WO2010023707A1 - Cellulose ester and process for producing the same - Google Patents

Abstract

A cellulose derivative that even in the use as the base material film of a viewing angle enlarging film with a discotic liquid crystal layer, would inhibit any occurrence of crater defects in the discotic liquid crystal layer. The cellulose derivative is obtained from a pulp of 20 ppm or less calcium content. The pulp may be derived from wood. The calcium content of the pulp may be in the range of about 0.01 to 15 ppm. The cellulose derivative may consist of a cellulose ester containing at least an acetyl. The calcium content of the cellulose derivative may be 120 ppm or less. This cellulose derivative is suitable for use as the base material film of a viewing angle enlarging film with a discotic liquid crystal layer.

Description

Cellulose ester and method for producing the same

The present invention relates to a cellulose ester useful for forming a base film of a viewing angle widening film of a liquid crystal display device and a method for producing the same.

Cellulose esters such as cellulose acetate (particularly cellulose triacetate) have been used as various photographic materials and optical film materials because of their high optical isotropy and excellent toughness and flame retardancy. Among these applications, in recent years, the importance of optical materials related to liquid crystal display devices in particular as optical films such as retardation films, polarizing plate protective films, optical compensation films, antireflection films, and viewing angle widening films has increased. Yes.
Cellulose triacetate used as a material for optical films is required to have high optical performance and quality as compared with cellulose triacetate used as a conventional film material for photographic films.

Hereinafter, the viewing angle widening film will be described. Liquid crystal display devices are used as display devices for electronic devices such as flat-screen televisions and personal computers. One of the technical problems with liquid crystal display devices is that the viewing angle is narrow. In recent years, the viewing angle has been improved by combining a STN (Super Twisted Nematic) system with a viewing angle widening film.
In the case of the STN method, the viewing angle is improved by 1.8 times by using the viewing angle widening film. Such viewing angle widening films include, for example, JP-A-7-146409 (Patent Document 1), JP-A-7-287120 (Patent Document 2), JP-A-8-5837 (Patent Document 3), and the like. It is described in.

These viewing angle widening films form a discotic liquid crystal to correct the orientation of transmitted light and widen the viewing angle. An alignment layer is necessary to align the discotic liquid crystal. The alignment layer is an inorganic vapor deposition film, an alignment film rubbed with an organic polymer, or the like. For example, an alkyl chain-modified poval is used as the alignment film obtained by laminating the organic polymer film. On the other hand, the base material (support) on which the discotic liquid crystal is applied is required to have optical properties close to isotropic in the front. This support (base film) is a cellulose triacetate film.
In the viewing angle widening film, the coating layer of the discotic liquid crystal on the cellulose triacetate film needs to have a uniform and smooth surface. However, crater-like uneven portions (crater-like defects) may occur in the coating layer. If a crater-like defect is present, the degree of polarization of light at that portion changes, so that it is recognized as an optical defect, which is a serious problem when used in a liquid crystal display device.

It can be presumed that the cause of such uneven portions is derived from the cellulose triacetate support. Such crater-like defects cannot be confirmed by quality inspection before applying the discotic liquid crystal layer. The present inventors analyzed crater-like defects in such a discotic liquid crystal layer using electron spectroscopy (SEM-XMA). As a result, it was found that calcium exists in the defect portion.
Japanese Patent Application Laid-Open No. 10-316701 (Patent Document 4) describes cellulose acetate having excellent optical characteristics. A cellulose acetate in which at least a part of carboxyl groups bonded to cellulose acetate and / or hemicellulose acetate exists in an acid form is disclosed. In this cellulose triacetate, it is described that alkali or alkaline earth metals such as sodium, calcium and magnesium affect the peelability. Examples of this document disclose cellulose triacetate having a calcium content of 2 to 10 ppm, and Comparative Example 3 discloses cellulose triacetate having 0 ppm calcium, 7.3 ppm magnesium, and 0 ppm sodium.

In this document, the content of alkali or alkaline earth metal in cellulose triacetate is reduced by reducing the amount of heat-resistant stabilizer added. However, simply reducing the alkali or alkaline earth metal content in cellulose triacetate cannot suppress the occurrence of crater-like defects.
In the cellulose triacetate production process, it is necessary to dry the hydrous flakes of cellulose triacetate obtained as a precipitate with hot air. Cellulose triacetate with too little calcium content has low heat resistance and low productivity. For this reason, there has been a demand for cellulose triacetate which contains an alkaline earth metal but does not have a crater-like defect when it is used as a viewing angle widening film.
JP 7-146409 A JP 7-287120 A JP-A-8-5837 JP-A-10-316701 (Claim 1, paragraphs [0001] [0031] [0047], Examples 5 to 9 and Comparative Example 3)

Accordingly, the present invention provides a cellulose ester capable of suppressing the occurrence of crater-like irregularities (crater-like defects) in a discotic liquid crystal layer when used as a base film of a viewing angle widening film having a discotic liquid crystal layer, and It is in providing the manufacturing method.
The present invention is to provide a cellulose ester having high heat resistance and wet heat stability and a method for producing the same.

If neutralization of the catalyst sulfuric acid after esterification is not performed in the production process of cellulose triacetate and heat treatment is not performed, alkali metals and alkaline earth metals in cellulose triacetate can be minimized. Cellulose triacetate produced by this method has low heat resistance. The present inventors have found that even when cellulose triacetate having a small amount of calcium obtained by such a production method is used, a crater-like defect occurs when a viewing angle widening film is produced using this cellulose triacetate. I found it. Furthermore, the calcium content contained in normal cellulose triacetate is 40 to 200 ppm per gram, and it has been found that the frequency of occurrence of crater-like defects does not change depending on the magnitude of this calcium content. From the above findings, the present inventors have found that the cause of the crater-like defects does not depend on all the calcium (final calcium content) contained in cellulose triacetate, but has other main factors. It was.

