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WO2011111484A1 - Procédé de production d'un ester de cellulose, ester de cellulose et film d'ester de cellulose - Google Patents

Procédé de production d'un ester de cellulose, ester de cellulose et film d'ester de cellulose Download PDF

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Publication number
WO2011111484A1
WO2011111484A1 PCT/JP2011/053229 JP2011053229W WO2011111484A1 WO 2011111484 A1 WO2011111484 A1 WO 2011111484A1 JP 2011053229 W JP2011053229 W JP 2011053229W WO 2011111484 A1 WO2011111484 A1 WO 2011111484A1
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Prior art keywords
cellulose ester
film
cellulose
acid
solvent
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English (en)
Japanese (ja)
Inventor
学 松岡
笠原　健三
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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Priority to JP2012504380A priority Critical patent/JPWO2011111484A1/ja
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    • 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
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/22—Post-esterification treatments, including purification
    • 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
    • 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
    • C08L1/12—Cellulose acetate
    • 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
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • 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
    • C08J2301/12—Cellulose acetate
    • 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
    • C08J2301/14—Mixed esters

Definitions

  • the present invention relates to a cellulose ester production method, a cellulose ester, and a cellulose ester film, and suppresses variation in performance between production lots of cellulose ester and reduces the film surface failure (diagonal streaks, horizontal dan, egg unevenness, etc.).
  • the present invention relates to a method for producing a cellulose ester capable of producing a film, a cellulose ester produced thereby, and a cellulose ester film using the cellulose ester.
  • cellulose ester has been suitably used as a raw material for a protective film of a polarizing plate used in a liquid crystal display device because of its high transparency, low birefringence, and excellent adhesion with a polarizer.
  • it is suitably used as a raw material for optical films such as a retardation film, a field-of-view expansion film, and an antireflection film.
  • Cellulose esters used in the above products are generally activated (pretreatment) in which the raw cellulose coarsely pulverized in the pulverization step is activated in order to react with acyl groups, and the cellulose ester is produced under carboxylic acid and acid catalyst.
  • An esterification step for esterifying a hydroxyl group an aging step for converting the acyl group substituted in the esterification step to a desired acyl group substitution degree by deacylation or the like, if necessary, hydrolyzing the carboxylic acid anhydride, and a base
  • the product is obtained by precipitating, purifying and drying the product through a neutralization step of neutralizing the acid catalyst.
  • cellulose ester films used for optical applications are generally formed into solutions, and are formed using a chlorinated solvent such as methylene chloride.
  • Cellulose esters are greatly involved in properties such as solubility and viscosity due to changes in acyl group substitution degree distribution and polymerization degree. If an optical film is made using cellulose ester whose distribution of acyl group substitution degree or degree of polymerization is not uniformly adjusted, insoluble matter may remain and cause bright spot foreign matter, or optically fatal such as phase difference Therefore, it is important to precisely adjust the esterification process and the aging process.
  • cellulose is a natural polymer, and there are large variations in the molecular weight, molecular chain, crystallinity, etc.
  • Patent Document 2 includes a step of activating cellulose with an activating agent, a step of esterifying cellulose with an acylating agent having at least 2 carbon atoms (particularly at least 3 carbon atoms) in the presence of an acylation catalyst, And a method for producing a cellulose ester, comprising a step of saponifying and ripening the produced cellulose ester, and after the esterification step, the esterification reaction terminator is added to 0.1 mol of the acylating agent remaining in the reaction system.
  • a technique for remarkably improving the generation of bright spot foreign matter by adding cellulose at a rate of 3 to 10 equivalents / minute to produce a cellulose ester is disclosed.
  • An object of the present invention is to provide a method for producing a cellulose ester capable of producing a cellulose ester film capable of producing a cellulose ester film with reduced film surface failures (diagonal streaks, horizontal dans, egg unevenness, etc.) by suppressing variation in performance between production lots of cellulose esters.
  • the object is to provide a produced cellulose ester and a cellulose ester film using the cellulose ester.
  • the pulverization step mixes and pulverizes the raw material cellulose and a solvent, and a mechanochemical pulverization step
  • the manufacturing method of the cellulose ester characterized by the above-mentioned.
  • the above-mentioned solvent is characterized in that the solvent is at least one solvent selected from carboxylic acids, alcohols, ketones, ethers and cellosolves, or a mixed solvent of at least one solvent and water.
  • the cellulose ester has an average acyl group substitution degree of 1.2 to 2.95, an acyl group total carbon number of 2.0 to 9.5, and an average weight molecular weight of 100,000 to 500,000. 3.
  • a cellulose ester film comprising the cellulose ester as described in 5 above.
  • a method for producing a cellulose ester capable of producing a cellulose ester film capable of producing a cellulose ester film with reduced film surface failures (diagonal stripes, horizontal dans, egg unevenness, etc.) by suppressing variation in performance between production lots of cellulose esters The produced cellulose ester and a cellulose ester film using the cellulose ester can be provided.
  • a conventional method for producing a cellulose ester is generally to dry-grind raw material cellulose to form a cotton, and then activate it with an acetic acid aqueous solution or hot water.
  • dry pulverization of the raw material cellulose it is easy to form a finely pulverized cotton-like product with uneven pulverized particle size, and a uniform cellulose ester is formed by the activation process and esterification process in the next step. There was a problem that it was difficult to be done.
  • the present inventor has found that in the cellulose ester production method including a raw cellulose pulverization step, an activation step, an esterification step, an aging step, and a post-treatment step, the pulverization step is the raw cellulose This is a mechanochemical pulverization process that mixes and pulverizes with a solvent. It has been found that the problem of streaks, horizontal dunes, egg unevenness, etc.) can be solved, and the invention according to claim 1 of the present application has been achieved.
  • the cellulose chains can be uniformly pulverized without damaging them as much as possible.
  • the reaction in the esterification step / ripening step can be performed smoothly.
  • the reaction time in the ripening step can be shortened, it has been possible to achieve both improvement in the uniformity of the reaction and prevention of a decrease in the degree of polymerization, which have been the trade-off.
  • raw material cellulose and solvent are mixed and mechanochemically pulverized to form a slurry state, and the cellulose is made into fine particles by effectively cutting the molecular force and hydrogen bonds of raw material cellulose.
  • the mixed solution of the solvent and water enters or bonds between cellulose molecules, so that hydrogen bonding between the hydroxyl groups of cellulose can be prevented, and the pulverized cellulose itself becomes activated.
  • the activation step which is the next step, it is possible to take a means to replace the activator according to the mixed solvent at the time of pulverization, so that cellulose activated by pulverization by these means can quickly undergo subsequent esterification reactions. It is performed uniformly and has the effect of reducing unacetylated components and impurities.
  • the invention according to claim 3 of the present application effectively removes impurities contained in the raw material cellulose and unacetylated components that could not be esterified by passing the esterified dope through a filter. This is a preferred embodiment for further enhancing the effects of the present invention.
  • the present invention has been found that not only variation between lots of cellulose ester after purification but also variation in lots can be remarkably suppressed by mixing and finely pulverizing (mechanochemical pulverization) a solvent and raw material cellulose. .
  • the cellulose ester of the present invention is preferably contained in a cellulose ester film for use in an optical film, and is preferably a cellulose ester having an aliphatic acyl group having 2 or more carbon atoms, and more preferably an acyl total of cellulose ester.
  • the total number of acyl groups in the cellulose ester is preferably 4.0 to 9.0, more preferably 5.0 to 8.5.
