is preferred to use the above-mentioned copolymer in addition to the above-mentioned copolymerization component, and it is possible to make other monomers into a small amount, for example, 5 mol, within the range not impairing the object of the present invention. % of the following are ugly persons, such as olefins, (iv), isobutylene, α-(tetra), α-wife, octadecene, etc.; acrylic acid, methacrylic acid, crotonic acid, butene Diacids, maleic anhydride, itaconic acid, unsaturated acids, pots, or mono- or dialkyl vinegars; nitriles such as acrylonitrile, methacrylonitrile, etc. , amines such as acrylamide, methyl acrylamide, etc.; olefins of ethylene sulfenic acid, allyl sulfonic acid, methyl propyl tartaric acid, etc. Or a salt thereof; glycerol monoallyl test, alkyl hydrazine, dimethylallyl ketene, N-ethylene hydrazine, vinyl chloride, vinylidene chloride, polyoxyethylene (methyl) a polyoxyalkylene (meth)allyl ether such as allyl ether or polyoxypropylene (meth)allyl ether; polyoxyethylene (methyl) Polyoxyalkylene (meth) propyl ester of olefin ester, polyoxypropylene (meth) acrylate, etc.; polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) propylene oxime. amine Polyoxyalkylene (meth) acrylamide; polyoxyethylene (1-(methyl) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxygen Propylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, ethyl carbonate, allyl acetate, and the like. Further, for example, N-propylene amidoxime trimethyl ammonium chloride, n-312XP/invention specification (supplement)/95-11/95127673 1〇200806719~ene-m-amine ethyl dimethyl group Ammonium chloride, N_propylene decyl propyl trimethyl ruthenium chloride, 2-propoxy oxyethyl trimethyl ammonium chloride, 2-methyl methoxy oxy sulphate, ammonium chloride, 2-hydroxyl -3-Methyl propylene oxime propyl trimethyl ammonium chloride, •, propyl, methyl chloride, methallyl trimethyl chloride, 3 butyl amide, one a cationic group-containing monomer such as diallyl ammonium chloride, diethyldiallyl gas=ammonium or the like, and an ethylidene-containing monomer. When the above vinyl ester monomer is copolymerized with 3,4-diethoxycarbonyl+butenyl monomer, a known vinyl group can be used as a polymerization method, polymerization, dispersion polymerization, and solution. polymerization. The same method as the polymerization conditions and polymerization methods of the early body. A well-known method such as bulk polymerization, solution polymerization, suspension or liturgical polymerization may be employed, but the method of shaking the monomer component usually in the form of == is not particularly limited: by: tr: human filling, sub-diving Any method such as secondary filling, continuous filling, etc., ethoxylated + butyl women's sentence is distributed in the sub-chain of the polyethylene-based i-system = the sub-chain of the product, and the physical properties of the polyvinyl alcohol drop point, etc. Polymerization is preferred, and it is particularly preferred that the polymerization system according to the ηα ugly method is a ketone such as methanol, ethyl or methyl ethyl ketone as a solvent used for such copolymerization, alcohol, propanol, and butyl. It is suitable for the use of methanol in the lower alcohols such as alcohols and in the same industry. The amount of the solvent used is in accordance with the purpose of the policy, X, the degree of polymerization of the complex, and the chain transfer constant of the media can be appropriately selected to be the heart's S (solvent) / M (monomer > 〇 · 0 ^ 咚Only 1 8% )), preferably 312XP / invention manual (supplement) / 95-11/95127673 11 200806719 〇 · 〇 5 3 (weight ratio) around the range to choose.

In the polymerization, a polymerization catalyst is used, and as such a polymerization, a known radical polymerization catalyst such as azobisisobutyronitrile, oxidized ethylene, benzoyl peroxide, etc., is known as a nitrogen bismethoxy dimethyl group. The amount of valeronitrile and other low-di-bis-dimethyl phthalonitrile and the squad' polymerization catalyst varies depending on the type of the catalyst, and the method is arbitrarily determined, but it can be arbitrarily selected in accordance with the polymerization rate: = 匕 醯 醯 , 相对 相对 相对 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 The reaction temperature of the total co-coupling reaction is set to be about 40 ° c to the boiling point depending on the solvent and pressure to be used. Knife: = = 3, 4-diethoxycarbonyl + butyl oxime copolymerization The stone is determined by the amount of 1,2-glycol bond introduced later.糸 ; = The copolymer is then saponified, and the crystallization is basically the same: the saponification conditions of the vinyl oxime resin are the same. That is, the resulting copolymer is dissolved or dispersed in an alcohol or an acid-containing catalyst. Examples of the alcohol include methanol, = test medium, and tributanol, and it is particularly preferable to use methanol. In the alcohol, take the =, propanol, the appropriate choice according to the viscosity of the system, usually ^ "body / Chen degree range. Used in the catalyst of Xihua; for example, 2_, heavy _ potassium, Sodium methoxide, sodium ethoxide, potassium methoxide, methanol: di- sulphate t-materials, and catalysts such as drunken chemicals; acid catalysts such as sulfuric acid, hydrochloric acid, acid, formazan, zeolite, cation exchange resin, etc. The amount of the catalyst used in the shell is appropriately selected according to the method of the fourth method, the target specialization 312XP/invention specification (supplement)/95-11/95127673 12 200806719 degree, etc., in the case of using the alkali catalyst. The total amount of the vinyl ester monomer and the 3,4-diethyloxy-1-butene is usually 0.1 to 30 millimolar, preferably 2 to 17 millimolar. Further, the reaction temperature of the saponification reaction is not particularly limited, and it is preferably 1 to 6 Torr, more preferably 20 to 50 ° C. The above polyvinyl alcohol-based resin (A) is saponified by the above. At the same time, the ester moiety of the vinyl oxime monomer and the ethyl oxime moiety of 3,diethoxymethoxy-1-butene are simultaneously converted to a hydroxyl group. Manufacturing.

