TWI254670B - A polyvinyl alcohol film and a process for producing the same - Google Patents

Abstract

To provide a PVA-based film not forming fine cracks or voids in a polarizing film even if increased in its draw ratio in order to obtain the polarizing film having a high degree of polarization for the purpose of achieving the high contrast of a liquid crystal monitor or television and capable of manufacturing the polarizing film of high quality in a high yield, and its manufacturing method. The PVA-based film has a three-layered structure wherein a core layer C is present between skin layers A and B and satisfies formula (I): DeltanMDA/DeltanMDB=1.0 to 1.5 and formula (II): DeltanMDB-DeltanMDC >= 0.2x10<-3> and at least either one of the formula (III): DeltanMDA < 3.0X10<-3> and the formula (IV): 0 <= |FA/FC-FB/FC| <= 0.1 (wherein DeltanMDA, DeltanMDB and DeltanMDC are each the birefringence in the length direction of the skin layer A, the skin layer B and the core layer C and FA, FB and FC are each the degrees of orientation of the skin layer A, the skin layer B and the core layer C). The manufacturing method of the PVA-based film is also disclosed.

Description

L254670 IX. Description of the Invention: [Technical Field of the Invention] The present invention is a poetic-poly-polymer based polymer, which is uniformly stretched based on the purpose of manufacturing a polarizing film, and can suppress the pulling. Stretch film: ==, etc., which can produce high quality and high performance with high yield _=; hole [previous technology] polarizer with light penetration and shielding performance, and liquid crystal with optical switching function The basic constituent elements of the liquid crystal display (LCD) are M+ and J. The application field of Gu Xuan has also expanded from the early stage of development, to the minicomputers such as Shiren thousand and fifty-five aliens and watches, to notebook computers, LCD monitors, projectors, LCD TVs, and car navigation systems in recent years. System:" Various fields such as measuring instruments used. Electric D indoors and outdoors, especially in the field of liquid crystal monitors, liquid helium TVs, large-scale smashing is fast, and 曰曰 can not be assembled into products to make yield (: There are defects in the two-degree polarizer, which can produce polarized light without defects: (::::) is reduced. Therefore, it is necessary to use a polymer film. A polarizing plate of a polarizing plate made of a polarizing plate is generally „B _ Uniaxial stretching, or dyeing at the same time, the film is dyed after the wood color is stretched and then dyed to form a dyed single: =, or a method of fixing it in a single heart' or six early axis stretching. And using the Sipeng compound while fixing with a boron compound: = uniaxial stretching and dyeing treatment, the surface of the polarizing film is attached; the method of making a σ-cellulose acetate (TAC) film of the polarizing film, B 5 1254670 Acid -: Acid fiber It is manufactured by a protective film such as a CAB film. In order to make a liquid crystal monitor or a liquid image of a ^ ^ ^ ^ ^ ^ image, it is necessary to make a: "Contrast-T m ^ is the first polarization" Membrane. However, the polarization of the polarizer is also used. 9. Using the existing polyvinyl alcohol-based polymer, only 4 疋 South stretching ratio is used to sip the mouth; And easy to form fine sputum

In the recent years, the demand for LCD image processing has increased. Therefore, the fine film on the problematic polarizing film is more and more favorable for the production of the turtle coat and the hole. It becomes a problem. If there is a large number of turtles in the polarizing film, the hole 'is easy to be used for the clouding of the film, and there is a problem that the product yield (M, '/H raw and sharp image yield) is reduced. Both the hole and the hole are defects in the manufacturing of the polarizing film. The phenomenon that the film surface is cracked in the direction of "Lian Lie" in the direction of the A stretching A + f clothing is called crack, and the gland is Φ 6 wm. The rod-shaped defect that has a long axis on the stretched side 6 due to cracking of the special part is generally called "hole run". Toward: 'In order to improve the stretchability of the polyvinyl alcohol polymer film In the production of a polyvinyl alcohol-based polymer film, the degree (film stretching) and the moisture content. For example, it is known that the average crystal of the molecular dichroic ratio 12 X-ray diffraction method is obtained in accordance with the resin. The film, and the polyvinyl alcohol is shaken to the % ♦ vinyl alcohol direction (MD) The stretching is in the direction of the machine (long Ρ soil 4 卜 (tea-seeking literature 1) 〇 and 曰m to the average birefringence _ ioxio ' varies by 0.13x10-3 below 7 ρ and birefringence to ethylene The alcohol-based polymer film is a film 2 when peeled off from the base material of the cast-in-the-spot 54670. Further, 31, 、, 、, 、 0%% C refers to the patent document, and the ratio is 1 〇 mass ^ dry In the process of making a film, the vulcanization rate of the film is Rf #, and the process speed Rc and the final winding ratio are taken as follows: r / Rf) is 〇·9~]" It is possible to use a method of polymer film with a height of 3), and a method of polymer film (refer to the patent document and the roll at the most upstream, and the mass of the film (four), to spread the film: the second: the volatile component reaches 1〇~, volume, and A method in which the speed and the speed ratio of the drum are 〇·8 1 ·3, and a method of drawing a polyvinyl alcohol 糸 5 5 film which is stretched at a sufficient ratio from the * | &amp; : The polyethylene glycol-based polymer film obtained by the above-mentioned prior art is uniaxially stretched by the stretching ratio of the Tada, so that excellent polarizing performance can be obtained. However, when the polyethylene glycol obtained by the above-mentioned conventional technique is uniaxially stretched at a south draw ratio, "there may be many fine cracks and pores on the film. Come, with the words of the LCD "fine development" in the past, the minor turtles in the polarizing film that are not valued too much: :: The problem is getting more and more attention. Many cracks are caused by stretching: hole: light film Since it cannot be applied to a polarizing plate, it is particularly required to have high fineness: a wide-sized 'polyvinyl alcohol-based polymer film which generates fine cracks and voids due to stretching causes a decrease in product yield." [Patent Document 1 Patent Document No. 325 1073 [Patent Document 2] Japanese Patent No. 3342516 [Patent Document 3] Japanese Patent No. 34*78533 [Patent Document 4] Japanese Patent No. 3480920 [Non-Patent Literature ] 栗屋裕, "Hyperpinone" Bureau of Light Microscopy 7 *1254670 Eight Doors First Edition" Page 8 5~9 1 page and wounded company Agu Nai technology [invention content] The object of the present invention is to provide _ &amp; ' , ♦ vinyl alcohol polymer film and i Luo Dan, Temple Light朕 做 做 咼 咼 咼 咼 咼 做 做 做 做 做 做 做 做 做 做 做 做 做 做 做 做 做 做 做 做 做 咼 做 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼 咼The use of sharp images, the high-quality polarizing film, etc., are produced in the south of the moon. In order to achieve the above object, the inventors of the present invention continued to carry out various studies. The knot of the fine-grained turtle produced by the single-stretching of the polyvinyl alcohol-based polymer film 槿 = ' mostly due to the polyethylene glycol system The polymer film is produced in the thickness direction by 〇I or a difference in physical properties. Based on the results of such a recognition, it was found that it is possible to manufacture a new polymer layer having a specific three-layer structure. The two surface sides of the film have a predetermined birefringence: the surface layer The core portion is lower than the birefringence of the surface layer. When the polyvinyl alcohol-based polymer film obtained by the h-like film is uniaxially stretched in the longitudinal direction (md) to produce a polarizing film, it is found that the fine turtle coat and the pores are not generated or rarely produced, and can be suitably applied to high definition and image formation. In addition, the inventors have found that the above-obtained three-layer structure: an ethyl alcohol polymer film, if the surface layer and the core layer have a predetermined degree of orientation, the uniaxial stretching is further reduced. Cracks and holes occur. In addition, the present inventors have found that the film H of a plurality of dry 8 1254670 sticks or a hot air dryer is disposed after the first drying roll and the second drying roll for the high-quality polyvinyl alcohol-based polymerization dop. Drying and film formation under specific conditions can be carried out in a large amount smoothly and efficiently [according to these various findings, the present invention has been completed. That is, the present invention is that (1) a polyvinyl alcohol-based polymer film is a three-layer structure in which a core layer C exists between the outer two surface layers A and the surface layer B; and is characterized in that the following formula (I) is satisfied. )~(hi): △n MDA'^n MDB^lO ~1.5 Δπ MDB_ MDC= 0.2x10' Δη Mda&lt; 3.0x10*

I) II: III ^ III) In the above formula, Δη MDA represents the birefringence of the mechanical running direction of the surface layer ,, and Δη MDB represents the birefringence of the mechanical running direction of the surface layer B, rainbow

1DC represents the birefringence of the mechanical running direction of the core layer C. Further, the present invention is, (2) a polyethylene glycol-based polymer film having a three-layer structure in which a core layer C exists between the outer two sounds A and the surface layer B; (I), (II) and (iv) · , ΔnMDA/AnMDB-1.0 ～1.5 (I) Δη mdb- Δη mdc^ 〇.2xl〇-3 ((1) 〇^ I Fa/Fc- Fb/fc 1 ( IV) In the above formula, Δη Mda represents the mechanical operating radiance of surface layer A, and An MDB represents the machine bamboo of surface layer B. &quot;spoon and crease 铖 仃 仃 仃 的 的 的 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示Year, Λη

Birefringence in the 仃 direction, F 对于 χ 对于 垂直 垂直 垂直 垂直 垂直 冬 冬 冬 冬 冬 冬 冬 冬 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 The degree of alignment of t, Fc is the degree of alignment calculated based on the X-ray diffraction image perpendicularly incident on the c-plane of the core layer. Further, in the present invention, (3) as a preferred aspect of the polyvinyl alcohol-based polymer film of the above (1), further satisfying the following formula (IV): 0 - i Fa/Fc~ fb/Fc 1 ^0.1 (IV)

In the above formula, FA is an orientation degree calculated based on the X-ray diffraction image perpendicularly incident on the surface of the surface layer A, and FB is an alignment degree calculated based on the X-ray diffraction image perpendicularly incident on the surface of the surface B, and Fc is The degree of alignment calculated based on the x-ray diffraction image perpendicular to the C-plane of the core layer. Further, the present invention is any one or both of polyvinyl alcohol-based polymer films: (V) (VI) (4) Any of the above (; [) to (3), further satisfying the following formula ( V) and (VI) Δn MDAMn tDA = 〇.9~1·2 Δη MDB/Δη tdb = 〇.9~1.2 ” In the above formula, An MDA indicates the birefringence of the mechanical running direction of the surface layer A, '/n TDA indicates the direction perpendicular to the mechanical running direction of the surface layer A: birefringence, Δη MDB indicates the birefringence of the mechanical running direction of the surface layer B. The heart (10) indicates that the surface layer B is perpendicular to the mechanical running direction.

