WO2004076490A1 - 湿熱安定性を改良したセルロースエステル - Google Patents
湿熱安定性を改良したセルロースエステル Download PDFInfo
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- WO2004076490A1 WO2004076490A1 PCT/JP2004/002230 JP2004002230W WO2004076490A1 WO 2004076490 A1 WO2004076490 A1 WO 2004076490A1 JP 2004002230 W JP2004002230 W JP 2004002230W WO 2004076490 A1 WO2004076490 A1 WO 2004076490A1
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- cellulose ester
- cellulose
- sulfuric acid
- calcium
- film
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
Definitions
- the present invention relates to a film (such as a protective film of a polarizing plate, a color filter, a film of a photographic light-sensitive material, etc.) and a cell opening ester useful for forming a fiber, and a film formed of the cell light cellulose ester.
- Cellulose ester films such as cellulose triacetate are tough and have high dimensional stability, heat resistance, optical isotropy, etc., support for optical films (for example, support films for photographic materials), and liquid crystal displays. It is used for applications such as polarizing plate protective films (liquid crystal protective films) and power filters in equipment.
- the refractive index in the thickness direction is smaller than the refractive index in the direction perpendicular to the thickness direction, and an appropriate retardation in the thickness direction (R t) is provided.
- a technique has been proposed in which a film (film) is produced and used as a retardation film (and WV film). Therefore, the cellulose ester film is required to have high optical properties, such as a yellow index, a low birefringence due to haze and a linear orientation in the plane of the film, and a high transparency. .
- liquid crystal display devices have been used not only as display devices for code processors and personal computers, but also for display devices such as television receivers and DVDs. Have been. And as LCD screens get larger, there is a growing demand for a wider viewing angle. Furthermore, portability is also required for liquid crystal display devices. Therefore, miniaturization, especially thinning is required.
- a method for producing a cellulose ester film that is, the above-mentioned liquid crystal protective film or WV film
- a method in which a film is generally formed by a solution casting method is used.
- a dope solution containing a cellulose ester dissolved in an organic solvent is cast from a die onto a stainless steel belt or a metal drum whose surface is polished, and the organic solvent is evaporated or cooled on the metal support. Then, the web is peeled off before the metal support goes around, and dried in a drying process to form a film.
- Controlling the peeling tension as low as possible during the process of peeling the web from the metal support during peeling is also effective in obtaining the desired Rt according to the application. That is, when the peeling tension is low, unnecessary linear orientation at the time of peeling can be avoided. Furthermore, if the releasability from the metal support during casting is high, the shrinkage on the metal support increases, and unnecessary linear orientation in the film forming direction and the width direction can be avoided.
- cellulose ester film in the cellulose ester Particularly, cellulose triacetate is preferably used, and some attempts have been made to use a mixed fatty acid cellulose ester esterified with a mixed fatty acid.
- Cellulose esters are susceptible to hydrolysis. Therefore, when used as a protective film for a polarizing plate (liquid crystal protective film), a color filter, or a retardation plate in a liquid crystal display device that is often used for a long time. Was required to have wet heat stability commensurate with the long-term usage time. In this regard, the recent increase in the screen size of liquid crystal display devices demands that the wet heat stability be further improved. That is, if the heat stability of the protective film is not sufficient, the polarizing plate may be damaged. And the possibility of the damage increases as the area of the cell opening becomes larger.
- cellulose acetate when a fiber is produced using a solution (dope) containing a cellulose ester such as cellulose diacetate and a solvent, high spinnability is required.
- the spinning method generally used for cellulose diacetate is as follows. A dope in which cellulose acetate is dissolved in an organic solvent such as acetone is discharged from a fiber discharge port (nozzle), and the solvent is dried with hot air or the like. Although the solvent spinning method is used, the release of cellulose acetate from metals is required to prevent clogging at the fiber discharge port (nozzle). In addition, it is required to increase the hydrolysis resistance of the fiber obtained by spinning cellulose ester to prevent the odor of the fatty acid resulting from the hydrolysis of the fiber from attaching to the fiber.
- a technique for suppressing hydrolysis by adding a metal salt or metal ion is disclosed.
- a technique utilizing the action of a buffer solution to which an alkali metal salt is added is disclosed in Japanese Patent Application Laid-Open No. 63-10 / 1988. This is disclosed in Japanese Patent Application Laid-Open No. 56665/1995 and Japanese Patent Application Laid-Open No. Hei 11-96231.
- Japanese Patent Application Laid-Open No. 196232/1992 discloses that a hydroxide such as sodium calcium is added to a dope to add cellulose hydroxide due to residual free acid. Techniques for preventing degradation are disclosed.
- the present applicant has disclosed in Japanese Patent Application Laid-Open No.
- hydrolysis can be effectively performed by adding a water-soluble metal salt containing an alkaline earth metal ion and / or a trivalent or higher metal ion. It discloses that it can be suppressed.
- These applications show that the greater the amount of metal ions, the greater the effect of inhibiting hydrolysis.
- the amount of metal ions is increased, there arises a problem that clogging or the like occurs in the nozzle portion due to the above-mentioned problem of releasability to metal at the time of discharging fibers.
- Japanese Patent Application Laid-Open No. H10-316701 discloses alkali metal in 1 gram of cellulose ester. if the 5. 5 X 1 CT 6 equivalents or less total content of alkaline earth metals, even with a small amount of residual solvent agent in the solution casting film forming method described above, has good releasability from the support A technology is disclosed.
- the applicant of the present invention disclosed in Japanese Patent Application Laid-Open No. 10-316701 an excellent solution casting film forming method by limiting the amount of alkaline earth metal in cellulose acetate. It discloses a cell mouth acetate having releasability from the support even if the amount of the residual solvent is small, but it did not satisfy wet heat stability.