J can be, as the side chain contains u-ethylene glycol bonded polyacetone eucalyptus (A) 'but in the present invention, the degree of chemical conversion of the polyvinyl alcohol resin is usually 90 moles % or more, particularly preferably 95% by mole or more, more preferably 98% by mass or more. If the degree of saponification is too small, the water of the polarizing film tends to be insufficient. $ T Still, the degree of interest in the present invention means that the ester portion of the vinyl ester monomer = and the total amount of the ethylene oxide moiety of the diethyl ethoxy group + butene is converted to 10 the rate of change of the wind oxy group. (% of Moer) (in the polychemical reaction, the ethoxylated moiety of 3 Å and bis of its 1-butene is almost completely saponified). Further, the viscosity of the above polyvinyl alcohol-based resin (4) is based on the material 3 The liquid viscosity 'is selected from the group consisting of only the polyethylene glycol-based resin (1) to the y-species, usually 8, 〇 · 40 40 ~ 300 mPa · s 'better 5 〇 ~ 27 〇 mPa · s, if the weight is too small, when the polarizing film is formed, when the tilting liquid 1 having insufficient elongation is excessively large, the planar smoothness and the transmittance of the film tend to be lowered. Further, the viscosity of the vinyl alcohol oxime resin (A) in the case of using the polyvinyl alcohol-based resin (1) and the polyvinyl alcohol-based resin (8) 312 ΧΡ / invention specification (supplement) / 95-11/95127673 13 200806719 4% by weight of water-soluble, night viscosity, usually 8~400mPa·s, especially preferably 12~30〇mpa·s, more preferably ~270mpa · s, if the viscosity of such 4% by weight aqueous solution is too small, it is made into polarizing film In the case where the elongation is insufficient, if the film size is too large, the smoothness and transparency of the film 2 tend to decrease. In addition, the amount of the ethylene glycol bond to be introduced into the side chain of the polyvinyl alcohol-based resin (A) is such that at least one selected from the group consisting of only the polyvinyl alcohol-based resin (A) is used. Next, it is 〇〇1~6 mol%, preferably 〇〇5~4 mol%, especially good 0·1~3 mol%, if the lower limit is not reached, the effect of the invention cannot be obtained, if the upper limit is exceeded The value is insufficient in water resistance when the polarizing film is formed. Moreover, the amount of 1,2-ethane bond bonding of the polyvinyl alcohol-based resin (A) in the case where the polyvinyl alcohol-based resin (A) and the polyvinyl alcohol-based resin (B) are used in combination is preferably 0. · 01~20% by mole, 〇佳〇·〇5~15% by mole, more preferably 〗·mole%, if the amount of combination is too small, it is difficult to obtain the effect of the present invention. The tendency of the vinyl alcohol resin. Further, as a method for producing the polyvinyl alcohol-based resin (A) used in the present invention, the method is directed to the above-mentioned (meth)-ester monomer and 3,4-diethyloxy-1-butene. The method of saponification of the copolymer is described in detail, but it is not limited to such a method, and for example, (B) a vinyl vinegar-based monomer and a vinyl ethyl carbonate which is not in the general formula (3) a method in which a copolymer is subjected to saponification and de-saltification; (c) copolymerization of a vinyl ester-based monomer with a 2,2-dialkyl-4-vinyl-u-dioxane represented by the general formula (4) a method of saponification and deketalization in combination; a method of saponifying a copolymer of a (but) vinyl ester monomer and glycerol monoallyl acid; and the invention is not particularly limited to 312XP/invention specification (supplement)/95 -11/95127673 14 200806719 定. Still, the retailer (for example, vinyl ethyl carbonate can be selected by the market for EASTMAN CHEMICAL). Also in Ping (3) R3 ft2

(3) Here, U and R3 are each independently hydrogen or alkyl (Chemical 4)

Here, R1, R2, R3, R4, and F are each independently hydrogen or alkane. (4) In the present invention, when the polyvinyl alcohol-based resin (A) is used as described above, the polyethylene-based resin exhibits excellent properties as an optical film, but in the present invention, It is more preferable to use the polyvinyl alcohol-based resin (A) other than the polyvinyl alcohol-based resin (A) in combination with the polyvinyl alcohol-based resin (A). In the present invention, as the polyvinyl alcohol-based resin (A), two or more kinds of polyvinyl alcohols having different 1,2-glycol bond amount, saponification degree, and 4% by weight aqueous solution viscosity may be used in combination. Resin. 312XP/Invention Manual (Supplement)/95_11/95127673 15 200806719 The polyvinyl alcohol-based resin (B) used in the present invention is not particularly limited, and the degree of saponification is preferably 90% by mole or more, and particularly preferably 95% by mole. More than %, = 98% of the total is ±. If the degree of saponification is too large, the water resistance tends to be insufficient when the polarizing film is formed. Further, the viscosity of the polyvinyl alcohol-based resin (B) is 41% by weight of the aqueous solution, and is usually 8 to 500 mPa·s, preferably 2 to 4 μm·

s is particularly good, with 40~40〇mPa.s as better. When the viscosity of the 4% by weight aqueous solution is too small, the elongation at the time of forming the polarizing film tends to be insufficient, and if it is too large, the planar smoothness and transparency of the film tend to be lowered. In addition, the polyvinyl alcohol-based resin (B) is not particularly limited as long as it is a polyvinyl alcohol-based resin other than the polyvinyl alcohol-based resin (a), and it is usually preferred to use an unmodified polyvinyl alcohol-based resin. Further, it may be an olefin (ethylene, propylene, n-butene, isobutylene, etc.) containing a small amount of an unsaturated carboxylic acid (including a salt, an ester, a guanamine, a nitrile, etc.), a carbon number of 2 to 3, or a vinyl ether. A % vinyl alcohol-based resin which is a component which can be copolymerized with vinyl acetate g, such as an unsaturated sulfonate. In addition, as the polyvinyl alcohol-based resin (B), two or more kinds of polyvinyl alcohol-based resins having different degrees of saponification degree and four-fold% aqueous solution viscosity may be used in combination. In the present invention, when the polyvinyl alcohol-based resin (human) and the polyvinyl alcohol-based resin (B) are contained, it is preferable to satisfy the following formula (1), and it is particularly preferable to satisfy the following formula (2), and more preferably The following formula (3) is satisfied. (1) (2) (3) 0. 01^ AxG/(A+B)^6 0. 