Birefringence. J and (5) In any one of the above polyvinyl alcohol-based polymer films (1) to (4), it is preferred that the diffraction is based on X-rays which are incident perpendicularly to the surface of the surface layer A 10 1254670

The degree of alignment h as calculated, the degree of orientation FB calculated from the diffraction image of the X and the line incident on the surface of the layer jg, and the diffraction of the X-ray according to the plane of the core layer. The value of the orientation degree Fc calculated by the image is 0.4 to 0.6. In the present invention, the polyvinyl alcohol-based polymer film-based optical film of any one of the above (1) to (5) is less. Further, the present invention is a. (7) A method for producing a polyvinyl alcohol-based polymer film, which is a method for continuously producing a polyvinyl alcohol-based polymer film by using a plurality of drying rolls or hot air after the j-roll and the second dry_; 'Precision is manufactured by the following process, and the patented range of the first alcohol-based polymer film··Beizhilai vinyl character') has a volatile component ratio of 5〇 to 90% by mass of polyethylene glycol. ... sprinkle on the dry report = the second round of polymer film is heated by the third dry heat report: the first dry of the polymer film of the market, the hot air of the 酉 系 ,, drying to the peeling from the "drying roll" Polyethylene: The ratio of the volatile component of the homogenous film is i5~(tetra)/ethylene alcohol, and Q' (b) is dried to the volatile component 15~3G: the polymer film is light from the first dry After peeling off, make two? The first &quot;drying roll non-contact surface of the polyethylene mash is dried with the ramming polymerization drying roll; L 4 is contacted with the second dry I254670 (c) in the process (a), • when the polyethylene glycol When the human a 糸 糸 糸 film is contacted with the 丨 丨 drying roll]. 5 minutes or less, the f 1 drying roller of the polyethylene glycol quaternary film on the sorghum It is taken from the material "the hot air of 10m / s; the blowing speed of the entire area of the M 妾 contact surface is ^, the time of the contact between the ΛΚ ΛΚ film and the first drying roller is over 1.5... : The position to the 1st roll of the 1st round is used to guide the 1 1 fighting field on the stable, the hot air of the wind speed horse 1~i〇m/s, and the polyvinyl alcohol in the position after 1/4 0 weeks Strictly blow the wind if A 1 on the 1/4 side, 糸 "# quot 膑 乞 乞 乞 乞 辊 辊 辊 辊 辊 辊 辊 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非(s) ratio (s/s) recognizes a brother 1 dry roll line the above-mentioned pass () 2] 'i·000~1 ·100 range to enter 'day' clothing fe (a) and process (b) 较佳亚和, the preferred mode of the invention comprises The method for producing the polyethylene glycol polymer film of the special 4 (7), the polyethylene glycol ... 糸 "... 1 dry roller is peeled off, the drying process, r less r sheep into 48% by mass of the cognac in the mechanical pull Stretching 0.950~; [〇5〇 and, ιυ:) υ in the target circumference.) As in the above (7) or (8) arm - manufacturing method, its special..." The inch is in the square; 'the lowering ratio of the acetylene alcohol is reduced to 13.../...the volatile component of the film of the compound film is 13 lb I %, so that the polythene ruthenium hydride film is connected to the nth of the 1254670 touch The peripheral speed (sn) of the drying rolls. The ratio of the peripheral speed (s...) of the next younger (n + 1) drying rolls (s out C;)

The ratio of the exit velocity (S〇ut) to the inlet affinity X distortion (S'n) (S0ut/sin) is 0.950 to 0.999 for drying.聚 The polyethylenic alcohol-based polymer film of the present invention stretches the film in the longitudinal direction (the rectangular, the 隹-mouth mouth, the 朕 朕 temple light) in the longitudinal direction in order to produce an optical film such as a polarizing film. No tiny 痱u* / imitation turtle I and holes are produced or rarely produced. Therefore, the use of the polyvinyl alcohol-based polymer film of the present invention, Fengshan, and the premise and smoothness of the production can be expressed, and, and the product of Zeng Dan and the product of Zeng Dan &lt; / meeting / white 丨 衫Like a polarizing film and a polarizing plate. According to the invention

At 衣运万法, it can be mass-produced smoothly and efficiently. It is able to obtain a small amount of hopper &amp; w &amp; . Between First and First Amines [Embodiment] Hereinafter, the present invention will be described in detail. The polyvinyl alcohol-based polymer film polymer film of the present invention") has a core layer C and a layer between the two surface layers of the outer layer and the layer of the coating layer B. The constructor satisfies the following formulas (1) and (11) hereinafter referred to as "PVA system Δη Δη Δη ^α / Δπ MDBy · 〇 ~ 1 5 mdb - Δη M〇c &gt; 〇 2χ1〇-· mda&lt; 3.〇 Xl 〇-: where Δη

I) Π) III MDA, An MDB and Λη MDc are the same as above. 13 1254670 Or, there is a core layer, (II) and (IV) c (Π) on the outer side of the two surface layer A and the surface layer B have a three-layer structure, which satisfies the following formula (I) Δ n MDA / △ η μ DB = 1 · 0 〜1 · 5

Δη MDB~ Δη MDC> 0.2xl〇·3丨 Fa/Fc—FB/Fc| $〇·ι 中 中 中

MDA Δη

MDB Δη (Π) (IV) MDC, FA, FB, and Fc and the above-described PVA-based PVA-based L&quot; κ mouth film of the present invention have a mechanical operation direction (far when a PVA-based polymer film is formed) Production line direction)[

The core layer c on the inner side of the small refraction ^, MD of the "senior", "long direction" or "long direction (MD),], and the birefringence μ (Δη MD) in the long direction (Md) are larger than the core layer C The outer layer of the surface layer a and the surface layer B form a three-layer structure. In the same case of the two skin layers on the outer side of the film, either B can be used. When the two skin layers are different, the double birefringence (An MD) will be used.

In the PVA-based polymer film of the present invention, the layer of the birefringence (Δη md) in the bit length direction (MD) is used as the surface layer A, and which layer is used as the birefringence (Δη md) refractive index in the surface length direction (MD) ( MD) The large surface layer is defined as surface layer A, and the small surface layer is defined as surface layer B. The range of the birefringence (Δη MDB) ratio of the surface layer A (ΔUmdaMumm) is preferably 1.〇~1.4 The PVA-based polymer film MDA of the present invention and the birefringence of the surface layer B (Δ n satisfy the above Formula (I), in the range of 1.0 to 1.5, more preferably in the range of 1 · 0 to 1.3. 14 1254670 0 If the value of _ Μ 咖 is too large, the pvA polymer film is pulled in the long direction (MD) uniaxially. When stretched, many fine pores and cracks are formed on the stretched film obtained, and the polarizing plate made of such a stretched film is whitened due to scattering of light by holes and cracks, and thus is difficult to exhibit when used for a liquid crystal display. Further, the PVA-based or polymer film of the present invention has a birefringence (Δη _ ) in the longitudinal direction (MD) of the surface b and a birefringence (An w , , in the rectangular direction of the core layer c). MD; an MDC) difference (An mdb - Δη MDC) satisfies the above formula 11, and 舄 0.2x10-3 or more. The pvA-based polymer film of the present invention, because of the birefringence (Δη_) of the surface layer A and the surface layer β Birefringence... is the same or greater than the birefringence (Δη_) of the surface layer B, so the table "birefringence (Αη _ ) and the core layer The difference between c f Λ ^ ν 11 mdc ) n MDA—AiImdc) is 〇·2χ1〇-3 or more. The birefringence of the surface B (Λη MDB) and the core layer c (Λη _) are two or two. The difference in birefringence...MDC) is preferably 2Xl〇~1·8Χΐ0-3, more preferably 〇2χ1〇·3 〜i 5χΐ〇_3. If birefringence (Δη_) of surface layer B and nucleus The difference in birefringence (Λη λ ^ MDC), n MDB - Δϋ MDC) is too small, the structure between the surface layer B and the core 曰C is poor, or the structure of the surface layer A and the surface layer B and the core layer c are If it does not exist or becomes small, the pvA-based polymer film cannot: = the three-layer structure of the surface layer A/core layer c/surface layer B, which becomes the 2^ structure, or the 1-layer structure or the structure similar thereto. If the difference between the birefringence (Δη) and the birefringence (^ MDC), and thus the birefringence (~Α) and the birefringence UnMDC) 15 l25467 过 is too large, the PVA 糸 polymer film is in the long direction (md) When uniaxially stretched, it is easy to produce a large number of fine cracks and pores in the stretched film. Further, the PVA-based polymer film of the present invention is

• satisfying the above formula (III), the birefringence of the surface layer A (a X + MDA"; 3·〇χΐ〇·3 (that is, the birefringence Γ Δη of the surface layer A, and the birefringence of the layer B ( Δη MDB ) is less than 3.〇χ1 〇-3 ); or,

' • satisfies the above formula (IV), FA (according to the calculated orientation of the X-ray diffraction image perpendicular to the surface of the surface) and Fc (calculated from the x-ray diffraction image perpendicular to the core plane) The ratio of the directionality (fa/fc), and FB (the degree of alignment calculated from the ray-ray diffraction image perpendicularly incident on the B plane of the surface layer) and Fc (the X-ray diffraction perpendicularly incident on the c-plane of the core layer) The absolute value of the difference (Fb / Fc) of the calculated degree of alignment is in the range of 〇~0_1. C

[Hereinafter, the degree of alignment calculated based on the surface layer A surface, the surface layer B surface, or the core layer C and the surface vertical human incidence @ x-ray diffraction image may be simply referred to as "alignment degree (fa)" and "alignment degree". (Fb)", "Orientation (8)". If the above formula (111) or any one of the formula (IV) is not satisfied, the formula ((1)) is not satisfied when the right side is not the formula (AV), and the birefringence of the surface layer A of the PVA-based polymer film is not satisfied. When the rate (Δ~) is 3 〇χΐ〇·3 or more, when uniaxial stretching is performed in the longitudinal direction (MD), many cracks and voids occur, and it is difficult to perform stretching at a magnification. If the birefringence of the surface layer A (both sides of the heart MDAV^^^ ΔηΜϋΒ) is in the range of (10) to 2 in the range of 3, especially in the range of 16 to 3, the PVA system is torn from the "+ axis". The Μ, 払, and sluice objects in the long direction (MD) single ▼ leaves uniform stretch, high tensile strength, Pu Shui J stretch skin cracks and holes, lift r 1 mouth The consideration of the point is better. If the above formula (111) is not satisfied

Convergence 铷γ L 守 does not satisfy formula (IV), and PVA. The ratio of the orientation (Fa) and the degree of orientation (d to the ratio of the degree of orientation (F) r: c) on the plate (Fa/Fc) is greater than the absolute difference between 0 j sl # € (Fb/Fc) In the case of ο·1, when the PVA-based polymer film is stretched, many cracks and pores are likely to occur, and (the absolute value of the difference in length...·0δ, especially in FaFc) and the right-hand side α 4 When 疋 is in the range of 0 to 〇_〇6, it is preferable to suppress the generation of voids and cracks more effectively. (The PVA-based polymer film of 111= preferably satisfies the above-mentioned formula. (IV) Both sides are capable of preventing generation of voids and turtles during stretching. The PVA-based polymer film of the present invention preferably satisfies the above formula, and (5)), or satisfying the above formulas (1), (8), and (Μ, and satisfying the following formula (ν)#σ(νι), or both, for the reason that the PVA-based polymer film can be prevented from being long Direction (Μ. During the stretching, cracks and holes are formed, and the stretching ratio is increased. Δn mda/An 0.9~1·2

TDA (V) (VI) (In the above formula, Δη MDA, Αη &amp; the same tda Δη mdb and AnTDB and the above-described PVA-based polyamine of the present invention / / Λ 亍 | mouth fe, can be realized in the long side # MD) The effect of suppressing the cracks and holes of the spurs in the uniaxial stretching and the direction of the long direction (MD) of the birefringence core layer A in the direction of the two stretching ratios (with _ ^ Birefringence Cn of the surface layer A perpendicular to the direction of travel) C") width direction (TD)" + square &amp; Τ〇Α ratio of the surface layer B (An MwMn TDA), and the width of the table, ΤΤΛ (Δη MDB) and the surface layer 见 see the birefringence of the universal (TD), both of ^ ^, preferably in the range of 0.9M ^ ^ ^ MDbMD side L10. ·In the dry circumference, it is more preferable to suppress the occurrence of cracks and holes during the early axial stretching and the degree of orientation (F) and direction (MD) of the stretchable stretching ratio. The orientation degree (FB) of the surface layer B and the c-degree (Fc) value of the core layer are in the range of the range of 〇·4~〇·6 of the d·〇·57. The soil is at 0.45. Here, the birefringence Δη η of the surface layer Α, the surface layer Β and the core (MD) of the present invention is (2) birefringence (~, Δ~ = ΐ^ι ί r? 1- and Further, AB and FC) were measured by the following method: P VA is the birefringence Δη MDA of the long direction (MD) of the U film and the birefringence of the l direction (TD) (Δ〇td a

