WO2010047176A1 - セルロース系樹脂組成物およびセルロース系樹脂フィルム - Google Patents
セルロース系樹脂組成物およびセルロース系樹脂フィルム Download PDFInfo
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- WO2010047176A1 WO2010047176A1 PCT/JP2009/065037 JP2009065037W WO2010047176A1 WO 2010047176 A1 WO2010047176 A1 WO 2010047176A1 JP 2009065037 W JP2009065037 W JP 2009065037W WO 2010047176 A1 WO2010047176 A1 WO 2010047176A1
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- cellulose resin
- film
- cellulose
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- 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
- C08L1/02—Cellulose; Modified cellulose
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- 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
Definitions
- the present invention relates to a cellulose resin composition and a cellulose resin film, and more specifically, a cellulose resin composition suitable for use in a polarizing plate, a protective film for a polarizing plate, and a cellulose resin obtained from the resin composition. Related to film.
- Cellulosic resins are generally tougher than other synthetic resins, have excellent characteristics such as transparency, gloss and gloss, and a smooth surface and good feel. For this reason, the use of the cellulose-based resin is very diverse, for example, a sheet, a film, a wire coating, a toy, a medical device or a food packaging material.
- the cellulosic resin does not have thermoplasticity, it is necessary to melt it at a high temperature during processing or to dissolve in a solvent. When it melts at a high temperature, it causes thermal decomposition at the same time, There was a problem of coloring. Therefore, in order to avoid this, it is necessary to add a suitable plasticizer to lower the softening point of the cellulosic resin.
- triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, triethyl Phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, toluenesulfonamide, triacetin or pentaerythritol tetraacetate have been used.
- plasticizers can satisfy a wide range of performance such as compatibility with cellulosic resins, plasticization efficiency, non-volatility, stability to heat and light, non-migration, non-extractability, and water resistance.
- the current situation is that it hinders further expansion of the use of the cellulose resin composition.
- Patent Document 1 proposes a plasticizer having a hydrocarbon ring
- Patent Document 2 proposes an ester compound of a polyhydric alcohol having different alkyl groups and aryl groups.
- a cellulose triacetate film has been widely used as a protective film for polarizing plates, and a plasticizer is added to the cellulose triacetate film for the purpose of improving the flexibility of the film and reducing moisture permeability. It had been.
- the retention property deterioration refers to a property that the mass of the film is reduced due to precipitation or volatilization of an additive such as a plasticizer outside the film in a high temperature and high humidity environment.
- the retentivity is poor and the function of the liquid crystal image display device is lowered.
- Patent Document 3 proposes to use a citrate ester and Patent Document 4 proposes to use pentaerythritol.
- Patent Document 5 proposes the use of glycerides, and Patent Document 6 proposes the use of diglycerin esters.
- the cellulose resin compositions described in Patent Documents 1 and 2 have a problem that the plasticizer bleeds on the resin surface, and none of them is satisfactory.
- the cellulose resin compositions described in Patent Documents 3 to 6 have the effect of improving transparency and retention, regarding the bleeding of the plasticizer to the resin surface when a large amount of plasticizer is added, Therefore, more sufficient improvement has been desired.
- an object of the present invention is to provide a cellulose resin composition and a cellulose resin film which do not have a bleeding problem even if a relatively large amount of plasticizer is blended.
- the present inventors have added a specific polyester plasticizer that uses succinic acid and adipic acid as a polybasic acid component and does not use a stopper. As a result, the inventors have found that the above object can be achieved, and have completed the present invention.
- the cellulose resin composition of the present invention is a cellulose resin composition obtained by adding (A) a polyester plasticizer to a cellulose resin, wherein the polyester plasticizer is a polybasic acid.
- the polybasic acid is obtained by reaction with a polyhydric alcohol, and 80 mol% or more of the polybasic acid is succinic acid and adipic acid.
- the polybasic acid preferably has a molar ratio of succinic acid to adipic acid of 80/20 to 40/60.
