JP2007047382A - Polarizing plate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polarizing plate for improving irregularity and distortion of the polarizing plate, in particular, due to drying and long time preservation while maintaining a degree of polarization and durability, and to provide a liquid crystal display superior in visibility and viewing angle characteristics using the polarizing plate. <P>SOLUTION: The polarizing plate comprises a polarizing film that uses a polyvinyl alcohol film consisting of a vinyl alcohol based polymer containing 0.01-20 mol% of a cation group contained unit and 0.5-24 mol% of an α-olefin unit of a carbon number of 4 or less, and has 5-18 μm of thickness subjected to extension and dye treatment; and a retardation plate having a retardation value Ro of 30-110 nm, Rt of 70-300 nm, and film thickness of 20-60 μm. The thickness of the polarizing plate is 70-140 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polarizing plate and a liquid crystal display device, and more particularly to a polarizing plate having a sufficient degree of polarization and durability, and a liquid crystal display device using the same even if it is a thin film.

  In recent years, liquid crystal display devices have been used not only for personal computer monitors but also for TVs, and have been increasing in size and brightness. For this reason, not only high durability is required, but also unevenness, which has not been noticeable in the past, has become a major problem due to the increase in luminance. There are various forms of unevenness that occur when creating polarizing plates, and those that occur after long-term use, but the increase in the size and brightness of liquid crystal display devices is the direction to amplify them. Working.

  In order to reduce the unevenness of the polarizing plate, it is effective to thin the polarizing film of polyvinyl alcohol (hereinafter also referred to as PVA). However, if an adhesive is applied to the PVA polarizing film by the conventional method, the effect of thinning the polarizing film is reduced. Therefore, the moisture content of the adhesive easily penetrates into the polarizing film, causing a decrease in the degree of polarization. Therefore, in order to create a thin film polarizing plate with an existing line, faster drying is necessary. However, drying is not sufficient just by shortening the drying time, and if the drying temperature is raised too much, the degree of polarization of the polarizing plate is reduced. There is a concern that the quality will deteriorate. Further, if it takes too much time to dry, distortion due to unevenness at the time of drying occurs, and further unevenness of light leakage due to long-time use occurs, which becomes a big problem.

Patent Document 1 proposes a thin film polarizing film using an ethylene-vinyl alcohol copolymer, and describes the improvement of polarization performance and water resistance. Is not mentioned at all.
JP 2003-248123 A

  In order to solve this problem, the present inventor has repeatedly investigated that a thin film PVA polarizing film can be used in order to suppress unevenness of the polarizing plate without degrading the properties of the polarizing plate such as the degree of polarization and durability. It has been found that distortion of the polarizing plate due to drying and storage over time can be greatly reduced by providing a retardation function and further thinning the polarizing plate.

  Accordingly, the object of the present invention is to maintain the degree of polarization and durability, and in particular to the polarizing plate with improved unevenness and distortion of the polarizing plate due to drying and storage over time, and the visibility and viewing angle characteristics using the polarizing plate. The object is to provide an excellent liquid crystal display device.

  The above object of the present invention is achieved by the following configurations.

  (1) A polyvinyl alcohol film comprising a vinyl alcohol polymer containing 0.01 to 20 mol% of a cationic group-containing unit and 0.5 to 24 mol% of an α-olefin unit having 4 or less carbon atoms. A polarizing film having a film thickness of 5 to 18 μm subjected to stretching and dyeing treatment, a retardation value Ro represented by the following formula of 30 to 110 nm, Rt of 70 to 300 nm, and a film thickness of 20 to 60 μm. A polarizing plate having a retardation plate, wherein the polarizing plate has a thickness of 70 to 140 μm.

Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
(Where nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is (The thickness of the film (nm).)
(2) The polarizing plate as described in (1) above, wherein a main component of the retardation plate is a cellulose ester.

  (3) The cellulose ester satisfying the following formulas (I) and (II) when the substitution degree of the acetyl group of the cellulose ester is X and the substitution degree of the propionyl group or butyryl group is Y: The polarizing plate according to item (2).

Formula (I) 2.0 ≦ X + Y ≦ 2.6
Formula (II) 0.1 ≦ Y ≦ 1.2
(4) The refractive index difference between one surface of the retardation plate and the surface on the opposite side thereof is in the range of 5 × 10 ⁻⁴ or more and 5 × 10 ⁻³ or less. 3. The polarizing plate according to any one of items 3).

  (5) A liquid crystal display device using the polarizing plate according to any one of the above items (1) to (4) on at least one surface of a liquid crystal cell.

  According to the present invention, while maintaining the degree of polarization and durability, a polarizing plate in which unevenness and distortion of the polarizing plate are improved particularly by drying and storage over time, and a liquid crystal display excellent in visibility and viewing angle characteristics using the polarizing plate. A device can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The polarizing plate of the present invention comprises a vinyl alcohol polymer containing 0.01 to 20 mol% of a cationic group-containing unit and 0.5 to 24 mol% of an α-olefin unit having 4 or less carbon atoms. A polarizing film having a film thickness of 5 to 18 μm subjected to stretching and dyeing treatment using a polyvinyl alcohol film, a retardation value Ro represented by the above formula of 30 to 110 nm, Rt of 70 to 300 nm, and a film thickness of It is a polarizing plate which has a retardation plate which is 20-60 micrometers, The thickness of this polarizing plate is 70-140 micrometers, It is characterized by the above-mentioned.

  As described above, the present invention has been studied so that a thin film PVA polarizing film can be used in order to suppress the unevenness of the polarizing plate due to drying and storage over time without deteriorating the properties of the polarizing plate such as the degree of polarization and durability. The polarizing plate of the present invention and a retardation plate having a retardation function in the polarizing plate protective film can be used as a polarizing plate protective film, so that the entire polarizing plate can be thinned and dried in the production of the polarizing plate. It has been found that the influence of storage over time can be reduced and the distortion of the polarizing plate can be greatly improved.

  As will be described later, the polarizing plate of the present invention preferably has a structure in which the thin film PVA polarizing film is sandwiched between the retardation plate and at least one polarizing plate protective film. The thickness of the polarizing plate is the total thickness of the thin film PVA polarizing film, the retardation plate and the polarizing plate protective film, and does not include the adhesive layer. When the said polarizing plate protective film contains a hard-coat layer, it is included.

  Hereinafter, the present invention will be described in detail for each element.

(Polarizing film: Polyvinyl alcohol film)
The polyvinyl alcohol film used in the polarizing film of the present invention contains 0.01 to 20 mol% of a cationic group-containing unit and 0.5 to 24 mol% of an α-olefin unit having 4 or less carbon atoms. It is a PVA film made of a vinyl alcohol polymer.

  In this invention, PVA used for manufacture of a PVA film can be obtained by saponifying a copolymer of a vinyl ester, a cationic group-containing monomer, and an α-olefin having 4 or less carbon atoms. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and the like, and generally vinyl acetate is used.

  In the present invention, the cationic group-containing unit introduced into PVA means a chemical structural unit that dissociates in an aqueous solution and is charged to a positive charge, and a cationic group-containing single unit having such a chemical structural unit. Specific examples of the body include, for example, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, 3-acrylamidopropyltrimethylammonium chloride, 3-methacrylamidopropyltrimethylammonium chloride, N- (3-allyloxy-2- Quaternary ammonium salt of hydroxypropyl) dimethylamine, quaternary ammonium salt of N- (4-allyloxy-3-hydroxybutyl) diethylamine, acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide Diacetone acrylamide, N- methylol acrylamide, methacrylamide, N- methacrylamide, N- methacrylamide, quaternary ammonium salts such as N- methylol methacrylamide. The content of the cationic group-containing unit in PVA is 0.01 to 20 mol%, more preferably 0.05 to 10 mol%, and particularly preferably 0.1 to 5 mol%. When the content of the cationic group-containing unit is less than 0.01 mol%, the effect due to the introduction of the cationic group is not exhibited. From the viewpoint of the adsorptivity of the dichroic dye to the polarizing film, the content of the cationic group-containing unit is more preferably 0.05 mol% or more, and particularly preferably 0.1 mol% or more. On the other hand, when the content of the cationic group-containing unit exceeds 20 mol%, it is difficult to produce PVA containing such a chemical structural unit. From the viewpoint of the water resistance of the polarizing film, the content of the cationic group-containing unit is more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

  Examples of the α-olefin having 4 or less carbon atoms used in the present invention include ethylene, propylene, isobutene, and 1-butene. Among these, ethylene is preferable. The content of α-olefin units in PVA is 0.5 to 24 mol%, preferably 0.8 to 15 mol%, particularly preferably 1 to 8 mol%. When the content of α-olefin is less than 0.5 mol%, the effect of modifying PVA with α-olefin is less likely to appear, and the higher the content of α-olefin, the more hydrophobic the PVA itself. The water-soluble nature of PVA becomes poor, the characteristics inherent to PVA tend to be impaired, and this tendency becomes prominent when the α-olefin content exceeds 24 mol%.

  In the present invention, PVA may be copolymerized with other copolymerizable ethylenically unsaturated monomers as long as the effects of the present invention are not impaired. Examples of such ethylenically unsaturated monomers include acrylic acid, methacrylic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, acrylonitrile, methacrylonitrile, acrylamide-2-methylpropane. Examples thereof include sulfonic acid or a sodium salt thereof, sodium vinyl sulfonate, sodium allyl sulfonate, ethyl vinyl ether, butyl vinyl ether, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene and the like. The content of ethylenically unsaturated monomer units in the vinyl alcohol polymer is preferably less than 10 mol%, more preferably less than 5 mol%, and even more preferably less than 2 mol%. As the PVA, a polymer terminal may be modified using a chain transfer agent at the time of production, or PVA or polyvinyl acetate may be modified by post-modification.

  The degree of polymerization of PVA used in the present invention is 20 mPa · s or more when expressed in terms of the viscosity of an aqueous solution having a concentration of 4% by mass, from the viewpoint of strength, stretchability, polarization performance and durability of the produced film. Desirable from. However, the viscosity of the aqueous solution specified here was measured using a Brookfield viscometer, rotor No. 1 is a value measured at 60 rpm and 20 ° C. The degree of polymerization of PVA should not exceed 1000 mPa · s when expressed in terms of the viscosity of a 4% by weight aqueous solution. When the viscosity of a 4% strength by weight aqueous solution of PVA exceeds 1000 mPa · s, it may be difficult to produce PVA. However, in this case, the rotor of the B-type viscometer used for measuring the viscosity of the PVA aqueous solution corresponds to the high-viscosity PVA aqueous solution. 1 to 3 are appropriately used. The degree of polymerization of PVA is preferably 22 to 500 mPa · s, and more preferably 25 to 250 mPa · s, when expressed in terms of the viscosity of a 4 mass% aqueous solution.

  The average saponification degree of the vinyl ester portion of the PVA used in the present invention is preferably 90 mol% or more, more preferably 96 mol% or more, and most preferably 98 mol% or more from the viewpoint of durability of the polarizing film to be produced. .

  As a method for producing a PVA film, for example, using a PVA solution in which PVA is dissolved in water, an organic solvent, or a mixed liquid of water and an organic solvent, a casting film forming method, a wet film forming method (in a poor solvent) Discharge), gel film forming method (a method in which the PVA aqueous solution is once cooled and gelated, and then the solvent is extracted and removed to obtain a PVA film), and a combination of these methods, and hydrous PVA (including organic solvents) Or a melt extrusion film-forming method in which it may be melted. Among these, it is preferable from the viewpoint of obtaining a good polarizing film to produce a PVA film by a casting film forming method and a melt extrusion film forming method.

