JP2005222076A - Cellulose acylate film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a good adhesion to hydrophilic materials to a cellulose acylate film without conducting a saponification treatment. <P>SOLUTION: The cellulose acylate film 50 is constructed into a multi-layer structure and an average acylation degree of the first layer 51 and fifth layer 55 adhered to the hydrophilic material is adjusted to 0.5 to 2.8. A second layer 52 and a fourth layer 54 include the cellulose acylate of the acylation degree higher than that of the first layer 51 and the fifth layer 55 and has the birefringence lower than that of the first layer 51 and the fifth layer 55. The cellulose acylate is formed by esterifying cellulose by using an acid catalyst and the acid after the esterification is neutralized by a Ca compound. In neutralization, the Ca compound is added thereto in such a manner that the concentration of Ca to the cellulose acylate attains ≤60 ppm. The obtained cellulose acylate film 50 has the excellent adhesion to the hydrophilic material without conducting the saponification treatment. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cellulose acylate film, and particularly to a cellulose acylate film used as a polarizing plate protective film.

  The cellulose acylate film is manufactured by a solution casting method. In this method, after polymer is doped with a solvent, the dope is cast from a casting die to a support and dried to form a film. . Cellulose acylate film is widely used as a support for optical materials because it has transparency, moderate moisture permeability, high mechanical strength, and low dimensional stability dependence on humidity and temperature. It has been.

  And the cellulose acylate film is used also as a protective film of the polarizing plate which comprises a liquid crystal display device. In the polarizing plate, a protective film is bonded to both surfaces of the polarizing film. Generally, the polarizing film is a polyvinyl alcohol (PVA) film, and the protective film is a cellulose acylate film. PVA is a hydrophilic polymer compound, and the surface of the film has excellent hydrophilicity. On the other hand, the surface of the cellulose acylate film is hydrophobic. Therefore, when making both contact | adhere, it is necessary to modify | reform at least any one surface.

  In the modification of the film surface, the cellulose acylate film is usually targeted for modification, and the modification is performed by saponification. As a saponification method, there are mainly a method of applying an alkaline solution to the surface of the film, a method of spraying, a method of immersing the film in an alkaline solution, and the like (for example, see Patent Document 1).

  Cellulose acylate is generally made from wood pulp or cotton linter. For example, in a general production method of cellulose acetate, first, cellulose obtained from wood pulp or cotton linter is treated with acetic acid and acetic anhydride to obtain cellulose triacetate having an acyl group substitution degree of 3. Acetic anhydride acts as an esterifying agent, but sulfuric acid or the like is often used as the reaction catalyst. The obtained cellulose triacetate is saponified and aged by the acetylation catalytic action of the remaining sulfuric acid and the like to control the acyl group substitution degree to obtain the desired cellulose acetate. In this case, excess amounts of various acids used are neutralized by adding Ca or the like.

  The cellulose acylate film contains various compounds for the purpose of promoting plasticization and imparting optical properties (see, for example, Patent Document 2). These compounds are often essential not only for cellulose acylate but also for various films for optical applications in order to improve the quality.

JP 2001-318228 A (page 3-4) JP 2002-192541 A (Page 6-8)

  However, any saponification treatment method as a surface modification of a cellulose acylate film is not continuously incorporated in the solution casting process due to restrictions on equipment. Therefore, in any of the above saponification treatment methods, the saponification treatment step is carried out after film formation. Thus, there is a problem that productivity, cost, and the like are limited by increasing one manufacturing process. Furthermore, the saponification treatment may cause streaks and unevenness in the film, and in this case, the transparency of the film is impaired.

  The cellulose acylate has different hydrophilicity depending on the acyl group substitution degree, that is, the average acyl group substitution degree. This means that if the average acyl group substitution degree is low, the number of hydroxyl groups contained in the same number of moles of cellulose acylate is large, so that the average acyl group substitution degree should be lowered in order to increase hydrophilicity. . However, when the average acyl group substitution degree is lowered, there is a problem that the hygroscopicity and dimensional stability of the film, the peelability from the support, and the like are impaired, and it is said that the film cannot be put into practical use.

  In addition, various compounds added for improving the quality of the film often have poor compatibility with cellulose acylate and the like, and are often deposited on the surface of the film or volatilized in the film forming process. Furthermore, there is a problem that these compounds that have been volatilized and adhered in the process are transferred to a film or dropped to impair quality.

  The present invention has been made in view of the above problems, and imparts adhesiveness with a hydrophilic material without undergoing a saponification step or the like after film formation, and a cellulose acylate film having excellent performance as an optical application; It aims at providing the solution casting method as the manufacturing method.

  In order to solve the above-mentioned problems, in the cellulose acylate film of the present invention, the average acyl group substitution degree is greater than that of the surface layer between a pair of surface layers containing cellulose acylate having an acyl substitution degree of 0.5 to 2.8. Including the cellulose acylate having a high degree of group substitution and an inner layer having a lower birefringence than the surface layer, the cellulose acylate is obtained by an esterification reaction of cellulose using an acid as a reaction catalyst, and after the esterification reaction This acid is characterized in that it is neutralized with a calcium compound having a calcium concentration of 60 ppm or less with respect to cellulose acylate.

  The pair of surface layers and the inner layer preferably contain triphenyl phosphate and biphenyl diphenyl phosphate as plasticizers.

  A cellulose acylate film that adheres well to a hydrophilic material without undergoing a saponification step or the like after film formation and has excellent performance as an optical application can be obtained. Furthermore, this cellulose acylate film can be suitably used as a polarizing plate, an optical compensation film, a liquid crystal display device and the like.