  • the acyl group total carbon number is the sum total of the products of the substitution degree and the carbon number of each acyl group substituted in the glucose unit of the cellulose ester.
  • the number of carbon atoms of the aliphatic acyl group is preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less, from the viewpoint of productivity and cost of cellulose synthesis.
  • the portion not substituted with an acyl group usually exists as a hydroxyl group.
  • the glucose unit constituting cellulose with ⁇ -1,4-glycosidic bonds has free hydroxyl groups at the 2nd, 3rd and 6th positions.
  • the cellulose ester in the present invention is a polymer obtained by esterifying some or all of these hydroxyl groups with an acyl group.
  • the acyl group substitution degree represents the total ratio of cellulose esterified at the 2nd, 3rd and 6th positions of the repeating unit. Specifically, the degree of substitution is 1 when the hydroxyl groups at the 2-position, 3-position and 6-position of cellulose are each 100% esterified. Therefore, when all of the 2nd, 3rd and 6th positions of cellulose are 100% esterified, the degree of substitution is 3 at the maximum.
  • acyl group examples include an acetyl group, a propionyl group, a butyryl group, a pentanate group, and a hexanate group.
  • cellulose ester examples include cellulose acetate, cellulose propionate, cellulose butyrate, and cellulose pentanate.
  • mixed fatty acid esters such as cellulose acetate, cellulose acetate propionate, cellulose propionate, cellulose acetate butyrate, and cellulose acetate pentanate may be used as long as the above-mentioned side chain carbon number is satisfied.
  • cellulose acetate, cellulose acetate propionate, and cellulose propionate are particularly preferable cellulose esters for optical film applications.
  • Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester including a cellulose ester that simultaneously satisfies I) and (II).
  • Formula (I) 1.2 ⁇ X + Y ⁇ 2.95
  • Formula (II) 0 ⁇ X ⁇ 2.5
  • cellulose acetate propionate is particularly preferably used, and 0.1 ⁇ X ⁇ 2.5 and 0.1 ⁇ Y ⁇ 2.8 are particularly preferable.
  • the portion that is not substituted with an acyl group usually exists as a hydroxyl group.
  • the method for measuring the degree of acyl group substitution can be measured according to ASTM-D817-96.
  • the cellulose ester of the present invention preferably has a weight average molecular weight Mw of 50,000 to 500,000, more preferably 100,000 to 300,000, still more preferably 150,000 to 250,000.
  • the measurement conditions are as follows.
  • the raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood. Softwood pulp is preferably used.
  • the cellulose ester made from these can be mixed suitably or can be used independently.
  • the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.
  • cellulose having a high degree of polymerization is preferable.
  • linter pulp is preferable, and it is preferable to use cellulose composed of at least linter pulp.
  • the ⁇ -cellulose content which is an index of the crystallinity of cellulose, is 90% or more (eg, 92 to 100%, preferably 95 to 100%, more preferably about 99.5 to 100%).
  • the cellulose ester production process is largely divided into a raw material cellulose crushing step, activation step, esterification step for substitution with acyl groups, aging step for promoting the elimination of acyl groups and adjusting the degree of substitution, and precipitation / washing of purified products. It is divided into the post-processing (finishing) process to dry.
  • FIG. 1 shows a production flow of the cellulose ester of the present invention.
  • a filtration step can be incorporated between the esterification step and the aging step.
  • the neutralization process can serve as both the ripening stop and the neutralization process, and both are shown by the dotted line.
  • the raw cellulose pulverization step according to the present invention is a mechanochemical pulverization step in which raw cellulose and a solvent are mixed and pulverized.
  • the solvent is preferably at least one solvent selected from carboxylic acids, alcohols, ketones, ethers and cellosolves, or a mixed solvent of the solvent and water.
  • carboxylic acids such as acetic acid and propionic acid are preferred, and carboxylic acid is particularly preferred in view of the subsequent activation treatment.
  • the said solvent is mixed with the solution of the range of 50 mass parts to 1000 mass parts with respect to 100 mass parts of raw material cellulose, and it grind
  • a more preferable range of the solvent amount is 75 parts by mass to 700 parts by mass, and a range of 95 parts by mass to 500 parts by mass is more preferable.
  • the raw cellulose may be crushed by adding a dry coarse pulverization step to a size that can be charged into a fine pulverization apparatus as a previous step. It is also preferable to perform pre-stirring at a low speed after adding the solvent in order to promote uniform mixing of the raw material cellulose and the solvent.
  • the apparatus for pulverizing the raw material cellulose is not particularly limited as long as it is an apparatus that can be finely pulverized in a wet manner, but a ball mill system (planetary ball mill, etc.), a wet pulverizer (ball-in-liquid collision type, slurry type, etc.), and a grinding type.
  • a ball mill system planetary ball mill, etc.
  • a wet pulverizer ball-in-liquid collision type, slurry type, etc.
  • a grinding type a grinding type.
  • Pulverizers stone mortar type, screen type, etc.
  • collision type pulverizers wet jet mill, etc.
  • screw type pulverizers, etc. are preferably used, and these may be used in combination.
  • the raw material cellulose at the time of pulverization is easily amorphized because it is finely pulverized in a liquid or slurry state where the raw material is wet, which is advantageous in the subsequent cellulose ester production process.
  • the pulverizer is preferably provided with a cooling function, and the temperature setting is preferably controlled at 60 ° C. or lower.
  • the temperature is preferably 10 to 50 ° C, more preferably 20 to 45 ° C.
  • the pulverization time can be appropriately determined, but is preferably 15 minutes to 45 minutes, and more preferably 20 minutes to 30 minutes.
  • the raw cellulose is refined by mechanochemical pulverization according to the present invention, and the average particle size of the raw cellulose after pulverization is 100 ⁇ m or less, but considering the addition of filtration before the aging step, the reaction in each step is performed in a short time. And from the viewpoint of preventing clogging of the filter medium, it is preferably 10 ⁇ m or more and 80 ⁇ m or less.
  • the particle size of the raw material cellulose can be measured by using a microscope or the like.
  • activation process In the activation step, cellulose is treated with an activator to activate the cellulose.
  • raw material cellulose is supplied in a slurry wet state.
  • acylation solvent organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid are used. Or an aliphatic carboxylic acid (linear or branched C1-6 alkanoic acid) such as valeric acid. These activators can be used alone or in combination of two or more.
  • an aqueous medium containing water is used as the activator.
  • This aqueous medium may be an aqueous medium containing an organic carboxylic acid.
  • it is economical. It is preferable to use many organic carboxylic acids.
  • the activation step is not limited to a single activation step, and may be composed of a plurality of activation steps, and can be performed using activators having different concentrations of the acylation catalyst.
  • the acylating catalyst may be composed of a first activating step for activating cellulose with an activating agent and a second activating step for activating cellulose with an activating agent containing an acylating catalyst. You may comprise in the 1st process of processing cellulose with the activator with a low density
  • the amount of the activator used is, for example, about 25 to 150 parts by weight, preferably 30 to 125 parts by weight, and more preferably 50 to 100 parts by weight (for example, 70 to 100 parts by weight) with respect to 100 parts by weight of cellulose. It may be.
  • the cellulose may be treated with an activator, the activator may be sprayed on the cellulose, or the cellulose may be immersed in the activator.
  • raw material cellulose is often added to the activator to form a slurry.