  Examples of the solvent for dissolving PVA used in producing the PVA film include dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Examples thereof include trimethylolpropane, ethylenediamine, diethylenetriamine, glycerin, water, and the like, and one or more of these can be used. Among these, dimethyl sulfoxide, water, or a mixed solvent of glycerin and water is preferably used.

  10-70 mass% is suitable for the PVA density | concentration in the PVA solution or water-containing PVA used when manufacturing a PVA film, 13-55 mass% is more suitable, and 15-50 mass% is the most suitable. is there. The PVA solution or the hydrous PVA may contain a plasticizer, a surfactant, a dichroic dye, or the like as necessary.

  As the plasticizer that can be contained in the PVA solution or the hydrous PVA used for the production of the PVA film, polyhydric alcohols are preferably used. Specific examples thereof include, for example, ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin. , Triethylene glycol, tetraethylene glycol, trimethylolpropane and the like. These polyhydric alcohols can be used alone or in combination of two or more. Among these polyhydric alcohols, diglycerin, ethylene glycol or glycerin is preferably used from the viewpoint of the effect of improving stretchability.

  As addition amount of a polyhydric alcohol, 1-30 mass parts is preferable with respect to 100 mass parts of PVA, 3-25 mass parts is more preferable, Especially 5-20 mass parts is the most preferable. If the amount is less than 1 part by mass, the dyeability and stretchability of the PVA film may be reduced. If the amount is more than 30 parts by mass, the PVA film may be too soft and the handleability may be reduced.

  There is no particular limitation on the type of surfactant that can be contained in the PVA solution or the hydrous PVA used in the production of the PVA film, but a nonionic surfactant is preferred. Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, alkyl ester types such as polyoxyethylene laurate, and polyoxyethylene laurylamino. Alkylamine type such as ether, alkylamide type such as polyoxyethylene lauric acid amide, polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether, alkanolamide type such as oleic acid diethanolamide, polyoxyalkylene allyl phenyl ether, etc. Nonionic surfactants such as allyl phenyl ether type are preferred. These surfactants can be used alone or in combination of two or more.

  As addition amount of surfactant, 0.01-1 mass part is preferable with respect to 100 mass parts of PVA, 0.02-0.5 mass part is more preferable, Especially 0.05-0.3 mass part is the most. preferable. If the amount is less than 0.01 parts by mass, the effect of improving the stretchability and dyeability of the PVA film is hardly exhibited. If the amount is more than 1 part by mass, the surfactant is eluted on the surface of the PVA film, causing blocking, and handling. May decrease.

  As the dichroic dye that can be contained in the PVA solution or the hydrous PVA used for the production of the PVA film, a dichroic dye used when dyeing the PVA film, which will be described later, can be used.

  The thickness of the PVA film is preferably 5 to 150 μm, more preferably 20 to 100 μm, still more preferably 30 to 90 μm, and most preferably 35 to 80 μm.

  In order to produce a polarizing film from a PVA film, for example, the PVA film may be dyed, uniaxially stretched, fixed, dried, and further heat treated as necessary. There is no particular limitation. In addition, the uniaxial stretching may be performed in two times or in more times.

  The PVA film of the present invention is particularly suitable for dyeing using a dichroic dye. By using the PVA film of the present invention, even when dyeing is performed using a dichroic dye, in addition to being excellent in water resistance and polarization performance, a polarizing film free from uneven dyeing can be produced. . In dyeing a PVA film using a dichroic dye, a treatment of immersing the PVA film in a solution containing the dichroic dye is generally performed. A dichroic dye may be added to the PVA solution or water-containing PVA used in production, and the treatment conditions and treatment method are not particularly limited.

  The treatment of immersing the PVA film in the solution containing the dichroic dye can be carried out at any operation stage before uniaxial stretching, during uniaxial stretching or after uniaxial stretching of the PVA film. Specific examples of the dichroic dye include, for example, direct black 17, 19, 154; direct brown 44, 106, 195, 210, 223; direct red 2, 23, 28, 31, 37, 39, 79, 81, 240, 242, 247; Direct Blue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; Direct Violet 9, 12, 51, 98; Direct Green 1, 85; Direct Yellow 8, 12, 44, 86, 87; direct orange 26, 39, 106, 107 and the like. Even when these dichroic dyes are used alone, a color polarizing film can be obtained, but by using two or more kinds of dyes in combination, the same absorption characteristics over the entire wavelength range of visible light of 380 to 780 nm. And a polarizing film having a high degree of polarization can be obtained. The dichroic dye referred to here refers to an organic compound dye excluding an inorganic dye such as iodine.

  The PVA film of the present invention can be dyed using not only a dichroic dye but also iodine-potassium iodide.

  In order to uniaxially stretch the PVA film, a wet stretching method in which the PVA film is stretched in a warm aqueous solution (in a solution containing the above-described dye or in a fixing treatment bath described later), or a PVA film after being hydrated in the air. A dry heat stretching method for stretching can be employed. The stretching temperature is not particularly limited, but is preferably 30 to 90 ° C. when the PVA film is stretched (wet stretching) in warm water, and 50 to 180 ° C. is suitable for dry heat stretching. Further, the stretching ratio by uniaxial stretching (the total stretching ratio when uniaxial stretching is performed in multiple stages) is preferably 4 times or more, and particularly preferably 5 times or more from the viewpoint of the polarization performance of the polarizing film. Although there is no restriction | limiting in particular about the upper limit of a draw ratio, Since uniform extending | stretching is easy to be obtained if it is 8 times or less, it is preferable.

  The PVA film containing the dichroic dye and uniaxially stretched is subjected to a fixing treatment, if necessary, by immersing it in an aqueous solution containing boric acid and / or boron compound according to a known method. Is done. By this treatment, the light transmittance, polarization degree and durability of the polarizing film can be improved. Furthermore, you may perform the fix process by the aqueous solution containing a cationic high molecular compound with a fixing process as needed.

  The uniaxially stretched film is preferably dried (heat treated) at a temperature of 30 to 150 ° C, more preferably 50 to 150 ° C.

  The polarizing film of the present invention is subjected to the above stretching and dyeing treatment, and its film thickness is in the range of 5 to 18 μm. Preferably it is the range of 7-15 micrometers. In conventional polarizing films of 20 μm or more, unevenness was likely to occur due to drying and storage over time of the polarizing plate preparation process, but by combining with the retardation plate according to the present invention, the unevenness was improved by making the thickness of the polarizing film in the above range. Is planned.

  In order to give sufficient mechanical strength, the polarizing film of the present invention is bonded to a polarizing plate protective film having optical transparency and mechanical strength on both sides or one side to form a polarizing plate. Preferably, a polarizing plate protective film is bonded to both surfaces, and at least one polarizing plate protective film is the retardation plate according to the present invention.

  As the polarizing plate protective film, a cellulose acetate film, an acrylic film, a polyester film or the like is usually used. Among these, a cellulose ester film described later is preferable.

(Retardation plate and polarizing plate protective film)
Next, the retardation plate and polarizing plate protective film of the present invention will be described in detail.

  The retardation film (hereinafter, also referred to as retardation film) having a film thickness of 20 to 60 μm according to the present invention and the polarizing plate protective film used in the present invention are easy to manufacture and adhesive to the polarizing film. However, it is preferable that the film is optically transparent and the like, and a polymer film is particularly preferable.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  The polymer film is not particularly limited as long as it has the above properties. For example, cellulose ester films such as cellulose diacetate film, cellulose triacetate film, cellulose acetate butyrate film, and cellulose acetate propionate film, polyester Film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film , Ethylene vinyl alcohol film, syndiotactic polystyrene film, polycar Nate film, cycloolefin polymer film (Arton (manufactured by JSR), Zeonex, Zeonea (manufactured by Zeon)), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film , Nylon film, polymethyl methacrylate film, acrylic film, glass plate and the like. Among these, a cellulose ester film, a polycarbonate film, and a polysulfone (including polyether sulfone) film are preferable. In the present invention, in particular, a cellulose ester film is used in terms of production, cost, transparency, adhesiveness, and the like. Are preferably used. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

  The polarizing plate protective film used in the present invention is not particularly limited in its components, but the preferred cellulose ester as the main component of the retardation film according to the present invention is preferably cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate. Of these, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or butyryl group is Y, a transparent film substrate having a mixed fatty acid ester of cellulose in which X and Y are in the following ranges is preferably used.

Formula (I) 2.0 ≦ X + Y ≦ 2.6
Formula (II) 0.1 ≦ Y ≦ 1.2
Further, 2.4 ≦ X + Y ≦ 2.6, 1.4 ≦ X ≦ 2.3 cellulose acetate propionate (total acyl group substitution degree = X + Y) is preferable. Among them, cellulose acetate propionate (total acyl group substitution degree = X + Y) of 2.4 ≦ X + Y ≦ 2.6, 1.7 ≦ X ≦ 2.3, and 0.1 ≦ Y ≦ 0.9 is preferable. The portion not substituted with an acyl group usually exists as a hydroxyl group. These cellulose esters can be synthesized by a known method.

  When the cellulose ester is used as the retardation film according to the present invention and the polarizing plate protective film used in the present invention, the cellulose used as the raw material for the cellulose ester is not particularly limited, but cotton linter, wood pulp (derived from conifers, hardwood) Origin), kenaf and the like. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or an organic solvent such as methylene chloride, and It can be obtained by reacting with a cellulose raw material using a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. In addition, the cellulose ester used in the present invention is obtained by mixing and reacting the amount of the acylating agent in accordance with the degree of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  As the cellulose ester used in the present invention, as described above, cellulose having propionate group or butyrate group in addition to acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate is used. The mixed fatty acid ester is particularly preferably used. Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for a liquid crystal image display device.

  The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably from 40000 to 200000, since it has a high mechanical strength when molded and an appropriate dope viscosity, and more preferably from 50000 to 150,000. The weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably in the range of 1.4 to 4.5.

  These cellulose esters are pressurized by applying a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transport or a support for casting of a rotating metal drum. It is preferable to manufacture the dope from a die by casting (casting).

  The organic solvent used for the preparation of these dopes is preferably capable of dissolving the cellulose ester and having an appropriate boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2 -Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 , 3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, etc. It is possible, organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, and the like are preferable organic solvents (i.e., good solvent), and as.

  Moreover, as shown in the following film forming process, it is used from the viewpoint of preventing foaming in the web when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation process. The boiling point of the organic solvent is preferably 30 to 80 ° C. For example, the good solvent described above has a boiling point of methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), acetone (boiling point 56.56 ° C). 3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

  Among the good solvents described above, methylene chloride or methyl acetate, which is excellent in solubility, is preferably used.

  It is preferable to contain 0.1 mass%-40 mass% of C1-C4 alcohol other than the said organic solvent. It is particularly preferable that the alcohol is contained at 5 to 30% by mass. After casting the dope described above onto a casting support, the solvent starts to evaporate and the alcohol ratio increases and the web (dope film) gels, making the web strong and peeling from the casting support. It is also used as a gelling solvent for facilitating the dissolution, and when these ratios are small, it also has a role of promoting dissolution of the cellulose ester of the non-chlorine organic solvent.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.

  Of these solvents, ethanol is preferred because it has good dope stability, relatively low boiling point, good drying properties, and no toxicity. It is preferable to use a solvent containing 5% by mass to 30% by mass of ethanol with respect to 70% by mass to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.

  When a cellulose ester film is used for the retardation film according to the present invention and the polarizing plate protective film used in the present invention, it is preferable to contain the following plasticizer from the viewpoint of flexibility, moisture permeability, and dimensional stability. . Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer or the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, and other trimellitic acid plasticizers include tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethylglycolate, butylphthalylbutylglycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include trimethylolpropane tribenzoate, butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The amount of these plasticizers used is preferably 1% by mass to 20% by mass and particularly preferably 3% by mass to 13% by mass with respect to the cellulose ester in terms of film performance, processability and the like.

