TWI375832B - - Google Patents

Description

1375832 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to a cellulose ester film used for a protective film for a polarizing plate, in other words, it is possible to suppress deterioration caused by a state of storage such as storage and transportation of a film (injury) A cellulose ester film produced and produced by foreign matter. [Prior Art] B In recent years, liquid crystal display devices (LCDs) have been used in various applications, and high productivity (increased throughput) of liquid crystal display elements used for LCDs, that is, polarizing plates, has also been demanded. Further, the thickness of the liquid crystal display device (LCD) is being reduced, and the polarizing plate used for the LCD is also required to be thinned. However, when the film of the protective film for a polarizing plate is developed and the film of the cellulose ester film using the film is developed, the load under the film quality is increased, 'for the storage state of the film, such as storage and transportation, In particular, when the φ is a film of a cellulose ester film, the appearance of the roll-shaped original roll film is likely to cause deterioration (injury and foreign matter). When the original roll of the cellulose ester film is deteriorated in such a manner, the appearance of the polarizing plate is deteriorated, and the resolution of the liquid crystal display is poor. Therefore, in order to prevent such deterioration in appearance, it is considered to package with a packaging material having a cellulose ester film as moisture proof. The prior patent documents relating to the preservation or packaging of such films are as follows, for example. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 5-28 No. 664. This patent document 1 relates to a packaging material for a photosensitive material (film), which has an easy-opening property of -4-(2) 1375832 and does not cause pinholes and The invention relates to a packaging material for a photosensitive material for curling, and a light-shielding bag having a completely light-shielding property using the same. This patent document! In the packaging material for a photosensitive material, one side of the reinforced sheet is an aluminum-deposited flexible sheet on which a vapor-deposited aluminum vapor-deposited film is deposited on the dust-free flexible sheet layer, and the aluminum-vapor-deposited film is laminated via the adhesive layer. The dusty flexible sheet layer has a 'direct lamination heat seal layer on the other side, and the peel strength of the reinforced sheet and the aluminum vapor-deposited film is determined. [Patent Document 2] JP-A-2001 - 3 1 5 8 8 5 This Patent Document 2 discloses the storage or transport of a polyvinyl alcohol-based polymer film for a useful polarizing film which is a raw material for producing a wide polarizing film. Invention of the method. The invention of the method for storage or transportation described in Patent Document 2 is that the material of the film and the contact portion is made of metal or plastic, and the polyvinyl alcohol-based polymerization is carried out on the cylindrical center of the film which is longer than the film width. The film is formed into a film roll which is packaged by a film for packaging having a predetermined moisture permeability and stored or transported. According to the inventions described in the above Patent Documents 1 and 2, the packaging material itself or the packaging material used for packaging the photosensitive material (film) has been widely used in the past, but as a liquid crystal display device. (LCD) The cellulose ester film used for the protective film for polarizing plates is more stringent than the photosensitive materials or other films, and the above-mentioned past methods have a certain degree of effect, but especially for cellulose. In the case of a film of an ester film, the effect is not sufficient. -5- 8 (3) 1375832 In particular, the film product in the case of storage of a cellulose ester film is an extremely important problem, and in the current packaging materials, the stability of the tube during storage is not sufficient. Therefore, the magnesium compound contained in the film raw material produced in the production stage of the cellulose ester film is caused by the magnesium content in the raw material, and is described in Patent Document 3 below. [Patent Document 3] JP-A-2000-3 1 4 8 1 1 This specification is as follows. That is, the cellulose ester film which is suitable for a polarizing film such as a liquid crystal display is affected by the differential contained in the cellulose ester. It is presumed that the component obtained by the water-related core used in the production step is less preferable, and for example, iron, calcium, magnesium, or the like, and a polymer decomposition product of an organic acid group form a salt to form a salt such that the amount of the metal ion is less. The better. However, in fact, it is related to other factors, so it simply reduces and fails to solve the problem completely. For example, for magnesium (Mg) components, groundwater is rich in • the cause of impurities. The magnesium component contained in the cellulose ester still produces insoluble components, so too much is not preferable. However, if too few words are not good. The optimum content of the magnesium component ranges from 15 to 70, and when it is wood pulp, it is 30 to 70 ppm. However, in the cellulose ester film having a relatively large thickness, as described in Patent Document 3, the content of a trace amount of gold contained in the cellulose ester: magnesium or calcium is controlled only within a certain range, and the appearance of the film is deteriorated. (Injury and foreign matter generation) can be improved, but the film quality of the film is increased, and the film quality of the negative film which increases the quality of the film is estimated to be a low-film raw material. However, insoluble may contain impurities, so there are several substances, which are still too much in characteristics and ppm, especially, such as the preservation of the above-mentioned genus, the vitamin Estermint makes -6-8 1375832 • (4) preservation of the film In the state of transportation such as transportation, the deterioration of the appearance of the film of the cellulose ester film cannot be sufficiently improved. In the film product of the cellulose ester thin film, it is desired to obtain a cellulose ester film which can suppress the deterioration of the flow state such as storage and transportation of the film (injury and foreign matter). An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a roll-shaped cellulose ester for use as a protective film for a polarizing plate with high productivity (increased throughput) of a liquid crystal display element, that is, a polarizing plate. Φ Film film of thin film, cellulose ester film which can suppress the deterioration of the flow state (injury and foreign matter) such as storage and transportation of the film. In order to achieve the above object, the inventors have found out in detail that the film of the cellulose ester film is transported by ship, for example, at a temperature of 30 to 40 ° C and a humidity of 80 to 90% RH for 1 to 3 weeks. Under the conditions, foreign matter will be generated, and the film will be stored in the summer, for example, the temperature is 35 to 45 ° C, the humidity is 80 to 90%, and under the condition of 0.5 to 1 month under RH, foreign matter is generated in the same manner, and the foreign matter becomes the original volume. Causes of scratches on the film in a state of storage. • The generation of the foreign matter is related to the amount of magnesium present on the outermost surface of the cellulose ester film, the moisture content of the film itself, and the moisture permeability. It has been found that it is impossible to determine the content of magnesium alone. In the case of magnesium, water acts to form crystals, which causes the generation of foreign matter nuclei. Under the conditions of film storage, crystal growth occurs, foreign matter is generated, and preservation is caused. The original film reel is scratched when it is stored. As a result of the foreign matter generated during the stagnation period of the high temperature and high humidity of the film, it is necessary to take measures in response to the conditions in the transportation, and the storage conditions must be set to be low temperature, low humidity, and prevention of packaging materials. Wetting can have an effect of preventing foreign matter from being generated for the film. (5) 1375832 The above object of the present invention can be attained by the following method. (Item 1) A cellulose ester film which is a cellulose ester film having a thickness of 20 to 60/zrn containing magnesium, which is characterized in that cellulose ester is produced in an untreated state (reference state) after production. When the magnesium is measured by the flight type secondary ion mass spectrometer (TOF-SIMS) on the outermost surface of the film, the detection probability of the magnesium of the total component φ detected is A, and the temperature of the cellulose ester film is 2 3 ° C. The equilibrium moisture content under the humidity of 5 5 % RH (reference state) is used as the enthalpy, the calcium chloride cup seal method is the temperature of 40 ° C, the humidity is 90% RH and the temperature is adjusted for 24 hours. The moisture permeability (g/m2) of the ester film is T, and ΑχΜ is 1.0x1 〇_4 to 3.0x10 to 3 ΑχΤ is 6.5x10-2 to 8.5 χ1〇-1 (g/m2). φ (Item 2) The cellulose ester film according to Item 1, wherein the content of the magnesium compound of the cellulose vinegar film is 50 ppm by weight or less based on the weight of the magnesium atom to the film. (Item 3) The cellulose ester film according to Item 1, wherein the temperature of the cellulose vinegar film is 2 3 T: and the humidity at 55% RH (reference state) is an equilibrium water content of 'the total amount of the cellulose ester film. The ratio is 1.0~3. The ratio of 〇% by weight is -8- 1375832