- the (A) polyester plasticizer is preferably an oligoester having a weight average molecular weight of 500 to 2,000.
- the cellulose resin composition of the present invention it is preferable that 3 to 50 parts by mass of the (A) polyester plasticizer is added to 100 parts by mass of the cellulose resin.
- the cellulose resin composition of the present invention it is preferable that the cellulose resin is cellulose triacetate.
- the cellulose resin film of the present invention is obtained from the cellulose resin composition.
- a plasticizer even if a plasticizer is blended in a relatively large amount, it is possible to take advantage of the excellent properties of the plasticizer without bleeding, a polarizing plate, a protective film for a polarizing plate, a retardation plate, a reflective plate, It is possible to provide a cellulose resin composition suitably used as a liquid crystal display member such as a viewing angle improving film, an antiglare film, an antireflection film, an antistatic film, and a cellulose resin film using the same. became.
- the cellulose-based resin used in the present invention is not particularly limited, but preferably contains a lower fatty acid ester of cellulose (hereinafter sometimes referred to as “cellulose ester”).
- the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms.
- Examples of the lower fatty acid ester of cellulose include cellulose acetate, cellulose propionate, and cellulose butyrate. Examples include mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in Japanese Patent No. -45804, Japanese Patent Application Laid-Open No. Hei 8-231761, and US Pat. No. 2,319,052. Can do.
- the cellulose lower fatty acid ester that is particularly preferably used is cellulose triacetate.
- the cellulose triacetate preferably has a degree of polymerization of 250 to 400 and an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5%, and an average degree of acetylation of 58.0 to 62.5 from the viewpoint of film strength. % Is more preferable.
- a particularly preferred lower fatty acid ester of cellulose has an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution degree of propionyl group or butyryl group is Y, (I), Formula (I) 2.6 ⁇ X + Y ⁇ 3.0 And (II), Formula (II) 0 ⁇ X ⁇ 2.5 Is a cellulose ester that simultaneously satisfies
- the lower fatty acid ester of cellulose is particularly preferably cellulose acetate propionate, and more preferably 1.9 ⁇ X ⁇ 2.5, and more preferably 0.1 ⁇ Y ⁇ 0.9.
- the part which is not substituted with an acyl group usually exists as a hydroxyl group.
- cellulose esters synthesized using cotton linter, wood pulp, kenaf and the like as raw materials can be used alone or in combination.
- a cellulose ester synthesized from cotton linter hereinafter sometimes simply referred to as linter
- linter a cellulose ester synthesized from cotton linter
- the polyester plasticizer is obtained from a polybasic acid and a polyhydric alcohol.
- polybasic acids include aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid, which may be used alone or in combination.
- aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid or aliphatic polybasic acids such as butanetricarboxylic acid, tricarbaryl acid, citric acid can also be used. .
- 80 mol% or more, preferably 86% or more, more preferably 90 mol% or more is succinic acid and adipic acid, preferably in the polybasic acid, succinic acid.
- adipic acid is used in a molar ratio of 80/20 to 40/60, particularly preferably 75/25 to 45/55.
- examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1, 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5- Aliphatic acids such as hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol
- Glycols can be used alone or in admixture, and in addition, a small percentage of glycerin, trimethylolpropane, E
- the (A) polyester plasticizer is preferably an oligoester having a weight average molecular weight of 500 to 2,000.
- the polyester plasticizer can be produced by a known method.
- the polyester plasticizer can be produced using the polybasic acid and the polyhydric alcohol in the presence of a catalyst such as dibutyltin oxide or tetraalkyl titanate.
- a catalyst such as dibutyltin oxide or tetraalkyl titanate.
- the ratio of each of the above components used in the production varies depending on the type of the component used and the characteristics, molecular weight, etc. of the target polyester plasticizer, but generally 10 to 80% by mass of an aliphatic polybasic acid and Polyhydric alcohol is used in a ratio of 10 to 80% by mass.