  In the embodiment of the present invention, since acetylation is performed as esterification of cellulose acylate, the acetyl substitution degree is used as the acyl group substitution degree, and the cellulose acylate used is cellulose acetate. However, in the present invention, esterification is not limited to acetylation, and cellulose acylate is not limited to cellulose acetate.

  As described above, the adjustment of the average acetyl substitution degree of cellulose acetate is generally performed by saponification and aging of cellulose triacetate to adjust the substitution degree. Such a conventional method is also applied in the present invention. That is, cellulose triacetate having an acetyl group substitution degree of 3 is obtained by treating cellulose obtained from wood pulp or cotton linter with acetic acid and acetic anhydride. Acetic anhydride acts as an esterifying agent, but sulfuric acid is usually used as the reaction catalyst. Then, the remaining sulfuric acid is neutralized and then ripened by a predetermined known method to obtain a target cellulose acetate having a controlled acyl group substitution degree. The remaining sulfuric acid is neutralized by adding a calcium (Ca) compound or the like. As for the addition amount of Ca used for neutralization, it is preferable that the weight ratio with respect to the said cellulose acylate is 60 ppm or less. However, in this embodiment, several types of cellulose acetates having different degrees of acetyl substitution produced by industrial production are prepared, and the mixing ratio thereof is appropriately set so that the degree of acetyl substitution is 0.5 to 2. It is adjusted to an arbitrary value in the range of 8 or less. Accordingly, there is an advantage that the average acetyl substitution degree can be easily and precisely controlled rather than producing various cellulose acetates having different average acetyl substitution degrees.

  In this embodiment, a cellulose acetate solution or dispersion having a desired average acetyl substitution degree (hereinafter referred to as a dope) is mixed with cellulose acetates having different average acetyl substitution degrees and dissolved in a solvent. Alternatively, it is prepared by dispersing, but is not limited to this preparation method. For example, cellulose acetates having different degrees of average acetyl substitution may be prepared as solutions or dispersions, and the solutions or dispersions may be mixed.

  In this embodiment, the birefringence as good optical characteristics is set to 0 ≦ Re ≦ 5 and 30 ≦ Rth ≦ 40. However, the above-described favorable birefringence value varies depending on the application, and the present invention does not depend on this value, and also applies to the variation of this good optical property value depending on the application. can do.

  FIG. 1 is a cross-sectional view of a cellulose acetate film as an embodiment of the present invention. In the present invention, a film, which has conventionally been a single layer structure, has a laminated structure without increasing the thickness, and the film 10 is made by a solution casting method. Then, the first layer 11, the second layer 12, and the third layer 13 are sequentially formed from the layer that becomes the separation surface from the casting support. As shown in FIG. 1, in the present embodiment, the film 10 is used so that the first layer is in close contact with the hydrophilic material 17. In these three layers, the main component is cellulose acetate and contains additives. In the embodiment of the present invention, plasticizers, fine particles such as silica (SiO2), and acidic compounds are used as additives, but the present invention is not limited to these. Other layers may exist between the first layer 11 and the second layer and between the second layer and the third layer.

  The raw material of the cellulose acetate of the first layer 11 is wood pulp, and the average degree of acetyl substitution is 1.8 or more and 2.8 or less. As additives, silica fine particles 15 and an acidic compound are contained. The cellulose acetate of the second layer 12 is made of wood pulp, and the average degree of acetyl substitution is 2.2 or more and 2.9 or less. Additives in this layer include plasticizers and ultraviolet absorbers. The cellulose acetate of the third layer 13 is also made of wood pulp, and the average degree of acetyl substitution is from 1.8 to 2.2 as in the first layer 11. The additive of the third layer is silica fine particles 15. Moreover, the thickness T10 of the film 10 is 10 μm or more and 300 μm or less.

  As described above, the average acetyl substitution degree of the cellulose acetate of the first layer 11 which is the surface layer is very low, and is also very low as compared with that of the second layer 12. Thus, adhesion to the hydrophilic material 17 such as polyvinyl alcohol can be imparted without saponification treatment. Since the third layer of the film 10 is used for adhering to a hydrophilic material (not shown) different from the hydrophilic material described above, the third layer 13 is also acetylated in the same manner as the first layer in consideration of this. The degree of substitution is set so that the third layer 13 side also has a good adhesion with another hydrophilic material. In addition, when the third layer does not require close contact with a hydrophilic material different from the first layer side, a layer may further exist on the third layer.

  Originally, in order to satisfy the predetermined moisture permeability and optical properties as a film for optical use such as that used for a polarizing plate, the cellulose acylate used in the film preferably has a higher degree of acetyl substitution. As described above, the film 10 has a multilayer structure, the first layer 11 in contact with the hydrophilic material 17 is a thin layer, the cellulose acylate has a low degree of acetyl substitution, and occupies much of the thickness of the film. By setting the layer 12 to a general degree of acetyl substitution, it is possible to obtain a film having suitable adhesive strength with a hydrophilic material while having optical characteristics substantially equivalent to those of a conventional cellulose acylate film. . In this way, regardless of whether the average acetyl substitution degree of the second layer 12 as the inner layer is high or low, the average acetyl substitution degree between the first layer as the surface layer and the third layer as needed is lowered. Is effective in obtaining adhesion to a hydrophilic material. Note that the average acetyl substitution degree of the first layer, which is the lowermost layer, and the third layer, which is the uppermost layer, are not necessarily the same.