(Item 4) The cellulose ester film of item 1, wherein the cellulose ester film is subjected to a temperature-controlled humidity control treatment at a temperature of 40 ° C and a humidity of 90 % RH for 24 hours. The moisture permeability afterwards is 650~8 5 0 g/m2. (Claim 5) The cellulose ester film according to Item 1, wherein the cellulose ester film is a compound containing a polyol ester of an aliphatic polyol and one or more monocarboxylic acids, and a polyol for a cellulose ester. The ester content is 4·5 to 12.5% by weight (Item 6). The cellulose ester film according to Item 5, wherein the monocarboxylic acid is a compound having an aromatic ring or a cycloalkyl group in the molecule. (Item 7) The cellulose ester film according to Item 5, wherein the aliphatic polyol is from 2 to 20,000. (Item 8) The cellulose ester film according to Item 5, wherein the aliphatic polyol is 2 to 3 valence. -9 - (7) 1375832 (Item 9) The cellulose ester film according to item 5, wherein the aliphatic polyol has a carbon number of 4 or more. (Item 1) The cellulose ester film of item 1, wherein the weight average molecular weight of the cellulose ester is Mw, and the number average molecular weight is Μη, the ratio of the weight average molecular weight to the number average molecular weight: Mw/Mn It is 1.0~5.0. (11) The cellulose ester film according to item 10, wherein a ratio of a weight average molecular weight to a number average molecular weight: Mw / Μη is from 1. 7 to 3.0. The present invention is a cellulose ester film which is a cellulose ester film containing magnesium having a thickness of 20 to 60/m, and is characterized in that the cellulose ester film is the most untreated (standard state) after manufacture. When the surface is measured by a flight type 2 φ secondary ion mass spectrometer (TOF - SIMS), the detection probability of the total composition of magnesium is taken as A, the temperature of the cellulose ester film is 23 t, and the humidity is 55% RH ( The equilibrium moisture content under the reference state is taken as the enthalpy, the calcium chloride cup seal method is the temperature of 40 ° C 'humidity 90% RH condition, and the moisture permeability of the cellulose ester film after being conditioned for 24 hours (g/m2) as T ' ΑχΜ is l.OxlO- 4 ~ 3.0x10 - 3 八 > <1' is 6.5 parent 1〇_2~8.5><1〇-|&/1112). In the above cellulose ester film, the content of the magnesium compound is 'as a ratio of -10-(8) 1375832 magnesium atom to film weight of 50 ppm or less. Further, in the cellulose ester film, the equilibrium moisture content at a temperature of 23 k ° C 'humidity 55% RH (reference state) of the cellulose ester film is 1.0 to 3.0 by weight for the total amount of the cellulose ester film. The ratio of % is better than that of the above cellulose ester film, the cellulose ester film is subjected to a calcium chloride-cup sealing method, and the temperature is adjusted to 40 ° C and the humidity is 90 % RH for 24 hours. The moisture permeability after the wet treatment is preferably 650 to 850 g/m2. In the cellulose ester film, the cellulose ester film is a compound containing a polyol ester of an aliphatic polyol and one or more monocarboxylic acids, and the polyol ester content of the cellulose ester is 4.5 to 12.5% by weight. It is better. In the above cellulose ester film, the monocarboxylic acid is preferably a compound having an aromatic ring or a decyl group in the molecule. In the above cellulose ester film, the aliphatic polyol is 2 to 20 valence, preferably 2 to 3 valence. # In the above cellulose ester film, the aliphatic polyol is preferably a carbon number of 4 or more. In the cellulose ester film, the weight average molecular weight of the cellulose ester is Mw, and the ratio of the weight average molecular weight to the number average molecular weight when the number average molecular weight is Μη: Mw/Mn is 1.0 to 5.0, preferably 1.7 to 3.0. The present invention is a cellulose ester film containing magnesium having a thickness of 20 to 60/m, which is characterized in that the outermost surface of the cellulose ester film is in an untreated state (reference state) after manufacture. When measuring the magnesium by the flight type secondary ion mass spectrometer (TOF-SIMS), the detection probability of the total composition of -11 - 8 (9) 1375832 magnesium is taken as A, and the temperature of the cellulose ester film is 23 °C. The equilibrium moisture content under the wetness degree of 5 5 % RH (reference state) is M, and the temperature is 40 °C and the humidity is 90% under the condition of calcium chloride __ cup sealing method. The moisture permeability (g/m2) of the cellulose ester film after the treatment is T, Αχ Μ is 1.0×xOO 3 to 3.OxlO-3 ΑχΤ is 6.5×10 -2 to 8.5×10 -1 (g/m 2 ). • The cellulose ester film of the present invention is obtained by specifically determining the amount of magnesium present on the outermost surface of the cellulose ester film, the water content of the film itself, and the physical properties related to moisture permeability. In the present invention, the polarizing plate, which is a liquid crystal display element, has high productivity (increased throughput), and can be improved for use in polarized light. The so-called roll quality of the 'cellulose ester film' of the protective film for a sheet can achieve high productivity (increased production) of the protective film for polarizing plates, and can suppress the generation of foreign matter and damage of the protective film for the polarizing plate. At the same time, it is possible to improve the water resistance such as moisture permeability, and to improve the wet heat durability of the polarizing plate and the stability of the polarizing film. The invention is specifically described below. The invention of the cellulose ester film of the present invention is a cellulose ester film containing magnesium having a thickness of 20 to 60/zm, which is characterized in that the outermost surface of the cellulose ester film is produced in an untreated state (reference state) after manufacture. When magnesium is measured by a flight type secondary ion mass spectrometer (TOF-SIMS), the detected probability of detecting magnesium as a whole component is taken as A, the temperature of the cellulose ester film is 23 ° C, and the humidity is 5 5 % RH ( The equilibrium moisture content under the reference state is (10) 1375832 Μ, the calcium chloride cup seal method is based on the temperature 4 (TC, humidity 90% RH conditions • 24 hours after the temperature and humidity treatment of the cellulose ester The moisture permeability of the film (g / m2) is T, ΑχΜ is 1.OxlO-4 〜3.0χ10_3 AxTg6.5xl0-2~8.5xl0_1 (g/m2). As the above-mentioned time-of-flight type secondary ion mass spectrometer ( T〇F-SIMS), for example, "φ TF S - 2 1 0 0" manufactured by Physical Electronics Co., Ltd., preferably measured by a method specified in the apparatus. Among the above cellulose ester films, a cellulose ester film The content of the magnesium compound is, as a weight ratio of the magnesium atom to the weight of the film It is preferably 50 ppm or less. This indicates that when the amount of metal ions which easily form impurities such as magnesium is reduced to a certain extent, it is possible to suppress deterioration of the flow state such as storage and transportation of the cellulose ester film (injury, foreign matter generation). Further, the parallel water content of the above cellulose ester film is the difference between the weight of the film at a temperature of 23 ° C and a humidity of 55% RH and the weight of the film after drying at 45 φ minutes at a temperature of i2 ° C. The water content was determined by the weight ratio of the film at a temperature of 23. (:, humidity of 55% RH. For the above cellulose ester film, the temperature of the cellulose ester film was 23 ° C, and the humidity was 5 5 % RH (reference state) The equilibrium moisture content under the film is preferably 1.0 to 3.0% by weight based on the total amount of the cellulose ester film. Thus, if the equilibrium moisture content of the cellulose ester film is less than 1.0% by weight, the product is produced. The adhesion due to charging is not preferable as a film property. Further, the moisture permeability is one of the important characteristics of the cellulose ester film, and is carried out according to the calcium chloride-cup sealing method specified in JIS Ζ 02 0 8 Determination, 1 m2 -13- (11) 1375832 Calculated by the amount of water (g) permeated in 24 hours. ^ The above cellulose ester film, in which the cellulose ester film is calcium chloride - • cup sealing method is the temperature of 40 ° C, humidity 9 0 Under the conditions of % R Η, the moisture permeability after conditioning for 24 hours is preferably 6 50~8 5 0 g/m2. The moisture permeability of the cellulose ester film is only within this range, and cellulose ester is used. The polarizing plate produced by the film can maintain the hygroscopicity and stability of the polarizer. The cellulose ester which is a main component of the cellulose ester film of the present invention, φ, the cellulose triacetate 'cellulose diacetic acid Ester, cellulose acetate butyrate, cellulose acetate propionate, and the like. The cellulose triacetate is particularly preferably a cellulose triacetate having a polymerization degree of from 25 to 400, and a combined amount of acetic acid of from 54 to 62.5%. It is preferred that the strength of the matrix in which the amount of acetic acid is 58 to 62.5% is relatively strong. The cellulose triacetate is used alone or in combination with cellulose triacetate synthesized from any cotton linters and cellulose triacetate synthesized from wood pulp. In the cellulose ester film of the present invention, the weight average molecular weight of the cellulose ester is Mw, and the ratio of the weight average molecular weight to the number average molecular weight when the number average molecular weight is Μη: Mw/Mn is 1.0 to 5.0. The ratio of the weight average molecular weight to the number average molecular weight: preferably Mw/Mn is 1.7 to 3.0. The average molecular weight of the cellulose triacetate can be measured by a gel permeation chromatography method to calculate a number average molecular weight (Mn) and a weight average molecular weight (Mw). The measurement conditions of the average molecular weight are as follows. The weight average molecular weight (Mw) and the average molecular weight (?η) of the cellulose peracetate of the gel permeation chromatography were measured using the following apparatus and materials to calculate the molecular weight distribution Mw/Mn. 5 (12) 1375832 Gel Permeation Chromatography Solvent (dissolved solution): Dichloroalkane column name: GPCk806 by Gyeonggi Electric Co., Ltd. - GPCk805-GPCk803 (3 pieces) Sample concentration: 0.1 (% by weight) Flow rate: 1 · 0 ( Ml / min) • Sample injection volume: 100 ( " L ) Standard sample: polystyrene (Mw: 5,000, 〇〇〇~6,700,000)

