TW200925193A - Process for producing polarizer - Google Patents

Abstract

The present invention provides a process for producing a polarizer by laminating a transparent protection film, through an adhesive layer, to only one side of a polarizing film comprising polyvinyl alcohol, resin and having a dimensional variation rate less than 2.7%. In this process, the transparent protection film is preferably an acetylcellulose resin film, and the other side of the polarizing film being preferably formed with an adhesive layer comprising acrylic resin.

Description

200925193 VI. Description of the Invention: [Technical Field to Be Invented] - A method of closing a polarizing film composed of a polyvinyl alcohol-based resin. The enamel agent layer is formed by laminating a transparent protective film to produce a polarizing plate. [Prior Art] A 2 series is widely used as a polarizing supply element for a liquid crystal display device. In the case of such a polarizing plate, the film is formed by a polarizing film composed of a cellulose plate made of cellulose triacetate, and a polarizing film composed of a polyether cellulose tree. A notebook PC with a liquid crystal display device, a mobile type, a lightweight device, and a large-scale TV, and must be thinner. In addition, because it is easy to carry, it can be used in a wide range of applications. Durability.....,

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Q _ / and 5 ′ polarizing film is impregnated with a dichroic dye represented by iodine or the like. Therefore, it is produced by uniaxial stretching at a high magnification in a 2-alcohol resin. When the polarizing film of the field is exposed to dry heat, the size is changed due to shrinkage. For example, as disclosed in Japanese Patent Laid-Open No. Hei 6-109922 (pre-proprietary), the polarizing film is heated at 100 ° C for 2 hours, and when the dimensional change rate is measured, it is observed to exceed (1) The shrinkage of the polarizing film is reduced by the thickness of the polarizing film, and the thickness of the polarizing film is reduced by laminating the adhesive layer on the both sides of the polarizing film. T 'Laminage of cellulose triacetate was formed on both sides of the polarizing film showing high shrinkage as described above to prepare a polarizing plate. The same table also shows the dimensional change rate after 3 hours of heating of 3 320733 200925193 plate, polarized light, polarized light The shrinkage ratio of the sheet was 2%, so that it was found that the shrinkage was suppressed by laminating the cellulose triacetate film on both sides.