  The preferable acetyl substitution degree of the cellulose acylate of the first layer 11 and the third layer 13 which are the surface layers is 0.5 or more and 2.8 or less, more preferably 1.8 or more and 2.2 or less.

  Since the birefringence increases as the acetyl substitution degree decreases, the cellulose acylate having good optical properties can be obtained by combining the first layer having a low acetyl substitution degree with the second layer 12 having a general acetyl substitution degree. A rate film can be obtained. In the present embodiment, the third layer 13 also has a lower acetyl substitution degree than general cellulose acylate as in the first layer. Therefore, by sandwiching the second layer between both layers, the hydrophilic material on both sides is obtained. Good adhesion and good optical properties can be obtained.

  The thickness T11 of the first layer 11 is preferably 1 μm or more and 10 μm or less, the thickness T12 of the second layer 12 is preferably 20 μm or more and 100 μm or less, and the thickness T13 of the third layer 13 is preferably 1 μm or more and 10 μm or less. As described above, as long as the adhesion to the hydrophilic material 17 such as polyvinyl alcohol is improved, the thicknesses T11 and T13 of the first layer 11 and the third layer 13 may be small and need to be the same. Absent. However, the present invention is not limited to the above range of thickness of each layer.

  By making the degree of acetyl substitution as low as the above range, the contact angle of the first layer 11 with respect to water is set to 60 ° or less. The magnitude of the contact angle with water is an index for measuring the affinity with water. If the contact angle is larger than 60 °, the adhesion with the hydrophilic material 17 is practically insufficient. The contact angle is more preferably 20 ° to 57 °, and most preferably 20 ° to 50 °. Therefore, the degree of acetyl substitution on the surface layer should be controlled so as to achieve a contact angle in the above range. When esterifying other cellulose acylates, the relationship between the contact angle and the degree of acyl group substitution is obtained in advance. Further, it is preferable to use a surface layer in which the degree of acyl group substitution is controlled based on the data.

  In addition, since the cellulose acylate film has a higher birefringence as the acyl group substitution degree is lower, the degree of acetyl substitution between the first layer 11 and the third layer 13 is lower than that of the second layer 12. As a result, good optical characteristics can be expressed.

  Furthermore, since the first layer 11 is a release surface from the support for dope casting as will be described in detail later, the first layer 11 has an acid dissociation constant pKa (= −−) in an aqueous solution at 25 ° C. logKa) is preferably contained in the first layer 11 at the time of peeling, containing an acidic compound of 2.0 or more and 4.5 or less. This is because, when the adhesion of the first layer 11 to the hydrophilic material 17 is improved, the adhesion with the cast support is also increased, so that the peeling load at the time of peeling becomes large. It is. Even when the acidic compound is contained, the first layer 11 maintains sufficient adhesion to the hydrophilic material 17, and the present invention is effective.

  As the acidic compound to be added to the first layer 11, those having an acid dissociation constant pKa in an aqueous solution at 25 ° C. of 2.0 or more and 4.5 or less are more preferred, and those having a acid dissociation constant of 2.0 or more and 3.0 or less are most preferred. The acidic compound may be a salt. Examples of the acidic compound having an acid dissociation constant pKa of 2.0 or more and 4.5 or less are effective in that, for example, acetic acid, lactic acid, tartaric acid, citric acid, citrate ester, etc. are industrially easy to use. May be used alone or in combination.

  In the cellulose acylate film of the present invention, ethyl citrate half ester as an acidic compound is added only to the first layer 11. The acidic compound is added for the purpose of improving the peelability from the support. By improving the hydrophilicity of the first layer in close contact with the support, the adhesion between the film and the support also increases and the peel load increases, but the film is supported by adding an acidic compound. As a result, the film can be peeled stably from the body, and as a result, the film formation can be stably continued. Therefore, the acidic compound as described above may be contained in the contact surface with the support of the first layer 11 at the time of peeling. Therefore, it is not necessary to stay on the first layer 11 after peeling, or to be scattered throughout the inside of the first layer 11. However, since it is impossible to easily control the position of the first layer 11 so that it is present only on the contact surface of the first layer 11 with the support, in the present embodiment, the entire first layer 11 is entirely contained. It is included. As described above, in this embodiment, the adhesion to the hydrophilic material is improved by controlling the degree of acetyl substitution, and the peelability from the support is controlled by adding an acidic compound. In addition, since addition of an acidic compound does not contribute to the improvement of adhesiveness with a hydrophilic material, the improvement of adhesiveness with the hydrophilic material in the present invention depends on the degree of acetyl substitution.

  In order to improve the peelability from the support, there are methods such as replacing the hydroxyl group of cellulose acylate with other substituents, but in terms of adhesion with the hydrophilic material that is the object of the present invention, It is preferable to leave the hydroxyl group. Therefore, in the present invention, it is preferable to add an acidic compound. However, since the film 10 is likely to be deteriorated as the addition amount increases, the object to be added is limited to the first layer 11, that is, the layer cast and formed in contact with the support as in this embodiment. It is preferable that the amount of addition be the same as that of ions of alkali metal or alkaline earth metal contained in the dope forming the first layer 11. In addition, even if an acidic compound is added to the first layer, the adhesion to the hydrophilic material 17 is not substantially impaired.

  Here, ethyl citric acid half ester means an average acyl group substitution degree of 50% with respect to the presence of only acetyl triethyl citrate esterified by substituting all the hydroxyl groups of the carboxyl group of citric acid with ethoxy groups. Means an ethyl ester mixture of citric acid.