Temperature: 2 5 ° C Detection: RI (refractive index refractive index) wherein, the ratio of the weight average molecular weight (Mw) of the cellulose triacetate to the number average molecular weight (?η) (Mw / Μη) is less than 1.0, The splitting of the film will decrease, which is not good. Further, when the ratio (Mw/Μη) exceeds 5.0, the dimensional stability of the film is deteriorated, which is not preferable. The cellulose ester film of the present invention is a compound comprising an aliphatic polyol and one or more monocarboxylic acids and a polyol ester, and the cellulose ester content of the compound is 4.5 to 12.5% by weight. In the cellulose ester film of the present invention, the monocarboxylic acid is preferably a compound having an aromatic ring or a cycloalkyl group in the molecule. Further, in the fibrous ester film of the present invention, the aliphatic polyol is 2 to 20 Å. Among them, although the function of the compound formed by the aliphatic polyol ester is not fully understood, the compound formed by using the aliphatic polyol ester can be considered to be -15-(13)!375832, which can reduce the effect of the past plasticizer. . Next, the aliphatic polyol ester used in the present invention will be described as an ester of an aliphatic polyhydric alcohol having two or more valences and one or more monocarboxylic acids. (Aliphatic Polyol) The aliphatic polyhydric alcohol used in the present invention is a divalent or higher alcohol as shown in the following formula (1). R, - ( OH ) η · (1) In the formula, Ri represents an η-valent aliphatic organic group, η represents a positive number of 2 or more, and fluorenyl represents an alcoholic and/or phenolic hydroxyl group. In addition, examples of the η-valent aliphatic organic group include an alkylene group (for example, an alkyl group, an ethyl group, a trimethyl group, a tetramethyl group, etc.), an alkenyl group (for example, a vinyl group), An alkynyl group (e.g., an ethynyl group, etc.), a cycloalkyl group (e.g., a 1,4-cyclohexanediyl group, etc.), an alkanetriyl group (e.g., 1,2 #, 3-propanetriyl, etc.). The η-valent aliphatic organic group contains a substituent (e.g., a hydroxyl group, an alkyl group, a halogen atom, etc.). η is preferably from 2 to 20. In the cellulose ester film of the present invention, the aliphatic polyol is preferably a carbon number of 4 or more. Examples of preferred polyhydric alcohols include ribitol, arabitol-, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, and 1,3-propanediol. , dipropylene glycol, tripropylene glycol, 1,2-butanediol, :I,3-butanediol, 1,4-butanediol, 1,2,4-butanetriol, 1,5-pentanediol, 1 ,6-hexanediol, hexanetriol, galactitol, mannose-16- (14) 1375832 alcohol, 3-methylpentane-1,3' 5-triol, tetramethyl glycol, sorbus • Sugar alcohol, trimethylolpropane, trimethylolethane, xylitol. In particular, ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferred. (monocarboxylic acid) In the present invention, the monocarboxylic acid in the polyol ester is not particularly limited to φ, but a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. Among them, an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is preferred because it improves moisture permeability and retention. The preferred examples of the monocarboxylic acid include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having 1 to 32 carbon atoms is preferably used. It is more preferable to use carbon number 1 to 2 0, and 1 to 1 is particularly preferable. It is preferred that the compatibility with cellulose ester is increased when acetic acid is contained, and that acetic acid may be mixed with other monocarboxylic acids. Preferred examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethylhexanoic acid, undecanoic acid, and ten. Dialkyl acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, behenic acid Saturated fatty acids such as tetradecanoic acid, hexadecanoic acid, heptacosanoic acid, __octadecanoic acid, triacontanic acid, and tridecanoic acid, undecylenic acid, oleic acid, sorbic acid Unsaturated fatty acids such as linoleic oil, linolenic acid, and peanut diced acid. These may have further substituents. -17-(15) 1375832 Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or these derivatives. Examples of preferred aromatic monocarboxylic acids include those in which a phenyl ring of benzoic acid such as benzoic acid or toluic acid is introduced into a benzene ring, and a benzene ring such as a biphenylcarboxylic acid, a naphthoic acid or a naphthyl carboxylic acid has 2 More than one aromatic monocarboxylic acid, or a derivative thereof. Especially benzoic acid is preferred. n (Polyol ester) The molecular weight of the polyol ester used in the present invention is not particularly limited, but is preferably 300 to 1,500, more preferably 350 to 750. The larger the retention point of view, the better, from the viewpoint of moisture permeability and compatibility with cellulose esters. In the present invention, the carboxylic acid in the polyol ester may be one type or two or more types. Further, the OH group in the polyol may be all esterified to leave a part of the OH group. It is preferred to have three or more aromatic rings or cycloalkyl groups in the molecule. Examples of the polyol ester used in the present invention are shown below. (16) 1375832 〔化i〕 C 羼 H9_C-Q—(CH^- 〇—(¢^2)2- 〇~ (CHjJj -Ο- C—C4H9o o

