JP4640129B2 - Manufacturing method of polarizing plate and display device using polarizing plate obtained by the manufacturing method - Google Patents

Description

  The present invention relates to a polarizing plate and a display device using the same, and more particularly, to a polarizing plate and a display device using the same, in which the retardation value in the polarizing plate manufacturing process is less likely to fluctuate.

  Liquid crystal display devices are attracting attention for use in large televisions. Large LCD TVs are becoming more demanding in terms of performance, such as viewing angle, contrast, and stability against changes in usage environment, compared to conventional notebook computers and LCD monitors. Therefore, strict performance is required for the polarizing plate used in the liquid crystal display device and the cellulose ester film used for the polarizing plate as well, and the stretched cellulose ester film has a great influence on the optical performance. Strict specifications are required as an important member. Therefore, various improvements are made every day to improve these specifications. There are cases where the retardation value of the manufactured polarizing plate changes due to changes in the conditions of the polarizing plate manufacturing process or unintentional fluctuations in the polarizing plate integrated with the retardation plate, and the polarizing plate has a large screen size. Then, the improvement has come to be especially demanded. Further, in order to improve the display performance of the liquid crystal display device, a backlight is arranged immediately below the liquid crystal cell. However, in the direct type using LEDs instead of fluorescent tubes as the backlight, the influence of temperature rise is no longer negligible, and it tends to vary from display device to display device, especially for making display devices with uniform contrast values. There is a need for improvement.

Conventionally, a retardation film with improved moisture permeability of a retardation film has been proposed in order to obtain a display device having stable display quality over time and excellent productivity (see, for example, Patent Document 1). In addition, in order to obtain a display device that does not leak light due to thermal distortion and has excellent display quality, a retardation film having a hygroscopic expansion coefficient within a predetermined range has been proposed (see, for example, Patent Document 2). In addition, a polarizing plate that is excellent in durability even under severe wet heat conditions by controlling the diffusion coefficient of boric acid in the cellulose acylate film has been proposed (for example, see Patent Document 3). However, none of them was sufficient for the above problem. For example, Patent Document 3 states that the free volume in the cellulose acylate film is reduced as a method for controlling the diffusion coefficient of boric acid. In paragraph [0015], the free volume in the cellulose acylate film is It is said that it is reduced by increasing the crystal content of the film. However, the fluctuation of the retardation value in the polarizing plate manufacturing process was insufficient. In particular, an amorphous cellulose resin such as a mixed acid ester such as cellulose acetate propionate cannot obtain a sufficient effect.
Japanese Patent Laid-Open No. 2002-14230 JP 2002-71955 A JP 2004-279931 A

  The present invention has been made in view of the above-mentioned problems, and the purpose thereof is a polarizing plate having a cellulose ester film having a retardation on one surface, and the retardation value hardly changes in the polarizing plate production process. It is an object of the present invention to provide a display device with improved quality uniformity by obtaining a polarizing plate with less variation in the thickness.

  The above object of the present invention is achieved by the following configurations.

1. A method for producing a polarizing plate having a retardation film containing at least a plasticizer and a cellulose ester on one side of a polarizing film, wherein the retardation film is dried to a residual solvent amount of less than 0.3% in a casting film forming step. After that, the free volume radius is 0.250 to 0.310 nm, which is produced by processing in an atmosphere having a substitution rate of 12 times / hour or more at 105 to 155 ° C. and determined by the positron annihilation lifetime method. method for producing a polarizing plate, wherein the retardation film, that has on one surface of the polarizing film.

2. 2. The method for producing a polarizing plate according to 1 above, wherein the total free volume parameter of the retardation film is 1.0 to 2.0.

3. 3. The method for producing a polarizing plate according to 1 or 2, wherein the cellulose ester is a mixed (fatty) acid ester having 2 to 22 carbon atoms.

4). Ro defined by the following formula of the said retardation film is 30-300 nm, Rt70-400 nm, The manufacturing method of the polarizing plate of any one of said 1-3 characterized by the above-mentioned.

Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
(In the formula, Ro is the retardation value in the film plane, Rt is the retardation value in the film thickness direction, nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, (nz represents the refractive index in the thickness direction of the film (the refractive index is measured at a wavelength of 590 nm), and d represents the thickness (nm) of the film.)
5. A display device having a direct type backlight and using a polarizing plate obtained by the method for producing a polarizing plate according to any one of 1 to 4 above.

  According to the present invention, in a polarizing plate having a cellulose ester film having a phase difference on one surface, the retardation value is hardly changed in the polarizing plate manufacturing process, and a polarizing plate with little variation in the retardation value is obtained. A display device with improved uniformity can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

  The features of the configuration of the present invention are as follows.

  1. A stretched cellulose ester film comprising at least a plasticizer and a cellulose ester, and having a free volume radius determined by a positron annihilation lifetime method of 0.250 to 0.310 nm.

  2. 2. The stretched cellulose ester film as described in 1 above, wherein the total free volume parameter is 1.0 to 2.0.

  3. 3. The stretched cellulose ester film as described in 1 or 2 above, wherein the cellulose ester is a mixed (fatty) acid ester having 2 to 22 carbon atoms.

  4). 4. The stretched cellulose ester film according to any one of 1 to 3, wherein the cellulose ester is cellulose acetate propionate or cellulose acetate butyrate.

  5. Ro is 30-300 nm, Rt70-400 nm, The stretched cellulose-ester film of any one of said 1-4 characterized by the above-mentioned.

  6. The stretched cellulose ester film as described in any one of 1 to 5 above, wherein retention at 80 ° C., 90% RH and 48 hours is within ± 2%.

  7. A polarizing plate comprising a retardation film containing at least a plasticizer and a cellulose ester and having a free volume radius determined by a positron annihilation lifetime method of 0.250 to 0.310 nm on one surface of a polarizing film.

  8). 8. The polarizing plate as described in 7 above, wherein the retardation film has a total free volume parameter of 1.0 to 2.0.

  9. 8. The polarizing plate as described in 7 above, wherein the retardation film has a total free volume parameter of 1.2 to 1.8.

  10. The polarizing plate according to any one of 7 to 9, wherein the cellulose ester is a mixed (fatty) acid ester having 2 to 22 carbon atoms.

  11. 11. The polarizing plate according to any one of 7 to 10, wherein Ro of the retardation film is 20 to 300 nm and Rt 70 to 400 nm.

  12 The polarizing plate according to any one of 7 to 11, wherein the retardation film has a retentivity within 80%, 90% RH, and 48 hours within ± 2%.

  13. Stretched cellulose containing at least a plasticizer and a cellulose ester, having a free volume radius determined by a positron annihilation lifetime method of 0.250 to 0.310 nm, and a total free volume parameter of 1.0 to 2.0 The ester film was manufactured by processing at 105 to 155 ° C. in an atmosphere having a substitution rate of 12 times / hour or more after being dried to a residual solvent amount of less than 0.3% in the casting film forming step. A polarizing plate using a stretched cellulose ester film characterized by being.

  14 A liquid crystal display device comprising a direct type LED backlight and the polarizing plate according to any one of 7 to 13 above.

  First, the features of the present invention will be described.

  The present invention is achieved by a polarizing plate containing a retardation film on one surface of a polarizing film, which contains at least a plasticizer and a cellulose ester and has a free volume radius of 0.250 to 0.310 nm determined by a positron annihilation lifetime method. I can do it. Furthermore, it is preferable that it is a polarizing plate using the retardation film whose total free volume parameter is 1.0-2.0.

  The free volume in this invention represents the space | gap part which is not occupied by the cellulose-ester molecular chain. This can be measured using the positron annihilation lifetime method. Specifically, by measuring the time from the incidence of positrons to the sample until annihilation, non-destructively observing information on the vacancies, the size of the free volume, the number concentration, etc. from the annihilation lifetime You can ask.

<Measurement of free volume radius and free volume parameters by positron annihilation lifetime method>
The positron annihilation lifetime and relative intensity were measured under the following measurement conditions.

(Measurement condition)
Positron beam source: 22 NaCl (strength 1.85 MBq)
Gamma ray detector: Plastic scintillator + photomultiplier tube Time resolution: 290ps
Measurement temperature: 23 ° C
Total count: 1 million counts Sample size: 20 sections cut to 20 mm × 15 mm were stacked to a thickness of about 2 mm. The sample was vacuum dried for 24 hours before measurement.

Irradiation area: About 10mmφ
Time per channel: 23.3ps / ch
According to the above measurement conditions, carried out positron annihilation lifetime spectroscopy, and 3 component analysis by non-linear least squares method, starting with the lowest annihilation lifetime, .tau.1, .tau.2, and τ3, I _1, I ₂ a strength corresponding thereto, I ₃ (I ₁ + I ₂ + I ₃ = 100%). From the average annihilation lifetime τ3 having the longest lifetime, the free volume radius R ₃ (nm) was determined using the following formula. It is considered that τ3 corresponds to positron annihilation in the vacancies, and that the larger the τ3, the larger the vacancy size.

τ3 = (1/2) [1- {R ₃ / (R ₃ +0.166)} + (1 / 2π) sin {2πR ₃ / (R ₃ +0.166)}] ⁻¹
Here, 0.166 (nm) corresponds to the thickness of the electron layer leached from the hole wall.

  Further, the total free volume parameter VP was obtained by the following equation.

V ₃ = {(4/3) π (R ₃ ) ³ } (nm ³ )
VP = I ₃ (%) × V ₃ (nm ³ )
Here, I ₃ (%) corresponds to the relative number concentration of vacancies, so VP corresponds to the relative amount of vacancies.

  The above measurement was repeated twice, and the average value was obtained.

  The positron annihilation lifetime method is described in, for example, MATERIAL STAGE vol. 4, no. 5 2004 p21-25, Toray Research Center THE TRC NEWS No. 80 (Jul. 2002) p20-22, “Bunseki, 1988, pp. 11-20”, “Evaluation of free volume of polymer by positron annihilation method” can be referred to. .

  The free volume radius of the retardation film used in the present invention is 0.250 to 0.310 nm, and a more preferable range is 0.270 to 0.305 nm. It may be industrially difficult to produce a cellulose ester phase difference film having a free volume radius of less than 0.250 nm or a total free volume parameter of less than 1.0. Further, in the conventional retardation film having a free volume radius exceeding 0.310 nm, the object of the present invention cannot be achieved, and the retardation tends to fluctuate during the production of the polarizing plate, and retardation spots easily occur. Moreover, the preferable range of a total free volume parameter is 1.0-2.0, and a more preferable range is 1.2-1.8. When the total free volume parameter is less than 1.8, the retardation is less likely to vary when the polarizing plate is produced, and retardation spots are less likely to occur.

  The method for bringing the free volume radius and the total free volume parameter of the retardation film containing at least a plasticizer and a cellulose ester into a predetermined range is not particularly limited, but these can be controlled by the following method.