M DB

测定 DC Δn tdb and An TDC ) Measurement method] (1) Birefringence (- leg, Δη μ and 丄, mdc of the surface layer A, surface layer B, and core layer of the PVA-based polymer film (MD) J and taste direction (TD) birefringence see (1) thousand, z\n TDA ΑΪ1 tdb and Δη TDC) are moxibustion 18 1254670 according to the non-patent document 1 described in the non-patent literature 1, mountain /, autumn] Wanfa, by It was measured by the method of τ ( 2 ) mouth ( 3 ). (2) Measurement of birefringence in the long direction (MD) (耵Q Λη MDA, Δ!! _ and Δη MDC ) (i) In the long direction of the ancient pancreas of the PVA 糸 polymer film (MD) Any position, as shown in Fig. 1 (a), cut the size of MDxTD = 2mmxl〇mm in the central part of the direction of the priest's pancreas (D), and the film '. Both sides of the fine piece were sandwiched by a PET film having a thickness of 舄1 〇〇//m, and then clamped in a wooden frame one by one and mounted on the splicing machine. (ii) Then prepare the above prepared fines; π “There are good fines, as shown in ® 1 (b) (PET film and wooden frame are not shown), 盥+”, ,, The direction (MD) is cut in parallel at intervals of 20 // m, and is used as 'with.../ ^ for 2 如图 as shown in Figure 1 (〇 for the observation slice (MDxTD= 2mmx20 &quot; as .^ mx20)). Among these slices, the cut surface was selected... and three slices with uneven thickness were placed on the slide, the sheet and the closed liquid were sealed, and the thickness was measured with an eyepiece micrometer. Among them, 2 疋 was 10 times in the eyepiece and 20 times in the objective lens ( After the field of view (in total), in order to observe the cut surface as shown in Fig. (4), ... above; · | glass "slices are placed down to set the same position in the measured thickness of the summer square; extinction direction + 45. + &do u. White light day", using the birefringence compensator to determine the delay of the interference disc on the undercut plane is below the wavelength. (4) Turn the light source into the nano D line (rotation birefringence compensation of the wavelength 589 plane) The angle of the ❹ 使 使 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 a. Then rotate the angle knob 19 1254670 to reverse the movement to ^ φ , , ^ / , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The operation is reversed 4 times, * the thousand mean values of the angles a and b are taken as the reading values. (v) a two a and b obtained above (where a&gt;b), for f Γη — ςι· 2 b) The optical constant inherent to the radiation compensator Γ, ψ山' wood and 〇 photon two 〇, find the delay amount R [R = f (1) x C], 3 thickness calculated birefringence, three times the same The measurement A takes the average value as the birefringence. At this time, the birefringence (Δη) of ❹ A is the birefringence (Δη _) of the surface layer as shown in Fig. 1 (d) The central portion of the thickness of the 戸B of the surface layer a is measured, and the birefringence (Δη m of the central portion and the surface layer of the 疋杈天11 is measured at the center of the tangent plane. (3) Width direction (TD) Birefringence (measurement of a: sheep (1) at any position in the long direction (md) of the PVA-based polymer film, as shown in the figure, 'cut in the center of the film width direction (TD) M DxTD: 1Gmmx2mm size fine piece, the two sides of the thin piece are clamped on the slicer with the thickness of the stomach iOO/zm ΡΕΤμμ^_ step. (9) Then the prepared fine piece is as shown in the figure 2(b) (there is no τ PET film and wooden frame in the figure)' is cut at 20" intervals in parallel with the width direction (td) of the fine piece, and 2 pieces are produced as shown in Fig. 2 (〇 for observation) Slice (MDXTD=20/Zmx2mm). In these sections, select 3 slices with smooth cut surface and no uneven thickness, and place them on a glass slide. 20 I254670 'Use the eyepiece micrometer to measure the slice thickness, and the objective lens 20 times (total 2 times) Sealed with closed liquids, the observations are carried out in the eyepieces. Enthusiasm, in order to observe the cut as shown in Figure 2 7 &quot; dish - file is a wind example &quot; No, will be the same as the above (η) measured thickness extinction direction + 45. Diagonal position In the white day ^ 扪钌 corner position, use the birefringence compensator to confirm the delay amount from the interference light of the slice in the daylight and the light below the 丨 wavelength. The tooth (4) turns the light source into a sodium D line (monochromatic light with a wavelength of 589 nm). The birefringence complements the crying &amp; ώ ^ J square 疋, the mouth of the spoon is angled, so that the center of the black stripe moves in the center of the field of view. Green p T ^ private to, ^ ten on the line, read the rotation angle a. Then rotate the angle in the opposite direction to move 〖 + and know the twist ~ help 1 wavelength, draw the angle b of the center of the black stripe when it is located at the center of the ten sub-line. Repeat this operation 4 times: the average value of 4 times is taken as the reading value. Take the angle ah /2 (iHt: found... two angles to find the compensation value 1 = (a, b) shot production. . . . ), multiply f (1) = Sln2lX ( 1+0.204 s ^) Double-split 仏 is the intrinsic optics and then divided by the thickness ^ r = C * R [R = f (1) XC], "- 3), : = birefringence 'three identical shifts , /, the sentence value as the birefringence (Δη). At this time, #射平(虹mDa) and the birefringence of the surface layer 疋 as shown in Figure 2 (d) pain - \, mdb) is not in the surface layer A The central neighbor of the thickness &amp; t B is in the center of the thickness of the eighth, the target a and the 邛 邛 和 and the surface layer e . . , ^ 刀 疋, the core layer C birefringence (Δη 疋 in the center of the section Position measurement. Semi-(Ώ _C) 21 1 PVa-based polymer film setting method: h, FC) 蜊-1254670 (1) In the long direction (md) of the PVA-based polymer film, as shown in Fig. 1) It is shown that in the central part of the width direction (TD) of the film, MDxTD = 2mm x 10 mm is known to be j:;,, f, ', and the film is made of PET having a thickness of 1 0 0 // m on both sides of the thin piece. Membrane clip, lack of Ming Tian, ^ person 1 king and then clamped in a wooden frame installed in thin on board.

Among the slices, one slice with smooth cut surface and no uneven thickness was selected, and the slice was placed on the goniometer head of the spinner so that the long direction (MD) of the slice coincided with the horizontal direction of the device. (in) using an X-ray microbeam (wavelength 1 2398A, beam diameter = (Π) and then cutting the prepared fine piece as shown in Item 1 (1), parallel to the MD of the thin piece at 40/zm intervals, making 1 One is similar to Figure 1 (C: a similar observation slice (the towel, MDxTD==2mmx4〇&quot;m). The alignment is measured at this heart (short diameter) x2.2//m (long diameter)), The microbeam is perpendicular to the tangent plane for the surface layer A and the surface layer B from the central position of the longitudinal direction (MD) of the slice, 彖1 mm) and from the inner side of the outermost layer ip of the surface layer a and the surface layer b; For the core layer c, the slice is facing from the center position of the slice=long direction (MD) (the position of the distance surface layer 40 when the blade is at the center position in the thickness direction of the blade (film) from the edge imm (for example, the film thickness is 80 Å) The cut surface is perpendicularly incident. The incident microbeam is detected by the penetrating method's imaging inverse (plate size: 127mmxl27mm, camera distance: 88 292 brain 1) placed at the rear of the sample. In order to detect the diffracted X-rays, the micro-t beam is irradiated with the stomach for a second.) The micro-beam is for the sliced section. Vertically entering J is indeed a Thomson scattering by moving the slice up and down with a high-precision pulse motor stage (〇.〇625 22 1254670 Am/pulse), and the detector is obtained from the slice. In the J-., ^ χ, the intensity curve of the slice shape, adjust the inclination of the rising part to 3 ^ bamboo slamming from X ★ # m below, and, to determine the correct illumination position of the U first beam 疋The position of the amine layer of the girl is determined as the center of the inclination of the rising edge of the above-mentioned intensity curve. (iv) The radiation of the diffraction in the imaging plate after the radiation to the ray resistance: 〇 是 是 是 是 beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams beams Into the 仃 仃 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 〇 〇 〇 〇 〇 The half-width value (ΡΓ) to , is calculated from the intensity distribution of γ, 180 by the formula. (180. One Η.) / 18 〇. For the width of the PVA-based polymer film of the present invention, the LCD TV and the monitor &amp; and the limitation of the year, the Masahiro X is used for this purpose, and the width is preferably 2 mj^, more preferably 2 5 4 The ground should be more than 3m. However, when using a solid m or more, especially good for the poor Lu, Μ (4) (9) light plate, if the film visibility is too large, 1 heart is carried out (4) single 纟 ★ fruit film

The width of the polymer film is 6 m or less. Therefore, it is preferred that the PVA considers practicability, ease of film formation, the PVA of the present invention, and the thickness of the Lelai film is preferably 5 to m, and particularly preferably 3 to 4 (4). - If the thickness of the film is too thin, the single: polymer is broken in order to manufacture the polarizing film. On the other hand, if the VA-based polymer film is easy to produce a polarizing film, and the uniaxial stretching is likely to cause stretching unevenness, the scorpion' is 23 1254670. The PV Λ β w 乐 4 of the present invention The mass swelling degree of the film is preferably from 180 to 250%, more preferably from 0 to 0 - 85 to 240%, and particularly preferably from 190 to 230%. If the fineness of the shell of the p VA 糸 polymer film is too low, the stretching becomes difficult, and it becomes difficult to produce a polarizing film which is produced by the light, and on the other hand, if the quality is swollen. When the film is over five', the process passability is deteriorated, and the case of a highly durable polarizing film cannot be obtained. The quality of the swelling in the foot is a pvΔ of about 3g which is cut into 3mm width. Cut piece (test piece) of VA water sputum film,