- Japanese Patent Application Laid-Open No. 2002-131530 the content of an alkaline earth metal in a cellulose-mixed fatty acid ester (cellulose acetate propionate) polarizing protective film is set to 1 to 50 ppm. Compositions are disclosed. In this document, it is described that the residual sulfuric acid content (as the content of sulfur element) in the mixed fatty acid ester is 1 to 50 ppm. Further, Japanese Patent Application Laid-Open No. H11-311064 discloses that a method for preparing a cell opening persalt is disclosed in The use of cellulose acylates containing 100 to 100 ppm of alkaline earth metals is disclosed. Furthermore, Japanese Patent Application Laid-Open No.
- 2000-314148 discloses a cell-mouth monoester film having a specific molecular weight distribution.
- No. 0 discloses an optical film containing a cellulose ester having a specific degree of substitution with an acyl group. These documents describe that the amount of calcium component is 60 ppm or less.
- Japanese Patent Application Laid-Open No. 2002-424 discloses a composition in which the content of alkaline earth metal is 30 ppm or less in a cellulose ester film.
- an object of the present invention is to provide a cellulose ester which is highly peelable from a support (having a low peel strength) and has excellent wet heat stability in a solution casting film forming method, and a dope containing the same. It is to do.
- Another object of the present invention is to provide a cellulose ester which has not only high releasability from a support and excellent wet heat stability in a solution casting film forming method but also high optical properties and a dope containing the same. In that You.
- Still another object of the present invention is to provide a cellulose ester having a high spinnability and a dope containing the same when producing fibers using a cell mouth monoester dope.
- Another object of the present invention is to provide a cellulose ester film having excellent releasability, optical properties and spinnability, and also having excellent wet heat stability. Disclosure of the invention
- the present inventors have conducted intensive studies and found that (a) in cellulose ester, the ratio of calcium to residual sulfate groups in the alkaline earth metals has a large effect on wet heat stability and releasability from metals. (B) Of the alkaline earth metals, only calcium has a significant effect on wet heat stability, and other alkaline earth metals have an effect on hydrolysis.
- the cellulose ester is cellulose acetate (cell triacetate), and the total acetyl substitution degree of the 2- and 3-position is 1.70 or more and 1.95 or less, and the acetyl substitution degree of the 6-position.
- the cellulose ester is cellulose acetate (cellulose triacetate), and the total acetyl substitution degree of the 2- and 3-position is 1.80 or more and 1.95 or less, and the acetyl substitution degree of the 6-position is 0.
- the cellulose ester is cellulose acetate (cellulose triacetate), and the total acetyl substitution degree of the 2- and 3-positions is 1.84 or more and 1.92 or less, and the acetyl substitution degree of the 6-position is 0.89.
- the optical film according to the above (15) which is any film selected from a polarizing plate protective film, a retardation film, a scattering film, and a viewing angle widening film (WV film).
- a method for producing a cellulose ester by acylating cellulose in the presence of sulfuric acid and then deacylating the cellulose, wherein the sulfuric acid is neutralized A method for producing the cellulose ester according to any one of the above (1) to (14) by adding a calcium component after at least partially neutralizing with the agent.
- cellulose acetate means that an acetyl group (substituted acetyl group) is substantially composed of only an acetyl group, and is substantially another acetyl group (for example, a propionyl group or the like). It means a cellulose ester which does not contain an acyl group having 3 or more carbon atoms.
- total sulfuric acid remaining free sulfuric acid remaining in cellulose ester (H 2 S 0 4) as well, the cell opening It is used to include a sulfate group (sulfo group) bonded to a source.
- the cellulose ester of the present invention can be obtained by esterifying pulp.
- the type of the pulp is not particularly limited, and various types of pulp can be used. Typically, at least one type selected from wood pulp (hardwood pulp, softwood pulp) and phosphorus pulp can be used. Wood pulp and phosphorus pulp may be used in combination.
- the ⁇ -cellulose content which is an index of pulp purity, can be selected, for example, from the range of about 90 to 100% by weight, and is usually about 92 to 99% for wood pulp.
- low-purity pulp for example, pulp having a cellulose content of about 90 to 97% (particularly 92 to 96%) can be used. Of these pulps, wood pulp (such as hardwood pulp) is usually used.
- low-quality cellulose raw materials for example, wood pulp having a hemicellulose content of about 3 to 20% by weight (particularly preferably about 4 to 8% by weight)
- wood pulp having a hemicellulose content of about 3 to 20% by weight particularly preferably about 4 to 8% by weight
- cellulose esters made from hardwood pulp generally have poor film releasability by a solution casting film forming method
- cellulose esters made from softwood pulp generally have transparency and the like.
- the present invention can improve the optical properties such as the releasability of the cellulose ester film and the transparency of the cellulose ester and the spinnability even with such a wood pulp (such as hardwood pulp).
- the cellulose ester can be produced by a conventional method, for example, a sulfuric acid catalyst method, an acetic acid method, a methylene chloride method and the like.
- Cellulose esters suitably used in the present invention can be roughly classified into the following three embodiments.
- mixed fatty acid esters of cellulose particularly preferably vinegar Cellulose mixed fatty acid ester esterified with mixed fatty acid containing acid.
- cellulose triacetate which is cellulose acetate (cellulose triacetate), the sum of the degree of substitution at the 2- and 3-positions is within a specific range, and the degree of substitution at the 6-position is within a specific range; Uru.
- Cellulose ester (cellulose acetate) is obtained by activating cellulose with an organic acid (such as acetic acid) if necessary, and then acylating (or esterifying, especially acetylating or acetylyl) cellulose in the presence of an acid catalyst (particularly sulfuric acid).
- the reaction can be carried out by adding water or dilute acetic acid to stop the esterification, and then, if necessary, partially neutralizing and deacylating [ie, hydrolyzing (aging)]. More specifically, cellulose acetate is usually prepared by activating pulp (cellulose) with acetic acid or the like (activation step) and then preparing triacetate with acetic anhydride using a sulfuric acid catalyst (acetylation step).
- the activation step can be performed by treating pulp (cellulose) by, for example, spraying acetic acid or aqueous acetic acid, or dipping in acetic acid or aqueous acetic acid.