In Table 1 of Japanese Laid-Open Patent Publication No. Hei 6*-59123 (Patent Document 2), it is described that the two ||acid cellulose __ is formed on both sides of the polarizing film = the polarizing plate is finely heated before the four dogs are heated. The dimensional change rate is such that the shrinkage ratio is G. 3仏, so that it is also known that the shrinkage is suppressed by laminating the cellulose triacetate film on both sides. However, in recent years, since thinner and lighter weights have been used, it is also desired to manufacture a polarizing plate in which only one transparent protective film is laminated on one surface of a polarizing film. When such a polarizing plate is exposed to a dry environment, polarization cannot be suppressed. The shrinkage of the film tends to cause a problem. Therefore, as described above, only the transparent protective film is laminated on one side of the polarizing film to form a polarizing plate, and the polarizing plate is bonded to the liquid crystal element (cryStai cel 1) by an adhesive, and is exposed to dryness. When the environment is diced, the adhesive at the end of the polarizing plate will fall off. 'The end of the polarizing plate will bulge and twist the screen display. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the invention is to provide a method for producing a polarizing plate which is provided with only a transparent protective film by a barrier layer. It is produced by laminating one of the polarizing films made of a polyvinyl alcohol-based resin, and its durability is excellent. (Means for Solving the Problem) The method for producing a polarizing plate of the present invention is characterized in that it is a dielectric protective film of a polarizing plate of the present invention, which is preferably a cellulose acetate system. Resin film. Further, in the method for producing a polarizing plate of the present invention, it is preferable to form an adhesive layer made of an acrylic resin on the other surface of the polarizing film. (Effect of the Invention) According to the present invention, a polarizing plate which is formed by laminating a transparent protective film on both surfaces of a polarizing film composed of a polyethylene glycol resin can be industrially advantageously manufactured although a polarizing plate is thinned. A polarizer that is thick but has excellent durability. [Embodiment] In the method for producing a polarizing plate of the present invention, a polarizing plate is produced by laminating only a transparent protective film on one surface of a polarizing film made of a polyvinyl alcohol-based resin. The polarizing film used in the present invention is specifically a uniaxially stretched film of a polyethylene glycol oxime resin film and a dyeing treatment using a bismuth dye, and the adsorption orientation of the dichroic dye is carried out (adsorption orienta U011) ). The method for producing a polarizing plate of the present invention basically includes: (1) a step of producing a polarizing film using a polyethylene resin; and (2) bonding a polarizing film and a transparent protective film with an adhesive; a laminating step of obtaining a laminated film; and a drying step of drying the laminated film by passing it through a drying oven. In the method of the present invention, the polarizing film is subjected to a step of producing the polarizing film, and the dimensional change rate of the polarizing film is 2.7% or less. Hereinafter, each step will be described in detail. 320733 200925193 (1) Polarizing film production step The polyethylene glycol resin constituting the polarizing film is usually obtained by saponifying a polyvinyl acetate resin. The saponification course of the polyvinyl alcohol-based resin is usually preferably 85 mol% or more, preferably 9 mol% or more, more preferably 99 to 1 mol%. The polyvinyl acetate vinegar resin may be a copolymer of vinyl acetate vinegar and other monomers copolymerizable therewith, in addition to the polyvinyl acetate of the 6 olefin vinegar homopolymer, for example, a vinylene-vinyl acetate. Copolymers, etc. Examples of other monomers which can be copolymerized with vinyl acetate include unsaturated new types, olefins, ethyl esters, and unsaturated acides. The degree of polymerization of the polyethylene glycol-based resin is usually in the range of from just 10,000 to 10,000, preferably in the range of from 1,500 to 5 Torr. The polyvinyl alcohol-based resin may also be modified, for example, polyvinyl phthalate (P〇lyvinyl f〇rmal), polyvinyl acetal (P〇lyvinyl acetal), and polybutanide Pc) lyvinyl to Kashan et al. In general, the original material for producing a polarizing film is an unstretched film of a polyethylene resin film having a thickness of (10) ❹ "m', preferably 30 to 8 Å/zm. Industrially, the width of the film is preferably 15 〇〇 to z 4000 丽 in terms of practicality. The unstretched film is treated in the order of swelling treatment, dyeing treatment, boric acid treatment, and water washing treatment, and uniaxially stretched in the step of treatment with boric acid, and finally dried to obtain a thickness of the polarizing film, for example, 5 to 50/im 〇 is roughly divided into two manufacturing methods in terms of a method for producing a polarizing film. In the first method, the polyvinyl alcohol resin film is uniaxially stretched in air or an inert gas, and then subjected to solution treatment in the order of swelling treatment step, dyeing step, and tannic acid step 200925193, and finally dried. Step method:, salad: polyethylene coffee cream is thin or difficult to uniaxially stretch in the previous step, and finally dry D 徊 in any method 'uniaxial stretching system can be in 1 step Carry out, or ❹ ❹ :: a: in the step of the step, preferably in a number of walks: the extension method can be used to protect the left from +α retracting the roller between the 1 right two, u 1 The two sheets of the film are conveyed and stretched between the rolls, and the hot roll stretching method, the tenter stretching method, etc., which are described in Japanese Patent No. 3,318, 13, for example, are described. =: The sequence is as described above, and the number of treatment baths and the treatment are as in the step of the method. In the case of such a step, it can be treated in a row (the impregnation treatment of the Wei-like mixed liquid containing the hemisphere) ^^)=The foreign matter on the surface of the film can be removed from the 19 (four) dip aqueous solution, and the film is removed. For the purpose of ... ♦ chromaticity, plasticity of the film, and in the range that can achieve the above objectives, the n-direction of the substrate film is strongly dissolved, opaque, etc. 2 will be thin. When the stretched film is swollen, for example, 1 to 20 is preferably in an aqueous solution of 20 to 耽. The immersion time of the enamel film is as fine as _ second, preferably 60 to 240 seconds. 