  • the activation treatment temperature can be selected from a range of 0 ° C. to 100 ° C. In order to perform the activation treatment without applying industrial load, it is usually 10 ° C. to 40 ° C., preferably about 15 ° C. to 35 ° C. It is.
  • the activation treatment time can be selected in the range of 0.1 to 72 hours, and is usually about 0.1 to 3 hours, preferably about 0.2 to 2 hours.
  • the activation process proceeds in the fine pulverization stage, so the standing time is short, and it is immediately put into the esterification reaction vessel. be able to.
  • Cellulose activated by the activation treatment is esterified with a carboxylic acid (containing at least one or more) having an acyl group having at least 2 carbon atoms and a carboxylic anhydride (containing at least one or more) in the presence of an acid catalyst.
  • a carboxylic acid containing at least one or more
  • carboxylic anhydride containing at least one or more
  • an acid catalyst Lewis acid or strong acid can be used, but sulfuric acid is generally used.
  • acid anhydrides for example, acid anhydrides of carboxylic acids having 2 or more carbon atoms (carboxylic anhydrides)
  • C2-6 alkanoic anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, etc. Things can be used.
  • a carboxylic acid having an acyl group having at least 2 carbon atoms (for example, at least a C2-6 carboxylic anhydride) is used. You may use these individually or in combination of 2 or more types. As long as it has an acyl group and is easily acylated, it is not limited to carboxylic acids, and organic acid halides can also be used.
  • the amount of acid catalyst (especially sulfuric acid) used in the esterification step is, for example, in the range of 3 to 20 parts by weight, preferably 5 to 18 parts by weight, more preferably about 7 to 15 parts by weight with respect to 100 parts by weight of cellulose. Usually, it is about 7 to 15 parts by mass.
  • an esterification solvent corresponding to at least an acyl group having 2 or more carbon atoms for example, a carboxylic acid (acid anhydride) may be used, and for example, selected from acid anhydrides corresponding to C2-6 carboxylic acid A plurality of acid anhydrides having different carbon numbers may be used.
  • a carboxylic acid acid anhydride
  • acid anhydrides having different carbon numbers
  • propionic anhydride and / or butyric anhydride and acetic anhydride may be used in combination.
  • Preferred esterification solvents are C2-4 alkanecarboxylic anhydrides, for example, at least one selected from C2-4 carboxylic anhydrides (such as acetic anhydride or propionic anhydride), a combination of acetic anhydride and propionic anhydride, A combination of acetic anhydride and butyric anhydride, and a combination of acetic anhydride, propionic anhydride and butyric anhydride.
  • C2-4 carboxylic anhydrides such as acetic anhydride or propionic anhydride
  • a combination of acetic anhydride and propionic anhydride such as acetic anhydride or propionic anhydride
  • a combination of acetic anhydride and butyric anhydride such as acetic anhydride and butyric anhydride
  • a combination of acetic anhydride, propionic anhydride and butyric anhydride are preferable.
  • Acetic anhydride is more reactive than propionic anhydride and the like, and in the case of obtaining a cellulose mixed fatty acid ester having a low degree of acetyl group substitution, acetic anhydride is not used or the object of the present invention is not impaired.
  • the esterification solvent having at least 3 carbon atoms and corresponding to the acyl group may be combined with a small amount of acetic anhydride.
  • the esterification solvent may correspond to an acyl group having 3 or more carbon atoms, for example, propionic anhydride, if acylation or aging can be performed in the presence of acetic acid.
  • acylation or aging can be performed in the presence of acetic acid.
  • What is necessary is just to comprise by butyric anhydride etc., and it does not necessarily need to contain the esterification solvent (acetic anhydride) corresponding to an acetyl group.
  • acetic anhydride is not necessarily used, and the reaction may be carried out in the presence of acetic acid.
  • Such acetic acid may be present in the reaction system in the esterification step and the ripening step (particularly at least the ripening step), and may be composed only of acetic acid derived from the activation treatment. May be newly added, and may be used as an esterification solvent in an ordinary esterification step.
  • a plurality of esterification solvents may coexist in the reaction system, and after esterifying cellulose with a specific esterification solvent
  • the cellulose may be esterified with another esterification solvent.
  • the amount of the esterification solvent used in the esterification step is, for example, about 1.1 to 4 equivalents, preferably 1.1 to 2 equivalents, more preferably about 1.3 to 1.8 equivalents relative to the hydroxyl group of cellulose. is there.
  • the amount of acetic anhydride used in the esterification step is 0.5 equivalent or less (about 0 to 0.3 equivalent) relative to the hydroxyl group of cellulose. ), Or less than 0.2 equivalent (0.01-0.1 equivalent), and may not be used substantially.
  • an esterification solvent organic carboxylic acid such as acetic acid, propionic acid, butyric acid
  • the amount of esterification solvent (carboxylic acid) used is about 50 to 700 parts by weight, preferably 150 to 600 parts by weight, and more preferably about 200 to 550 parts by weight with respect to 100 parts by weight of cellulose.
  • the esterification reaction can be performed at a temperature of about 0 to 50 ° C., preferably 5 to 45 ° C., more preferably about 10 to 40 ° C.
  • the esterification reaction may be initially performed at a relatively low temperature of 10 ° C. or lower (0 to 10 ° C.).
  • the reaction time at such a low temperature may be, for example, 30 minutes or more, 40 minutes to 2 hours, preferably about 45 to 100 minutes from the start of the esterification reaction.
  • the esterification time at 10 to 50 ° C. is 10 minutes or more and 20 to 90 minutes, preferably 30 to 80 minutes, 40 minutes to 75 minutes.
  • the hydrolysis reaction may be started, or the esterification solvent, the esterification solvent, and the acid catalyst may be left as they are, and the aging step may be performed.
  • the quenching agent that promotes hydrolysis may be composed of at least one selected from water, an esterification solvent, an alcohol, and a neutralizing agent. More specifically, examples of the quenching agent include water alone, a mixture of water and carboxylic acid, a mixture of water and alcohol, a mixture of water and neutralizing agent, water, an organic carboxylic acid and alcohol, and the like. Examples thereof include a mixture with a hydrating agent.
  • Examples of the neutralizing agent include bases that can neutralize part of the acid catalyst or esterification solvent, such as alkali metal compounds (hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, etc. , Organic acid salts such as sodium acetate and potassium acetate), alkaline earth metal compounds (eg, hydroxides such as calcium hydroxide, carbonates such as calcium carbonate, organic acid salts such as calcium acetate and magnesium acetate) And may be used alone or in combination of two or more.
  • Examples of the alcohol include straight chain alcohols (ethanol, methanol, propanol, etc.). These alcohols can also be used alone or in combination of two or more.
  • the ratio of water and esterification solvent or water and alcohol can be selected from the range of about 20 to 140 parts by mass of esterification solvent or alcohol with respect to 100 parts by mass of water, usually 25 to 120 parts by mass, preferably 50 parts by mass. ⁇ 100 parts by mass.
  • a neutralizing agent may be included at a ratio of partially neutralizing the acid catalyst, or a neutralizing agent may not be included.
  • the preferred deactivator may be water alone, but since water is a poor solvent for cellulose esters, there is a high possibility that cellulose esters other than the desired degree of substitution will precipitate. And a mixed solution is preferable.
  • reaction component contained in the raw material cellulose is not 100%, an unreacted component is included at this stage, so a process of filtering the reaction solution once may be introduced.
  • This reaction stopping step can be omitted if necessary.
  • the solution after completion of the esterification reaction contains unacetylated, low-acetylated components and impurities that did not react with the raw material cellulose. Time is further shortened, and specific cleavage of molecular chains and substituents occurring in the reaction solution is difficult to occur.