- the amount is 10 to 100 parts by weight, preferably 20 to 80 parts by weight, more preferably about 30 to 60 parts by weight, based on 100 parts by weight of the pulp (cellulose).
- the amount of acetic anhydride used in the acetylation step (the acetylation step, ie, the esterification step) can be selected within the above range of the acetylation degree. For example, based on 100 parts by weight of pulp (cell mouth) The amount is about 230 to 300 parts by weight, preferably about 240 to 290 parts by weight, and more preferably about 250 to 280 parts by weight.
- acetic acid is usually used as a solvent.
- the amount of acetic acid used is, for example, 2 parts per 100 parts by weight of pulp (cellulose). It is about 700 to 700 parts by weight, preferably about 300 to 600 parts by weight, and more preferably about 350 to 500 parts by weight.
- sulfuric acid is usually used as the esterification or aging catalyst.
- the amount of sulfuric acid to be used is generally 1 to 15 parts by weight, preferably 5 to 15 parts by weight, particularly about 5 to 10 parts by weight, based on 100 parts by weight of cellulose.
- Saponification and aging can be performed, for example, at a temperature of about 50 to 70 ° C.
- the acid catalyst sulfuric acid
- the acid catalyst may be partially neutralized with a neutralizing agent if necessary, and then used as a catalyst for hydrolysis or aging.
- the acid catalyst (especially sulfuric acid) is used in a suitable step after acylation (acetylation) in the process of producing the cellulose ester (cellulose acetate) [for example, after the acetylation step and before the hydrolysis, hydrolysis or Is neutralized by adding a neutralizing agent (or stabilizer) such as an alkali or alkaline earth metal compound (eg, metal oxide, metal hydroxide, metal salt) There are many.
- a neutralizing agent such as an alkali or alkaline earth metal compound (eg, metal oxide, metal hydroxide, metal salt)
- the addition of the neutralizing agent may be performed in a plurality of times. For example, after acetylation (step), a neutralizing agent is added to partially neutralize the acid catalyst (sulfuric acid) (partial neutralization). After aging, it may be further neutralized (completely neutralized).
- the produced cellulose acetate may be treated with an oxidizing agent after an appropriate stage in the production process of cellulose acetate, for example, after acetylation or saponification and ripening.
- the oxidizing agent include hydrogen peroxide; peracids such as formic acid, peracetic acid, and perbenzoic acid; and organic peroxides such as diacetyl peroxide.
- the oxidizing agents can be used alone or in combination of two or more.
- Preferred oxidizing agents include those that are easy to remove from cellulose acetate and have low persistence, such as hydrogen peroxide, formic acid, and peracetic acid. Particularly preferred.
- the amount of the oxidizing agent to be used can be selected according to the level of the desired optical properties, and is, for example, 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of cellulose acetate. 5 parts by weight, especially about 0.1 to 1 part by weight You.
- the treatment with the oxidizing agent can be performed at, for example, about 20 to 100 ° C., preferably about 30 to 70 ° C., depending on the type of the oxidizing agent.
- the average degree of acetylation can be selected from the range of about 30 to 62.5% depending on the application and characteristics, but industrially useful cellulose acetate is usually cellulose diacetate or cell. Roast rear acetate.
- the average acetylation degree of cellulose acetate (cellulose diacetate to cellulose triacetate) may be usually 43.7 to 62.5%, preferably about 45 to 62%.
- the average acetylation degree of cellulose diacetate is, for example, 43.7 to 58.0% (average degree of substitution of acetyl group 1.7 to 2.6), preferably 4 It is about 5 to 57.0% (average degree of substitution 1.8 to 2.6), and more preferably about 48 to 57.0% (average degree of substitution 2.0 to 2.6). Particularly preferably, it is 53.0 to 56.0%.
- the average degree of acetylation is usually 58 to 62.5%, preferably to improve dimensional stability, moisture resistance and heat resistance. 58.5 to 62%, more preferably about 59 to 62% (for example, 60 to 61%).
- Cellulose acetate films having an average acetylation degree of 58.0 to 62.5% are commonly used for photographic materials and optical materials. Cellulose acetate having an average acetylation degree of 58% or more is classified as cellulose triacetate.
- Cellulose acetate films are generally produced by a solvent casting method. In the solvent casting method, a solution (dope) in which cellulose acetate is dissolved in a solvent is cast on a support, and the solvent is evaporated to form a film.
- a solution can be prepared even with a combination of cellulose acetate and an organic solvent, which cannot be dissolved by the conventional method. can do.
- the cooling dissolution method is an effective means for producing films from low-solubility one-cell-striacetate (average acetylation degree of 58% or more).
- the cooling dissolution method was developed to produce films from cellulose triacetate with low solubility (average acetylation degree of 58% or more).
- films manufactured using cellulose acetate with an average degree of acetylation of 55.0 to 58.0% have a high resin dispersion value (R t) in the thickness direction.
- R t resin dispersion value
- a higher retardation value can be obtained. If the amount of residual solvent during peeling from the metal support during casting film formation is reduced and the peeling tension is controlled to be as low as possible during peeling, this Rt is large (high). Thus, a suitable film is obtained.
- the degree of acetylation means the amount of bound acetic acid and refers to the percentage by weight of bound acetic acid per unit weight of cellulose.
- the degree of esterification of ASTM: D—8 17—91 (test method for cell acetate, etc.) It can be measured according to the measurement method of. Specifically, 1.9 g of dried cellulose acetate was precisely weighed and dissolved in 150 ml of a mixed solvent of acetone and dimethyl sulfoxide (volume ratio: 4: 1). Add 0 ml and saponify at 25 ° C for 2 hours. Add phenolphthalein as an indicator and titrate excess sodium hydroxide with 1 N sulfuric acid (concentration factor: F).