05^ AxG/(A+B)^ 4 0. AxG/(A+B)^2 Here, A It is a polyvinyl alcohol-based resin (A) based on the total amount of the polyvinyl alcohol-based resin (A) and the polyvinyl alcohol-based tree 312XP/invention specification (supplement)/95-11/95127673 16 200806719 fat (B) Content ratio (weight ratio); B is a content ratio (weight ratio) of the polyvinyl alcohol-based resin (B) with respect to the above total amount; G is a ratio of 1,2-ethane bond indicating a side chain (mole) %). In the above formula (1), it is difficult to obtain the effect of the present invention when the lower limit is not exceeded. Conversely, if it exceeds the upper limit, the water resistance tends to be insufficient when the polarizing film is formed. In the present invention, the side chain is opposite to the side chain. The total amount of the polyethylenyl alcohol-based resin (A) containing ruthenium and 2_glycol bonds and the above-mentioned polyvinyl alcohol-based resin (8), from the viewpoint of extensibility and optical properties, polyvinyl alcohol The content of the resin (A) is preferably 50% by weight or less, more preferably 5 to 5% by weight, more preferably 10 to 40% by weight. When the content of the polyvinyl alcohol-based resin is too small, it tends to be difficult to obtain excellent polarizing performance in the vicinity of a wavelength of 46 〇 nm, and if it is too large, the elongation at the time of forming a polarizing film tends to be lowered. When the polyvinyl alcohol-based resin (A) and the polyvinyl alcohol-based resin are contained, the difference in saponification degree between the polyvinyl alcohol-based resin (A) and the polyvinyl alcohol-based resin (B) is considered from the viewpoint of film transparency. It is preferably 6 mol% or less, and particularly preferably 3 mol% or less. If the difference in saponification degree is too large, the film transmittance tends to decrease. Further, in the present invention, in addition to the polyvinyl alcohol resin (A) and poly In addition to the vinyl alcohol-based resin (B), it is preferable to further contain a plasticizer (c) and a surfactant. The plasticizer (C) used in the present invention effectively contributes to the elongation when the polarizing film is produced. Examples are ethylene glycol, glycerol, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trishydroxypropyl propane, and poly 312XP / invention specification (supplement) / 95-11/95127673 17 200806719 Polyethylene glycol with a mouth width of 300 or less, alone or in person Shop Tiansi can use this special alcohol. Among them, the combination of glycerin and diglycerin alone, or the content of glycerol-~ 4I oil methyl dimethyl methacrylate / such plasticizer (6) is relative to the The total polyethylene glycol resin used is 10 parts by weight, preferably 1 q, the tongue θ, the alcohol is 8 to 30 parts by weight, and particularly preferably 3 to 30 parts by weight, more preferably W5 parts by weight. When the content of the plasticizer (c) is too small, the elongation tends to decrease when the second coating is used as a polarizing film, and if it is too large, the stability of the polyvinyl alcohol-based film to be used tends to decrease with time. Further, the present invention is used. The surfactant (D) is used for the production of optical polyvinyl alcohol (tetra) film to have the effect of smoothing the surface of the film and inhibiting the adhesion of the films when wound into a roll, which may, for example, be an anionic surfactant and The nonionic surfactants may be used singly or in combination of two or more. However, from the viewpoint of film transparency, it is particularly preferable to use an anionic surfactant and a nonionic surfactant in combination. Active agents, for example, (1) fat Alkane sulfonate; (2) alkyl sulfate salt; (3) polyoxyethylene alkyl ether sulfate; (4) polyoxyethylene alkyl phenyl ether sulfate; (5) higher fatty acid alkane oxime Amine sulfate; etc. As a specific example of the (1) aliphatic ketone acid salt, for example, sodium hexyl sulfonate, sodium heptanoate, sodium octyl phthalate, sodium decyl phthalate, sodium decyl sulfonate , 12-burning sodium sulphate, tetradecyl sulphate, sodium sulphate sodium sulphate, octadecyl sulfonate sodium, carbon number 6~18 aliphatic sodium sulfonate 312XP / SUMMARY OF THE INVENTION (Supplement) / 95-11/95127673 18 200806719, etc., preferably using sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, carbon number 10 to 18 a mixture of sodium secondary alkyl sulfonate, and the like. Further, the counter cat ion of the aliphatic alkyl sulfonate is not particularly limited, and examples thereof include Na+, Ca2+, NH/ or the like, and among them, Na+ is particularly preferable. . Specific examples of the (2) alkyl sulfate salt include sodium hexyl sulfate, sodium heptyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium decyl sulfate, sodium lauryl sulfate, and tetradecene. An alkali metal salt such as sodium sulfite, sodium hexasulfate, sodium octadecyl sulfate, sodium lacosyl sulfate, or the like, or an alkali metal salt such as a calcium salt or an ammonium salt. As the organic amine salt, sodium dodecyl sulfate, sodium octadecyl sulfate or the like is preferably used. Further, the anti-cation is not particularly limited, and examples thereof include Na+, Ca2+, ruthenium, or the like, and among these, Na+ is particularly preferable. Specific examples of the (3) polyoxyethylene alkyl ether sulfate include, for example, polyoxyethylene hexyl ether sulfate, polyoxyethylene heptyl ether sulfate, polyoxyethylene octyl ether sulfate, and polyoxyethylene fluorenyl group. Sodium ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tetradecyl ether sulfate, sodium polyoxyethylene cetyl ether sulfate, polyoxyethylene ten Sodium octacarboxylate, sodium polyoxyethylene eicosyl ether sulfate, or an alkali metal salt of such a potassium salt, an organic amine salt of an ammonium salt, etc., preferably polyoxyethylene 'dodecyl group Sodium ether sulfate and the like. Further, the counter cation is not particularly limited, and examples thereof include Na+, Ca2+, NH/ or a mixture thereof, and among these, Na+ is particularly preferable. Specific examples of (4) polyoxyethylene alkylphenyl ether sulfate can be exemplified by 312XP/invention specification (supplement)/95-11/95127673 19 200806719 such as polyoxyethylene hexyl phenyl ether sulfate, polyoxyethylene Sodium heptyl phenyl ether ether, sodium polyoxyethylene octyl phenyl ether sulfate, sodium polyoxyethylene nonylphenyl ether ether, sodium polyoxyethylene nonylphenyl ether ether, polyoxyethylene lauryl phenyl Sodium sulphate, polyoxyethylene decyl phenyl ether sulfate, polyoxyethylene • cetyl phenyl ether sulfate, polyoxyethylene octadecyl phenyl ether sulfate, polyoxyethylene eicosane As the sodium phenyl ether sulfate, an alkali metal salt of such a potassium salt, an organic amine salt such as an ammonium salt, or the like, sodium polyoxyethylene nonylphenyl ether sulfate is preferably used. Further, the counter cation is not particularly limited, and examples thereof include Na+, Ca2+, NH4+ or a mixture of these, and among these, Na+ is particularly preferable. Specific examples of the (5) higher fatty acid alkanoguanamine sulfate include sodium decyl hexanoate, sodium decyl citrate citrate, sodium decyl citrate citrate, sodium laurate citrate, and sodium laurate. Sodium palmitate sodium sulphate, sodium sulphate sulphate, sulphate oleate, or the like, and the ethanol decylamine is changed to propanolamine or butanolamine. Further, the counter cation is not particularly limited, and examples thereof include a mixture of Na+, Ca2+, NH4+ or m stomach, and among these, Na+ is particularly preferable. Further, in addition to the anionic surfactants of the above (1) to (5), a sulfated salt such as a sulfated oil, a higher alcohol ethoxysulfate or a monoglysulfate may be used in combination; a fatty acid soap; a carboxylate of N-mercaptoamine acid and a salt thereof, a polyoxyethylene alkyl carboxylate or a thiolated peptide; an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, a naphthalene Sulfonic acid gas aldehyde condensate, melamine acid chlorohydrazine condensate, dicalcium sulfonate, sulfosuccinate alkyl salt, polyoxyethylene alkyl sulfosuccinate di salt, alkane 312XP/Invention Manual (Supplement)/95-11/95127673 20 200806719 Sulfoacetate, α-olefin sulfonate, N_mercaptomethyltaurate, dimethyl-5-sulfoisophthalate a sulfonate type such as a sodium formate; a phosphate salt of a polyoxyethylene ether alkyl phosphate, a polyoxyethylene phenyl ether alkyl phosphate, an alkyl phosphate, etc.; an anionic surfactant . On the other hand, as a nonionic surfactant, for example, (7) is generally used.