  • the film surface quality of the film formed using the obtained cellulose ester is cellulose without filtration. Even better than the ester.
  • Filter media used for filtration preferably have low absolute filtration accuracy, but if the absolute filtration accuracy is too low, the filter media is likely to be clogged, and the filter media must be replaced frequently, reducing productivity. There is a problem of making it.
  • the filter medium used in the cellulose ester slurry after the esterification step of the present invention preferably has an absolute filtration accuracy of 10 ⁇ m or less, more preferably in the range of 1 to 8 ⁇ m, and still more preferably in the range of 3 to 5 ⁇ m.
  • the material of the filter medium is not particularly limited, and a normal filter medium can be used. However, a filter medium made of plastic such as polypropylene, polyester, and PTFE, a filter medium made of glass fiber, and a metal filter medium such as stainless steel fiber can be used. This is preferable because there is no dropout.
  • the metal filter Since the cellulose ester slurry contains an acid, the metal filter is easily corroded, and therefore, a filter made of glass fiber or plastic fiber is more preferable.
  • the required amount of acid catalyst may be added again, or used in the aging process without neutralizing the acid catalyst (especially sulfuric acid) used in the esterification process. May be.
  • An acid catalyst other than the acid catalyst used in the esterification may be added.
  • the acid catalyst used in the esterification step as it is in the aging step without adding an acid catalyst in the aging step.
  • the alkali metal or alkaline earth metal contained in the neutralizing agent is added in the neutralizing agent, and remains in the purified cellulose ester. It is preferable not to add sulfuric acid in the aging process because it can be an obstacle.
  • a deacylation solvent such as a mixed solution of water and carboxylic acid
  • a deacylation solvent such as a mixed solution of water and carboxylic acid
  • the reaction temperature during the ripening step is preferably 20 ° C. to 90 ° C., preferably 25 ° C. to 80 ° C., more preferably 30 ° C. to 70 ° C.
  • the ripening reaction may be performed in a nitrogen atmosphere or in an air atmosphere You may go on.
  • the aging reaction time can be selected from the range of 20 minutes or more and 25 minutes to 6 hours, preferably 30 minutes to 5 hours, more preferably 1 to 3 hours.
  • the reaction product (dope containing cellulose mixed fatty acid ester) is put into a precipitation solvent (water, aqueous acetic acid solution, etc.) to separate the cellulose mixed fatty acid ester, and free metal components and sulfuric acid components are removed by washing with water. May be.
  • a neutralizing agent can also be used in the case of washing with water.
  • a mixed solution of water and carboxylic acid is preferably used.
  • These precipitation solvents are not limited, and ketones, alcohols, ethers, esters and the like alone or water mixed solvents may be used.
  • the process of filtering and washing the precipitated product is repeated until the free acid concentration is 500 ppm or less, preferably 300 ppm or less, more preferably 150 ppm or less.
  • the residual sulfuric acid content in the cellulose ester used in the present invention is preferably in the range of 0.1 to 40 ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 40 ppm, the deposit on the die lip during heat melting increases, such being undesirable. Moreover, since it becomes easy to fracture
  • a smaller amount is preferable, but if it is less than 0.1, it is not preferable because the burden of the washing step of the cellulose resin becomes too large. This is not well understood, although an increase in the number of washings may affect the resin. Furthermore, the range of 0.1 to 30 ppm is preferable.
  • the residual sulfuric acid content can be similarly measured by ASTM-D817-96.
  • the residual sulfuric acid content can be within the above range, and when producing a film by the melt casting method.
  • adhesion to the lip portion is reduced, and a film having excellent flatness can be obtained.
  • a cellulose ester film for use in an optical film is produced using the cellulose ester obtained by the above operation.
  • the method for producing a cellulose ester film is roughly classified into a solution casting film forming method and a melt casting film forming method, and the effects of the present invention can be achieved by using either method.
  • melt casting method In the method for producing a cellulose ester film comprising the cellulose ester of the present invention, at least a polymer forming the film, particulate matter and additives are mixed and melted, the melt is filtered by a filtration device, and then extruded from a normal die. Cast on a cooling roll.
  • the mixture of the polymer, particulate matter, plasticizer and other additives that form the film used for melt extrusion is preferably kneaded in advance and pelletized.
  • Pelletization may be performed by a known method.
  • a polymer, a plasticizer, and other additives that form a film are supplied to an extruder with a feeder, and are kneaded using a single-screw or twin-screw extruder. Extruded into a shape, water-cooled or air-cooled and cut.
  • Pre-drying of raw materials before extrusion is important for preventing decomposition of the raw materials.
  • the polymer forming the optical film is likely to absorb moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air dryer or a vacuum dryer so that the moisture content is 300 ppm or less, further 100 ppm or less.
  • Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders. A small amount of an additive such as an antioxidant is preferably mixed in advance in order to mix uniformly.
  • Mixing of the antioxidants may be performed by mixing solids, and if necessary, the antioxidant may be dissolved in a solvent and impregnated with a polymer forming an optical film, or may be mixed or sprayed. May be mixed.
  • a vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Further, if the contact with air, such as the exit from the feeder unit or die, it is preferable that the atmosphere such as dehumidified air and dehumidified N 2 gas.
  • the extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shear force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.).
  • a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
  • Film formation is performed using the pellets obtained as described above. It is also possible to feed the raw material powder directly to the extruder with a feeder and form a film as it is without pelletization.
  • the produced pellets are extruded using a single-screw or twin-screw type extruder, the melting temperature Tm is about 200 to 350 ° C., filtered by the filtration device of the present invention to remove foreign matters, and then formed into a film from the T die. And solidified on a cooling roll and cast while pressing with an elastic touch roll.
  • Tm is the temperature of the die exit portion of the extruder.
  • defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable to have a structure in which the resin retention portion is minimized in the piping from the extruder to the die. . It is preferable to use a die that has as few scratches as possible inside the lip.
  • the inner surface that comes into contact with the molten resin is preferably subjected to surface treatment that makes it difficult for the molten resin to adhere to the surface by reducing the surface roughness or using a material with low surface energy.
  • a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.
  • the cooling roll is a roll having a structure in which a heat medium or a cooling medium whose temperature can be controlled flows with a high-rigidity metal roll, the size of which is not limited, but a melt-extruded film
  • the diameter of the cooling roll is usually about 100 mm to 1 m.
  • the surface material of the cooling roll includes carbon steel, stainless steel, aluminum, titanium and the like. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to perform a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.
  • the surface roughness of the cooling roll surface is preferably 0.1 ⁇ m or less in terms of Ra, and more preferably 0.05 ⁇ m or less.
  • the smoother the roll surface the smoother the surface of the resulting film.
  • the surface processed is further polished to have the above-described surface roughness.
  • Examples of the elastic touch roll of the present invention include JP-A-03-124425, JP-A-08-224772, JP-A-07-1000096, JP-A-10-272676, WO97-028950, JP-A-11-235747, JP-A-11-235747.
  • a thin-film metal sleeve-covered silicon rubber roll can be used.
  • the film obtained as described above is preferably stretched by a stretching operation after passing through a step in contact with a cooling roll.
  • the stretching method a known roll stretching machine or tenter can be preferably used.
  • the stretching temperature is usually preferably in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.
  • the end Before winding, the end may be slit and cut to the product width, and knurled (embossed) may be applied to both ends to prevent sticking or scratching during winding.