On the other hand, when the calcium content of the pulp used as the raw material for cellulose triacetate was analyzed, a low amount of 25 ppm and a high amount of calcium of about 50 ppm were detected. The present inventors obtained raw material pulp with a low calcium content by not using a recovered recycled product for sodium hydroxide used in the cooking process of Kraft method hardwood pulp. Then, this special raw material pulp having a low calcium content and a normal raw material pulp having a high calcium content were acetylated under the same conditions to obtain cellulose triacetate. In addition, these pulps were pulps manufactured using the same raw material wood and using different cooking liquors. Using the obtained cellulose acetate film, a film with a wide viewing angle was produced and the occurrence frequency of crater defects was compared. Cellulose triacetate obtained from raw pulp with a high calcium content was clearly more crater defects. There were many. For this reason, it was concluded that the calcium detected in the part corresponding to the crater-like defect of the liquid crystal layer is derived from calcium contained in the raw material pulp.

From the above knowledge, we can guess as follows. That is, lignin, hemicellulose, protein, higher fatty acid, etc. are contained in the wood chip that is the raw material of the pulp. In the cooking step of these rough linters and wood chips, when alkaline earth metal, especially calcium is present in the cooking liquid, at least some of these specific components, for example, higher fatty acids, carboxyl groups in hemicellulose, Combines with calcium to form a calcium salt. Furthermore, such a specific component of the calcium salt type is insolubilized in the subsequent pulp refining process and tends to remain in the pulp. The specific component remains in the cellulose ester even in the acetylation step. Finally, it is presumed that the specific component is not removed even in the filtration step after the dissolution step, and is contained in the film and causes crater-like defects. That is, it is presumed that the causative substance is not calcium itself but some specific component combined with calcium. In addition, the specific component containing calcium contained in the pulp as a raw material may be in an acid form in the acetylation process. However, even in the acid form, it reacts with metal ions (calcium ions and the like) used in neutralization and heat-resistant treatment, and again becomes salt form and finally exists in the cellulose ester. Furthermore, when this causative substance is present in the raw pulp, it may remain in the cellulose triacetate film, although some chemical reaction may occur in the acetylation process or hydrolysis process.

As described above, calcium contained in the pulp is a process contaminant. And it mixes in the manufacturing process of the raw | dissolving pulp (Dissolving pulp).
Hereinafter, it demonstrates in detail along the manufacturing process of a dissolving pulp. In the process of manufacturing dissolving pulp, first, wood chips are manufactured by removing dust, cutting and peeling off the wood. Next, the lignin and a considerable amount of hemicellulose are removed from the wood chips by chemical treatment to obtain a dissolving pulp. The α cellulose content of the dissolving pulp is as high as 92% to about 98%.
Further, depending on the delignification treatment method, the dissolving pulp production process is divided into two types, a sulfite method (sulfite method; sulfit) and a sulfate method (craft method; kraft). In either method, lignin is removed using a delignification agent, but bisulfite (generally, calcium salt) is used as the delignification agent in the sulfite method. In the Kraft method, a mixed solution of sodium hydroxide and sodium sulfide is used. In the kraft method, a calcium component is not used, but as described later, calcium oxide is added in the sodium sulfide recovery and regeneration step. The calcium component used in these methods is usually brought into the pulp cooking step as calcium carbonate, and as described above, it is presumed that it is decomposed during the cooking step and exists in the form of calcium ions.

Based on such knowledge, the present inventors limited the calcium content of the dissolving pulp used as a raw material for cellulose esters such as cellulose acetate (by using raw pulp having a calcium content of a specific amount or less). It has been found that the migration of the causative substance to cellulose ester can be suppressed and the occurrence of crater-like defects in the viewing angle widening film can be suppressed.
That is, the cellulose ester of the present invention is obtained using wood pulp having a calcium content of 20 ppm or less. The pulp is a pulp derived from wood. The calcium content of the pulp is about 0.01 to 15 ppm. The cellulose ester may be composed of a cellulose ester containing at least an acetyl group. The cellulose ester may be composed of a cellulose ester having an average substitution degree of 2.6 to 2.9. Furthermore, the calcium content of the cellulose ester may be 120 ppm or less. Such a cellulose ester of the present invention is suitable for a base film of a viewing angle widening film having a discotic liquid crystal layer.

The present invention includes a method of producing a cellulose ester by reacting a pulp having a calcium content of 20 ppm or less with an esterifying agent or an etherifying agent. In this method, a sulfuric acid catalyst may be used to react a pulp having a calcium content of 0.01 to 15 ppm with an acylating agent. Furthermore, in order to inactivate the sulfate group introduced by the sulfuric acid catalyst, a step of heat-treating with a stabilizer composed of an alkali metal compound and / or an alkaline earth metal compound may be included.

The cellulose ester can be usually obtained by using various pulps such as wood pulp (for example, softwood pulp, hardwood pulp, etc.) and linter pulp (for example, cotton linter pulp) as raw materials. In the present invention, cellulose esters using wood pulp can be used alone or in combination of two or more. Moreover, you may combine linter pulp (refined cotton linter pulp) and the wood pulp with few calcium contents of this invention.
The α-cellulose content (weight basis) in the pulp is, for example, about 94% or more, preferably 96 to 100%, more preferably 98 to 100% (particularly 99 to 100%). Moreover, the said pulp normally contains different components, such as hemicellulose. Therefore, in the present specification, the term “cellulose” is used in the sense that it also contains different components such as hemicellulose. Furthermore, the cellulose may contain some carboxyl groups in the state couple | bonded with the cellulose molecule and / or hemicellulose molecule | numerator normally.

The mannose content (weight basis) in the pulp is, for example, about 0.01 to 3% (preferably 0.1 to 1%), and the xylose content is, for example, 0.05 to 5% (preferably about 0.1%). 5 to 5%).

[Calcium content of pulp]
In the present invention, it is preferable to use a pulp having a low calcium content as a raw material pulp. By using a pulp having a low calcium content, a crater can be used as a base material for an optically homogeneous film (such as a viewing angle widening film). Occurrence of the shape defect can be suppressed. However, for example, calcium may be present as an impurity even in an alkali metal reagent. For this reason, it is industrially difficult to completely eliminate calcium ions present as impurities in the raw material and cooking process. Also, from the crater-like defect estimation mechanism described later, the surface smoothness of the liquid crystal layer can be remarkably improved if the calcium content is below a specific amount.