320733 7 200925193 When the unstretched raw film is initially swollen, for example, the film is impregnated in an aqueous solution of 10 to 5 Torr, preferably 20 to 40 ° C. The film is immersed for 30 to 300 seconds. Preferably, it is 60 to 240 seconds. In the swelling treatment step, since the film is easily swollen in the width direction and » is caused by wrinkles or the like of the film, it is preferable to use a widening roller (spreading roller), a spiral roller, and a convex A well-known widening device such as a crown roll, a cloth guide, a bending rod, a tenter clip, etc., while carrying the film while removing the wrinkles of the film. For the purpose of film handling, and using water to drench It is also helpful to control the flow of water in the swelling bath, and to use EPC (Edge Position Control device: detecting the end of the film to prevent the film from being snaking). In this step, the film is also swollen in the direction of film transport. In order to eliminate the slack of the film in the conveyance direction, it is preferable to take measures such as controlling the speed of the conveyance of the groove before and after the treatment tank. Further, the swelling treatment used is: in addition to pure water, it can be used at M1 to In the range of 0.1% by weight, bismuth boric acid (described in JP-A-H05-153709), chloride (in Japanese Patent Publication No. Hei 06-281816), inorganic acids, inorganic salts, water-soluble organic solvents, and alcohols are added. An aqueous solution. The dyeing treatment step of the dichroic dye is carried out for the purpose of adsorbing and aligning the dichroic dye in the film. The treatment conditions are within the range in which the above object can be attained, and are determined within a range in which the substrate film is not strongly dissolved or tempered. When iodine is used as the dichroic dye, it is, for example, 10 炱 45 ° C, preferably 20 to 35. (Under temperature conditions, use an aqueous solution with a weight ratio of iodine / potassium iodide / water = 〇 · 〇〇 3 to 0.2 / 0.1 to 10/1 320 320733 8 200925193 concentration 'ride secret _ seconds, preferably 6q to Fine-period impregnation treatment. It can also be replaced by other Wei materials, such as Wei zinc. In addition, 'other iodides can be used together with potassium iodide. Also, compounds other than the dish compound' In fact, when it is added with a monoacid, it is distinguished from the following treatments by the characteristics of the inclusive. As long as it contains 100 parts by weight of water, it is more than 3 parts by weight of moth. It can be regarded as a dyeing tank. ❹ When using a water-soluble dichroic dye as a dichroic dye, for example, at 20 to 80 C, preferably at 30 to 7 (at a temperature of rc, use two (4) ♦ 0 ·Thank you (the aqueous solution of ΜΛ敎 concentration, 3 is 〇 6 〇〇 private 'preferably 60 to 300 seconds of impregnation treatment. The use of dichromatic dye 3 water ★ liquid ' can also contain dyeing auxiliaries, etc. 'For example, an inorganic salt such as sodium sulphate or a surfactant may be contained. The dichroic dye may be used alone or in combination. Two or more types of dichroic dyes are used. As described above, the film may be stretched in the dyeing tank. The stretching is carried out by a method in which the nip rolls before and after the 〇1 color tank have a peripheral speed difference or the like. Similar to the swelling treatment step, it can also be set in the dyeing bath and/or the entrance and exit of the Luo, and widen the 輭 (expansion roller), the spiral roller, the convex roller, the cloth guide, the curved handle, etc. The boric acid treatment is performed by The polyvinyl alcohol dyed with the dichroic dye is impregnated with respect to 100 parts by weight of water in an aqueous solution containing 丨 to (7) by weight of the water, and the dichroic dye is iodine. The iodide may be exemplified by potassium iodide, zinc iodide, etc. This may also be combined with compounds other than moth compounds such as zinc chloride, lead chloride, 320733 9 200925193 chlorinated hammer, sodium thiosulfate, Potassium sulfite, sodium sulfate, etc. coexist. 硼 Boric acid treatment is carried out in order to achieve hydration resistance (prevention of cyan, etc.) due to bridging, etc. In order to achieve hydration resistance by bridging method, Need, except for the acidity = will Acid and bridging agents such as Ep. II and E. sylvestris are used for money. In addition, the name of the water-resistant treatment, bridging treatment, and immobilization treatment is used to refer to the boric acid treatment for achieving water resistance. In addition, it can also be used for complementary color treatment. The name of the re-staining treatment is referred to as a boric acid treatment for achieving hue adjustment. The boric acid treatment is carried out by changing the concentration of boric acid and iodide and the temperature of the treatment bath as needed for the purpose of obtaining boric acid treatment for water resistance. The boric acid treatment for achieving the hue adjustment is not particularly distinguished, but can be carried out under the following conditions: in the case of swelling, dyeing, or boric acid treatment of the original film, wherein boric acid is treated to prevent water from bridging For the purpose of use, a boric acid treatment bath containing 3 to 1 part by weight of boric acid and 1 to 20 parts by weight of the broken product with respect to 100 parts by weight of water is used, usually at a temperature of 5 to 703⁄4, preferably at 55. It is carried out at a temperature of 65 °C. The impregnation time is 90 to 300 seconds. Further, the temperature of the boric acid treatment bath is usually from 5 Torr to 85 when the pre-stretched film is subjected to dyeing treatment or boric acid treatment. (:, preferably 55 to 80 ° C. It is also possible to carry out boric acid treatment for achieving hue adjustment after the boric acid treatment for achieving hydration resistance. For example, the dichroic dye is broken, in order to achieve this, Using a boric acid treatment bath containing 1 to 5 parts by weight of boric acid and 3 to 30 parts by weight of iodide with respect to 100 parts by weight of water, usually at a temperature of from 1 to 45 ° C. The impregnation time is usually from 3 to 300 seconds, most It is preferably 1 to 240 seconds. Subsequent 10 320733 200925193 The cardio acid treatment used to achieve the hue adjustment 'compared with the boric acid treatment for far-reaching water resistance' is usually at a lower boric acid concentration, a higher iodide concentration, The above-mentioned rotten acid treatment can also be composed of a plurality of steps, usually carried out in 2 to 5 steps. At this time, the aqueous solution I of each rotten acid treatment tank is used and is formed and/or set. The above-mentioned range may be the same or different. The above-mentioned boring acid treatment for hydration resistance and boric acid treatment for achieving hue adjustment may be carried out in a plurality of steps. Medium, can also be dyed The film is stretched in the same manner. The final cumulative stretching ratio is 4 to 7 times, preferably 4.5 to 6.5 times. The so-called cumulative stretching ratio means that the length direction of the original film is in the reference length. How long is the length of the film after the completion of the stretching treatment, for example, the portion of lm in the original film becomes 5 m in the film after all the stretching treatments, and the cumulative stretching ratio at this time is After treatment, ride the water secret. Look for the storage by the name J up to $ hydration and / or hue adjustment by boric acid treatment of polyethylene - water towel, and spray with water as a shower, or use diffuse / The temperature of the water is usually 2 to the machine and the dipping time is 2 to 120 seconds during the washing process. Six: This can also be used in each step after the stretching process to make the thin ^ The tension control is performed in a substantially fixed manner. Specifically, the + t color processing step ends the drawing, and the subsequent shouting step and the washing step step (4). In the dyeing step, the step 320733 11 200925193 When the end of the stretch, in the fast Tension control step in the subsequent steps