In 40 C of warm water, kiosk, and sputum; eight and 15 knives for 4 knives, and then centrifuged at 3000 rpm for 5 minutes, and then try η 曰 / , .趸] A test piece (Wi) and the test piece mass (w2) after the centrifugally dehydrated test piece was dried at 105 C for 16 hours, and the degree of swelling was calculated according to the following formula. Mass swelling degree (%) (Wl) / (w2) xl00 The PVA-based polymer film of the present invention can be formed, for example, by saponifying a polyvinyl ester obtained by polymerizing ethylene. Polyethylene S (hereinafter abbreviated as r PVA); in the main chain of PVA, unsaturated Wei or its derivatives, unsaturated sulfonic acid or its derivatives, α-olefin having 2 to 30 carbon atoms, etc. a denatured pvA-based polymer obtained by graft copolymerization; making a vinyl ester and an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, and an α-olefin having 2 to 30 carbon atoms A copolymerized denatured polyethylene® is a denatured PVA-based polymer produced by saponification; a part of a hydroxyl group of an undenatured PVA or a denatured PVA-based polymer is crosslinked with an aldehyde such as formaldehyde, butyl or aldehyde. Acetal resin. Examples of the vinyl ester used for the production of the PVA-based polymer include vinyl acetate, vinyl phthalate, vinyl propionate, vinyl butyrate, 24 1254670 trimethyl vinyl acetate, and ethyl keto acid. Vinegar, lauric acid, vinegar, hard-brewed acid, vinyl acetate, etc. Further, the above-mentioned comonomers for producing a denatured PVA polymer are mainly used for the purpose of copolymerizing PVA, and are used without departing from the scope of the present invention. These comonomers may be exemplified as Ethylene: olefins such as propylene, 1-butene and isobutylene; acrylic acid and its salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Dingzhi, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.; methacrylic acid and its salts; methyl methacrylate, ethyl methacrylate, methyl N-propyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecane methacrylate a methacrylate such as a carboxylate or octadecyl decyl acrylate; acrylamide, n: methacrylamide, N-ethyl acrylamide, N,N-dimercapto acrylamide, two Acetone acrylamide, propylene Amine propane sulfonic acid and its salt, propylene oxime, propylene ketone and its salt, N-methacrylamide amine derivative and its derivatives such as acrylamide derivatives; methacrylamide, N-methyl Methyl acrylamide, N-ethyl decyl acrylamide, methacrylamide propylene sulfonic acid and salts thereof, methacrylic propyl propyl monomethylamine and its salts, N-methyl methyl propyl N-vinyl decylamine such as methacrylamide derivative, N-vinyl decylamine, N-vinylacetamide, N-vinylpyrrolidone, etc., methyl ethylene Ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 25 I254670 one: k-vinyl ether, octadecane Vinyl ethers such as vinyl ether; nitriles such as acrylonitrile and mercapto acrylonitrile; halogenated vinyls such as vinyl chloride, vinylidene chloride, vinylidene or vinylidene fluoride; allyl acetates and allylic groups such as chloropropene a compound; maleic acid and its salt or its ester; itaconic acid and its salt or its purpose; ethylene trioxane, sulphur, etc. Compound; cold isopropyl acetate and the like where relatively good purpose is 0; - olefins, particularly preferably ethylene.

The amount of denaturation of the denatured PVA-based polymer is preferably less than 5% by weight, particularly preferably at least 5 mol%. The degree of polymerization of the pVA-based polymer of the present PVA-based polymer film is improved, and the polarizing performance and the long-term property when manufacturing the polarizing film and the polarizing plate are considered to be better than the above. Good for above, W: for 2000 or above. In addition, from the viewpoint of producing a homogeneous pvA-based polymer film: the ease of polymerization, the stretchability, and the like, the degree of polymerization of the Μ'-form of the pvA-based polymer film is preferably 8 Å or less. For the following. The degree of polymerization of the PVA-based polymer referred to in the present specification means that the degree of polymerization determined by K _ is determined from the ultimate viscosity measured by re-supplied the pvA-based polymer and purified in water of &lt; 30 c. : Saponification of the PVA-based polymer of the PVA-based polymer film of the invention: long-term (4) Polarization performance and % or more when the polarizing film and the polarizing plate are produced: in consideration of the surface, more preferably, it is preferably -1, and preferably 99 mol. More than %, especially preferably 99 3m〇i% or more. In the present specification, "the soap s becomes one of the units of the acetol unit; the upper:: two can be converted from the unit to the vinyl group, and the t case (mol%) means The degree of saponification measured according to the method of 26 Ϊ 254670 of JIS κ 6726. The PVA-based polymer film of the present invention is lightly dried and thereafter (downstream), and is used in a configuration in which a plurality of dry handles are light or... The film apparatus continuously manufactures a polyethylene glycol-based polymer film by the following method of manufacturing the present invention characterized by the following steps: 'it is produced by means of: 1 page and effective") to volatilize the composition ratio #50 The production liquid of the ~90 complex is in the first layer of the first drying roller non-contact surface of the first drying roller of the light polymer film in the third drying device of the film forming apparatus. The area is read by the wind, and it is dried until it is peeled off from the 丨 丨 轻 : : : : : : : : : : : : : : : : : : 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发After the alcohol polymer film is peeled off from the "dry" report, The first dry 俨妒洮 杂 归 系 聚合 聚合 # 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏 犏), • When the polyethylene glycol polymer film is in contact with the ith drying roller, the first dry soldering of the polyethylene 旷v film on the first drying roller is known. The hot air of the KWs is aggregated; the entire area of the contact surface blows the wind speed! ~ • When the polyethylene glycol polymer film and the first &quot; 乞 over 1.5 minutes, the step to recognize &quot; Λ 丨 j j ¥ between the super pair of "攸 film raw liquid spit out to the first dry light on the 27 1254670 The first dry film 1 non-contact surface of the polyvinyl alcohol-based polymer film at the first light 1/4 circumferential position is blown by a hot air having a wind speed of 1 to 10 m/s, and is placed at a position after the 1/4 circumference. The second drying roller of the alcohol-based polymer film has a non-contact surface of a hot air having a wind speed of 1 to 60 m/s;

The above process (a) is carried out in the range of l.ooo~1.100 from the ratio of the peripheral speed of the drying roller (§ 2) to the first dry light circumferential speed (S) (s2/S). And process (b). Hereinafter, the method for producing the PVA-based polymer film of the present invention described above will be specifically described. First, the membrane-forming stock solution of the pVa-based polymer used in the above process (a) can be dissolved in a liquid medium by mixing a PVA-based polymer with a liquid medium, or a PVA-based polymer containing a liquid medium or the like. The particles are fused to form a melt to prepare. The dissolution of the PVA-based polymer in a liquid medium and the melting of PVA polymer particles containing a liquid medium or the like can be carried out by a stirring type mixing device, a melt extruder or the like. Examples of the liquid plate used in this case include water, dimethyl sulfoxide, mercaptocarbamide, methyl ethylamine, N-decyl pyrrolidone, ethylene diamine, diamine, etc., which can be -U For the liquid medium, it is preferred that & - wu is water, monomethyl hard or a mixture of the two. 4 inch is used. Water. From the promotion of the dissolution of PVA-based polymer in a liquid medium or the smelting of the engineered, improved pVA door T, the stretchability of the nozzle plate, etc. - preferably in the PVA polymer Adding plasticizing 28 to 254670 months as a plasticizer is preferred for the film-forming stock solution. The alcohol-based plasticizer can be exemplified by a polyethylene di- phthalate plasticizer. As a poly-diglyceride, di-glycan #子glycerin, propylene glycol, - Glycol, monoethylene glycol, tetraethylene glycol, 3-glycodonium, or two or more of them can be used, and it is preferable to use glycerin, &lt; Use glycerin. 'From and / or ethylene glycol, better plasticizer addition, phase, 1 to 3. Quality , more preferably = system 2 ^ ^ parts by mass, ri, particularly good for 5 ~ 2 〇 plasticizer added less, pv, stretchability will decrease, another. 糸 糸 film The dyeing becomes too much in the face of the sheep. If too much 'PVA system, the polymer film is in the wood, the usability will be reduced. 舄Improve the PVA 糸 糸 得到 得到 制造 制造 制造 制造 制造The film-forming stock solution of the P VA 糸 polymeric film is added to the surface of the film forming solution, and the smear is added to the surface of the PVA-based polymer. The lingual agent is not limited to the type of the surfactant. Preferably, it is an anionic surfactant (IV); == surfactant; anion; preparation of φ, 4 and non-ionic 糸 绩 酸 acid, bismuth sulphate and other two lingual agents are preferably, for example, potassium laurate Anionic surface::: genus benzoic acid ester, etc. S. The nonionic surfactant is preferably exemplified by: 4 oxyethylene oil 垸 _ _ type, polyoxyethylene octyl benzene _ 酉Alkyl ester type such as squaring type, flat 7, μχ i laurate, alkylamine type such as polyoxyethylene laurylamine, polyoxyethylene laurylamine, etc. Alkyl oxime type, poly(propylene glycol ether type) such as poly(X) oxypropylene ether, alkanol such as oleic acid diethanolamine, allyl phenol ether type such as polyoxyalkylene propyl ether, etc. Nonionic system 29: 25467ο Surfactant. These surfactants are used in two or more types. The amount of the surfactant or combination of surfactants, preferably, is called quality denier / for PVA-based polymer, the quality is preferably 1.~0.3 mass: 'better than 〇·02~〇·5 parts by mass , it is difficult to show >, 壬 & 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果 如果Dissolving and dissolving into the PVA system for use in the production of the present day results in a decrease in the use performance. Preferably, the ratio of the volatile component is two: in the range of 55 to 85% by mass, particularly preferably in the range of 55 to 85% by mass. Scope. If the wax in the film preparation solution (four) kg, p 5G @里% 'the viscosity of the manufacturer liquid will become too high, adjust the wear :::::: defoaming will become difficult, it is difficult to obtain no The difference between the other two is that the ratio of the volatile component in the film solution of Ueda '° 1 is super-bei ^ ^ The viscosity of the film-forming solution becomes too low, and it is difficult to dream of having the required thickness. And a pVA-based polymer film with a thickness accuracy. The "volatile composition ratio of the film forming solution" as described in the present specification "According to the formula for the calculated ratio of volatile components. Volatile film forming solution composition ratio (mass%) = {(Wa- wb) /

XlOO

[In the formula, Wa represents the mass (g) of the film forming solution, and the fly means that the film forming solution (Wa) (g) is dried in a vacuum dryer having a temperature of 5 〇t and a pressure of lk lkpaaT for 4 hours. the quality of. 30 1254670 Nandang film-forming stock solution is prepared by plasticizing with PVA-based polymer, glycerin and other polyols, and by using surfactants and water. Brother, under the above conditions, it is mainly only water volatilization. The composition of the water material is almost unexpected: in the PVA-based polymer film, the ratio of the volatile component of the film-forming stock solution can be regarded as the water content contained in the film-forming stock solution.

/ The above-mentioned PVA: a film-forming stock solution of a polymer having a ratio of a volatile component in the range of 50 to 90% by mass, for example, as shown in Item 3, using a plurality of drying rolls (2a, holes, 2c, Μ....... The film forming apparatus is slowly dried to produce a PVA-based polymer film. The number of drying rolls on the film forming apparatus is preferably 3 or more, more preferably 4 or more: It is particularly preferably 5 to 2 (M solid. The plurality of drying rolls are preferably formed of a metal such as nickel, copper, copper, or stainless steel, and particularly preferably a light surface formed of a metal material which is not knitted and has a glossy surface. In order to improve the durability of the dry report

The film stock solution may also contain a dichroic dye as needed: a single layer or a combination of a nickel layer, a chromium layer, a nickel/chromium alloy layer or the like, or a plated drying roller.制 The film-making device that needs to be used by trr' is followed by a plurality of dry-drying kun, which can be used according to the seven-eighth, wind-type hot air drying device (not shown), heat device (Fig. 3), and humidity control device. In the ',, r ^ process (a), for example, a 狭缝-type slit die, a funnel plate, and the like are used! A known film-like discharge device (film-like casting device) such as a roll-type coating die is formed on a first drying roll by a membrane-forming stock solution of a film: soil P: ... (in a boat shape (casting)). Then, in the present invention, the PVA-based polymer film on which the spit is "extended to UlL" to the first drying roll (2a) 31 1254670 is dried by the PVA, and the heat is heated while the (2a) is heated. , the surface of the WA polymer film is not in contact with the ^ sometimes called red bird b (2a) (the following reading 舄 $ 1 dry no light non-contact surface) ... dry to the first dry welding _ f ' sentence uniform When the hot air is blown, the ratio of the hair component to the glutinous rice glutinous rice (2a) is 15 to 30% by mass. If the ratio of the volatile component is less than 15% by mass from the i-th drying roll (2a), Second, the property of the film is reduced, on the other hand, 4, the production rate of the film of the film is Q 3〇#%, the double fold of the surface layer A, the rate (△« MDA) will be 3 〇x〗 〇 3 or more, helmet