That is, there is a critical point in the relationship between the occurrence of crater-like defects and the calcium content, and the calcium content of the pulp needs to be 20 ppm or less (eg, 0.01 to 18 ppm), preferably It is 15 ppm or less (for example, 0.01 to 15 ppm), more preferably 10 ppm or less (for example, 0.05 to 10 ppm), particularly 5 ppm or less (for example, 0.1 to 5 ppm).
Regarding the calcium content, the molar amount is, for example, 0.5 × 10 ⁻⁶ mol or less per gram of cellulose, preferably 0.375 × 10 ⁻⁶ mol or less, more preferably 0.25 × 10 ⁻⁶ mol or less. By setting it to (especially 0.125 × 10 ⁻⁶ mol or less), the occurrence of crater-like defects can be suppressed, and the performance of the viewing angle widening film can be dramatically improved.

In addition, the calcium content in the wood-derived pulp (dissolving pulp) is preferably as small as possible from the viewpoint of optical quality. In the study by the present inventors, for example, in the case of kraft pulp, a dissolved pulp having a calcium content of about 3 ppm can be obtained by switching sodium hydroxide used in the cooking process from a recovered and regenerated product to a virgin product. It was. And although the cellulose triacetate made from such a pulp has a calcium content of 100 ppm or more by heat-resistant treatment, it was possible to greatly reduce crater-like defects.

As mentioned above, alkaline earth metals such as calcium are not an essential cause of crater-like defects, but may be insolubilized by binding of specific components contained in crude linters and wood chips, which are pulp raw materials, to calcium. Responsible. Therefore, in order to reduce the crater-like defects that are the object of the present invention, (1) a method for limiting the types of cellulose sources (crude linters and wood chips) that are originally low in calcium components, and (2) a pulp cooking step And (3) a method of combining the methods (1) and (2). By these methods, the calcium content in the pulp can be reduced, and the occurrence of crater-like defects in the viewing angle widening film can be reduced.

In the method (1), when only linter pulp is used as a raw material for cellulose ester, cooking is generally performed using sodium hydroxide, and there is little possibility that calcium is mixed. That is, only the case where calcium contained in water for dissolving sodium hydroxide is brought into the cooking process and calcium contained as impurities of sodium hydroxide become a problem.
However, the calcium content of linter pulp is surprisingly high, about 20 ppm. The cause of this is clearly unknown, but it is thought to be caused by contamination from industrial water that dissolves sodium hydroxide. In the case of cotton linters, the coarse linters themselves may contain a lot of calcium. Furthermore, since linter pulp is expensive and the supply of crude linter is unstable, it is desirable to use wood pulp (dissolving pulp) for cellulose esters such as cellulose acetate.
In wood pulp, the amount of calcium can be reduced by selecting the type of wood chip that is the raw material of the pulp. However, wood pulp requires a cooking process, and calcium is mixed in the cooking process. That is, it is difficult to reduce the calcium content in the pulp only by the method (1). Therefore, the method (2) or (3) is preferable in order to reduce the calcium content even when the amount of hemicellulose is about the pulp used in cellulose triacetate for optical films.

In the method (2), the pulp cooking step is a step in the production of dissolving pulp. Various methods for producing dissolving pulp have been proposed. Industrially, two types of methods are used: a sulfite method and a kraft method. For the method for producing these dissolving pulps, for example, the method described in detail in “Wood Chemistry” (written by E. Sjostrom, translated by Tamio Kondo, published by Kodansha, published in 1986, pages 104 to 147) and the like are used. it can. The cooking process is carried out by any method, and its main purpose is to remove lignin contained in pulp raw materials (wood chips and the like).
In the sulfite method, an aqueous solution containing sulfite and bisulfite is used as the cooking solution. As the base of bisulfite, for example, calcium, sodium, magnesium or ammonium is used, but industrially, calcium is mainly used. Therefore, in the sulfite method, since alkaline earth metals, especially calcium are often mixed, the calcium content can be reduced by not using calcium salts as bisulfites.

In the Kraft method, the cooking solution is a mixed solution of sodium hydroxide and sodium sulfide. And sodium sulfide reacts with lignin to produce thiolignin and solubilize lignin. The digested pulp cleaning liquid contains thiolignin, excess sodium sulfide and sodium hydroxide. Furthermore, the cleaning liquid containing impurities such as lignin is burned in a reducing atmosphere, and the sulfur content becomes sodium sulfide. On the other hand, the other sodium component is sodium carbonate. Sodium sulfide and sodium carbonate are recovered as a sediment remaining in the furnace and dissolved in water. Next, calcium oxide or calcium hydroxide obtained by dissolving calcium oxide in water is added to the residue solution. By this operation, sodium carbonate is causticized to become sodium hydroxide and calcium carbonate. The residual solution is a solution containing sodium sulfide, sodium hydroxide and calcium carbonate. At this stage, the calcium carbonate precipitates for the portion exceeding the solubility limit and is separated from the solution in the filtration process. That is, when calcium carbonate is precipitated and filtered, sodium hydroxide used for cooking is recovered and calcium carbonate and sodium hydroxide are separated. However, in the filtration process of this precipitate, since both cannot be completely separated industrially, it is conventionally allowed that a small amount of calcium carbonate is mixed in the cooking liquid. For this reason, it is a manufacturing process by a normal kraft method that a trace amount of calcium carbonate is mixed in the sodium hydroxide solution added in the process of delignification.

Therefore, as a method of reducing calcium in the Kraft method, (1) About the sodium hydroxide and sodium sulfide used, the method that does not use recovered (regenerated) products, (2) About the sodium hydroxide and sodium sulfide used (Recycled) Method to reduce the usage rate of the product, (3) In the filtration of calcium carbonate and the solution containing sodium sulfide and sodium hydroxide, completely separate the solid and liquid by filtration using a membrane filter etc. And (4) a method of industrially filtering by installing filtration steps in multiple stages by filtration of calcium carbonate and a solution containing sodium sulfide and sodium hydroxide. However, it is not limited to these methods. In addition, when using these methods, there is no restriction | limiting in the kind of wood chip used as a raw material of a pulp. For this reason, it is not influenced by the raw material of a pulp, It can apply to the pulp for obtaining the cellulose ester of the physical property optimal for the target film by the conventional knowledge, and is suitable.