R-0(C2H4〇)nH (wherein R is an alkyl group or an alkenyl group having a carbon number of 6 to 22, preferably 8 to Μ. These may be a single alkyl group or a mixed alkyl group. Further, a polyoxyethylene alkyl ether having an alkyl group having a distribution of a base obtained from coconut oil, eucalyptus oil, palm kernel oil, tallow or the like may be used; (8)

R - X-〇(C2H4〇)nH (wherein R is an alkyl group or an alkenyl group having a carbon number of '6 to 22, preferably. These may be a single alkyl group or a mixed yarn. X It is also possible to use an alkyl group having a distribution of a base obtained from coconut oil, palm oil, palm kernel oil, tallow, etc. X is an integer of phenylene n n, preferably 2 to 1 )) (6) General formula RC0NH-R, -〇H or rc〇N-(R, _〇h)2 (where R is an alkyl or alkenyl group, The carbon number is 6 to 22, preferably 818. These may be separate alkyl or mixed yarns. X, may also be used, palm kernel oil, butter, etc. , -C3H6-, -d- 任--. 312XP/Invention Manual (supplement)/95·11/95127673 200806719 Two-stage fatty acid mono- or di-alkanol decylamine; (1 〇) - General RC0NH2 (wherein R is an alkyl group or an alkenyl group having a carbon number of 6 to 22, preferably 818. These may be individual filaments or mixed yarns. Also, it may be used with coconut oil, The base of the burnt base obtained from palm oil, palm kernel oil, butter, etc. Amides of fatty acids; (11) General formula

• RNH(C2H4〇)xH or H(C2H4〇)yN(R)(C2H4〇)xH (wherein R is an alkyl group having a carbon number of 6 to 22, preferably 818. These may be separate burnings. The base may also be a mixed alkyl group. Alternatively, an alkyl group having an alkyl group obtained from Nymphalic oil, palm oil, palm kernel oil, tallow or the like may be used. X and y are 1^30, more ^ a polyoxyethylene alkylamine represented by an integer of 3 to 15; (12) a polyoxyethylene higher fatty acid amine; (13) an amine peroxide; Specific examples of the (7) polyoxyethylene alkylphenyl ether include polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, and polyoxyethylene oxime. Ether, polyoxyethylene lauryl ether, polyoxyethylene tetradecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Eicosyl ether and the like. In particular, oxyethylene lauryl ether, polyoxyethylene stearyl ether and the like are suitable. (8) Specific examples of the polyoxyethylene alkylphenyl ether include polyoxyethylene hexyl phenyl ether, polyoxyethylene heptyl phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene decyl benzene. Ether, polyoxyethylene methyl phenyl ether, polyoxyethylene 312XP / invention specification (supplement) / 95-11/95127673 22 200806719 dilute decyl phenyl ether, polyoxyethylene tetradecyl phenyl Scale, polyoxyethylene hexadecyl phenyl ether, polyoxyethylene ten phenyl phenyl ether, polyoxyethylene decyl phenyl bond, and the like. In particular, polyoxyethylene nonylphenyl ether is suitable. Specific examples of the terminal fatty acid mono- or dialkanol decylamine include, for example, hexanoic acid mono or diethanol decylamine, octanoic acid mono or diethanol decylamine, citric acid mono or diethanol decylamine, lauric acid single or two. Ethanol decylamine, palmitic acid mono or diethanolamine, stearic acid mono or diethanolamine, oleic acid mono or diethanolamine, coconut; oil fatty acid mono or diethanol amine, or ethanol The indoleamine is changed to propanol diamine and butanolamine. Among them, alkyldiethanolamine is preferred, and the specific one is only suitable for use in the case of sulphuric acid, ethanolic acid, diethanolamine, and coconut oil, especially from the viewpoint of water solubility. It is advantageous that the diethanolamine produced by the manufacturing process is: a mixture of ethanolamine [NH_cafe mouth compound (1: 2 molar type). (10) Specific examples of the higher fatty acid guanamine include, for example, decyl hexanoate, decylamine, decyl decylamine, decyl laurate, decyl palmitate, strontium stearate, decyl oleate, etc. Among them, decyl palmitate and decylamine stearate are more suitable for use. Specific examples of the σ (11) polyoxyethylene (tetra)amine include, for example, polyoxyethylene methylmercaptoamine, polyoxyethylene heptylamine, polyoxyethylene octylamine, polyoxyethylene decylamine diacetyl sulfonium oxime a base amine, a polyoxyethylene dodecylamine, a polyoxyethylene decanoamine, a polyoxyethylene hexadecylamine, a polyoxyethylene octadecylamine, a poly(alkylene) decylamine, etc. Specific examples of the (12) polyoxyethylene higher fatty acid decylamine which are suitable for the polyoxyethylene diced 12 (tetra)amine include, for example, polyoxygen oxime/invention specification (supplement)/95_ η/95127673 23 200806719 f-hexanoic acid Indoleamine, polyoxyethylene decanoate, polyoxyethylene decanoate, polyoxyethylene laurate decylamine, polyoxyethylene citrate, polyoxyethylene decylamine, polyoxyethylene stearic acid The acid amide, the polyoxyethylene oleic acid decylamine and the like, among which polyoxyethylene laurate decylamine and polyoxyethylene stearyl decylamine are suitable for use. (13) Specific examples of the peroxylamine include, for example, didecyl peroxide lauryl f, dimethyl stearyl peroxide, di-vinyl ethyl peroxide laurylamine temple, wherein dimethyl group Oxalyl amine oxide is more suitable for use. Further, in addition to the nonionic surfactants of the above (7) to (13), an oxyethylene derivative of a silk phenyl group (tetra) compound, a polyoxyethylene polyoxypropylene block polymer, and a poly Oxyethylene glycerin fatty acid vinegar, polyoxyethylene sesame oil and hardened E sesame oil, polyoxyethylene sorbitan fatty acid vinegar, t ethene sorbitol fatty acid ester, etc. ether ester type non-material interface activity:; Alcohol fatty acid vinegar, sorbitan fatty acid vinegar, fatty acid single:: fat, propylene glycol fatty acid vinegar, recommended sugar fat agent. The content of the surfactant (8) of the soil W W /3⁄4 is 1 part by weight based on the weight of the dilute alcohol resin, preferably a part by weight 'more preferably U parts by weight. If the content of the boundary is too small, it is difficult to obtain an anti-adhesion effect, and if it is too large, the transparency of the film tends to be low. In addition, in the case of using an anionic boundary agent in combination, the anionic surfactant is 312XP/invention specification (supplement)/95-11/95127673 surfactant and nonionic interfacial activity with respect to the portion used. Total polyvinyl alcohol resin 1 〇〇 〇 〇 〇 ~ 1~1 parts by weight, especially good 〇〇 2 〇 2 200806719 畺 better 0. 03~〇. 1 heavy | @, 卜 1 part by weight, especially good G G2 〜 n; / ionic surfactant is in parts by weight. If the anion is in the middle part, it is more preferably 0. 03~0. 