  An ultraviolet absorber is preferably used for the retardation film of the present invention.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of the ultraviolet absorber preferably used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these.

  Specific examples of the benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers, but the present invention is not limited thereto.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Moreover, although the following specific example is shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorbers described in the general formula (1) or general formula (2) described in JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039 ( Alternatively, an ultraviolet absorbing polymer) is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  Moreover, in order to provide slipperiness to the retardation film according to the present invention and the polarizing plate protective film used in the present invention, fine particles similar to those described in the coating layer containing an actinic radiation curable resin can be used. .

  The primary average particle diameter of the fine particles added to the retardation film according to the present invention and the polarizing plate protective film used in the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably. 5-12 nm. These fine particles preferably form secondary particles having a particle size of 0.1 to 5 μm and are contained in the retardation film, and a preferable average particle size is 0.1 to 2 μm, more preferably 0.2 to 0.6 μm. Thereby, the unevenness | corrugation about 0.1-1.0 micrometer high can be formed in the film surface, and, thereby, appropriate slipperiness can be given to the film surface.

  The primary average particle diameter of the fine particles used in the present invention is measured by observing the particles with a transmission electron microscope (magnification 500,000 to 2,000,000 times), observing 100 particles, measuring the particle diameter, and measuring the average. The value was taken as the primary average particle size.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter. A larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

  Silicon dioxide fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. For example, it is marketed by the brand name of Aerosil 200V and Aerosil R972V (above, Nippon Aerosil Co., Ltd. product), and can use them.

  The apparent specific gravity described above is calculated by the following equation by taking a certain amount of silicon dioxide fine particles in a graduated cylinder, measuring the weight at this time.

Apparent specific gravity (g / liter) = silicon dioxide mass (g) / volume of silicon dioxide (liter)
Examples of the method for preparing the fine particle dispersion used in the present invention include the following three types.

<< Preparation Method A >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose triacetate to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

  Preparation method A is excellent in dispersibility of silicon dioxide fine particles, and preparation method C is excellent in that silicon dioxide fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a preferable preparation method that is excellent in both dispersibility of the silicon dioxide fine particles and difficulty in reaggregation of the silicon dioxide fine particles.

《Distribution method》
The concentration of silicon dioxide when the silicon dioxide fine particles are mixed with a solvent and dispersed is preferably 5% by mass to 30% by mass, more preferably 10% by mass to 25% by mass, and most preferably 15% by mass to 20% by mass. A higher dispersion concentration is preferable because liquid turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

  The addition amount of silicon dioxide fine particles relative to cellulose ester is preferably 0.01 parts by mass to 5.0 parts by mass, and more preferably 0.05 parts by mass to 1.0 part by mass with respect to 100 parts by mass of cellulose ester. Preferably, 0.1 mass part-0.5 mass part is the most preferable. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the less aggregates.

  As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersing silicon dioxide fine particles, a medialess disperser is preferred because of its low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. The high pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.613 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  Examples of the high-pressure dispersion apparatus include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and a Manton Gorin type high-pressure dispersion apparatus such as a homogenizer manufactured by Izumi Food Machinery. And UHN-01 manufactured by Sanwa Machinery Co., Ltd.

  In addition, casting a dope containing fine particles so as to be in direct contact with the casting support is preferable because a film having high slip properties and low haze can be obtained.

  Moreover, after peeling and drying after casting, and winding up in a roll shape, functional thin films, such as a hard-coat layer and an antireflection layer, are provided. Until processing or shipment, packaging is usually performed in order to protect the product from dirt, static electricity, and the like. The packaging material is not particularly limited as long as the above purpose can be achieved, but a material that does not hinder volatilization of the residual solvent from the film is preferable. Specific examples include polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various non-woven fabrics, and the like. Those in which the fibers are mesh cloth are more preferably used.

(Production method of retardation film of the present invention and polarizing plate protective film used in the present invention)
Next, the manufacturing method of the retardation film of this invention and the polarizing plate protective film used for this invention is demonstrated in detail.

  Production of the retardation film of the present invention and the polarizing plate protective film used in the present invention is a step of preparing a dope by dissolving an additive such as cellulose ester and the plasticizer in a solvent, and forming the dope into a belt shape or a drum shape. The process of casting on a metal support, the process of drying the cast dope as a web, the process of peeling off from the metal support, the process of stretching, the process of further drying, the process of further heat-treating the resulting film, after cooling It is performed by a winding process. The retardation film of the present invention preferably contains 70 to 95% by mass of cellulose ester in the solid content.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope of the present invention may be used alone or in combination of two or more. However, it is preferable from the viewpoint of production efficiency that a good solvent and a poor solvent of cellulose ester are mixed and used. The more solvent is preferable from the viewpoint of solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the acyl group substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4) and cellulose acetate propionate are good. As a solvent, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  A general method can be used as a method of dissolving the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of a solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

A bright spot foreign substance is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably 100 / cm ² or less, more preferably 50 or / m ² or less, more preferably 0 to 10 / cm ² or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by an ordinary method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or flatness may deteriorate. The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Moreover, in the drying process of the cellulose ester film, the web is peeled off from the metal support, further dried, and dried until the residual solvent amount is 0.5% by mass or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a tenter method is used while drying the web.

  When peeling from the casting support, the film can be stretched in the longitudinal direction by the peeling tension and the subsequent conveying tension. For example, it is preferable to peel at a peeling tension of 210 N / m or more, and particularly preferably 220 to 300 N / m.

  An example of a stretching process (also referred to as a tenter process) for producing the retardation film according to the present invention will be described with reference to FIG.

  In FIG. 2, step A is a step of gripping the web conveyed from the web conveyance step D0 (not shown). In the next step B, the web is stretched in the width direction (at the stretching angle as shown in FIG. In the process C, the stretching is completed and the web is transported while being held.

  It is preferable to provide a slitter that cuts off the end in the web width direction after the web is peeled from the casting support and before the start of step B and / or immediately after step C. In particular, it is preferable to provide a slitter that cuts off the end of the web immediately before the start of step A. When the same stretching is performed in the width direction, particularly when the web edge is cut before the start of the process B and the condition in which the web edge is not cut is compared, the former has an effect of improving the distribution of the orientation angle. can get.

  This is considered to be an effect of suppressing unintended stretching in the longitudinal direction from the peeling with a relatively large amount of residual solvent to the width stretching step B.

  In the tenter process, it is also preferable to intentionally create compartments with different temperatures in order to improve the orientation angle distribution. It is also preferable to provide a neutral zone between different temperature zones so that the zones do not interfere with each other.

  The stretching operation may be performed in multiple stages, and it is preferable to perform biaxial stretching in the casting direction and the width direction. Also, when biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise. In this case, stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.

  In order to obtain the effect of the present invention, it is particularly preferable that the web peeled from the metal support is conveyed while being dried, and further stretched in the width direction by a tenter method in which both ends of the web are gripped by pins or clips. A predetermined phase difference can be given. At this time, it may be stretched only in the width direction, or simultaneous biaxial stretching is also preferred. The preferred draw ratio is preferably 1.05 to 2 times, and preferably 1.15 to 1.5 times. In the case of simultaneous biaxial stretching, the film may be contracted in the longitudinal direction, or may be contracted so as to be 0.8 to 0.99, preferably 0.9 to 0.99. Preferably, the area is preferably 1.12 times to 1.44 times and more preferably 1.15 times to 1.32 times due to transverse stretching and longitudinal stretching or shrinkage. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction.

  Further, the “stretch direction” in the present invention is usually used to mean a direction in which a stretching stress is directly applied when performing a stretching operation, but in the case of being biaxially stretched in multiple stages, In some cases, it is used in the sense of the one having a higher draw ratio (that is, the direction usually serving as the slow axis).

  When the web is stretched in the width direction, it is well known that the optical slow axis distribution (hereinafter, orientation angle distribution) deteriorates in the width direction of the web. In order to perform widthwise stretching with the values of Rt and Ro being a constant ratio and with a good orientation angle distribution, there is a preferred web temperature relative relationship in steps A, B, and C. When the web temperatures at the end points of Steps A, B, and C are Ta ° C., Tb ° C., and Tc ° C., respectively, it is preferable that Ta ≦ Tb−10. Moreover, it is preferable that Tc ≦ Tb. More preferably, Ta ≦ Tb−10 and Tc ≦ Tb.

  In order to improve the orientation angle distribution, the web heating rate in step B is preferably in the range of 0.5 to 10 ° C./second.

  The stretching time in step B is preferably a short time. However, the minimum required stretching time range is defined from the viewpoint of web uniformity. Specifically, the range is preferably 1 to 10 seconds, and more preferably 4 to 10 seconds. Moreover, the temperature of the process B is 40-180 degreeC, Preferably it is 100-160 degreeC.

In the tenter process, the heat transfer coefficient may be constant or changed. The heat transfer coefficient preferably has a heat transfer coefficient in the range of 41.9 to 419 × 10 ³ J / m ² hr. More preferably, in the range of ^{41.9~209.5 × 10 3 J / m 2} hr, and most preferably a range of ^{41.9~126 × 10 3 J / m 2} hr.

  The stretching speed in the width direction in step B may be constant or may be changed. The stretching speed is preferably 50 to 500% / min, more preferably 100 to 400% / min, and most preferably 200 to 300% / min.

  In the tenter process, it is preferable that the temperature distribution in the width direction of the atmosphere is small from the viewpoint of improving the uniformity of the web. The temperature distribution in the width direction in the tenter process is preferably within ± 5 ° C, and within ± 2 ° C Is more preferable, and within ± 1 ° C. is most preferable. By reducing the temperature distribution, it can be expected that the temperature distribution at the width of the web is also reduced.

  In step C, it is preferable to relax in the width direction. Specifically, it is preferable to adjust the web width so that the final web width after stretching in the previous step is in the range of 95 to 99.5%.

  After the treatment in the tenter process, it is preferable to further provide a post-drying process (hereinafter referred to as process D1). It is preferable to carry out at 50-160 degreeC. More preferably, it is the range of 80-140 degreeC, Most preferably, it is the range of 110-130 degreeC.

  In step D1, it is preferable that the atmospheric temperature distribution in the width direction of the web is small from the viewpoint of improving the uniformity of the web. Within ± 5 ° C is preferable, within ± 2 ° C is more preferable, and within ± 1 ° C is most preferable.

  The web conveyance tension in the step D1 is affected by the physical properties of the dope, at the time of peeling and the residual solvent amount in the step D0, the temperature in the step D1, etc., but is preferably 120 to 200 N / m, preferably 140 to 200 N / m. Further preferred. 140 to 160 N / m is most preferable.

  It is preferable to provide a tension cut roll for the purpose of preventing the web from stretching in the transport direction in step D1.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 30 to 160 ° C.

  In order to produce the retardation film of the present invention, it is preferable to apply a pressure of 0.5 kPa or more and 10 kPa or less to the film in the thickness direction in the heat treatment step after drying. For example, the pressure is uniformly applied by a nip roll. Is preferred. When the pressure is applied in the thickness direction, it is preferable that the drying is sufficiently completed. At that time, by applying a pressure of 0.5 kPa to 10 kPa from both sides of the film, the free volume and total freedom of the retardation film are applied. Volume parameters can be controlled. Specifically, the pressure is applied to the film with two parallel nip rolls. A method such as a calendar roll may be used. It is preferable that the temperature at the time of pressurization is 105-155 degreeC.