Of these methods, the craft method is preferred from the viewpoint of simplicity. This is because calcium is an impurity in the Kraft method, and sodium hydroxide used in the process can be easily suppressed by not using a recovered and recycled product. On the other hand, in the sulfite method, the process itself needs to be changed, and other characteristics of the pulp may change due to the process change.
There seems to be a linear function relationship between the calcium content of raw material pulp and the frequency of occurrence of crater-like defects, but by making the calcium content 20 ppm or less (especially 15 ppm or less), the crater dramatically The frequency of occurrence of the shape defects can be reduced. The reason is estimated as follows.

That is, it is difficult to remove the specific substance containing calcium contained in the pulp even in the acylation step or the casting solution filtration step. For example, in the case of cellulose acylate, the specific substance is mixed in the cellulose acylate product even in the acylation step. These specific substances are at least partially soluble in the solvent of the casting solution of cellulose acylate. For this reason, in the solution state melt | dissolved in order to cast cellulose acylate, it melt | dissolves at least partially. However, in the casting process, the solvent evaporates on the drum to form a concentrated solution, and the specific substance is incompatible with cellulose acylate or has little compatibility, causing phase separation and depositing on the surface of cellulose acylate. Come on. At this stage, if the concentration of the specific substance present in the cellulose acylate is small, the specific substance only forms a small population. On the other hand, if the concentration of the specific substance is high, the specific substance associates in the process of phase separation to form a group having a certain size.

In the manufacturing process of the viewing angle widening film, in order to align the discotic liquid crystal, an alignment layer composed of modified polyvinyl alcohol or the like is applied as the first layer after the saponification process. At this stage, the surface tension is different in the portion where the specific substance exists as a group having a certain size. For this reason, the alignment layer is not uniformly applied. The portion where the alignment layer is not applied becomes a crater-like defect (concave portion) because the discotic liquid crystal layer is not applied. On the other hand, when the specific substance exists as a small group, the difference in surface tension does not act, so the alignment layer is uniformly applied.

Thus, the existence of the specific substance becomes a crater-like defect because the specific substance phase-separates and associates when the cellulose acylate film is formed, resulting in a size larger than the specific diameter. Whether or not this association is formed largely depends on the concentration of a specific substance in the cellulose acylate. When the concentration is low, the association is not possible, or even if the association is made, only a small group is formed, and there is no crater-like defect. . And it can be estimated that the critical ratio of whether a specific substance associates and becomes a large group is a calcium content of about 20 ppm (especially 15 ppm). That is, by setting the calcium content in the pulp to 20 ppm or less, the frequency of occurrence of crater defects can be greatly reduced. In experiments conducted by the present inventors, the number of crater-like defects was reduced to 20% of the number of calcium content of 30 ppm by reducing the calcium content contained in the pulp from 30 ppm to 20 ppm. I was able to.

[Measurement method of calcium content in pulp]
The calcium content in the pulp is measured by the atomic absorption method. The following method is used as a specific measurement pretreatment procedure.
(1) Immerse the washed 50 ml capacity magnetic crucible in 2N aqueous nitric acid solution overnight.
(2) A magnetic crucible soaked in 2N nitric acid is washed with pure water, rinsed with ultrapure water, and dried in a drier.
(3) Weigh accurately 2 g of sample into a magnetic crucible.
(4) Carbonize the sample in the magnetic crucible on the electric heater.
(5) Place the magnetic crucible in an electric furnace and incinerate at 500 ° C. for about 1 hour and at 600 ° C. for about 1.5 hours.
(6) When the ash is completely white, stop the electric furnace and let it cool in the furnace.
(7) Put 10 ml of 0.5N hydrochloric acid aqueous solution in a magnetic crucible and dissolve by heating on a sand bath.
(8) The solution is allowed to cool and then transferred to a 50 ml volumetric flask using a washed funnel, and the magnetic crucible is washed with ultrapure water to make up the volume (hydrochloric acid concentration: 0.1 N).
(9) As a standard solution, a calcium standard solution having a concentration of 1000 ppm is diluted with a 0.1N hydrochloric acid aqueous solution and prepared at concentrations of 0.1 ppm, 0.75 ppm, and 1.5 ppm.
(10) Measured by flame atomic absorption.
The calibration curve was created by the following method. The standard solution for the calibration curve was prepared by diluting a commercially available standard solution for atomic absorption with 0.1N hydrochloric acid solution to concentrations of 0.1, 0.75, and 1.5 ppm. The atomic absorption device used is a product name “AA-680” manufactured by Shimadzu Corporation.

[Cellulose ester]
The cellulose ester of the present invention is not particularly limited as long as it is obtained by using the pulp having the calcium content. Examples of the cellulose ester include organic acid esters [cellulose C _2-6 acylates such as cellulose acetate (cellulose acetate), cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate], and the above organic acids. Derivatives of esters (grafts such as polycaprolactone-grafted cellulose acetate), organic acid esters and ethers (C _2-6 acyl cellulose C _1-6 alkyl ethers such as acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose, acetyl hydroxy) ethylcellulose, such as _{C 2-6} acyl cellulose hydroxyalkyl _{C 2-6} alkyl ethers such as acetyl hydroxypropylcellulose), etc. can be mentioned, et al. That. These cellulose esters can be used alone or in combination of two or more.

Among these cellulose esters, cellulose esters having at least an acetyl group, particularly cellulose acylates having at least an acetyl group (for example, cellulose acetates such as cellulose triacetate, cellulose acetates such as cellulose acetate propionate and cellulose acetate butyrate) Etc.) is preferable. At present, cellulose triacetate is mainly used as a substrate for optical films such as viewing angle widening films. However, the viewing angle widening film for OCB or VA may be stretched to obtain desired optical suitability. Since cellulose triacetate has low stretchability, cellulose mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate are preferable for applications that require stretching. Furthermore, from the viewpoint of improving stretchability, it may be an esterified cellulose ester after cellulose has been etherified, or a cellulose derivative in which a cyclic lactone or the like is allowed to act on the cellulose ester.