Q- /^~C-〇-(CH2)2-〇-(CH^2-〇-(CH^2-〇**C-(^ '~f 〇O '-"f〇-『. ~,2 -.)^O5 C4H9-C-0-^CH2-CH2-0^-C-C4H9 o 0 6 CaHiy-CO-^CHi-CHj-O^-C-CflHtTo o QCO-fcHrCH.-O ^CQ 3 4 7 8 〇Ή—)r|-〇9 c,h9-co-^· ch2ch2ch2- 0 )7- C-C4H9o 0 10 ^Η17-0-〇4-0Η20Η20Η2-Ο^ς-〇- 0βΗ17 O 〇11 ^^-j-〇+CH2CH2CH2-〇h-^^ 12 /~V-?-〇4ch2?h-*〇W-p"^~^

\=J 13 〇 C4H9-C-0 11o ch3

/3S W C-C4H9 IIo

14 CaH17-C-0-^CH2CH-0^-C-C,HlT 0 ch3 3 0 15 cH^TM°)rf-〇 5 1375832

CH3CH2-C-CH2-〇-C-CeH17 o I 〇 CH»~ 0_C—C«Hi7 II o 20 CHi-O- CH3CHa-C-CH2-0-C-CHs I 〇 ch2-o-c-ch3

II o

-20- 25 (18) 1375832 〔化3〕 24

ό ό II ch2—ch-ch-ch-ch2 〇=co=c PP o=co=cό ό ?„2-έΗ.?Η-έΗ-?Η2 oo 0 c=oc=oc=o 0 1 c= o

0 I oc=oc=o 26 ό ό ό ό ό ό27 9 φρ ch3 ch3 〇=co=c I » 0 〇ch2-ch-ch-ch-ch2 o 0 ? c=oc=oo=c 〇=c 0 o CH2-CH2-C-CHa-CH2 ch3 28 o=c I oo=co=coo 29 CHa-CHi-C-CHj-CH2 CH, 0 I c=o ό -21 - (19)1375832