A polymer film. The effect is not obtained; the volatile component of the PVA polymer film of the invention is more than 2 when the pro-(5) is peeled off. The ratio of the content of the 5% to 25% by mass is preferably 17 to 28% by mass. [The ratio of the volatile component ratio of the PVA-based polymer film to the volatile component of the ruthenium-based polymer film in the present specification" is determined by the following formula. Calculate the ratio of volatile components. ; PVA-based polymer film (film) volatile component ratio - Wd) / Wc} xl 〇〇) UWc [where Wc represents pva human ^ + / sample mass (1), Wd: ... PVA polymer 臈) _ The clothes were not placed in a mass of the PVA-based polymer film (w 糸 polymer film) (Wc) (g) after drying for 4 hours in a vacuum dryer under temperature and pressure g. When a pVA-based polymer film formed using a PVA-based polymer or a polyol-based plasticizer such as glycerin and a water-formed film-forming stock solution is dried under conditions, only water is volatilized, and components other than water are almost 32 1254670. Since it remains in a PVA type polymer film without volatilization, the ratio of the volatile component of a PVA type polymer film can be calculated|required by the 2 (water content) of PVA type polymer film. When the knives are dried by the first drying roll (2a), the surface temperature of the i-th drying roll (2a) is preferably from 2 to 100 ° C, more preferably from 65 to 98, in terms of uniform drying property, drying speed, and the like. , especially good for 75~96. ~ Tooth 7 1 Guide B less than 聋曰 (8) circumferential speed 'from the hook dryness, drying speed, etc. Widely: preferably 3~2〇m/min, more preferably 3.5~l7m/min, especially good : 15m/_. Further, the PVA, which is discharged onto the first dry light (2a), is: :: the contact time of the film with the &quot;drying roll (2a), taking into account the dryness: preferably 〇·5~5 minutes or so More preferably 〇.7~3.5 minutes or so. 〃When the hot air is blown to the non-contact surface of the drying roll of the pvA-based polymer film 1 discharged onto the first drying roll (2a), the time when the p-film contact with the first drying roll is L5 minutes or less is 1 Obtaining a bilayer structure PVAM composite film of the present invention having a birefringence of the above formula, or, and a a ^ ^ ^ , having a birefringence and an alignment degree satisfying the above various formulas,

In the first section of the PVA-based polymer film, the entire area of the PVA polymer film is blown away by the wind. 〗 〖N / Bu contact surface #接扪e, ', ms hot air, non-contact for the first drying roller The wind speed of the hot air blown from the entire area is preferably, preferably - in this case, if the wind speed of the hot air is less than two "; then: the three-layer structure of the icicle amine required for the present invention cannot be obtained, and Use the first 〖 ^ water-based gas will occur when drying the dryer

Condensation, the water droplets will drip onto the P..., the hole-seeking, the J-series, and the defects will easily occur on the most formed film. ^ ' ^ f 4 is easy to be in the PVA system 33 1254670 The film exhibits a spread of $ μ θ and unevenness in the growth and accompanying dyeing (when the wind speed is too high). j. In the case of the temple, I asked Zhao and said, "Pu- 钇 吐 吐 第 第 第 第 第 第 第 第 P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P 1 on the drying roller, "the time when the film is in contact with it for more than 15 minutes, has a double fold which satisfies the above formula, or has a refractive index, or has a birefringence and an alignment degree." Layer structure parent: film, from the position where the film forming solution is discharged on the second drying roller;;: the portion of the pvA Lee contact surface of the 1 / 4 circumferential position of the drying roller is blown by the wind, ... (4) Brother 1 drying roller Non-connected U-knife reaches the wind speed of 4 1~ chest S, preferably 2~ms' more 44~7m/s' for the ith drying of the polyethylene film at the position after 1/4 circumference The hot air of the wind speed of 〇m/s is preferably blown at a portion of the area of the contact surface of the Kun-Nu, preferably 2 to 40 m/s, more preferably 4 to 2 〇 m/s. In the case of k kinds of f months, if the wind speed of the hot air is outside the above range, not only the pVA polymer film of the three-layer structure required for the present invention is obtained, but also condensation of water vapor or the like occurs when dry and lightly dried. The water droplets will drip onto the PVA-based polymer film, and it is easy to cause defects on the finally formed PVA-based polymer film (when the wind is fast), or it is easy to produce a thickness unevenness sentence on the lanthanide polymerization system and accompanying Problems such as uneven dyeing (when the wind speed is too high). ^, the degree of hot air blown by the non-contact surface of the i-th dry roll of the PVA-based polymer film, preferably 5 〇 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 70~i2(rc. Soil 1 is not particularly limited to the method of blowing the heat of the 1254670 non-contact surface to the PVA-based polymer film, drying the light non-contact surface; PVA polymerization The first method of the film can be used, and the hot air of the sentence hook and the temperature of the hook are used by Harbin.. or the combination of these. The formula, the 1 flow plate method can be used, for example. The surface of the stone 1 drying roller (2a) # Θ 3 is shown in the first part of the gap between the outer surface and the first part of the gap between the outer and the outer surface. 1 dry welding _ M, 'the king's limb (at least the PVA polymerization • cover (7) on the two non-contact surfaces) cover (1), etc... • Multiple hot air outlets (4), from the m exit (4) The PVA draws the first wind of the hot air blowing system of the human body, and the first half of the blown air velocity is uniform and (5) cold* I is the first of the non-contact surface film. Dry_North Lafa Temple. Converging 3m- &amp; PVA-based non-contact surface blowing hot air, can be 3 ^ ^ 3 no, facing the i, as shown in Figure 糸 人 人 人 幸 幸 幸 幸 幸Direction, roughly Hu Wei Λ

The first dry hole of the 糸 polymer film / mouth PVA caused along the first! The direction of the circumferential shape of the dry bomb (other directions other than the large direction. Θ) _ These are the square φ dry welding PV 第 on the first drying roll (2a) έ 为 为 将 将 Δ Δ Δ Δ 聚合物 聚合物 聚合物 聚合物At the time, it is preferable to smelt and the hot air after the production of the PVA-based polymer film is Μ j j j j j j j j j j j j j j j j j j j j j j j j j j j j VA VA VA VA VA VA VA VA VA The i-th dry welding I ten sets of contact hot air wind speed uneven wood friction than non-hook and / non-uniform exhaust method. "b) towel's dry welding to the first drying roller (2a) to a good ratio of the composition to 15~3Qf4^PVA ^ to the dry electricity such as r, a water. Fe, from the i', After the peeling of a), the second non-contact surface of the PVA-based polymer film roll is finished, and the second (1) light contact (2b) is dried by the second drying roll (2b) 35 * 1254670. The birefringence f Λ of the double layer B of the surface layer A of the VA-based hydrate film, the hand mDA) and the table 〜), vary with the circumferential speed ratio (from) of the second drying roll (2a) and the first drying: . Therefore, this X 舄 obtains the birefringence "η" of the surface layer A, the acoustic layer Α and the surface layer B birefringence μολ) ό, ρνΔ. The luminosity (Δη _ and the heart MDB) is less than 3χι〇-3

糸 polymer film, PVA when peeled from the first drying roll (2a)

When the volatile component of the film is 15 to 3 〇 mass%, the ratio of the circumference of the second (2) to the circumference of the quotient (10) is necessary. In the range of 2: no roll (2b) to the first dry report (8), the peripheral speed ratio (s2/Sl) is preferably 1.005~i〇9D, and the tongue is up to Ί. Further, it is L010~1.080. If the circumference When the speed (Α) is less than L000, the peeling point of the ρνΑ 糸 polymer film peeled off from the first dry light (2a) will be unevenly hooked, so the phase difference in the width direction is uneven. Yida can't be used as an optical film. In addition, 'if the peripheral speed II exceeds 1.1.', the birefringence (heart_) of the surface layer A, and the birefringence (Δ~A and -_) of the surface layer B will be 3.0x10 or more 'the invention cannot be obtained. The pvA-based polymer film. When drying on the second dry Xingkun (2b), the surface of the second drying report (2b) is preferably from the point of drying, drying speed, etc. The pvA-based polymer film dried with the second dry parent (2b) is peeled off from the second dry grain (2b) to correspond to the drying provided on the film forming apparatus. The number of 'etc.' is dried sequentially on the 3rd drying roll (2c), the 4th dry (2d), the 5th dry 36 1254670 drying roll, or by a hurricane dryer. Use 敎n # When drying with a wind dryer, you can arrange one or two or more drying rolls between the dry 2 (2b) #, (b) and the hot air dryer as needed. "#", the father of the car is a device that can uniformly blow hot air to both sides of the continuously transported PVA-based polymer film. In the present invention, it is a chu, a right, a dry roll and After the second drying roller, use a drying device equipped with a plurality of I, no light or devotional machine to the PVA-based polymer, and when you are in the second dry light (II, I) ·) The ratio of the PVA-based polymer film component is as follows: In the dry process of the "A-type polymer film", it is preferable to mechanically stretch it at 0.950" (4). It is in the line. Μ眇, the target area of the 曰 曰 P VA polymer film of the volatile component ratio & S θ % The dry shovel is made up of 8 people in the flat knives. It does not produce a slack in the film. It can be used to make the smashing of the smashing shovel. The house, the temple, and the birefringence of the surface layer and the surface layer. ^ Refractive index (Δ, 廿σ, Λη MDA) and double film. A PVA-based polymer that satisfies the values specified in the present invention. Here, the "mechanical stretching roller is 妒ρ π々+ A 疋 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周 圆周The private monument neck, u-cycle speed), and the PVA system at the outlet of the hot polymer film, the scoop wheel speed) / (the speed of the hot air drying film). 4 PVA system of the inlet In the present invention, when the ratio of the volatile component of the PVA-based polymer film is lowered to 37,125,470 to as low as 13% by mass, the (n + ) drying of the PVA-based polymer film is made. The ratio of the peripheral speed (S...) to the nth dry light circumferential speed (Sn) (Sn+l/S„), or the exit speed of the hot air dryer through which the PVA polymer film passes () relative to the inlet The ratio (^) of the velocity (§ η ) becomes 0.950 to 0.999, preferably 〇96〇~ 〇 995, more preferably 0.970 to 0.990 for drying. When ratio () or ratio (S^t) /Sin) In the above range, no relaxation or entanglement of the PVA-based polymer film occurs, and the surface layer A/core layer c/surface layer B which can be obtained smoothly and has the birefringence and orientation required for the present invention Such a PVA-based polymer film having a three-layer structure, and a P-sea JA-composite film which has been subjected to the above-mentioned dry-dancing treatment, can be subjected to 4 亍..., treatment, humidity control, etc., and finally 4 scorpions. Take the PVA-based polymer film which is wound into a roll shape and the cost of the invention. 〃 Ή 4 string processing ' The PVA-based polymer finally obtained has a ratio of 1 to 5 mass%, particularly 2 to 4 mass%, and Z is: week, that is, drying temperature, drying treatment time, whether heat treatment is performed, or jinjinjin ...the temperature and time of the treatment, the condition of the humidity control treatment, the PVA-based polymer film 5 of the temple 0' month is uniaxially stretched in the long direction (MD), even if the stretching ratio * π 八八裂 and the hole, Therefore, the fine turtle v, ° may not be generated or rarely produced to be effectively applied to the optical use including the polarizing film. 0 There is no particular limitation on the method of using the present invention. The manufacture of the polarizing film of the PVA-based polymer film can be borrowed. 38 1254670 can be produced by a conventionally known method or the like. For example, the PVA-based polymer film of the present invention can be used, subjected to dyeing treatment, uniaxial stretching treatment, fixing treatment, drying treatment, and heat treatment according to the requirements 2 In order to manufacture a polarizing film, the order of operations such as dyeing treatment, uniaxial stretching treatment, and fixing treatment is not particularly limited, and if necessary, one or two of the above-described treatment processes may be employed. One or more of them are performed twice or more.