  Moreover, a volatile compound can be contained only in the inner layer by multilayering the cellulose acylate film. Here, the volatile compound is a compound that does not stay in the contained layer but moves out of the layer, and is substantially low in molecular weight, for example, a sublimable substance that becomes a gas from a solid or liquid, Vaporizable substances. In the present embodiment, a plasticizer as a volatile compound is added only to the second layer 12 that is the inner layer, and is not added to the first layer 11 and the third layer 13 that are the outermost layers. Thereby, in the film forming process, the speed and frequency at which the plasticizer diffuses and moves to the surface of the film can be reduced, the volatilization phenomenon can be suppressed, and process contamination can be prevented.

  In general, fine particles such as silica are often added in order to improve the slipperiness as a film, but in this embodiment, both surface layer portions are not added to the second layer 12 as the inner layer. The fine particles 15 are added only to the first layer 11 and the third layer 13. If such a fine particle component is too much, the light transmittance of the film 10 is remarkably impaired. Therefore, it is desirable that the amount added is as small as possible. In this embodiment, it is effective in that the addition distribution can be controlled by adopting a multilayer structure as a conventional single layer, and while maintaining the slipperiness of the conventional film surface, The total amount of fine particles added can be reduced to prevent a decrease in the transmittance of the film, and the manufacturing cost can be reduced. Here, SiO2 is used as the additive fine particles for the purpose of imparting slipperiness, but the present invention is not limited to this.

  FIG. 2 is a cross-sectional view showing the main part of the film forming process embodying the present invention. The casting die 21 is a multi-manifold system, and here, the three layers shown in FIG. 1 can be formed simultaneously. When the dopes forming the first layer 11, the second layer 12, and the third layer 13 in FIG. 1 are respectively denoted by reference numerals 22, 23, and 24, they are respectively casted from a dope supplier that is not shown. 21 is supplied. On the back surface of the casting die 21, supply ports 26, 27, and 28 for the dopes 22, 23, and 24 are provided, and the three types of dopes 22, 23, and 24 are respectively inserted into the slots 30, 31, and 32. It temporarily stays in the provided pockets 33, 34, and 35 and is cast from the tip lip 37 to a band 38 as a support. The slots 30, 31, and 32 are merged in the vicinity of the tip lip, and the three types of dopes are layered and cast simultaneously. This method is generally called a co-casting method. Further, the support here is not limited to the band 38 but may be a drum.

  Further, in the film forming process, the extrusion pressures of the respective dopes 22, 23, 24 can be controlled independently. Thereby, the film thickness of each layer can be adjusted arbitrarily. Control of the film thickness of each layer may be performed by appropriately setting the slot diameter at the confluence of the three types of dope flow paths, or using this method and a method by adjusting the dope extrusion pressure.

  In the casting die, the positions of the dope supply ports 26, 27, 28, the shapes of the slots 30, 31, 32, the shapes of the pockets 33, 34, 35, the structure of the slot joining portion in the tip lip 27, etc. However, the present invention is not limited to this, and a general multi-manifold type casting die capable of co-casting may be used. Although not shown, in the case of a multi-manifold type casting die capable of simultaneously forming N layers (N represents a natural number of 2 or more), it has N dope flow paths. The configuration is the same as described above.

  FIG. 3 is a schematic view showing a cross section of a casting die according to another embodiment. The casting die 41 is a feed block system having a single slot. Here, as in the case of using the multi-manifold type casting die of FIG. 2, the three-layer multilayer film of cellulose acetate shown in FIG. 1 can be formed simultaneously. One feed block 42 is installed on the back surface of the casting die 41, and the feed block 42 has dope supply ports 42a, 42b, and 42c. Although not shown, the dopes 22 to 24 forming the first layer 11, the second layer 12, and the third layer 13 of FIG. 1 are supplied from the supply ports 42a to 42c. Inside the feed block 42, slots continuing from the supply ports 42 a, 42 b, and 42 c are merged, and the dopes 22, 23, and 24 are merged to form a layer and sent to the inside of the casting die 41. Then, it passes through a single slot 43 and is simultaneously cast from the tip lip 44 to a drum 45 as a support. Further, the support here is not limited to the drum 45 but may be a band 38 (see FIG. 2).

  Furthermore, in the present invention, a co-casting method combining the multi-manifold method of FIG. 2 and the feed block method of FIG. 3 may be used. Even in this case, either the band 38 (see FIG. 2) or the drum 45 (see FIG. 3) may be used as the support.

  The casting can be performed not by the above co-casting method but also by the sequential casting method. When the N layer is formed by sequential casting, casting can be performed at any casting number NC satisfying 2 ≦ NC ≦ N, where NC is a casting number (NC is a natural number of 2 or more). . Obviously, when NC <N, it is necessary to perform co-casting in at least one casting step. Moreover, it is preferable to use a support as a band in the successive casting.

  As the solvent used for the dopes 22, 23, 24, in addition to halogenated organic compounds such as dichloromethane and dichloromethylene, alcohols such as methyl alcohol, ethyl alcohol and n-butyl alcohol, and various esters such as methyl acetate and ethyl acetate. A non-chlorine organic compound such as an organic compound or acetone can be used. For this reason, this embodiment can be said to be a solution casting method in consideration of the environment.

  FIG. 4 is a cross-sectional view of a cellulose acetate film 50 as another embodiment. As in the case of FIG. 1, the film structure which has conventionally been a single layer structure is a laminated structure, and FIG. 4 shows a case where the number of layers is five, in order from the peeling surface side from the support. The first layer 51, the second layer 52, the third layer 53, the fourth layer 54, and the fifth layer 55, but other layers may exist between the layers or on the fifth layer. Each raw material is either wood pulp or cotton linter. However, in the present embodiment, at least one of the multilayers may be a mixture of wood pulp and cotton linter. Here, the thickness T50 of the film 50 is not less than 10 μm and not more than 300 μm. In the present embodiment, the following description will be given assuming that both the first layer 51 and the fifth layer 55 are layers that are in close contact with the hydrophilic material, but the illustration of the hydrophilic material is omitted.

