JP4389517B2 - Manufacturing method of optical film - Google Patents

Description

The present invention relates to the production how light optical film, and more particularly relates to flatness, smoothness, producing how the optical film for producing the optical film excellent in optical properties.

  Cellulose ester films are used for transparent resin films (sometimes simply referred to as “fill”) used in applications such as polarizing plate protective films for liquid crystal displays and polarizing plate protective films used in organic EL displays. Several functional layers are provided to provide functions.

  For example, an antistatic layer for providing an antistatic function, a cured resin layer for improving surface hardness, a subbing layer for improving film adhesion, an anti-curl layer for preventing curling, or an anti-curling layer. For example, a glare layer and an antireflection layer.

  On the other hand, as a technique for improving visibility, a technique for forming an antireflection layer using a cellulose ester film formed using a solvent that does not substantially contain a halogenated hydrocarbon (see, for example, Patent Document 1). ) Is described. When thin films are laminated by this method, film thickness unevenness is likely to occur, and improvement thereof has been demanded.

  In addition, an optical film using a cellulose ester film formed by a melt casting method has been proposed (see, for example, Patent Document 2). With this configuration, an optical film excellent in optical properties, physical properties, flatness, and adhesion can be obtained, and since an organic solvent is not used in the production of the film, the film is advantageous in terms of environment and cost.

  In addition, the cellulose ester film produced by the melt casting method contains additives such as a plasticizer and an ultraviolet absorber, as in the case of the cellulose ester film of the solution casting method that uses an organic solvent during normal production. However, these additives are added to improve the processability and moisture permeability of the cellulose ester film.

  However, although the cellulose ester film has excellent environmental characteristics and various performances, when a resin layer such as a cured resin layer is provided on the cellulose ester film by including these additives, usually, It was found that although the flatness and adhesion were improved as compared with the film produced by the solution casting method, it was not sufficient. In particular, it has been found that when a resin layer containing a large amount of an organic solvent is coated on the film, the flatness and adhesion deteriorated due to the diffusion of the organic solvent into the film.

  In addition, the planarity deteriorates when stored under high temperature and high humidity with the optical film coated with a cured resin layer containing a large amount of organic solvent on the cellulose ester film substrate produced by the melt casting method. A unique problem occurred. In this case, the portion where the flatness has deteriorated must be discarded, and the productivity is significantly reduced. In particular, a polarizing plate or an antireflection film used for the front surface of a display device has strict performance requirements, and an optical film having better flatness has been desired.

  As a method for reducing the amount of organic solvent used from the hard coat layer coating composition as much as possible, for example, as a method for forming a hard coat film and a composition for hard coating, a coating composition in which the amount of organic solvent used is reduced is disclosed. (For example, see Patent Document 3) However, the main purpose of this patent is a coating composition for coating optical members such as plastic lenses using an ink jet method, and it is highly productive to thin film and wide cellulose ester films. There was a problem to apply.

As mentioned above, along with environmental issues related to film production, the recent trend is that there is a great demand for thinner display devices and larger display areas. Moreover, the thing of the width | variety is calculated | required and the request | requirement with respect to the flatness of the optical film surface and smoothness exists in the severer situation. However, by reducing the film thickness or increasing the width, the flatness and smoothness of the film surface tend to be inferior, and an immediate improvement of the above problem is desired.
JP 2002-182005 A JP 2000-352620 A JP 2003-126770 A

Accordingly, an object of the present invention, provides a thin film excellent in environmental adaptability during manufacture, flatness even when a wide film, the adhesion, the preparation how the optical film for producing the optical film excellent in optical properties To do.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
A coating composition comprising at least a resin and a solvent composed of water and an organic solvent, having a solid content of 10 to 70% by mass and a water content of 30% by mass or more in the solvent. The film layer is applied to a cellulose ester film substrate that is biaxially stretched after film formation and has a residual amount of chlorinated solvent of less than 0.01% by mass, and is further cured by actinic radiation to form a resin layer. A method for producing an optical film, comprising: providing an optical film .
(Claim 2)
2. The method for producing an optical film according to claim 1, wherein a cellulose ester solution containing substantially no chlorinated solvent is used in carrying out the solution casting film forming method .
(Claim 3)
The method for producing an optical film according to claim 1, wherein the cellulose ester film substrate is a film formed by solution casting using a cellulose ester solution prepared by a cooling dissolution method .
(Claim 4)
The said cellulose-ester film base material is surface-modified before apply | coating the said coating composition, The manufacturing method of the optical film of any one of Claims 1-3 characterized by the above-mentioned .
(Claim 5)
The method for producing an optical film according to claim 4, wherein the surface modification treatment is corona discharge treatment, ultraviolet irradiation treatment, plasma discharge treatment, or alkali saponification treatment .

According to the present invention, to provide excellent environmental suitability during production, film, flatness even when a wide film, the adhesion, the preparation how the optical film for producing the optical film excellent in optical properties Can do.

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

The method for producing an optical film of the present invention has been made in view of the above problems, and at least a resin, containing a solvent consisting of water and an organic solvent, solid content 10 to 70 wt%, the solvent The residual amount of the chlorinated solvent is less than 0.01% by mass , in which the coating composition having a water content of 30% by mass or more is biaxially stretched after film formation using the solution casting film forming method. It is characterized in that it is coated on a cellulose ester film substrate and further cured by actinic radiation to provide a resin layer .

In the present invention, and a film using a solution casting film forming method, the residual amount of the chlorinated solvent is used in the coating fabric compositions that will be applied on the cellulose ester film base is less than 0.01 wt% organic By replacing the solvent with a mixed system of water and an organic solvent, planarity deterioration due to diffusion of the organic solvent is improved. Further, in the present invention, it has been found that the planarity can be further improved by replacing a specific plasticizer in the cellulose ester film base material that adversely affects the planarity by diffusion of the organic solvent with a plasticizer having a small influence. it is intended to provide a manufacturing how the overall excellent optical fill-time.

  Hereinafter, the present invention will be described in more detail.

<Cellulose ester film substrate>
The method for obtaining the cellulose ester film having a residual amount of the chlorinated solvent according to the present invention of less than 0.01% by mass is not particularly limited. For example, the cellulose ester film is immersed in water or the like previously heated to absorb water, The chlorinated solvent can be driven out by drying. Particularly preferably, it is possible to preferably obtain a cellulose ester film in which the residual amount of the chlorinated solvent is adjusted to less than 0.01% by mass by forming a film using a solvent that does not substantially contain the chlorinated solvent.

  Conventionally, a triacetyl cellulose film is produced only by a solution casting method using methylene chloride. Although it is sufficiently dried so that methylene chloride and other solvents do not remain in the drying process, a large-scale drying facility is required, and it is extremely difficult to make it completely zero. It was difficult to further reduce the residual solvent of less than 0.1% by mass within a short time of drying in the apparatus. Moreover, although the manufactured triacetyl cellulose film is stored in a roll shape, since the volatilization of the remaining solvent is suppressed in the roll shape, it was sent to the next step in a state where the solvent remained. Such a chlorinated solvent is required to reduce the amount of use from the viewpoint of the environment, and a method for forming a cellulose ester film using a solvent that does not substantially contain a chlorinated solvent has been proposed. Yes. There are many problems such as inferior solubility as compared with chlorinated solvents, and it has not yet been put into practical use, but in the present invention, the present invention has substantially chlorine as shown below. By adopting a solvent that does not contain a system solvent, the above problem could be solved.

  Examples of the chlorinated solvent according to the present invention include allyl chloride, 2-ethylhexyl chloride, amyl chloride, isopropyl chloride, ethyl chloride, butyl chloride, hexyl chloride, methyl chloride, methylene chloride (methylene chloride), o-chlorotoluene, p- Chlorotoluene, chlorobenzene, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1.2-dichloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, 1,1,1,2-tetrachloroethane, 1,1, Examples include 2,2-tetrachloroethane, tetrachloroethylene, tetramethylene chlorobromide, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, and the like.

The solvent which does not substantially contain a chlorinated solvent means that the content of a chlorinated solvent such as methylene chloride is 5 % or less, preferably 3 % or less, most preferably Is 0%.

  As the solvent substantially not containing a chlorine-based solvent, for example, ether having 2 to 12 carbon atoms, ketone having 3 to 12 carbon atoms, ester having 2 to 12 carbon atoms, and the like are preferably used.

  The above ethers, ketones and esters may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.

  Examples of the ether having 2 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.

  Examples of the ketone having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone.

  Examples of the ester having 2 to 12 carbon atoms include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  You may use the solvent which mixed 2 or more types of organic solvent. Particularly preferred organic solvents are three or more different mixed solvents. In the mixed solvent of 3 or more types, the first solvent is a ketone having 3 to 4 carbon atoms and an ester having 2 to 4 carbon atoms or a mixed solvent thereof, and the second solvent has 5 carbon atoms. It is preferable to use an alcohol having a boiling point of 30 ° C. to 170 ° C. or a hydrocarbon having a boiling point of 30 ° C. to 170 ° C. as a third solvent. As the ketone and ester of the first solvent, acetone, methyl acetate, methyl formate and ethyl formate are preferable. As the second solvent, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetoacetate, dioxane and 1,3-dioxolane are preferable.

  The alcohol of the third solvent is preferably monovalent. The hydrocarbon portion of the alcohol may be linear, branched or cyclic. The hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of alcohols include methanol (boiling point: 64.65 ° C.), ethanol (78.325 ° C.), 1-propanol (97.15 ° C.), 2-propanol (82.4 ° C.), 1-butanol (117. 9 ° C), 2-butanol (99.5 ° C), t-butanol (82.45 ° C), 1-pentanol (137.5 ° C), 2-methyl-2-butanol (101.9 ° C) and cyclo Hexanol (161 ° C.) is included. Two or more kinds of alcohols may be used in combination.

  The hydrocarbon of the third solvent may be linear, branched or cyclic. As the hydrocarbon, either an aromatic hydrocarbon or an aliphatic hydrocarbon can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane (boiling point: 80.7 ° C), hexane (69 ° C), benzene (80.1 ° C), toluene (110.6 ° C) and xylene (138.4-144.4 ° C). Is included.