  After the predetermined heat treatment, it is preferable to provide a slitter and cut off the end portion before winding to obtain a good winding shape. Furthermore, it is preferable to knurling both ends of the width.

  The knurling process can be formed by pressing a heated embossing roll. Fine embossing is formed on the embossing roll. By pressing this embossing roll, unevenness can be formed on the film and the end can be made bulky.

  The height of the knurling at both lateral ends of the retardation film of the present invention and the polarizing plate protective film used in the present invention is preferably 4 to 20 μm and a width of 5 to 20 mm.

  In the present invention, the knurling process is preferably provided after the drying in the film forming process and before winding.

  A retardation film having a multilayer structure by a co-casting method can also be preferably used. Even when the retardation film has a multilayer structure, it has a layer containing a plasticizer, which may be a core layer, a skin layer, or both.

  The center line average roughness (Ra) of the surface of the retardation film according to the present invention is preferably 0.001 to 1 μm.

  The retardation Ro defined by the following formula in the in-plane direction of the retardation film according to the present invention is 30 to 110 nm, and more preferably 50 to 100 nm. The retardation Rt in the thickness direction is 70 to 300 nm, and more preferably 100 to 250 nm.

  The angle θ0 (°) formed by Ro, Rt or the width direction of the retardation film and the slow axis can be measured using an automatic birefringence meter. Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments), the birefringence measurement at 590 nm of the cellulose ester film is performed in an environment of 23 ° C. and 55% RH, and the refractive indexes nx and ny , Nz, and Ro and Rt were calculated according to the following formula.

Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
(Where nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is (The thickness of the film (nm).)
The retardation Ro of the polarizing plate protective film used in the present invention is preferably 20 nm or less, and the retardation Rt is preferably 50 nm or less.

  The retardation film according to the present invention has a thickness of 20 to 60 μm. In general, the thicker the retardation film, the easier it is to increase the retardation. However, in the present invention, the polarizing plate protective film is provided with a retardation function, and by using a thin retardation film, the entire polarizing film is formed. By reducing the thickness, the influence of drying and storage over time in the production of the polarizing plate could be reduced, and the distortion of the polarizing plate could be greatly reduced.

  Although there is no restriction | limiting in particular in the thickness of the polarizing plate protective film used for this invention, Since the thickness of the polarizing plate of this invention is the range of 70-140 micrometers, it is naturally preferable that it is a thin film. Preferably it is the range of 20-60 micrometers like a phase difference film.

Moisture permeability, JIS Z 0208 (25 ℃, RH 90%) as a value measured according to is preferably not more than 200g / m ² · 24 hours, more preferably, 10~180g / m ² · 24 hours Or less, particularly preferably 160 g / m ² · 24 hours or less. In particular, it is preferable that the film thickness is 20 μm to 60 μm and the moisture permeability is within the above range.

The retardation film of the present invention has a refractive index difference between one surface and the opposite surface (also referred to as film surface or back surface) of 5 × 10 ⁻⁴ or more and 5 × 10 ⁻³ or less. Is preferred. When this is a thin film polarizing plate, the stiffness of the polarizing plate becomes weak, and bubbles are likely to be generated or misaligned when bonded to a liquid crystal cell. Therefore, the above-mentioned failure at the time of pasting to a liquid crystal cell can be reduced by giving an intentional curl to a retardation film and giving a stiffness to a polarizing plate.

  Specifically, the retardation film of the present invention and the polarizing plate protective film used in the present invention are about 100 m to 5000 m, and are usually provided in a roll shape. In addition, the width of the retardation film of the present invention is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.

  Moreover, the polarizing plate protective film used for this invention is a film arrange | positioned preferably at the visual recognition side, and it is preferable to provide the following functional layer in at least one surface.

(Hard coat layer)
The polarizing plate protective film used in the present invention is preferably provided with a hard coat layer as a functional layer.

  The hard coat layer used in the present invention is provided on at least one surface of the polarizing plate protective film. The polarizing plate protective film of the present invention preferably comprises an antireflection film in which an antireflection layer (high refractive index layer, low refractive index layer, etc.) is provided on the hard coat layer.

  As the hard coat layer, an actinic radiation curable resin layer is preferably used.

  The actinic radiation curable resin layer refers to a layer mainly composed of a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. As the actinic radiation curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and a hard coat layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added thereto, and reacted to form an oligomer. The thing as described in 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. I can list them.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Commercially available UV curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seica Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (Sanyo Chemical Industries, Ltd.); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), etc. Can be selected as appropriate.

  Specific examples of compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. .

  These actinic ray curable resin layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured coating layer, any light source that generates ultraviolet rays can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. These light sources are preferably air-cooled or water-cooled. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is preferably 5 to 150 mJ / cm ² , particularly preferably 20 to 100 mJ / cm ² .

  Further, it is preferable to reduce the oxygen concentration to 0.01% to 2% by nitrogen purge in the irradiated portion.

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roll, or the tension may be applied in the width direction or the biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  Examples of the organic solvent for the UV curable resin layer composition coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl). Ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, other organic solvents, or a mixture thereof. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  In addition, it is particularly preferable to add a silicon compound to the ultraviolet curable resin layer composition coating solution. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1000 to 100000, preferably 2000 to 50000. If the number average molecular weight is less than 1000, the drying property of the coating film decreases, and conversely, the number average When the molecular weight exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, it is preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  As a coating method of the ultraviolet curable resin composition coating solution, the above-described methods can be used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm, as the wet film thickness. The dry film thickness is 0.1 to 20 μm, preferably 1 to 10 μm.

The ultraviolet curable resin composition is preferably irradiated with ultraviolet rays during or after coating and drying, and the irradiation time for obtaining the active ray irradiation amount of 5 to 150 mJ / cm ² is from 0.1 seconds to 5 seconds. Minutes are good, and 0.1 to 10 seconds is more preferable from the viewpoint of curing efficiency or work efficiency of the ultraviolet curable resin.

Moreover, it is preferable that the illuminance of these active ray irradiation parts is 50-150 mW / cm < ² >.

  In order to prevent blocking, to improve scratch resistance, to give antiglare property or light diffusibility, and to adjust the refractive index in the cured resin layer thus obtained, fine particles of an inorganic compound or an organic compound Can also be added.

  It is preferable to add fine particles to the hard coat layer used in the present invention, and as the inorganic fine particles used, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, Examples include calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  The organic fine particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder. Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added to the ultraviolet curable resin composition. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical) and polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical).

  The average particle diameter of these fine particle powders is preferably 0.005 to 5 μm, and particularly preferably 0.01 to 1 μm. As for the ratio of a ultraviolet curable resin composition and fine particle powder, it is desirable to mix | blend so that it may be 0.1-30 mass parts with respect to 100 mass parts of resin compositions.

  The ultraviolet curable resin layer is a clear hard coat layer having a center line average roughness (Ra) defined by JIS B 0601 of 1 to 50 nm or an antiglare layer having an Ra of about 0.1 to 1 μm. Is preferred. In particular, in the case of an antiglare layer, an antiglare antireflection film is formed by coating an antireflection layer described later, and the visibility of the liquid crystal display device can be further improved by incorporating the film. The center line average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, RST / PLUS manufactured by WYKO.

The hard coat layer used in the present invention preferably contains an antistatic agent. Examples of the antistatic agent include Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W and A conductive material containing at least one element selected from the group consisting of V as a main component and having a volume resistivity of 10 ⁷ Ω · cm or less is preferable.

  Examples of the antistatic agent include metal oxides and composite oxides having the above elements.

Examples of metal oxides include, for example, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or complex oxides thereof. ZnO, In ₂ O ₃ , TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of Sb, Nb and halogen elements to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%. In addition, the volume resistivity of these metal oxide powders having conductivity is 10 ⁷ Ω · cm or less, particularly 10 ⁵ Ω · cm or less.

(Antireflection layer)
The polarizing plate protective film used in the present invention is preferably provided with an antireflection layer as a functional layer on the hard coat layer. In particular, a low refractive index layer containing hollow fine particles is preferable.

(Low refractive index layer)
The low refractive index layer used in the present invention preferably contains hollow fine particles, and more preferably contains a silicon alkoxide, a silane coupling agent, a curing agent and the like.

<Hollow particles>
The low refractive index layer preferably contains the following hollow fine particles.

  The hollow fine particles referred to here are (1) composite particles composed of porous particles and a coating layer provided on the surface of the porous particles, or (2) hollow inside, and the content is a solvent, gas or Cavity particles filled with a porous material. In addition, the coating liquid for low refractive index layers should just contain either (1) composite particle | grains or (2) cavity particle | grains, and may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such inorganic fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The inorganic fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and may be in the range of 2/3 to 1/10 of the film thickness of the formed transparent film such as a low refractive index layer. desirable. These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the low refractive index effect may not be sufficiently obtained. On the other hand, when the thickness of the coating layer exceeds 20 nm, the porosity (pore volume) of the composite particles may be lowered, and the low refractive index effect may not be sufficiently obtained. In the case of hollow particles, when the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles preferably contains silica as a main component. The coating layer of the composite particle or the particle wall of the hollow particle may contain a component other than silica, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO _2. and _{CeO 2, P 2 O 3,} Sb 2 O 3, MoO 3, ZnO 2, WO 3 and the like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MOX / SiO ₂ of less than 0.0001, and even if it is obtained, conductivity is not exhibited. On the other hand, if the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that particles having a small pore volume and a low refractive index may not be obtained.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such inorganic fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the inorganic compound particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. As an alkali metal silicate, sodium silicate (water glass) or potassium silicate is used. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  Moreover, the alkali-soluble conductive compound is used as a raw material for inorganic compounds other than silica.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. I can do it. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the above-described alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when seed particles are used, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. Particle growth occurs by depositing on the top. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, a silicic acid solution obtained by removing the alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step. Alternatively, it is preferable to form a silica protective film by adding a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Moreover, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore, the silica coating layer described later is formed without reducing the pore volume. I can do it. Note that when the amount of the inorganic compound to be removed is small, it is not always necessary to form a protective film because the particles are not broken.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor comprising a silica protective film, a solvent in the silica protective film, and an undissolved porous solid, and the hollow particles When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  In the case where the dispersion medium of the porous particle precursor is water alone or the ratio of water to the organic solvent is high, it is possible to form a silica protective film using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film using a silicic acid liquid and the said alkoxysilane together.

Third step: Formation of silica coating layer In the third step, a hydrolyzable organosilicon compound or silicic acid solution is added to the porous particle dispersion prepared in the second step (in the case of hollow particles, a hollow particle precursor dispersion). Is added to coat the surface of the particles with a polymer such as a hydrolyzable organosilicon compound or a silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilanes, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particles (cavity particle precursor in the case of hollow particles) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. A silicic acid solution may be used in combination with the alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of the hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.44. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

The low refractive index layer used in the present invention preferably contains a hydrolyzate of an alkoxysilicon compound and a condensate formed by a subsequent condensation reaction in addition to the hollow fine particles. In particular, it is preferable to contain a SiO ₂ sol prepared by adjusting an alkoxysilicon compound represented by the following general formula (1) and / or (2) or a hydrolyzate thereof.

General formula (1) R1-Si (OR2) ₃
General formula (2) Si (OR2) ₄
(In the formula, R1 represents a methyl group, an ethyl group, a vinyl group, or an organic group containing an acryloyl group, a methacryloyl group, an amino group or an epoxy group, and R2 represents a methyl group or an ethyl group)
Hydrolysis of the silicon alkoxide and silane coupling agent is performed by dissolving the silicon alkoxide and silane coupling agent in a suitable solvent. Examples of the solvent to be used include ketones such as methyl ethyl ketone, alcohols such as methanol, ethanol and isopropyl alcohol butanol, esters such as ethyl acetate, and mixtures thereof.