- Degree of acetylation (%) [6.5 X (B—A) XF] / W (where A is the titer of 1 N-sulfuric acid in the sample (m 1), B is 1 in the blank test) The titer of N-sulfuric acid (m 1), F is the concentration factor of 1 N-sulfuric acid and W is the weight of the sample). Further, the degree of polymerization of cellulose acetate is a viscosity-average degree of polymerization of about 200 to 400, preferably about 250 to 400, more preferably about 270 to 400 (for example, about 290 to 400).
- the viscosity average degree of polymerization is about 270 to 350.
- the average degree of polymerization can be measured by the ultimate viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, Journal of the Textile Society of Japan, Vol. 18, No. 1, pp. 105-122, 1962).
- the viscosity of a 6% by weight solution of cellulose acetate is, for example, 200 to 700 cps (mPa ⁇ s ), Preferably about 250 to 600 cps, particularly about 250 to 500 cps.
- a cellulose mixed fatty acid ester is obtained by mixing and esterifying an aliphatic acid other than acetic acid in the esterification of the cellulose ester.
- the mixed fatty acid ester of cellulose can be synthesized using an acid anhydride or an acid chloride as an acylating agent.
- the acylating agent is an acid anhydride
- an organic acid eg, acetic acid
- methylene chloride is used as a reaction solvent.
- a protic catalyst such as sulfuric acid is used.
- the acylating agent is an acid chloride
- a basic compound is used as a catalyst.
- cellulose as an organic acid (acetic acid, propionic acid, butyric acid) or an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride) corresponding to acetyl and other acyl groups.
- cellulose such as cotton linter (linter pulp) or wood pulp is activated with an organic acid such as acetic acid, and then mixed with an organic acid component as described above in the presence of a sulfuric acid catalyst. Esterify using
- the organic acid anhydride component is generally used in an excess amount relative to the amount of hydroxyl groups present in cellulose.
- a hydrolysis reaction depolymerization reaction
- the degree of polymerization of the cellulose ester decreases, and the physical properties of the produced cellulose ester film decrease. Therefore, the reaction conditions such as the reaction temperature must be determined in consideration of the degree of polymerization and the molecular weight of the obtained cellulose ester.
- a cellulose ester can be produced using only other organic acids without using acetic acid as an organic acid.
- a film produced from the obtained cellulose ester such as cellulose propionate or cellulose butylate has mechanical strength and Since the durability is inferior to cellulose acetate film, it is not practical.
- the most suitable alternative to cellulose acetate is a mixed fatty acid ester of cellulose obtained by esterifying cellulose with an organic acid corresponding to acetyl and other acyl groups.
- the mixed fatty acid ester of a specific cellulose, cellulose acetate propionate, cellulose acetate C 3 6 Ashireto such as cellulose ⁇ cetearyl one Topuchire one DOO, preferably cellulose acetate C 3 4 Ashireto can be exemplified.
- the degree of acetyl substitution at the second or third position is higher than the degree of acetyl substitution at the sixth position. Therefore, in order to make the total acetyl substitution degree of the 2-, 3-, and 6-positions 2.67 or more while keeping the total acetyl substitution degree of the 2- and 3-positions at 1.95 or less, Special adjustment of the reaction conditions is required.
- the amount of the sulfuric acid catalyst it is preferable to reduce the amount of the sulfuric acid catalyst and lengthen the time for the acetylation reaction. If the amount of the sulfuric acid catalyst is large, the progress of the acetylation reaction is accelerated, but a sulfate ester is generated between the cellulose and the cellulose depending on the amount of the catalyst, and is liberated at the end of the reaction to generate a residual hydroxyl group. Sulfuric acid ester is generated more at the highly reactive 6-position. Therefore, when the amount of the sulfuric acid catalyst is large, the degree of acetyl substitution at the 6-position decreases.
- cellulose acetate used in the present invention, it is necessary to adopt a production method in which the amount of the sulfuric acid catalyst is reduced as much as possible and the reaction time is extended in order to compensate for the reduced reaction rate. it can.
- a method for producing cellulose acetate comprising a step of aging in the presence of a medium (sulfuric acid) can be used.
- the present inventors have concluded that such a cellulose acetate having a high degree of substitution at the 6-position is combined with the cellulose acetate of the present invention having a specific ratio of sulfate group (sulfo group) to calcium content in methylene chloride. It has been found that it is particularly convenient to dissolve in a solvent other than a solvent, and it is easy to obtain a solution of cellulose acetate that achieves both wet heat resistance and releasability from a metal support during solution casting film formation.
- the degree of acetyl substitution at the 2-, 3-, and 6-positions of the cellulose acetate can be determined by 13 C-NMR after the cellulose acetate is subjected to a propionylation treatment.
- the details of the measurement method are described in Tezuka et al. (Carbohydr. Res. 273 (195) 83-91).
- the details of these cellulose acetates having an increased degree of acetyl substitution at the 6-position are described in JP-A-11-18551 and JP-A-2002-380861. I have.
- the sum of the acetyl substitution degree (average substitution degree) at the 2nd and 3rd positions is 1.70 or more and 1.95 or less, and the acetyl substitution degree (average substitution degree) at the 6th position.
- cellulose ester in the 19th form.
- Cell mouth esters usually in flake or granular form, contain 20-40% moisture and must be removed prior to measurement.
- plasticizers and additives these plasticizers and additives are removed by a separation method utilizing the difference in solubility by immersion in an organic solvent. Thereby, a cell mouth monoester can be obtained.
- the details of the method of removing these plasticizers and additives are described in “Analysis Chemistry Society of Japan, Polymer Analysis Handbook” (published by Asakura Shoten Co., Ltd.).
- a cellulose raw material is reacted with an acid such as acetic anhydride using acetic acid as a solvent.
- an acid such as acetic anhydride using acetic acid as a solvent.
- a strong acid having a dehydrating action is used as a catalyst.
- sulfuric acid is used, but this sulfuric acid not only acts as a catalyst but also causes a reaction to become cellulose sulfate. As a result, depending on the reaction, this sulfate group remains in the reaction product. Therefore, such a cellulose ester is usually used to improve thermal stability and wet heat stability.