  In the three kinds of mixed solvents, the first solvent is preferably contained in an amount of 30% by mass to 95% by mass, more preferably 40% by mass to 90% by mass, and more preferably 50% by mass to 90% by mass. Is more preferable. The second solvent and the third solvent are preferably contained in an amount of 1% by mass to 40% by mass, and more preferably 3% by mass to 30% by mass. Examples of solvent combinations include cellulose ester / methyl acetate / cyclohexanone / methanol / ethanol (X / (70-X) / 20/5/5, parts by mass), cellulose ester / methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol. (X / (50-X) / 20/20/5/5, parts by mass), cellulose ester / acetone / methyl acetoacetate / ethanol (X / (75-X) / 20 // 5, parts by mass), cellulose Ester / methyl acetate / cyclopentanone / methanol / ethanol (X / (80-X) / 10/5/5, parts by mass), cellulose ester / methyl acetate / 1, 3 dioxolane / methanol / ethanol (X / (70 -X) / 20/5/5, parts by mass), cellulose ester / methyl acetate / dioxane / acetone / meta And ethanol / ethanol (X / (60-X) / 20/10/5/5, parts by mass) and cellulose ester / 1,3-dioxolane / cyclohexanone / methyl ethyl ketone / methanol / ethanol (X / (55-X) / 20/10/5/5/5, parts by mass). Said X is a mass part of a cellulose ester, Preferably it is 10-25, More preferably, it is 13-25.

  In dissolving the cellulose ester, it is preferable to swell the cellulose ester in a non-halogen organic solvent in advance at room temperature. That is, a cellulose ester swelling liquid can be prepared by adding cellulose ester powder to a non-halogen organic solvent with good stirring, or vice versa by adding a non-halogen organic solvent to the cellulose ester. The non-halogen organic solvent means that the content of the halogen organic solvent is less than 5% by mass (preferably less than 3% by mass). The time required for swelling is preferably 0.1 to 24 hours, more preferably 0.2 to 6 hours, and further preferably 0.5 to 3 hours.

  In addition, as the organic solvent used for preparing the dope by dissolving the cellulose ester, it is preferable to use a solvent that does not substantially contain a chlorinated solvent as described above. And has an appropriate boiling point, for example, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 1,3- Examples thereof include dimethyl-2-imidazolidinone and methyl acetoacetate.

  Among them, dioxolane derivatives, methyl acetate, ethyl acetate, methyl acetoacetate, acetone and the like are preferable organic solvents (that is, good solvents). More preferably, it is preferable to add an alcohol having 1 to 6 carbon atoms, and the proportion of the alcohol in the solvent is preferably 1% by mass to 35% by mass.

  Here, the cellulose ester (cellulose acylate) used in the present invention will be described.

  The ratio Mw / Mn of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the cellulose ester used in the optical film of the present invention is preferably 1.0 to 3.0 or less, more preferably 1.4. ~ 2.5.

  Since the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight and the weight average molecular weight can be calculated using this, and the ratio 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 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 500 to 1,000,000 13 calibration curves were used.

  The cellulose ester according to the present invention is obtained by ester-bonding a hydroxyl group of cellulose and an aliphatic carboxylic acid or aromatic carboxylic acid having 2 to 22 carbon atoms, particularly an acyl group having 2 to 4 carbon atoms, It is preferable to use a cellulose ester having a total acyl group substitution degree of 2.60 to 2.85.

  Examples of such cellulose esters include cellulose acetate, cellulose triacetate, cellulose acetate butyrate, and cellulose acetate propionate. Among these, cellulose triacetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. In these preferable cellulose esters, it is particularly preferable that the substitution degree of the acetyl group is 1.6 or more.

  The cellulose used as a raw material for the cellulose ester is not particularly limited, and examples thereof include cotton linters, wood pulp (derived from coniferous trees and hardwoods), kenaf and the like. 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.

  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 156,400, 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.

  In the case of a mixed acid cellulose ester, it can be obtained by a reaction described in JP-A-10-45804. The measuring method of the substitution degree of an acyl group can be measured according to the rule of ASTM-D817-96. The total acyl group substitution degree of the cellulose ester used in the present invention is preferably 2.6 to 2.85.

  The number average molecular weight (Mn) of the cellulose ester is preferably 70,000 to 250,000 because the mechanical strength when molded is high and an appropriate dope viscosity is preferable, and more preferably 80,000 to 150. , 000.

  The cellulose ester thus obtained is dissolved in a solvent that does not substantially contain a chlorinated solvent to form a viscous liquid called a dope, which is generally produced by a method called a solution casting film forming method. It is preferably used when (film formation) is performed.

  The production of the cellulose ester film according to the present invention will be described.

  In the present invention, when the cellulose ester is dissolved in a solvent, it can be dissolved at around room temperature, but the physical properties of the film formed and the good characteristics of the metal oxide layer formed thereon are obtained. Therefore, it is preferable to dissolve by a method called a cooling dissolution method.

  The cooling dissolution method will be described below.

(Swelling process)
In the swelling step, the cellulose ester and the organic solvent are mixed, and the cellulose ester is swollen with the solvent. The temperature of the swelling process is preferably −10 ° C. to 55 ° C. Usually performed at room temperature. The ratio between the cellulose ester and the organic solvent is determined according to the concentration of the solution finally obtained. In general, the amount of the cellulose ester in the mixture is preferably 5% by mass to 30% by mass, more preferably 8% by mass to 20% by mass, and most preferably 10% by mass to 15% by mass. preferable.

  The mixture of the solvent and the cellulose ester is preferably stirred until the cellulose ester is sufficiently swollen. The stirring time is preferably 10 minutes to 150 minutes, and more preferably 20 minutes to 120 minutes. In the swelling step, components other than the solvent and the cellulose ester, that is, a plasticizer, a deterioration preventing agent, a dye, and an ultraviolet absorber may be added.

(Cooling process)
In the cooling step, the swollen mixture is cooled to −100 ° C. to −10 ° C. The cooling temperature is preferably a temperature at which the swollen mixture is solidified. The cooling rate is preferably 1 ° C./min or more, more preferably 2 ° C./min or more, further preferably 4 ° C./min or more, and most preferably 8 ° C./min or more. . The higher the cooling rate, the better. However, about 100 ° C./second is practical. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature. In the cooling process, it is desirable to use an airtight container in order to avoid moisture mixing due to condensation during cooling. Further, if the pressure is reduced during cooling, the cooling time can be shortened. In order to perform decompression, it is desirable to use a pressure resistant container. Various methods or apparatuses can be adopted as specific cooling means.

  For example, when the swollen mixture is stirred and conveyed in a cylindrical container and the swollen mixture is cooled from the periphery of the container, the swollen mixture can be cooled quickly and uniformly. For this purpose, a cylindrical container, a spiral conveyance mechanism provided in the container for conveying the inside of the cylindrical container while stirring the swollen mixture, and the periphery of the container for cooling the swollen mixture in the container A cooling device composed of a cooling mechanism provided in is preferably used. Moreover, the solvent cooled to -105 degreeC--15 degreeC can be added to a swelling mixture, and can also be cooled more rapidly.

  Further, the swollen mixture is further rapidly cooled by extruding the swollen mixture into a thread having a diameter of 0.1 to 20.0 mm into a liquid cooled to −100 ° C. to −10 ° C. It is also possible.

(Heating process)
In the heating step, the cooled swelling mixture is heated. The final temperature of the heating step is usually room temperature. The heating rate is preferably 1 ° C./min or more, more preferably 2 ° C./min or more, further preferably 4 ° C./min or more, and most preferably 8 ° C./min or more. preferable. The heating rate is preferably as high as possible, but about 100 ° C./second is practical. The heating rate is the value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. is there. When heating is performed while applying pressure, the heating time can be shortened. In order to perform pressurization, it is desirable to use a pressure-resistant container. In addition, when the dissolution is insufficient, the cooling process to the heating process may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye. Various methods or apparatuses can be adopted as specific heating means.

  For example, when the swollen mixture is stirred and conveyed in a cylindrical container, and the swollen mixture is heated from the periphery of the container, the swollen mixture can be quickly and uniformly heated. For this purpose, a cylindrical container, a spiral conveyance mechanism provided in the container for conveying the inside of the cylindrical container while stirring the swollen mixture, and a container for heating the swollen mixture in the container. A warming device comprising a warming mechanism provided around is preferably used.

  In addition, the swollen mixture is heated by adding a thread-like swollen mixture having a diameter of 0.1 to 20.0 mm into a liquid heated to 0 to 55 ° C., so that the swollen mixture can be warmed more rapidly. It is also possible to do. In the cooling step, when a method of extruding the swollen mixture into a thread shape is adopted, the thread-like swollen mixture may be put into a heating liquid.

  Further, the cooled swollen mixture is introduced into a cylindrical container, the flow of the swollen mixture is divided into a plurality of parts in the container, and the direction of the flow of the divided mixture is rotated in the container. Repeatedly, the swollen mixture can be warmed from around the container. As described above, a container provided with a partition for dividing and rotating a substance flow is generally known as a static mixer. In the static mixer TM (Kenix), which is a typical static mixer, the substance flow is divided into two parts and rotated clockwise by 180 degrees, and the substance flow is divided into two parts. The counterclockwise elements that are rotated 180 degrees counterclockwise are alternately shifted 90 degrees in the container. Furthermore, the swollen mixture may be heated to a temperature equal to or higher than the boiling point of the solvent under a pressure adjusted so that the solvent does not boil. Although temperature is determined according to the kind of solvent, it is generally 60-200 degreeC. The pressure is determined by the relationship between the temperature and the boiling point of the solvent.

(Process after solution production)
The produced solution can be subjected to treatment such as concentration adjustment (concentration or dilution), filtration, temperature adjustment, and component addition as necessary. The component to be added is determined according to the use of the cellulose ester film. Typical additives are the plasticizers, deterioration inhibitors, dyes and ultraviolet absorbers described above. Details of the additive will be described later.

《Solution casting film formation》
The dope thus obtained can be manufactured (film formation) by a method called a solution casting film formation method.