- polyester plasticizer used in the present invention are specifically shown in Table 1 below.
- Table 1 AV is the acid value
- OHV is the hydroxyl value
- Mw is the molecular weight
- () in the mixture is the molar ratio.
- the acid value of the polyester plasticizer is preferably 1 or less.
- the amount of the polyester plasticizer added is 3 to 50 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the cellulose resin. If the amount added is less than 3 parts by mass, the effect of imparting flexibility may not be obtained, and if it exceeds 50 parts by mass, bleeding may occur, which is not preferable.
- composition of the present invention may further contain various additives such as phosphorus antioxidants, phenol antioxidants or sulfur antioxidants, ultraviolet absorbers, hindered amine light stabilizers, and the like. You can also.
- Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tri
- phenol-based antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3 Bis (4-hydroxy-3-tert-but
- sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). And ⁇ -alkyl mercaptopropionic acid esters.
- Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 ′-(2 -Methacryloyloxyethoxyethoxy) benzophenone, 2-hydroxybenzophenones such as 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-tert Butyl-5-methylphenyl) -5-chlorobenzotriazole 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7-9
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2, , 6,6-tetramethyl-4-piperidyl) -bis (tridecyl) -1
- the cellulose resin composition of the present invention may further include various additives as necessary, for example, fillers, colorants, crosslinking agents, antistatic agents, plate-out preventing agents, surface treatment agents, lubricants, flame retardants. , Fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents, and the like.
- the cellulose resin composition of the present invention can be used for various applications by various known processing methods, and in particular, it is used as a cellulose resin film such as a polarizing plate and a polarizing plate protective film because of its characteristics. Is preferred.
- the cellulose resin film of the present invention is obtained from the above cellulose resin composition, and then a cellulose ester film comprising the cellulose resin composition (hereinafter sometimes referred to as “cellulose ester film of the present invention”). The manufacturing method will be described.
- the production of the cellulose ester film of the present invention is performed by applying and drying a dope solution in which cellulose ester is dissolved in a solvent.
- Various additives can be mixed in the dope liquid as necessary.
- the concentration of the cellulose ester in the dope is preferably higher because the drying load after casting on the support can be reduced. However, if the concentration of the cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become.
- the concentration at which these are compatible is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.
- the solvent used for the preparation of the dope liquid of the present invention may be used alone or in combination, but it is preferable in terms of production efficiency to use a good solvent and a poor solvent of cellulose ester, and the mixing ratio of the good solvent and the poor solvent is A preferable range is 70 to 98% by mass of the good solvent and 30 to 2% by mass of the poor solvent.
- the good solvent and the poor solvent used in the present invention those that dissolve the cellulose ester used alone are defined as good solvents, and those that swell or cannot dissolve alone are defined as poor solvents. Therefore, depending on the average degree of acetylation of cellulose, the good solvent and the poor solvent change. For example, acetone becomes a good solvent for cellulose esters having an average degree of acetylation of 55%, and poor for cellulose esters having an average degree of acetylation of 60%. It becomes a solvent.
- the good solvent and the poor solvent are not uniquely determined in all cases, but as the good solvent used in the present invention in the case of cellulose triacetate, organic halogen compounds such as methylene chloride and dioxolane are used. Furthermore, in the case of cellulose acetate propionate, methylene chloride, acetone, methyl acetate and the like can be mentioned, and examples of the poor solvent include methanol, ethanol, n-butanol, cyclohexane and cyclohexanone.
- a general method can be used, but under pressure, a temperature in a range not lower than the boiling point of the solvent at normal pressure and not causing the solvent to boil.
- the method of heating with stirring and dissolving with stirring is preferred in order to prevent the generation of bulk undissolved material called gel or mako.
- a method in which cellulose ester is mixed with a poor solvent and wetted or swollen, and then mixed with a good solvent and dissolved is also preferably used.