- a stabilizer such as an alkali metal (lithium, potassium, sodium or the like) or a salt or a compound thereof, or an alkaline earth Contains a large excess of metals (calcium, magnesium, strontium, barium, etc.) or their salts and compounds. This provides stability without freeing the sulfate groups (sulfo groups).
- the cellulose ester contains metal and metal earth, and its purpose is to improve heat resistance and wet heat stability as described above.
- Alrikari metal and the Alrioli earth metal affect the releasability and spinnability from the metal support in the solution casting film forming method (JP-A-10-31). No. 6701).
- the amount of alkaline earth metal added was reduced, the stability was poor, and the wet heat stability was not satisfactory.
- the wet heat stability and the releasability (spinnability) from the metal support in the solution casting film forming method were mutually exclusive properties.
- the present inventors have found that the effect of individual elements on the amount of addition differs even for alkaline earth metals, and calcium is specifically contained in the alkaline metal and / or alkaline earth metal to be added. It has been found that the composition has an effect on wet heat stability, and that the ratio of calcium and remaining sulfuric acid (or sulfate group) is related to wet heat stability and mold releasability to metals.
- the amount of sulfuric acid remaining in the cellulose ester can be adjusted by the amount of sulfuric acid used as described later.
- the total sulfuric acid remaining in 1 g of cellulose ester is, for example, 0. 1 X 1 0 7 ⁇ : L 0 0 0 X 1 0- 7 mo 1 , preferably about 1 X 1 0-' ⁇ 5 0 0 X 1 0 _7 mo 1 ( e.g., 5 X 1 0- 7 ⁇ 3 0 0 X 1 0- 7 m ⁇ 1) , and more preferably about 1 0 X 1 0 ' ⁇ : L 0 0 X 1 0- 7 mo 1 ( e.g., 1 0 X 1 0 _7 ⁇ 5 0 X 1 0 _7 mo 1).
- the present invention relates to a cellulose ester (e) comprising the above-mentioned cellulose ester (particularly, cellulose acetate) (a), (b), (c) or (d), and containing a specific amount of calcium shown below. Or (f).
- the step of adding these stabilizers varies depending on the method for producing the cellulose ester. That is, it is added as a neutralizing agent at the end of esterification.
- the compound is added in the form of a metal acetate before the ripening step after esterification or during the ripening step.
- the same metal acetate may be added after the aging step.
- it is added in the form of alkali metal ions and Z or alkaline earth metal ions to a coagulating solution for coagulating and precipitating a liquid cellulose ester after aging.
- the above-mentioned ions may be added in the step of washing the cellulose ester obtained by coagulation and precipitation. Further, it may be added by spraying an aqueous solution of a water-soluble alkali metal or alkaline earth metal salt onto the dried cellulose ester flakes and particles. These methods may be used in combination.
- a cellulose ester (cellulose acetate, especially cellulose triacetate) which is acylated (especially acetylated with an acetylating agent) in the presence of sulfuric acid and then deacylated [especially, hydrolyzed (aged)].
- the sulfuric acid usually used as a catalyst is neutralized with a neutralizing agent [in particular, magnesium oxide, magnesium hydroxide, magnesium salts (magnesium salts of inorganic acids such as magnesium carbonate, magnesium salts of inorganic acids such as magnesium acetate)
- a neutralizing agent in particular, magnesium oxide, magnesium hydroxide, magnesium salts (magnesium salts of inorganic acids such as magnesium carbonate, magnesium salts of inorganic acids such as magnesium acetate)
- calcium components especially calcium oxide, calcium hydroxide, calcium salts (such as calcium carbonate)
- the above-mentioned heat stabilizer can be usually added after acylation (or after esterification, particularly after acetylation).
- acylation or after esterification, particularly after acetylation.
- aging before hydrolysis (aging)
- II aging It may be added later and before the coagulation precipitation step, or may be added in combination.
- cellulose is acylated (particularly acetylated) with an acetylating agent in the presence of sulfuric acid, and the sulfuric acid is converted into An appropriate stage after the silation (especially acetylation or acetylation) process [eg
- the termination step of acylation or esterification (acetylation) (ie, after acylation (especially acetylation) and before hydrolysis (or aging)), and / or (ii) after aging, and At least partially neutralized with a neutralizing agent [eg, a neutralizing agent containing at least a magnesium component (eg, magnesium acetate)], and a subsequent step [eg, after aging (eg, (Coagulation precipitation step, washing step, etc.)] and adding a calcium component [eg, calcium hydroxide and Z or calcium salts, especially calcium hydroxide].
- a neutralizing agent eg, a neutralizing agent containing at least a magnesium component (eg, magnesium acetate)
- a subsequent step eg, after aging (eg, (Coagulation precipitation step, washing step, etc.)
- a calcium component eg, calcium hydroxide and Z or calcium salts, especially calcium hydroxide.
- the ratio of sulfuric acid to calcium can be efficiently adjusted within the above range (for example, 0.5 ⁇ (B) / (A) ⁇ 1.5, etc.).
- the concentration and amount of the agent can be determined in consideration of the content of Karushiu arm of the finally obtained cellulose ester.
- cellulose ester lg (In terms of weight), usually, can be selected from the range of 30 ppm or less (for example, 0 to 30 ppm), for example, 0 to 25 ppm, preferably 20 ppm or less (for example, 0.1 to 0.1 ppm). 20 p pm), more preferably about 15 p pm or less (for example, 0.3 to 12 p pm), and about l O p pm or less (for example, about 0.5 to 9 p pm). It may be.
- the ratio of calcium to sulfate groups becomes a problem, and 0.5 times the number of moles of calcium relative to the number of moles of sulfate groups is required.
- alkali metals and / or alkaline earth metals have been added in large excess to sulfate groups. This is due to the fact that some of the hydroxyl groups of cellulose have been converted to hydroxyl groups during the esterification process. Due to the presence of these hydroxyl groups, approximately two times the amount of sulfuric acid groups was added to Alkyri metal and / or Alkyrie earth metal.