/~^C-〇^CH2-CH2-CH2-〇^〇~C-/~\ — Ο 0

c=o ό -22- (20) 1375832 Among the above polyol esters, trimethylolpropane tribenzoate (TMPTB), trimethylolpropane triacetate, trimethylolpropane Tripropionic acid-ester, dipropylene glycol dibenzoate, tripropylene glycol dicarboxylate, 1,3-butanediol dibenzoate, tetraethylene glycol dibenzoate, trimethylolpropane Mixed ester with acetic acid and benzoic acid, ester of trimethylolpropane with cyclohexanecarboxylic acid, mixed ester of trimethylolpropane with acetic acid and cyclohexanecarboxylic acid '3 - methylpenterine-1,3 '5_Triol and Cyclohexanol Residual Acid Vinegar, 3-Methylpentaphthyl-1,3' 5-triol and benzoic acid ester, xylitol and benzoic acid ester, xylitol and ring An ester of hexanecarboxylic acid is preferred. Further, the amount of the polyol ester used is preferably from 4.5 to 12.5 % by weight, preferably from 6 to 12% by weight, particularly preferably from 7 to 11% by weight, based on the cellulose ester. In the present invention, as the solvent of the above cellulose ester, for example, lower alcohol such as methanol, ethanol, n-propanol, isopropanol or n-butanol, cyclohexane, dioxane or lower aliphatic of dichloromethane Chlorinated hydrocarbons, etc. As the solvent ratio, for example, 70 to 95% by weight of methylene chloride is preferable, and the other solvent is preferably 5 to 30% by weight. Further, the concentration of the cellulose ester is preferably from 1 〜 to 50% by weight. The heating temperature of the solvent to be added is preferably a temperature in which the boiling point of the solvent is not more than the boiling point of the solvent, and is preferably in the range of 6 ° C or higher and 80 to 10 10 ° C. Also, the pressure is set to such an extent that the solvent does not boil at a given temperature. After it is dissolved, it is taken out from the container by cooling, or it is pulled out by a container or the like, and then cooled by a heat exchanger or the like, and this is supplied to the film. The cellulose ester film of the present invention contains a cellulose ester and a solvent, and a compound of the above-mentioned -23-5 (21) I375832 polyol ester, and also contains an additive such as an ultraviolet absorber. 'Additional additives such as cellulose ester and solvent, additives such as ultraviolet light absorbers, etc., may be mixed with a solvent in advance, dissolved or dispersed, and then added to the solvent before dissolution of the cellulose ester, or the glue after the cellulose ester is dissolved. The plasticizer used in the present invention is not particularly limited, but the phosphoric acid ester may be used alone or in combination with triphenyl phosphate (TPP), biphenyl diphenyl phosphate (BDP), or cresol phosphate. , cresol diphenyl phosphate, octyl diphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc., in the phthalate type, diethyl phthalate, dimethoxy B can be used. Base phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate 'di-2-ethylhexyl phthalate, butyl butyl butyl glycolate, ethyl hydrazine Mercaptoethyl glycolate (EPEG), methylmercaptoethyl glycolate, butyl decyl butyl glycolate, etc. are preferred. If necessary, the above plasticizers can be used in combination with two types of #. By containing these plasticizers, it is possible to obtain an excellent dimensional stability and water resistance film. In the present invention, the amount of the plasticizer to be added is preferably a weight percent of the cellulose ester of 12% by weight or less, based on the specific water absorption ratio and the water content. Two or more types of plasticizers may be used in combination, and the total amount of these plasticizers may be 12% by weight or less. These plasticizers may be used alone or in combination of two or more. Further, in the present invention, the above polyol ester has a plasticizer function, and such a polyol ester and a conventional plasticizer can be used at the same time. In this case, the polyol ester is as described above in the above -24-(22) 1375832, and it can be used in the range of 4.5 to 12.5% by weight of the cellulose ester, and the total amount of the polyol ester and the plasticizer is for the cellulose ester. 2.5% by weight or less is preferred. Further, the amount of the plasticizer to be used at this time is preferably 8.0% by weight or less based on the cellulose ester. The amount of the polyol ester used is preferably 7% by weight or more based on the cellulose ester, and the amount of the plasticizer used is preferably 5.5% by weight based on the cellulose ester, which is because the polyol ester is used. The effect of the present invention can be exhibited by reducing the amount of plasticizer used in the past. It is preferable to add an ultraviolet absorber to the cellulose ester film of the present invention, and it is excellent in ultraviolet light absorption of a wavelength of 3 70 nm or less from the viewpoint of preventing deterioration of liquid crystal as an ultraviolet absorber, and from the viewpoint of good liquid crystal display properties. It is preferable that the visible light having a wavelength of 400 nm or more is used as a general user, and examples thereof include a hydroxybenzophenone compound, a benzotriazole compound, a salicylate compound, and a benzophenone system. A compound, a cyanoacrylate compound, a nickel-substituted salt compound, or the like, φ is not limited thereto. Further, in order to improve the smoothness of the cellulose ester film of the present invention and prevent the hindrance after the winding, the fine particles as the matting agent to be added may be added to the main dope, but from the viewpoint of productivity It is preferably added to the addition liquid. It is added to the addition liquid and is contained in the film. Further, although it may be contained in the main glue, any substance as fine particles may be used. Examples of the inorganic compound used in the microparticles of the present invention include ceria, titania, alumina, zirconia, calcium carbonate, talc, clay, barbecue ceramics, barbecued calcium citrate, calcium citrate hydrate, and aluminum citrate. , 8 (23) 1375832 Magnesium citrate and calcium phosphate. As the fine particles of zirconia, for example, those of Aerosil R976 and R811 (produced by Japan Aerosil Co., Ltd.) can be used, and those containing fine particles are preferred because of turbidity, and particularly preferably cerium oxide. As these examples, commercial products such as Aerosil R972, R972V, R974, R812, 200, 200V, R202, 0X50, and TT600 (the above are manufactured by Japan Aero Sil Co., Ltd.) can be used. Further, it is preferable that the cerium oxide microparticles have a primary average particle diameter of φ 20 nm or less and an apparent specific gravity of 70 g/L or more. As the fine particles satisfying these cerium oxides, Aerosil 200V and Aerosil R972V are particularly preferable because they have an effect of lowering the friction coefficient at a lower temperature. In the present invention, the fine particles are cellulose esters, and are used in an amount of 0.4% by weight or less, preferably 0.05 to 0.3% by weight, and 0.05 to 0.2% by weight. In the present invention, after the cement obtained by dissolving the cellulose ester is cast (cast #) on the support, heating is performed to remove a part of the solvent (the support is applied), the support is peeled off, and the peeled film is dried to obtain a fiber. The support in the pour casting step may use a mirror-shaped or cylindrical mirror-finished support. The temperature of the support in the casting step can be cast at a temperature ranging from 〇 °c to the boiling point of the solvent, and the casting on the support of -30 ° C is preferred because the gelizable