- a known cooling dissolution method may be used. When the cooling dissolution method is used, methyl acetate or acetone can be used as a good solvent.
- the pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.
- the heating temperature after addition of the solvent is preferably in the range where the solvent does not boil at or above the normal pressure of the solvent used from the viewpoint of the solubility of the cellulose ester, but is required if the heating temperature is too high.
- the pressure increases and productivity is reduced.
- the range of the preferred heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and further preferably 70 to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.
- the cellulose ester solution is filtered using an appropriate filter medium such as filter paper.
- an appropriate filter medium such as filter paper.
- the filter medium it is preferable that the absolute filtration accuracy is small in order to remove unnecessary substances and the like, but if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. Therefore, a filter medium having an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium in the range of 0.001 to 0.008 mm is more preferable, and a filter medium in the range of 0.003 to 0.006 mm is more preferable.
- a normal filter medium can be used. However, a plastic filter medium such as polypropylene and Teflon (registered trademark) and a metal filter medium such as stainless steel are preferable because fibers do not fall off.
- the dope solution can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at a normal pressure and in a range where the solvent does not boil is a differential pressure before and after the filter medium. (Hereinafter, it may be called a filtration pressure.)
- the raise of a small is preferable.
- the filtration temperature is preferably 45 to 120 ° C, more preferably 45 to 70 ° C, and further preferably 45 to 55 ° C. A smaller filtration pressure is preferred.
- the filtration pressure is preferably 1.6 ⁇ 10 6 Pa or less, more preferably 1.2 ⁇ 10 6 Pa or less, and further preferably 1.0 ⁇ 10 6 Pa or less.
- the support used in the casting process is preferably a support having a mirror-finished endless belt-like or drum-like stainless steel.
- the temperature of the support in the casting step is preferably from 0 ° C. to less than the boiling point of the solvent. The higher the temperature, the faster the drying speed. However, if the temperature is too high, foaming may occur or the flatness may deteriorate.
- the support temperature is preferably 0 to 50 ° C, more preferably 5 to 30 ° C.
- the method for controlling the temperature of the support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of bringing a hot water bat into contact with the support.
- the residual solvent amount when peeling from the support is preferably 10 to 120%, more preferably 20 to 40% or 60 to 120%, and particularly preferably. Is 20-30% or 70-115%.
- the means for drying the film is not particularly limited, and is performed with hot air, infrared rays, a heating roll, a microwave, or the like. It is preferable to carry out with hot air from the point of simplicity.
- the drying temperature is preferably increased stepwise in the range of 40 to 150 ° C., and more preferably 50 to 140 ° C. in order to improve dimensional stability.
- the film thickness of the cellulose ester film is preferably smaller because the resulting polarizing plate becomes thinner and the liquid crystal display can be made thinner, but if it is too thin, the moisture permeability increases and the tear strength and the like are insufficient.
- the film thickness of the cellulose ester film that achieves both of these is preferably 10 to 65 ⁇ m, more preferably 20 to 60 ⁇ m, and even more preferably 35 to 50 ⁇ m.
- the cellulose ester film of the present invention can be preferably used as a liquid crystal display member because of its low moisture permeability and high dimensional stability.
- a liquid crystal display member is a member used in a liquid crystal display device.
- a polarizing plate, a protective film for a polarizing plate, a retardation plate, a reflective plate, a viewing angle improving film, an antiglare film, an antireflective film, and a charge Prevention films and the like are examples.
- the cellulose ester film of the present invention is preferably used for a polarizing plate and a protective film for a polarizing plate.
- the polarizing plate can be prepared by a general method. For example, there is a method in which the cellulose ester film of the present invention is bonded to both surfaces of a polarizing film prepared by immersing and stretching in an iodine solution using an alkali saponification type aqueous polyvinyl alcohol solution.
- the alkali saponification treatment refers to a treatment in which the cellulose ester film is immersed in a high-temperature strong alkaline solution in order to improve the wetness of the water-based adhesive and improve the adhesion.