  • the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.
  • grip part of the clip of both ends of a film is cut out and reused.
  • Organic solvent useful for forming a dope when a cellulose ester film is produced by a solution casting method can be used without limitation as long as it dissolves cellulose ester and other additives simultaneously.
  • methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
  • Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.
  • the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • the proportion of alcohol in the dope increases, the web gels and peeling from the metal support becomes easy.
  • the proportion of alcohol is small, thermoplastic acrylic resins and cellulose ester resins in non-chlorine organic solvent systems There is also a role of promoting dissolution of the.
  • thermoplastic acrylic resin in particular, cellulose ester resin, and acrylic particles are used.
  • a dope composition in which 45% by mass is dissolved is preferable.
  • linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.
  • a step of preparing a dope by dissolving a cellulose ester and an additive in a solvent a step of casting the dope on a belt-shaped or drum-shaped metal support, and casting. It is performed by a step of drying the dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
  • the concentration of the cellulose ester and the additive in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of the cellulose ester is too high, the load during filtration increases. Thus, the filtration accuracy is deteriorated.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 ⁇ 4m.
  • the surface temperature of the metal support in the casting step is set to ⁇ 50 ° C. to below the temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.
  • a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably 5 to 30 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Particularly preferred is 0 to 0.01% by mass or less.
  • a roll drying method (a method in which a plurality of rolls arranged at the top and bottom are alternately passed through the web for drying) or a tenter method for drying while transporting the web is employed.
  • a plasticizer in combination with the cellulose ester film.
  • the plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, a polyhydric alcohol ester plasticizer, or a polyester. It is selected from plasticizers, acrylic plasticizers, carbohydrate ester plasticizers and the like. Of these, when two or more plasticizers are used, at least one plasticizer is preferably a polyhydric alcohol ester plasticizer.
  • the polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
  • the polyhydric alcohol preferably used in the present invention is represented by the following general formula (a).
  • Ra- (OH) n (However, Ra represents an n-valent organic group, n represents a positive integer of 2 or more, and an OH group represents an alcoholic and / or phenolic hydroxyl group.)
  • n represents a positive integer of 2 or more
  • an OH group represents an alcoholic and / or phenolic hydroxyl group.
  • preferred polyhydric alcohols include the following, but the present invention is not limited to these.
  • Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol.
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited to this.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used.
  • the number of carbon atoms is more preferably 1-20, and particularly preferably 1-10.
  • acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.
  • the carboxylic acid used in the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • citrate plasticizer examples include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
  • fatty acid ester plasticizers examples include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
  • carbohydrate ester plasticizer examples include glucose pentaacetate, glucose pentapropionate, glucose pentabtylate, saccharose octaacetate, saccharose octabenzoate and the like.
  • saccharose octaacetate, saccharose Octabenzoate is more preferred, and sucrose octabenzoate is particularly preferred.
  • monopet SB manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • monopet SOA manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can be cited as commercially available products.
  • the plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the cellulose ester film. If the added amount of the plasticizer exceeds 30 parts by mass, the surface becomes sticky, which is not preferable for practical use.
  • the cellulose ester film preferably contains an ultraviolet absorber, and examples of the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
  • the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
  • 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone And benzophenones.
  • ultraviolet absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high
  • Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Such as til] -4- [3- (3,5-di-tert-butyl
  • 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.
  • antioxidants can be added to the cellulose ester film in order to improve the thermal decomposability and thermal colorability during molding. It is also possible to add an antistatic agent to give the optical film antistatic performance.
  • a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used.
  • Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.
  • triphenyl phosphate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
  • a matting agent in the cellulose ester film, can be added in order to impart slipperiness, optical and mechanical functions.
  • the matting agent include inorganic compound fine particles and organic compound fine particles.
  • the shape of the matting agent is preferably a spherical shape, rod shape, needle shape, layer shape, flat plate shape or the like.
  • the matting agent include oxidation of metals such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate.
  • Inorganic fine particles such as materials, phosphates, silicates, carbonates and crosslinked polymer fine particles.
  • silicon dioxide is preferable because it can reduce the haze of the film.
  • These fine particles are preferably surface-treated with an organic substance because the haze of the film can be reduced.
  • thermoplastic acrylic resin may be mixed with the cellulose ester as a resin.
  • the acrylic resin used in the present invention preferably exhibits negative birefringence with respect to the stretching direction of the film, and the structure is not particularly limited, but is obtained by polymerizing an ethylenically unsaturated monomer. It is preferable that a polymer having a weight average molecular weight of 500 or more and 1000000 or less is appropriately selected.
  • the proper molecular weight range of the acrylic polymer is as described above, but when it is contained in an amount of 30% by mass or more, the weight average molecular weight is preferably 80,000 to 1,000,000 from the viewpoint of compatibility with the cellulose ester.
  • Thermoplastic acrylic resin includes methacrylic resin.
  • the thermoplastic acrylic resin is not particularly limited, but is preferably composed of 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith.
  • Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 alkyl carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, alkyl acrylates such as acrylic acid and methacrylic acid.
  • Unsaturated group-containing divalent carboxylic acids such as saturated acid, maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, Examples thereof include maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like, and these can be used alone or in combination of two or more monomers.
  • methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
  • n-Butyl acrylate is particularly preferably used.
  • the weight average molecular weight (Mw) is preferably 80,000 to 500,000, and more preferably 110,000 to 500,000.
  • the weight average molecular weight of the thermoplastic acrylic resin can be measured by the gel permeation chromatography described above, including the measurement conditions.
  • thermoplastic acrylic resin there is no restriction
  • a polymerization initiator a normal peroxide type and an azo type can be used, and a redox type can also be used.
  • the polymerization temperature may be 30 to 100 ° C. for suspension or emulsion polymerization, and 80 to 160 ° C. for bulk or solution polymerization.
  • polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent. Commercial products can also be used.
  • thermoplastic acrylic resin a graft copolymer obtained by grafting a (meth) acrylic resin to a copolymer of (meth) acrylic rubber and an aromatic vinyl compound described in JP-A-2009-84574 is used. May be.
  • graft copolymer a copolymer of (meth) acrylic rubber and an aromatic vinyl compound forms a core, and the (meth) acrylic resin forms a shell around the copolymer.
  • -A shell-type graft copolymer is preferred.
  • the cellulose ester film according to the present invention is preferably a “film that does not cause ductile fracture”.
  • the ductile fracture is a fracture caused by applying a stress larger than the strength of a certain material, and is defined as a fracture accompanied by significant elongation or drawing of the material until the final fracture.
  • the fracture surface is characterized by numerous indentations called dimples.
  • the size of liquid crystal display devices is increasing, and the brightness of backlight light sources is increasing.
  • the use of digital signage and other outdoor applications demands higher brightness.
  • the cellulose ester film of the present invention is required to be able to withstand use in a high temperature environment, and if the tension softening point is 105 ° C. to 145 ° C., it can be determined that it exhibits sufficient heat resistance, In particular, it is preferable to control at 110 ° C. to 130 ° C.
  • the cellulose ester film is cut out at 120 mm (length) ⁇ 10 mm (width) with a tension of 10 N. While pulling, the temperature can be raised at a rate of 30 ° C./min. The temperature at the time when the temperature reaches 9 N is measured three times, and the average value can be obtained.
  • the cellulose ester film preferably has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, it is 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.
  • Tg glass transition temperature
  • the glass transition temperature referred to here is an intermediate value determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min. Point glass transition temperature (Tmg).