  A retardation film having a free volume radius of 0.250 to 0.310 nm and a total free volume parameter of 1.0 to 2.0 determined by a positron annihilation lifetime method is cast a dope containing at least a plasticizer and a cellulose ester. After the web was made and stretched in a state containing a solvent, it was dried until the residual solvent amount was less than 0.3% to obtain a cellulose ester film, which was further subjected to an atmosphere at 105 to 155 ° C. A retardation film having a predetermined free volume radius and total free volume parameters can be obtained by carrying out the treatment while transporting in an atmosphere having a substitution rate of 12 times / hour or more, preferably 12 to 45 times / hour.

The atmosphere replacement rate is defined as follows. When the atmosphere capacity of the heat treatment chamber is V (m ³ ) and the fresh air flow rate is FA (m ³ / hr), the atmosphere of the heat treatment chamber per unit time determined by the following formula is Fresh-air. Is the number of replacements by. “Fresh-air” means that the air blown into the heat treatment chamber is not a wind that is recirculated and does not contain a volatilized solvent or plasticizer or a fresh air from which they are removed. Yes.

Atmosphere replacement rate = FA / V (times / hour)
Further, when the temperature exceeds 155 ° C., the effect of the present invention cannot be obtained, and even when the temperature is lower than 105 ° C., the effect of the present invention cannot be obtained. The treatment temperature is more preferably 110 to 150 ° C. Furthermore, it is necessary to perform the treatment in an atmosphere in which the atmosphere substitution rate is maintained at an atmosphere substitution rate of 12 times / hour or more in the treatment section. If the treatment portion is less than 12 times / hour, the effect of the present invention cannot be obtained. .

  This is because when the atmosphere substitution rate is 12 times / hour or more, the plasticizer concentration in the atmosphere due to the plasticizer volatilized from the retardation film can be sufficiently reduced, and reattachment to the film is reduced. It is presumed that this contributes to obtaining the effect of the present invention. In a normal drying process, the atmosphere substitution rate is 10 times / hour or less. Increasing the substitution rate more than necessary is not preferable because it increases the cost, and in addition, there is a tendency for in-plane retardation spots to increase due to flapping of the web. Although it is not preferable, the atmosphere substitution rate can be increased after the drying is completed and the residual solvent amount is reduced. However, if it exceeds 45 times, the cost of the air conditioner will increase extremely, which is not practical. The treatment time under these conditions is preferably 1 minute to 1 hour. If it is less than 1 minute, it is difficult to make the free volume radius within a predetermined range.

  Further, in this treatment step, pressure treatment in the thickness direction can also control the free volume radius and the free volume parameter to a more preferable range. A preferable pressure is 0.5 to 10 kPa. The amount of residual solvent when applying pressure is desirably less than 0.3%. Where the amount of residual solvent is large, the effect of the present invention cannot be obtained although 0.3% or more is effective in improving the flatness.

  The conventional retardation film not subjected to such a treatment has a free volume radius larger than 0.315.

  The present invention will be described in more detail, but the present invention is not limited thereto.

<Cellulose ester>
As the molecular weight of the cellulose ester used in the present invention, those having a number average molecular weight (Mn) of 80,000 to 200,000 are used. More preferable are 100,000 to 200,000, and particularly preferable are 150,000 to 200,000.

  The cellulose ester used in the present invention preferably has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio, Mw / Mn of 1.2 to 3.0 as described above, preferably 1 The range is from 7 to 2.2.

  The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high performance liquid chromatography. Using this, the number average molecular weight and the weight average molecular weight can be calculated, and the ratio (Mw / Mn) can be calculated.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000 to 500 samples were used. It is preferable to obtain 13 samples at approximately equal intervals.

  The cellulose ester used in the present invention is an aliphatic carboxylic acid ester having about 2 to 22 carbon atoms, an aromatic carboxylic acid ester, or a mixed ester of an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester. Therefore, it is preferably used.

  In particular, a lower fatty acid ester of cellulose is preferable. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. Specifically, it is described in cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate and the like, JP-A-10-45804, 8-2311761, U.S. Pat. No. 2,319,052, and the like. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate can be used. Among the above description, the lower fatty acid esters of cellulose that are particularly preferably used are cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate propionate butyrate. These cellulose esters can be used as a mixture. Since these are amorphous unlike cellulose triacetate, they are particularly preferably used in the present invention.

  The total acyl group substitution degree is preferably 2.4 to 2.9. A particularly preferable cellulose ester has an acyl group having 2 to 22 carbon atoms as a substituent, the substitution degree of the acetyl group is X, and the substitution degree of the acyl group of 3 to 22 carbon atoms is Y, It is a cellulose ester that simultaneously satisfies the formulas (I) and (II).

Formula (I) 2.4 ≦ X + Y ≦ 2.9
Formula (II) 0 ≦ X ≦ 2.5
Among them, cellulose acetate propionate (total acyl group substitution degree = X + Y) satisfying 1.7 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 1.2 is preferable. The portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.

  These acyl group substitution degrees can be measured according to the method prescribed in ASTM-D817-96.

  As the cellulose ester, cellulose ester synthesized from cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cotton linter (hereinafter sometimes simply referred to as a linter) or a cellulose ester synthesized from wood pulp alone or in combination.

  Moreover, the cellulose ester obtained from these can be mixed and used in arbitrary ratios, respectively. These cellulose esters are prepared by using an organic acid such as acetic acid or an organic solvent such as methylene chloride when sulfuric acid is used as the acylating agent (acetic anhydride, propionic anhydride, butyric anhydride). It can obtain by making it react by a conventional method using a protic catalyst like.

  In the case of acetylcellulose, it is necessary to extend the time for the acetylation reaction in order to increase the acetylation rate. However, if the reaction time is too long, the decomposition proceeds at the same time, and the polymer chain is broken and the acetyl group is decomposed, resulting in undesirable results. Therefore, it is necessary to set the reaction time within a certain range in order to increase the degree of acetylation and suppress decomposition to some extent. It is not appropriate to define the reaction time because the reaction conditions are various and greatly change depending on the reaction apparatus, equipment and other conditions. As the decomposition of the polymer progresses, the molecular weight distribution becomes wider. Therefore, in the case of cellulose ester, the degree of decomposition can be defined by the value of weight average molecular weight (Mw) / number average molecular weight (Mn) that is usually used. In other words, in the process of acetylation of cellulose triacetate, the weight average molecular weight is used as one index of the reaction degree for allowing the acetylation reaction to be carried out for a sufficient time for acetylation without being too long and being decomposed too much. The value of (Mw) / number average molecular weight (Mn) can be used.

  An example of a method for producing a cellulose ester is shown below: 100 parts by mass of a flocculent linter was crushed as a cellulose raw material, 40 parts by mass of acetic acid was added, and pretreatment activation was performed at 36 ° C. for 20 minutes. Thereafter, 8 parts by mass of sulfuric acid, 260 parts by mass of acetic anhydride and 350 parts by mass of acetic acid were added, and esterification was performed at 36 ° C. for 120 minutes. After neutralization with 11 parts by mass of a 24% magnesium acetate aqueous solution, saponification aging was carried out at 63 ° C. for 35 minutes to obtain acetylcellulose. This was stirred for 160 minutes at room temperature using a 10-fold acetic acid aqueous solution (acetic acid: water = 1: 1 (mass ratio)), then filtered and dried to obtain purified acetylcellulose having an acetyl substitution degree of 2.75. . This acetylcellulose had Mn of 92,000, Mw of 156,000, and Mw / Mn of 1.7. Similarly, cellulose esters having different degrees of substitution and Mw / Mn ratios can be synthesized by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester.

  The synthesized cellulose ester is preferably purified to remove low molecular weight components or to remove unacetylated or low acetylated components by filtration.

  In the case of mixed acid cellulose ester, it can be obtained by the method described in JP-A-10-45804. The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  Cellulose esters are also affected by trace metal components in cellulose esters. These are considered to be related to water used in the production process, but it is preferable that there are few components that can become insoluble nuclei, and metal ions such as iron, calcium, and magnesium contain organic acidic groups. Insoluble matter may be formed by salt formation with a polymer degradation product or the like that may be present, and it is preferable that the amount is small. The iron (Fe) component is preferably 1 ppm or less. As for the calcium (Ca) component, it is easy to form a coordination compound, that is, a complex with an acidic component such as carboxylic acid or sulfonic acid, and many ligands. Starch, turbidity).

  The calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm. The magnesium (Mg) component is preferably in the range of 0 to 70 ppm, and more preferably 0 to 20 ppm, because too much will cause insoluble matter. Metal components such as iron (Fe) content, calcium (Ca) content, magnesium (Mg) content, etc. are pre-processed by completely digesting cellulose ester with micro digest wet cracking equipment (sulfuric acid decomposition) and alkali melting. After performing, it can analyze using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer).

<Plasticizer>
The total content of the plasticizer in the retardation film used in the present invention is preferably 1 to 20% by mass, particularly preferably 3 to 18% by mass, based on the total solid content.

  The type of plasticizer to be used is not particularly limited. Phosphate ester plasticizer, glycolate plasticizer, citrate ester plasticizer, phthalate ester plasticizer, polyhydric alcohol ester plasticizer, polyvalent Examples thereof include carboxylic acid ester plasticizers, fatty acid ester plasticizers, polyester plasticizers, and polyurethane plasticizers.

For example, phosphate ester plasticizers include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. Examples of glycolate plasticizers Alkylphthalylalkyl glycolates can be preferably used. Examples of 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 glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.

  Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

  Examples of the citrate ester plasticizer include acetyltrimethyl citrate, acetyltriethyl citrate, and acetyltributyl citrate.

  Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.

  Polycarboxylic acid ester plasticizers can also be preferably used. Specifically, it is preferable to add the polyvalent carboxylic acid ester described in paragraphs [0015] to [0020] of JP-A No. 2002-265639 as one of the plasticizers.

  The property that the mass of the film is reduced due to precipitation or volatilization of the additive such as a plasticizer outside the film in a high temperature and humidity environment is called retention. In the conventional cellulose ester film, the retentivity is poor and the function of the liquid crystal image display device is lowered. In the present invention, it is preferable to contain a plasticizer having a retentivity within ± 2% at 80 ° C., 90% RH and 48 hours.

  The retention property in the present invention is measured by the following procedure.

<Measurement of holdability>
The sample was cut into a size of 10 cm × 10 cm, the mass after being allowed to stand for 24 hours in an atmosphere of 23 ° C. and 55% RH was measured, and left for 48 hours under the conditions of 80 ° C. and 90% RH. The surface of the sample after the treatment was lightly wiped, the mass after standing for 1 day at 23 ° C. and 55% RH was measured, and the retention was calculated by the following method.

Retention property (mass%) = {(mass before leaving-mass after leaving) / mass before leaving} × 100
Examples of the plasticizer having a retention of within ± 2% at 80 ° C., 90% RH and 48 hours include polyhydric alcohol esters, polyester plasticizers, polyurethane plasticizers, and the like.

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  The polyhydric alcohol used in the present invention is represented by the following general formula (i).