  To the solution obtained by dissolving the silicon alkoxide or the silane coupling agent in a solvent, an amount of water slightly larger than that required for hydrolysis is added, and the temperature is 15 to 35 ° C., preferably 20 to 30 ° C. for 1 to 48 hours. The stirring is preferably performed for 3 to 36 hours.

  In the hydrolysis, a catalyst is preferably used. As such a catalyst, an acid such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid is preferably used. These acids are used in an aqueous solution of about 0.001N to 20.0N, preferably about 0.005 to 5.0N. The water in the catalyst aqueous solution can be water for hydrolysis.

  The alkoxy silicon compound is hydrolyzed for a predetermined time, the prepared alkoxy silicon hydrolyzed solution is diluted with a solvent, and other necessary additives are mixed to prepare a coating solution for a low refractive index layer. The low refractive index layer can be formed on the base material by applying and drying on a base material such as a film.

<Alkoxy silicon compound>
In the present invention, the alkoxysilicon compound (hereinafter also referred to as alkoxysilane) used for the preparation of the low refractive index layer coating solution is preferably represented by the following general formula (3).

General formula (3) R4-nSi (OR ') n
In the general formula, R ′ represents an alkyl group, R represents a hydrogen atom or a monovalent substituent, and n represents 3 or 4.

  Examples of the alkyl group represented by R ′ include groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, which may have a substituent, and the substituent exhibits properties as an alkoxysilane. If it is, there is no restriction | limiting in particular, For example, although you may substitute by halogen atoms, such as a fluorine, an alkoxy group, etc., More preferably, it is an unsubstituted alkyl group, and especially a methyl group and an ethyl group are preferable.

  The monovalent substituent represented by R is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aromatic heterocyclic group, and a silyl group. Of these, an alkyl group, a cycloalkyl group, and an alkenyl group are preferable. These may be further substituted. Examples of the substituent for R include a halogen atom such as a fluorine atom and a chlorine atom, an amino group, an epoxy group, a mercapto group, a hydroxyl group, and an acetoxy group.

  As preferable examples of the alkoxysilane represented by the general formula, specifically, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetra t- Butoxysilane, tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , N-butyltrimethoxysilane, i-butyltrimethoxysilane, n-hexyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4- (Poxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, acetoxytriethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, ( 3,3,3-trifluoropropyl) trimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, pentafluorophenylpropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltri Examples include methoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

  Alternatively, quantified silicon compounds such as silicate 40, silicate 45, silicate 48, and M silicate 51 manufactured by Tama Chemical, in which these compounds are partially condensed may be used.

  Since the alkoxysilane has a silicon alkoxide group that can be hydrolyzed and polycondensed, these alkoxysilanes are crosslinked by hydrolysis and condensation to form a network structure of the polymer compound. A layer containing uniform silicon oxide is formed on the base material by applying it on the base material and drying it as a refractive index layer coating solution.

  The hydrolysis reaction can be carried out by a known method and dissolved in the presence of a predetermined amount of water and a hydrophilic organic solvent such as methanol, ethanol or acetonitrile so that the hydrophobic alkoxysilane and water can be easily mixed. -After mixing, a hydrolysis catalyst is added to hydrolyze and condense the alkoxysilane. Usually, by carrying out hydrolysis and condensation reaction at 10 ° C. to 100 ° C., a liquid silicate oligomer having two or more hydroxyl groups is generated, and a hydrolyzed solution is formed. The degree of hydrolysis can be appropriately adjusted depending on the amount of water used.

  In the present invention, as a solvent to be added to alkoxysilane together with water, methanol and ethanol are preferable because they are inexpensive and the properties of the resulting film are excellent and the hardness is good. Although isopropanol, n-butanol, isobutanol, octanol, and the like can be used, the hardness of the obtained film tends to be low. The amount of the solvent is 50 to 400 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the tetraalkoxysilane before hydrolysis.

  In this way, a hydrolyzed solution is prepared, diluted with a solvent, and if necessary, an additive is added and mixed with components necessary to form a low refractive index layer coating solution. A coating solution is used.

<Hydrolysis catalyst>
Examples of the hydrolysis catalyst include acids, alkalis, organic metals, metal alkoxides, etc. In the present invention, inorganic acids or organic acids such as sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, and boric acid are preferable. In particular, carboxylic acids such as nitric acid and acetic acid, polyacrylic acid, benzenesulfonic acid, paratoluenesulfonic acid, methylsulfonic acid and the like are preferable, and among these, nitric acid, acetic acid, citric acid, tartaric acid and the like are preferably used. In addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvic acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D- Gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are also preferably used.

  Of these, those which volatilize the acid during drying and do not remain in the film are preferred, and those having a low boiling point are preferred. Therefore, acetic acid and nitric acid are particularly preferable.

  The added amount is 0.001 to 10 parts by mass, preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the alkoxysilicon compound (for example, tetraalkoxysilane) to be used. In addition, the amount of water added may be equal to or greater than the amount that the partial hydrolyzate can theoretically hydrolyze to 100%, and an amount equivalent to 100 to 300%, preferably an amount equivalent to 100 to 200% is added.

  When the alkoxysilane is hydrolyzed, the following inorganic fine particles are preferably mixed.

  The hydrolysis solution is allowed to stand for a predetermined time after the start of hydrolysis, and used after the progress of hydrolysis reaches a predetermined level. The standing time is a time during which the above-described crosslinking by hydrolysis and condensation proceeds sufficiently to obtain desired film characteristics. Specifically, depending on the type of acid catalyst used, for example, acetic acid is preferably 15 hours or more at room temperature, and nitric acid is preferably 2 hours or more. The aging temperature affects the aging time. Generally, the aging proceeds quickly at high temperatures, but when heated to 100 ° C. or higher, gelation occurs, so heating at 20 to 60 ° C. and keeping the temperature are appropriate.

  The above-mentioned hollow fine particles and additives are added to the silicate oligomer solution formed by hydrolysis and condensation in this way, and necessary dilution is performed to prepare a low refractive index layer coating solution, which is applied onto the above-described film. By drying, a layer containing an excellent silicon oxide film as a low refractive index layer can be formed.

  In the present invention, in addition to the above alkoxysilane, for example, a modified product modified with a silane compound (monomer, oligomer, polymer) having a functional group such as an epoxy group, an amino group, an isocyanate group, or a carboxyl group. It may be used alone or in combination.

<Fluorine compound>
The low refractive index layer used in the present invention preferably contains hollow fine particles and a fluorine compound, and as a binder matrix, a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”). It is preferable to contain. By including the fluorine-containing resin, a good antifouling antireflection film can be provided.

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical), M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. No. 147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is cross-linked by heating by a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., it is an ionizing radiation curable type. .

  Further, in addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), OPSTAR (JSR), etc. Can be mentioned.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

<Additive>
If necessary, the low refractive index layer coating solution may further contain additives such as a silane coupling agent and a curing agent. The silane coupling agent is a compound represented by the general formula (2).

  Specific examples include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 3- (2-aminoethylaminopropyl) trimethoxysilane.

  Examples of the curing agent include organic acid metal salts such as sodium acetate and lithium acetate, and sodium acetate is particularly preferable. The amount of addition to the silicon alkoxysilane hydrolysis solution is preferably in the range of about 0.1 to 1 part by mass with respect to 100 parts by mass of the solid content present in the hydrolysis solution.

  Moreover, it is preferable to add low surface tension substances such as various leveling agents, surfactants, and silicone oils to the coating solution for the low refractive index layer used in the present invention.

  Specific examples of the silicone oil include L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, and FZ-3504 of Nippon Unicar Co., Ltd. , FZ-3508, FZ-3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54 , KF965, KF968, KF56, KF995, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100 and the like.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. When these components are added in an excessive amount, they cause repelling during coating. Therefore, it is preferable to add them in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

<solvent>
Solvents used in the coating solution for coating the low refractive index layer are alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; benzene, toluene, Aromatic hydrocarbons such as xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, propylene glycol monomethyl Examples include glycol ethers such as ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, water, etc., and these may be used alone or in combination of two or more. That.

<Application method>
As a method of applying the low refractive index layer, known methods such as dipping, spin coating, knife coating, bar coating, air doctor coating, blade coating, squeeze coating, reverse roll coating, gravure roll coating, curtain coating, spray coating, die coating, etc. A coating method or a known inkjet method can be used, and a coating method capable of continuous coating or thin film coating is preferably used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm in terms of wet film thickness. The coating speed is preferably 10 to 80 m / min.

  When the composition of the present invention is applied to a substrate, the thickness of the layer, coating uniformity, and the like can be controlled by adjusting the solid content concentration and the coating amount in the coating solution.

  In the present invention, it is also preferable to further provide the following medium refractive index layer and high refractive index layer to form an antireflection layer having a plurality of layers.

  Although the structural example of the antireflection layer which can be used for this invention is shown below, it is not limited to these.

Cellulose ester film / hard coat layer / low refractive index layer Cellulose ester film / hard coat layer / medium refractive index layer / low refractive index layer Cellulose ester film / hard coat layer / high refractive index layer / low refractive index layer Cellulose ester film / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Cellulose ester film / Antistatic layer / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Cellulose ester film / Hard coat Layer / antistatic layer / medium refractive index layer / high refractive index layer / low refractive index layer antistatic layer / cellulose ester film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer cellulose ester film / Hard coat layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer (medium refractive index layer, high refractive index layer)
The medium refractive index layer and the high refractive index layer are not particularly limited as long as a predetermined refractive index layer is obtained, but are preferably composed of metal oxide fine particles, a binder and the like having the following high refractive index. In addition, you may contain an additive. The refractive index of the middle refractive index layer is preferably 1.55 to 1.75, and the refractive index of the high refractive index layer is preferably 1.75 to 2.20. The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The coating can be performed in the same manner as the coating method for the low refractive index layer.

<Metal oxide fine particles>
Although metal oxide fine particles are not particularly limited, for example, titanium dioxide, aluminum oxide (alumina), zirconium oxide (zirconia), zinc oxide, antimony-doped tin oxide (ATO), antimony pentoxide, indium-tin oxide (ITO), Iron oxide or the like can be used as a main component. A mixture of these may also be used. When titanium dioxide is used, photocatalytic activity can be achieved by using metal oxide particles having a core / shell structure in which titanium dioxide is the core and the shell is coated with alumina, silica, zirconia, ATO, ITO, antimony pentoxide, or the like. It is preferable in terms of suppression.

  The refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, more preferably 1.90 to 2.50. The average particle diameter of the primary particles of the metal oxide fine particles is 5 nm to 200 nm, more preferably 10 to 150 nm. If the particle size is too small, the metal oxide fine particles tend to aggregate and the dispersibility deteriorates. If the particle size is too large, the haze increases, which is not preferable. The shape of the inorganic fine particles is preferably a rice grain shape, a needle shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

  The metal oxide fine particles may be surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent described later is most preferable. Two or more kinds of surface treatments may be combined.

  By appropriately selecting the kind and addition ratio of the metal oxide, a high refractive index layer and a medium refractive index layer having a desired refractive index can be obtained.

<Binder>
The binder is added to improve the film formability and physical properties of the coating film. As the binder, for example, the aforementioned ionizing radiation curable resin, acrylamide derivative, polyfunctional acrylate, acrylic resin or methacrylic resin can be used.

(Metal compounds, silane coupling agents)
As other additives, a metal compound, a silane coupling agent, or the like may be added. Metal compounds and silane coupling agents can also be used as binders.