  This method is a metal support for casting such as an endless metal belt (for example, a stainless steel belt) that moves indefinitely or a rotating metal drum (for example, a drum whose surface is chrome-plated with cast iron) (hereinafter also simply referred to as a metal support). The dope (cellulose ester solution) is cast on a pressure die, and the web (dope film) on the support is peeled off from the support and dried. . In addition, a cellulose ester having two or more layers can be obtained by a co-casting method.

  In the present invention, an optical film in which a cured resin layer is formed using a film obtained by peeling within 60 seconds after casting and drying while applying tension is cracked in the metal oxide layer formed thereon. Is particularly preferable.

  The peel tension at the time of peeling from the casting metal support is preferably 300 N / m or less, the transport tension is preferably 300 N / m or less, more preferably 250 N / m or less, More preferably, it is 100-200 N / m.

  In the drying step of the present invention, after peeling from the metal support, the metal oxide layer is formed on the cured resin layer formed by the method of the present invention by drying while applying tension in the width direction or the longitudinal direction by a tenter. Durability of the optical film having is preferable. The application of tension in the width direction or the longitudinal direction is preferably a biaxial stretching method in which tension is applied not only in one direction but also in the width direction and the longitudinal direction.

  Alternatively, it is also preferable to stretch the film once or more when it has a high residual solvent amount of 10% by mass or more and a low residual solvent amount of less than 10% by mass. It is preferable to adjust so as to relieve the strain generated during drying by stretching twice.

  The preferred stretch ratio of the cellulose ester film is preferably one in which the stretch ratio in one direction is stretched to 1.01 to 2.0 times and the other stretch ratio is stretched to 0.9 to 1.5 times. It is more preferable that the stretching ratio in the direction is 1.01 to 1.5 times, and the other stretching ratio is 1.0 to 1.4 times, and the stretching ratio in one direction is 1.05 to 1.05. It is particularly preferred that the film is stretched 1.4 times and the other stretch ratio is stretched 1.0 to 1.3 times. Thereby, the cellulose ester film excellent in optical isotropy can be preferably obtained, and the cellulose ester film having good flatness can be obtained. These width restrictions or lateral stretching in the film forming process is preferably performed by a tenter, and a pin tenter or a clip tenter may be used, and a biaxial stretching tenter is particularly preferably used.

  The stretching of the cellulose ester film is preferably performed before coating the cured resin layer in order to maintain excellent flatness.

  The film of the present invention preferably has a width of 1 to 4 m.

  When the cured resin layer of the present invention is applied, an optical film excellent in flatness can be obtained, so that it can be applied to a wide cellulose ester film. In particular, those having a width of 1.4 to 4 m are preferably used, and particularly preferably 1.4 to 2 m. If it exceeds 4 m, conveyance becomes difficult.

  The in-plane retardation value (Ro) of the cellulose ester film according to the present invention is preferably 0 to 70 nm or less. More preferably, it is 0-30 nm or less, More preferably, it is 0-10 nm or less.

  The retardation values (Ro) and (Rt) can be obtained by the following formula.

Ro = (nx−ny) × d
Rt = ((nx + ny) / 2−nz) × d
Here, d is the thickness (nm) of the film, the refractive index nx (also referred to as the maximum refractive index in the plane of the film, the refractive index in the slow axis direction), ny (in the direction perpendicular to the slow axis in the film plane). ) (Refractive index of the film in the thickness direction).

  The retardation values (Ro) and (Rt) can be measured using an automatic birefringence meter. For example, it can be obtained at a wavelength of 590 nm using KOBRA-21ADH (Oji Scientific Instruments) under an environment of 23 ° C. and 55% RH.

  The slow axis is preferably in the width direction ± 1 ° of the film or in the longitudinal direction ± 1 °.

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

Residual solvent amount (%) = [(mass before heat treatment of web−mass after heat treatment of web) / (mass after heat treatment of web)] × 100
The heat treatment for measuring the residual solvent amount was performed at 110 ° C. for 3 hours.

  The residual amount of the chlorinated solvent can be determined by gas chromatography connected to a headspace sampler as described below.

  Specifically, the collected web (which may be a film) is put in a predetermined vial, and heat treatment is performed at 110 ° C. for 3 hours to collect volatile components, and then the volatile components are analyzed by gas chromatography. The amount of chlorinated solvent in the component is determined.

  Here, when the amount is ag and the mass after the heat treatment of the web (film) is bg, the residual amount of the chlorinated solvent according to the present invention is obtained by the following general formula.

Chlorinated solvent residual amount (% by mass) = (a / b) × 100 (%)
Moreover, the measurement conditions of gas chromatography are as follows.

  In the present invention, gas chromatography 5890 type SERISII manufactured by Hewlett-Packard Company and headspace sampler HP7694 type were used, and the measurement was performed under the following measurement conditions.

Headspace sampler heating conditions: 120 ° C, 20 minutes GC introduction temperature: 150 ° C
Temperature rise: 40 ° C, hold for 5 minutes → 100 ° C (8 ° C / min)
Column: J-W DB-WAX (inner diameter 0.32 mm, length 30 m)
(Film thickness of cellulose ester film)
The film thickness of the cellulose ester used for the optical film of the present invention is not particularly limited, and is usually 10 μm to 500 μm, preferably 10 μm to 150 μm.

  Among these, a cellulose ester film having a thickness of 10 μm to 60 μm in which unevenness of the thickness of the metal oxide thin film layer easily occurs is particularly preferably used since the effect of the present invention is remarkably recognized.

  The optical film of the present invention may contain a plasticizer, an ultraviolet absorber, a slip agent, a matting agent and the like as desired in addition to the cellulose ester.

  Examples of the plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixyl phosphate, tris ortho-biphenyl phosphate, 1 Phosphate ester plasticizers such as 1,4-phenylene-tetraphenyl phosphate, phthalate plasticizers such as diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, Triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl Lil ethyl glycolate, butyl phthalyl butyl glycolate, etc. glycolic acid ester based plasticizers. Of these, phthalate ester and glycolate ester plasticizers are preferred because they are unlikely to cause hydrolysis of cellulose esters, and the optical film of the present invention preferably contains two or more plasticizers.

  Specific examples of preferred plasticizers in the present invention are illustrated below.

  In particular, the cellulose ester film used in the present invention preferably contains at least two kinds of plasticizers, and at least one kind is preferably a polyhydric alcohol ester type plasticizer. Other plasticizers are not particularly limited. Preferably, a polyhydric alcohol ester, a phthalic acid ester, a citric acid ester, a fatty acid ester, a glycolate plasticizer or the like of a different type from the polyhydric alcohol ester plasticizer is used.

  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 (1).

General formula (1)
R _1- (OH) _n
Here, R ₁ is an n-valent organic group, n is a positive integer of 2 or more, and the OH group represents an alcoholic or phenolic hydroxyl group.

  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, xylitol and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  In the present invention, the monocarboxylic acid used in the polyhydric alcohol ester is not particularly limited, and known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like 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 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 preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or 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 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

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

  The total content of the plasticizer in the cellulose ester film is preferably 5 to 20% by mass, more preferably 6 to 16% by mass, and particularly preferably 8 to 13% by mass with respect to the total solid content. The contents of the two kinds of plasticizers are each at least 1% by mass, preferably 2% by mass or more.

  The polyhydric alcohol ester plasticizer is preferably contained in an amount of 1 to 12% by mass, particularly preferably 3 to 11% by mass. If the amount is too small, deterioration of flatness is recognized, and if it is too large, bleeding out tends to occur. The mass ratio between the polyhydric alcohol ester plasticizer and the other plasticizer is preferably in the range of 1: 4 to 4: 1, more preferably 1: 3 to 3: 1. If the amount of the plasticizer added is too large or too small, the film is liable to be deformed, which is not preferable.

  The cellulose ester film according to the present invention preferably contains an ultraviolet absorber from the viewpoint of preventing deterioration when placed outdoors as an image display device. As the ultraviolet absorber, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more can be preferably used. For example, the transmittance at 380 nm is preferably less than 20%, more preferably less than 10%, and particularly preferably less than 5%.

  Examples of ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like in the present invention. It is not limited to.

  Although the specific example of an ultraviolet absorber 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 (Straight and side chain dodecyl) -4-methylphenol (TINUVIN171: Ciba Specialty Chemicals)
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 Specialty Chemicals)
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)
In the optical film of the present invention, a benzotriazole-based UV absorber or a benzophenone-based UV absorber that is highly transparent as an UV absorber and excellent in the effect of preventing deterioration of a polarizing plate and liquid crystal can be preferably used. A benzotriazole-based ultraviolet absorber with less unnecessary coloring is particularly preferred. Further, it is preferable that the ultraviolet absorber does not bleed out or volatilize in the film forming process.

  The ultraviolet absorber is preferably added in an amount of 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 5% by mass.

  Furthermore, as a more preferable additive such as a plasticizer or an ultraviolet absorber used in the present invention, an additive having three or more aromatic rings, cycloalkyl rings or cycloalkenyl rings in the molecule is 0.5. It is preferable to contain -30 mass%, and the additive etc. which are non-phosphoric acid type and have at least 3 ring in a molecule | numerator chosen from a benzene ring, a cyclohexane ring, and a cyclohexene ring can be mentioned. Furthermore, these rings may have a substituent.

  A non-phosphate type web containing a plasticizer having at least three benzene, cyclohexyl or cyclohexene rings in the molecule hardly moves from the inside to the surface during drying and does not collect on the surface. It seems that local residual stress is less likely to remain in the cellulose ester film obtained by drying while imparting water.

  In addition, a cellulose ester film containing a non-phosphoric acid-based additive having at least three benzene, cyclohexyl or cyclohexene rings in the molecule can improve moisture permeability and increase stability at high temperature and high humidity. .

  Non-phosphoric acid additive having at least three rings selected from benzene, cyclohexane and cyclohexene rings may be 3 or more benzene rings, 3 or more cyclohexane rings, 3 or more cyclohexene rings However, it may be a condensed ring in which these rings are condensed, or may contain a condensed ring with a hetero ring.

  In the present invention, the number of each benzene ring, cyclohexane ring or cyclohexene ring in the condensed ring is the number of these rings. For example, the naphthalene ring is counted as two. These rings may have a substituent. In the present invention, those having 3 to 20 of these rings in the molecule are preferred, and 3 to 10 are more preferred.