- the retardation Ro (nm) in the in-plane direction of the cellulose ester film is preferably as small as possible, preferably 100 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less.
- Ro (nm) is preferably 50 to 1000 nm.
- the cellulose ester film is measured for a three-dimensional refractive index at a wavelength of 590 nm using an automatic birefringence meter, and the slow axis angle ⁇ 1 and the refractive indexes Nx and Ny are determined.
- Nx the refractive index of the film in a direction parallel to the film forming direction
- Ny the refractive index of the film in the direction perpendicular to the film forming direction
- d the thickness (nm) of the film.
- the angle ⁇ 0 formed between the film forming direction (corresponding to the longitudinal direction) of the film and the slow axis of the film is close to 0 °, + 90 °, or ⁇ 90 °. The more preferable.
- the slow axis is the direction in which the in-plane refractive index is the highest.
- ⁇ 1 (radian) ( ⁇ 1 is obtained by converting ⁇ 0 into radians) and retardation Ro in the in-plane direction are represented by the following formula: p ⁇ 1-sin 2 (2 ⁇ 1 ) ⁇ sin 2 ( ⁇ Ro / ⁇ ) It is more preferable that the relationship is p is preferably at least 0.99900, more preferably at least 0.99999, even more preferably at least 0.99995, and particularly preferably at least 0.99999.
- ⁇ represents the wavelength (nm) of light in the three-dimensional refractive index measurement for determining Ro and ⁇ 1 and is in the range of 380 to 650 nm. The above formula is preferably satisfied when ⁇ is 590 nm, and the above formula is more preferably satisfied when ⁇ is 400 nm.
- Example 1-1 to 1-6 and Comparative Examples 1-1 to 1-5) Acetyl cellulose (manufactured by Daicel Chemical Industries, Ltd .; LT-35) was dissolved in a solvent consisting of 100 parts by mass of methylene chloride with stirring to obtain a solution having a concentration of 15%.
- a plasticizer described in Table 2 below was mixed with 30% by mass with respect to acetylcellulose, and the solution was cast on a metal support to form a film having a thickness of about 0.1 mm to produce a film.
- the plasticizers 1 to 6 are those in Table 1.
- the plasticizers A to E are those shown in Table 3 below.
- AV represents an acid value
- OHV represents a hydroxyl value
- Mw represents a molecular weight
- () in the mixture represents a molar ratio.
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Abstract
Description