  • the dimensional change rate (%) is preferably less than 0.5%, and more preferably less than 0.3%.
  • the cellulose ester film preferably has a defect of 5 ⁇ m or more in diameter in the film plane of 1 piece / 10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.
  • the diameter of the defect indicates the diameter when the defect is circular, and when it is not circular, the range of the defect is determined by observing with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
  • the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object. If the defect is a change in surface shape, such as transfer of a roll flaw or an abrasion, the size is confirmed by observing the defect with the reflected light of a differential interference microscope.
  • the film When the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film during processing in a later process, the film may be broken with the defect as a starting point and productivity may be reduced. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
  • the coating agent may not be formed uniformly, resulting in defects (coating defects).
  • the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to the foreign matter (foreign matter defect) in the film.
  • the cellulose ester film preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, as measured in accordance with JIS-K7127-1999.
  • the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
  • the thickness of the cellulose ester film is preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more.
  • the upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 ⁇ m from the viewpoint of applicability, foaming, solvent drying and the like.
  • the thickness of the film can be appropriately selected depending on the application.
  • the cellulose ester film preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film.
  • the slit film is dissolved again in the solvent at a relatively low temperature, so that the properties equivalent to those of the new raw material can be maintained, and there is no particular problem in the properties even when the optical film is formed.
  • the cellulose ester of the present invention is extremely uniform and has few impurities, even if the film obtained by melt casting is used again as a recycled material, there is little occurrence of deterioration and coloring, and optical use It turns out that the quality of the film has been fully achieved.
  • the use ratio of the recycled material is preferably 0 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass with respect to the solid content of the main unused raw material.
  • the additives contained in the cellulose ester film such as plasticizers, ultraviolet absorbers, and fine particles are reduced according to the amount used, and the final cellulose ester film composition becomes the design value. It is preferable to make such adjustments.
  • the cellulose ester film of the present invention can be provided with functional layers such as an antistatic layer, a backcoat layer, an antireflection layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer.
  • functional layers such as an antistatic layer, a backcoat layer, an antireflection layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer.
  • the hard coat layer used in the present invention contains an actinic radiation curable resin, and is a layer mainly composed of a resin that cures through a crosslinking reaction by irradiation with an actinic ray (also referred to as an active energy ray) such as an ultraviolet ray or an electron beam. Preferably there is.
  • an actinic radiation curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams.
  • Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but the resin that is cured by ultraviolet irradiation is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable.
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.
  • the hard coat layer contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
  • the hard coat layer preferably contains fine particles of an inorganic compound or an organic compound.
  • silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated silicic acid Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate.
  • silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.
  • polymethacrylic acid methyl acrylate resin powder acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder,
  • a polyolefin resin powder, a polyester resin powder, a polyamide resin powder, a polyimide resin powder, a polyfluoroethylene resin powder, or the like can be added.
  • the average particle diameter of these fine particle powders is not particularly limited, but is preferably 0.01 to 5 ⁇ m, and more preferably 0.01 to 1.0 ⁇ m. Moreover, you may contain 2 or more types of microparticles
  • the average particle diameter of the fine particles can be measured by, for example, a laser diffraction particle size distribution measuring device.
  • the ratio of the ultraviolet curable resin composition and the fine particles is desirably 10 to 400 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the resin composition.
  • These hard coat layers are coated using a known method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, ink jet method, and the like. And can be formed by UV curing.
  • the dry film thickness of the hard coat layer is an average film thickness of 0.1 to 30 ⁇ m, preferably 1 to 20 ⁇ m, particularly preferably 6 to 15 ⁇ m.
  • any light source that generates ultraviolet rays can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm 2 , preferably 5 to 200 mJ / cm 2 .
  • a back coat layer may be provided on the surface opposite to the side on which the hard coat layer is provided to prevent curling and sticking.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxide. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.
  • the particles contained in the backcoat layer are preferably 0.1 to 50% by mass with respect to the binder.
  • the increase in haze is preferably 1.5% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less.
  • the binder is preferably a cellulose ester resin such as diacetylcellulose.
  • the cellulose ester film of the present invention can be used as an antireflection film having an external light antireflection function by coating an antireflection layer on the hard coat layer.
  • the antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference.
  • the antireflection layer is preferably composed of a low refractive index layer having a refractive index lower than that of the support, or a combination of a high refractive index layer having a refractive index higher than that of the support and a low refractive index layer. Particularly preferably, it is an antireflection layer composed of three or more refractive index layers, and three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support).
  • an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
  • the layer structure of the antireflection film the following structure can be considered, but it is not limited to this.
  • the refractive index layer preferably contains silica-based fine particles, and its refractive index is lower than the refractive index of the cellulose film as the support, and is in the range of 1.30 to 1.45 when measured at 23 ° C. and wavelength of 550 nm. It is preferable.
  • the film thickness of the low refractive index layer is preferably 5 nm to 0.5 ⁇ m, more preferably 10 nm to 0.3 ⁇ m, and most preferably 30 nm to 0.2 ⁇ m.
  • the composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles.
  • the particles having the outer shell layer and having a porous or hollow interior are preferably hollow silica-based fine particles.
  • composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1), a hydrolyzate thereof, or a polycondensate thereof.
  • OSi-1 organosilicon compound represented by the following general formula (OSi-1)
  • hydrolyzate thereof a hydrolyzate thereof
  • polycondensate thereof a polycondensate thereof.
  • R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.
  • a solvent and if necessary, a silane coupling agent, a curing agent, a surfactant and the like may be added.
  • the polarizing plate can be produced by a general method.
  • the back side of the cellulose ester film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizing film prepared by immersing and stretching the treated cellulose ester film in an iodine solution. It is preferable to bond them together.
  • the cellulose ester film may be used on the other surface, or another polarizing plate protective film may be used.
  • a non-oriented film having retardation Ro of 590 nm at 0 to 5 nm and Rt of ⁇ 20 to +20 nm described in JP-A No. 2003-12859 can be mentioned as an example.
  • an optical compensation film (retardation film) having a retardation of in-plane retardation Ro of 590 nm, 20 to 70 nm, and Rt of 70 to 400 nm may be used to obtain a polarizing plate capable of widening the viewing angle. it can.
  • These can be produced, for example, by the method of JP-A-2002-71957.
  • the optically anisotropic layer can be formed by the method described in JP-A-2003-98348.
  • polarizing plate protective films preferably used include KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-2, KC4FR-2, KC4FR-2, KC8FR-2 KC4UE (Konica Minolta Opto Co., Ltd.) etc. are mentioned.
  • the polarizing film which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction.
  • a typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film.
  • polarizing film a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound.
  • a polarizing film having a thickness of 5 to 30 ⁇ m, preferably 8 to 15 ⁇ m is preferably used.
  • a polarizing plate is formed by laminating one side of the cellulose ester film of the present invention on the surface of the polarizing film. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.
  • ⁇ Liquid crystal display device> By incorporating a polarizing plate produced using the cellulose ester film of the present invention into a display device, various image display devices with excellent visibility can be produced.
  • the cellulose ester film of the present invention is incorporated in a polarizing plate and is a reflective type, transmissive type, transflective liquid crystal display device or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type. It is preferably used in liquid crystal display devices of various driving systems such as OCB type.