1 • The dispersibility of the material is lowered, and when there is less than ==, the unevenness of the dyeing of the β-bar is increased when the polarizing enamel is made, and the resin is The foaming during the dissolution is fierce, and it is difficult to obtain a tendency to reduce the smoothness of the anti-adhesive plane when the bubble is easily dissolved. On the eve of the day, there is 'transparency of money and, in addition, the towel of the present invention, in order to prevent the thin, ^ ^ ^ ^ antioxidant, can be dried as a seed γ can also effectively match t, X2 f to 2, 6-two third Butyl-D-methyl--6-nu, Γ 'methylene bis(4-methyldiyl, dibutyl benzyl), 4,4,-butylene bis(3-methyl.third butyl Base, base: etc.. The antioxidant is used in the range of about 2 to 100 ppm relative to the polyethylene (4). The present invention is used in the side chain containing hydrazine, 2-ethylene glycol linkage. The polyvinyl alcohol-based resin (A) or the poly-enol group other than the polyglycol-based resin (A) and the polyvinyl alcohol-based resin (A) in the side chain. The resin (B) is more preferably a plasticizer (c) and/or a surfactant (D), and a polyvinyl alcohol-based film is produced. The method for producing the t-vinyl alcohol-based film of the present invention will be specifically described below. When the polyvinyl alcohol-based resin (1) and the polyvinyl alcohol-based resin (B) are combined, the term "polyvinyl alcohol-based resin" is used. In the present invention, the side chain contains a 1,2-glycol bond. Polyethylene glycol Resin (A), or polyvinyl alcohol-based resin (A) and polyvinyl alcohol-based resin 312XP / invention specification (supplement y9541/95127673 25 200806719 preparation ', for re-use of plasticizer (c) and / or interface activity The agent (8) is prepared by adjusting an aqueous solution of the ethylenic resin composition, and the aqueous solution is cast to a rolling type light or endless belt (preferably a roller type roller)* to produce a polyvinyl alcohol-based film. In the method of making a garment, first, the polyvinyl acetate resin powder is washed in order to remove sodium acetate contained in the resin. When washing, it can be washed with alcohol or water, but washed with methanol. The net method must be carried out:: recovery, so it is better to use water to wash. The system = X will dissolve the water-containing polyvinyl alcohol-based resin wet cake after the fight, and adjust = = system of wax solution, However, if the aqueous polyacetate is directly irritated in water, the desired high-concentration aqueous solution cannot be obtained, so the dehydration method is the first. The dehydration method is not particularly limited to the method using a centrifugal knife. And dehydration' makes the water content of the aqueous polyethylene glycol tree wet cake 3 into 5G weight % or less, more preferably 3 () to 45% by weight. If the water content is too large, there is a tendency that it is difficult to obtain a desired aqueous solution concentration. An aqueous solution of a polyglycolic alcohol-based resin obtained from a poultry polyvinyl alcohol (IV) film. ' By filling the water, the dehydrated water-containing polyethylene disulfide tree: wet sputum, plasticizer (c), surfactant (D), etc. into the solution: the Asian ship, disturbed and dissolved In the case of the 4-turn property of the = method, it is particularly preferable to dissolve the alcohol-based resin wet cake in the dissolution tank having the upper and lower 搅拌L-type stirring blades. When the water-containing polyglycol-based resin wet cake is dissolved in the dissolution tank of the upper and lower circulation flow-type mixing wings, it can be carried out by blowing water vapor 312XP/invention specification (supplement)/95-11/95127673 26 200806719 From the viewpoint of dissolution of the homologous sentence, it is preferred to start with water vapor blowing and the resin temperature of 赃, preferably 45 to 70 ( (4). If the resin temperature is too high, the load on the motor becomes large, and if it is too large, the polyethylene glycol-based resin is solidified, and there is a tendency that it cannot be dissolved uniformly. Further, from the viewpoint of being able to dissolve the homologous sentence, it is preferable to pressurize the water vapor and the resin temperature to 9 (M 〇 (TC, preferably 95 to 1 GG ° C, pressurize (4). If the resin temperature If it is too small, the tendency of the sputum will appear. Then, the resin temperature will be 13 〇 15 (the rc day will end the blowing of water vapor, continue the spectrum, and the solution will be ... * 3 hours, so that it dissolves. The concentration of the obtained polyethylene glycol-based resin composition is preferably from 10 to 50% by weight, ΐς ^ in the stomach of the stomach / ° more than 15 ～40% by weight, particularly preferably 20 to 30% by weight. If the concentration is too small, the drying load will increase and the production capacity will be poor. If the right is too large, the viscosity will become high, and it will be difficult to dissolve the whole. The water-soluble bubble method of the vinyl alcohol-based resin composition may, for example, be a static defoaming and a multi-axis extruder. In the manufacturing method of the invention, from the viewpoint of productivity, it is preferable to use a multi-axis. Defoaming method of the extruder. After the defoaming treatment, the polyvinyl alcohol season tree month discharged by the multi-axis extruder The aqueous solution of the sputum is divided into a tumbler-shaped roller or an endless belt, and is formed into a film roll and an endless belt, and is formed into a film and dried. The slit die 859 i 3 degree is preferably 80 to 10 generations, and the resin temperature at the outlet of the right τ-type slit die is too small, and the flow is 312XP/invention specification (supplement)/95-11/95127673 200806719, However, from the broadening of the 'best of the best, the roller type roller is poor, and if it is too large, there is a tendency to foam. The flow delay is based on the viewpoint of the roller type or the endless belt and the lengthening and film thickness uniformity. In the case of row 0 = casting with a roller _, for example, the rotation speed t::: wide minute 'extra good 6 gamma minutes. The surface of the roller type roller is 7 Wc, more preferably 75 to coffee. If the roller type When the surface of the roll is too small, the drying becomes poor, and if it is too large, foaming tends to occur. The drying of the polyethylene glycol film made by the roll is performed by interacting the surface with the back surface. The drying surface temperature is not particularly limited, compared with (4) 6 (Morc, better 65 to 90) C. If the surface temperature is too small, the drying becomes poor, and if it is too large, the drying is too dry, resulting in a tendency for the outer shirt to be good. Further, in the present invention, the heat treatment is preferably performed after drying. Regarding the heat treatment, the surface is subjected to (1) Hard chrome shovel treatment or mirror treatment of the diameter G · 2 ~ 2m light (1 ~ 30) adjusted to a temperature of 6 () ~ 18 (rc to pass it; (2) Xiang floating type dryer (long m temperature The method of 80 to 180 ° C) is carried out. The polyethtyl alcohol-based film of the present invention thus obtained is very effective as a polyvinyl alcohol for optical use in the entire visible light region: light transmittance is 9 Å. Thus, the polyvinyl alcohol system for optical use of the present invention is suitable for use as an original film as a polarizing film. The following is a description of a method for producing a polarizing film of the present invention using the polyvinyl alcohol-based film for optical use of the present invention. x 312XP/Invention Manual (Supplement)/95_ι 1/95127673 28 200806719 The polarizing film of the present invention is produced by the usual steps of dyeing, stretching, boric acid crosslinking, heat treatment, and the like. As a method for producing a polarizing film, a method in which a polyvinyl alcohol-based film is stretched and impregnated in a solution of a dye or a one-color dye, followed by dyeing, and a boron compound treatment is carried out in the