Ο Ο ===: The processing step up to the tension control in each step of the water washing step; or the stretching of the film in the acid treatment step from the first to the third stage and the stretching treatment is performed: The acid treatment step is followed by the acid treatment step until the water washing step is performed on the middle of the process, and the film is stretched in the tilting step of the most or the most From the next (four) (four) cis processing (four) to the next boric acid treatment step until the water washing step (four) towel into (four) force control. Further, when the above-described stolen material treatment or zinc treatment is performed after the shouting treatment, the tension control can be performed in these steps. For the nip roller for tension control and the guide roller for controlling the conveyance direction of the film, a rubber pro, a non-recording steel grinding, a rubber roller or the like can be used. In the case of a rubber roller, it is composed of NBR (Nitrile-bUtadieneRubber, etc.), and its hardness is JIS (JaPaneSe Industrial Standard 'Japanese Industrial Standard) measured by the test method of JIS K 6301. Re)c scale is 6〇 to 90°' preferably 70 to 8 degrees, and the surface roughness is a partial top of the rough seam curve of JIS b 〇6〇1 (surface roughness) 5至15。 When the average interval S is expressed, it is 0.1 to 5S, preferably 〇. 5 to 15. The stainless steel polishing roll is made of SUS304, SUS316, etc., and the surface roughness is JIS B 〇6〇1 (surface roughness) from the viewpoint of the uniformity of film thickness 12 320733 200925193. 2 to is preferably expressed as an average interval of 5 in the local peak of the roughness curve. 6g。 The sponge, the hardness of the sponge is measured by the JIS 〇丨 63 〇丨 measured by JIS Shaw C scale of 20 to 60 degrees, preferably 25 to 50 degrees, 1 and the density of 0.4 to 0. 6g /m3, preferably from 0.42 to 57.57 g/cm3, and the surface roughness is from 1 〇 to 30 s, preferably from 1 〇 to 30 s, in terms of the average interval S of the partial peaks of the roughness curve of JIS B 0601 (surface roughness). 15 to 253. _ The tension in each step from the swelling treatment to the water washing treatment may be the same or different. The tension of the tension-controlled film is not particularly limited, and is 150 to 2000 N/m per unit width, preferably in the range of 6 Torr to 1500 N/m as appropriate. When the tension is less than 15 〇N/m, wrinkles and the like are likely to occur in the film. On the other hand, when the tension exceeds 2 〇〇 ON/m, there is a problem that the film is broken due to the breakage of the film and the wear of the bearing. Further, the tension per unit width is calculated from the film width in the vicinity of the entrance of the step and the tension value of the tension detector. Further, when tension control is performed, inevitably, there are cases where stretching and shrinkage occur, and in the present invention, this case is not included in the stretching treatment. At the end of the polarizing film production step, a drying treatment is performed. Although the drying treatment is preferably carried out by gradually changing the tension in a large number of stages, it is usually carried out in 2 to 3 stages due to limitations in equipment and the like. When the second stage is carried out, the tension of the front stage is preferably set from the range of 600 to 1500 N/m, and the tension of the rear stage is preferably set from the range of 250 to 1200 N/m. When the tension becomes too large, the cracking of the film becomes large, and the tension becomes too small, and the occurrence of wrinkles becomes large and unsuitable. Further, it is preferable to set the drying temperature of the front stage from 30 to 9 (the range of TC, and from 5 〇) To 320733 13 200925193 100 C range to set the dry temperature of the latter stage. When the temperature becomes too high, the film breaks more. 'In addition, the optical characteristics are also lowered. When the temperature becomes too low, the streaks become more unsuitable. Drying treatment The time can be set, for example, to 60 to 600 seconds, and the drying time of each stage can be the same or different. When the time is too long, the material is suitable from the aspect of productivity, and the _ too short axis is sufficient and unsuitable. In the manufacturing method of the hairpin (4), the dimensional change rate of the polarizing film obtained in the polarizing film production step is 27% or less. Further, regarding the dimensional change rate of the polarizing film, the test piece is used. The side dimension is parallel to the direction of the stretching axis of the polarizing film, and the initial dimension A in the direction perpendicular to the direction of the stretching axis of the test piece which is the size of the rigid surface i_m (10), and the muscle dry Keep the test piece in a hot environment The size B' of the TD direction after 96 hours is calculated according to the following mathematical formula. Dimensional change rate (%) = (a ~ b) / Ax100 纟 制造 的 的 的 的 纟 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供 供The layer of the ruthenium protective film is laminated on the fine monolithic slab, and the polarizing plate is bonded to the bear of the liquid crystal element with the polarizing film side intervening adhesive to expose the eccentricity in a dry heat environment. In the case of the lower side, the deformation of the image display due to the bulging of the end portion of the polarizing plate can be remarkably observed, and the phenomenon that the adhesive at the end portion of the polarizing plate is detached with the bulging may occur. Again, the 'degree of visual deformation' is the height of the ridge that can be transmitted through the end of the deformation (the difference between the height of the highest top of the end and the ancient level of the main part) and the deformation distance (from the end to the main The straight line distance from the area where the surface is not observed is shown in the section, and the higher the height of the ridge or the longer the deformation distance, the greater the degree of deformation. In the method for producing a polarizing plate of the present invention, the dimensional change ratio of the polarizing film at the time of performing the bonding step is preferably 5% or less, more preferably 1% or less. When the dimensional change rate is 1% or less, deformation of the image display due to the bulging of the end portion of the polarizing plate is hardly observed by visual observation. Further, the dimensional change rate of the polarizing film for the bonding step is generally 〇% or more. ❹ ❹ In order to reduce the dimensional change rate of the polarizing film for performing the bonding step to the above method, for example, at least one selected from the following methods: at a high temperature (preferably to i 〇〇 °) c) a method of drying a polarizing film. A method of drying at a high temperature in a low tension state (preferably 250 to 400 N/m); and a method of increasing a glass transition temperature of a polyvinyl alcohol resin film (for example, ' a method of reducing the amount of the plasticizer contained in the polyvinyl alcohol-based resin film, or a method of copolymerizing a monomer having a glass transition temperature higher than a glass transition temperature of the polyvinyl alcohol-based resin when the homopolymer is formed) A method of reducing the amount of partial light film in a range that does not impair the effect of boric acid bridging (for example, boric acid treatment is carried out in at least two stages, and the concentration of boric acid in the last treatment bath is lower than that of the initial treatment bath; The method and the method for treating the mosquito into the bridge by boric acid (for example, the method of setting the temperature of the Wei treatment to (four) higher, or the method of increasing the stretching ratio of the boric acid treatment bath), etc. In the method for producing a polarizing plate of the present invention, the polarizing film is formed into a polarizing film, and the moisture (4) is not particularly limited, but is preferably in the range of 3 to 14% by weight, more preferably in the range of 3 to 14% by weight. Technology 1〇320733 15 200925193 Within the range of wt%, preferably in the range of 3 to 8 wt%. When the moisture ratio of the polarizing film is less than 3% by weight, the polarizing film becomes brittle and becomes along the stretching direction. When the moisture ratio of the polarizing film exceeds 14% by weight, the polarizing film becomes easily contracted in a dry heat environment, and the moisture ratio of the polarizing film is further improved. For example, it can be calculated from the change in weight before and after holding at a dry heat of 10 ° C. The polarizing film having the moisture ratio within the above-mentioned appropriate range can be controlled, for example, by controlling the drying temperature and drying time of the polarizing film. Thus, a polarizing film can be obtained by applying a uniaxial stretching, a dyeing treatment of a dichroic dye, and a boric acid treatment to a polyvinyl alcohol-based resin film. The thickness of the polarizing film is usually in the range of 5 to 40 #m. 2) Fit step ❹ Afterwards In the bonding step, a transparent protective film is laminated on one surface of the polarizing film obtained in the polarizing film production step, and a transparent protective film is laminated to form a polarizing plate. The transparent protective film may be a conventional transparent film. The film widely used in the field, such as a cycloolefin resin film, vinegar, acid fiber = genus tree, film, polyethylene terephthalate, and polyethylene naphthalate A polyester resin film such as an ester, a polycarbonate tree ruthenium film, a propylene-based resin film, a polypropylene resin film, etc. The grease is a cycloolefin system used for a transparent protective film of a polarizing plate of S Ming. For example, a norbornene, a polycyclic norbornene, a rare monomer, or the like is called a thermoplastic resin which is widely used as a unit of a monomer (which may also be the above-mentioned 1 olefin-based resin). In the present invention, a cycloolefin-based resin, a ring-opening polymer of ruthenium or two or more kinds of cyclic olefins and 320,733