  As the metal compound, a compound represented by the following general formula (4) or a chelate compound thereof can be used.

General formula (4): AnMBx-n
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the above formula (4) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxides, zirconium alkoxides, silicon alkoxides, and chelate compounds thereof from the viewpoints of the effect of reinforcing the refractive index and coating film strength, ease of handling, material cost, and the like. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Silicon alkoxide has a slow reaction rate and a low refractive index, but is easy to handle and has excellent light resistance. Since the silane coupling agent can react with both the inorganic fine particles and the organic polymer, a tough coating film can be formed. Moreover, since titanium alkoxide has the effect of accelerating the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  The silicon alkoxide and the silane coupling agent are compounds represented by the following general formula (5).

Formula (5): RmSi (OR ′) n
In the formula, R is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), or a reaction such as a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group, a carboxyl group, or an alkoxyl group. R ′ represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), and m + n is 4.

  Specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapenta Ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane , Γ-glycidoxypropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane and the like.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against moisture mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably less than 5% by mass in terms of metal oxide in the medium refractive index composition, and less than 20% by mass in terms of metal oxide in the high refractive index composition. Is preferred.

<Polarizer>
The polarizing plate of the present invention will be described.

  The polarizing plate of the present invention is characterized by a thickness of 70 to 140 μm. As described above, the polarizing plate preferably has a structure in which the thin film PVA polarizing film according to the present invention is sandwiched between the retardation plate and at least one polarizing plate protective film. The thickness of the polarizing plate is the total thickness of the thin film PVA polarizing film, the retardation plate, and the polarizing plate protective film, does not include the adhesive layer, and the polarizing plate protective film includes the hard coat layer. If you include it.

  In order to obtain the effect of the present invention, the thickness of the polarizing plate is essential to be in the above range, but is preferably in the range of 80 to 120 μm. When the thickness is less than 70 μm, the stiffness of the polarizing plate is reduced, and failure such as wrinkles and entrainment of bubbles is likely to occur when bonding to a liquid crystal cell. When the thickness exceeds 140 μm, unevenness and distortion of the polarizing plate due to drying and storage over time are generated, which is not preferable.

  The polarizing plate can be produced by a general method. The retardation film of the present invention is preferably subjected to alkali saponification treatment, and the treated retardation film is preferably bonded to at least one surface of the polarizing film according to the present invention using a completely saponified polyvinyl alcohol aqueous solution. The retardation film of the present invention may be used on the other surface, or another polarizing plate protective film may be used. With respect to the retardation film of the present invention, a commercially available cellulose ester film can be used as the polarizing plate protective film used on the other surface. For example, as a commercially available cellulose ester film, KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UX-RHA (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.

  Alternatively, it is also preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optical anisotropic layer formed by aligning liquid crystal compounds such as discotic liquid crystal, rod-shaped liquid crystal, and cholesteric liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. Moreover, when the polarizing plate protective film used for this invention is a polarizing plate protective film with an anti-reflective layer, it can also obtain the polarizing plate which is excellent in anti-reflective property and has the stable viewing angle expansion effect.

  Since the polarizing film is stretched in a uniaxial direction (usually the longitudinal direction), when the polarizing plate is placed in a high-temperature and high-humidity environment, the stretching direction (usually the longitudinal direction) shrinks, and the direction perpendicular to the stretching (usually the width direction) ) Will grow. As the thickness of the polarizing plate protective film becomes thinner, the expansion / contraction ratio of the polarizing plate increases, and in particular, the amount of contraction in the stretching direction of the polarizing film increases. Normally, the stretching direction of the polarizing film is bonded to the casting direction (MD direction) of the polarizing plate protective film. Therefore, when making the polarizing plate protective film thin, it is particularly important to suppress the stretching rate in the casting direction. It is. Since the retardation film of the present invention is excellent in dimensional stability, it is suitably used as such a polarizing plate protective film.

  That is, even in the durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness does not increase, and good visibility can be provided without changing the viewing angle characteristics after the durability test.

  The polarizing plate can be constituted by further bonding a protective film on one surface of the polarizing plate and a separate film on the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal board, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.

  By using this polarizing plate, a liquid crystal display device with high display performance can be provided. In particular, in a liquid crystal display device using a direct type backlight, it is possible to obtain a liquid crystal display device in which environmental fluctuation is small and light leakage at the periphery of the screen is reduced.

<Display device>
By using the polarizing plate of the present invention for a display device, the display device of the present invention having various visibility can be manufactured. The retardation film of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), and IPS. A VA (MVA, PVA) type liquid crystal display device is preferable. In particular, even a large-screen liquid crystal display device having a 30-inch or larger screen can provide a liquid crystal display device with little environmental fluctuation and reduced light leakage at the periphery of the screen. In particular, in the group of liquid crystal display devices manufactured using the retardation film of the present invention, the frequency of occurrence of light leakage can be reduced.

In addition, the backlight used in the liquid crystal display device using the polarizing plate of the present invention may be a sidelight type, a direct type, or a combination of these. Preferably there is. A particularly preferred direct type backlight is an LED backlight for a color liquid crystal display device having a red (R) LED, a green (G) LED, and a blue (B) LED, for example, the peak of the red (R) LED. Preferably, the wavelength is 610 nm or more, the peak wavelength of the green (G) LED is in the range of 530 ± 10 nm, and the peak wavelength of the blue (B) LED is 480 nm or less. Examples of types of green (G) LEDs having a peak wavelength within the above range include DG1112H (manufactured by Stanley Electric Co., Ltd.), UG1112H (manufactured by Stanley Electric Co., Ltd.), and E1L51-3G (manufactured by Toyoda Gosei Co., Ltd.). E1L49-3G (manufactured by Toyoda Gosei Co., Ltd.), NSPG500S (manufactured by Nichia Chemical Co., Ltd.), and the like. The types of LEDs used as red (R) LEDs include, for example, FR1112H (manufactured by Stanley Electric Co., Ltd.), FR5366X (manufactured by Stanley Electric Co., Ltd.), NSTM515AS (manufactured by Nichia Corporation), GL3ZR2D1COS (Sharp) GM1JJ35200AE (manufactured by Sharp Corporation) and the like. As types of LEDs used as blue (B) LEDs, DB1112H (manufactured by Stanley Electric Co., Ltd.), DB5306X (manufactured by Stanley Electric Co., Ltd.), E1L51-3B (manufactured by Toyoda Gosei Co., Ltd.), E1L4E-SB1A (manufactured by Stanley Electric Co., Ltd.) Toyoda Gosei Co., Ltd.), NSPB630S (Nichia Chemical Co., Ltd.), NSPB310A (Nichia Chemical Co., Ltd.), and the like.
A backlight can be formed by combining the above-described three-color LEDs. Alternatively, a white LED can be used.

  In addition, as a direct type backlight (or direct type), a direct type backlight described in JP-A No. 2001-281656, a direct type backlight using a point light source such as an LED described in JP-A No. 2001-305535, Examples include a direct type backlight described in JP-A-2002-311412, but are not limited thereto.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “%” and “part” represent “% by mass” and “part by mass”, respectively, unless otherwise specified. The dichroic ratio in the examples was evaluated by the following method.

Dichroic ratio: The dichroic ratio was used as an index for evaluating the polarizing performance of the polarizing film. This dichroic ratio is a transmittance Ts obtained by measuring and calculating with a spectrophotometer in a C light source and a two-degree field of view in accordance with the Japan Electronic Machinery Manufacturers Association (EIAJ) LD-201-1983. (%) And polarization degree P (%) were used to obtain the following formula.
Dichroic ratio = log (Ts / 100− (Ts / 100) × P / 100) / log (Ts / 100 + (Ts / 100) × P / 100)
Example 1
<Production of polarizing film>
(Preparation of polarizing film 1)
Cationic group-containing unit (3-methacrylamideamidopropyltrimethylammonium chloride unit) 0.3 mol%, ethylene unit 2.5 mol%, saponification degree of vinyl acetate part 99.2 mol%, 4% aqueous solution 12% of glycerin and water were added to PVA having a Brookfield viscosity (using rotor No. 1) of 38 mPa · s at 20 ° C., and an aqueous solution having a water content of 85% was prepared on a hot water bath. This aqueous solution was discharged from a slit onto a roll having a surface temperature of 70 ° C., followed by heat treatment after drying to obtain a PVA film having a thickness of 75 μm. In order to confirm the degree of swelling of the PVA film, the PVA film was swollen in distilled water at 30 ° C. for 10 minutes with stirring, and the degree of swelling was 180%. The PVA film was continuously processed in the order of uniaxial stretching, dyeing, fixing treatment, and drying to prepare a polarizing film. That is, the PVA film was immersed in 4% boric acid aqueous solution (bath temperature 55 ° C.), then uniaxially stretched and stretched 6 times, and 0.65% dichroic dye (direct Sky Blue 6B) Immerse in an aqueous solution (bath temperature 40 ° C.) for 1 minute to adsorb the dye, then treat in 4% boric acid aqueous solution (bath temperature 35 ° C.) for 4 minutes, then dry with hot air at 50 ° C. A polarizing film was obtained. The thickness of the polarizing film was 15 μm. The swelling degree of the PVA film used for the production of the polarizing film (the PVA film was swollen in distilled water at 30 ° C. for 10 minutes with stirring) was 185%. A triacetyl cellulose film whose surface was saponified was bonded to both surfaces of the obtained polarizing film using an aqueous solution of PVA117H (manufactured by Kuraray Co., Ltd.) to prepare a polarizing plate. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

(Preparation of polarizing film 2)
A cationic group-containing unit (3-methacrylamidopropyltrimethylammonium chloride unit) is contained in an amount of 2.0 mol%, an ethylene unit is contained in an amount of 4.5 mol%, and the degree of saponification of the vinyl acetate moiety is 98.7 mol%, 4% aqueous solution. A PVA film having a Brookfield viscosity at 20 ° C. (using rotor No. 1) of 25 mPa · s was used as a raw material, and a 75 μm thick PVA film was obtained, and a dichroic dye (Direct Sky Blue 6B) A polarizing film and further a polarizing plate were produced in the same manner as in Example 1 except that the concentration of the aqueous solution was 0.5%. The thickness of the obtained polarizing film was 13 μm. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

(Preparation of polarizing film 3)
A PVA film similar to that used in Example 2 was used, and this was continuously processed in the order of uniaxial stretching, dyeing, fixing treatment, and drying to produce a polarizing film. That is, the PVA film was uniaxially stretched in air at 75 ° C. by a dry method and stretched 8 times, and a 0.5% dichroic dye (direct sky blue 6B) aqueous solution (bath) in the stretched state. The dye was adsorbed by immersion for 1 minute in a temperature of 40 ° C., then treated for 4 minutes in a 4% aqueous boric acid solution (bath temperature 35 ° C.) and then dried with hot air at 50 ° C. to obtain a polarizing film. The thickness of the polarizing film was 5 μm. Then, the triacetylcellulose film which saponified the surface was bonded together on both surfaces of the obtained polarizing film using PVA117H (made by Kuraray Co., Ltd.) aqueous solution, and the polarizing plate was produced. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

(Preparation of polarizing film 4)
A cationic group-containing unit (3-methacrylamidopropyltrimethylammonium chloride unit) is contained in an amount of 2.0 mol%, an ethylene unit is contained in an amount of 5.2 mol%, and the degree of saponification of the vinyl acetate portion is 98.9 mol%, a 4% aqueous solution. In the same manner as in Example 2, except that a PVA film having a Brookfield viscosity at 20 ° C. (using rotor No. 1) of 17 mPa · s was used as a raw material and a 75 μm-thick PVA film was obtained, Furthermore, a polarizing plate was produced. The thickness of the obtained polarizing film was 14 μm. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