- the necessary wet heat stability can be obtained if the amount of calcium is more than 0.5 times the number of moles of the sulfate group.
- a more preferred range is the amount of calcium exceeding 0.6 times the number of moles of the sulfate group.
- the amount of calcium needs to be less than 1.5 times the number of moles of the sulfate group due to the releasability from the metal support in the solution casting film forming method. More preferably, the amount of calcium is less than 1.0 times the number of moles.
- the sulfuric acid catalyst is used in the esterification step of the cellulose ester, the remaining sulfuric acid is produced even if the cellulose ester is produced using the production method most suitable for the aspect of the cellulose ester in the present invention.
- As a sulfate group at least about 10 X 10 -7 mo 1 remains per 1 g of cellulose ester. Therefore cellulose ester 1 g per 5 X 1 0 "7 mo 1 about arbitrary preferable that the contain a calcium amount.
- the calcium content exceeds 2 0 X 1 0- 7 m 0 1 about the amount In such a case, there may be a problem in the releasability from the metal support and the spinnability in the solution casting film forming method, and the preferable range is that the calcium content is 5 ⁇ 10-7 or more per 1 g of the cellulose ester. 20 X 10 0-7 or less (unit is mo 1) Particularly preferred range is 8 X 10
- the ash content after completely burning the cellulose ester can be quantified by performing a pretreatment in which the ash is dissolved in hydrochloric acid, followed by analysis by atomic absorption spectrometry, and The cellulose ester is pretreated by a wet digester with a mic mouth digestion (sulfuric acid and nitric acid decomposition) and melting with an alcohol, and then analyzed by ICP-AES (dielectric coupled plasma emission spectroscopy). be able to.
- Such a cell-mouth monoester has high releasability from a support in the production of a film by a solution casting film-forming method, and a cellulose ester has excellent optical properties such as transparency.
- the transparency of cellulose ester is, for example, about 60 to 100% (preferably 70 to 100%, more preferably 75 to 100%), and usually 70 to 90%.
- the haze is about 1 to 8 (preferably 1 to 5).
- the Yellowness Index (YI) which is an index of the yellowness of the cellulose ester, is, for example, about 1-10.
- the transparency, haze and yellowness index (Y I) can be measured by the following methods.
- the cellulose ester of the above embodiment is characterized by It has excellent properties, filtration properties and spinning properties, and can greatly reduce the frequency of thread breakage even when spinning continuously over a long period of time.
- the present invention relates to a method for preparing a total amount of sulfuric acid (A) [unit: mo 1] remaining in 1 g of cellulose ester and a total amount of calcium (B) [unit: mo 1] contained in 1 g of the cellulose ester. From A method for improving the wet heat stability of the cellulose ester by adjusting the required molar ratio (B) / (A) to the above range (for example, 0.5 ⁇ (B) / (A) ⁇ 1.5) is also available. Include.
- the wet heat stability can be measured as follows.
- Moist heat stability (%) (A_B) XF X 0.06 ⁇ Sample weight (gr.) (However, A: 0.01 N titration of NNaOH solution (aqueous solution) (m1) B: Blank test Titer of 0.01 N—Na ⁇ H solution (aqueous solution) at (m 1) F: Factor of 0.01 N—Na ⁇ H solution (aqueous solution)
- the wet heat stability (%) of the cellulose ester according to the above method is 0.08% or less (for example, 0.01 to 0.08%), preferably 0.07% or less (for example, 0.07%). 2 to 0.065%), more preferably 0.06 or less (for example, 0.02 to 0.055%), particularly 0.05% or less (for example, 0.02 to 0%). 0.5%).
- the cellulose acetate of the present invention having such properties is useful for preparing a cellulose acetate solution (dope) and producing films and fibers.
- the dope of the present invention contains at least one kind of cellulose acetate among the above embodiments (1) to (3) of the cell ester.
- the dope of the present invention belongs to at least one of the above embodiments (1) to (3) of the present invention.
- a plurality of cellulose esters are mixed to form a mixture of the embodiments (1) to (3) of the cellulose ester of the present invention. It is also possible to belong to at least one of the embodiments (1) to (3) of the invention.
- the dope is usually composed of a cellulose ester and a solvent (organic solvent).
- the solvent include, for example, halogenated hydrocarbons (methylene chloride, ethylene chloride, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) according to the average acetylation degree of the cellulose ester.
- Esters formic acid ester such as ethyl formate, acetate ester such as methyl acetate, ethyl acetate, etc., ethyl lactate, etc.
- ethers dioxane, dimethoxetane, etc.
- cellosolves methylcellosolve, (E.g., ethyl ethyl solvate), cellosolve acetates (e.g., methyl cellosolve acetate, ethyl ethyl solv acetate), and mixtures thereof.
- Solvents may include two-mouthed compounds (nitromethane, nitroethane, nitropropane, etc.), lower alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.).
- a stable dope can be obtained without using a halogenated hydrocarbon as a solvent.
- the organic solvent can be dissolved by cooling the organic solvent without using octogenated hydrocarbons as a solvent.
- the amount of the solvent to be used can be selected within a range that does not impair castability, spinnability, handleability, and the like in film forming.
- the loop is useful for film formation by the solution casting method.
- cellulose diacetate to cellulose triacetate is used.
- the film formed by the solution casting method is usually obtained by casting a dope on a support, partially drying the dope, peeling the dope from the support, and then drying.
- a conventional support for example, a mirror-finished metal support (for example, a stainless steel support) can be used.
- the cellulose ester of the present invention has a high releasability (releasability) from the support, so that the semi-dried film can be smoothly released from the support, and a cellulose ester film having a high surface smoothness is obtained. be able to. Therefore, the method using the dope of the present invention is useful as a method for improving the removability of the film from the support.
- the cellulose ester film of the present invention is composed of the cellulose ester, it has excellent optical properties (yellowness (Y I), haze and transparency).