Formula _{(i) R 1 - (OH} ) n
However, R ₁ 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. Preferably, the polyhydric alcohol has 5 or more carbon atoms,
Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  There is no restriction | limiting in particular as monocarboxylic acid used for the polyhydric alcohol ester of this invention, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the 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. When 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 cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. The aromatic monocarboxylic acid which has, or those derivatives can be mentioned. Benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300-1500, and more preferably 350-1000. A higher molecular weight is preferred because it is less likely to evaporate, and a smaller one is preferred in terms of compatibility with the cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds.

  Below, the specific compound of a polyhydric alcohol ester is illustrated.

  As the polyester plasticizer, those described in paragraph numbers [0051] to [0056] of JP-A No. 2002-22756 are preferably used. Alternatively, polyurethane plasticizers described in paragraph numbers [0031] to [0039] of JP-A No. 2003-171499 can also be used.

  Alternatively, an aromatic terminal ester plasticizer, one of which is represented by the following general formula (I), can also be preferably used.

General formula (I) B- (GA) n-GB
(In the formula, B is a benzene monocarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms or an oxyalkylene glycol residue having 4 to 12 carbon atoms, and A is an alkylene dicarboxylic acid having 4 to 12 carbon atoms. Represents a residue, and n represents an integer of 0 or more.)
In the general formula (I), it is composed of a benzene monocarboxylic acid residue represented by B, an alkylene glycol residue or oxyalkylene glycol residue represented by G, and an alkylene dicarboxylic acid residue represented by A. It can be obtained by the same reaction as a normal polyester plasticizer.

  Examples of the benzene monocarboxylic acid component of the aromatic terminal ester used in the present invention include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, and normalpropyl. There exist benzoic acid, aminobenzoic acid, acetoxybenzoic acid, etc., and these can be used as 1 type, or 2 or more types of mixtures, respectively.

  Examples of the alkylene glycol component having 2 to 12 carbon atoms of the aromatic terminal ester of the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, and 1,3-butanediol. 2-methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1 , 3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexanediol There are 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, etc., and these glycols are used as one kind or a mixture of two or more kinds. The

  In addition, examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester of the present invention include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. It can be used as one kind or a mixture of two or more kinds.

  Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester of the present invention include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are each used as one or a mixture of two or more.

  The aromatic terminal ester used in the present invention has a number average molecular weight of preferably 250 to 2000, more preferably 300 to 1500. The acid value is preferably 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.

(Acid value and hydroxyl value of aromatic terminal ester)
The acid value means the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxyl group present at the molecular end) contained in 1 g of the sample. The acid value and hydroxyl value are measured in accordance with JIS K0070.

  Hereinafter, synthesis examples of the aromatic terminal ester plasticizer will be shown.

<Sample No. 1 (Aromatic terminal ester sample)>
In a reaction vessel, 365 parts of adipic acid (2.5 moles), 418 parts of 1,2-propylene glycol (5.5 moles), 610 parts of benzoic acid (5 moles) and 0.30 part of tetraisopropyl titanate as a catalyst Then, while stirring in a nitrogen stream, a reflux condenser is attached to reflux excess monohydric alcohol, and heating is continued at 130 to 250 ° C. until the acid value becomes 2 or less. Removed. Subsequently, the distillate was removed under reduced pressure of 1.33 × 10 ⁴ to 4 × 10 ² Pa or less at 200 to 230 ° C., followed by filtration to obtain an aromatic terminal ester having the following properties. .

Viscosity (25 ° C., mPa · s); 815
Acid value: 0.4
<Sample No. 2 (Aromatic terminal ester sample)>
Sample No. 1 was used except that 365 parts (2.5 moles) of adipic acid, 610 parts (5 moles) of benzoic acid, 583 parts (5.5 moles) of diethylene glycol and 0.45 parts of tetraisopropyl titanate as a catalyst were used in the reaction vessel. In the same manner as in No. 1, an aromatic terminal ester having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 90
Acid value: 0.05
<Sample No. 3 (Aromatic terminal ester sample)>
Sample No. except that 365 parts (2.5 moles) of adipic acid, 610 parts (5 moles) of benzoic acid, 737 parts (5.5 moles) of dipropylene glycol and 0.40 parts of tetraisopropyl titanate as the catalyst were used in the reaction vessel. . In the same manner as in No. 1, an aromatic terminal ester plasticizer having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 134
Acid value: 0.03
From these plasticizers, it is preferable to contain two or more kinds of plasticizers. Thereby, the elution of the plasticizer can be reduced. The reason is not clear, but it seems that elution is suppressed by the ability to reduce the amount added per type and the interaction between the two plasticizers and the cellulose ester.

<Ultraviolet absorber>
The cellulose ester film according to the present invention preferably contains an ultraviolet absorber. The ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less, and the transmittance at a wavelength of 370 nm is particularly preferably 10% or less, more preferably 5% or less. Preferably it is 2% or less.

  Although the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.

  For example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (linear and side Chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., and tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, etc. These are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used.

  For example, as the benzotriazole ultraviolet absorber, a compound represented by the following general formula (A) can be used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber which concerns on this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN 109, manufactured by Ciba)
Furthermore, the ultraviolet absorber preferably used in the present invention is a benzophenone ultraviolet absorber or a triazine ultraviolet absorber, and particularly preferably a triazine ultraviolet absorber.

  As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (B) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
Moreover, the compound which has a 1,3,5-triazine ring can be used preferably as a ultraviolet absorber of the optical film of this invention.

  Among them, the compound having a 1,3,5-triazine ring is preferably a compound represented by the following general formula (C).

In the general formula (C), X ₁ is a single bond, —NR ₄ —, —O— or —S—; X ₂ is a single bond, —NR ₅ —, —O— or —S—; X ₃ is a single bond, —NR ₆ —, —O— or —S—; R ₁ , R ₂ and R ₃ are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The compound represented by the general formula (C) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (C), X ₁ , X ₂ and X ₃ are —NR ₄ —, —NR ₅ — and —NR ₆ —, respectively, or X ₁ , X ₂ and X 3 ₃ is a single bond, and R ₁ , R ₂ and R ₃ are heterocyclic groups having a free valence on the nitrogen atom. _{-X 1 -R 1, -X 2 -R} 2 and -X ₃ -R ₃ are preferably the same substituents. R ₁ , R ₂ and R ₃ are particularly preferably aryl groups. R ₄ , R ₅ and R ₆ are particularly preferably a hydrogen atom.

  The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferred to a branched alkyl group.

  The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-8, 6 is most preferred. The alkyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy). The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or an acyloxy group (for example, each group such as acryloyloxy and methacryloyloxy).

  The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

  Specific examples of the substituent include, for example, a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxy Carbonyl group, aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carmoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio Groups, alkenylthio groups, arylthio groups and acyl groups are included. The said alkyl group is synonymous with the alkyl group mentioned above.

  The alkyl group of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamido group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group is also synonymous with the alkyl group described above.

  The said alkenyl group is synonymous with the alkenyl group mentioned above.

  The alkenyl part of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamide group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is also synonymous with the alkenyl group described above.

  Specific examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecyloxyphenyl. Can be mentioned.

  Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group and acyl group have the same meanings as the above aryl group.

When X ₁ , X ₂ or X ₃ is —NR—, —O— or —S—, the heterocyclic group preferably has aromaticity.

  The heterocyclic ring in the heterocyclic group having aromaticity is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.

  The hetero atom in the heterocyclic ring is preferably each atom such as N, S or O, and particularly preferably an N atom.

  As the heterocyclic ring having aromaticity, a pyridine ring (as the heterocyclic group, for example, each group such as 2-pyridyl or 4-pyridyl) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X ₁ , X ₂ or X ₃ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms.

  Moreover, the hetero atom in a heterocyclic group may have hetero atoms other than a nitrogen atom (for example, O atom, S atom). The heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the aryl moiety.

  Specific examples of the heterocyclic group having a free valence on the nitrogen atom are shown below.

  The molecular weight of the compound having a 1,3,5-triazine ring is preferably 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.).

  Specific examples of the compound having a 1,3,5-triazine ring are shown below.

  In addition, several R shown below represents the same group.

(1) Butyl (2) 2-Methoxy-2-ethoxyethyl (3) 5-Undecenyl (4) Phenyl (5) 4-Ethoxycarbonylphenyl (6) 4-Butoxyphenyl (7) p-Biphenylyl (8) 4 -Pyridyl (9) 2-naphthyl (10) 2-methylphenyl (11) 3,4-dimethoxyphenyl (12) 2-furyl

(14) phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxyphenyl (17) m-biphenylyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzoylphenyl (21) 3 -Acetoxyphenyl (22) 3-benzoyloxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methoxyphenyl (25) 3-anilinophenyl (26) 3-isobutyrylaminophenyl (27) 3-phenoxy Carbonylaminophenyl (28) 3- (3-ethylureido) phenyl (29) 3- (3,3-diethylureido) phenyl (30) 3-methylphenyl (31) 3-phenoxyphenyl (32) 3-hydroxyphenyl (33) 4-Ethoxycarbonylphenyl (34) 4-butoxyphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl ( 41) 4-phenoxycarbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethyl (Ureido) phenyl (47) 4- (3,3-diethylureido) phenyl (48) 4-methylphenyl (49) 4-phenoxyphenyl (50) 4-hydroxyphenyl (51) 3,4-diethoxycarbonylphenyl ( 52) 3,4-dibutoxyphenyl (53) 3 -Diphenylphenyl (54) 3,4-diphenylthiophenyl (55) 3,4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyl Oxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxy Phenyl (64) 3,4-dihydroxyphenyl (65) 2-naphthyl (66) 3,4,5-triethoxycarbonylphenyl (67) 3,4,5-tributoxyphenyl (68) 3,4,5- Triphenylphenyl (69) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribenzoylphenyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74) 3,4,5-triphenoxycarbonylphenyl (75) 3,4,5-trimethoxyphenyl (76) 3,4,5-trianilinophenyl (77) 3,4,5-trimethylphenyl (78) 3,4,5-triphenoxyphenyl (79 ) 3,4,5-trihydroxyphenyl