The calcium content of the cellulose ester may be 120 ppm or less (for example, 100 ppm or less), preferably 70 ppm or less (for example, 0.01 to 40 ppm), more preferably 20 ppm or less (for example, 0.1 to 5 ppm). May be. When the calcium content in the cellulose ester is in such a range, when the optical film is used, the optical properties and film-forming properties are improved.
The magnesium content of the cellulose ester is, for example, about 100 ppm or less (for example, 0.01 to 100 ppm), preferably about 0.1 to 50 ppm, more preferably about 1 to 40 ppm (particularly 10 to 30 ppm). When the magnesium content is in such a range, the balance between optical properties and heat resistance is excellent. When the calcium content is 20 ppm or less, the magnesium content may be 10 ppm or more (for example, about 10 to 100 ppm).

The total sulfuric acid content (including bound sulfuric acid) of the cellulose ester is, for example, 200 ppm or less (for example, 0.01 to 200 ppm), preferably 150 ppm or less (for example, 0.1 to 150 ppm), preferably 100 ppm or less (for example, 1 About 100 ppm). When the sulfuric acid content is in such a range, heat resistance and wet heat stability are high.
The average degree of substitution of cellulose esters (particularly cellulose acetate, cellulose acetate propionate) can be selected from a range of about 2 to 3, for example, 2.5 to 2.99, preferably 2.60 to 2.965, more preferably Is about 2.80 to 2.965, more preferably about 2.85 to 2.965. In the case of cellulose acetate, the average degree of acetylation can be selected from the range of about 48 to 62.5%, for example, 55.0 to 62.0%, preferably 60 to 62.0, more preferably 61.0 to 62. It may be about 0.0% (particularly 61.1 to 61.4%). When the average degree of substitution such as the degree of acetylation is within this range, a film excellent in moldability and optical properties can be produced.
The polymerization degree of the cellulose ester is not particularly limited, and is a viscosity average polymerization degree of 200 to 400, preferably 230 to 400, and more preferably about 250 to 350.

[Method for producing cellulose ester]
The cellulose ester production method of the present invention is a method in which a pulp having a calcium content of 20 ppm or less is reacted with an esterifying agent or an etherifying agent, except that a raw material pulp having a low calcium content is used. Manufacturing methods are available.
In the case of cellulose esters such as cellulose acylate, it can be produced by the method described in “Fibrous resin” (Kazuo Uta, Jun Marusawa, published by Nikkan Kogyo Shimbun). For example, raw pulp (cellulose) is activated. An activation step for acylating the activated cellulose with an esterifying agent (acylating agent), a deactivation step for deactivating the acylating agent after the acylation reaction is completed, and It can be produced through an aging step of aging (saponifying and hydrolyzing) cellulose acylate.

(Activation process)
In the activation step, the raw pulp (cellulose) is usually crushed by a dry method or the like. Examples of the method for activating the pulverized pulp include spraying with an organic carboxylic acid or hydrous organic carboxylic acid (acetic acid or hydrous acetic acid), or immersion in an organic carboxylic acid or hydrous organic carboxylic acid. It can be carried out by treating pulp (cellulose). The amount of the organic carboxylic acid (such as acetic acid) used may be about 10 to 100 parts by weight, preferably 20 to 80 parts by weight, and more preferably about 30 to 60 parts by weight with respect to 100 parts by weight of cellulose.

(Acylation step)
In the acylation step, the activated cellulose is acylated with an acylating agent in the presence of an acylation catalyst (particularly a strong acid such as sulfuric acid). The amount of the acylation catalyst used is, for example, about 1 to 15 parts by weight, preferably about 5 to 13 parts by weight, and more preferably about 7 to 10 parts by weight with respect to 100 parts by weight of cellulose.
The acylating agent may be an organic acid halide such as acetic acid chloride, but is usually a C _2-6 alkanecarboxylic acid anhydride such as acetic anhydride, propionic anhydride, butyric anhydride, and the like. These acylating agents (such as acid anhydrides) may be used alone or in combination of two or more. Moreover, the mixture of an acid anhydride and different carboxylic acid may be sufficient. Preferred acylating agents include C _2-4 alkanecarboxylic anhydrides, particularly at least acetic anhydride. The amount of the acylating agent (such as acetic anhydride) to be used is, for example, 1.40 to 2.0 molar equivalents, preferably 1.45 to 1.9 molar equivalents, more preferably 1 mol of the hydroxyl group of cellulose. About 1.5 to 1.8 molar equivalents. In particular, when acetic anhydride is used as the acylating agent, the amount of acetic anhydride used in the acetylation step is 200 to 400 parts by weight, preferably 250 to 350 parts by weight, more preferably 260 parts by weight based on 100 parts by weight of cellulose. It may be about 300 parts by weight.

The acylation step is usually often performed in a solvent (or diluent). As such a solvent (or diluent), an organic carboxylic acid (C _2-6 alkane carboxylic acid such as acetic acid, propionic acid, butyric acid, etc., in particular, an organic carboxylic acid corresponding to an acyl group such as acetic acid) is used. The The amount of the organic carboxylic acid (such as acetic acid) used is, for example, about 200 to 700 parts by weight, preferably 300 to 600 parts by weight, and more preferably about 350 to 500 parts by weight with respect to 100 parts by weight of cellulose. The acylation reaction can be carried out under conventional conditions, for example, a temperature of about 0 to 60 ° C., preferably 5 to 55 ° C., more preferably about 15 to 50 ° C. (for example, 20 to 45 ° C.).

(Deactivation process)
In the deactivation step, a reaction terminator is added to the reaction system in order to deactivate the quenching agent remaining in the reaction system after completion of the acylation reaction. The reaction terminator may be water or a mixed solvent of water and organic carboxylic acids, but an aqueous base solution (particularly an aqueous solution) is preferred. Examples of the base include alkali metal compounds [hydroxides (sodium hydroxide, potassium hydroxide, etc.), carbonates (sodium carbonate, potassium hydrogencarbonate, etc.), organic acid salts (acetates such as sodium acetate, potassium acetate, etc.) ), Etc.], alkaline earth metal compounds [hydroxides (magnesium hydroxide, calcium hydroxide, etc.), carbonates (calcium carbonate, calcium bicarbonate, etc.), organic acid salts (acetates such as magnesium acetate, calcium acetate, etc.) ) Etc.].
The amount of the base used can be adjusted according to the amount of sulfuric acid (residual sulfuric acid amount) in the ripening reaction described later, and is, for example, 0.1 to 0.00 per one equivalent of sulfuric acid catalyst (prepared sulfuric acid catalyst) in the reaction system. It is 9 equivalents, preferably 0.2 to 0.8 equivalents, more preferably about 0.3 to 0.7 equivalents.