  The raw material of the cellulose acetate of the first layer 51 is cotton linter, and the average degree of acetyl substitution is 1.8 or more and 2.2 or less. As additives, silica fine particles 57 and an acidic compound are contained. The cellulose acetate of the second layer 52 and the fourth layer 54 is made of wood pulp, and the average degree of acetyl substitution is 2.2 or more and 2.9 or less. The cellulose acetate of the third layer 53 is also made of wood pulp, and the average degree of acetyl substitution is 1.8 to 2.2. The additives of the second to fourth layers 52 to 54 are a plasticizer and an ultraviolet absorber. Further, the fifth layer is made of wood pulp, and the average degree of acetyl substitution is 1.8 or more and 2.2 or less. The thickness T50 of the film 50 is set to 10 μm or more and 300 μm or less.

  The degree of acetyl substitution of the cellulose acetate of the first layer 51 that is the surface layer is very low, and is also very low compared to that of the second to fourth layers 52 to 54, thereby, for the film 50, Adhesion with a hydrophilic material such as polyvinyl alcohol is imparted without saponification treatment. In addition, in the use which makes the 5th layer 55 also adhere | attach with a hydrophilic material, although it is good to provide favorable adhesiveness with a hydrophilic material as an acetyl substitution degree similar to the 1st layer 51 like a present Example, What is necessary is just to determine the acetyl substitution degree of the 5th layer 55 according to a use. Also in this embodiment, the acetyl substitution degree of the first layer 51 as the lowermost layer and the fifth layer 55 as the uppermost layer are not necessarily the same.

  By the way, the lower the acyl group substitution degree including the acetyl substitution degree, the higher the optical anisotropy. Therefore, a predetermined birefringence can be expressed by combining a layer with a low acyl group substitution degree and a layer with a higher acyl group substitution degree. For example, the first layer 51, the fifth layer 55, and the third layer 53 have an average acyl group substitution degree lower than that of the second and fourth layers 52 and 54. Thus, by combining a layer having a low acyl group substitution degree with a layer having a higher acyl group substitution degree, and further sandwiching a layer having a higher acyl group substitution degree between the lower layers, the hydrophilic material Adhesiveness can be imparted and optical properties as a film can be improved. Here, the optical characteristic contributes to the viewing angle characteristic which is an important property for a liquid crystal display device or the like, and means the birefringence described above.

  Furthermore, by using cellulose acetate derived from cotton linter for the first layer 51, the optical properties and the peelability from the support are improved. Cellulose acetate derived from cotton linter and wood pulp have different properties such as optical properties, and it is effective to select them appropriately according to the purpose. In particular, the peelability from the support is remarkably superior to that derived from wood pulp, and can be peeled off with a small peel load. In addition, the releasability is further stabilized by adding ethyl citrate half ester as an acidic compound. Also in the present embodiment, the slipperiness is imparted to the film 50 by adding the silica fine particles 56 to the first layer 51 and the fifth layer 55 which are the outermost layers. It is not necessary to add the fine particles 56 to the fourth layer 54.

  As described above, it is preferable that at least one layer is derived from cotton linter, or the main component is derived from cotton linter, but since the cost derived from cotton linter is high, other layers are made of wood. It is preferable that it is derived from pulp. Therefore, in the case of a multilayer structure, it is preferable that at least the layer on the release surface from the support is derived from cotton linter and at least another layer is derived from wood pulp.

  Moreover, regarding each of the first to fifth layers 51 to 52, the raw material is not limited to only cotton linter or wood pulp, but may be replaced with a mixture of both. That is, in consideration of the necessity of highly accurate control over film properties such as optical properties and peelability from the support, product costs, and the like, it is also effective to form a layer by appropriately mixing the two. For example, regarding the layer on the release surface from the support, a mixture of both may be used as long as a predetermined peelability can be obtained from the support. Here, the mixing ratio of both is determined by the film forming speed and the solvent content at the time of peeling from the support. In addition, for the purpose of precisely controlling the properties as a film, it may be effective to provide at least one mixed layer of different materials, and it is more preferable to provide multiple layers.

  Also in this embodiment, the plasticizer is added only to the second to fourth layers 52 to 54 that are the inner layers, and is not added to the first layer 51 and the fifth layer 55 that are the outermost layers. Thereby, the volatilization phenomenon is suppressed and process contamination is prevented. However, when the number of layers is four or more as in the present embodiment, the layer to which no volatile compound such as a plasticizer is added is not limited to the outermost layer, and at least the outermost layer is not added. State.

  In the present embodiment, the first layer 51 and the fifth layer 55 that are the outermost layers are preferably thin layers. This is because if the layer containing no plasticizer or the like is too thick, the mechanical strength such as the tensile strength and bending strength of the film is lowered. In addition, if the cellulose acetate layer with an extremely low degree of acetyl substitution becomes thick, the stability of the film properties is impaired due to an increase in hygroscopicity and water absorption, resulting in problems such as curling and other shape changes. To do. The thickness of the outermost layer is 1 μm or more and 50 μm or less, and more preferably 1 μm or more and 10 μm or less.