same manner. After extending and dyeing, the method of treating the shed compound; after dyeing and stretching by hydrazine or a dichroic dye, the method of treating the borax is carried out; after the dyeing, the method of stretching in the solute compound solution, etc. . Thus, the polyethylene glycol-based film (unstretched film) can be stretched and dyed separately, and further treated with a boron compound, and the above treatment can be simultaneously performed, but from the viewpoint of productivity, it is preferable to dye. The uniaxial stretching is carried out in at least one step of the step of treating the boron compound. It is better to extend the uniaxial direction by 3 to 1 () times, which is better and better. The square can be slightly extended in the direction perpendicular to the direction of extension (degree of prevention, or extension thereof). The temperature at the time of extension is 2C. Further, if the stretching ratio is finally set to upper, the stretching operation is performed not only for the stage of any range of the stage. The dyeing in the step of coating is to expose the film to a dye containing a hard or dichroic dye. Usually, the aqueous solution of potassium is preferably used. The concentration of single-denier g/L'-W-potassium is 10 to 5 orbits, and the potassium/deuterium is broken, and the weight ratio is 2 〇~1 〇 〇. The door of the time is right. The mm Γ is 30~5GG seconds left, and can also be 5~50c. In addition to the aqueous solvent, the aqueous solution contains an organic solvent that is compatible with water in the y〇 可, and is applicable to the main gas/spiral. Any means such as contact, use, shelling, coating, spraying, and the like. 3_W^__)/951i/95 to 3 29 200806719 The wood-colored film is then treated with a boron compound. As a butterfly compound, there are practically, for example, boric acid and borax. The boron compound is preferably in the form of an aqueous solution or a water-organic solvent mixture at a concentration of about 3 to 2 mol/L, so that a small amount of Wei potassium is preferably coexisted in the solution. Preferably, the method is a dipping method, but it is of course possible to carry out a coating method or a spraying method. The temperature during the treatment is preferably from 2 G to 6 Gt: about the left, and the treatment time is preferably from about 3 to 2 (minutes), and the stretching operation can be carried out during the treatment as needed. work

The polarizing film of the present invention thus obtained is a polymer film or sheet having a single-sided or two-sided adhesive optical isotropy as a protective film, and is used as a polarizing plate. The protective film used in the present invention may, for example, be cellulose triacetate, cellulose diacetate, polycarbonate, polymethyl methacrylate, polystyrene, poly(tetra) acid, poly(aryl), poly —4—Film or sheet soil of a mevalonol, a polyphenylene ring, a ring system, or a (4) polyolefin. In addition, the protective film may be used in place of the protective film, and a curable resin such as an amino phthalic acid ethyl ester resin, an acrylic resin, or a urea resin may be applied to the early or both sides of the polarizing film to form a layer. Hehe. The polarizing film (including those laminated on at least one side of the protective film or the curable resin) may be applied to a surface thereof as needed, and a transparent adhesive layer may be formed by a conventionally known method. As the pressure-sensitive adhesive layer, for example, acrylate such as butyl acrylate, ethyl acetoacetate, decyl acrylate, acrylic acid ethyl hexanyl acrylate, or the like, and acrylic acid, maleic acid , Yikang, methacrylic acid, crotonic acid and other t α-monoolefin tickered copolymers include the addition of acrylonitrile, g acid vinyl vinegar, styrene monomer, etc. Because it does not hinder the polarizing characteristics of the polarizing film, it is not limited to this, but it is also possible to use a pressure-sensitive adhesive having transparency. The agent may be, for example, a polyvinyl ether type or a rubber type. * The polarizing film of the present invention is used in liquid crystal display devices such as electronic desk computers, electronic clocks, word processors, personal computers, televisions, mobile information terminals, automobiles, or mechanical devices, sunglasses, and protectors. Eyepieces, stereo glasses, display elements (CRT, LCD, etc.) are used for reflection reduction layers, medical devices, building materials, toys, and the like. (Embodiment) The present invention will be more specifically described by the following examples, and the present invention is not limited to the following examples without departing from the gist of the invention. In addition, the "parts" and "%" of the examples are based on the weight limit without limitation. The physical properties were carried out as follows. (1) The amount of 1,2-glycol bond in the side chain is 1H-NMR (internal standard material Zeng Tiantian # ^ w

|钿+物贝·tetradecyldecane, solvent: d6-DMS was measured and calculated. (2) The degree of saponification of the polyvinyl alcohol resin • Analysis of the consumption required for the hydrolysis of the remaining ethyl acetate unit (3) The viscosity of the 4% aqueous solution of the polyvinyl alcohol resin adjusts the water temperature to 2 Gt and borrows Determined by a Herpbar viscometer. _ (4) Optical characteristics Using a high-speed multi-wavelength birefringence measuring device (Otsuka Electronics Co., Ltd. "RETS-20G0"), the polarizing film obtained by measuring the polarizing film at a wavelength of 50, 640 nm, transmittance, and transmittance Color ratio. 312XP/Invention Manual (Supplement)/95-11/95127673 31 200806719 (Example i) A 4% aqueous solution having a viscosity of 107 mPa·s, a degree of saponification of 99·3 mol%, and a side chain are embedded in a 200 L tank. 2-glycol-bonded amount of 1 mol% of polyvinyl alcohol-based resin (A) 42 kg, water l〇〇kg, plasticizer glycerin (c) 4. 2 kg, surfactant (D) dodecane 21 g of sodium sulfonate and 8 g of polyoxyethylene laurylamine were heated to i5 〇〇c while stirring, and uniformly dissolved, and an aqueous solution of a polyvinyl alcohol-based resin composition having a concentration of 26% was obtained by concentration adjustment. _ Next, an aqueous solution (liquid temperature: 147 匚) of a polyvinyl alcohol-based resin composition was supplied to a twin-screw extruder to perform defoaming. The aqueous solution of the defoamed polyvinyl alcohol-based resin composition was cast through a t-type slit die (straight tube mold) to form a film. The conditions for such cast film formation are as follows. Roller type roll diameter (Rl): 3200mm, width: 4. 3m, rotation speed: 8111/min, surface temperature: 9 (TC, T-slot die exit resin temperature: 95. 〇 "

Roll drying roller drying roller