(80) phenyl (81) 3-ethoxycarbonylphenyl (82) 3-butoxyphenyl (83) m-biphenylyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzoylphenyl (87) 3 -Acetoxyphenyl (88) 3-benzoyloxyphenyl (89) 3-phenoxycarbonylphenyl (90) 3-methoxyphenyl (91) 3-anilinophenyl (92) 3-isobutyrylaminophenyl (93) 3-phenoxy Carbonylaminophenyl (94) 3- (3-ethylureido) phenyl (95) 3- (3,3-diethylureido) phenyl (96) 3-methylphenyl (97) 3-phenoxyphenyl (98) 3-hydroxyphenyl (99) 4-Ethoxycarbonylphenyl (100) 4-butoxyphenyl (101) p-biphenylyl (102) 4-phenylthiophenyl (103) 4-chlorophenyl (104) 4-benzoylphenyl (105) 4-acetoxyphenyl (106) 4-benzoyloxyphenyl ( 107) 4-phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethyl (Ureido) phenyl (113) 4- (3,3-diethylureido) phenyl (114) 4-methylphenyl (115) 4-phenoxyphenyl (116) 4-hydroxyphenyl (117) 3,4-diethoxycarbonylphenyl ( 118) 3 , 4-dibutoxyphenyl (119) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121) 3,4-dichlorophenyl (122) 3,4-dibenzoylphenyl (123) 3,4- Diacetoxyphenyl (124) 3,4-dibenzoyloxyphenyl (125) 3,4-diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (127) 3,4-dianilinophenyl (128) 3,4 -Dimethylphenyl (129) 3,4-diphenoxyphenyl (130) 3,4-dihydroxyphenyl (131) 2-naphthyl (132) 3,4,5-triethoxycarbonylphenyl (133) 3,4,5- Tributoxyphenyl (134) 3,4,5-triphenylphenyl (135) 3 4,5-triphenylthiophenyl (136) 3,4,5-trichlorophenyl (137) 3,4,5-tribenzoylphenyl (138) 3,4,5-triacetoxyphenyl (139) 3,4 5-tribenzoyloxyphenyl (140) 3,4,5-triphenoxycarbonylphenyl (141) 3,4,5-trimethoxyphenyl (142) 3,4,5-trianilinophenyl (143) 3,4 , 5-trimethylphenyl (144) 3,4,5-triphenoxyphenyl (145) 3,4,5-trihydroxyphenyl

(146) phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenylyl (150) 4-phenylthiophenyl (151) 4-chlorophenyl (152) 4-benzoylphenyl (153) 4 -Acetoxyphenyl (154) 4-benzoyloxyphenyl (155) 4-phenoxycarbonylphenyl (156) 4-methoxyphenyl (157) 4-anilinophenyl (158) 4-isobutyrylaminophenyl (159) 4-phenoxy Carbonylaminophenyl (160) 4- (3-ethylureido) phenyl (161) 4- (3,3-diethylureido) phenyl (162) 4-methylphenyl (163) 4-phenoxyphenyl (164) 4-hydroxyphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenylyl (169) 4-phenylthiophenyl (170) 4-chlorophenyl (171) 4-benzoylphenyl (172) 4 -Acetoxyphenyl (173) 4-benzoyloxyphenyl (174) 4-phenoxycarbonylphenyl (175) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutyrylaminophenyl (178) 4-phenoxy Carbonylaminophenyl (179) 4- (3-ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (182) 4-phenoxyphenyl (183) 4-hydroxyphenyl

(184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenylyl (188) 4-phenylthiophenyl (189) 4-chlorophenyl (190) 4-benzoylphenyl (191) 4 -Acetoxyphenyl (192) 4-benzoyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4-methoxyphenyl (195) 4-anilinophenyl (196) 4-isobutyrylaminophenyl (197) 4-phenoxy Carbonylaminophenyl (198) 4- (3-ethylureido) phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl

(203) phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (206) p-biphenylyl (207) 4-phenylthiophenyl (208) 4-chlorophenyl (209) 4-benzoylphenyl (210) 4 -Acetoxyphenyl (211) 4-benzoyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutyrylaminophenyl (216) 4-phenoxy Carbonylaminophenyl (217) 4- (3-ethylureido) phenyl (218) 4- (3,3-diethylureido) phenyl (219) 4-methylphenyl (220) 4-phenoxyphenyl (221) 4-hydroxyphenyl

(222) phenyl (223) 4-butylphenyl (224) 4- (2-methoxy-2-ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenylyl (227) 4-ethoxy Carbonylphenyl (228) 4-butoxyphenyl (229) 4-methylphenyl (230) 4-chlorophenyl (231) 4-phenylthiophenyl (232) 4-benzoylphenyl (233) 4-acetoxyphenyl (234) 4-benzoyl Oxyphenyl (235) 4-phenoxycarbonylphenyl (236) 4-methoxyphenyl (237) 4-anilinophenyl (238) 4-isobutyrylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240) 4- ( 3-ethylureido Phenyl (241) 4- (3,3-diethylureido) phenyl (242) 4-phenoxyphenyl (243) 4-hydroxyphenyl (244) 3-butylphenyl (245) 3- (2-methoxy-2-ethoxyethyl) ) Phenyl (246) 3- (5-nonenyl) phenyl (247) m-biphenylyl (248) 3-ethoxycarbonylphenyl (249) 3-butoxyphenyl (250) 3-methylphenyl (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253) 3-benzoylphenyl (254) 3-acetoxyphenyl (255) 3-benzoyloxyphenyl (256) 3-phenoxycarbonylphenyl (257) 3-methoxyphenyl (258) 3-anilinophenyl (259) 3-I Butyrylaminophenyl (260) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl (262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3 -Hydroxyphenyl (265) 2-butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl) phenyl (267) 2- (5-nonenyl) phenyl (268) o-biphenylyl (269) 2-ethoxycarbonyl Phenyl (270) 2-Butoxyphenyl (271) 2-Methylphenyl (272) 2-Chlorophenyl (273) 2-Phenylthiophenyl (274) 2-Benzoylphenyl (275) 2-Acetoxyphenyl (276) 2-Benzoyloxy Phenyl (277) 2 Phenoxycarbonylphenyl (278) 2-methoxyphenyl (279) 2-anilinophenyl (280) 2-isobutyrylaminophenyl (281) 2-phenoxycarbonylaminophenyl (282) 2- (3-ethylureido) phenyl ( 283) 2- (3,3-diethylureido) phenyl (284) 2-phenoxyphenyl (285) 2-hydroxyphenyl (286) 3,4-dibutylphenyl (287) 3,4-di (2-methoxy-2) -Ethoxyethyl) phenyl (288) 3,4-diphenylphenyl (289) 3,4-diethoxycarbonylphenyl (290) 3,4-didodecyloxyphenyl (291) 3,4-dimethylphenyl (292) 3, 4-dichlorophenyl (293) 3,4-dibenzoyl Enyl (294) 3,4-diacetoxyphenyl (295) 3,4-dimethoxyphenyl (296) 3,4-di-N-methylaminophenyl (297) 3,4-diisobutyrylaminophenyl (298) 3 , 4-diphenoxyphenyl (299) 3,4-dihydroxyphenyl (300) 3,5-dibutylphenyl (301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (302) 3,5- Diphenylphenyl (303) 3,5-diethoxycarbonylphenyl (304) 3,5-didodecyloxyphenyl (305) 3,5-dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoyl Phenyl (308) 3,5-diacetoxyphenyl (309) 3,5-dimethoxyphenyl (3 0) 3,5-di-N-methylaminophenyl (311) 3,5-diisobutyrylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl (314) 2,4 -Dibutylphenyl (315) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylphenyl (318) 2,4-di Dodecyloxyphenyl (319) 2,4-dimethylphenyl (320) 2,4-dichlorophenyl (321) 2,4-dibenzoylphenyl (322) 2,4-diacetoxyphenyl (323) 2,4-dimethoxyphenyl ( 324) 2,4-di-N-methylaminophenyl (325) 2,4-diisobutyrylaminopheny (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxyphenyl (328) 2,3-dibutylphenyl (329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (330) 2,3-diphenylphenyl (331) 2,3-diethoxycarbonylphenyl (332) 2,3-didodecyloxyphenyl (333) 2,3-dimethylphenyl (334) 2,3-dichlorophenyl (335) 2, 3-dibenzoylphenyl (336) 2,3-diacetoxyphenyl (337) 2,3-dimethoxyphenyl (338) 2,3-di-N-methylaminophenyl (339) 2,3-diisobutyrylaminophenyl (340) 2,3-diphenoxyphenyl (341) 2,3-dihydroxyphenyl (342 ) 2,6-dibutylphenyl (343) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl (344) 2,6-diphenylphenyl (345) 2,6-diethoxycarbonylphenyl (346) 2 , 6-didodecyloxyphenyl (347) 2,6-dimethylphenyl (348) 2,6-dichlorophenyl (349) 2,6-dibenzoylphenyl (350) 2,6-diacetoxyphenyl (351) 2,6 -Dimethoxyphenyl (352) 2,6-di-N-methylaminophenyl (353) 2,6-diisobutyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (356 ) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2-ethoxy) Til) phenyl (358) 3,4,5-triphenylphenyl (359) 3,4,5-triethoxycarbonylphenyl (360) 3,4,5-tridodecyloxyphenyl (361) 3,4,5- Trimethylphenyl (362) 3,4,5-trichlorophenyl (363) 3,4,5-tribenzoylphenyl (364) 3,4,5-triacetoxyphenyl (365) 3,4,5-trimethoxyphenyl ( 366) 3,4,5-tri-N-methylaminophenyl (367) 3,4,5-triisobutyrylaminophenyl (368) 3,4,5-triphenoxyphenyl (369) 3,4,5 -Trihydroxyphenyl (370) 2,4,6-tributylphenyl (371) 2,4,6-tri (2-methoxy-2-ethoxyethyl) B) phenyl (372) 2,4,6-triphenylphenyl (373) 2,4,6-triethoxycarbonylphenyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6- Trimethylphenyl (376) 2,4,6-trichlorophenyl (377) 2,4,6-tribenzoylphenyl (378) 2,4,6-triacetoxyphenyl (379) 2,4,6-trimethoxyphenyl ( 380) 2,4,6-tri-N-methylaminophenyl (381) 2,4,6-triisobutyrylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6 -Trihydroxyphenyl (384) Pentafluorophenyl (385) Pentachlorophenyl (386) Pentamethoxyphenyl (38 7) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2-naphthyl (389) 6-N-phenylsulfamoyl-2-naphthyl (390) ) 5-Ethoxy-7-N-methylsulfamoyl-2-naphthyl (391) 3-methoxy-2-naphthyl (392) 1-ethoxy-2-naphthyl (393) 6-N-phenylsulfamoyl-8 -Methoxy-2-naphthyl (394) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl (395) 1- (4-methylphenyl) -2-naphthyl (396) 6,8-di-N -Methylsulfamoyl-2-naphthyl (397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl (398) 5-acetoxy-7 N-phenylsulfamoyl-2-naphthyl (399) 3-benzoyloxy-2-naphthyl (400) 5-acetylamino-1-naphthyl (401) 2-methoxy-1-naphthyl (402) 4-phenoxy-1 -Naphtyl (403) 5-N-methylsulfamoyl-1-naphthyl (404) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl (405) 5-methoxy-6-N-ethylsulfamoyl- 1-naphthyl (406) 7-tetradecyloxy-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl (408) 6-N-methylsulfamoyl-1-naphthyl (409) 3- N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylsulfamoyl -1-naphthyl (411) 3,6-di-N-phenylsulfamoyl-1-naphthyl (412) methyl (413) ethyl (414) butyl (415) octyl (416) dodecyl (417) 2-butoxy- 2-Ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

(424) Methyl (425) Phenyl (426) Butyl

(430) methyl (431) ethyl (432) butyl (433) octyl (434) dodecyl (435) 2-butoxy-2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

  In the present invention, a melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction between a melamine compound represented by the following general formula (D) and a carbonyl compound.