200925193 The ammonia and yk' of the ring-opening copolymer may also be an addition polymer of cyclomethine and chain olefins, compounds and the like. In addition, when a cyclodane hydrocarbon and a chain-like rare olefin are used, and the form of B = 敎 is mentioned, it can be mentioned that ethylene, propyl benzene, m base (four), and the polymer towel can be mentioned. , ^ & Wei Si Dai H material. In this way, gather. The product is composed of _hydrocarbons (preferably 15 to 50 m θ , "5 G Mo, hopper", especially ternary using aromatic compounds of cyclohexane hydrocarbon and chain olefin method rLit vinyl In the case of a copolymer, the unit of the monomer constituting the ring-dilute smoke can be set to a smaller amount as described above. In such a triterpene copolymer, a single unit of a monomer composed of a chain _ is generally 5 The unit of the monomer composed of the aromatic compound having an ethyl fluorenyl group is generally from 5 to 80 mol% to 80 mol%. The cycloolefin resin 'for use in an appropriate commercial product, for example, can be used.

Topas (manufactured by T1 cona), ARTON (manufactured by JSR), ZE〇N〇R (manufactured by Nippon Co., Ltd.), ΖΕ0ΝΕΧ (manufactured by Nippon Co., Ltd.), APEL (manufactured by Mitsui Chemicals Co., Ltd.) Wait. When the cycloolefin-based resin is formed into a film to form a film, a generally known method such as solvent casting or melt extrusion can be used as appropriate. Further, for example, a film of a cycloolefin-based resin which has been previously formed into a film such as Scena (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (manufactured by Sekisui Chemical Co., Ltd.), or a ZE0N0R film (manufactured by PTES) may be used. Commercial products. The cycloolefin resin film may also be subjected to uniaxial stretching or biaxial stretching 320733 17

Ο

200925193 Stretching is usually a staggered phase difference of % thin smoke resin film. The film roll 'continuously proceeds, and is heated in a direction perpendicular to the direction of progress, or the two-side glass is rotated by a heating furnace; the temperature of the second furnace is usually from the glass olefin of the cycloolefin resin to the glass. The range of transfer temperature side generations. The stretching ratio is usually from 1.1 to 6 times, preferably 5 times. When the resin is thin (4), the film tends to adhere to each other and tends to occur (4) (bc) eking. Therefore, the protective film is usually attached as a roll. In addition, the 'cycloalkyne resin film—in general, its surface activity is poor ', so it is more than (4) on the surface of the material, riding plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, and utilization. Processing and other surface treatments. Among them, it is preferable to carry out plasma treatment and battery treatment which are relatively easy to implement. In addition, part or all of the cellulose acetate-based resin cellulose which can be used for the transparent protective film of the polarizing plate of the present invention is an acetate compound, and examples thereof include cellulose triacetate, cellulose diacetate, and propionic acid acetate. Cellulose, etc. For the film of the cellulose ester-based resin, a commercially available product such as Fujitac TD80 (manufactured by Fujifilm Co., Ltd.), Fujitac TD80UF (manufactured by Fujifilm Co., Ltd.), and Fujitac TD80UZ (for Fujifilm) can be suitably used. Kung Fu Film (manufactured by Konica Minolta Opto Co., Ltd.), KC8U2 (manufactured by Konica Minolta Opto Co., Ltd.), KC8UY (manufactured by Konica Minolta Opto Co., Ltd.), and the like. Further, in the polarizing plate of the present invention, a cellulose acetate-based resin film ‘which imparts a phase difference characteristic can be suitably used, and the phase difference is given by this. 18 320733 200925193

The commercially available product of the cellulose acetate-based resin film is WVBZ 438 (manufactured by Shiki Film Co., Ltd.) and KC4FR-1 (Konica Minolta 〇 Dto (m) Pw PL0 " Acid cellulose is also known as acetaminophen or cellulose acetate. It is also possible to apply anti-glare treatment, hard coating treatment, antistatic treatment, anti-reflection to the surface of cellulose acetate-based resin film according to the application. Further, in order to improve the viewing angle characteristics, a liquid crystal layer or the like may be formed. ❹ In addition, the cellulose resin film may be stretched for the purpose of retarding the phase difference. The cellulose-based resin film is usually subjected to a saponification treatment. In the saponification treatment, a method of immersing in an aqueous alkaline solution such as sodium hydroxide or potassium hydroxide can be used. The transparent protective film to be used is preferably a cellulose acetate-based resin film. The polarizing film and the protective film are conventionally formed using a water-based adhesive, and the cellulose acetate-based resin film is transparent. It is preferable that the cellulose acetate-based resin film is generally used as a protective film for a polarizing plate, and there are various additional functions. (It is easy to expand to various applications by forming a surface treatment layer and a coating layer such as a liquid crystal compound.) When the transparent protective film is in a roll state, the films tend to adhere to each other and tend to stick, so at the roll end The concave and convex processing is performed, or a ribon is inserted into the creeping portion, or a protective film is bonded to form a roll. The thickness of the transparent protective film is preferably thin, but if it is too thin, the strength is lowered and the workability is not On the other hand, when it is too thick, it will produce a transparency drop of 19 320733 200925193 and the hardening time required after lamination can be lengthened, etc. Therefore, the appropriate thickness of the transparent protective film is, for example, 5 to 200 &quot m' is preferably from 1 〇 to 15 〇 in m, more preferably from 20 to 100/zm. In the method for producing a polarizing plate of the present invention, the polarizing film and the transparent protective film are separated by The aqueous solvent-based adhesive is used as the aqueous solvent-based adhesive, such as a water-based solvent-based adhesive, an organic solvent-based adhesive, a hot-melt adhesive, or a solvent-free adhesive, and examples thereof include a polyvinyl alcohol-based aqueous solution. The water-based two-component urethane-based latex-type adhesive Ζ 媒 媒 媒 媒 媒 媒 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如A liquid-type θ-based adhesive, an epoxy-based adhesive, etc., may be used as a transparent protective film when the surface of the polarizing film is hydrophilized by a chemical treatment or the like. The use of ❹ is an aqueous solution of polyglycolyl alcohol resin used as an adhesive agent. In the polyvinyl alcohol-based resin used in the process, in addition to the purpose of (4), the modified polyglycol-based polymer such as the modified base of the base may be added to the polyamine. a water-soluble epoxy compound, - the use of the compound or the like as an additive, and the "adhesive" layer is usually not observed in the first layer of the layer. When the cross section is 'factually ^ 320733 20 200925193, the material of the transfer film is bonded and transferred, for example, the adhesive is applied uniformly to the polarizing film and the roll to = and the other film is superposed on the coated surface and utilized. The roller is attached and dried, usually, and then applied at a temperature of rr rc and applied to a range of about 3 ° C. The ruthenium is often in the case of 15 (3) drying step After the polarizing film and the transparent protective film are affixed to the moisture contained in the water-based adhesive, the laminated film is dried. The dry_ is continuously ordered by the drying oven maintained at the appropriate temperature. There is no special flaw in drying. For example, it can be continuously passed through a drying oven while drying. Light board be wound into a roll. ❹