312ΧΡ/Invention Manual (Supplement)/95-11/95127673 32 200806719 The method is to obtain a bias field and evaluate the polarization characteristics. = The optical polyvinyl alcohol-based film was stretched to 5 times in the water tank which was immersed in the water bath. Secondly, the side = the dyeing tank (10) composed of potassium 15g/L. c) medium impregnation 24 〇 = I enter 仃 extended to h 3 times, then impregnated with boric acid 50g / L, Chenghua cream tank called and simultaneously uniaxial extension two = calendar clock, acid treatment. Thereafter, drying was carried out, and then a polyvinyl alcohol-based aqueous solution was used as a film of diethyl phthalocyanine of ^, 80/ΖΠ1 on both sides of the obtained polarizing film, and dried at 5 〇〇c to obtain a polarizing plate. For this polarizing plate, the degree of polarization and light transmittance. The measurement results are shown in Table i, and the polarizing performance of the wavelength (10) is extremely high. Further, unlike this, the extension is performed under the conditions shown below, and the limit extension ratio is obtained. The evaluation results are shown in Table 1. (Evaluation of Boundary Extension Ratio) The polyvinyl alcohol-based film was stretched to 1.5 times while being immersed in a water bath having a water temperature of 3 〇〇c. Next, it was extended to 13.3 times while being immersed in a dyeing tank (3 (rc) consisting of 2 g/L and molybdenum 15 g/L for 24 sec., and then immersed in boric acid 5 a boric acid treatment tank consisting of 〇g/L and potassium iodide 3〇g/L (40 〇, and 40% of the uniaxial extension of the film before the impregnation of the boric acid treatment tank, relative to the rupture The total stretch ratio of the original film is regarded as the limit stretch ratio, and is evaluated according to the following evaluation criteria in 312XP/Invention Manual (Supplement)/95-11/95127673 33 200806719. A: Boundary extension ratio β·3 times or more Β: Boundary The extension ratio is 6. 〇 or more, less than 6.3 times C. The limit extension ratio is 5.7 times or more, less than 6. 〇 times • D: the limit extension ratio is less than 5.7 times (Example 2) 1 'In addition to changing 4〇/〇 aqueous solution viscosity i〇7mpa · s, saponification degree 99·3 mol%, side chain 丨, 2-glycol bond amount 丨 mol% of poly 10 vinyl alcohol resin (A) 21 kg of an unmodified polyvinyl alcohol-based resin (B) having a viscosity of 64 mPa·s and a 4% aqueous solution of 64 mPa·s, a degree of saponification "8 mol%, as a polyvinyl alcohol-based tree The same was carried out to obtain a polyvinyl alcohol-based film (length: 4000 m, width: 4 m, thickness: 5 Å/zm). The obtained polyvinyl alcohol-based film was obtained in the same manner as in the example, and a polarizing film and a polarizing plate were obtained. The measurement results are shown in Table 1. As shown in Table 1, the polarizing performance at a wavelength of 460 was obtained, and the evaluation of the limit stretching ratio was performed in the same manner as in Example 1. Table 1 is shown in Table 1. (Example 3) In Example 1, except that the viscosity of 4% aqueous solution was changed, I6mpa · s, the degree of saponification was 99. 7 mol%, and the amount of 1,2-glycol bond of the side chain was 6 mol. Polyvinyl alcohol-based resin (A) 6·3kg and 4% aqueous solution viscosity 64mPa · s, interest rate 99.8% by mole of unmodified polyvinyl alcohol resin (B) 357kg as polyvinyl alcohol resin The same procedure was carried out in the same manner to obtain an optical polyethylene film (length 4000 m, width 4 m, thickness 65/zm). 312XP/invention specification (supplement)/95-11/95127673 34 200806719 + A polyvinyl alcohol-based film was obtained in the same manner as in Example! A polarizing film and a polarizing plate were obtained. The polarization degree and the light transmittance were measured. As shown in Table, the polarization performance of the wavelength tree nm was obtained = fruit height 7 In addition, the limit stretching ratio was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. (Example 4) In Example 10, except that the viscosity of the 4% aqueous solution was changed by 3 〇 mPa·s, the degree of saponification was 99. 2 mol%, and the side chain was 丨, the amount of 2 _ glycol bond i mol% The same is true for the poly-vinyl alcohol-based resin (A) 12.6 kg and the 4% aqueous solution having a viscosity of 64 mPa·s and the degree of deuteration of 99. 8 mol% of the unmodified polyvinyl alcohol-based resin (B) 29 4 kg. The film was obtained to obtain an optical polyethylene film (length: 4000 m, width: 4 m, thickness: 65//m). In the same manner as in Example i, a polarizing film and a polarizing plate were obtained on the obtained polyethylene-based film, and the degree of polarization and light transmittance were measured. The results are shown in Table 1. As shown in Table 1, the polarizing performance of the wavelength 46〇11111 is very high. Further, in the same manner as in the yoke example 1, the evaluation of the limit stretch ratio was additionally performed. The evaluation results are shown in Table 1. (Example 5) In Example 1, except that the viscosity of 4% aqueous solution was changed by 1〇7 mPa.s, the degree of saponification was 99. 3 mol%, and the side chain was changed, the amount of 2-ethylene glycol bond was 5%. The polyethylene-based resin (A) 25·2kg and the 4% aqueous solution having a viscosity of 64 mPa·s and a saponification degree of 99.8 mol% of the unmodified polyvinyl alcohol-based resin (other than the illusion of 6.8 kg) were obtained in the same manner to obtain optics. A polyvinyl alcohol-based film (length 4 μm, width 4 m, thickness 65/zm). 312XP/invention specification (supplement)/95-11/95127673 35 200806719 The obtained polyvinyl alcohol-based film is implemented In the same manner, the polarizing film and the polarizing plate were obtained in the same manner, and the degree of polarization and the light transmittance were measured. The measurement results are shown in Table 1. The polarizing performance at a wavelength of 460 nm was extremely high. 'In addition, the same as in Example 1. The evaluation of the limit extension ratio was carried out separately. The evaluation results are shown in Table 1. (Example 6) In Example 1, except that the viscosity of the 4% aqueous solution was changed to i6 mPa·s, the degree of saponification was 99. 8 mol%, and the side chain was 1,2-glycol bond amount 8 mol% of poly 10 vinyl alcohol resin (A) 2 · lkg and 4% aqueous solution viscosity 64 mP a s, a saponification degree of 99·8 mol% of the unmodified polyvinyl alcohol-based resin (β) 39·9 kg, the same was carried out in the same manner to obtain an optical polyvinyl alcohol-based film (length 4 〇〇〇m) In the same manner as in the examples, a polarizing film and a polarizing plate were obtained, and the degree of polarization and light transmittance were measured. The measurement results are shown in Table 1. As shown in Table 1, the polarizing performance at a wavelength of 460 nm was extremely high. 10 Further, the evaluation of the limit stretch ratio was carried out in the same manner as in Example 1. The evaluation results are shown in Table 1. (Comparative Example 1) In Example 1, Except that the unmodified polyethylene resin which changed the viscosity of 4% of the aqueous solution of 64 mPa·s and the soap of the group of 8 mol% was carried out in the same manner as the polyethyl alcohol resin, the polyvinyl alcohol was obtained in the same manner. Film (length: 40 μm, width: 4 m, thickness: 50 # m). A polarizing film and a polarizing plate were obtained in the same manner as in the example of the polyvinyl alcohol-based film, and the degree of polarization and light transmittance were measured. The results are shown in 312XP / Invention Manual (supplement) / 95-11/95127673 36 200806719 : As shown in Table 1, the dichroism at a wavelength of 460 nm was 31·72, and sufficient polarization performance could not be obtained. Further, in the same manner as in Example 1, the evaluation of the limit stretching ratio was carried out. The evaluation results are shown in Table 1. Comparative Example 2), in Example 1, except that the polyvinyl alcohol-based resin (Α) was changed to a 4% water/liquid viscosity of 10 mPa·s, a saponification degree of 99.8 mol%, and a side chain of 1, A polyvinyl alcohol-based film (length 4 〇〇〇 m, width 〇 5 〇em) was obtained in the same manner except that the polyethylene glycol resin (a) having a polyethylene glycol bond amount of 8 mol% was used in the same manner. . In the same manner as in Example 丨, a polarizing film was tried in the same manner as in Example ,, but the water resistance was insufficient, and a polarizing film could not be obtained. (Comparative Example 3) In Example 1, except that the viscosity of 4% aqueous solution was changed to 27 mPa·s, the degree of saponification was 99. 