/, In terms of body, the dyeing treatment can be carried out before uniaxial stretching, uniaxial stretching, and at any stage after uniaxial stretching. Further, as the dye used for the wood color treatment, for example, iodine-potassium iodide; direct black 1 7 , i 9 , 154 'direct brown 44, 106, 195, 210, 223; direct red 2, 23, 28, 31, 37, 39, 79, 81, 240, 242, 247; direct blue Bu 15, 22, 78, 9 〇, 98, 151, 168, 2 〇 2, 236, 249, 27 〇; direct purple 9, 12, 51 , 98; direct green 丨, 85; direct yellow 8, 12, 44, %,; direct 1 26, 39, 106, 107 and other dichroic dyes 'can be used in combination or in combination of two or more. Eight-color treatment, generally impregnating a pVA-based polymer plate in a dye-containing solution, 'but is not limited thereto, and a method of coating a dye on a PVA-based polymerization::: 'pvA-based polymer may also be employed. A method of directly producing a dyed pvA-based polymer film by film formation is added to a raw material for a film: there is no limitation on the processing conditions and specific treatment methods at the time of dyeing treatment. Further, in addition, the uniaxial stretching treatment of the PVA-based polymer film by wet drawing may be carried out by a stretching method or a dry heat stretching method. Further, in the solution of the uniaxially stretched material of the product 390 254 670 or the fixed treatment bath described later, the PVA-based polymer film containing the above-mentioned dyeing may be used in the air to be immersed in water. Stretching temperature when uniaxial stretching can be simplified by other methods

The polymer film is stretched in warm water (wet = will "A" using 3 〇 Q n. The factory temperature is preferably / more preferably 40 ~ 70 ° c, especially good 45 ~ price, while in dry heat It is better to use 50~180 when stretching

The degree of pulling of the uniaxial stretching treatment. In addition, for ^^_ sheep (into the multi-stage uniaxial stretching, the _ stretching ratio), from the perspective of polarizing performance, it is preferably 4: 5 times better than 5 times, especially 5 5 More than the above, D, or more, more special restrictions, ^ Λ 上限 The upper limit of the stretching ratio is not, „古〇进巧巧勾的 stretching is preferably 8 times or less. The thickness of the PVA-based polymer after stretching is the thickness of the 考 刭偬氺 4 4 〈 〈 〈 〈 〈 〈 〈 〈 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届 届"3~75&quot;m' When manufacturing a polarizing film, in order to make the dye adhere to p, most of the fixing treatments are fixed.

It is widely used in the preparation of PVA and Han/Bei in the presence of boric acid and/or deuteration. In the treatment solution of this day ϋ I + π ° ^ : the guo compound can be added to the treatment liquid. ...,: After the uniaxial stretching treatment, the pva system is taken into the private + early axis ancestral extension and the fixed treatment m film (polarizing film) is dried (埶 treatment). "The temperature of the treatment (heat treatment) is preferably 30 to 15 〇. 22 )) 140 C. If the drying treatment (heat 50 of the polarized 膣 MP 4 ~ y ^ degree is too low, then the size of the pancreas is easy to determine If the other side is accompanied by dyeing and smearing, if it is too high, then /,;, and the knife will be able to produce a decrease in polarizing performance. 40 1254670 The two polarizing films obtained by the process are transparent and have mechanical strength. You can form a polarizing plate with your heart. At this time, Baowei Yin ΓΓ cellulose acetate (tag) membrane, acetic acid ~ butyric acid fiber = B) membrane, acrylic acid membrane, mesangium, etc. The adhesive for the adhesive film is generally used as a pv "adhesive, poly: sputum agent, etc.", wherein a PVA-based adhesive is preferably used. The polarizing plate obtained by the above process is used as a liquid crystal display device after being laminated on a glass substrate:::: When the polarizing plate is attached to the glass substrate, the side is attached to the pancreas and the viewing angle is raised. Film, brightness enhancement film, etc. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but

It is not limited to the following examples. X

In the following examples and comparative examples, the volatile component ratio of the PVA film-forming stock solution, the volatile component ratio of the PVAM (PVA-based polymer film) U:), the physical properties of the PVA film, and the optical properties of the polarizing film were determined by the following methods: 〇(1) The volatile component ratio (water content) of the PVA film-forming stock solution was measured by the above method. (2) Volatile component ratio (water fraction) of the PVA film (PVA-based polymer film): The PVA film (PVA film) was taken out from the drying roll, and the volatile component ratio (water content) was measured by the above method. For the measurement position at the time of measurement, the PVA film was aliquoted in the width direction (TD), and the volatile components of (7) 41 1254670 positions were measured.

^ λ ~ ratio ' takes the average value as the volatile component ratio of the PVA film (PVA Moon). Measurement of 厶11 mda, Δη MnR, 八η Λ mdb Δη MDC, ^ ..., Δη τ j The birefringence of the surface layer A, the surface layer b and the core layer of the film, η —— TDB / , 甶 were measured by the above method. The following instruments are used for the determination of the 疋 疋 : : : : : : : : : : : :

Nikon Moon Co., Ltd. manufactures " OPTIPHOT SET: Knife knives. Manufactured by Sakamoto Optical Co., Ltd. • Birefringent compensator: manufactured by Olympus Co., Ltd. (4) Alignment of PVA polymer film (Fa, The measurement of fb, fc) is determined by the above method. The BL24XU (Qiuku County first beam line) scheme 0 in the measurement of the gentleman _ Q., inch 'Using a large-scale radiological facility SPring temple corporation high-brightness optical science research center' The ray microbeam is measured. C 5 ) Optical properties of the polarizing plate: (i) Monomer transmittance: Central Deng from the width direction of the polarizing film in the following examples or comparisons For the long direction (MD), the product has 2 slices, the oblique r mouth, and the ten-footed square (4cmx4cm). The water mouth is 2 pieces of the mouthpiece. ΐ 日 日 日 & & & & & & & & & & & & & & & & & & & & The spectroscopic sound produced by the company is 410 Θ (with integral sphere), according to the method of Is, and the ancient ice, 隹 π p, 広 8 722 (measurement method of the object color), the C light source, 2 Tang phase The positive direction of the visible light region of the X field of view, and the tensile axis of the polarizing film is measured. α degree from the right π pregnant universal inclination of the inclined γ2 a value of 45 degrees, and the average γ-inch, and a value ΑΑ V / who added, and 1 [mu] A value of each value obtained Υ Yang opening. Then, the orphan mouth values of the two samples were added and then divided by 2 to obtain the transmittance (%) of the light film of 42 1254670. (ii) Polarization: : ^ The two polarized film samples cut out in (1) above, in the direction of the direction of the weight of the Nie, should be in the form of a match, in the same manner as in (1) above, the polarized light of the stack The stretching axis of the film W is measured for the value of γ when the weight of the glaze is inclined at 45 degrees, and the average value and the inclination of 45 are taken as Υ||. And the two cut-offs of the sputum were taken up (the skin-like buckle, overlapping with the aligning direction of the fish on the ilR fi, FI i . , ', ) sample, respectively, for the overlapping polarizing film. , the stretching direction of the film is tilted ± one of the Yang Xian film, the value of Υι at the angle of 45 degrees and the Υ at the angle of 45 degrees, and the average value as γ丄' is calculated by the following formula degree. 2 Polarization degree (%) = {(γ丨丨γγ/(Υ||+γ丄)}, (10) (6) Number of cracks and number of holes of the polarizing film: From the following examples or comparative examples In the width direction of the polarizing film: in the central portion, a square (4 cm x 4 cm) sample was cut in parallel with the long direction (assisted), and a central portion of the sample was taken at a magnification of 4 using a microscope ("ECLIpsEE6" manufactured by Nikon) When observing "匕, the number of cracks (cracking perpendicular to the direction of stretching) and the number of holes and holes (rod-like defects having a long axis in the direction of stretching) are fixed in the microscope, and the counting is able to The number can be confirmed in the fixed field of view of the microscope, and the same operation is repeated twice, and the average value is taken. &lt;&lt;&lt;1&gt; Example 1 &gt;&gt; (1) PVA (saponification degree: 99.9 mol%, degree of polymerization 2400) 100 夤虿, glycerin (plasticizer) 12 parts by mass, lauric acid diethanolamine 〇. j content and water 2 1 7.6 parts by mass, melt mixed by melt extruder, 43 1254670 t bamboo To the plate version of the raw material [volatile component ratio (moisture rate) μ胄%]

The same film forming device as shown in Fig. 3, from which ϋ i pairs U 灿 幸 幸 (2 a ) ( 矣 矣 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The whole area of the non-contact surface of the first dry roll of the moon fruit on the circumferential surface of the drying roll (h) is blown out from the hot air: 4) at 5 m/s The moisture rate of the dry olefin to the PVA film is 24% by mass on the first dry t...[PVA 朕兴弟1 dry roll (2a) contact time is 〇 ·8 minutes]. (2)..., and after the ratio of the peripheral speed (S2) of the second drying roll (2b) to the peripheral speed (Si) of the first drying roll (2a) (8) = 1 〇 35, from the first The age, the 曰 曰 q q, the 1 秦 b ( 2a ) peeling (the PVA film at the time of peeling, the fraction: 24% by mass), and drying after the second drying stick. The τ second dry 'bird t (2b) has a roll surface temperature of 85. . After the second drying roll (7)), the circumferential speed ratio between the two drying rolls (the two drying rolls) is one side. At the same time, the water content of the pva film on the fourth drying roll (2d) is 13 %% 'The ratio of the fifth drying roll (circumferential speed U5 of 2〇) to the peripheral speed (8) of the fourth dry light (2d) (s5/S4) was adjusted to 0.990, and then dried by subsequent drying, and finally used. Heat treatment at a surface temperature of 1 〇 5 t is light (3), and after heat treatment, a PVA film (mass swell degree shoulder, thickness 纟 75 Å, width ¥ mass %) is obtained by winding. (3) Double of each layer of the pVA film obtained in the above (7) The refractive index and the degree of alignment are measured by the above method, and the results are shown in the following table. The PVA film obtained in the above (7) is discharged from the discharge device and the 44 1254670 is initially contacted with the third dry light J rvA surface to form a surface layer. A, the phase /5 side becomes the surface layer B. /, on the contrary (4) the ΡνΑ film of the above r 9 , π z;, ^ ^ ν , ♦) is immersed in 3 〇t of water] (4) After the run, the mass ratio of 'moth&quot; to normalized potassium is (7) (8), honest, and agricultural ^ 30~5Gg / liter, the temperature is 赃Moth moth of 'the times> shellfish given time and eliminating the rod into the Luo _ Ding wood color. The dyeing process is to make the early tooth permeability of the polarizing film obtained after the single-axis stretching is 43 5% ± 〇 2% in the polarizing film, and the temperature is 30~5〇g/liter. # gj $ _