In the above synthetic reaction scheme, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  The alkyl group, alkenyl group, aryl group, heterocyclic group and substituents thereof have the same meanings as the groups and substituents described in the general formula (C).

  The polymerization reaction between the melamine compound and the carbonyl compound is the same as the method for synthesizing a normal melamine resin (for example, melamine formaldehyde resin). Moreover, you may use a commercially available melamine polymer (melamine resin).

  The molecular weight of the melamine polymer is preferably 2,000 to 400,000. Specific examples of the repeating unit of the melamine polymer are shown below.

MP-1: R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ : CH ₂ OH
_{MP-2: R 13, R} 14, R 15, R 16: CH 2 OCH 3
_{MP-3: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-4: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-5: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
_{MP-6: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-7: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
_{MP-8: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
_{MP-9: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
_{MP-10: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
_{MP-11: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
_{MP-12: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
_{MP-13: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
_{MP-14: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{MP-15: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{MP-16: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-17: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{MP-18: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-19: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{MP-20: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
MP-21: R ₁₃ , R ₁₄ , R ₁₅ : CH ₂ OH; R ₁₆ : CH _{2 On} -C ₄ H _{9
MP-22: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-23: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-24: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
_{MP-25: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-26: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
_{MP-27: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{MP-28: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-29: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-30: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-31: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-32: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-33: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-34: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-35: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-36: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-37: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-38: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{MP-39: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-40: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-41: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-42: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-43: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-44: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{MP-45: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-46: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-47: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-48: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-49: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-50: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

_{MP-51: R 13, R} 14, R 15, R 16: CH 2 OH
_{MP-52: R 13, R} 14, R 15, R 16: CH 2 OCH 3
_{MP-53: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-54: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-55: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
_{MP-56: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-57: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
_{MP-58: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
_{MP-59: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
_{MP-60: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
_{MP-61: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
_{MP-62: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
_{MP-63: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
_{MP-64: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{MP-65: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{MP-66: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-67: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{MP-68: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-69: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{MP-70: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
_{MP-71: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-72: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-73: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-74: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
_{MP-75: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-76: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
_{MP-77: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{MP-78: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-79: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-80: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-81: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-82: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-83: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-84: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-85: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-86: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-87: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-88: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{MP-89: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-90: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-91: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-92: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-93: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-94: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{MP-95: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-96: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-97: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-98: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-99: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-100: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

_{MP-101: R 13, R} 14, R 15, R 16: CH 2 OH
_{MP-102: R 13, R} 14, R 15, R 16: CH 2 OCH 3
_{MP-103: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-104: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-105: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
_{MP-106: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-107: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
_{MP-108: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
_{MP-109: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
_{MP-110: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
_{MP-111: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
_{MP-112: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
_{MP-113: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
_{MP-114: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{MP-115: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{MP-116: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-117: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{MP-118: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-119: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{MP-120: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
_{MP-121: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-122: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-123: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-124: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
_{MP-125: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-126: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
_{MP-127: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{MP-128: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-129: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-130: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-131: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-132: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-133: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-134: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-135: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-136: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-137: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-138: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{MP-139: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-140: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-141: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-142: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-143: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-144: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{MP-145: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-146: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-147: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-148: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-149: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-150: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

_{MP-151: R 13, R} 14, R 15, R 16: CH 2 OH
_{MP-152: R 13, R} 14, R 15, R 16: CH 2 OCH 3
_{MP-153: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-154: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-155: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
_{MP-156: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-157: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
_{MP-158: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
_{MP-159: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
_{MP-160: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
_{MP-161: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
_{MP-162: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
_{MP-163: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
_{MP-164: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{MP-165: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{MP-166: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-167: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{MP-168: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{MP-169: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{MP-170: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
_{MP-171: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-172: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-173: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-174: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
_{MP-175: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
MP-176: R ₁₃ , R ₁₄ , R ₁₆ : CH _{2 On} -C ₄ H ₉ ; R ₁₅ : CH ₂ OH
_{MP-177: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{MP-178: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-179: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-180: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-181: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{MP-182: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{MP-183: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{MP-184: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{MP-185: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-186: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{MP-187: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{MP-188: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{MP-189: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-190: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-191: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-192: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{MP-193: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{MP-194: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{MP-195: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-196: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-197: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{MP-198: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{MP-199: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{MP-200: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
In the present invention, a copolymer obtained by combining two or more of the above repeating units may be used. Two or more homopolymers or copolymers may be used in combination.

  Moreover, you may use together the compound which has a 2 or more types of 1,3,5- triazine ring. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

  These additives are preferably contained in an amount of 0.2 to 30% by mass, particularly preferably 1 to 20% by mass with respect to the cellulose ester film.

  Moreover, the triazine type compound shown by the general formula (I) of Unexamined-Japanese-Patent No. 2001-235621 is also preferably used for the cellulose ester film which concerns on this invention.

  The cellulose ester film according to the present invention preferably contains two or more ultraviolet absorbers.

  As the UV absorber, a polymer UV absorber can be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.

  The method for adding the UV absorber is to add the UV absorber to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition. For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and cellulose ester to disperse and then added to the dope.

  The amount of UV absorber used is not uniform depending on the type of UV absorber, operating conditions, etc., but when the dry film thickness of the cellulose ester film is 30 to 200 μm, it is 0.5 to 4 with respect to the cellulose ester film. 0.0 mass% is preferable, and 0.6 to 2.0 mass% is still more preferable.

<Fine particles>
The cellulose ester film according to the present invention preferably contains fine particles.

  As fine particles used in the present invention, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, and hydrated silicic acid. Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

  The average primary particle diameter of the fine particles is preferably 5 to 50 nm, and more preferably 7 to 20 nm. These are preferably contained mainly as secondary aggregates having a particle size of 0.05 to 0.3 μm. The content of these fine particles in the cellulose ester film is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass. In the case of a cellulose ester film having a multilayer structure by the co-casting method, it is preferable to contain fine particles of this addition amount on the surface.

  Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). I can do it.

  Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Examples of the polymer include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the cellulose ester film low. In the cellulose ester film used in the present invention, the dynamic friction coefficient on the back side of the actinic radiation curable resin layer is preferably 1.0 or less.

<Antioxidant>
In the present invention, the following antioxidant is preferably used.

  Antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, heat-resistant processing stabilizers, oxygen scavengers, etc. Among them, phenolic antioxidants, particularly alkyl-substituted phenolic compounds Antioxidants are preferred. By blending these antioxidants, it is possible to prevent coloration and strength reduction of the molded product due to heat during molding or oxidative degradation without lowering transparency, heat resistance and the like. These antioxidants can be used singly or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but the cellulose ester 100 according to the present invention. Preferably it is 0.001-5 mass parts with respect to a mass part, More preferably, it is 0.01-1 mass part.

  As antioxidants, hindered phenol antioxidant compounds are known compounds, such as those described in columns 12-14 of US Pat. No. 4,839,405, such as 2, 6-dialkylphenol derivative compounds are included. Such compounds include those of the following general formula (1).

  In the above formula, R 1, R 2 and R 3 represent a further substituted or unsubstituted alkyl substituent. Specific examples of hindered phenol compounds include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t-butyl- 4-hydroxyphenyl) -acetate, n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-tert-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3, 5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl β (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octade Sil α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n -Octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenylacetate, 2- (n- Octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (2- Hydroxyethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di-t-butyl-4) -Hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide N, N-bis- [ethylene 3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2- (2-stearoyloxyethylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5-tert-butyl-4- Hydroxyphenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5-di-tert-butyl-4-hydroxyl Nyl) propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentyl glycol bis- [3- (3,5-di-t-butyl-) 4-hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin-1-n-octadecanoate-2,3-bis- (3 5-di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol-tetrakis- [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,1,1 -Trimethylolethane-tris- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], sorbite Ruhexa- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, 2- Stearoyloxyethyl 7- (3-methyl-5-t-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ′, 5′-di-t-butyl-4-hydroxy Phenyl) propionate], pentaerythritol-tetrakis (3,5-di-t-butyl-4-hydroxyhydrocinnamate). Hindered phenolic antioxidant compounds of the above type are commercially available, for example, from Ciba Specialty Chemicals under the trade names “Irganox 1076” and “Irganox 1010”.

  Specific examples of other antioxidants include phosphorus antioxidants such as trisnonylphenyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and dilauryl-3. , 3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), etc. System antioxidant, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5- Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate 3,4-dihydro-2H-1-benzopyran compound, 3,3′-spirodichroman compound, 1,1-spiroindane compound, morpholine, thiomorpholine, thiomorpholine oxide, described in JP-B-08-27508, Examples thereof include thiomorpholine dioxide, compounds having a piperazine skeleton in the partial structure, oxygen scavengers such as dialkoxybenzene compounds described in JP-A No. 03-174150, and the like. These antioxidant partial structures may be part of the polymer, or may be regularly pendant to the polymer, and introduced into part of the molecular structure of additives such as plasticizers, acid scavengers, and UV absorbers. May be.

(Acid scavenger)
As the acid scavenger, an epoxy compound as an acid scavenger described in US Pat. No. 4,137,201 may be contained. Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of various polyglycol diglycidyl ethers, particularly about 8-40 moles of ethylene oxide per mole of polyglycol. Glycol, diglycidyl ethers of glycerol, metal epoxy compounds (such as those conventionally used in and with vinyl chloride polymer compositions), epoxidized ether condensation products, diphenols of bisphenol A Glycidyl ether (ie, 4,4′-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of an alkyl of about 2 to 2 carbon atoms of a fatty acid of 2 to 22 carbon atoms (eg butyl Epoxy stearate) ), And various epoxidized long chain fatty acid triglycerides and the like (e.g., epoxidized vegetable oils and other unsaturated natural oils, which may be represented and exemplified by compositions such as epoxidized soybean oil, these are sometimes epoxidized natural) These are referred to as glycerides or unsaturated fatty acids and these fatty acids generally contain 12 to 22 carbon atoms)). Particularly preferred are commercially available epoxy group-containing epoxide resin compounds EPON 815c and other epoxidized ether oligomer condensation products of general formula (2).

  In the above formula, n is equal to 0-12. Further possible acid scavengers that can be used include those described in paragraphs 87 to 105 of JP-A-5-194788.

(Light stabilizer)
Light stabilizers include hindered amine light stabilizer (HALS) compounds, which are known compounds, such as columns 5-11 of US Pat. No. 4,619,956 and US Pat. , 839, 405, as described in columns 3 to 5, including 2,2,6,6-tetraalkylpiperidine compounds, or acid addition salts thereof or complexes thereof with metal compounds It is. Such compounds include those of the following general formula (3).