8 mol%, and the side chain was changed, the amount of 2 ethylene glycol bond was h 8 mol%. 42 kg of polyvinyl alcohol-based resin was used in the same manner as the polyvinyl alcohol-based resin, and a polyvinyl alcohol-based film (length 4 〇〇〇 m, width 妯, zero degree 50/zm) was obtained. ▲ ▲ A polarizing film and a polarizing plate were obtained in the same manner as in Example 对 for the known polyvinyl alcohol-based film, and the degree of polarization and light transmittance were measured. The results of the measurements are shown in Table 1. As shown in Table 1, the dichroism at a wavelength of 460 nm was 27.01, and sufficient polarizing performance could not be obtained. Further, in the same manner as in Example 另外, the evaluation of the boundary extension magnification was additionally performed. 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PQ (a+v)/o*v muos iuu〇 inch g J9 inch muosmuos J9 inch muimuosmi (v)VAd SVAd ¥(I) 斋乐^^^岭(v)VAd SVAd e(I) —ΙΦ拿1^ 3⁄4一岭 e 卜9ACNIS/II, s/ffffii) 誃纗 誃纗 / / dxCNl e 200806719 Although the present invention is described in detail in the specific embodiments, without departing from the spirit and scope of the present invention, practitioners It is known that various changes and modifications can be made. The present application is based on Japanese Patent Application No. 2005-024466 (Application of January 31, 2005), 2005-024467 (Application of January 31, 2005), 2005-336441 (Application of November 22, 2005), 2005 -336442 (applied November 22, 2005), the contents of which are hereby incorporated by reference. (Industrial Applicability) _ The polyvinyl alcohol-based film for optical use of the present invention is a polyvinyl alcohol-based resin containing only a 1,2-glycol-bonded polyvinyl alcohol-based resin (A) a film having a 1,2-ethylene glycol bond amount of 1 to 6 mol% in the side chain, or a polyethylene having a side chain containing ruthenium and 2-ethylene glycol bond in a specific ratio The polyvinyl alcohol-based resin (B) other than the alcohol-based resin (A) and the polyvinyl alcohol-based resin (A) is a film of a polyvinyl alcohol-based resin, and is a polyvinyl alcohol-based film excellent in stretchability and visible light. The entire area of the line, especially around the 460mn length, has the effect of obtaining excellent polarization characteristics, and is very useful as an electronic desktop computer, an electronic clock, a word processor, a personal computer, a television, a mobile information terminal, a car. Liquid crystal display devices such as mechanical instruments, sunglasses, goggles, stereo glasses, display elements (10), LCDs, etc., are used for reflective films of reflective layers, medical devices, materials, toys, etc.丨/2 wavelength plate and 1 / The original film of the 4-wavelength plate, and the phase of the liquid crystal display device, the original film of the film. < Difference 312XP / invention manual (supplement) / 95·11/95127673 39

Claims (1)

200806719 X. Patent application scope: The type of polyethylene film used in the study is a polyvinyl alcohol-based resin. The polyvinyl alcohol-based resin is characterized in that the polyvinyl alcohol-based resin contains only 丨2_•acetol bond in the side chain. The polyvinyl alcohol-based resin (A) is a knot, and the ul-ethyl alcohol linkage amount of the side chain is 0.01 to 6 mol%. 2. A polyvinyl alcohol-based film for optical use comprising a polyvinyl alcohol-based resin, characterized in that the polyvinyl alcohol-based resin is a polyethylene having a 1,2-ethylidene-alcohol-bonded bond at a side bond. The alcohol resin (1) and the polyvinyl alcohol resin (8) other than the polyvinyl alcohol resin (A) are satisfied, and satisfy the following formula (1); 〇·°1^AxG/(A+B)^6 ... (1) Here, A is a content ratio (weight ratio) of the polyvinyl alcohol-based resin (A) in a total amount of the polyvinyl alcohol-based resin (A) and the polyvinyl alcohol-based resin (B); The content ratio (weight ratio) of the polyvinyl alcohol-based resin (B) in relation to the above total amount; G represents the amount of 1,2-glycol bond (mol%) of the side chain. 3. The polyvinyl alcohol-based film for optics according to item 2 of the patent application, wherein the polyvinyl alcohol-based resin (A) and the polyethylene are contained in a side chain containing 1 > The total amount of the polyvinyl alcohol-based resin (B) other than the alcohol resin is such that the content of the polyvinyl alcohol-based resin (A) is 5% by weight or less. 4. The polyvinyl alcohol-based film for optical use according to the second or third aspect of the patent application, wherein the 1,2-glycol bond of the side chain of the polyvinyl alcohol-based resin (A) is 0·01~ 20 moles %. 5. The polyvinyl alcohol-based film for optical use according to claim 1 or 2, wherein the polyvinyl alcohol-based resin (A) has a degree of saponification of 90 mol% or more. 312XP/Invention Manual (Supplement)/95-11/95127673 40 200806719 6. The optical polyvinyl alcohol film according to claim 1 or 2, wherein the viscosity of the polyvinyl alcohol resin (Α), 4 The weight % aqueous solution has a viscosity of 8 to 400 mPa · s. [7] The polyvinyl alcohol-based film for optics according to the second or third aspect of the invention, wherein the polyvinyl alcohol-based resin (B) has a degree of saponification of 9 〇 mol% or more. 8. The polyvinyl alcohol-based film for optical use according to the second or third aspect of the invention, wherein the polyvinyl alcohol-based resin (8) has a viscosity of 4% by weight and a liquid state of 8 to 500 mPa·s. "9. The optical polyglycol film according to the second or third aspect of the patent application, wherein the difference in saponification degree between the polyvinyl alcohol resin (A) and the polyvinyl alcohol resin (b) is 6 Less than the ear. 〇. If you apply for a patent scope! Or two optical films for optics, further comprising a plasticizer (c). An optical film according to the item of claim 2, further comprising a surfactant (D).糸/Specially applied to the optical polyvinyl alcohol film of the 142th patent scope, wherein the film width is 2m or more.糸 is 13· Declaring the optical film of the first or second item of the patent, wherein the film thickness is 3Q to 7Mm.糸 Η Η 申请 申请 Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学The premise of the spear is 16] - the polarizer is made of a protective film on at least one side of the polarizing film 312XP / invention manual (supplement) / 95·! 1/95127673 200806719 . 312XP/Inventive Manual (Supplement)/95-11/95127673 42 200806719 VII. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: 'No eight, this case When there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: 312XP / invention manual (supplement) /9541/95127673 4