  FIG. 5 is a cross-sectional view showing the main part of the casting die 61 used in the solution casting method for the cellulose acetate film 50 having the five-layer structure shown in FIG. Here, the casting die 61 is a feed block system having a single slot, and can form five layers simultaneously. Two feed blocks 62 and 63 are installed on the back surface of the casting die 61, and the feed blocks 62 and 63 have dope supply ports 62a, 62b and 63a to 63c. The dopes (not shown) forming the first layer 51 to the fifth layer 55 in FIG. 4 are supplied from the supply ports 62a, 62b, 63a to 63c, respectively. Inside the feed block 63, slots continuing from the supply ports 63a to 63c merge, and further, inside the feed block 62, dope from the feed block 63 and dope from the supply ports 62a and 62b form five layers. The five types of dopes that have joined together are simultaneously cast from a tip lip 66 to a drum 67 as a support through a single slot 65. Further, the support here is not limited to the drum 67 but may be a band 38 (see FIG. 2).

  As the cellulose acylate in the present invention, cellulose acetate is most preferable, but various other cellulose acylates may be used. Further, these can be applied to the present invention even if each of them is used alone or in combination. Furthermore, even polymers other than cellulose acylate can be applied to the present invention as long as the molecular structure can control the acyl substitution degree of the hydroxyl group, and have optical anisotropy. In particular, it is particularly effective when the solution can be formed into a film.

  The present invention is not limited to the multilayer film of 5 layers or less as shown in FIGS. 1 and 4, and is particularly effective when it is 20 layers or less. More preferably, they are 3 layers or more and 15 layers or less, Most preferably, they are 3 layers or more and 10 layers or less. Further, this is preferably applied when the thickness of the cellulose acylate film having a multilayer structure is 10 μm or more and 300 μm or less. However, the thickness and thickness ratio of each layer are not limited. Further, when a multilayer structure of three or more layers is used, the target structure does not have to be the center of the multilayer structure, that is, the front and back.

  Further, in the present invention, when a single-layer cellulose acylate film has a multilayer structure, the entire layer does not have to be cellulose acylate. However, in that case, other materials are selected so as not to impair the properties of the cellulose acylate film as an optical application. Moreover, when this cellulose acylate film is laminated with another film to form a laminate, the cellulose acylate film may be located on the surface side of the laminate from which the cellulose acylate is obtained, or may constitute the inside. In addition, when the cellulose acylate is used as the inside, what is configured on both sides of the cellulose acylate may be a single layer or a laminate that is mutually targeted with respect to the cellulose acylate that is inside, or a non-target single layer or a laminate. It may be.

  Furthermore, even if two consecutive layers are composed of cellulose acylate having the same degree of acetyl substitution, the type and composition ratio of the dope solvent forming each layer, the presence or absence of the additive, the type, and the amount added If there is a difference, these are considered as two different layers.

  When laminating the obtained film with a hydrophilic material or other materials, both can be bonded by a known bonding method. For example, the obtained film may be pressure-bonded to a hydrophilic material, adhered using an adhesive, or a cellulose acylate solution may be applied thereon using the hydrophilic material as a support. When laminating with a hydrophilic material by coating, a cellulose acylate layer having a single-layer structure is conventionally applied on a support made of a hydrophilic material by coating. The present invention is applied to the rate. In the case of coating, various multilayer coating dies such as a known multi-manifold type or feed block type similar to the casting die in the above embodiment can be used as the coating die. In addition, in the case of using an adhesive, for example, the adhesive used in bonding with PVA which is a polarizing film of a polarizing plate is often a hydrophilic material itself, and by using the film of the present invention, A polarizing plate with improved adhesion between the adhesive and the film can be obtained. In addition, when PVA is used as a polarizing film, it is common to use PVA aqueous solution as an adhesive agent. Thus, the hydrophilic material in the present invention is not necessarily limited to a film, a sheet, a plate and the like, but includes an adhesive and the like.

  A polarizing plate, an optical compensation film, and a liquid crystal display device can be produced using the film produced by the above solution casting method. Furthermore, this film can also be used as a photographic light-sensitive material. The polarizing plate of this embodiment is a protective film on the cellulose acetate films 10, 40, and 50 produced by the solution casting method of each of the above embodiments on both sides of a polarizing film made of a polyvinyl alcohol (PVA) film. Can be obtained by pasting together. The polarizing film is obtained by dyeing a polyvinyl alcohol film, and as this dyeing method, a gas phase adsorption method and a liquid phase adsorption method are generally used, and both can be applied. Dyeing was performed by liquid phase adsorption.

  For dyeing by liquid phase adsorption, iodine is used here, but the present invention is not limited to this. The polyvinyl alcohol film was immersed in an iodine / potassium iodide (KI) aqueous solution with an immersion time of 30 seconds to 5000 seconds. The aqueous solution at this time preferably has an iodine concentration of 0.1 g / liter to 20 g / liter and a potassium iodide concentration of 1 g / liter to 100 g / liter. Moreover, it is preferable that the temperature of the aqueous solution at the time of immersion is set to the range of 5 degreeC or more and 50 degrees C or less.

  The liquid phase adsorption method is not limited to the above immersion method, and a known method such as a method of applying iodine or other dye solution to a polyvinyl alcohol film or a method of spraying may be applied. Dyeing may be performed before or after the polyvinyl alcohol film is stretched, but the polyvinyl alcohol film is appropriately swelled and easily stretched by being dyed, so that the stretching step It is particularly preferable to provide a dyeing step before the step.