(Preparation of polarizing film 5)
It contains 2.0 mol% of a cationic group-containing unit (3-acrylamidopropyltrimethylammonium chloride unit) and 4.7 mol% of an ethylene unit, and the saponification degree of the vinyl acetate portion is 98.6 mol% and 4% of an aqueous solution. Using a PVA film having a Brookfield viscosity at 20 ° C. (using rotor No. 1) of 26 mPa · s as a raw material and obtaining a 75 μm-thick PVA film, a polarizing film, Produced a polarizing plate. The thickness of the obtained polarizing film was 18 μm. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

(Preparation of polarizing film 6: comparative example)
A cationic group-containing unit (3-methacrylamidopropyltrimethylammonium chloride unit) is contained in an amount of 1.0 mol%, an ethylene unit is contained in an amount of 2.5 mol%, and the degree of saponification of the vinyl acetate moiety is 99.0 mol%, 4% aqueous solution. A PVA film having a thickness of 80 μm, a polarizing film, and a polarizing film, except that PVA having a Brookfield viscosity at 20 ° C. (using rotor No. 1) of 27 mPa · s was used as a raw material. A board was produced. The thickness of the obtained polarizing film was 20 μm. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

(Preparation of polarizing film 7: comparative example)
PVA-HC (manufactured by Kuraray Co., Ltd., unmodified, saponification degree of vinyl acetate part 99.9 mol%, Brookfield type viscosity at 20 ° C. of 4% aqueous solution (using rotor No. 1) of 25 mPa · s) Polarization was performed in the same manner as in Example 1 except that a PVA film having a thickness of 75 μm was obtained using PVA as a raw material and that the concentration of the aqueous solution of the dichroic dye (direct sky blue 6B) was 1.0%. A film and further a polarizing plate were produced. The thickness of the obtained polarizing film was 15 μm. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

(Polarizing film: Comparative example)
Brookfield type viscosity (rotor) at 20 ° C. of a cationic group-containing unit (3-acrylamidopropyltrimethylammonium chloride unit) containing 0.2 mol%, saponification degree of vinyl acetate part 99.6 mol%, 4% aqueous solution A PVA film having a thickness of 75 μm was obtained in the same manner as in Example 2 except that PVA having a No. 1 use of 27 mPa · s was used as a raw material, and a polarizing film and a polarizing plate were further produced. The thickness of the obtained polarizing film was 18 μm. The transmittance, polarization degree, and dichroism ratio of the polarizing plate were measured and shown in Table 1.

<< Production of retardation film >>
(Preparation of retardation film 101)
About the cellulose ester, what changed the substitution degree and the kind of substituent which are shown in Table 2 was used.

<Fine particle dispersion>
Fine particles (Aerosil R972V (produced by Nippon Aerosil Co., Ltd.)) 11 parts by mass (average diameter of primary particles 16 nm, apparent specific gravity 90 g / liter)
89 parts by mass of ethanol or more was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle additive solution>
Cellulose ester A was added to a dissolution tank containing methylene chloride and heated to completely dissolve, and this was then added to Azumi filter paper No. 3 manufactured by Azumi Filter Paper Co., Ltd. Filtered using 244. While finely stirring the filtered cellulose ester solution, the fine particle dispersion was slowly added thereto. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.

Methylene chloride 99 parts by weight Cellulose ester A 4 parts by weight Fine particle dispersion 11 parts by weight A main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose ester A was added to a pressurized dissolution tank containing a solvent while stirring. This was heated and stirred to completely dissolve, and a plasticizer and an ultraviolet absorber were further added and dissolved. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.

  In addition to adding 100 parts by mass of the main dope solution and 5 parts by mass of the fine particle additive solution, mix thoroughly with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then use a belt casting device to It was cast uniformly on a 2 m stainless steel band support. On the stainless steel band support, the solvent was evaporated until the residual solvent amount became 110%, and the stainless steel band support was peeled off. When peeling, the film is stretched so that the longitudinal (MD) stretch ratio is 1.1 times, and then both ends of the web are held by a tenter, and the stretch ratio in the width (TD) direction is 1.3. It extended | stretched so that it might become double. After stretching, hold for several seconds while maintaining its width, release the width holding after relaxing the tension in the width direction, further carry for 30 minutes in the third drying zone set at 125 ° C., and perform drying, A retardation film 101 having a film thickness of 60 μm having a width of 1.5 m, a knurling having a width of 1 cm at the end and a height of 8 μm was produced.

<Composition of main dope solution>
Methylene chloride 390 parts by weight Ethanol 80 parts by weight Cellulose ester A 100 parts by weight Plasticizer: Trimethylolpropane tribenzoate 5 parts by weight Plasticizer: Ethylphthalyl ethyl glycolate 5.5 parts by weight Ultraviolet absorber: Tinuvin 109 (Ciba Specialty Chemicals) (Made by Co., Ltd.)
1 part by mass UV absorber: Tinuvin 171 (manufactured by Ciba Specialty Chemicals)
1 part by mass Retardation films 102 to 108 were produced in the same manner as described above except that the composition (cellulose ester) of the dope solution and the film thickness were changed as shown in Table 3.

  With respect to the obtained retardation films 101 to 108, the in-plane retardation value Ro, the retardation value Rt in the thickness direction, and the refractive index of the front and back surfaces were measured by the following measurements, and the results are shown in Table 3.

<Measurement of retardation value>
Ro = (nx−ny) × d
Rt = ((nx + ny) / 2−nz) × d
(In the formula, nx, ny, and nz represent the refractive indexes in the principal axis x, y, and z directions of the refractive index ellipsoid, respectively, and nx and ny represent the refractive index in the film in-plane direction, and nz represents the thickness direction of the film. (In addition, nx> ny, and d represents the thickness (nm) of the film.)
Attach eyepiece with polarizing plate to Abbe refractometer (1T), and use a spectral light source to measure the refractive index in one direction in the film surface of both sides of the retardation film, the direction perpendicular to it and the direction perpendicular to the film surface. The average refractive index was determined from the average value obtained by measurement. Moreover, the thickness of the film was measured using a commercially available micrometer.

  Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments), film retardation measurement at a wavelength of 590 nm was performed under the same environment for 24 hours in an environment of 23 ° C. and 55% RH. went. The above-mentioned average refractive index and film thickness were input into the above formula to obtain in-plane retardation value (Ro) and thickness direction retardation value (Rt).

<Measurement of refractive index of front and back surfaces>
The sample (film) was allowed to stand for 24 hours in an environment of 23 ° C. and 55% RH, and the average refractive index of the front and back surfaces of the retardation film was measured using an Abbe refractometer (1T) in the same environment. Here, the film surface is the surface opposite to the stainless steel band support when casting the dope, and the film back surface is the surface on the stainless steel band support side when casting the dope.

<< Production of polarizing plate protective film >>
(Preparation of polarizing plate protective film 201)
(Silicon dioxide dispersion)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass (average primary particle diameter 16 nm, apparent specific gravity 90 g / liter)
88 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution.

(Production of in-line additive solution)
Tinuvin 109 (Ciba Specialty Chemicals Co., Ltd.) 11 parts by mass Tinuvin 171 (Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass Methylene chloride 100 parts by mass Dissolved and filtered.

  To this, 36 parts by mass of the silicon dioxide dispersion diluted solution was added with stirring, and further stirred for 30 minutes, and then 6 parts by mass of cellulose acetate propionate (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8). Was added with stirring, and the mixture was further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution.

(Preparation of dope solution)
Cellulose ester (cellulose triacetate synthesized from linter cotton)
100 parts by mass (Mn = 148000, Mw = 310000, Mw / Mn = 2.1, acetyl group substitution degree 2.92)
Trimethylolpropane tribenzoate 5.0 parts by weight Ethylphthalylethyl glycolate 5.5 parts by weight Methylene chloride 440 parts by weight Ethanol 40 parts by weight The above is put into a closed container, heated and stirred, and completely dissolved. Azumi Filter Paper No. manufactured by Azumi Filter Paper Co., Ltd. No. 24 was used for filtration to prepare a dope solution.

  The dope solution was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the film production line. In the inline additive solution line, the inline additive solution was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. Add 2 parts by weight of the filtered in-line additive to 100 parts by weight of the filtered dope solution, mix thoroughly with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then use a belt casting apparatus. Used at a temperature of 35 ° C. and a width of 1.8 m and uniformly cast on a stainless steel band support. With the stainless steel band support, the solvent was evaporated until the residual solvent amount became 120%, and then peeled off from the stainless steel band support. The peeled cellulose ester web was evaporated at 35 ° C., slit to 1.65 m width, and then stretched by 1.05 times in the TD direction (direction perpendicular to the film transport direction) with a tenter. Drying was performed at a drying temperature of ° C. At this time, the residual solvent amount when starting stretching with a tenter was 30%.

  Then, drying is completed while transporting a drying zone of 110 ° C. and 120 ° C. with a number of rolls, slitting to a width of 1.5 m, and knurling of a width of 15 mm and an average height of 10 μm is performed on both ends of the film, and the average film thickness Produced a polarizing plate protective film 201 having a thickness of 80 μm.

  When the retardation value was measured, Ro and Rt were 3 nm and 20 nm, respectively, and it was not a retardation film referred to in the present invention.

(Preparation of polarizing plate protective film 202)
A polarizing plate protective film 202 having a width of 1.5 m and an average film thickness of 60 μm was prepared in the same manner as the polarizing plate protective film 1 except that the average film thickness was changed to 60 μm.

  The retardation values were Ro and Rt of 2 nm and 17 nm, respectively, and were not retardation films as referred to in the present invention.

(Preparation of polarizing plate protective film 203)
A polarizing plate protective film 203 having a width of 1.5 m and an average film thickness of 40 μm was prepared in the same manner as the polarizing plate protective film 1 except that the average film thickness was changed to 40 μm.

  The retardation values were Ro and Rt of 1 nm and 15 nm, respectively, and were not retardation films as referred to in the present invention.

<Production of polarizing plate>
<Preparation of polarizing plate>
The polarizing films 1 to 8 prepared according to the following steps 1 to 5 are bonded together in the combinations shown in Table 4 below so as to be sandwiched between the prepared retardation films 101 to 108 and the polarizing plate protective films 201 to 203. Thus, polarizing plates 1 to 26 were produced.

  Step 1: It was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to obtain a retardation film and a polarizing plate protective film in which the side to be bonded to the polarizing film was saponified.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was gently wiped off and placed on the retardation film and polarizing plate protective film treated in Step 1.

Step 4: the retardation film and the polarizing film and the back face side-polarizing plate protective film pressure 20-30 N / cm ² were laminated in step 3, the conveying speed was pasted at approximately 2m / min.

  Process 5: The sample which bonded together the polarizing film produced in the process 4, the phase difference film, and the polarizing plate protective film was dried in 80 degreeC dryer for 5 minutes, and the polarizing plates 1-26 were produced.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the characteristics as a polarizing plate and a liquid crystal display device were evaluated.

  The polarizing plates on both sides of the Sony 20-type display KLV-20AP2 previously bonded were peeled off, and the prepared polarizing plates 1 to 26 were bonded to the glass surfaces of the liquid crystal cells, respectively.

  At that time, the direction of bonding of the polarizing plate is performed so that the surface of the retardation film is on the liquid crystal cell side and the absorption axis is directed in the same direction as the polarizing plate previously bonded, Liquid crystal display devices 1 to 26 were produced respectively.