paste can be used to increase the stripping time. The casting is carried out on a support of 5 to 15 ° C to cast the dope in the drying step of the support. Once the gelation is carried out, the product name is limited to 300, and the company diameter is the particle. For example, there is a film turbidity plus 0.04. It is better to note that the step-drying of the v-sodium ester stainless steel is generally mild but at 5 minutes. When the time from casting -26-(24) 1375832 to peeling is 100%, the temperature of the glue is set to 4 ° C to 70 by casting to 30% or less. (: It can promote evaporation of the solvent, can be quickly peeled off from the support - and can increase the peel strength, and is preferable. It is preferable to set the temperature of the paste to 55 ° C to 70 ° C within 3 %. It is better to maintain the temperature at 20% or more, and more preferably 40% or more. The drying factor on the support can remove 60% to 150% of the residual solvent from the support, so that the peel strength of the support is small. Preferably, 80 to φ 120% is preferable. When the temperature of the glue at the time of peeling is set to or 3 〇r, the strength of the substrate at the time of peeling can be improved, and the matrix breakage at the time of peeling can be prevented, so that it is preferably 5 to 20 ° C. Further, in the film drying step, the film which is peeled off from the support is dried, and the amount of the residual solvent is 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less, and a film having good dimensional stability is obtained. Therefore, the film drying step is generally carried out by means of a drum suspension method, a needle plate type setting machine, and a clip setting machine to transport the film under the film. As a liquid crystal display element, the drying element can be improved by the setting machine while maintaining the amplitude. Dimensional stability The method of drying the film is not particularly limited, and it can be generally carried out using hot air, infrared rays, a heating drum, a microwave oven, etc. From the viewpoint of convenience, it is preferably carried out by hot air. The drying temperature is in the range of 4 〇 t to 150 ° C. It is divided into 3~5 stage temperature, and the stage type raises the temperature better. 8 (The stability of the size is good when it is carried out in the range of TC~140 °C. The steps from the casting to the post-drying can be performed in the air environment, or It can also be used in an inert gas atmosphere such as nitrogen. The coiler associated with the manufacture of the cellulose ester film of the present invention can be used by a general user of -27-5 (25) 1375832, or by a fixed tensile method, a constant torque method, The coiling method of the conical tension method, the _ internal stress constant program tension control method, etc. is performed. The thickness of the cellulose ester film of the present invention is not particularly limited, but the liquid crystal display element used for the LCD is used for a polarizing plate. When the protective film is used, it is preferable that a cellulose ester film having a thickness of 30 to 50/m is preferable, and the cellulose ester film having a thickness of 50/zm or less is used for, for example, a polarizing plate. use In the case of protecting the film, φ strict performance is required for high quality. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Example 1 φ (modulation of cement) The cellulose triacetate cement slurry was prepared as follows. Cellulose triacetate (TAC): l〇〇kg TINUVIN 326 (manufactured by Chiba Specialty Chemical Co., Ltd.): 〇.3kg TINUVIN 171 (made by Chiba Special Chemical Co., Ltd.) ): 〇.5kg TINUVIN 109 (manufactured by Chiba Specialty Chemical Co., Ltd.): 5.5kg Trimethylolpropane tribenzoate (TMPTB) : 13kg Ethyl decyl ethyl glycolate (EPEG) : 9.7kg Aerosil 200V (manufactured by Aerosil, Japan): 0.09 kg -28- 5 (26) 1375832 Dichloromethane: 320 kg • Ethanol: 20 kg • Each of these materials is placed in a closed container, kept under pressure and stirred at 80 °C. It is completely dissolved. (Manufacturing of a film material) After filtering the above-mentioned dope, a tape casting device (not shown) was used, and the glue was cast at a temperature of 33 ° C by a casting nozzle and cast on a support made of a stainless steel endless belt. The support was held for 60 seconds and then peeled off from the support and dried while being conveyed by a plurality of rollers. At this time, the film was dried by stretching the film to 1.07 times in the transverse direction using a clip setting machine. After drying, it was taken up in a roll shape to obtain a cellulose triacetate (TAC) film having a film thickness of 40 #m. Continuing, the obtained cellulose triacetate film was subjected to an untreated state (reference state) after manufacture, and the outermost surface of the cellulose triacetate film was measured by a flight type secondary ion mass spectrometer (T OF - SIMS). The detection probability of the total component magnesium is as follows. The results obtained are shown in Table 1 below. The detection probability of the magnesium is as A, the temperature of the cellulose acetate film is 2 3 ° C, and the humidity is 5 5 . The equilibrium moisture content under % RH (reference state) is the temperature of 40 ° C and the humidity of 90% under the condition of M' calcium chloride-cup sealing method. The cellulose acetate after conditioning for 24 hours under the condition of RH When the moisture permeability (g/m2) of the ester film was taken as T, the enthalpy of enthalpy and enthalpy were calculated, and the results are shown in Table 1 below. -29- 5. (27) 1375832 Examples 2 to 4 - As in the case of Example 1 above, a cellulose triacetate ( _ TAC) film was produced, but a polyol ester of trimethylolpropane trishydroxyl Ethylmercaptoethyl glycolate (TMPB) with plasticizer ethyl decyl ethyl glycolate (EPEG), or plasticizer ethyl decyl ethyl glycolate (£1 > £(3) And triphenyl phosphate (TPP) are each added in an amount as shown in Table 1, and the detection probability (%) of magnesium in cellulose diacetate: A is as shown in Table 1, and other than φ is the same as in Example 1. A cellulose triacetate film was obtained in the case. The contents of the polyol ester and the plasticizer of each example are shown in Table 1 below, and 'the content of the polyol ester or the polyol ester and the plasticizer is The weight % of cellulose triacetate (TAC). Thus, the detection probability of magnesium in the cellulose triacetate film in each example is taken as A, and the temperature of the cellulose acetate film is 23 T: humidity 55 The equilibrium moisture content under % RH (reference state) is Μ, and the calcium chloride-cup seal method is used for 24 hours at a temperature of 40 ° C and a humidity of 90% RH. • The moisture permeability (g/m2) of the cellulose acetate film after the temperature-controlled and humidity-control treatment was calculated as T, and the results were as shown in the following Table 1. Comparative Examples 1 to 4 For comparison, the type and content of the polyol ester and the plasticizer used are as shown in Table 1 below. The detection probability of the magnesium of the cellulose triacetate film is A, and the temperature of the cellulose acetate film is 23 °. C, humidity 55% RH (reference state) under the equilibrium moisture content as Μ 'calcium chloride - cup seal method is 5 (28) (28) 1375832 temperature 40t, humidity 90% RH placed for 24 hours When the moisture permeability (g/m2) of the cellulose acetate film after the temperature-controlled wet treatment was taken as T, the enthalpy of enthalpy and enthalpy were calculated, and the results are shown in Table 1 below.