本発明に用いられるセルロース系樹脂は、特に限定されないが、セルロースの低級脂肪酸エステル(以下、「セルロースエステル」ということもある)を含有するものであることが好ましい。セルロースの低級脂肪酸エステルにおける低級脂肪酸とは、炭素原子数が6以下の脂肪酸を意味し、セルロースの低級脂肪酸エステルとしては、例えば、セルロースアセテート、セルロースプロピオネート、セルロースブチレート等や、特開平10-45804号公報、特開平8-231761号公報、米国特許第2,319,052号明細書等に記載されているようなセルロースアセテートプロピオネート、セルロースアセテートブチレート等の混合脂肪酸エステルを挙げることができる。上記のセルロースの低級脂肪酸エステルの中でも、特に好ましく用いられるセルロースの低級脂肪酸エステルは、セルローストリアセテートである。
式(I) 2.6≦X+Y≦3.0
および(II)、
式(II) 0≦X≦2.5
を同時に満たすセルロースエステルである。
残留溶剤量=〔(加熱処理前のフィルム質量-加熱処理後のフィルム質量)/(加熱処理後のフィルム質量)〕×100(%)
で定義される。尚、残留溶剤量を測定する際の加熱処理とは、フィルムを115℃で1時間加熱することをいう。また、セルロースエステルフィルムの乾燥工程においては、支持体より剥離したフィルムをさらに乾燥し、残留溶剤量を3質量%以下にすることが好ましく、さらに0.5質量%以下が好ましい。フィルム乾燥工程では一般にロール懸垂方式か、テンター方式でフィルムを搬送しながら乾燥する方式が採られる。
Ro=(Nx-Ny)×d
に従って面内方向のレターデーションRoを算出する。式中、Nxはフィルムの製膜方向に平行な方向におけるフィルムの屈折率、Nyは製膜方向に垂直な方向におけるフィルムの屈折率、dはフィルムの厚み(nm)をそれぞれ表す。
p≦1-sin2(2θ1)・sin2(πRo/λ)
の関係にあることがより好ましい。pは、0.99900以上であることが好ましく、0.99990以上であることがより好ましく、0.99995以上であることがさらに好ましく、0.99999以上であることが特に好ましい。λは、Roおよびθ1を求めるための三次元屈折率測定の際の光の波長(nm)を表し、380~650nmの範囲にある。λが590nmのときに上式を満たすことが好ましく、λが400nmのときに上式を満たすことがさらに好ましい。
アセチルセルロース(ダイセル化学工業株式会社製;LT-35)をメチレンクロライド100質量部からなる溶剤に撹拌しながら溶解し、濃度15%の溶液とした。これに下記表2記載の可塑剤をアセチルセルロースに対して30質量%混合し、溶液を金属支持体上に流延し約0.1mmの厚さに製膜し、フィルムを作製した。なお、表2中、No.1~6の可塑剤は、表1中のものであり、No.A~Eの可塑剤は下記表3中の可塑剤である。また、表3中、AVは酸価、OHVは水酸基価、Mwは分子量、混合物の( )内はモル比を示す。
サンプルを10cm×10cmのサイズに裁断し、23℃、55%RH(相対湿度)で1日放置後、80℃、90%RHの条件下で2週間放置し、さらに23℃、55%RHで1日放置した後、サンプル表面のブリードを目視観察し、評価基準は、以下の三段階とした。
○;ブリードが無く、フィルムの変化が無いもの、
△;ブリードは無いが、フィルムに濁りが見られるもの、
×;ブリードがあるもの
Claims (6)
- セルロース系樹脂に、(A)ポリエステル系可塑剤を添加して得られるセルロース系樹脂組成物であって、前記(A)ポリエステル系可塑剤が、多塩基酸と、多価アルコールとの反応により得られたものであり、前記多塩基酸の80モル%以上がコハク酸およびアジピン酸であることを特徴とするセルロース系樹脂組成物。
- 前記多塩基酸中、コハク酸とアジピン酸のモル比が80/20~40/60である請求項1記載のセルロース系樹脂組成物。
- 前記(A)ポリエステル系可塑剤が、重量平均分子量500~2000のオリゴエステルである請求項1記載のセルロース系樹脂組成物。
- 前記セルロース系樹脂100質量部に対して、前記(A)ポリエステル系可塑剤が3~50質量部添加されている請求項1記載のセルロース系樹脂組成物。
- 前記セルロース系樹脂が、セルローストリアセテートである請求項1記載のセルロース系樹脂組成物。
- 請求項1記載のセルロース系樹脂組成物から得られることを特徴とするセルロース系樹脂フィルム。
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CN2009801420093A CN102197079A (zh) | 2008-10-21 | 2009-08-28 | 纤维素系树脂组合物及纤维素系树脂薄膜 |
EP09821876.1A EP2351788A4 (en) | 2008-10-21 | 2009-08-28 | CELLULOSE RESIN COMPOSITION AND CELLULOSE RESIN FILM |
US13/125,350 US8597421B2 (en) | 2008-10-21 | 2009-08-28 | Cellulose resin composition and cellulose resin film |
JP2010534748A JP5469079B2 (ja) | 2008-10-21 | 2009-08-28 | セルロース系樹脂組成物およびセルロース系樹脂フィルム |
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EP (1) | EP2351788A4 (ja) |
JP (1) | JP5469079B2 (ja) |
KR (1) | KR101602751B1 (ja) |
CN (1) | CN102197079A (ja) |