  • Example 1 Manufacture of cellulose ester> ⁇ Production Example 1> 100 parts by mass of raw material pulp ( ⁇ cellulose 93% or more) and 100 parts by mass of glacial acetic acid were put into a mixer and stirred to form a slurry, and then put into a stone mortar pulverizer and ground at 40 ° C. for 30 minutes. The average pulverized particle size of the pulverized raw material pulp was 63 ⁇ m by microscopic observation.
  • the acetic acid-containing pulp is put into a reactor, and 250 parts by mass of propionic anhydride, 400 parts by mass of propionic anhydride, and 9 parts by mass of sulfuric acid are sequentially added, and the temperature is gradually raised from room temperature to 40 ° C. and kept at 40 ° C. The mixture was kept warm for 1 hour to allow the esterification reaction to proceed.
  • the cellulose ester precipitated in the precipitation process was filtered off, washed 5 times with warm water at 50 ° C., and the remaining acetic acid aqueous solution was eluted, followed by drying at 70 ° C. for 3 hours, acetyl substitution degree 0.61, propionyl substitution
  • Mw weight average molecular weight
  • a cellulose ester film 1 was produced according to the following melt casting method.
  • ⁇ Melt casting method> A cellulose ester film was prepared by the melt casting method with the following composition.
  • Cellulose ester film composition Production Example 1 Cellulose ester 94 parts by mass Plasticizer: Glycerin tribenzoate 5 parts by mass Irganox 1010 (manufactured by BASF Japan Ltd.) 0.5 parts by mass Irgafos P-EPG (manufactured by BASF Japan Ltd.) 0.3 parts by mass HP-136 (manufactured by BASF Japan Ltd.) 0.2 parts by mass The cellulose ester was dried under reduced pressure at 70 ° C. for 3 hours and cooled to room temperature, and then each additive was mixed.
  • Glycerin tribenzoate 5 parts by mass Irganox 1010 (manufactured by BASF Japan Ltd.) 0.5 parts by mass Irgafos P-EPG (manufactured by BASF Japan Ltd.) 0.3 parts by mass HP-136 (manufactured by BASF Japan Ltd.) 0.2 parts by mass
  • the cellulose ester was dried under reduced pressure at 70 ° C. for 3 hours and cooled
  • the above mixture was formed into a film by a manufacturing apparatus using an elastic touch roll. In a nitrogen atmosphere, it was melted at 240 ° C., extruded from the casting die onto the first cooling roll, and molded by pressing the film between the first cooling roll and the touch roll. Further, silica particles (manufactured by Nippon Aerosil Co., Ltd.) were added as a slip agent from the hopper opening in the middle of the extruder so as to be 0.1 part by mass.
  • the heat bolt was adjusted so that the gap width of the casting die was 0.5 mm within 30 mm from the end in the width direction of the film and 1 mm at other locations.
  • 80 degreeC water was poured as cooling water in the inside.
  • the length L along the surface was set to 20 mm.
  • the touch roll was separated from the first cooling roll, and the temperature T of the melted part immediately before being sandwiched in the nip between the first cooling roll and the touch roll was measured.
  • the temperature T of the melted portion immediately before being sandwiched between the first cooling roll and the touch roll is 1 mm upstream from the nip upstream end P2, and a thermometer (HA-200E manufactured by Anritsu Keiki Co., Ltd.) It was measured by.
  • the temperature T was 141 ° C.
  • the linear pressure of the touch roll against the first cooling roll was 14.7 N / cm.
  • cooling to 30 ° C while relaxing 3% in the width direction, then releasing from the clip, cutting off the clip gripping part was subjected to a knurling process having a width of 20 mm and a height of 25 ⁇ m, and wound on a winding core with a winding tension of 220 N / m and a taper of 40%.
  • the film thickness was 40 micrometers
  • the winding length was 4000 m
  • the cellulose-ester film 1 of refractive index 1.49 was produced.
  • cellulose ester films 2 to 20 were produced using the cellulose esters produced in Production Examples 2 to 20.
  • the melt casting temperature when the cellulose esters of Production Examples 3 to 5 were used was adjusted to 260 ° C.
  • acyl group substitution degree of cellulose ester The acyl group substitution degree was measured in accordance with ASTM-D817-96.
  • Pr propionyl group
  • AC acetyl group
  • Bu butyrate group
  • total total acyl group (average molecular weight)
  • Mw weight average molecular weight
  • the measurement conditions are as follows.
  • ⁇ Dispersion of cellulose ester (vinegar cotton)> 1.
  • Variation in molecular weight distribution standard deviation of 1/10 width of molecular weight distribution of 10 samples of different production lots.
  • Variation of acyl group substitution degree standard deviation of 1/10 width of acyl group substitution degree distribution of vinegar cotton of 10 samples of different production lots ⁇ Film surface failure of cellulose ester film> The film surface failure was visually evaluated on the following evaluation scale.
  • ⁇ There is no variation in film surface failure among lots.
  • ⁇ The cellulose ester of different production lots has a probability of 10%, and the level of film surface failure is shifted by 1.
  • ⁇ The cellulose ester of different production lots has a probability of 20%.
  • the level of surface failure shifts by 1 ⁇ The cellulose ester of different production lots has a probability of 40%, and the level of film surface failure shifts 1 to 2 ⁇ :
  • the cellulose ester of different production lots has a probability of 60% of film surface failure The level is not stable.
  • X The cellulose ester in different production lots has a probability of 80% and the film surface failure level is not stable.
  • Tables 1 to 9 A list of the production conditions of the cellulose ester and the above evaluation results are shown in Tables 1 to 9 below.
  • the cellulose esters of Production Examples 1 to 16 produced by the method for producing cellulose esters of the present invention have small variations in vinegared cotton, and film surface failure when film is formed (oblique lines, horizontal dunes, egg unevenness, etc.) It is clear that this is superior.
  • the cellulose esters of Production Examples 10 to 12 in which a filtration step is added between the esterification step and the aging step are more excellent in film surface failure when a film is formed.
  • Example 2 The cellulose ester film 1 using the cellulose ester produced in Production Example 1 of Example 1 was chipped as a return material, and a cellulose ester film 21 was produced according to the following formulation.
  • ⁇ Melt casting method> A cellulose ester film was prepared by the melt casting method with the following composition.
  • ⁇ Cellulose ester film composition Production Example 1 Cellulose ester 54 parts by mass Returning material cellulose ester film 1 chip 40 parts by mass Plasticizer: Glycerin tribenzoate 5 parts by mass Irganox 1010 (manufactured by BASF Japan Ltd.) 0.5 parts by mass Irgafos P-EPG (manufactured by BASF Japan Ltd.) 0.3 parts by mass HP-136 (manufactured by BASF Japan Ltd.) 0.2 parts by mass The cellulose ester was dried under reduced pressure at 70 ° C. for 3 hours and cooled to room temperature, and then each additive was mixed.
  • Glycerin tribenzoate 5 parts by mass Irganox 1010 (manufactured by BASF Japan Ltd.) 0.5 parts by mass Irgafos P-EPG (manufactured by BASF Japan Ltd.) 0.3 parts by mass HP-136 (manufactured by BASF Japan Ltd.) 0.2 parts by mass
  • the cellulose ester was
  • a cellulose ester film 21 was produced by the melt casting method in the same manner as in Example 1.
  • cellulose ester films 2 to 20 using the cellulose ester produced in Production Example 2 to Production Example 20 of Example 1 were used as recycled materials, and cellulose ester films 22 to 41 were produced by a melt casting method. .
  • an optical film it is preferable that it is 15 pieces / m ⁇ 2 > or less, More preferably, it is less than 10 pieces / m ⁇ 2 >.