(Aging process)
In the aging step, after the acylation reaction is stopped, the produced cellulose acylate (cellulose triacylate) is saponified (deacylation reaction and desulfurization ester reaction) to adjust the acylation degree and substitution degree distribution. The obtained cellulose acylate is obtained.
The aging step may be carried out by newly adding another acid catalyst, but can usually be carried out in the presence of the acylation catalyst (particularly sulfuric acid) used in the acylation step. In particular, a part of the sulfuric acid catalyst used for acylation may be neutralized and the remaining sulfuric acid catalyst may be used as an aging catalyst, or all sulfuric acid catalysts remaining without neutralization may be used as an aging catalyst. Good. Moreover, you may neutralize all the sulfuric acid catalysts.
The ratio of the sulfuric acid catalyst is 15 parts by weight or less (for example, about 0.5 to 12 parts by weight), preferably 0.8 to 10 parts by weight, more preferably 100 parts by weight of cellulose (raw cellulose). About 1 to 8 parts by weight.
The aging is usually carried out in the presence of an aqueous solvent (usually water) in addition to the sulfuric acid catalyst. The amount of the aqueous solvent used is, for example, about 5 to 100 mol with respect to 100 mol of the organic carboxylic acid (particularly acetic acid) corresponding to the acylating agent.

Furthermore, a neutralizing agent composed of a base may be added as necessary after the deacylation reaction in order to stop the ripening reaction after producing a predetermined cellulose acylate. As the base, alkali metal compounds and alkaline earth metal compounds exemplified in the deactivation step can be used. The total amount of use of the neutralizing agent (including the amount of base used for partial neutralization) is, for example, 0.9 to 2 equivalents, preferably 1 to 1. It is about 5 equivalents, more preferably about 1 to 1.3 equivalents (particularly 1 to 1.2 equivalents).
Furthermore, the cellulose acylate produced by adding the reaction product (dope containing cellulose acylate) to a precipitation solvent (water, aqueous acetic acid solution, etc.) is separated, and free metal components and sulfuric acid components are removed by washing with water. May be. In addition, a neutralizing agent can also be used in the case of washing with water.

(Heat-resistant treatment)
In such a cellulose acylate production process (for example, the final stage of the production process), it is desirable to perform heat treatment. That is, cellulose acylate normally undergoes hydrolysis in an environment where heat acts and moisture is present. Therefore, in order to improve thermal stability and wet heat stability, as a stabilizer, for example, an alkali metal (lithium, potassium, sodium, etc.) or a salt thereof or a compound thereof, an alkaline earth metal (calcium, magnesium, strontium, barium, etc.) ) Or a salt thereof or a compound thereof, the sulfuric acid group introduced when sulfuric acid is used as a catalyst may be inactivated, and heat stability may be imparted.

The stabilizer is usually an alkali metal compound, an alkaline earth metal compound, etc. exemplified in the deactivation step, particularly an acetate metal salt such as calcium acetate or magnesium acetate, or a hydroxide such as calcium hydroxide. May be. Examples of a method for adding the stabilizer include a method in which a dilute aqueous solution of the metal compound is added to a suspension in which a cellulose ester is dispersed. In particular, in the present invention, even when alkaline earth metal calcium is mixed in the acylation process, the aging process, and the heat treatment process (particularly the heat treatment process), a crater-like defect occurs in the viewing angle widening film. The heat resistance and wet heat stability can be improved by the calcium component.

[Example]
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the text, “part” and “%” are based on weight unless otherwise specified. Moreover, the measuring method of the physical property of a pulp and cellulose acetate is as follows.
[Α-cellulose content of pulp]
Take 5 g of sample in a 300 ml beaker and add 50 ml of 17.5% sodium hydroxide solution. After 3.5 minutes, crush with a flat glass rod at the tip to break apart and leave for 20 minutes. While stirring, 50 ml of pure water is added, and after 35.5 minutes from the start of measurement, the contents of the beaker are transferred to a Buchner funnel with a known width of gold and filtered with suction. After filtration, refilter and squeeze until the filtrate reaches 80 ml, then wash with 900 ml water. Add 40 ml of 10% acetic acid to the residue after washing with water and leave it for 5 minutes. Finally, it is washed with 1000 ml of pure water, and the residue is dried at 80 ° C. for 30 minutes together with the gold width, and then dried at 105 ° C. to obtain a constant weight, and the weight% relative to the sample weight (dry weight) is calculated.

[Mannose content and xylose content of pulp]
The pulp is hydrolyzed by cooling with 72% sulfuric acid in an ice water bath for 4 hours, then diluting to 6% sulfuric acid and treating at 110 ° C. for 3 hours. After neutralizing this with barium carbonate, the filtrate obtained by filtration was subjected to liquid chromatography analysis with a sugar analysis system (manufactured by Dionex), and the ratio (mol%) of each component to the total amount of glucose, mannose and xylose was determined. calculate.

[Calcium content in pulp]
The calcium content in the pulp was measured according to the measurement method described above.

[Degree of acetylation of cellulose acetate]
The degree of acetylation means the weight percentage of bound acetic acid per unit weight, and was measured as follows. 1.9 g of dried cellulose acetate is precisely weighed and dissolved in 150 ml of a mixed solution of acetone and dimethyl sulfoxide (volume ratio 4: 1), 30 ml of 1N sodium hydroxide aqueous solution is added, and the mixture is stirred at 25 ° C. for 2 hours. Turn into. Phenolphthalein is added as an indicator, and excess sodium hydroxide is titrated with 1N-sulfuric acid (concentration factor: F). Moreover, a blank test is performed by the same method and the acetylation degree is calculated according to the following formula.
Degree of acetylation (%) = {6.5 × (BA) × F} / W
(Where A is the 1N-sulfuric acid titration (mL) of the sample, B is the 1N-sulfuric acid titration (mL) of the blank test, F is the concentration factor of 1N-sulfuric acid, and W is the weight of the sample. Indicates)

[Viscosity average polymerization degree of cellulose acetate]
The dried cellulose acetate is dissolved in a mixed solution of methylene chloride / methanol = 9/1 (weight ratio) to prepare a solution having a predetermined concentration C (2.00 g / liter). This solution was poured into an Ostwald viscometer, and the time t (second) for the solution to pass between the markings of the viscometer at 25 ° C. was measured. On the other hand, the passage time (seconds) t ₀ was measured in the same manner for the mixed solvent alone, and the viscosity average polymerization degree was calculated according to the following formula.
η _rel = t / t ₀
[Η] = (ln η _rel ) / C
DP = [η] / (6 × 10 ⁻⁴ )
[Where t is the solution transit time (seconds), t ₀ is the solvent transit time (seconds), C is the cellulose acetate concentration (g / liter) of the solution, η _rel is the relative viscosity, and [η] is the intrinsic viscosity. , DP represents the viscosity average degree of polymerization].