If &quot; floor, "* mouth ° dry circumference within the appropriate choice of cold iodine concentration, &°; choose the color between the %. Then take the PVA film from the dye bath, in the lyophilized solution of t (concentration concentration of 3 mass% After immersing and doubling the uniaxial stretching, it is immersed for 4 minutes in an aqueous solution of potassium borohydride (Iodized 3 〇 4 〇 g / liter, Wei content ~ liter) for fixing 〆 = further (4) The hot-air drying was carried out by scratching to produce (5) the monomer transmittance, degree, number of cracks, and number of pores of the polarizing film obtained in the above (4) were measured by the above method, and the results were as follows. As shown in the figure, 43.7% of the monomer feed, 99 99% of the degree of polarization, a number of cracks, and 16 holes can be applied to the production of the polarizing plate without any problem. &lt;&lt;Example 2&gt;&gt; 1) Using the same film forming apparatus as in Example i, the same film forming stock solution as used [the volatile component ratio (moisture rate) 66) was also listed as 1 ^Berry % 1, and the gland membrane stock solution was discharged from the discharge device 1 In the i-th drying roll (2, the flat surface temperature is selected to be 85t, the peripheral speed is llm/min), the film formation is discharged, and the outer surface of the drying pupa (2a) is substantially The area (pvA film tb, the younger roller 1 non-45 1254670 contact: the entire area) from the hot air outlet (4) at a speed of 5 m / s 2 also 迗 9 〇 t: hot air, in the first drying roller (2a) The moisture content of the dried fruit to PVA is 21% by mass [the contact time of the PVA film with the first drying roll (2a) is 1 · 0 minutes] - (2) Then, at the second drying roll (2b) The ratio of the circumferential speed (s2) to the peripheral speed (S) of the two drying rolls (2a) is (S2/Sl) = 1._ under the condition of 'from the first drying (2a) peeling (when peeling) The protection of the PVA film is 21夤$%, and the drying after the second drying roll is performed. This is the surface temperature of the younger dry light (2b) of 85 ° C. After the second drying roll) The film was formed under the condition that the peripheral speed ratio between the rolls of the dry olefin roll (2d) was 1 〇〇〇. In order to make the moisture content of the P-film of the first drying roller (2d) 13% by mass 'Adjust the ratio (VS4) of the circumferential speed (S5) of the fifth drying roller (2e) to the peripheral speed (8) of the fourth drying roller (2d) to G.99G' and then dry it with a subsequent drying roller, and finally use Surface temperature (8). (3) Heat (5) After heat treatment, it is wound and applied to a PVA film (mass swelling degree: 2〇9%, thickness 75 (four), width: water content: 3.2% by mass). (" Double of each layer of the ρνΑ film obtained in the above (7) The refractive index and the degree of alignment were measured by the above method, and the results are shown in the following table. The PVA film obtained in the above (2) was discharged from the discharge device and initially contacted with the PVA film surface of the "dry" report. Becomes the surface layer B, and the opposite side becomes the surface layer A. (4) Using the PVA film obtained in the above (7), the same treatment as in the treatment of (4) of Example 1, the acid-cutting treatment, and the uniaxial stretching were carried out to produce a polarized film 46 1254670. The polarizing performance (monomer transmittance, polarization) of the obtained polarizing film, and the number of cracks and voids were measured by the above methods, and the results are as follows: Table 1 shows the monomer transmittance of 43 meals and the degree of polarization 99.99. %, number of cracks. The number of holes is ίο, which can be applied to the manufacture of polarizing plates without any problem. &lt;Example 3:&gt; (1) Using the same film forming apparatus as in the example &quot;, the same film forming stock solution as [the volatile component ratio (moisture rate) 66] was discharged from the discharge device to the i-th drying roll. (2a) (the surface temperature C' peripheral speed: 4 m/min) is discharged into a film form, and the film is discharged to the first drying roll non-contact surface of the first dry light 1/4 circumference. The outlet (4) blows the hot air of (4) at the speed of the domain, and blows the heat of 25_ on the non-contact surface of the i-th dry roll after the week

Ur: 1 drying roller (the moisture content of the PVA crucible is dried to 21, the contact time of the "film with the first} drying roller (2a) is 27 minutes]. &amp; (2) then 'in the second dry pro ( 2b) circumferential speed (S2) versus *1 drying pro (2a) circumferential speed (M ratio (S2/S)) = 1 〇 2 〇: under conditions, peeling from the light dry (2a) The dryness of the second dryness is 2%.) The drying of the second drying light (2b) is the order of the light surface temperature.

=: 2;) The circumferential film I between the light of the fourth dry light (10). At the same time, in order to make the PVA degree on the fourth drying roll (10): the knives become "3 mass%", the circumferential speed of the fifth drying roll (the circumferential speed T 5 of 2 相对 relative to the dry 4 (2d)) (s4) The ratio of 5) is adjusted to 0. 975' and then dried by subsequent drying, with a surface temperature of 105 after the maximum of 12 1254670. . After the heat treatment roll (3) was subjected to heat treatment, a PVA film (mass swelling degree: 2%, thickness: 75_, width of three claws, water content of 2.4% by mass) was obtained. (3) The birefringence and the degree of alignment of each layer of the pVA film obtained in the above (2) were measured by the above method, and the results are shown in the following Table 。. In the pVA film obtained in the above (2), the PVA film surface which is discharged from the discharge device 且 and first contacted with the first drying roll becomes the surface layer A, and the opposite surface thereof becomes the surface layer B. (4) Using the Pva film obtained in the above (2), a polarizing film was produced in the same manner as in (4) of Example 1, and the polarization properties, cracks, and the number of voids were measured by the above method, and the results are as follows. As shown in the figure, the monomer transmittance is 43.4%, the degree of polarization is 99.98%, the number of cracks is one, and the number of holes is five, which can be applied to the production of a polarizing plate without any problem. &lt;&lt;Example 4>> (1) In (1) of Example 3, the wind speed of the hot air blown toward the first dry light non-contact surface of the pVA film was adjusted to the entire first dry light non-contact surface. The area was 5 m/s, and the rest of the operation was the same as (2) of Example 3. 'The moisture content of the first drying roll (2a) dried to the pVA film was 2% by mass. ^1 (2) Then, the same operation as (2) of Example 3 was carried out (wherein the moisture content of the PVA film when peeled off from the first drying roll (2a) was 2 i% by mass), and a PVA film (quality) was obtained. The degree of swelling is 195%, the thickness is 75/rn, the width is 3 m, and the water content is 2.5% by mass. (3) The birefringence of each layer of the PV A film obtained in the above (2) and the degree of alignment of 48 254670 were measured by the above method, and the results are shown in the following table! Shown. In the above, the pvA film obtained in the above (2) is discharged from the discharge device, and the first contact with the first drying roll becomes μβ, and the opposite surface thereof becomes the surface layer A. (4) Using the PVA film of the above (2) for stone |), the same drilling as in the example j scoop (4) was carried out to produce a polarizing film, and the polarizing property and the number of voids were measured by the above method, and the results were as follows. As described, the monomer transmittance is 43.3%, the on 择 select onri — / the partiality is 99.y/%, the number of cracks is ,, and the number of holes is 8 'can be applied to the manufacture of the polarizing plate without any problem. «Comparative Example 1&gt; (1) The same film forming apparatus as in Example 1 was used, except for the discharge position of the wind speed two-film raw liquid which was blown toward the i-th dry non-contact surface of the PVA film in the example (1). The same operation as in (1) of Example i is carried out, except that the 圆周i drying roll is set to 5 m/s on the second circumference, but the remaining 八 〜 〜 泣 / / / / 疋 疋 疋 25 25 25 25 25 25 疋 疋 疋 疋 疋 疋 疋 疋 疋} The moisture content of the drying roller (2a) to the PVA film was 24 f% by % [contact time on the i-th drying (8) was 0.8 minutes]. (2) Then, the same as (2) of Example 1 was carried out. The water content of the pVA film at the time of peeling from the first drying roll (2a) was 24 masses: a PVA film (mass swelling degree: 2〇9%, thickness 75_, width-divided ratio: 3.0% by mass) was obtained. (7) The birefringence and the degree of alignment of each layer of the PVA film obtained in the above (7) are measured by the above method, and the results are shown in Table 2 below. The 'pVA film obtained in the above (2) is 'discharged from the discharge device 49 1254670'. The surface of the PVA film that first came into contact with the first drying roll became the surface layer B, and the surface opposite thereto became the surface layer A. (4) Using the above (2) The pvA film was subjected to the same procedure as in the example (4) to produce a polarizing film, and the polarizing performance and the number of cracks and voids were measured by the above method, and the results were as follows. The volume of teeth is 43.7%, the degree of polarization is 99.99%, the number of cracks is 3, and the number of holes is 26. When a polarizing plate is produced by using a polarizing film like a polarizing film, light is scattered at the portion where the turtle coat and the hole are formed on the polarizing film. In addition, it is difficult to form a clear and detailed image. <Comparative Example 2>&gt; (1) In (2) of Comparative Example 1, the circumferential speed of the second drying roller (several) was S2) The ratio (SyS!) of the circumferential speed (S!) of the first dry welding boulder (2a) becomes 1 2 〇〇, and the wind is the same as that of Comparative Example 1 except that the PVA is known. Film (mass swelling degree: 21% by weight, thickness, width: 3 m, moisture content: 2.8% by mass). • The birefringence and the degree of alignment of each layer of the PVA film transmitted by J were measured by the above method, and the results are shown in Table 2 below. In the above, the Ρλ/Α film of the above (), pz^, / / is discharged from the discharge device i and is initially contacted to the #! The PV A film surface becomes the surface layer b, and the surface layer A is reversed. () Using the PVA film obtained in the above (1), the same operation as in (4) of Example 1 is carried out to produce a polarizing film, and the polarizing property thereof is obtained. The number of cracks and holes is determined by the above method. The results are as follows: the monomer penetration rate hole 43·/%, the degree of polarization 99.97%, and the number of cracks 7 50 1254670 number 43. When a polarizing film is used for a polarizing film, a portion where cracks and holes are formed in the polarizing film scatters light and becomes cloudy, making it difficult to form a sharp and detailed image.

51 1254670 Table 1

Example 1 Example 2 Example 3 Example 4 &lt;Production of PVA film> Volatile component ratio (water content) of film-forming stock solution (% by mass) 66 66 66 66 1st drying roll temperature (°C) 93 85 85 85 First drying roller contact time (minutes) υ 0.8 1.0 2.7 2.7 Hot air blowing speed (m/s) 5 2) 5 2) 5 3) 25 4) 52) Volatile content ratio when the first drying roller is peeled off (% 5) 24 21 21 21 Circumferential speed ratio (S&) 6) 1.035 1.080 1.020 1.020 Circumferential speed ratio (S5/S4) 7) 0.990 0.990 0.975 0.975 &lt;Physical properties of PVA film〉 Quality swell (%) 210 209 200 195 Film thickness (Mm) 75 75 75 75 Volatile content ratio (water content) (%) 2.6 3.2 2.4 2.5 Birefringence of surface layer A (ΔηMDA) 2.2xl0'3 2.1xl〇-3 2.6x1 O'3 2.4xl〇 ·3 core layer C birefringence (Διιμιχ:) 0.9xl〇·3 1.2xl〇·3 l.lxlO·3 1.7xl〇·3 Birefringence of surface layer Δ (ΔηΜΜ) 2.0xl〇-3 1.8xl〇 -3 2.5xl〇·3 2.0χΐσ3 MDA'An mdb 1.10 1.17 1.04 1.20 △n MDB —△ n MDC l.lxlO-3 0.6xl〇-3 1.4xl〇·3 0.3x1 O'3 Birefringence of surface layer A (AnTDA) 1.9xl 〇·3 1.9xl〇·3 2.4xl〇·3 2.0x103 Birefringence of core layer C (ΔηΤΙ^) 0.9x10&quot;3 1.2xl〇-3 1.2xl〇·3 1.6xKT3 Birefringence of surface layer ( (AnTDB ) 1.8xl〇·3 1.8xl〇·3 2.3xl〇·3 1.9xl〇·3 Orientation of surface layer A (Fa) 0.55 0.54 0.55 0.56 Alignment of core layer C (Fc) 0.52 0.53 0.51 0.52 Alignment of surface layer B Degree (Fb) 0.53 0.53 0.52 0.53 | Fa/Fc-Fb/Fc 1 0.05 0.02 0.06 0.06 MDA'AU TDA 1.16 1.11 1.08 1.20 MDB'An TDB 1.00 1.00 1.09 1.05 &lt;Physical properties of polarizing film&gt; Polarization properties: Monomer Penetration (%) 43.7 43.6 43.4 43.3 Polarization 99.99 99.99 99.98 99.97 Number of cracks (units) 0 0 0 0 Number of holes (units) 16 10 5 8 In the above table: 1) The PVA film is in contact with the first drying roll 2) The hot air blowing speed of the entire area of the non-contact surface of the first drying roll toward the PVA film; 52 ^ 254670 3) 1/4 round 闽 gl η, Λ from the film forming raw material discharge roller toward the first drying roll点 点 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 ... ... ... ... 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 1/4 After weeks of PVA film silk! The drying roller starts to the hot air blowing speed of the younger; μ _ the contact surface 5) moisture rate; 6) the circumferential speed of the second drying roller (the ratio of D to the first speed (S!); 7) the peripheral speed of the fifth drying roller (s5) The ratio of speed (S4). Dry area 1 dry area circumference circumference drying roll