- the thickness of the cellulose ester film thus obtained is, for example, 5 to 500 m, preferably 10 to 200 im, more preferably 20 to 14011, depending on the intended use. Preferably, it can be selected from a range of about 30 to 1301, particularly about 50 to 120 m.
- the cellulose ester of the present invention can be obtained by the solution casting method according to the above-mentioned method. Not only is it useful for film-forming optical films such as, but also has excellent releasability from the support, so it can be used for the production of thin optical films by spin coating, etc.
- the cellulose ester of the present invention is also excellent in stove stability, filterability and spinnability.
- the cellulose ester in the cell mouth is usually cellulose diacetate or Cellulose triacetate is used.
- Spinning can be obtained by spinning a dope from a spinneret having a large number of pores and drying it, using a conventional method, and may be stretched if necessary.
- the method using the dope of the present invention is useful as a method for improving spinnability.
- the cellulose ester or dope of the present invention may be a plasticizer, for example, a phosphate such as triphenylphosphate (TPP) or tricresyl phosphate ( ⁇ ⁇ CP), dimethylphthalate (DMP), or diethyl phthalate.
- a phosphate such as triphenylphosphate (TPP) or tricresyl phosphate ( ⁇ ⁇ CP), dimethylphthalate (DMP), or diethyl phthalate.
- Phthalates such as (DEP), dibutyl phthalate (DBP), dimethyl phthalate (DOP), and di-2-ethylhexyl phthalate (DEHP); butyl oleate; methyl acetyl ricinoleate; and sebacic acid.
- the cellulose ester may contain an antioxidant, for example, an antioxidant, an ultraviolet absorber, a peroxide decomposer, a radical inhibitor, a metal deactivator, an acid scavenger, and the like.
- the cellulose ester may contain other additives such as a crystal nucleating agent, an inorganic powder (for example, diatomaceous earth, calcium carbonate, titanium oxide, etc.), a heat stabilizer, a flame retardant, and a colorant. Etc. may be included.
- the cellulose ester of the present invention (the cellulose ester having an alkali metal and alkaline earth metal content in a specific range) is excellent in wet heat stability, but is detached from a support in a solution casting film forming method. A film having high surface smoothness and high optical characteristics can be obtained. Further, the cellulose ester of the present invention has a stable dope. It has excellent heat resistance, filterability, spinnability and heat resistance.
- reaction temperature, time, catalyst amount, and the like described in this example are those obtained by the inventor's apparatus, and the reaction of cellulose ester is a complicated solid-liquid reaction.
- the results obtained vary depending on the size, shape, temperature measurement site, etc.
- the peelability of the film by the solution casting method was evaluated as follows. 100 parts by weight of cellulose ester, 320 parts by weight of methylene chloride, 40 parts by weight of methanol, 25 parts by weight of butanol, and 15 parts by weight of triphenyl phosphate (TPP) are mixed to form a dope. Prepare. The dope was cast on a smooth stainless steel plate (support) to a thickness of about 1 mm at room temperature (20 to 25 ° C), and left at room temperature for 3 to 4 minutes. The releasability from is evaluated according to the following criteria.
- ash was dissolved in hydrochloric acid, pre-treated, and then measured by an atomic absorption method.
- the measured value is the content of each alkaline earth metal in 1 g of cell mouth monoester in absolutely dry condition. The quantity is obtained in units of ppm.
- the dried cellulose ester is baked in an electric furnace at 1300 ° C, and the sublimated sulfur dioxide gas is trapped in 10% hydrogen peroxide solution, and this is trapped in a specified sodium hydroxide aqueous solution (specified degree of hydroxylation).
- the solution was titrated with an aqueous sodium solution (usually, an aqueous solution of sodium hydroxide of 0.01 to 1 N).
- the value obtained is the amount of S 0 4 2 — conversion.
- the measured value is obtained in units of ppm as the sulfuric acid content in 1 g of the absolutely dried cellulose ester.
- C a / S 0 4 ratio Ru molar ratio der. That is, by dividing the above sulfuric acid amount by 96, (1) the sulfuric acid content in 1 g of cellulose ester can be obtained in units of mo1. Similarly, (2) By dividing the calcium content of the alkaline earth metal content by 40.1, the calcium content in 1 g of cell mouth monoester can be obtained in units of mo1. By dividing 2 by 2, C a
- Wet heat stability is an index of the difficulty of hydrolysis of cellulose ester when there is sufficient moisture and it is exposed to high temperature.If it is 0.08% or less, it is evaluated as stable. You. That is, when a film is obtained by the above-described method using the obtained cell-acetate, a long time (eg, 100 hours) under a condition of high temperature and high humidity (eg, 40 ° C. ⁇ 90 RH%) ) Even when retained, problems associated with hydrolysis of cellulose ester are unlikely to occur.
- CTA Cellulose triacetate
- the flakes of the cellulose triacetate described above are immersed in calcium hydroxide aqueous solutions having different concentrations of 5 to 30 ppm, respectively, treated, filtered, and dried to contain the metal components described in Table 1. Cell roast rear acetate was obtained. Table 1 also shows the results of evaluating the wet heat stability and the peelability of the film by the solution casting method. Examples 6 to 9 Examples 6 to 9 are described below.
- Example 2 100 parts by weight of hardwood kraft pulp ( ⁇ ; —cellulose content: 98.5%) was sprayed with 50 parts by weight of glacial acetic acid to activate the pretreatment.
- magnesium acetate was added as a neutralizing agent, and the mixture was aged at about 10 ° C. higher than that of Example 1 for about 70 minutes. Triacetate is precipitated, the obtained precipitate is divided into four parts, and the solid and liquid are separated by dehydration and washing with pure water.
- the acetylation degree (average acetylation degree) is 60. 8%, viscosity average Cellulose triacetates (CTA) of Examples 6 to 9 having a degree of polymerization of 303 were obtained.