  It is also preferable to dye with a dichroic dye instead of iodine. Examples of dichroic dyes include dye compounds such as azo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes, anthraquinone dyes. it can. Water-soluble dye compounds are most preferable. Further, it is preferable that a hydrophilic functional group such as a sulfonic acid group, an amino group, or a hydroxyl group is introduced into the molecule of these dichroic dyes.

  In the production process of a polarizing film by stretching a dyed polyvinyl alcohol film, a compound that crosslinks polyvinyl alcohol is used. Specifically, a polyvinyl alcohol film is immersed in a crosslinking agent solution in the pre-stretching step or the stretching step to contain a crosslinking agent. It may be applied instead of dipping. The polyvinyl alcohol film is sufficiently hardened by the inclusion of the crosslinking agent, and as a result, appropriate orientation is imparted. In addition, as a crosslinking agent of polyvinyl alcohol, boric acids are most preferable, but are not limited thereto.

  For the adhesive between the obtained polarizing film and the cellulose acetate film, various known adhesives that can be used for bonding the polarizing film and the protective film are used. Among these, an aqueous solution of a polyvinyl alcohol polymer or a boron compound containing a modified polyvinyl alcohol having an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group or the like is preferable. This adhesive is preferably applied so that the thickness after drying is 0.01 μm or more and 10 μm or less, and more preferably 0.05 μm or more and 5 μm or less. Furthermore, an antireflection layer, an antiglare layer, a slippage imparting layer, an easy adhesion layer, and the like can be imparted to the surface of the cellulose acetate film layer imparted to the polyvinyl alcohol layer as a protective film.

  Furthermore, an optical compensation sheet can be stuck on the obtained cellulose acetate film and used as an optical compensation film. An antireflection film provided with an antireflection layer on the polarizing plate is obtained, and this is used as one side of the surface protective film, and twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), impression A transmissive, reflective, or transflective liquid crystal display device in a mode such as in-switching (IPS) or optically compensated bend cell (OCB) is obtained. Further, an optical compensation film such as a viewing angle widening film for improving the viewing angle of the liquid crystal display device, a retardation plate, and the like can be used in combination. When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separating film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). In addition, a display device with higher visibility can be obtained.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to this.

[Experiment 1]
A cellulose acetate film 10 having a three-layer structure was prepared, and the adhesion with polyvinyl alcohol was evaluated. The film 10 was produced by co-casting using a feed block method such that the first layer 11 had a thickness of 18 μm, the second layer had a thickness of 4 μm, the third layer had a thickness of 18 μm, and the total thickness T10 was 40 μm. A band 38 was used as a support. Cellulose acetate of each layer has the first layer 11 and the third layer 13 made of wood pulp raw materials and the average acetyl substitution degree is 2.8, and the second layer 12 is also made of wood pulp raw materials and average acetyl substitution degree. Is 1.8. Additives added to each layer are as follows, and the dopes 22, 23 and 24 forming each layer are solvents in which the mixed volume ratio of dichloromethane, methyl alcohol, and n-butyl alcohol is 85; 12; 3. The mixing ratio of the solid components in each layer is shown below. As a plasticizer, a mixture of triphenyl phosphate (TPP) and biphenyl diphenyl phosphate (BDP) in a weight ratio of 3: 1 is used. The surface of the first layer was saponified and this surface was bonded to polyvinyl alcohol. Adhesion with polyvinyl alcohol was performed by adjusting and applying an aqueous solution of modified polyvinyl alcohol.

(First layer)
Cellulose acetate 19 parts by weight Silica fine particles 0.13 parts by weight Citric acid 300 ppm (vs. cellulose acetate)
(Second layer)
Cellulose acetate 19 parts by weight Plasticizer 16 parts by weight UV absorber 2 parts by weight (third layer)
Cellulose acetate 19 parts by weight Silica fine particles 0.13 parts by weight

  The adhesion between the obtained cellulose acetate and polyvinyl alcohol was evaluated by visually observing peeling of the cellulose acetate film from polyvinyl alcohol after immersing it in warm water at 60 ° C. for 10 hours. In addition, the evaluation method of dimensional stability is a method in which a cellulose acetate film is placed in an atmosphere of 90 ° C., and a change in dimensionality after 120 hours is measured. This was done by measuring.

  As a result of this experiment 1, the obtained cellulose acetate film has a birefringence Rth of 40 nm, which is very preferable for optical use. The laminated polymer film with polyvinyl alcohol has adhesion, dimensional stability, support The peelability from each was good.

[Experiment 2]
A cellulose acetate film 50 having a five-layer structure as shown in FIG. 4 was prepared and evaluated for adhesion to polyvinyl alcohol. The film 50 was prepared such that the first layer 51 and the fifth layer 55 had a thickness of 3 μm, the second layer 52 and the fourth layer 54 had a thickness of 15 μm, and the third layer 53 had a thickness of 4 μm. In each layer of cellulose acetate, the second to fifth layers 52 to 54 are made of wood pulp raw material, and only the first layer 51 is made of cotton linter raw material. The degree of acetyl substitution is 1.8 for the first layer 51 and the fifth layer 55, 2.8 for the second layer 52 and the fourth layer 54, and 2.7 for the third layer 53. The blending ratio of the solid components in each layer and the added additive were as follows, and the surface of the first layer 51 was bonded to polyvinyl alcohol without saponification treatment. Other conditions such as the types of plasticizers and fine particles and evaluation methods were the same as in Experiment 1.