  Examples of the additive having at least three benzene rings, cyclohexane rings or cyclohexene rings in the molecule in the present invention include the following compounds.

P-1: Dibenzyl phthalate P-2: Dibenzyl isophthalate P-3: Dibenzyl terephthalate P-4: Diphenyl phthalate P-5: Diphenyl isophthalate P-6: Diphenyl terephthalate P-7: Dicyclohexyl phthalate P-8 : Dicyclohexyl isophthalate P-9: Dicyclohexyl terephthalate P-10: Phenyl cyclohexyl isophthalate P-11: Phenyl cyclohexyl terephthalate P-12: Phenyl cyclohexyl phthalate P-13: Benzyl cyclohexyl phthalate P-14: Benzyl cyclohexyl terephthalate P-15: Benzylcyclohexyl isophthalate P-16: Dibenzylcyclohexane diacetate P-17: 1,3-cyclohexanedimethyldibenzo P-18: 1,3-dibenzylcyclohexanedicarboxylate P-19: 1,2-dibenzyltetradehydrophthalate P-20: 1,2-dicyclohexyltetrahydrophthalate P-21: 1,3-dicyclohexylcyclohexyldi Carboxylate P-22: Glycerin tribenzoate P-23: Glycerin triphenyl acetate P-24: Tribenzyl acetyl citrate P-25: Tricyclohexyl citrate P-26: Methyl abietic acid P-27: Ethyl abietic acid P -28: butyl abietic acid P-29: methyl dehydroabietic acid P-30: butyl dehydroabietic acid P-31: methyl parastrate, etc.
P-32: KE-604 (Arakawa Chemical)
P-33: KE-85 (Arakawa Chemical)
P-34: Araldide EPN1139 (Asahi Ciba Co., Ltd.)
P-35: Araldide GY260 (Asahi Ciba Co., Ltd.)
P-36: Hi-Luck 110H (manufactured by Hitachi Chemical Co., Ltd.)
P-37: Hilac 111 (manufactured by Hitachi Chemical Co., Ltd.)
Preferred examples include resin oligomers and the like, but the present invention is not limited to these, and other compounds shown in the detailed description and examples are also preferably used.

  In the present invention, the following additives can be used.

  Moreover, as a preferable additive used for the optical film of the present invention, a compound having a 1,3,5-triazine ring can be preferably used.

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

In the general formula (III), 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 (I) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (I), 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 in 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 are the same as the above aryl group.

The heterocyclic group in the case where X ¹ , X ² or X ³ is —NR—, —O— or —S— 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 an 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 (IV) 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 (III).

  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 2O -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-C4H9; 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 2O -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.

(Fine particles)
In the present invention, it is preferable to add fine particles in order to adjust the dynamic friction coefficient of the cellulose ester film. The dynamic friction coefficient of the cellulose ester film is preferably 0.9 or less, and particularly preferably 0.1 to 0.8.

  As fine particles, for example, inorganic fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, Polymethyl methacrylate methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, Examples thereof include polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluorinated ethylene resin powder. Crosslinked polymer fine particles are particularly preferable. In the bright, but it is not limited to these.

  Among these, silicon dioxide is particularly preferable for adjusting the dynamic friction coefficient, and is preferable because the haze of the film can be reduced. The average particle diameter of the primary particles or secondary particles of the fine particles is in the range of 0.01 μm to 1 μm, and the content is preferably 0.005% by mass to 1% by mass with respect to the cellulose ester film. In many cases, fine particles such as silicon dioxide are surface-treated with an organic material, but such particles are preferable because they can reduce the haze of the film.

  Preferred organic materials for the surface treatment include halosilanes, alkoxysilanes, silazanes, siloxanes, and the like.

  The larger the average particle size of the fine particles, the greater the sliding effect. On the other hand, the smaller the average particle size, the better the transparency. Therefore, the preferable average particle size of the primary particles is preferably 20 nm or less, preferably 5 nm to 16 nm, and particularly preferably 5 nm to 12 nm. These fine particles are preferably added to the cellulose ester film to form irregularities of 0.01 μm to 1.0 μm on the surface of the cellulose ester film.

  Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 manufactured by Nippon Aerosil Co., Ltd., preferably Aerosil 200V, R972, R972V, R974, R202, and R812.

  Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios.

  In this case, fine particles having different average particle sizes and materials, such as Aerosil 200V and R972V, can be used in a mass ratio of 0.1: 99.9 to 99.9 to 0.1. Commercially available products such as Aerosil R976 or R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used as zirconium oxide.

  As the organic fine particles, for example, commercially available products such as Tospearl 103, 105, 108, 120, 145, 3120, 240 (manufactured by Toshiba Silicone Co., Ltd.) can be used as the silicone resin.

  In the present invention, the primary average particle diameter of the fine particles is measured by observing the particles with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), observing 100 particles, and using the average value, the primary average is obtained. The particle diameter was taken.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 g / liter to 200 g / liter, and particularly preferably 100 to 200 g / liter. A larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

  Silicon dioxide fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / l or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. In the present invention, the apparent specific gravity described above was calculated by the following equation by measuring a weight of silicon dioxide fine particles in a graduated cylinder and measuring the weight at that time.

Apparent specific gravity (g / L) = silicon dioxide mass (g) / silicon dioxide volume (L)
Examples of the method for preparing a dispersion of fine particles useful in the present invention and the method for adding it to the dope include the following three methods.

<< Preparation Method A >>
After stirring and mixing the organic solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the organic solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a fine particle dispersion is added to a solution obtained by adding a small amount of cellulose ester to an organic solvent and stirring and dissolving the mixture, followed by stirring. This is used as a fine particle addition solution and sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose ester to the organic solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

  Preparation method A is excellent in dispersibility of silicon dioxide fine particles, and preparation method C is excellent in that silicon dioxide fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a preferable preparation method that is excellent in both dispersibility of the silicon dioxide fine particles and that the silicon dioxide fine particles are less likely to reaggregate.

《Distribution method》
The concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with an organic solvent is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass.

  The amount of silicon dioxide fine particles added to cellulose ester is preferably 0.01 to 0.5 parts by mass, more preferably 0.05 to 0.2 parts by mass, and more preferably 0.0 to 0.2 parts by mass with respect to 100 parts by mass of cellulose ester. Most preferred is 08 to 0.12 parts by mass. A larger amount is superior in the dynamic friction coefficient of the cellulose ester film, and a smaller amount is superior in that the haze is low and the aggregates are also small.

  The organic solvent used in the dispersion is preferably a lower alcohol, and examples of the lower alcohol include methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, and the like. Although it does not specifically limit as organic solvents other than a lower alcohol, The organic solvent used at the time of dope preparation is preferable. For example, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, etc. are used at the time of dope preparation.

  As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. The latter is preferable for dispersing silicon dioxide fine particles because the haze is lowered.

  Examples of the media disperser include a ball mill, a sand mill, and a dyno mill.

  The medialess disperser includes an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure type is preferable, and a high pressure dispersion device is preferable.

  The high-pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and an organic solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.8 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.6 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  The high-pressure dispersion apparatus as described above includes an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersion apparatuses such as a homogenizer manufactured by Izumi Food Machinery, Inc. There is UHN-01 manufactured by Wakki Co., Ltd.

  In the present invention, when the fine particles are contained, it is preferably uniformly distributed in the thickness direction of the cellulose ester film, but is more preferably distributed so as to exist mainly in the vicinity of the surface. Preferably, two or more kinds of dopes are cast simultaneously from the die by a co-casting method, and the dope containing fine particles is arranged on the surface layer side. By doing in this way, a haze can be reduced and a dynamic friction coefficient can be lowered. More preferably, it is preferable to use a dope arrangement in which fine particles are contained in both surfaces or one layer on the surface layer side using three kinds of dopes.

In the method for producing an optical film of the present invention is characterized by the Coating trees fat layer after stretching. Various functional layers such as an antistatic layer, an antireflection layer, a slippery layer, an adhesive layer, an antiglare layer, an antifouling layer, and a gas barrier layer may be coated. For example, an antistatic layer between the cellulose ester film and tree fat layer, may be provided intermediate layers such as subbing layers.

In the present invention, for the purpose of improving the adhesion between the coating composition for forming the resin layer and the substrate and further improving the wettability, the surface of the coating object is previously subjected to alkali saponification treatment, acid treatment, surfactant treatment, inorganic or organic matter. Surface modification by polishing with fine particles, oxidizing agent treatment, primer treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma discharge treatment by high frequency discharge in argon or oxygen atmosphere, ion beam treatment of argon, oxygen or nitrogen, etc. It is preferable to carry out the treatment.

  Among these surface activation treatments, corona discharge treatment, ultraviolet irradiation treatment, plasma discharge treatment, or alkali saponification treatment is particularly preferred in practice.

  The corona discharge treatment is a treatment performed by applying a high voltage of 1 kV or higher between the electrodes at atmospheric pressure and discharging it, and is commercially available from Kasuga Electric Co., Ltd. and Toyo Electric Co., Ltd. This can be done using an apparatus. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. As one electrode (A electrode) of the corona discharge treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona discharge treatment is carried out stably and uniformly. . A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof, and a roll lined with ceramic, silicon, EPT rubber, hyperon rubber, or the like. It is done.

  In the present invention, the frequency used for the corona discharge treatment is a frequency of 20 kHz to 100 kHz, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona discharge treatment is deteriorated, and unevenness of the corona discharge treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing a high output corona discharge treatment, but when performing a low output corona discharge treatment, it becomes difficult to perform a stable treatment. Processing unevenness occurs.

In the present invention, the output of the corona discharge treatment is 1 to 5 w · min. / M ² but ² to 4 w · min. An output of / m ² is preferred.