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WO (1) | WO2010047176A1 (ja) |
Cited By (6)
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JP2011127045A (ja) * | 2009-12-18 | 2011-06-30 | Fujifilm Corp | セルロースアシレートフィルム、偏光板及び液晶表示装置 |
JP2012025804A (ja) * | 2010-07-20 | 2012-02-09 | Fujifilm Corp | ポリマーフィルム、偏光板及び液晶表示装置 |
JP2012144627A (ja) * | 2011-01-11 | 2012-08-02 | Fujifilm Corp | セルロースアシレートフィルム、偏光板、及び液晶表示装置 |
JP2012198529A (ja) * | 2011-03-07 | 2012-10-18 | Fujifilm Corp | 光学フィルム、位相差フィルム、偏光板及び液晶表示装置 |
CN102898685A (zh) * | 2011-07-29 | 2013-01-30 | 富士胶片株式会社 | 树脂膜及其制作方法、起偏器和液晶显示装置 |
JP2013018895A (ja) * | 2010-07-20 | 2013-01-31 | Fujifilm Corp | 光学フィルム、位相差フィルム、偏光板及び液晶表示装置 |
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JP5312812B2 (ja) * | 2008-01-23 | 2013-10-09 | 株式会社Adeka | セルロース系樹脂組成物およびセルロース系樹脂フィルム |
US20130150498A1 (en) | 2011-12-07 | 2013-06-13 | Eastman Chemical Company | Cellulose esters in pneumatic tires |
JP2013234273A (ja) * | 2012-05-09 | 2013-11-21 | Adeka Corp | セルロース系樹脂組成物 |
CN105785718A (zh) * | 2015-01-09 | 2016-07-20 | 三星显示有限公司 | 光敏树脂组合物、使用所述光敏树脂组合物的颜色转换面板和显示装置 |
US10077342B2 (en) | 2016-01-21 | 2018-09-18 | Eastman Chemical Company | Elastomeric compositions comprising cellulose ester additives |
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Cited By (7)
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JP2011127045A (ja) * | 2009-12-18 | 2011-06-30 | Fujifilm Corp | セルロースアシレートフィルム、偏光板及び液晶表示装置 |
JP2012025804A (ja) * | 2010-07-20 | 2012-02-09 | Fujifilm Corp | ポリマーフィルム、偏光板及び液晶表示装置 |
JP2013018895A (ja) * | 2010-07-20 | 2013-01-31 | Fujifilm Corp | 光学フィルム、位相差フィルム、偏光板及び液晶表示装置 |
JP2014240980A (ja) * | 2010-07-20 | 2014-12-25 | 富士フイルム株式会社 | 偏光板及び画像表示装置 |
JP2012144627A (ja) * | 2011-01-11 | 2012-08-02 | Fujifilm Corp | セルロースアシレートフィルム、偏光板、及び液晶表示装置 |
JP2012198529A (ja) * | 2011-03-07 | 2012-10-18 | Fujifilm Corp | 光学フィルム、位相差フィルム、偏光板及び液晶表示装置 |
CN102898685A (zh) * | 2011-07-29 | 2013-01-30 | 富士胶片株式会社 | 树脂膜及其制作方法、起偏器和液晶显示装置 |
Also Published As
Publication number | Publication date |
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EP2351788A1 (en) | 2011-08-03 |
US8597421B2 (en) | 2013-12-03 |
KR101602751B1 (ko) | 2016-03-11 |
CN102197079A (zh) | 2011-09-21 |
TWI465515B (zh) | 2014-12-21 |
JP5469079B2 (ja) | 2014-04-09 |
JPWO2010047176A1 (ja) | 2012-03-22 |
EP2351788A4 (en) | 2013-10-02 |
KR20110074619A (ko) | 2011-06-30 |
TW201030089A (en) | 2010-08-16 |
US20110197784A1 (en) | 2011-08-18 |
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