- Comparative Example 1 1.3 17.0 190 0.02 0.3 7.0 ⁇ Comparative Example 2 23.3 15.0 1 90 0.29 5.8 6.2 ⁇ Comparative Example 3 34.7.14.0 200 0.42 0.096 8.7.5.8 ⁇ Example 1 40.5 14.0 190 0.51 0.077 10.1 5.8 ⁇ Example 2 46.7 14.0 200 0.56 1 1.7 5.8 ⁇ Example 5 66.2 20.0 180 0.88 0.040 16.5 8.2 2 Example 6 41.5 9.0 0 100 0.99 10.4 3.7 ⁇ Example 7 31.5 8.7 100 0.75 0.048 7.9 3.6 ⁇ Example 8 21.4 9.4 100 0.51 0.060 5.3 3.9 ⁇ Example 9 57.5 9.0 100 1.38 0.048 14.3 3.7 ⁇ Comparative examples in Table 1 1-3 and Example 1-2, inflection between apparent from Examples 5-9, wet heat stability of C a / S 0 4 ratio 0.4 2 0.5 6 If there is a point and it is 0.50 or more, it can be 0.08% or less.
- Alkaline earth metal content is almost the same, compared with Examples 6 to 8. As is clear from Example 3, the alkaline earth metal content is about 50 ppm or cellulose ester dry weight. — Even if it is contained in 7 mol, good resistance to wet heat is not obtained, indicating that the ratio of sulfuric acid to calcium is an important factor for the stability of wet heat. Examples 3 and 4
- Wood pulp having a cellulose content of about 98.5% (moisture content: 7.3% by weight) was crushed.
- 30 parts by weight of glacial acetic acid was uniformly dispersed and stirred, and then left at room temperature for 90 minutes.
- the pulp was charged and mixed in a pre-cooled mixture of 270 parts by weight of acetic anhydride, 380 parts by weight of acetic acid, and 7 parts by weight of 98% sulfuric acid.
- the reaction temperature was linearly increased to 37 ° C 60 minutes after 0 ° C at the start of the reaction by external cooling / heating, and maintained at 37 ° C for 90 minutes.
- cellulose acetate was synthesized.
- acetic acid aqueous solution was added to the synthesized cellulose acetate dope, the temperature was raised to 54 ° C., and the mixture was kept for 115 minutes to ripen the cellulose acetate.
- the mixing ratio was 199 parts by weight of acetic acid (acetyl group donor), 64 parts by weight of water, and 21 parts by weight of sulfuric acid (catalyst) based on 499 parts by weight of cellulose acetate. . Therefore, the amount of water relative to acetic acid (acetyl donor) was 11 mol%.
- the resulting solution was kept at 30 ° C. for 3 hours to ripen cellulose acetate.
- the degree of substitution at the 2-position (2DS), the degree of substitution at the 3-position (3DS), the degree of substitution at the 6-position (6DS), and the degree of polymerization were measured.
- the substitution degree was measured according to the method of Tezuka (Tezuka, Carbohydr. Res. 273, 83 (1995)). That is, the free hydroxyl groups of the sample cellulose acetate are propionylated with propionic anhydride in pyridine. The obtained sample is dissolved in a double-mouthed form, and the spectrum of carbon 13 is measured.
- the signal of the alkenyl carbon is in the range of 169 ppm to 171 ppm
- the signal of the propionyl group is 1 in the order of 2nd, 3rd, and 6th from the high magnetic field. Appears in the same order in the region from 72 ppm to 174 ppm.
- the distribution of acetyl groups in the original cellulose acetate can be obtained from the abundance ratios of acetyl and propionyl at the corresponding positions.
- 6DS was 0.901
- 2DS was 0.945
- 3DS was 0.941.
- the degree of polymerization (average degree of polymerization) was 284. No significant difference was observed between Examples 3 and 4 for these values.
- Example 3 and Example 4 were immersed in calcium hydroxide aqueous solutions having different concentrations, filtered to remove water, and dried with hot air. Furthermore, the wet heat stability and the peelability of the film by the solution casting method were evaluated. Table 2 shows the results.
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Abstract
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EP04714483A EP1619209B1 (en) | 2003-02-25 | 2004-02-25 | Cellulose ester having improved stability to wet heat |
JP2005502910A JP4435086B2 (ja) | 2003-02-25 | 2004-02-25 | 湿熱安定性を改良したセルロースエステル |
US10/546,838 US7863439B2 (en) | 2003-02-25 | 2004-02-25 | Cellulose ester having improved stability to wet heat |
KR1020057015328A KR101057509B1 (ko) | 2003-02-25 | 2004-02-25 | 개선된 습열 안정성을 갖는 셀룰로오스 에스테르 |
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- 2004-02-25 JP JP2005502910A patent/JP4435086B2/ja not_active Expired - Fee Related
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Cited By (27)
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JP2005082744A (ja) * | 2003-09-10 | 2005-03-31 | Daicel Chem Ind Ltd | セルロースエステル又はそのフイルム及びその製造方法 |
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JP2006089574A (ja) * | 2004-09-22 | 2006-04-06 | Daicel Chem Ind Ltd | セルロースエステル及びその製造方法 |
JP2012128434A (ja) * | 2004-09-27 | 2012-07-05 | Fujifilm Corp | セルロースアシレートフイルム並びにそれを用いた光学補償フィルム、偏光板及び液晶表示装置 |
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JPWO2017158639A1 (ja) * | 2016-03-15 | 2019-01-31 | 株式会社ダイセル | セルロースアセテート |
JP2019143039A (ja) * | 2018-02-20 | 2019-08-29 | リンテック株式会社 | 粘着シート |
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Also Published As
Publication number | Publication date |
---|---|
KR101057509B1 (ko) | 2011-08-17 |
EP1619209B1 (en) | 2012-12-19 |
EP1619209A4 (en) | 2007-07-18 |
US20060142559A1 (en) | 2006-06-29 |
KR20050102127A (ko) | 2005-10-25 |
JPWO2004076490A1 (ja) | 2006-06-01 |
EP1619209A1 (en) | 2006-01-25 |
US7863439B2 (en) | 2011-01-04 |
JP4435086B2 (ja) | 2010-03-17 |
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