<Evaluation>
(Polarization film deterioration: polarization degree change)
For the polarizing plate produced by the above method, first, the parallel transmittance and the orthogonal transmittance were measured, and the degree of polarization was calculated according to the following formula. Thereafter, each polarizing plate was subjected to forced degradation for 1000 hours under the conditions of 60 ° C. and 90%, and then the parallel transmittance and the orthogonal transmittance were measured again, and the degree of polarization was calculated according to the following formula. The amount of change in polarization degree was determined by the following formula.

Polarization degree P (%) = ((H0−H90) / (H0 + H90)) 1/2 × 100
Polarization degree change = P0−P1000
H0: parallel transmittance H90: orthogonal transmittance P0: degree of polarization before forced degradation P1000: degree of polarization after 1000 hours of forced degradation (polarizer dimensional stability)
In order to evaluate the distortion of the polarizing plate, the dimensional stability of the polarizing plate was evaluated under the following conditions.

  After conditioning the polarizing plate in a room at 23 ° C and 55% RH for 24 hours, in the same room, mark the surface of the polarizing plate with two crosses at 100 mm intervals in the longitudinal direction and the width direction of the film to accurately measure the dimensions. And measure the distance between the two marks with a categorometer, treating it for 60 hours at 60 ° C and 90% RH, adjusting the humidity again in a room at 23 ° C and 55% RH for 24 hours. Then, with the value as b, the dimensional stability of the polarizing plate was obtained as a dimensional change rate by the following formula.

Dimensional change rate (%) = [(ba) / a] × 100
(Light leakage)
Each of the produced liquid crystal display devices was treated for 300 hours at 60 ° C. in order to see deterioration due to heat, and then returned to 23 ° C. and 55% RH. Then, after turning on the power and turning on the backlight, light leakage at the time of black display after 2 hours was visually evaluated according to the following criteria.

A: There is no light leakage. O: There are 1 to 2 weak light leaks. Δ: There are 1 to 2 strong light leaks. X: There are 3 or more strong light leaks.

  If the light leakage is evaluated as ◯ or higher, there is no practical problem.

(Visibility evaluation)
About each produced said liquid crystal display device, after leaving for 100 hours on 60 degreeC and 90% RH conditions, it returned to 23 degreeC and 55% RH. As a result, when the surface of the display device was observed, the one using the polarizing plate of the present invention was excellent in flatness, whereas the comparative display device was observed for a long time because fine wavy unevenness was observed. And eyes were easy to get tired.

A: No wavy unevenness is observed on the surface. O: A slight wavy unevenness is observed on the surface. Δ: A slight wavy unevenness is slightly observed on the surface. X: A fine wavy unevenness is observed on the surface. The above evaluation results are shown in Table 5 below.

  From the above table, the polarizing films 1 to 5 of the present invention are used, the retardation films 101 to 103 and 105 to 107 having the ranges of the film thickness and retardation of the present invention are combined, and the thickness of the polarizing plate is adjusted to 70 to 140 μm. The polarizing plate and the liquid crystal display devices 7 to 12 and 14 to 23 of the present invention are excellent in the polarization degree change of the polarizing plate and the distortion of the polarizing plate, and are excellent in light leakage and visibility as a liquid crystal display device. It is clear.

  In particular, it is understood that the polarizing plate and the liquid crystal display devices 14 to 23 whose thickness is adjusted to 80 to 120 μm are more excellent and preferable.

Example 2
The polarizing plates 11 and 12 prepared in Example 1 were each bonded to one surface of the liquid crystal cell, and the following polarizing plate 27 was prepared and bonded to the opposite surface of the liquid crystal cell. Similarly, liquid crystal display devices 27 and 28 of the present invention were produced.

(Preparation of polarizing plate 27)
In the same manner as the production of the polarizing plate of Example 1, the polarizing film 1 was bonded so as to be sandwiched from both sides by the polarizing plate protective film 203 which is not a retardation film according to the present invention, and a polarizing plate 27 was produced.

<Evaluation>
(Viewing angle evaluation)
For viewing angle evaluation, the viewing angle of the liquid crystal panel bonded with the polarizing plate of the present invention obtained above was measured using EZ-contrast manufactured by ELDIM.

  As the evaluation of the viewing angle, the contrast ratio between the white display and the black display of the liquid crystal panel was 10 or more, and the range of the tilt angle from the normal direction with respect to the panel surface indicating the region causing the inversion was evaluated. As a result, it was found that the liquid crystal display devices 27 and 28 of the present invention have extremely high viewing angle improvement characteristics, and sufficient optical compensation can be achieved by using a single retardation film.

Example 3
(Preparation of polarizing plate protective film with antireflection layer)
Using the above-prepared polarizing plate protective films 201 to 203, polarizing plate protective films with an antireflection layer were prepared by the following procedure.

  The refractive index of each layer constituting the antireflection layer was measured by the following method.

(Refractive index)
The refractive index of each refractive index layer was determined from the measurement result of the spectral reflectance of a spectrophotometer for a sample in which each layer was coated on the hard coat film prepared below. The spectrophotometer uses U-4000 type (manufactured by Hitachi, Ltd.), and after roughening the back side of the measurement side of the sample, light absorption treatment is performed with black spray to prevent reflection of light on the back side. The reflectance in the visible light region (400 nm to 700 nm) was measured under the condition of regular reflection at 5 degrees.

(Particle size of metal oxide fine particles)
As for the particle diameter of the metal oxide fine particles used, 100 fine particles were observed with an electron microscope (SEM), the diameter of a circle circumscribing each fine particle was taken as the particle diameter, and the average value was taken as the particle diameter.

<< Formation of hard coat layer >>
On the produced polarizing plate protective films 201 to 203, the following hard coat layer coating solution is filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution, which is then used with a micro gravure coater. After coating at 90 ° C. and drying at 90 ° C., a hard coat layer having a dry film thickness of 5 μm is cured by using an ultraviolet lamp to cure the coating layer with an irradiance of 100 mW / cm ² and an irradiation amount of 0.1 J / cm ^2. To form a hard coat film.

(Hard coat layer coating solution)
The following materials were stirred and mixed to obtain a hard coat layer coating solution.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 220 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 20 parts by mass Propylene glycol monomethyl ether 110 parts by mass Ethyl acetate 110 parts by mass << Antireflection layer Preparation of protective film with polarizing plate >>
On the hard coat film produced as described above, an antireflection layer was applied in the order of a high refractive index layer and then a low refractive index layer as described below to produce a polarizing plate protective film with an antireflection layer.

<Formation of antireflection layer: high refractive index layer>
On the hard coat film, the following high refractive index layer coating composition was applied with an extrusion coater, dried at 80 ° C. for 1 minute, then cured by irradiation with ultraviolet rays of 0.1 J / cm ² , and further at 100 ° C. for 1 minute. A high refractive index layer was provided so as to have a thickness of 78 nm by thermosetting.

  The refractive index of this high refractive index layer was 1.62.

<High refractive index layer coating composition>
Isopropyl alcohol solution of metal oxide fine particles (solid content 20%, ITO particles, particle size 5 nm) 55 parts by mass Metal compound: Ti (OBu) ₄ (tetra-n-butoxytitanium) 1.3 parts by mass Ionizing radiation curable resin : Dipentaerythritol hexaacrylate 3.2 parts by mass Photopolymerization initiator: Irgacure 184 (manufactured by Ciba Specialty Chemicals)
0.8 parts by mass 10% propylene glycol monomethyl ether solution of linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Unicar Co., Ltd.) 1.5 parts by mass Propylene glycol monomethyl ether 120 parts by mass Isopropyl alcohol 240 parts by mass Methyl ethyl ketone 40 parts by mass << Formation of antireflection layer: low refractive index layer >>
The following low refractive index layer coating composition is applied onto the high refractive index layer by an extrusion coater, dried at 100 ° C. for 1 minute, and then cured by irradiating with an ultraviolet lamp at 0.1 J / cm ^2. The film was wound around a heat-resistant plastic core at a winding length of 2500 m, and then heat-treated at 80 ° C. for 3 days to prepare polarizing plate protective films 301 to 303 with an antireflection layer.

  The low refractive index layer had a thickness of 95 nm and a refractive index of 1.37.

(Preparation of low refractive index layer coating composition)
<Preparation of tetraethoxysilane hydrolyzate A>
Hydrolyzate A was prepared by mixing 289 g of tetraethoxysilane and 553 g of ethanol, adding 157 g of 0.15% aqueous acetic acid solution thereto, and stirring in a water bath at 25 ° C. for 30 hours.

Tetraethoxysilane hydrolyzate A 110 parts by mass Hollow silica-based fine particles (P-2 below) 30 parts by mass KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass Linear dimethyl silicone-EO block copolymer (FZ) -2207, manufactured by Nippon Unicar Co., Ltd.) 10% propylene glycol monomethyl ether solution 3 parts by mass Propylene glycol monomethyl ether 400 parts by mass Isopropyl alcohol 400 parts by mass <Preparation of dispersion of hollow silica fine particles (P-2)>
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass. (Process (a))
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid content concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Subsequently, a dispersion of hollow silica-based fine particles (P-2) having a solid content concentration of 20% by mass in which the solvent was replaced with ethanol using an ultrafiltration membrane was prepared.

The thickness of the first silica coating layer of the hollow silica-based fine particles was 3 nm, the average particle size was 47 nm, MOx / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter was measured by a dynamic light scattering method.

  Using the obtained polarizing plate protective films 301 to 303 with an antireflection layer, the polarizing films 1 to 8 and the retardation films 101 to 108 prepared in Example 1, the polarizing plates 1 to 26 of Example 1 and the liquid crystal Polarizing plates 301 to 326 and liquid crystal display devices 301 to 326 were produced in the same manner as in Example 1 so as to correspond to the configurations of the display devices 1 to 26, respectively. Although the polarizing plate of this invention provided the hard-coat layer, the thickness of the polarizing plate was all within 70-140 micrometers.

  The obtained polarizing plate and liquid crystal display device were evaluated in the same manner as in Example 1 for polarizing film deterioration, polarizing plate dimensional stability, light leakage, and visibility. Each of the polarizing plate and the liquid crystal display device had excellent characteristics. Furthermore, by using the polarizing plate protective films 301 to 303 with the antireflection layer, the reflection of the surroundings on the screen can be greatly reduced, and the scratch resistance is improved.

It is a figure explaining the extending | stretching angle in an extending | stretching process. It is the schematic which shows an example of the tenter process used for this invention.

Claims (5)

Stretching using a polyvinyl alcohol film comprising a vinyl alcohol polymer containing 0.01 to 20 mol% of a cationic group-containing unit and 0.5 to 24 mol% of an α-olefin unit having 4 or less carbon atoms A retardation film having a dyed film thickness of 5 to 18 μm, a retardation value Ro represented by the following formula of 30 to 110 nm, an Rt of 70 to 300 nm, and a film thickness of 20 to 60 μm. A polarizing plate comprising a plate, wherein the polarizing plate has a thickness of 70 to 140 μm.
Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
(Where nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is (The thickness of the film (nm).) The polarizing plate according to claim 1, wherein a main component of the retardation plate is a cellulose ester. The cellulose ester satisfying the following formulas (I) and (II) when the substitution degree of the acetyl group of the cellulose ester is X and the substitution degree of the propionyl group or butyryl group is Y: 2. The polarizing plate according to 2.
Formula (I) 2.0 ≦ X + Y ≦ 2.6
Formula (II) 0.1 ≦ Y ≦ 1.2 The refractive index difference between one surface of the retardation plate and the surface on the opposite side thereof is in the range of 5 × 10 ⁻⁴ or more and 5 × 10 ⁻³ or less. The polarizing plate as described in a term. A liquid crystal display device comprising the polarizing plate according to claim 1 on at least one surface of a liquid crystal cell.

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