  In the above formula, R1 and R2 are H or a substituent. Specific examples of hindered amine light stabilizer compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl. -4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyl Oxy-2,2,6,6-tetramethylpiperidine, 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6 6-pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidin-4-yl-β (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, -Benzyl-2,2,6,6-tetramethyl-4-piperidinyl maleate, (di-2,2,6,6-tetramethylpiperidin-4-yl) -adipate, (di- 2,2,6,6-tetramethylpiperidin-4-yl) -sebacate, (di-1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) -sebacate, (di -1-allyl-2,2,6,6-tetramethyl-piperidin-4-yl) -phthalate, 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, trimellitic acid- Tri- (2,2,6,6-tetramethylpiperidin-4-yl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, dibutyl-malonic acid-di -(1,2,2,6,6-pentamethyl-piperidin-4-yl) -ester, dibenzyl-malonic acid-di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidine- 4-yl) -ester, dimethyl-bis- (2,2,6,6-tetramethylpiperidine-4-oxy) -silane, tris- (1-propyl-2,2,6,6-tetramethylpiperidine- 4-yl) -phosphite, tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphate, N, N′-bis- (2,2,6,6- Tetramethylpiperidin-4-yl) -hexamethylene-1,6-diamine, N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6- Diacetamide, 1-acetyl -4- (N-cyclohexylacetamide) -2,2,6,6-tetramethyl-piperidine, 4-benzylamino-2,2,6,6-tetramethylpiperidine, N, N'-bis- (2, 2,6,6-tetramethylpiperidin-4-yl) -N, N′-dibutyl-adipamide, N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N , N′-dicyclohexyl- (2-hydroxypropylene), N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylene-diamine, 4- (bis-2 -Hydroxyethyl) -amino-1,2,2,6,6-pentamethylpiperidine, 4-methacrylamide-1,2,2,6,6-pentamethylpiperidine, α-cyano-β-methyl-β- [N- (2,2 6,6-tetramethyl-piperidin-4-yl)] - amino - acrylic acid methyl ester. Examples of preferred hindered amine light stabilizers include the following HALS-1 and HALS-2.

  These hindered amine light resistance stabilizers can be used alone or in combination of two or more, and used together with these hindered amine light resistance stabilizers and additives such as plasticizers, acid scavengers, and UV absorbers. Alternatively, it may be introduced into a part of the molecular structure of the additive. The blending amount is appropriately selected within a range not impairing the object of the present invention, but is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts with respect to 100 parts by mass of the cellulose ester according to the present invention. Part by mass, particularly preferably 0.05 to 10 parts by mass.

<dye>
A dye may be added to the cellulose ester film used in the present invention to adjust the color. For example, a blue dye may be added to suppress the yellowness of the film. Preferred examples of the dye include anthraquinone dyes.

  The anthraquinone dye may have an arbitrary substituent at an arbitrary position from the 1st position to the 8th position of the anthraquinone. Preferred substituents include an anilino group, hydroxyl group, amino group, nitro group, or hydrogen atom. In particular, it is preferable to contain a blue dye described in paragraphs [0034] to [0037] of JP-A No. 2001-154017, particularly an anthraquinone dye.

  Various additives may be batch-added to a dope that is a cellulose ester-containing solution before film formation, or an additive solution may be separately prepared and added in-line. In particular, it is preferable to add a part or all of the fine particles in-line in order to reduce the load on the filter medium.

  When the additive solution is added in-line, it is preferable to dissolve a small amount of cellulose ester in order to improve mixing with the dope. The amount of the cellulose ester is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.

  In order to perform in-line addition and mixing in the present invention, for example, an in-line mixer such as a static mixer (manufactured by Toray Engineering) or SWJ (Toray static type in-tube mixer Hi-Mixer) is preferably used.

<Method for producing retardation film>
Next, the manufacturing method of the cellulose ester phase difference film of the present invention will be described.

  The production of the retardation film of the present invention includes the steps of preparing a dope by dissolving a cellulose ester and an additive in a solvent, the step of casting the dope on a belt-like or drum-like metal support, and the cast dope. It is performed by a step of drying as a web, a step of peeling from a metal support, a step of stretching, a step of further drying, a step of further heat-treating the obtained film, and a step of winding after cooling. The retardation film of the present invention preferably contains 70 to 95% by mass of cellulose ester in the solid content.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope of the present invention may be used alone or in combination of two or more. However, it is preferable from the viewpoint of production efficiency that a good solvent and a poor solvent of cellulose ester are mixed and used. The more solvent is preferable from the viewpoint of solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what melt | dissolves the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not dissolve is defined as a poor solvent. Therefore, depending on the acyl group substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4) and cellulose acetate propionate are good. As a solvent, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  A general method can be used as a method of dissolving the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of 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 with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

A bright spot foreign substance is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by an ordinary method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has 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 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and 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. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount 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. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
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.

  Moreover, in the drying process of the cellulose ester film, the web is peeled off from the metal support, further dried, and the residual solvent amount is dried to 0.5% by mass or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  When the casting support is peeled, it can be stretched in the longitudinal direction by the peeling tension and the subsequent conveying tension. For example, it is preferable to peel at a peeling tension of 210 N / m or more, and particularly preferably 220 to 300 N / m.

  An example of a stretching process (also referred to as a tenter process) for producing the retardation film according to the present invention will be described with reference to FIG.

  In FIG. 2, step A is a step of gripping the web conveyed from the web conveyance step D0 (not shown). In the next step B, the web is stretched in the width direction (at the stretching angle as shown in FIG. In the process C, the stretching is finished and the web is conveyed while being gripped.

  It is preferable to provide a slitter that cuts off the end in the web width direction after the web is peeled from the casting support and before the start of step B and / or immediately after step C. In particular, it is preferable to provide a slitter that cuts off the end of the web immediately before the start of step A. When the same stretching is performed in the width direction, particularly when the web edge is cut before the start of the process B and the condition in which the web edge is not cut is compared, the former has an effect of improving the distribution of the orientation angle. can get.

  This is considered to be an effect of suppressing unintended stretching in the longitudinal direction from the peeling with a relatively large amount of residual solvent to the width stretching step B.

  In the tenter process, it is also preferable to intentionally create compartments with different temperatures in order to improve the orientation angle distribution. It is also preferable to provide a neutral zone between different temperature zones so that the zones do not interfere with each other.

  The stretching operation may be performed in multiple stages, and it is preferable to perform biaxial stretching in the casting direction and the width direction. Also, when biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise. In this case, stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible. That is, for example, the following stretching steps are possible.

-Stretching in the casting direction-Stretching in the width direction and simultaneously stretching in the casting direction-Stretching in the casting direction-Stretching in the width direction and simultaneously shrinking in the casting direction Residual solvent of the web immediately after peeling from the metal support In order to obtain the effect of the present invention, it is particularly preferable to stretch in the width direction by a tenter method in which the web is stretched in the conveying direction at a large amount and further grips both ends of the web with clips or the like, thereby giving a predetermined phase difference. I can do it. Moreover, it is estimated that it contributes also to control of free volume. At this time, it may be stretched only in the width direction, or simultaneous biaxial stretching is also preferred. The preferred draw ratio in both the machine direction and the transverse direction is preferably 1.05 to 2 times, preferably 1.15 to 1.5 times. In the simultaneous biaxial stretching, the film may be contracted in the longitudinal direction, or may be contracted so as to be 0.8 to 0.99, preferably 0.9 to 0.99. Preferably, the area is preferably 1.12 times to 1.44 times and more preferably 1.15 times to 1.32 times due to transverse stretching and longitudinal stretching or shrinkage. This can be obtained by the drawing ratio in the longitudinal direction × the stretching ratio in the transverse direction.

  Further, the “stretch direction” in the present invention is usually used to mean a direction in which a stretching stress is directly applied when performing a stretching operation, but in the case of being biaxially stretched in multiple stages, In some cases, it is used in the sense of the one having a higher draw ratio (that is, the direction usually serving as the slow axis).

  When the web is stretched in the width direction, it is well known that the optical slow axis distribution (hereinafter, orientation angle distribution) deteriorates in the width direction of the web. In order to perform widthwise stretching with the values of Rt and Ro being a constant ratio and with a good orientation angle distribution, there is a preferred web temperature relative relationship in steps A, B, and C. When the web temperatures at the end points of Steps A, B, and C are Ta ° C., Tb ° C., and Tc ° C., respectively, it is preferable that Ta ≦ Tb−10. Moreover, it is preferable that Tc ≦ Tb. More preferably, Ta ≦ Tb−10 and Tc ≦ Tb.

  In order to improve the orientation angle distribution, the web heating rate in step B is preferably in the range of 0.5 to 10 ° C./second.

  The stretching time in step B is preferably a short time. However, the minimum required stretching time range is defined from the viewpoint of web uniformity. Specifically, the range is preferably 1 to 10 seconds, and more preferably 4 to 10 seconds. Moreover, the temperature of the process B is 40-180 degreeC, Preferably it is 100-160 degreeC.

In the tenter process, the heat transfer coefficient may be constant or changed. The heat transfer coefficient preferably has a heat transfer coefficient in the range of 41.9 to 419 × 10 ³ J / m ² hr. More preferably, in the range of ^{41.9~209.5 × 10 3 J / m 2} hr, and most preferably a range of ^{41.9~126 × 10 3 J / m 2} hr.

  The stretching speed in the width direction in step B may be constant or may be changed. The stretching speed is preferably 50 to 500% / min, more preferably 100 to 400% / min, and most preferably 200 to 300% / min.

  In the tenter process, it is preferable that the temperature distribution in the width direction of the atmosphere is small from the viewpoint of improving the uniformity of the web, and the temperature distribution in the width direction in the tenter process is preferably within ± 5 ° C, and within ± 2 ° C. Is more preferable, and within ± 1 ° C. is most preferable. By reducing the temperature distribution, it can be expected that the temperature distribution at the width of the web is also reduced.

  In step C, it is preferable to relax in the width direction. Specifically, it is preferable to adjust the web width so that the final web width after stretching in the previous step is in the range of 95 to 99.5%.

  After the treatment in the tenter process, it is preferable to further provide a post-drying process (hereinafter referred to as process D1). It is preferable to carry out at 50-160 degreeC. More preferably, it is the range of 80-140 degreeC, Most preferably, it is the range of 110-130 degreeC.

  In step D1, it is preferable that the atmospheric temperature distribution in the width direction of the web is small from the viewpoint of improving the uniformity of the web. Within ± 5 ° C is preferable, within ± 2 ° C is more preferable, and within ± 1 ° C is most preferable.

  The web conveyance tension in the step D1 is affected by the physical properties of the dope, at the time of peeling and the residual solvent amount in the step D0, the temperature in the step D1, etc., but is preferably 120 to 200 N / m, preferably 140 to 200 N / m. Further preferred. 140 to 160 N / m is most preferable.

  It is preferable to provide a tension cut roll for the purpose of preventing the web from stretching in the transport direction in step D1.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 30 to 160 ° C.

  In the present invention, it is possible to control the free volume or the total free volume parameter to be within a predetermined range by performing the predetermined heat treatment described above after completion of drying.