-31 - (29)1375832 ΑχΤ (xlO·1) 3.75 〇1 1.34 4.00 9.00 9.50 8.00 0.60 ΑχΜ (χΐ〇'3) 〇〇0.40 0.26 CN ψ 3.20 3.20 3.50 0.90 moisture permeability T(g/m2) 750 750 670 800 900 950 800 Equilibrium water content Μ (% by weight) 〇〇 (N m (Ν fN CN m On 〇Mg detection rate A 0.0005 0.0002 0.0002 0.0005 0.0010 0.0010 0.0010 0.0001 Mg (ppm) Ο oo 〇 polyol ester + plasticizer Content (% by weight) 6.0+4.5 6.0+4.5 8.0+2.5 9.5+2.0 4.0+6.5 8.5+2.0 9.5+2.0 13.0 Type TMPTB+EPEG TMPTB+EPEG TMPTB+EPEG TPP+EPEG TMPTB+EPEG TPP+EPEG TPP+EPEG TMPTB Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 1 Comparative Example 3 Comparative Example 4 - 32- (30) (30) 1376832 Examples 5 and 6 The same as in the case of the above-described Example 1 A cellulose triacetate (TAC) film was produced in which the ratio of the weight average molecular weight (Mw) of the cellulose triacetate (taC) to the number average molecular weight (?η): Mw / Μη ' was changed as shown in Table 2 The cellulose triacetate film was produced as shown in Table 2. The cellulose 3 of the above Example 1 and Examples 5 and 6 is described in Table 2. The ratio of the weight average molecular weight (Mw) of the acid ester (TAC) to the number average molecular weight (?η): 値 of Mw/Mn. And for the average molecular weight of cellulose triacetate (TAC), gel permeation chromatography is used. The measurement was carried out to calculate the number average molecular weight (?η) and the weight average molecular weight (Mw), and calculate the ratio (Mw / Μη) of the weight average molecular weight (Mw) and the average molecular weight (?η) of the cellulose triacetate. 2