  In the present invention, the distance between the electrode and the film is preferably 5 mm or more and 50 mm or less, and more preferably 10 mm or more and 35 mm or less. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. On the other hand, if the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

Examples of the ultraviolet irradiation treatment include lamps such as metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, low pressure mercury lamps, and high pressure mercury lamps. For example, a commercially available product such as an H lamp, a D lamp, or a V lamp manufactured by Fusion System can be used. The metal halide lamp has a continuous spectrum as compared with a high-pressure mercury lamp (main wavelength is 365 nm), has high luminous efficiency in the range of 200 to 450 nm, and has a long wavelength range. Irradiation conditions vary depending on each lamp. For example, a low-pressure mercury lamp is used to irradiate mainly 185 nm and 254 nm ultraviolet rays with a light amount of 1 to 3,000 mJ / cm ² , and an excimer lamp is used mainly for the wavelength. Can irradiate ultraviolet rays of 172 nm with a light amount of 1 to 3,000 mJ / cm ² . Such ultraviolet rays generate active oxygen and ozone, and can decompose organic substances on the surface of the object to be coated. Also, they act directly on the surface of the object to be coated, so that hydroxyl groups and carboxyl groups are formed on the surface of the object to be coated. It is possible to generate a hydrophilic group such as a carbonyl group and improve adhesion.

  The plasma discharge treatment can be performed by exposing the base material to a high-frequency discharge atmosphere in an argon or oxygen atmosphere with a plasma discharge treatment apparatus or the like described later.

  The alkali saponification treatment is preferably carried out by immersing in an alkaline aqueous solution such as 0.1 to 10 mol / L sodium hydroxide or potassium hydroxide at room temperature to 60 ° C. for 1 to several minutes, followed by neutralization and washing with water. Can do.

  After gripping the clip grips at both ends of the film cut during the film-forming process, or after performing granulation or depolymerization / repolymerization as necessary, as a raw material for film of the same type Or you may reuse as a raw material for films of a different kind.

In the present invention, it is preferable that the vertical and horizontal dimensional shrinkage ratios of the cellulose ester film formed as described above at 105 ° C. for 5 hours are ± 0.1% or less. Moreover, it is preferable that the haze in 80 micrometer conversion of a cellulose-ester film is 0.6% or less, The thing whose haze value is 0.5% or less is especially preferable, More preferably, it is 0.1% or less. The lower limit of the haze value is not particularly limited. Further, the tear strength of the optical film of the present invention is preferably 10 g or more, more preferably 12 g or more, further preferably 15 g or more, further preferably 18 g or more, and 20 g or more. Is more preferable, and it is still more preferable that it is 22 g or more. The tensile strength of the cellulose ester film is preferably 50 N / mm ² or more, and the elastic modulus is preferably 3 kN / mm ² or more. The coefficient of dynamic friction of the cellulose ester film is 1 or less, preferably 0.4 or less, and more preferably 0.35 or less.

  The optical film of the present invention is excellent in dimensional stability, and the dimensional shrinkage at 80 ° C. and 90% RH is less than ± 0.5%, more preferably less than 0.3%, and still more preferably 0.1. %, More preferably less than 0.08%, still more preferably less than 0.06%, and even more preferably less than 0.04%.

< Resin layer>
Resin layer according to the present invention is a curable resin layer which is coated on the cellulose ester film.

In yet hard coat film of the present invention, a resin layer which is cured by actinic radiation comprising an active ray curable resin as the tree fat layer is preferably that (hereinafter, referred to as the active ray curable resin layer).

  The active ray curable resin layer of the optical film of the present invention will be described in detail.

In the present invention , a coating composition containing at least a resin, water and an organic solvent, having a solid content of 10 to 70% by mass, and a water content of 30% by mass or more in the solvent is used. It is characterized by. With this configuration, an optical film with little deterioration in flatness can be obtained.

  The actinic radiation curable resin layer refers to a layer mainly composed of a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. As the actinic radiation curable resin (polymerizable compound), a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an actinic radiation such as an ultraviolet ray or an electron beam. Is formed. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Hereinafter, the polymerizable compound used in the present invention will be described.

(Polymerizable compound)
The preferred polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond capable of radical polymerization, and any compound having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. A thing with chemical forms, such as a monomer, an oligomer, and a polymer, is contained. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties.

In addition, the compound having an ethylenically unsaturated bond capable of radical polymerization used in the present invention is preferably a compound having at least one carboxyl group in one molecule, and as such a compound, (1) 2 bases Reaction product of acid anhydride and hydroxy group-containing acrylic acid ester or methacrylic acid ester: representative compounds thereof include succinic anhydride, orthophthalic anhydride, maleic anhydride, 2-hydroxyethyl methacrylate, It is a reaction product with 3-chloro-2-hydroxypropyl methacrylate.

  (2) Compound obtained by reacting dibasic acid anhydride with secondary hydroxyl group of acrylic ester of epoxy resin: As representative compounds thereof, bisphenol type epoxy resin Epicoat 828, Epicoat 1001 (trade name; oil Deacol (trade name; manufactured by Nagase Kasei), such as 1,4-butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, pentaerythrtriglycidyl ether, cyclic It can be obtained by reacting acrylate with aliphatic epoxy resin such as Celoxide (trade name; manufactured by Daicel Chemical Industries) and then reacting it with residual cocic anhydride or maleic anhydride. A compound.

  (3) A compound obtained by reacting a polybasic alcohol ester of acrylic acid or methacrylic acid with a dibasic acid anhydride: Typical examples of these compounds include succinic anhydride and maleic anhydride on glycol of acrylic acid or polyethylene glycol ester. It is a compound obtained by reacting. The glycol or polyethylene glycol used here preferably has a molecular weight of about 600 or less.

  (4) Water-soluble urethane acrylates and methacrylates having carboxyl side chains in the molecular chain: synthesis of oligomers as UV curable resins is known, but to synthesize oligomer compounds having carboxyl side chains, oligomers In the course of the synthesis reaction, a polybasic acid typified by trimellitic anhydride, or a compound having two hydroxyl groups and one carboxyl group in one molecule typified by dimethylolpropionic acid or the like is used. .

  In addition, the compounds (1) to (4) exemplified above are neutralized with a base and become easily soluble in water. Specific examples of the base used include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, n-butylamine, di-n-butylamine, trimethylamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetoaethylenepentamine, propylenediamine, and ethanol. Examples include amine, hexylamine, laurylamine, diethanolamine, triethanolamine, morpholine, piperidine, propylamine, isopropylamine, isobutylamine, NaOH, LiOH, and KOH.

  Moreover, a water-soluble radically polymerizable compound is mentioned as a polymeric compound used for this invention. Examples of such compounds include the following compounds, but the present invention is not limited thereto.

  X in the above formulas (1) to (4) and (13) represents a hydrogen atom or a methyl group.

  The polymerizable substance that undergoes radical polymerization by ultraviolet rays is selected from, for example, general formula group A in which R is a residue of a polyol in the following general formula, or general formula group B in which R is a residue of an epoxy ester of a polyol. And water-soluble polymerizable compounds. General formula groups A and B will be described later.

  When the above general formula is expressed more clearly, the following general formula is obtained.

  Furthermore, as the substance of the general formula group A, it is preferable to use those exemplified below. Here, A, X, Rx, Ry, Rz, and Rp in the polymerizable substance groups A1 to A11 represented by the following general formula independently represent the following atomic groups.

  In addition, as a halogen atom of X2 in the above formula (1-4) showing one of the structures of Rp, for example, a fluorine atom, a chlorine atom, a bromine atom or the like can be mentioned, and as an alkoxyl group, a carbon atom can be used. Examples are an alkoxyl group of 1 to 3 and the like.

  First, polymerizable compounds included in the polymerizable substance group A1 having the general formula shown below are exemplified, and specifically, the polymerizable compounds A1-1 and A1-2 represented by the following formula are used. Can do.

  Moreover, although the polymeric compound contained in polymeric substance group A2 consisting of the general formula shown below is mentioned, Specifically, polymeric compound A2-1 represented by a following formula can be used.

  Moreover, although the polymeric compound contained in polymeric substance group A3 which consists of the general formula shown below is mentioned, Specifically, polymeric compound A3-1-A3-4 represented by a following formula should be used. Can do.

  Moreover, although the polymeric compound contained in polymeric substance group A4 which consists of a general formula shown below is mentioned, Specifically, polymeric compound A4-1 represented by a following formula can be used.

  Moreover, although the polymeric compound contained in polymeric substance group A5 which consists of the general formula shown below is mentioned, Specifically, polymeric compound A5-1 represented by a following formula can be used.

  Furthermore, each polymeric compound contained in polymeric substance group A6-A11 which consists of a general formula shown below is mentioned.

  The previously exemplified polymerizable compounds A10-1, A10-2 and the like can be produced by adding an amine having a carboxyl group to the vinyl group of acrylic acid, that is, a broad amine acid. That is, it is generally represented by the following formula.

  Here, R is a methylene group in the case of the polymerizable compound A10-1, and a phenylene group in the case of A10-2. Examples of the amine having a carboxyl group used in this method include paraaminobenzoic acid, glycine, valine, leucine, isoleucine, serine, threonine, methionine, and phenylalanine. In addition, substances having equivalent performance can be derived from amino acids having two carboxyl groups such as glutamic acid and aspartic acid.

  On the other hand, examples of the polymerizable compound belonging to the general formula group B include polymerizable substance groups B1 to B4 represented by the following general formula. In the general formulas of the polymerizable substance groups B1 to B4, A and Rp represent the following atomic groups.

  Specific examples of the polymerizable substance groups B1 to B4 represented by the above general formula are shown below.

  Among the many groups of compounds listed above, compounds having three polymerizable functional groups in the molecule are particularly excellent in the polymerization rate, the hardness of the cured product, and the water friction resistance. The main reason for this tendency is considered to be that when a compound having three or more reactive groups is polymerized, the crosslink density is high, and the polymer has an effect of greatly reducing hydrophilicity.

(Photopolymerization initiator)
The water-soluble photopolymerization initiator that constitutes the aqueous photocurable resin composition according to the present invention will be described. As an example, for example, a catalyst having a wavelength of up to about 400 nm may be mentioned. As such a catalyst, for example, a photopolymerization initiator represented by the following general formula (hereinafter abbreviated as TX series) which is a substance having functionality in a long wavelength region, that is, a sensitivity to generate a radical upon receiving ultraviolet rays. In the present invention, it is particularly preferable to select and use them appropriately.