With the 4th drying roller

53 1254670 Table 2 Comparative Example 1 Comparative Example 2 &lt;Production of PVA Film 〉 Volatile Component Ratio (Moisture Ratio) of Film-Forming Stock Solution (% by Mass) 66 66 First Drying Roller Temperature (°C) 93 93 First Dry Roller Contact Time (minutes) n 0.8 0.8 Hot air blowing speed (m/s) 5 3) 25 4) 5 3) 25 4) Volatile component ratio (%) when the first drying roller is peeled off 5) 24 24 Circumferential speed ratio (S2 /S〇6) 1.035 1.200 Peripheral speed ratio (S5/S4) 7) 0.990 0.990 &lt;Physical properties of PVA film&gt; Mass swelling degree (%) 209 210 Film thickness (μηι) 75 75 Volatile component ratio (water content) %) 3.0 2.8 Birefringence of surface layer Δ (ΔπΜΙ)Α) 3·7χ1〇-3 5.8χΐσ3 Birefringence of core layer C (AnMDC) l.lxlO'3 1·5χ10_3 Birefringence of surface layer B (ΔηΜΟΒ) 3·0χ10_3 2.7χ1〇-3 Δπ ΜΟΑ/Δη MDB 1.23 2.15 △n MDB—such as MDC 1.9xl〇-3 1.2χ1〇·3 Birefringence of surface layer A (ΔηTDA) 2.3xl〇·3 2.5χ1〇·3 Core layer C birefringence (AnTDC) 1.0x1 Ο·3 1.4χ1〇·3 Birefringence of surface layer B (Δητ:)Β) 2·3χ10_3 2.5χ1〇·3 Matching of surface layer Degree (Fa) 0.61 0.70 Alignment of core layer C (Fc) 0.51 0.53 Degree of orientation of surface layer B (Fb) 0.52 0.54 | Fa/Fc-Fb/Fc I 0.18 0.30 An MDA'An tda 1.61 2.32 △n mdr/Ah TDR 1.30 1.08 &lt;Physical properties of polarizing film> Polarizing property: monomer penetration (%) 43.7 43.7 Polarization degree 99.99 99.97 Number of cracks (units) 3 7 Number of holes (units) 26 43 In the above table: 1) PVA film The time of contact with the first drying roll; 2) the hot air blowing speed toward the entire area of the non-contact surface of the first drying roll of the PVA film; 3) the first drying roll from the film forming raw material discharge point to the first drying 54 1254670 The hot air blowing speed of the Pva film up to the 1/4 circumference of the roll of the non-contact surface of the dry roll; 1 dry area 4) from the discharge point of the film forming raw material to the first drying roll to the first drying light 1/ 4th hot air blowing speed of the non-contact surface of the drying roller of the PVA film after the circumference;

S2) a ratio of the circumference of the first drying roller 6) the circumferential speed velocity (S) of the second drying roller;

7) The ratio of the peripheral speed (S5) of the fifth drying roller to the circumferential speed (S 4 ) of the fourth drying parent. When the PVA-based polymer film of the present invention is uniaxially stretched in the longitudinal direction (longitudinal direction), even if it is stretched at a high magnification, the emission of light and the film whitening with p-return are not caused or rarely occur. Fine cracks and holes. Therefore, the PVA-based polymer film of this month can be effectively applied to an optical film including a polarizing film. When the production method of the present invention is employed, the pVA-based polymer film of the present invention having the above-described excellent characteristics can be continuously produced with high productivity and high efficiency, and thus the practical value is high. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1(a) to 1(d) are birefringences (Λη_, Λη_, Λη(10)) of the surface layer a, the surface layer B, and the core layer C of the PVA-based polymer film in the longitudinal direction (MD). The measurement method map. 2U) to (d) are the surface layer, surface layer and core of the PVA polymer film.

1254670 Birefringence of the core layer C in the width direction (TD) (measurement pattern of An TDA, An TD. Fig. 3 is a view showing an example of a PVA-based polymer film of the present invention. Δη T£) c) ! Membrane device, main component symbol description 1 PVA polymerization 2a 1st drying roller 2b 2nd drying roller 2c 3rd drying roller 2d 4th drying roller 3 Cover 4 Hot air discharge port 5 Heat treatment roller

56

Claims (1)

1254670 X. Patent application scope: It is attached to the outer two surface layers A and the surface structure; it is characterized in that: 1. A polyvinyl alcohol-based polymer film, the star layer C between the layers B has a star satisfying the following formula ( I)~(Πι) · mda/Δπ mdb; MDB~~ Δη MDC^ ^·2χΐ0- Δη Λ ( II) mda&lt; 3.0xl〇-3 (III) In the above formula, Δίΐ MDA table six main The rate of incidence, Δη # - ® 丨, 双 Α 机械 机械 机械 机械 M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M Birefringence in the direction of travel. 2·-polyethylene glycol-based polymer film, which exists between the outer two surface layers B and has a core layer C and is below the right lance, ... τ... layer structure; characterized in that it satisfies the following formula (I) , (Π) and (Iv) ·· △n MDA'An MDB= 1 ·〇~1.5 ( I) Δη MDB- Δη MDC^ 0.2xl〇-3 ( π) I FA/FC— FB/FC I $ ( Iv). In the above formula, Δη MDA represents the birefringence of the mechanical running direction of the surface layer A, Δη mdb represents the birefringence of the mechanical running direction of the surface layer B, and MDC represents the birefringence of the mechanical running direction of the core layer C, and Fa is based on The 2-direction h calculated by the X-ray diffraction image perpendicularly incident on the surface A of the surface layer A is the alignment degree calculated based on the 乂 ray diffraction image perpendicularly incident on the surface B surface, and Fc is based on the normal incidence of the C-plane of the core layer. The alignment of the x-ray diffraction image. 3 · As for the polyvinyl alcohol-based polymer film of the first application of the patent scope, 57 1254670 further satisfies the following formula (1¥): I FA/FC—fb/fc 1 $ (IV) In the above formula, FA In order to calculate the alignment degree based on the vertical ray diffraction image on the surface A surface, U h h 4 is calculated based on the X-ray diffraction image incident on the surface layer B Δn tdb^O-9~1·2 The degree of alignment, h is the degree of alignment calculated based on the x-ray diffraction image of the (four) C-plane perpendicular incidence. / 4 · If the polyethylene glycol-based polymer film of the scope of claim i, it is desirable to satisfy either or both of the following formulas (V) and (VI):, Δn tda = 〇 ·9~1 ·2 (V) VI) In the above formula, Δη MDA represents the birefringence of the mechanical direction of the surface layer A, and Δη TDA represents the birefringence of the surface layer A perpendicular to the mechanical running direction Δη MDB The birefringence 'h (d) of the mechanical running direction of the surface layer B indicates the square birefringence of the surface layer B perpendicular to the mechanical running direction. 5. The polyethylene glycol-based polymer film of claim 2, wherein the step further satisfies either or both of the following formulas (V) and (VI): Δ n MDAMn tDA = 〇 _ 9~1·2 (γ) In the above formula, Δη MDA represents the birefringence of the mechanical direction of the surface layer A Δη TDA represents the birefringence of the surface layer A in the direction perpendicular to the mechanical running direction, and Δη MDB represents the surface layer B The birefringence 'TDB of the mechanical running direction indicates the birefringence of the surface B perpendicular to the mechanical running direction. 58 I254670 6) The polyvinyl alcohol-based polymer film of claim 2 or 3, "T, the degree of orientation Fa calculated from the diffraction image generated by the pupil rays incident perpendicularly to the surface of the surface layer a, The degree of orientation calculated by the diffracted image of the X-ray which is perpendicularly incident on the surface of the surface layer, and the value of the orientation Fc calculated from the diffraction image of the X-ray which is perpendicular to the core layer and the surface. Both are 0.4 to 0.6. The polyvinyl alcohol-based polymer film of the first or second aspect of the invention is an optical film. • The method for producing a polymer film is to use a plurality of dry light or hot air dryers after the second drying report to produce a patented range of decadienyl polymer film by the following process: Mussels of mussels (a) will have a volatile component ratio of 5〇~9 〇 的 袢; δ y 制 制 制 的 的 承 〜 〜 〜 〜 〜 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在In the form of a film, the polyvinyl alcohol-based polymer is smear-like, and the yttrium-yield is heated. At the same time, the seventh scorpion-based polymer film is extracted. The first drying light: the ratio of the volatile component of the film is 15~3〇; i(4) is poly and 〇' 丁7 is from the π ping 1 5~3 〇 to the ethylene polymerization 2 dry: Poly: After the film is peeled off from the first drying roll, the non-contact surface of the drying roll of the 罘1 is dried with the drying roll; guide 蜀59 !254670 (c) in the process (a) , • When the polyethylene glycol polymer film is in contact with the lighter &quot;drying time for less than A minutes, 'for the first&quot; Polyethylene glycol alcohol on the polymer: The first dry soldering station of the film is salt 2 ^ & chest "salt; contact surface ... Lai speed is Bu · When the polymer film and the third drying 峨 = : : "The hot air blown at a speed of -1 to the circumference of the polyethylene glycol-based contact surface from the film-forming raw material discharge to the first drying position", and the polyvinyl alcohol season surface at the position after two weeks Blowing the wind... H "The first drying roller of the object is a non-contact surface with a wind speed of 1 to 60 m/s. In addition, the circumference = Λ = peripheral speed (8) and the first drying _ line of the above system... and two ~ In the range of (10), the method of applying the patented ribs, and the method of preparing the polyvinyl alcohol-based polymer film of J, and the vinyl alcohol-based polymer film from the second drying: : The polyethylene glycol-based polymer film is: m m mechanically stretched in the range of g.95g~1•(4). ·〇申%% patent scope item 8 method, 1 , 7 arsenic system ♦The composition of the compound to 13% by mass of the Japanese, the ratio of the volatile component of the dilute alcohol-based polymer film is reduced by a dry corpse. The circumferential speed fv ^1 of the (n+1) iu 乙 辊 roller in contact with the film; tl · rQ n" of the velocity (S) is for the circumference of the eleventh drying roller n n+1/SJ ' or PVA The polymer film was dried by a ratio of the outlet speed () of the hot air dryer of 60 1254670 to the inlet speed (sin) (S^t/Sm) of 0.95 0 to 0.999. XI. Schema: as the next page 61