[NMP intrinsic viscosity]
About 0.500 g of cellulose acetate which has been dried at 105 ° C. for 1 hour and then transferred to a desiccator for 30 minutes and cooled is weighed. This weighed sample is dissolved in 100 ml of N-methylpyrrolidone to obtain a solution of about 0.5 g / dl. Accurate concentration (C) is calculated in advance from the weighed sample weight. This solution was poured into an Ostwald viscometer at 65 ° C., and the time t (second) for the solution to pass between the markings of the viscometer at 25 ° C. was measured. On the other hand, for the N-methylpyrrolidone solvent alone, the passage time (second) t ₀ was measured in the same manner, and the relative viscosity and specific viscosity were calculated according to the following formula.
η _rel = t / t ₀
η _sp = η _rel -1
[Wherein, t is the solution passage time (second), t ₀ is the solvent passage time (second), η _rel is the relative viscosity, and η _sp is the specific viscosity].
Using the obtained relative viscosity η _rel and specific viscosity η _sp , the NMP intrinsic viscosity was calculated from one-point measurement by substituting it into the following Solomon-Gottman equation.
[Η _NMP ] = 2 [η _rel −ln (η _sp )] ^1/2 / C
[ _Wherein [η _NMP ] is the intrinsic viscosity in NMP, and C is the cellulose acetate concentration of the solution (indicating g / dL).

[Alkaline earth metal content in cellulose acetate]
The alkaline earth metal content in cellulose acetate was measured according to the above-mentioned “Method for measuring calcium content in pulp”.

[Heat resistance of cellulose acetate]
The cellulose acetate film was dried for 90 minutes with a hot air dryer at 60 ° C., and the discoloration after drying was visually observed and evaluated according to the following criteria.
○: Deterioration and discoloration do not occur after heating and drying at 60 ° C. ×: Deterioration and discoloration occur after heating and drying at 60 ° C.

[Detection of crater defects]
About the viewing angle expansion film obtained by the Example and the comparative example, the fault (crater-like recessed part) was detected with the fault detection apparatus (made by FUTEC). This defect detection device is composed of a light receiver, a projector, a signal processing board, a marker, and an encoder. The transmission method used was a transmission method. A camera using a CCD line sensor (operation clock: 20 MHz, number of pixels: 1024 pixels) was used as the light receiver. Five cameras were installed for a detection width of 5 meters. The projector was a fluorescent lamp with a slit, and the slit width was 10 mm. Moreover, the polarizing film was installed in the projector side. Furthermore, since the polarization direction of the viewing angle widening film and the polarization direction of the light of the projector are different, the crater-like defect is detected as a bright defect. Standard signal processing boards, markers, and encoders were used. The results of defect detection performed as described above are described in% display relative to Comparative Example 1 with respect to the other examples and comparative examples, with the number of defects in Comparative Example 1 being 100%.

Pulp production examples 1-3
Pulp was produced using hardwood wood chips. Pulp was refined using the kraft method. About the sodium hydroxide used at the cooking process of a wood chip, the pulp 1 was obtained by cooking using industrial sodium hydroxide, without using a collection | recovery reproduction | regeneration product. In addition, pulps 2 and 3 were obtained by changing the ratio of use of recovered and recycled products and industrial sodium hydroxide. The properties of the obtained pulps 1 to 3 are shown in Table 1.

Pulp Production Example 4
Pulp was produced using hardwood wood chips. Pulp was refined using the kraft method. For sodium hydroxide used in the cooking process of wood chips, the entire amount recovered and recycled was used. The properties of the obtained pulp 4 are shown in Table 1.

Examples 1 to 3 and Comparative Example 1
(Acetylation step: acetylation method 1)
Cellulose acetate was produced using Pulp 1 to 4 according to the following method. That is, after 50 parts of glacial acetic acid was sprayed on 100 parts of pulp (5% water content) to activate the pretreatment, a mixture of 470 parts of glacial acetic acid, 265 parts of acetic anhydride and 8.3 parts of sulfuric acid was added. According to the method, the mixture was cooled to −5 ° C. and then heated to 45 ° C. for reaction. Thereafter, water was added to deactivate the acetylating agent, and the mixture was heated to 50 ° C. and hydrolyzed. After completion of the hydrolysis, the dope was dropped into dilute acetic acid, allowed to settle, washed and drained. The obtained hydrous flakes were immersed in a dilute aqueous solution containing calcium acetate and magnesium acetate, and then subjected to a stabilization treatment by draining to obtain cellulose acetate having an acetylation degree of 61.3%. These cellulose acetates are referred to as Examples 1 to 3 and Comparative Example 1, respectively. Table 2 shows the pulp used for each cellulose acetate, the method for producing cellulose acetate, and the properties of the obtained cellulose acetate.

(Preparation of cellulose acetate solution)
100 parts of the cellulose acetate obtained, 7.8 parts of triphenyl phosphate (plasticizer), 3.9 parts of biphenyl diphenyl phosphate (plasticizer), 336 parts of methylene chloride (first solvent) and 29 parts of methanol (second solvent) The composition constituted by the above was put into a mixing tank and stirred while heating to 50 ° C. to dissolve each component to prepare a cellulose acetate solution.

(Production of cellulose acetate film)
The obtained cellulose acetate solution was cast using a band casting machine. The film having a residual solvent amount of 50% was peeled off from the band, and the film having a residual solvent amount of 40% was transversely stretched at a stretch ratio of 17% using a tenter under the condition of 130 ° C. Hold at 30 ° C. for 30 seconds. Thereafter, the clip was removed to produce a cellulose acetate film.