The temperature of the drying oven should be set to (10) it. In the polarizing plate manufactured by the method of the present invention, only the laminated transparent protective film is formed on one surface of the polarizing film, so that the temperature of the drying furnace is excessive. ^, (4) due to the shrinkage of the polarizing film, the temperature of the dry film is less than 3 (rc, there is a tendency to peel off between the polarizing film and the transparent protective film. The temperature of the drying furnace It is preferably 35 ° C or more. The residence time of the laminated film in the drying furnace can be, for example, 1 Torr to 1 Torr, especially from the viewpoint of productivity, preferably 6 Torr to 75 Torr, and Preferably, it is 150 to 600 seconds. After drying, it can be hardened at room temperature or slightly higher temperature, for example, at a temperature of about 2 to 50 C, and the temperature is usually 12 to 600 hours. It is set to be lower than the temperature used for drying. 21 320733 200925193 (4) Other steps of manufacturing polarizing plate The polarizing plate manufactured by the manufacturing method of the present invention as described above is preferably used in the other side of the polarizing film (that is, The surface opposite to the side on which the transparent protective film is laminated) is formed by forming an adhesive layer made of an acrylic resin. The adhesive preferably has a storage of 0.15 to IMPa in a temperature range of 23 to 8 (TC). Elastic modulus (st〇rage elastic m〇dulus), Such

The φ adhesive layer can be formed by using an adhesive such as an acrylic, a rubber, an amine ester, or a silica fluorene adhesive which has been conventionally used for a liquid crystal display device. Further, it is also possible to use an energy-line hardening type or a heat-curing adhesive, and it is preferable to use an adhesive such as transparency, weather resistance, heat resistance, etc., in comparison with the (c) C (four)-based resin base polymer. The vuase acrylic adhesive is not particularly limited, and the base polymer (tetra) acid vinegar, (meth) acrylic acid isooctane II), the second base of the (meth) vinegar (tetra) acid (tetra) acid, or the base polymer A copolymerization system formed by the above-mentioned (meth) sulphuric acid vinegar or the like; in the above-mentioned base polymer, a copolymer of a polar monoterpene (methyldiyl group = ethylene group (: group), an amine) The oil ester or the like has a carboxyl group, _A ▲-曰 methyl methacrylate, and the like, a monomer, an amine group, an epoxy group and the like; and the acrylic adhesive is used in combination with a scorpion. The bridging agent can be exemplified by the compound described in the example: ^^ 320733 22 200925193, and the (tetra) metal salt is formed between the compound and the ruthenium; or, for example, a polyamine compound, and a chiral amine bond is formed between the compound and the secret group. Or, for example, a polyepoxy compound or a polyterpene alcohol compound, and is different from the point of the lean base: an acid vinegar compound, a wall base shape: a guanamine bond agent. As an organic bridge φ, the energy-hardening type _ refers to the type of 胄 which is hardened by the energy line of the (10) line and the electronic line.