In the above general formulas TX-1 to TX-3, R ₂ represents — (CH ₂ ) x — (x = 0 or 1), —O— (CH ₂ ) y — (y = 1 or 2), substituted or not Represents a substituted phenylene group. When R ₂ is a phenylene group, at least one hydrogen atom in the benzene ring is, for example, a carboxyl group or a salt thereof, a sulfonic acid or a salt thereof, a linear or branched chain having 1 to 4 carbon atoms. Even if it is substituted with one or more groups or atoms selected from alkyl groups, halogen atoms (fluorine, chlorine, bromine, etc.), C1-C4 alkoxyl groups, aryloxy groups such as phenoxy groups, etc. Good. M represents a hydrogen atom or an alkali metal (for example, Li, Na, K, etc.). Furthermore, R ₃ and R ₄ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group include, for example, a linear or branched alkyl group having about 1 to 10 carbon atoms, particularly about 1 to 3 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms (fluorine atoms, chlorine atoms, sulfur atoms, etc.), hydroxyl groups, alkoxyl groups (about 1 to 3 carbon atoms), and the like. Moreover, m represents the integer of 1-10.

  Thioxanthone substituted with these hydrophilic atomic groups is water-soluble and co-soluble with an anionic aqueous pigment dispersion, and is less affected by the absorption of the organic pigment itself. Therefore, it is a highly sensitive catalyst in pigment-based compositions. Works.

  Furthermore, as the water-soluble photopolymerization initiator constituting the aqueous photocurable resin composition according to the present invention, a water-soluble derivative of a photopolymerization initiator Irgacure 2959 (trade name: manufactured by Ciba Specialty Chemicals) having the following general formula ( Hereinafter, the abbreviated IC system) can also be used. Specifically, IC-1 to IC-3 having the following formulas can be used.

  The above-described IC-1 to IC-3 are nonionic, but the wavelength region that can be sensitive to ultraviolet rays is shorter than the photopolymerization initiators shown as TX-1 to TX-3 mentioned above. In the area. Moreover, since IC-1 to IC-3 are water-soluble like the above-described TX-1 to TX-3, they are useful as components of the aqueous photocurable resin composition of the present invention. Furthermore, it is considered possible to produce an aqueous derivative from a catalyst material (photopolymerization initiator) for an existing ultraviolet polymerization system and use it as a photopolymerization initiator constituting the aqueous photocurable resin composition of the present invention. It is done.

  In addition, the following ultraviolet curable resins can be used as appropriate.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.

  Examples of the UV curable polyester acrylate resin include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyol.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  In addition, for the purpose of adjusting the refractive index, improving coating properties, or improving physical properties, metal alkoxides such as tetraethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, and tetrabutoxytitanium, and hydrolysates thereof can be contained. Can use 1 to 50 mass% of the solid content as these components.

  Content of the ultraviolet curable resin in a coating composition is the range of 10 mass%-70 mass% as solid content. If it is less than 10% by mass, film thickness unevenness is likely to occur due to drying, and if it exceeds 70% by mass, the viscosity of the coating composition becomes too high and streak-like failures are likely to occur. Especially preferably, it is the range of 20 mass%-50 mass%, and this range is excellent in coating suitability and drying suitability, and it is preferable that a coating failure does not occur easily.

  These actinic ray curable resin layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, or a die coater.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation light amount may be about ²⁰ to 10000 mJ / cm ² , preferably 40 to 2000 mJ / cm ² , and particularly preferably 50 to 500 mJ / cm ² .

In the present invention, as a solvent for the coating composition used for forming the resin layer, a mixed solvent of water and an organic solvent is used, and a water ratio is 30% by mass or more with respect to the total solvent contained in the coating composition. It is a feature. The present inventor has found that the flatness deterioration phenomenon when a cured resin layer containing a large amount of an organic solvent is applied onto a cellulose ester film is improved by increasing the moisture ratio. The water ratio in the solvent of the coating composition is preferably 30 to 100% by mass, particularly preferably 30 to 80% by mass, further preferably 35 to 75% by mass, and particularly preferably 40%. It is mass%-70 mass%. If the moisture ratio is less than 30% by mass, the flatness improving effect of the present invention cannot be obtained, and 30% by mass to 80% by mass is preferable because it is excellent in coatability.

  In the present invention, the organic solvent to be mixed with water is not particularly limited. For example, the organic solvent is appropriately selected from hydrocarbons, alcohols, ketones, esters, glycol ethers, and other organic solvents, or these Can be mixed and used.

  A particularly preferable organic solvent is a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane, etc.), urea, acetonitrile, acetone and the like. Polyhydric alcohol ethers are particularly preferable in terms of achieving both coating properties and flatness. Among polyhydric alcohol ethers, specifically, cellosolves are preferable, and butyl cellosolve, isopropyl cellosolve, ethyl cellosolve, methyl cellosolve, etc. have appropriate wettability with respect to the object to be coated, and thus show good coating properties. Uniform coating can be formed.

  In the present invention, an oil-based solvent can also be used as appropriate.

  Examples of oil-based solvents include alcohols (eg, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anil alcohol) in addition to those exemplified as the water-miscible organic solvent. Etc.), esters (ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol diacetate, ethyl acetate, amyl acetate, benzyl acetate, phenylethyl acetate, phenoxyethyl acetate, ethyl ethyl acetate, propionic acid Benzyl, ethyl benzoate, butyl benzoate, butyl laurate, isopropyl myristate, triethyl phosphate, tributyl phosphate, diethyl phthalate, Dibutyl tartrate, diethyl malonate, dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate , Diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, cinnamate-3-hexenyl, etc.), ethers (for example, butyl phenyl ether, benzyl ethyl ether, hexyl ether) Etc.), ketones (eg benzyl methyl ketone, benzyl acetone, diacetone alcohol, cyclohexanone, etc.), hydrocarbons (eg petroleum ether, petroleum benzyl, tetralin, decalin, tertiary amyl) Benzene, dimethyl naphthalene, etc.), amides (e.g., N, N-diethyldodecanamide, etc.).

  These organic solvents are preferably used in an amount of 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 10% by mass to 30% by mass with respect to the coating composition.

Further, the coating composition used for forming the ultraviolet curable resin layer preferably contains a surfactant, and a cationic, nonionic or anionic surfactant is appropriately selected, and the amount of the coating composition per unit solid content is 0.00. From 01 to 3% by weight is added.

  It is also preferable to add a silicon compound as a surfactant. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1000 to 100000, preferably 2000 to 50000. If the number average molecular weight is less than 1000, the drying property of the coating film decreases, and conversely, the number average When the molecular weight exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207), and the like.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

As a coating method of the coating composition used for forming the ultraviolet curable resin layer , the above-described methods can be used. The coating amount is suitably from 0.1 to 30 μm, preferably from 0.5 to 15 μm, as the wet film thickness. The dry film thickness is 0.1 to 10 μm, preferably 1 to 10 μm. These may be a single layer or a laminate of two or more layers.

The coating composition is preferably irradiated with ultraviolet rays during or after coating and the irradiation time for obtaining the irradiation amount of the active rays is preferably about 0.1 seconds to 5 minutes. From the viewpoint of curing efficiency or work efficiency, 0.1 to 10 seconds is more preferable.

  In order to prevent blocking, to improve scratch resistance, or to provide antiglare properties, or to adjust the refractive index, fine particles of an inorganic compound or an organic compound may be added to the cured resin layer thus obtained. it can.

  Inorganic fine particles used for the resin layer include silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate And magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder. Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added to the ultraviolet curable resin composition.

The average particle diameter of these fine particle powders is preferably 0.005 to 5 μm, and particularly preferably 0.01 to 1 μm . Ratio of the dendritic fat composition and fine powder, the resin composition 100 parts by weight, it is desirable to formulate such that 0.1 to 30 parts by weight.

Tree fat layer, or the center line average roughness defined in JIS B 0601 (Ra) is a clear hard coat layer 0.001～0.1Myuemu, or Ra is antiglare layer about 0.1~1μm It is preferable that The center line average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, RST / PLUS manufactured by WYKO.

<Back coat layer>
On a surface opposite to the tree fat layer provided side of the optical film according to the present invention may be provided with a back coat layer. The back coat layer is applied to prevent blocking, and therefore, it is preferable that fine particles are added to the back coat layer. Or the like coating or CVD, a backcoat layer may be provided to correct the curl caused by providing a tree fat layer and other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface provided with the backcoat layer inside.

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and indium oxide. And zinc oxide, ITO, hydrated calcium silicate, 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, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available, for example, under the trade names 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. In the optical film of the present invention, the dynamic friction coefficient on the back surface side of the cured resin layer is preferably 0.9 or less, particularly preferably 0.1 to 0.9.

  The fine particles contained in the backcoat layer are 0.1 to 50% by weight, preferably 0.1 to 10% by weight, based on the binder. When the back coat 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 back coat layer is formed by applying a composition containing a solvent for dissolving or swelling a 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.

  In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to decrease the ratio of the solvent not to be dissolved. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Examples of the solvent for dissolving or swelling the transparent resin film contained in such a mixed composition include 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 water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, and hydrocarbons (toluene, xylene, cyclohexanol).

  These coating compositions are preferably applied to the surface of the transparent resin film with a gravure coater, dip coater, reverse coater, wire bar coater, die coater, etc., with a wet film thickness of 1 to 100 μm, particularly 5 to 30 μm. Preferably there is. Examples of the resin used as the binder of the backcoat 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 / or Or acrylic acid copolymer, acrylic acid ester copolymer, polyvinyl alcohol, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer , Rubber such as acrylic resin, 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, resins, 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 and can also be selected preferred mono from this appropriate.

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

  The order of coating the backcoat layer may be before or after coating the cellulose ester film on the opposite side of the backcoat layer (cured resin layer or other layer such as an antistatic layer). When the back coat layer also serves as an anti-blocking layer, it is desirable to coat it first. Alternatively, the back coat layer can be applied in two or more layers.

  The optical film of the present invention is suitable for uniformly forming a thin film of a metal compound layer by coating or plasma CVD, particularly atmospheric pressure plasma treatment, and these are useful as an antireflection layer.