Mw/Mn Example 1 2.3 _ Example 5 2.9 Example 6 1.8 Next, film foreign matter generation was performed on the cellulose acetate triacetate films of Examples 1 to 6 and Comparative Examples 1 to 4 of the present invention. Determination. The results obtained are shown in Table 3 below. -33- (31) 1375832 (Evaluation of foreign matter production) The foreign matter production test of the cellulose triacetate film was carried out by placing the original cellulose triacetate film at a temperature of 50X: and a humidity of 80% RH after manufacture. One month later, the number of foreign matter generated in the film size of each cellulose triacetate film at a range of 1 〇〇 mm x 100 mm was observed at 30 times using a polarizing microscope, and evaluated based on the following evaluation criteria. A: the number of foreign matter 〇~1〇 B: the number of foreign matter 11 to 50 C: the number of foreign matter 51 to 100 D: the number of foreign matter is 101 or more and the examples 1 to 6 of the present invention are used. And the cellulose acetate film of each of Comparative Examples 1 to 4, a polarizing plate was produced, and the obtained polarizing plate was subjected to durability test and polarizing film stability test, and the results were as shown in Table 3 below. Preparation) Each cellulose acetate film was subjected to alkali treatment for 60 seconds in a 2.5 M aqueous sodium hydroxide solution at 40 ° C, and after washing with water for 3 minutes, a saponified layer was formed to obtain an alkali-treated film. The polyvinyl alcohol film having a thickness of 120 was continuously immersed in an aqueous solution containing ruthenium by weight of ruthenium and 4 parts by weight of boric acid in an amount of 1 part by weight, and extended to 4 times at 50 Torr to obtain a polarizing film. On both surfaces of the polarizing film, the alkali-treated cellulose acetate film was bonded together with a completely saponified polyvinyl alcohol 5% aqueous solution as an adhesive to obtain a polarizing plate sample. -34- 5 (32) 1375832 • (Polarizer durability test) 2 pieces of 10 cmxlO cm of each polarizing plate obtained, at a temperature of 8 ° C, humidity of 90% RH, after 50 hours of high temperature After high humidity treatment, the surface state was observed and evaluated by the following evaluation criteria. A: The turbid portion due to the bleed out of the surface of the polarizing plate is less than 5% φ B: the turbid portion due to the bleed out of the surface of the polarizing plate is 5% or more, less than 1 〇% C: due to the surface of the polarizing plate The turbidity caused by the oozing is 10% or more, less than 20%. D: The turbid portion due to the bleed out of the surface of the polarizing plate is 20% or more. Further, in the above evaluation criteria, "C" or more indicates that it can be used on a polarizing plate, and there is no problem in practical technology. (Polarization film stability test) Further, the obtained polarizing plates were subjected to high-temperature and high-humidity treatment under the same conditions as those of the above-mentioned polarizing plate durability test, and the state of the polarizing film was observed and evaluated based on the following evaluation criteria. A: The range of deterioration of the polarizer was not observed at all after the polarizing plate was processed. B: The range of deterioration of the polarizer was observed after the polarizing plate was processed. C: The range of deterioration of the polarizer observed after the polarizing plate was processed. D: Observation after processing of the polarizing plate To the extent of severe photon degradation -35- (33) 1375832 Table 3

Foreign matter-generating polarizing plate Durable polarizing film stability Example 1 BBB Example 2 ABB Example 3 AAA Example 4 BAB Example 5 BBB Example 6 AAA Comparative Example 1 CDD Comparative Example 2 CDD Comparative Example 3 CCC Comparative Example 4 As a result of BCB Table 3, it was found that in the cellulose acetate film of Examples 1 to 6 of the present invention, each cellulose acetate film was produced almost free of foreign matter, and was produced by using each cellulose acetate film. There is no problem in the durability test of the polarizing plate and the polarizing film stability test of the polarizer, and the wet heat durability of the polarizing plate can be improved. [Industrial Applicability] The present invention provides a cellulose ester film for use in a protective film for a polarizing plate, in other words, a cellulose ester which can suppress deterioration (injury, foreign matter generation) in a flow state such as storage and transportation of a film. film. -36- 5

Claims (1)

(1) 1375832 X. Patent application scope 1. 1. A cellulose ester film which is a cellulose ester film containing magnesium having a thickness of 20 to 60 - "m, which is characterized by being untreated after manufacture (reference In the state), when the outermost surface of the cellulose ester film is measured by a flight type secondary ion mass spectrometer (TOF-SIMS), the detection probability of the total component magnesium is determined as A, the cellulose ester film. The equilibrium moisture content at a temperature of 23 ° C and a humidity of 5 5 % RH (reference state) is adjusted as Μ ' φ calcium chloride cup seal method at a temperature of 40 ° C and a humidity of 90% RH for 24 hours. The moisture permeability (g / m2 ) of the cellulose ester film after the temperature-controlled wet treatment is taken as T, ΑχΜ is 1.〇χ1〇-4~3·0χ10_ 3 ΑχΤ is 6.5χ10-2 〜8_5χ10 - 1 (g/m2) . 2. The cellulose ester film of claim 1 wherein the content of the magnesium compound of the cellulose ester film is ' as a weight ratio of magnesium atom to film weight of 50 ppm or less. φ 3. The cellulosic vine film according to item 1 of the patent application, wherein the temperature of the cellulose ester film is 23t, the humidity is 55% RH (reference state), and the total amount of the cellulose ester film is A ratio of 1.0 to 3.0% by weight. 4. The cellulose ester film according to claim 1 of the patent scope, wherein the cellulose ester film is subjected to a calcium chloride cup sealing method, the temperature is 40 ° C, the humidity is 90%, and the temperature adjustment is set for 24 hours. The moisture permeability after wet treatment is 650 ~ 850 g / m2. 5. The cellulose ester film according to claim 1 of the invention, wherein the fiber-37-(2) (2) 1785832 Uzide ester film is a polyol ester containing an aliphatic polyol and one or more monocarboxylic acids The resulting compound has a polyol ester content of from 4.5 to 12.5% by weight for the cellulose ester. 6. The cellulose ester film of claim 5, wherein the monocarboxylic acid is a compound having an aromatic ring or a cycloalkyl group in the molecule. 7. The cellulose ester film of claim 5, wherein the aliphatic polyol is 2 to 20 valence. 8. The cellulose ester film of claim 5, wherein the aliphatic polyol is 2 to 3 valence. 9. The cellulose ester film of claim 5, wherein the aliphatic polyol has a carbon number of 4 or more. 10. The cellulose ester film according to claim 1, wherein the weight average molecular weight of the cellulose vinegar is Mw, and the ratio of the weight average molecular weight to the number average molecular weight when the number average molecular weight is Μη: Mw / Μη is 1· 0~5.0. 11. The cellulose ester film according to claim 10, wherein the ratio of the weight average molecular weight to the number average molecular weight: Mw/Mn is 1.7 to 3.0 - 38 -