=:==Adhesively adhered to the adhered body such as a film, because the I-line hardening type adhesive is particularly effective; Energy line hardening type adhesive - The hardening type adhesive is a main component of a source polymerizable compound. = often ^_ adhesive and energy can also be used as needed to adjust the photopolymerization initiator or optical bridge agent 'in addition' φ in the adhesive composition, in addition to the above, in order to adjust the adhesion of the adhesive $% And the number of bridging agents, the temperature of the sag, etc., can also be used as needed = example == system (four), dyes, pigments, defoamer: inhibition = poly, etc., agent. Further, it may be made to contain;] a particle 2 = a light-scattering adhesive layer. It is better to be as a thinner in the park, and to keep it good: plus long time =: partial vanity 320733 23 200925193 From the point of view of the clever change of wealth, it is expected to be 3 to 25_. The adhesive layer is too (4) the adhesiveness is lowered, and when it is too thick, the adhesiveness is too strong and the like is likely to occur. t The adhesive used in forming the adhesive layer of the present invention, as described above, is preferably a storage elastic modulus of 0.15 to 1 MPa at a temperature of 23 to 8 Gt:. The pressure-sensitive adhesive used in the optical film used in the conventional image device or the device has a storage elastic modulus of at most about 0.1 MPa. In contrast, the ideal storage of the adhesive used in the present invention. The modulus of elasticity is as high as 0.15 to iMPa. In addition, storage flexibility (4) can be measured using the city (four) viscoelasticity measuring device, manufactured by ANALYZER RDA IKREOMETRIC. In the method for producing a polarizing plate of the present invention, by using an adhesive having a storage elastic modulus higher than that of a general adhesive in the above range, the shrinkage of the polarizing film which occurs in a high temperature environment can be suppressed. The dimensional change 'is a polarized plate with good durability. In addition, in the method for producing a polarizing plate of the present invention, the method of forming the adhesive layer on the polarizing film is not particularly limited, and the other component including the above-mentioned base polymer may be contained on the other side of the polarizing film. After the solution is applied and dried to form an adhesive layer, a spacer which is subjected to a demolding treatment such as polyoxazine is laminated, or a layer of a coating agent may be formed. After the spacer is applied, it is transferred to a polarizing film to be laminated. Further, when the adhesive layer is formed on the polarizing film, at least one of the polarizing film and the adhesive layer may be subjected to an adhesion treatment as needed, for example, a corona treatment or the like. Furthermore, the surface of the formed adhesive layer is usually protected by a spacer film which is subjected to a mold release portion 320733 24 200925193, and the spacer film is attached to the liquid crystal element or other optical film. It has been stripped before. The polarizing plate manufactured as described above may be laminated with an optical film having an optical function other than the polarizing plate to the protective film surface or the adhesive agent layer of the polarizing plate. Examples of such an optical film include the following: a liquid crystal compound is applied to the surface of the substrate, and the optically compensated film is subjected to alignment treatment to penetrate a certain polarized light (p〇larizeciLight). And a reflective polarizing film which exhibits erbium and opposite polarized light; a retardation film made of a polycarbonate resin; a retardation film made of a cyclic polyolefin resin; and a concave-convex shape on the surface A film with anti-glare function; a film with a surface anti-reflection function; a reflective film with a reflective function on the surface; and a semi-transparent reflective film with both reflection and penetration functions. A commercially available product of an optical compensation film which is coated with a liquid crystal compound on the surface of a substrate and which is subjected to an alignment treatment may be a film (Fuji Film Co., Ltd.) or an NH film (Nippon Oil Co., Ltd.) ) Manufacturing), NR film (Nippon Oil Co., Ltd.) & etc. Reflecting a certain polarized light to reflect the opposite