  As the atmospheric pressure plasma treatment method, for example, an atmospheric pressure plasma discharge treatment method for applying a high-frequency pulse voltage described in JP-A-11-181573, JP-A-2000-26632, JP-A-2002-110397, or the like can be used. Alternatively, the conductive layer can be provided by an atmospheric pressure plasma discharge processing method described in JP-A-2001-337201. Alternatively, the antireflection layer can be provided by the methods described in JP-A No. 2002-228803, Japanese Patent Application No. 2002-369679, Japanese Patent Application No. 2002-317883, and Japanese Patent Application No. 2003-50823. Alternatively, the antifouling layer can be provided by the method described in Japanese Patent Application No. 2003-50823. Alternatively, the antireflection layer can be applied by the method described in JP-A No. 2003-93963 and Japanese Patent Application No. 2002-49724.

  On the optical film of the present invention, a metal compound (for example, SiOx, SiOxNy, TiOxNy, SiOxCz (x = 1 to 2, y = 0.1 to 1, z = 0.1) is mostly obtained under an atmosphere of nitrogen gas. It is preferable to form a thin film of metal oxide or the like among metal oxides, metal nitrides, metal oxynitrides, metal carbides, etc. The nitrogen gas contained in the gas is 60 to 99.9% by volume, preferably 75 to 99.9% by volume, and more preferably 90 to 99.9% by volume. In addition to nitrogen gas, a rare gas such as argon or helium may be contained, a gas of a metal compound for forming a thin film is contained, and further a gas (addition gas) for promoting a reaction such as oxygen and hydrogen. Or an auxiliary gas). By these, a low refractive index layer, a high refractive index layer, a medium refractive index layer, a transparent conductive layer, an antistatic layer, an antifouling layer and the like containing a metal compound can be formed.

Next, a description will be given anti-reflective layer formed on this RaTatsuki fat layer.

(Antireflection layer)
In the present invention, the method for providing the antireflection layer is not particularly limited, and the antireflection layer can be formed by coating, sputtering, vapor deposition, CVD (Chemical Vapor Deposition), or a combination thereof.

  As a method of forming the antireflection layer by coating, a method of dispersing metal oxide powder in a binder resin dissolved in a solvent, coating and drying, a method of using a polymer having a crosslinked structure as a binder resin, ethylenic unsaturated Examples of the method include a method of forming a layer by containing a monomer and a photopolymerization initiator and irradiating actinic rays.

In the present invention, it can be provided with anti-reflection layer on the optical film provided with tree fat layer. A low refractive index layer is formed on the uppermost layer of the optical film, and a metal oxide layer of a high refractive index layer is formed between them. It is preferable to provide a metal oxide layer in which the refractive index is adjusted by changing the content of the product or the ratio to the resin binder and the type of metal to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted so as to be an intermediate value between the refractive index (about 1.5) of the cellulose ester film as the substrate and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of each layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm. The haze of the metal oxide layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the metal oxide layer is preferably 3H or more, and most preferably 4H or more, with a pencil hardness of 1 kg. When the metal oxide layer is formed by coating, it is preferable to include inorganic fine particles and a binder polymer.

The inorganic fine particles used for the metal oxide layer such as the middle refractive index layer or the high refractive index layer preferably have a refractive index of 1.80 to 2.80, more preferably 1.90 to 2.80. . The primary particles of the inorganic fine particles preferably have a weight average diameter of 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the inorganic fine particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and most preferably 10 to 80 nm. . The average particle diameter of the inorganic fine particles is measured by a light scattering method if it is 20-30 nm or more and by an electron micrograph if it is 20-30 nm or less. The specific surface area of the inorganic fine particles, a measured value by the BET method, is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, a 30 to 150 m ² / g Is most preferred.

  The inorganic fine particles are particles formed from a metal oxide. Examples of metal oxides or sulfides include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, and the like. Of these, titanium dioxide, tin oxide, and indium oxide are particularly preferable. The inorganic fine particles can contain oxides of these metals as main components and further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The inorganic fine particles may be surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable. It may be processed by combining two or more types of surface treatments.

  The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a layer shape, a spindle shape, or an indefinite shape. Two or more kinds of inorganic fine particles may be used in combination in the metal oxide layer.

  The proportion of the inorganic fine particles in the metal oxide layer is preferably 5 to 90% by volume, more preferably 10 to 65% by volume, and still more preferably 20 to 55% by volume.

  The inorganic fine particles are supplied to a coating liquid for forming a metal oxide layer in a dispersion state dispersed in a medium. As the dispersion medium for the inorganic fine particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, Examples include dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), and ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The inorganic fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The metal oxide layer preferably uses a polymer having a crosslinked structure (hereinafter also referred to as “crosslinked polymer”) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as “polyolefin”), crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Moreover, it is more preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  The refractive index of the low refractive index layer used in the antireflective layer of the present invention is preferably 1.46 or less, and particularly preferably 1.3 to 1.45, by silicon alkoxide as a coating composition by a sol-gel method. A low refractive index layer can be formed. Alternatively, a low refractive index layer can be formed using a fluorine resin. In particular, it is preferably composed of a cured product of a thermosetting or ionizing radiation curable fluorine-containing resin and the cured product and silicon oxide ultrafine particles.

  The dynamic friction coefficient of the cured product is preferably 0.02 to 0.2, and the pure water contact angle is preferably 90 to 130 °. Examples of the curable fluorine-containing resin include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane) and fluorine-containing copolymers (crosslinkable groups). Monomer and fluorine-containing monomer as structural units). Specific examples of the fluorine-containing monomer unit include, for example, hexafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and fluoroolefins (for example, vinylidene fluoride perfluoro-2,2-dimethyl-1,3-dioxole, fluoroethylene, etc.) Fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical Co., Ltd.) and M-2020 (manufactured by Daikin)), fluorinated vinyl ethers, and the like. As a monomer having a crosslinkable group, a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, and a (meth) acrylate having a carboxyl group, an amino group, a hydroxyl group, a sulfonic acid group, etc. And monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It has been described in JP-A-10-25388 and JP-A-10-147739 that a crosslinked structure can be introduced after copolymerization.

  Further, not only a polymer having the above-mentioned fluorine-containing monomer as a structural unit but also a copolymer with a monomer not containing a fluorine atom can be used. There are no particular limitations on the monomer units that can be used in combination, for example, acrylic acid esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, Butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, α-methylstyrene, vinyltoluene, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, acrylonitrile Derivatives, olefins (ethylene, propylene, isoprene, vinylidene chloride, vinyl chloride, etc.), vinyl ethers (methyl vinyl ether, etc.), vinyl esters (vinyl acetate, propionic acid) Alkenyl, vinyl cinnamate) may be mentioned.

  It is preferable to add silicon oxide fine particles to the fluorine-containing resin used for forming the low refractive index layer in order to improve scratch resistance. The addition amount is adjusted in consideration of the refractive index and scratch resistance. As the silicon oxide fine particles, silica sol dispersed in a commercially available organic solvent can be added to the coating composition as it is, or various commercially available silica powders can be dispersed in an organic solvent and used.

  The coating composition for forming the low refractive index layer of the antireflection film coated on the optical film of the present invention preferably contains mainly a low boiling point solvent. Specifically, the solvent having a boiling point of 100 ° C. or less is preferably 50% by mass or more of the total solvent. As a result, even when coated on the surface of a substrate having irregularities such as an antiglare layer, it can be dried quickly, fine film thickness unevenness due to the flow of the coating liquid is reduced, and an increase in reflectance is suppressed. The Moreover, since the drying nonuniformity and white turbidity nonuniformity are suppressed when the solvent whose boiling point is 100 degreeC or more is contained, it is preferable that the solvent whose boiling point is 100 degreeC or more contains 0.1-50 mass%.

  Low boiling point solvents used in coating compositions for the low refractive index layer include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ether alcohols such as methyl cellosolve, methanol, ethanol, and isopropanol. Among these alcohols, those having high solubility of the solid content contained in the coating composition are preferably used. Coating solvents having a boiling point exceeding 100 ° C. include ketones such as cyclohexanone, cyclopentanone and methyl-isobutyl ketone, ether alcohols such as diacetone alcohol and propylene glycol monomethyl ether, and alcohols such as 1-butanol and 2-butanol. Etc. are used.

  Each layer of the antireflection film can be formed by coating by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a micro gravure coating method or an extrusion coating method. it can.

  In the present invention, a method of forming a metal oxide layer by plasma discharge treatment is particularly preferably used.

  Hereinafter, a method for forming a metal oxide layer by plasma discharge treatment will be described with reference to FIGS.

  Plasma discharge treatment under atmospheric pressure or a pressure in the vicinity thereof as a method for forming a metal oxide layer on the optical film of the present invention is performed by using a plasma discharge treatment apparatus as described below.

  FIG. 1 is a diagram showing an example of a plasma discharge treatment apparatus used for forming a surface treatment or a metal oxide layer on an optical film.

  In FIG. 1, this apparatus has a pair of rotating electrodes 10A and 10B. A power supply 80 to which a voltage for generating plasma discharge can be applied is connected to the rotating electrodes 10A and 10B. Connected to ground, 82 is connected to ground.

  The rotating electrodes 10A and 10B are transported while winding an optical film, and are preferably roll electrodes or belt-like electrodes, and FIG. 1 shows the roll electrodes.

  A gap (electrode gap) between these rotating electrodes is a place where discharge is performed, and is set to an interval at which the optical film F can be conveyed. The gap between the electrodes becomes the discharge part 50.

  The gap between the electrodes is maintained at atmospheric pressure or a pressure near atmospheric pressure, and the reaction gas G is supplied from the reaction gas supply unit 30 to the plasma film on the surface of the optical film F.

  Here, the optical film F unwound from the original winding roll or the optical film F conveyed from the previous step is first transferred through the guide roll 20 while being in contact with the rotating electrode 10A rotating in the transfer direction, and the discharge unit Through 50, a thin film is formed on the surface of the optical film F.

  The optical film F that has once exited from the discharge unit 50 is U-turned by the U-turn rolls 11A to 11D, and this time, the optical film F is transferred while being in contact with the rotating electrode 10B rotating in the opposite direction to the rotating electrode 10A. After passing through the discharge part 50 again, the surface of the optical film F on which the thin film has been formed is further subjected to plasma discharge treatment to form a thin film. The U-turn is usually performed in about 0.1 seconds to 1 minute.