(First layer)
Cellulose acetate 19 parts by weight Silica fine particles 0.13 parts by weight Citric acid 300 ppm (vs. cellulose acetate)
(Second layer)
Cellulose acetate 19 parts by weight Plasticizer 16 parts by weight UV absorber 2 parts by weight (third layer)
Cellulose acetate 19 parts by weight Plasticizer 16 parts by weight UV absorber 2 parts by weight (4th layer)
Cellulose acetate 19 parts by weight Plasticizer 16 parts by weight UV absorber 2 parts by weight (5th layer)
Cellulose acetate 19 parts by weight Silica fine particles 0.13 parts by weight

  As a result of this experiment 2, the birefringence Rth of the obtained cellulose acetate film is 40 nm, which is very preferable for optical use, and the laminated film with the polyvinyl alcohol film has its adhesion and dimensional stability, The peelability from the support was very good.

[Comparative Experiment 1]
A cellulose acetate having an average acyl group substitution degree of 2.8 was used as a film having a single-layer structure having a thickness of 40 μm. The raw material for cellulose acetate is wood pulp. The blending ratio of the solid component of the dope is as follows. The other conditions including various evaluation methods such as the type of solvent and adhesion were the same as in Experiment 1. In addition, the saponification process was made into the peeling surface side from a support body.
Cellulose acetate 19 parts by weight Silica fine particles 0.13 parts by weight Plasticizer 16 parts by weight UV absorber 2 parts by weight

  As a result of this comparative experiment, the laminated film obtained with the polyvinyl alcohol film had good adhesion, dimensional stability, and peelability from the support, but the birefringence index Rth was 24 nm. Therefore, it is not preferable as an optical application in the present embodiment.

[Comparison experiment 2]
Cellulose acetate having an average acyl group substitution degree of 2.7 was used as a film having a single-layer structure of 40 μm thickness. The raw material for cellulose acetate is wood pulp. The blending ratio of the solid component of the dope is as follows. The other conditions including various evaluation methods such as the type of solvent and adhesion were the same as in Experiment 1. In addition, the saponification process was made into the peeling surface side from a support body.
Cellulose acetate 19 parts by weight Silica fine particles 0.13 parts by weight Plasticizer 16 parts by weight UV absorber 2 parts by weight

  As a result of this comparative experiment, the birefringence Rth of the obtained cellulose acetate film is 39 nm, which is preferable for optical applications, and the laminated film with the polyvinyl alcohol film has good adhesion and dimensional stability. The peelability from the support was not good.

  An aqueous solution having an iodine concentration of 0.3 g / liter and potassium iodide of 18.0 g / liter was set at 25 ° C., and a polyvinyl alcohol film (thickness, Kuraray Co., Ltd.) having a film thickness of 75 μm was immersed in the aqueous solution. did. Furthermore, this film was stretched 5.0 times in an aqueous solution at 50 ° C. with a boric acid concentration of 80 g / liter and a potassium iodide concentration of 30 g / liter to obtain a polarizing film. The cellulose acetate film obtained in Experiment 2 was laminated on the polarizing film using an adhesive. A 4% aqueous solution of polyvinyl alcohol (trade name; PVA-117H, manufactured by Kuraray Co., Ltd.) was used as the adhesive. This was dried in an air constant temperature bath at 80 ° C. for about 30 minutes to obtain a polarizing plate.

With the spectrophotometer, the parallel transmittance Yp and the orthogonal transmittance Yc in the visible region were determined for the obtained polarizing plate, and the polarization degree PY was determined based on the following equation.
PY = {(Yp−Yc) / (Yp + Yc)} ^1/2 × 100 (%)

  As a result of this example, the degree of polarization PY is 99.6% or more in any of the polarizing plates constructed using the film produced from Experiment 2, and the film of the present invention is preferably used for the polarizing plate. You can see that

  The viewing-side polarizing plate of the liquid crystal display device of the notebook computer on which the transmissive TN liquid crystal display device was mounted was replaced with the polarizing plate produced in Example 2. In addition, this liquid crystal display device has a polarized light separation film (trade name; D-BEF, manufactured by Sumitomo 3M Co., Ltd.) having a polarization selection layer between the backlight and the liquid crystal cell.

  As a result of this example, the obtained liquid crystal display device had very little display of the background and a very high display quality. This shows that the film of this invention is suitable as a liquid crystal display device.

It is sectional drawing of the cellulose acetate film which is embodiment of this invention. It is sectional drawing which shows the principal part of the casting die of a multi-manifold system. It is sectional drawing which shows the principal part of the casting die of the feed block system which is another embodiment. It is sectional drawing of the cellulose acetate film which is another embodiment. It is sectional drawing of the casting die which is another embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Film 11 1st layer 12 2nd layer 13 3rd layer 15 Fine particle 17 Hydrophilic material 21 Casting die 38 Band 41 Casting die 42 Casting die 45 Drum 50 Film 51 First layer 52 Second layer 53 Third layer 54 Fourth layer 55 Fifth layer 56 Fine particles 61 Casting die 67 Band

Claims (2)

Between the pair of surface layers containing a cellulose acylate having an average acyl group substitution degree of 0.5 or more and 2.8 or less, the cellulose acylate having an average acyl group substitution degree higher than that of the surface layer is included and more than the surface layer. With an inner layer with a low refractive index,
The cellulose acylate is obtained by an esterification reaction of cellulose using an acid as a reaction catalyst,
The multilayer cellulose acylate film, wherein the acid after the esterification reaction is neutralized with a calcium compound having a calcium concentration of 60 ppm or less with respect to the cellulose acylate. 2. The multilayer cellulose acylate film according to claim 1, wherein the pair of surface layers and the inner layer include triphenyl phosphate and biphenyl diphenyl phosphate as plasticizers.

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