  • Yellow index> The yellow index (yellowness) is obtained by the method described in JIS standard K7105-6.3.
  • the tristimulus values X, Y, and Z of the color were determined using a spectrophotometer U-3200 manufactured by Hitachi, Ltd. and the attached saturation calculation program, and the yellow index was determined according to the following formula.
  • Yellow index 100 (1.28X-1.06Z) / Y Evaluation was performed on the following scale from the obtained yellow index.
  • the cellulose ester films 1 to 16 produced using the cellulose esters of Production Examples 1 to 16 of the present invention have a small number of deteriorated foreign matters even when used as recycled materials in the melt casting method. It turns out that coloring is excellent and it can be used as an optical use film.
  • Example 3 Using the cellulose ester produced in Production Example 1 to Production Example 20 of Example 1, a cellulose ester film was produced under the conditions of the following solution casting method 1 and solution casting method 2, and the same membrane as in Example 1 When the surface failure was determined, the cellulose ester film using the cellulose ester produced in Production Examples 1 to 16 according to the present invention by reproducing Example 1 was excellent in film surface failure.
  • ⁇ Solution casting method 1> (Preparation of dope solution) The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. .
  • the silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester.
  • This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution A.
  • the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 80% by mass.
  • the web is transported while being dried with a drying air of 90 ° C. in a transport and drying process using a plurality of rolls arranged on the top and bottom, subsequently gripping both end portions of the web with a tenter, and then before stretching in the width direction at 130 ° C.
  • the film was stretched so as to be 1 time.
  • the web was dried with a drying air of 130 ° C. in a transport drying process using a plurality of rolls arranged vertically.
  • the film After heat treatment for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying step, the film was subjected to a knurling process with a width of 10 mm and a height of 10 ⁇ m at both ends of the film, cooled to room temperature, and wound on a core.
  • thermoplastic acrylic resin (Dianar BR85 (manufactured by Mitsubishi Rayon Co., Ltd.) Mw 280000) 70 parts by weight Cellulose ester of Production Example 1 (to Production Example 20) 30 parts by weight Methylene chloride 300 parts by weight Ethanol 40 parts by weight The above composition was sufficiently dissolved with heating to prepare a dope solution B.
  • the produced dope solution B was uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support.
  • the peeled thermoplastic acrylic resin / cellulose ester resin web was evaporated at 35 ° C., slit to 1.6 m width, and then stretched 1.1 times in the width direction with a tenter, followed by a drying temperature of 130 ° C. And dried. At this time, the residual solvent amount when starting stretching with a tenter was 10%. After stretching with a tenter, relaxation was performed at 130 ° C.
  • a drying zone at 120 ° C. and 140 ° C. with many rolls, slitting to a width of 1.5 m, and a width of 10 mm at both ends of the film
  • a knurling process having a height of 10 ⁇ m was applied and wound around the core to obtain a cellulose ester film.
  • the film thickness was 40 ⁇ m and the winding length was 4000 m.
  • Example 4 Preparation of Polarizing Plate 101> According to the following steps 1 to 4, the polarizing plate 101 was produced by laminating the cellulose ester film 1 produced in Example 1 on both sides of the polarizing film.
  • PVA polyvinyl alcohol
  • the obtained PVA film had an average thickness of 25 ⁇ m, a moisture content of 4.4%, and a film width of 3 m.
  • the obtained PVA film was continuously processed in the order of pre-swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to produce a polarizing film. That is, the PVA film was immersed in water at a temperature of 30 ° C. for 30 seconds to be pre-swelled, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C. for 3 minutes. Subsequently, the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under a tension of 700 N / m.
  • the potassium iodide concentration was 40 g / liter, and the boric acid concentration was 40 g / liter. Then, it was immersed in an aqueous solution having a zinc chloride concentration of 10 g / liter and a temperature of 30 ° C. for 5 minutes for fixing treatment. Thereafter, the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further heat-treated at a temperature of 100 ° C. for 5 minutes. The obtained polarizing film had an average thickness of 13 ⁇ m, a polarizing performance of a transmittance of 43.0%, a polarization degree of 99.5%, and a dichroic ratio of 40.1.
  • Step 2 The cellulose ester film 1 was subjected to alkali saponification treatment under the following conditions. Next, excess adhesive adhered to the polarizing film immersed in the polyvinyl alcohol adhesive solution in Step 1 was lightly removed, and the cellulose ester film 1 was bonded to the polarizing film so as to be sandwiched from both sides.
  • Step 3 The laminate was laminated with two rotating rollers at a pressure of 20 to 30 N / cm 2 and a speed of about 2 m / min. At this time, it was carried out with care to prevent bubbles from entering.
  • Step 4 The sample prepared in Step 3 was dried in a dryer at a temperature of 100 ° C. for 5 minutes to prepare a polarizing plate.
  • Step 5 A commercially available acrylic pressure-sensitive adhesive is applied to one side of the cellulose ester film 1 of the polarizing plate prepared in Step 4 so that the thickness after drying is 25 ⁇ m, and dried in an oven at 110 ° C. for 5 minutes to form an adhesive layer. And a peelable protective film was attached to the adhesive layer. This polarized light was cut (punched) into a size of 576 ⁇ 324 mm, and the polarizing plate 101 was produced.
  • the polarizing plate of the NEC notebook PC LaVie G type liquid crystal panel was peeled off, and the adhesive layer of the produced polarizing plate 101 and the liquid crystal cell glass were bonded as a polarizing plate on the viewing side. Moreover, the polarizing plate 101 was bonded to the liquid crystal cell also on the backlight side in the same manner as the above procedure, and the liquid crystal display device 101 was produced.
  • the use of the cellulose ester films 1 to 16 of the present invention for the polarizing plate shows no film surface failure and good visibility (clearness). It was found that a liquid crystal display device can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract

L'invention porte sur un procédé de production d'un ester de cellulose, à l'aide duquel les variations des propriétés entre les lots de production de l'ester de cellulose, sont supprimées, et sur un film d'ester de cellulose présentant moins de défauts superficiels du film (tels que des stries obliques, des étagements latéraux, ou une irrégularité en forme d'œuf). L'invention porte aussi sur un ester de cellulose produit par le procédé, et sur un film d'ester de cellulose utilisant l'ester de cellulose. Le procédé de production d'un ester de cellulose comprend une étape de broyage consistant à broyer la cellulose de départ, une étape d'activation, une étape d'estérification, une étape de vieillissement et une étape de post-traitement. L'étape de broyage est une étape de broyage mécanico-chimique, dans laquelle la cellulose de départ et un solvant sont mélangés et broyés.
PCT/JP2011/053229 2010-03-09 2011-02-16 Procédé de production d'un ester de cellulose, ester de cellulose et film d'ester de cellulose Ceased WO2011111484A1 (fr)

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CN111171161A (zh) * 2020-02-19 2020-05-19 江苏瑞佳新材料有限公司 一种醋酸丁酸纤维素及其制备方法
CN116333173A (zh) * 2023-05-31 2023-06-27 成都普什医药塑料包装有限公司 一种醋酸纤维素及其制备方法

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CN111171161B (zh) * 2020-02-19 2020-09-11 江苏瑞佳新材料有限公司 一种醋酸丁酸纤维素及其制备方法
CN116333173A (zh) * 2023-05-31 2023-06-27 成都普什医药塑料包装有限公司 一种醋酸纤维素及其制备方法

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