For example, DBEF (manufactured by 3M Company, available from Sumitomo 3M (share) in Japan), ApF (manufactured by 3M Company, Sumitomo 3M in Japan) can be cited as a commercial product of a polarized polarizing film. ))). In addition, as a commercial item of a retardation film which consists of a cyclic polyolefin resin, the ART0N film (made by JSR), Escena (made by Sekisui Chemical Co., Ltd.), ZE0N0R film (manufactured by PTES) and so on. In this way, other optical films are placed on the protective film side of the polarizing plate. Usually, the two are laminated with an adhesive. The adhesive at this time can use 320733 25 200925193 as the adhesive described above, but the storage elastic modulus can be used without being high. Further, when another optical film is provided on the side of the adhesive layer of the polarizing plate, the optical film is adhered by the adhesive layer. At this time, it is generally attached to the outer side of the optical film, and an adhesive layer for bonding to the liquid crystal element is provided. The polarizing plate with the adhesive layer manufactured by the manufacturing method of the present invention generally has a form of a large roll material or a sheet material in order to obtain a desired shape and a transmission axis. The polarizing plate is cut by a cutting tool having a sharp blade, that is, a chip cut. Therefore, the polarizing plate sheet obtained by the cutting is in a state in which the polarizing film is exposed to the outside at the outer peripheral end portion. When the polarizing plate sheet in this state is subjected to a long-term test such as a heat shock (heat _shock) test, the polarizing plate used in the above-described manner is used to protect both sides of the polarizing film from a cellulose resin film or the like. In the case of the slab, there is a tendency to cause problems such as peeling and cracking. In order to avoid the problem of 0 _*, the partial field sheet of the present invention is preferably subjected to continuous cutting of the outer peripheral end surface by fly cutting or the like. Hereinafter, the present invention will be further described in detail based on examples, but the present invention is not limited thereto. In the examples, "%" and "parts" indicating the content or the amount used are based on weight unless otherwise specified. <Example 1> (A) Production of polarizing film A polyvinyl alcohol film having an average degree of polymerization of about 99.9 mols (4) and a thickness of 75/zm was used as a dry feed „ 叮5 times, and 320733 26 200925193 Keep it in a tight state, after immersing it in pure water at 60 ° C for 1 minute, at 28 ° (: the ratio of immersion in iodine / potassium iodide / water is 〇 · 1 / The aqueous solution of 5/100 is 6 sec. After that, the aqueous solution of the potassium sulphonate/sand acid/water is immersed at a concentration of 10. 5/7. 5/100 for 300 seconds at 72 ° C. Then 1 ( Pure water cleaning of TC 5 &gt; After a second 'drying at 90 ° C for 180 seconds', a polarizing film for adsorbing the moth in the polyvinyl alcohol is obtained. (B) Preparation of the subsequent agent ❹ In addition, in the water 3 parts of fully saponified polyethylene glycol (manufactured by Kuraray poval 117H 'Kuraray), acetonitrile modified polyvinyl alcohol (Gohsefimer Z-200, manufactured by Sakamoto Chemical Industry Co., Ltd.) 3 Part, chlorinated (nacalai tesque), 18 parts, and glyoxal (nacalai tesque) are dissolved in 1.4 parts to prepare a polyvinyl alcohol resin. C) Production of a polarizing plate A film of G thickness 4 〇 #m composed of saponified cellulose triacetate (KC4UY, manufactured by Konica Minolta Opto Co., Ltd.) is laminated by the above-mentioned adhesive by a nip roll. On one side of the polarizing film obtained before, while maintaining the tension of the laminate at 320 N/m, drying was carried out at 38 ° C for 5 minutes to obtain a polarizing plate. (C0 adhesive layer was formed in butyl acrylate and An adhesive layer prepared by adding an amine acetoacetate oligomer and an isocyanate bridging agent to a copolymer of acrylic acid, and a polyethylene terephthalate film (spacer) subjected to release treatment The release treatment surface 'is a thin plate-like adhesive formed with a thickness of 15 pm, and 27 320733 200925193 forms an adhesive layer. The storage elastic modulus of the adhesive layer is 231 〇.4, and at the time G.22 MPa The thin plate-shaped adhesive is attached to the other side of the polarizing film of the polarizing plate manufactured as described above to form a polarizing plate having an adhesive. The laminated layer of the (相位) retardation film is composed of norbornene. a stretched film of resin, A phase difference film having an in-plane retardation with a wavelength λ of -4 to 140 nm and having a thickness of 扛 (Escena film, Sekisui Chemical Industry Co., Ltd., laminated with a thin plate-like acrylic adhesive, and produced A phase difference film with an adhesive. The storage modulus of the acrylic adhesive is 〇5 MPa' at the time of 80 〇C and 0. 04 MPa at 80 〇C. The adhesive surface of the adhesive-attached polarizing plate manufactured in the above (D) is adhered to the phase difference film surface (the surface on which the adhesive layer is not formed) of the phase-contacting film with the adhesive; An adhesive-attached polarizing plate having a phase difference function. The 10 polarizing plate with the phase difference function and having the adhesion J manufactured by the above (E) is cut into a size of 40 mm x 40 mm, and is bonded to the glass by an adhesive layer provided on the outer side of the phase ginger selection. Assess the sample. <Example 2 to Example 5 and Comparative Example> As shown in Table 1, a calender film was produced by changing the drying temperature and time of the polarizing film, and a polarizing plate with an adhesive layer was produced in the same manner as in Example 1. <Reference Example> The polyethylene glycol film 'has been operated in the same manner as (A) in which the life is performed, except that the drying conditions after the dyeing treatment, the boric acid treatment, and the water washing are changed to 9 (rc for 14 sec.). A polarizing film 320733 28 200925193 obtained by dispersing the adsorptive dispersion in the polyethylene glycol is obtained. The polyvinyl alcohol-based adhesive prepared by the method of the present invention can be used as the user of the embodiment (C). A film having a thickness of 40 #m composed of the saponified cellulose triacetate was attached to both surfaces of the polarizing film by a nip roll. While maintaining the tension of the composition at 32 〇N/m, it is 5 一边. 〇, dried for 5 minutes to obtain a polarizing plate. The single side of the obtained polarizing plate will be the same as that of the user of the embodiment. (The storage modulus of the time is 〇. 〇5Mpa and at 8〇°c, the storage elastic modulus is 〇. 04MPa acrylic adhesive film is bonded to the polarizer with the adhesive layer In the adhesive surface, the storage elastic modulus at 23 〇c, which is the same as that of the user of Example 1 (E), is 0.05 MPa and 8 (the storage elastic modulus at TC is 〇〇4 MPa). The acrylic adhesive layer is laminated on the phase difference film surface (the surface on which the adhesive layer is not formed) of the retardation film of one side, and is formed into a polarizing plate with an adhesive having a phase difference function. 〉 When the polarizing plates are produced in the examples, the comparative examples, and the reference examples, the polarizing film before being bonded to the film made of cellulose triacetate is formed in the direction of the stretching axis of the side of the domain film and the polarizing film. In a parallel manner, a test piece having a size of 10 μm nm x 100 mm was cut out from an initial dimension A in a direction perpendicular to the direction of the stretching axis of the test piece (TD direction), and the test piece was subjected to a dry heat environment of 85 C. Maintain the size B in the up direction after 96 hours The dimensional change rate of the polarizing film was calculated according to the following mathematical formula: Dimensional change rate (%) = (Α_Β) / Αχ 100 Further, each of the examples, the comparative examples, and the reference examples was provided with an adhesive layer of 29 320733 200925193. The polarizing plate was held in a dry heat environment at 85 ° C for 96 hours as a deformation state of the end portion of the polarizing plate, and the deformation distance of the end portion in the TD direction was measured (from the end portion to the horizontal plane with respect to the main portion) The linear distance from the uneven region (匪), the height of the ridge in the end portion of the TD direction (the difference between the height of the highest top of the end portion and the height of the horizontal portion of the main portion) (mm), and the end portion is visually observed. The results are shown in Table 1. 表:. Table 1 ❹ Polarizing film polarizing plate drying conditions Dimensional change rate (%) Deformation distance (mm) Height of bulge (/zm) Deformation Example 1 90°C180 sec 2.68 1.1 3.6 Example 2 90 ° C 180 seconds + 80 ° C 300 seconds 2.31 1.1 2.9 Medium Example 3 90 ° C 180 seconds + 80 ° C 1800 seconds 1.24 1.0 1.9 Small Example 4 90 ° C 180 seconds + 80 ° C 7200 seconds 0.77 0.9 1.1 No example 5 95 °C152 sec 2.50 1.1 3,3 Comparative Example 90°C140 sec 2.76 1.1 3.9 Large Reference Example 90°C140 sec 2.76 0.7 0.5 No 30 320733 200925193 From the results shown in Table 1, as in the comparative example, it can be seen that when the transparent protection is applied When the dimensional change rate of the polarizing film in front of the film exceeds 2.7%, the degree of deformation is large, and the reflected light is skewed by visual observation. Further, as in the reference example, when the transparent protective film is bonded to both sides of the polarizing film, the rate of conversion is large, and the degree of deformation is also small. [Simple description of the diagram] None [Description of main component symbols] ❹No The size of the polarizing film before the bonding changes ❿ 31 320733

Claims (1)

The sizing of the transparent protective film is made up of a polyvinyl alcohol-based resin and the dimensional change rate is 2.7%. One of the following polarizing films. The method for producing a polarizing plate according to the first aspect of the invention, wherein the transparent protective film is a cellulose acetate resin film. 3. The method of producing a polarizing plate according to claim 1 or 2, wherein a ruthenium adhesive layer made of an acrylic resin is formed on the other surface of the polarizing film. 32 320733 200925193 IV. Designated representative map: There is no schema in this case (1) The representative representative figure of this case is: (). (2) A brief description of the symbol of the representative figure: 7 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ❹ This case is not represented by the chemical formula Ο 2 320733