(Saponification treatment of cellulose acetate film)
The obtained cellulose acetate film was immersed in an aqueous 1.5 N sodium hydroxide solution at 55 ° C. for 2 minutes. It wash | cleaned in the room temperature water-washing bathtub, and neutralized using 0.1 N sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. to saponify the surface of the cellulose acetate film. Table 2 shows the evaluation results of the heat resistance of the obtained film.

(Formation of alignment film)
One side of a saponified cellulose acetate film (transparent support) is composed of 20 parts of modified polyvinyl alcohol represented by the following composition formula, 360 parts of water, 120 parts of methanol and 1 part of glutaraldehyde (crosslinking agent). The applied coating solution was applied at 24 ml / m ² with a # 14 wire bar coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds. Next, the formed film was rubbed in the direction of 45 ° with the stretching direction of the cellulose acetate film (transparent support).

(Formation of optically anisotropic layer)
On the obtained alignment film, 41.01 parts of discotic liquid crystal molecules represented by the following formula, 4.06 parts of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), Cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co.) 0.9 part, Cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co.) 0.23 part, Photopolymerization initiator (Irgacure 907) , Manufactured by Ciba Geigy Co., Ltd.) and 1.35 parts of a sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 102 parts of methyl ethyl ketone was applied with a # 3 wire bar. did. This was attached to a metal frame and heated in a thermostatic chamber at 130 ° C. for 2 minutes to align the discotic liquid crystalline molecules. Next, UV irradiation was performed for 1 minute using a 120 W / cm high-pressure mercury lamp at 130 ° C. to polymerize the discotic liquid crystal molecules. Then, it stood to cool to room temperature. In this way, an optically anisotropic layer was formed. In this way, a viewing angle widening film was produced. The evaluation results for the crater-like defects of this film are shown in Table 2.

Example 4
A cellulose acetate film and a viewing angle widening film were produced in the same manner as in Example 1 using the following acetylation process. The evaluation results are shown in Table 2.
(Acetylation step: acetylation method 2)
A mixture of 11.7 parts of sulfuric acid, 260 parts of acetic anhydride and 450 parts of acetic acid was added to 100 parts of pulp 1 (water content 5%), and acetylation degree 60. A cellulose acetate having a viscosity average degree of polymerization of 267% and an NMP intrinsic viscosity of 1.61 was obtained.

Example 5
A cellulose acetate film and a viewing angle widening film were produced in the same manner as in Example 1 using the following acetylation process. The evaluation results are shown in Table 2.
(Acetylation step: acetylation method 3)
After pretreatment activation by spraying 50 parts of glacial acetic acid on 100 parts of pulp (water content 5%), a mixture of 470 parts of glacial acetic acid, 265 parts of acetic anhydride and 8.3 parts of sulfuric acid was added, and according to a conventional method. The mixture was cooled to −5 ° C. and then heated to 45 ° C. for reaction. Thereafter, a dilute aqueous solution of magnesium acetate was added to deactivate the acetylating agent, the temperature was raised to 50 ° C., and hydrolysis and partial neutralization of the sulfuric acid catalyst were performed. After completion of the hydrolysis, the dope was dropped into dilute acetic acid, allowed to settle, washed and drained. The obtained hydrous flakes were drained without heat-treating to obtain cellulose acetate having an acetylation degree of 61.3%.

As is apparent from the results in Table 2, the films of the examples have high heat resistance and few crater defects. In particular, the films of Examples 1 to 4 have high heat resistance. On the other hand, the film of Comparative Example 1 has many crater-like defects.
In the present invention, when a discotic liquid crystal layer of a viewing angle widening film is applied by reducing calcium contamination in the manufacturing process of pulp which is a raw material of cellulose ester such as cellulose acylate, the optical property of the liquid crystal layer is increased. A cellulose ester suitable for a base film capable of reducing crater-like defects that affect performance can be obtained. Furthermore, in the present invention, in order to maintain the heat resistance and wet heat stability required for cellulose esters, even when alkaline earth metal ions, particularly calcium ions are added, crater-like defects are not increased in the discotic liquid crystal layer. Is possible.

The cellulose ester of the present invention can be used in a wide range of applications as a material such as a film or a fiber. Among them, since it has high optical characteristics, it is an optical film used for liquid crystal display devices (protecting polarizing plates, retardation plates, etc.). It can be effectively used as a material (base film) of a film, in particular, a base film of a viewing angle widening film having a discotic liquid crystal layer. The viewing angle widening film having a discotic liquid crystal layer is liable to generate crater-like defects by coating, and requires a high degree of uniformity of the liquid crystal layer. Therefore, the cellulose ester of the present invention is particularly suitable for this application. Examples of the discotic liquid crystal include discotic liquid crystals described in JP-A-7-146409, JP-A-7-287120, JP-A-8-5837, and the like.

Claims (10)

1. The cellulose ester whose calcium content contained in the pulp in a raw material is 20 ppm.
2. The cellulose ester according to claim 1, wherein the pulp is a pulp obtained from wood, and the calcium content contained in the pulp is 0.01 to 15 ppm.
3. The cellulose ester according to claim 2, comprising at least a cellulose ester containing an acetyl group.
4. The cellulose ester according to claim 1, wherein the average degree of substitution of the cellulose ester is in the range of 2.600 to 2.965.
5. The cellulose ester according to claim 4, wherein a calcium content contained in the cellulose ester is 120 ppm or less.
6. The cellulose ester according to claim 1 for use in a viewing angle widening film having a discotic liquid crystal layer.
7. A method for producing a cellulose ester by reacting a pulp having a calcium content of 20 ppm or less with an esterifying agent.
8. The method according to claim 7, wherein a pulp having a calcium content of 0.01 to 15 ppm is reacted with an acylating agent using a sulfuric acid catalyst.
9. The method according to claim 8, further comprising a heat treatment with a stabilizer composed of an alkali metal compound and / or an alkaline earth metal compound.
10. The method of Claim 8 which obtains the cellulose ester for using for the viewing angle expansion film which has a discotic liquid crystal layer.