  In order to produce the retardation film of the present invention, it is preferable to apply a pressure of 0.5 kPa or more and 10 kPa or less to the film in the thickness direction in the heat treatment step after drying, and the pressure can be uniformly applied by a nip roll. preferable. When the pressure is applied in the thickness direction, it is preferable that the drying is sufficiently completed. At that time, by applying a pressure of 0.5 kPa to 10 kPa from both sides of the film, the free volume and total freedom of the retardation film are applied. Volume parameters can be controlled. Specifically, the pressure is applied to the film with two parallel nip rolls. A method such as a calendar roll may be used. It is preferable that the temperature at the time of pressurization is 105-155 degreeC.

  After the predetermined heat treatment, it is preferable to provide a slitter and cut off the end portion before winding to obtain a good winding shape. Furthermore, it is preferable to knurling both ends of the width.

  The knurling process can be formed by pressing a heated embossing roll. Fine embossing is formed on the embossing roll. By pressing this embossing roll, unevenness can be formed on the film and the end can be made bulky.

  The height of the knurling at both ends of the width of the retardation film of the present invention is preferably 4 to 20 μm and a width of 5 to 20 mm.

  In the present invention, the knurling process is preferably provided after the drying in the film forming process and before winding.

  A retardation film having a multilayer structure by a co-casting method can also be preferably used. Even when the retardation film has a multilayer structure, it has a layer containing a plasticizer, which may be a core layer, a skin layer, or both.

  The center line average roughness (Ra) of the retardation film surface is preferably 0.001 to 1 μm.

  In the present invention, Ro defined by the following formula is 30 to 300 nm under conditions of 23 ° C. and 55% RH, and Rt is 70 to 400 nm under conditions of 23 ° C. and 55% RH. A film is preferred.

Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
(In the formula, Ro is the retardation value in the film plane, Rt is the retardation value in the film thickness direction, nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, (nz represents the refractive index in the thickness direction of the film (the refractive index is measured at a wavelength of 590 nm), and d represents the thickness (nm) of the film.)
The retardation value Ro, Rt or the angle θ0 (°) between the width direction of the long film and the slow axis can be measured using an automatic birefringence meter. For example, the wavelength can be obtained at 590 nm in an environment of 23 ° C. and 55% RH using KOBRA-21ADH (Oji Scientific Instruments).

  Furthermore, in the retardation film of the present invention, the degree of polarization p obtained according to the following formula is preferably 0.9990 or more, more preferably 0.9999 or more, and further preferably 0.99995 or more. Preferably, 0.99999 or more is particularly preferable.

p = 1−sin ² (2θ1) · sin ² (πR0 / λ)
(In the formula, λ represents a measurement wavelength (nm) and is 590. θ1 (radian) was obtained from θ0 (°).)
In order to achieve the object of the present invention, specifically, the retardation film used for the polarizing plate of the present invention preferably has a film thickness of 30 μm to 150 μm or less prepared by a casting film forming method. In addition to the effects of the invention, this is derived from the viewpoint of achieving both the physical strength of the film and the production surface. The film thickness is more preferably in the range of 40 μm to 120 μm.

(Measurement of transmittance)
The transmittance T is 380, 400, 500 nm from the spectral transmittance τ (λ) obtained every 10 nm in the wavelength region of 350-700 nm using a spectral altimeter U-3400 (Hitachi, Ltd.). Transmittance can be calculated.

  The haze by the following measurement of the retardation film used in the present invention is preferably less than 1%, particularly preferably 0 to 0.1%.

(Haze value)
It can be measured using a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) and can be used as an index of transparency.

<Anti-blocking layer>
The retardation film of the present invention is preferably provided with an antiblocking layer. An antiblocking layer is a layer which provides a slip property by forming a fine convex part on the film surface by providing the coating layer containing microparticles | fine-particles. The shape of the fine particles to be added is not particularly limited, and particles such as a spherical shape, a rod shape, a flat plate shape, a needle shape and an indefinite shape are used.

  Examples of the fine particles added to the antiblocking layer include inorganic oxides such as metal oxides, hydroxides, silicates, carbonates, and phosphates. Specifically, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, indium oxide, zinc oxide, ITO, hydrated silicic acid Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low haze, and silicon dioxide is particularly preferable.

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large anti-blocking effect while keeping haze low. Thus, the dynamic friction coefficient is preferably 0.9 or less, particularly 0.1 to 0.9.

  The fine particles contained in the anti-blocking layer are 0.1 to 50% by mass, preferably 0.1 to 10% by mass, based on the binder. When the anti-blocking layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Specifically, the anti-blocking layer is formed by applying a composition containing a solvent that dissolves or swells the cellulose ester film. The solvent used may include a solvent to be dissolved and / or a solvent to be swollen in addition to a solvent to be swelled, a composition in which these are mixed at an appropriate ratio depending on the degree of curling of the transparent resin film and the type of resin, and This is done using the coating amount. The retardation film used in the present invention is preferable because the retardation value hardly fluctuates by these coatings.

  When curling is adjusted by application of an anti-blocking layer, for example, in order to curl to the surface side where the anti-blocking layer is provided, the mixing ratio of the solvent for dissolving the solvent used and / or the solvent for swelling is increased and not dissolved. It is effective to reduce the ratio of the solvent. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Solvents that dissolve or swell the transparent resin film contained in such a mixed composition include, for example, dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, and ethylene chloride. , Tetrachloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanol, and hydrocarbons (toluene, xylene).

  These coating compositions are preferably applied to the surface of the transparent resin film with a wet film thickness of 1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. Is particularly preferably 5 to 30 μm. Examples of the resin used as a binder for the antiblocking layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and Acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin Rubber resins such as polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin, Examples thereof include, but are not limited to, silicone resins and fluorine resins. For example, as an acrylic resin, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR -80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105 BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) acrylic and The methacrylic monomers such as various homopolymers and copolymers were prepared as raw materials are commercially available, can also be selected preferred mono from this appropriate.

  Particularly preferred are cellulose resin layers such as diacetylcellulose and cellulose acetate propionate.

  The anti-blocking layer can maintain the flatness of the retardation film and reduce retardation fluctuation.

<Polarizer>
The polarizing plate of the present invention will be described.

  The polarizing plate can be produced by a general method. At least one surface side of the retardation film of the present invention is subjected to alkali saponification treatment, and the cellulose ester film thus treated is immersed and stretched in an iodine solution. It is preferable to stick together. The retardation film of the present invention may be used on the other surface, or another polarizing plate protective film may be used. With respect to the retardation film of the present invention, a commercially available cellulose ester film can be used as the polarizing plate protective film used on the other surface. For example, as a commercially available cellulose ester film, KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3, KC8UCR-4 (above, manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used. Alternatively, it is also preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optical anisotropic layer formed by aligning liquid crystal compounds such as discotic liquid crystal, rod-shaped liquid crystal, and cholesteric liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. Moreover, by using it in combination with an antireflection film, it is possible to obtain a polarizing plate having excellent flatness and a stable viewing angle expansion effect.

  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. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the 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. On the surface of the polarizing film, one side of the retardation film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  Since the polarizing film is stretched in a uniaxial direction (usually the longitudinal direction), when the polarizing plate is placed in a high-temperature and high-humidity environment, the stretching direction (usually the longitudinal direction) shrinks, and the direction perpendicular to the stretching (usually the width direction) ) Will grow. As the thickness of the polarizing plate protective film becomes thinner, the expansion / contraction ratio of the polarizing plate increases, and in particular, the amount of contraction in the stretching direction of the polarizing film increases. Normally, the stretching direction of the polarizing film is bonded to the casting direction (MD direction) of the polarizing plate protective film. Therefore, when making the polarizing plate protective film thin, it is particularly important to suppress the stretching rate in the casting direction. It is. Since the retardation film of the present invention is excellent in dimensional stability, it is suitably used as such a polarizing plate protective film.

  That is, even when the durability test is performed at 60 ° C. and 90% RH, the wavy unevenness does not increase, and even if the polarizing plate has an optical compensation film on the back side, the viewing angle characteristics fluctuate after the durability test. Good visibility can be provided without doing so.

  The polarizing plate can be constituted by further bonding a protective film on one surface of the polarizing plate and a separate film on the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal board, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.

  In the conventional polarizing plate manufacturing process, the retardation value may fluctuate for each manufacturing line. Although the cause is not specified, it is considered that, for example, the arrangement of the rolls in the transport system or the transport conditions are related. Even in the same line, it is considered that the saponification treatment temperature, time, alkali concentration, pH, drying temperature, bonding speed, conveying tension, bonding pressure, and the like change due to changes in settings or changes over time. Basically, these conditions should not be changed, but if there are entrainment of bubbles, occurrence of failure, occurrence of wrinkles, etc., the line speed can be changed or each condition can be fine-tuned accordingly. is there. Or when changing the kind of polarizing plate protective film used on the other side, the said manufacturing conditions may be changed according to it. Or if you stop the line due to trouble and start moving again, it took a considerable amount of time to stabilize. As described above, the retardation value may fluctuate due to fine adjustment of the line-by-line and manufacturing conditions, troubleshooting, line fluctuation over time, etc. A polarizing plate with little variation in phase difference values could be obtained. By using this polarizing plate, a liquid crystal display device with high display performance could be provided. In particular, in a liquid crystal display device using an LED backlight, a liquid crystal display device having high performance with high front contrast and little variation in contrast value among the display devices could be obtained.

<Display device>
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The cellulose ester film of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), and IPS. Particularly preferred is a VA (MVA, PVA) type liquid crystal display device. In particular, even in the case of a large-screen liquid crystal display device with a 30-inch screen or more, a liquid crystal display device with uniform performance with little variation in contrast value among the display devices could be obtained.
Has less color unevenness and wavy unevenness, and has the effect that eyes are not tired even during long-time viewing.

Further, the backlight used in the liquid crystal display device of the present invention may be a sidelight type, a direct type, or a combination thereof, but is preferably a direct type backlight. A particularly preferred direct type backlight is an LED backlight for a color liquid crystal display device having a red (R) LED, a green (G) LED, and a blue (B) LED, for example, the peak of the red (R) LED. Preferably, the wavelength is 610 nm or more, the peak wavelength of the green (G) LED is in the range of 530 ± 10 nm, and the peak wavelength of the blue (B) LED is 480 nm or less. Examples of types of green (G) LEDs having a peak wavelength within the above range include DG1112H (manufactured by Stanley Electric Co., Ltd.), UG1112H (manufactured by Stanley Electric Co., Ltd.), and E1L51-3G (manufactured by Toyoda Gosei Co., Ltd.). E1L49-3G (manufactured by Toyoda Gosei Co., Ltd.), NSPG500S (manufactured by Nichia Chemical Co., Ltd.), and the like. The types of LEDs used as red (R) LEDs include, for example, FR1112H (manufactured by Stanley Electric Co., Ltd.), FR5366X (manufactured by Stanley Electric Co., Ltd.), NSTM515AS (manufactured by Nichia Corporation), GL3ZR2D1COS (Sharp) GM1JJ35200AE (manufactured by Sharp Corporation) and the like. As types of LEDs used as blue (B) LEDs, DB1112H (manufactured by Stanley Electric Co., Ltd.), DB5306X (manufactured by Stanley Electric Co., Ltd.), E1L51-3B (manufactured by Toyoda Gosei Co., Ltd.), E1L4E-SB1A (manufactured by Stanley Electric Co., Ltd.) Toyoda Gosei Co., Ltd.), NSPB630S (Nichia Chemical Co., Ltd.), NSPB310A (Nichia Chemical Co., Ltd.), and the like.
A backlight can be formed by combining the above-described three-color LEDs. Alternatively, a white LED can be used.
In addition, as a direct type backlight (or direct type), a direct type backlight described in JP-A No. 2001-281656, a direct type backlight using a point light source such as an LED described in JP-A No. 2001-305535, Examples include a direct backlight described in JP-A-2002-311412, but are not limited thereto.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Preparation of dope solution>
The following materials were sequentially put into a sealed container, and the temperature in the container was raised from 20 ° C. to 80 ° C., and then stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester . Then, stirring was stopped and the liquid temperature was lowered to 43 ° C. This dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope A.

(Preparation of dope solution A)
Cellulose ester (cellulose acetate propionate; acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 100 parts by mass Trimethylolpropane tribenzoate 5 parts by mass Ethylphthalylethyl glycolate 5 parts by mass Silicon oxide fine particles (Aerosil) R972V (Nippon Aerosil Co., Ltd.))
0.1 parts by mass Methylene chloride 300 parts by mass Ethanol 40 parts by mass (Preparation of dope solution B)
Dope B was obtained in the same manner except that the material used was changed to the following material.

Cellulose ester (acetyl group substitution degree 2.7) 100 parts by weight Triphenyl phosphate 10 parts by weight Biphenyl diphenyl phosphate 2 parts by weight Silicon oxide fine particles (Aerosil R972V (produced by Nippon Aerosil Co., Ltd.))
0.1 parts by mass Methyl acetate 260 parts by mass Ethanol 80 parts by mass The dope prepared as described above was cast on a 30 ° C. support made of a stainless steel endless belt through a casting die kept at 30 ° C. Then, the web was formed, dried on the support, dried on the support until the residual solvent amount of the web reached 80% by mass, and then the web was peeled from the support with a peeling roll.

  Next, the web is dried with a drying air of 70 ° C. in a conveying and drying process using a plurality of rolls arranged on the upper and lower sides, and subsequently held at both ends of the web with a tenter, and then stretched in the width direction at 120 ° C. 1.3 times the width. It extended | stretched so that it might become. After stretching with a tenter, the web was dried with a drying air at 105 ° C. in a conveying and drying process using a plurality of rolls arranged vertically, and dried to a residual solvent amount of 0.3% by mass to obtain a film. Furthermore, after heat-treating the obtained film for 15 minutes in an atmosphere with a predetermined temperature and atmosphere substitution rate, the film was cooled to room temperature and wound up, and a long cellulose ester film having a film thickness of 80 μm and a length of 1000 m (retardation film) 20) 1 were produced. When measured at 590 nm under conditions of 23 ° C. and 55% RH, in-plane retardation Ro = 50 nm and thickness direction retardation Rt = 130 nm.

  Films 2 to 22 were produced in the same manner except that the treatment temperature after drying, the atmosphere substitution rate, and the dope were changed as shown in Table 1. For the cellulose ester films 4, 5, 7, 8, 10, 12, 19, and 20, nip rolls were provided in multiple stages during the heat treatment so that a predetermined pressure was applied in the thickness direction of the film.

The atmosphere replacement rate is determined by substituting the atmosphere per unit time determined by the following formula with Fresh-air when the atmosphere capacity is V (m ³ ) and the fresh air flow rate is FA (m ³ / hr) in the heat treatment chamber. It is the number of times.

Atmosphere replacement rate = FA / V (times / hour)
The obtained retardation film was used as a polarizing plate protective film, and the following polarizing plate protective film C was used on the opposite side to prepare a polarizing plate.

<Polarizing plate protective film C>
(Silicon dioxide dispersion dilution C)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass (average primary particle diameter 16 nm, apparent specific gravity 90 g / liter)
88 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution C.

(Preparation of inline additive solution C)
Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 11 parts by mass Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 5 parts by weight 100 parts by weight of methylene chloride Dissolved and filtered.

  To this, 36 parts by mass of silicon dioxide dispersion diluent C was added with stirring. After further stirring for 30 minutes, cellulose acetate propionate (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 6 masses. The mixture was added with stirring, and further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution C.

(Preparation of dope solution C)
Cellulose ester (cellulose triacetate synthesized from linter cotton: Mn = 148000, Mw = 310000, Mw / Mn = 2.1, acetyl group substitution degree 2.92)
100 parts by weight Trimethylolpropane tribenzoate 5 parts by weight Ethylphthalyl ethyl glycolate 5 parts by weight Methylene chloride 440 parts by weight Ethanol 40 parts by weight Azumi filter paper No. 1 manufactured by Filter Paper Co., Ltd. 24, and the dope liquid C was prepared. The dope solution C was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the film production line. In-line additive solution line was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. Add 2 parts by mass of the filtered inline additive C to 100 parts by mass of the filtered dope liquid C, mix thoroughly with an inline mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then cast the belt. Using the apparatus, it was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm. With the stainless steel band support, the solvent was evaporated until the residual solvent amount became 120%, and then peeled off from the stainless steel band support. The peeled cellulose ester web was evaporated at 35 ° C., slit to 1650 mm width, and then dried at a drying temperature of 135 ° C. while stretching 1.1 times in the width direction with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 30%.

  Then, drying is completed while transporting the drying zone of 110 ° C. and 120 ° C. with many rolls, slitting to a width of 1.4 m, a knurling process of 15 mm in width and 10 μm in average height is applied to both ends of the film, and the initial winding is performed A polarizing plate protective film C was obtained by winding it around a 6-inch inner diameter core with a tension of 220 N / m and a final tension of 110 N / m. The draw ratio in the web conveyance direction immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.07. The residual solvent amount of the polarizing plate protective film C was 0.3%, the average film thickness was 80 μm, and the number of turns was 1000 m.

<Saponification treatment of retardation film>
Using 20 of each of the produced long retardation films 1 to 22, one roll was conveyed and subjected to the alkali saponification treatment described below.

<Alkali saponification treatment>
Saponification step 2M-NaOH 50 ± 3 ° C. 1.5 minutes Water washing step Water 30 ± 3 ° C. 1 minute Neutralization step 10% by mass HCl 30 ± 3 ° C. 1 minute Water washing step Water 30 ± 3 ° C. 1 minute After saponification treatment, Washing with water, neutralization and water washing were carried out in this order, followed by drying at 90 ° C.

  Sampling is performed on 20 long films that have been saponified and sampled at two locations, the head and tail, respectively, and the retardation before and after the saponification is measured. Variations in later retardation were determined. Similarly, with respect to another retardation film, the retardation fluctuation before and after the saponification treatment and the variation in the retardation after the saponification treatment were obtained. The variation in retardation after the saponification treatment is practically acceptable as long as it is within ± 3%.

  Retardation values Ro and Rt were determined at a wavelength of 590 nm under an environment of 23 ° C. and 55% RH using KOBRA-21ADH (Oji Scientific Instruments).

(Preparation of polarizing plate)
Next, each of the 40 retardation films and the polarizing plate protective film C subjected to the same saponification treatment were bonded to a polarizing film prepared by the following method to prepare 40 sets of polarizing plates.

  Step 1: The retardation film and the polarizing plate protective film C were saponified by the method described above.

  Step 2: The following polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was lightly wiped off and placed so as to be sandwiched between the retardation film treated in Step 1 and the polarizing plate protective film C.

Step 4: retardation layered in step 3 film and the polarizing film and the polarizing plate protective film C pressure 20-30 N / cm ^2, the conveyance speed was pasted at approximately 2m / min.

  Step 5: The bonded sample prepared in Step 4 in a dryer at 80 ° C. was dried for 5 minutes to prepare a polarizing plate.

  The polarizing film is a 120-μm thick polyvinyl alcohol film that is uniaxially stretched (temperature 110 ° C., stretch ratio 5 times) and immersed in an aqueous solution of 0.075 g iodine, 5 g potassium iodide, and 100 g water for 60 seconds. Then, it was immersed in a 68 ° C. aqueous solution composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water, washed with water and dried to obtain a polarizing film.

(Production of liquid crystal display device)
40 sets of the obtained polarizing plates were respectively bonded to the glass surfaces on both sides of the liquid crystal cell, and 40 liquid crystal display devices using LEDs as direct type backlights were produced. The obtained liquid crystal display device (VA type, 37 type) was subjected to a durability test at 60 ° C. and 90% RH for 1000 hours, and then the front contrast value was measured using EZ-contrast manufactured by ELDIM. When the highest contrast among the 40 units was 100, the number of display devices in the range of contrast 90 to 100 was counted, and the following ranking was performed. As a result, it was confirmed that those using the polarizing plate of the present invention can provide a uniform liquid crystal display device with uniform front contrast.

A 39-40 units / 40 units B 37-38 units / 40 units C 35-36 units / 40 units D 33-34 units / 40 units E 32 units or less / 40 units Evaluation C or higher is judged to be practically acceptable. did.

  The above evaluation results are summarized in Table 1.

  From the above table, the retardation film in the present invention has a free volume radius controlled by the treatment temperature after drying, atmosphere substitution rate, pressure treatment, etc., and the total free volume parameters. Further, it can be seen that the variation in Ro and Rt after the saponification treatment is small, and an excellent polarizing plate and liquid crystal display device can be provided.

It is a figure explaining the extending | stretching angle in an extending | stretching process. It is the schematic which shows an example of the tenter process used for this invention.

Claims (5)

A method for producing a polarizing plate having a retardation film containing at least a plasticizer and a cellulose ester on one side of a polarizing film, wherein the retardation film is dried to a residual solvent amount of less than 0.3% in a casting film forming step. After that, the free volume radius is 0.250 to 0.310 nm, which is produced by processing in an atmosphere having a substitution rate of 12 times / hour or more at 105 to 155 ° C. and determined by the positron annihilation lifetime method. method for producing a polarizing plate, wherein the retardation film, that has on one surface of the polarizing film. The method for producing a polarizing plate according to claim 1, wherein a total free volume parameter of the retardation film is 1.0 to 2.0. The method for producing a polarizing plate according to claim 1 or 2, wherein the cellulose ester is a mixed (fatty) acid ester having 2 to 22 carbon atoms. Ro defined by the following formula of the said retardation film is 30-300 nm, Rt70-400 nm, The manufacturing method of the polarizing plate of any one of Claims 1-3 characterized by the above-mentioned.
Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
(In the formula, Ro is the retardation value in the film plane, Rt is the retardation value in the film thickness direction, nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, (nz represents the refractive index in the thickness direction of the film (the refractive index is measured at a wavelength of 590 nm), and d represents the thickness (nm) of the film.) A display device comprising a polarizing plate obtained by the method for producing a polarizing plate according to claim 1, which has a direct type backlight.

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