  The reaction gas G used for the treatment is discharged from the gas discharge port 40 as exhaust gas G ′ after the reaction. It is preferable that the reaction gas G is heated to room temperature to 250 ° C., preferably 50 to 150 ° C., more preferably 80 to 120 ° C., and then fed into the discharge part 50.

  In addition, it is preferable that the discharge part 50 is provided with the rectification | straightening board 51, and while making the flow of the reaction gas G and waste gas G 'smooth, the discharge part 50 spreads and unnecessary discharge is made between electrodes 10A and 10B. The rectifying plate 51 is preferably made of an insulating member.

  In the figure, the thin film formed on the optical film F is omitted. The optical film F having a thin film formed on the surface is conveyed in the direction of the next process or a take-up roll (not shown) via the guide roller 21.

  Therefore, the optical film F is subjected to plasma discharge treatment by reciprocating the discharge part 50 in a state of being in close contact with the rotary electrodes 10A and 10B.

  Although not shown in the drawing, the devices such as the rotating electrodes 10A and 10B, the guide rolls 20 and 21, the U-turn rolls 11A to 11D, the reactive gas supply unit 30, and the gas discharge port 40 are in a plasma discharge processing vessel that is shielded from the outside. It is preferable that it is enclosed and enclosed.

  Although not shown, a temperature control medium for controlling the temperature of the rotating electrodes 10A and 10B is circulated as necessary to control each electrode surface temperature to a predetermined value. . The diameters of the rotating electrodes 10A and 10B are 10 to 1000 mm, preferably 50 to 500 mm, and those having different diameters may be used in combination.

  FIG. 2 is a view showing an example of a plasma discharge treatment apparatus having a rotating electrode and a fixed electrode useful for forming a surface treatment or a metal oxide thin film layer on an optical film.

  A rotating electrode 110 and a plurality of fixed electrodes 111 arranged opposite to the rotating electrode 110, and an optical film F conveyed from a not-shown original winding roll or a previous process passes through a guide roll 120 and a nip roll 122, and the rotating electrode 110. The optical film F is transferred in synchronization with the rotation of the rotating electrode 110 while being in contact with the rotating electrode 110, and is prepared by the reaction gas generator 131 to the discharge unit 150 under atmospheric pressure or a pressure in the vicinity thereof. The reactive gas G is supplied from the supply pipe 130, and a thin film is formed on the optical film surface facing the fixed electrode 111.

  A power source 180 capable of applying a voltage for generating plasma discharge is connected to the voltage supply means 181 between the rotating electrode 110 and the fixed electrode, one of which is connected to the ground, and 182 is connected to the ground.

  Further, the rotating electrode 110, the fixed electrode 111, and the discharge unit 150 are covered with a plasma discharge processing vessel 190 and are shielded from the outside. The treated exhaust gas G ′ is discharged from a gas exhaust port 140 at the lower part of the processing chamber.

  The optical film F subjected to the plasma discharge treatment is conveyed to the next process or a winding roll (not shown) through the nip roll 123 and the guide roll 121.

  The optical film F is provided with partition plates 124 and 125 to the outside at the nip rolls 122 and 123 at the entrance and exit of the plasma discharge processing vessel, and blocks the air accompanying the optical film F from the outside together with the nip roll 122. In addition, at the outlet, the reaction gas G or the exhaust gas G ′ is prevented from leaking to the outside. Although not shown, the rotating electrode 110 and the fixed electrode 111 are provided for temperature adjustment as necessary. A temperature-controlled medium is circulated inside.

  Thus, in the present invention, the optical film on which the thin film is formed is preferably subjected to plasma discharge treatment while being transferred on the rotating electrode.

  The surface where the rotating electrode is in contact with the optical film is required to have high smoothness, and the surface roughness of the surface of the rotating electrode is the maximum surface roughness (Rmax) specified by JIS-B-0601 is 10 μm or less. Is more preferably 8 μm or less, and particularly preferably 7 μm or less. In addition, it is necessary to prevent dust and foreign matter from adhering to the electrodes for uniform film formation.

The surface of the electrode used for the plasma discharge treatment is preferably coated with a solid dielectric, and in particular, a conductive base material such as metal is preferably coated with the solid dielectric. Examples of the solid dielectric include plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, silicon dioxide, aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), metal oxides such as titanium oxide (TiO ₂ ), Examples thereof include double oxides such as barium titanate.

  It is particularly preferable that the dielectric material is a ceramic-coated dielectric that has been thermally sprayed with ceramics and then sealed with an inorganic material. Here, examples of the conductive base material such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing.

  As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass and the like are preferably used. However, among these, borate glass is more preferably used because it is easy to process.

  The electrode used for the plasma discharge treatment can be heated or cooled as necessary from the back side (inside). In the case where the electrode is a belt, it can be cooled with gas from the back side, but it is preferable to control the temperature of the electrode surface and the temperature of the optical film by supplying a medium to the inside of the rotating electrode using a roll.

  As the medium, an insulating material such as distilled water, oil, particularly silicon oil is preferably used.

  The temperature of the optical film during the discharge treatment varies depending on the treatment conditions, but is preferably room temperature to 200 ° C or less, more preferably room temperature to 120 ° C or less, and further preferably 50 to 110 ° C.

  In addition, the curling may occur due to the rise of the film surface temperature or the like due to discharge, but according to the present invention, the curling can be remarkably reduced.

  It is desirable to prevent temperature unevenness particularly in the width direction of the optical film surface during the discharge treatment, preferably within ± 5 ° C., more preferably within ± 1 ° C., particularly preferably ± Within 0.1 ° C.

  In the present invention, the electrode gap is determined in consideration of the thickness of the solid dielectric, the applied voltage and frequency, the purpose of using plasma, and the like. The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes is uniform in any case From the viewpoint of generating discharge plasma, 0.5 mm to 20 mm is preferable, and 1 mm ± 0.5 mm is particularly preferable.

  In the present invention, the flow rate of the mixed gas generated by the gas generator is controlled in the discharge portion of the electrode gap and introduced into the plasma discharge portion from the reaction gas supply port. The concentration and flow rate of the reaction gas are appropriately adjusted, but it is preferable to supply the processing gas to the electrode gap at a speed sufficient for the conveyance speed of the optical film. In the discharge section, it is desirable to set the flow rate and discharge conditions so that most of the supplied reaction gas reacts and is used for thin film formation.

  In order to prevent the atmosphere from being mixed into the discharge part and the reaction gas from leaking out of the apparatus, it is preferable that the electrode and the optical film being transferred are surrounded and shielded from the outside. In the present invention, the atmospheric pressure of the discharge part is maintained at atmospheric pressure or a pressure in the vicinity thereof. In addition, the reaction gas may be decomposed in the gas phase to generate metal oxide fine powder, and it is desirable to set the flow rate and discharge conditions so as to reduce the generation.

  Here, the vicinity of atmospheric pressure represents a pressure of 20 to 200 kPa, but 93 to 110 kPa is preferable in order to preferably obtain the effects described in the present invention. The discharge part is preferably slightly positive with respect to the atmospheric pressure outside the apparatus, more preferably atmospheric pressure outside the plasma apparatus +0.1 kPa to 5 kPa.

  In the plasma discharge treatment apparatus useful for the present invention, it is preferable that one electrode is connected to a power source to apply a voltage, and the other electrode is grounded to generate a discharge plasma to generate a stable plasma. .

  The value of the voltage applied to the electrode from the high frequency power source used in the present invention is appropriately determined. For example, the voltage is about 0.5 to 10 kV, the applied frequency is adjusted to 1 kHz to 150 MHz, and the waveform is a pulse wave. Or a sine wave. In particular, it is preferable to apply a high frequency of more than 100 kHz and 50 MHz or less because a preferable discharge part (discharge space) is obtained. Alternatively, a method of simultaneously applying high-frequency voltages having two frequencies of 1 kHz to 200 kHz and 800 kHz to 150 MHz is also preferably used.

Preferably the discharge density in the discharge portion are 5~1000W · min / m ^2, in particular it is desirable that 50~500W · min / m ^2.

  It is desirable that the plasma discharge processing unit is appropriately surrounded by a Pyrex (R) glass processing container or the like, and it is possible to use a metal as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be affixed to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to achieve insulation. In addition, the reaction gas and the exhaust gas can be appropriately supplied to the discharge unit or exhausted by surrounding the discharge unit, the side surface of the rotating electrode, the side surface of the cellulose ester film transport unit, and the like.

  The reaction gas used in the method for forming a metal oxide thin film layer of the present invention will be described.

  The reaction gas for forming the thin film layer preferably contains nitrogen or a rare gas.

  That is, the reactive gas is preferably a mixed gas of nitrogen or a rare gas and a reactive gas described later.

  Here, the noble gas is a group 18 element of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc., and in the present invention, helium or argon is preferably used. it can. These may be used as a mixture, for example, in a ratio of helium 3: argon 7 or the like.

  The concentration of the rare gas or nitrogen in the reaction gas is preferably 90% or more in order to generate a stable plasma discharge, and desirably 90 to 99.99% by volume.

  A rare gas or nitrogen is used to generate a stable plasma discharge, and the reactive gas is ionized or radicalized in the plasma, and is deposited or adhered to the surface of the substrate to form a thin film.

  As the reactive gas useful in the present invention, a thin film having various functions can be formed on an optical film by using a reactive gas added with reactive gases of various substances.

  For example, the low refractive index layer or the antifouling layer of the antireflection layer can be formed using a fluorine-containing organic compound or a silicon compound as the reactive gas.

  Further, these metal oxide layers (metal oxide nitride layers) using organometallic compounds, metal hydrides, and metal halides containing Ti, Zr, In, Sn, Zn, Ge, Si or other metals. Or a metal nitride layer or the like, and these layers may be a middle refractive index layer or a high refractive index layer of the antireflection layer, or may be a conductive layer or an antistatic layer.

  Further, the antifouling layer and the low refractive index layer can be formed with a fluorine-containing organic compound, and the gas barrier layer and the low refractive index layer can be formed with a silicon compound. The present invention is particularly preferably used for forming an antireflection layer formed by alternately laminating high, medium refractive index layers and low refractive index layers.

  The film thickness of the formed metal oxide layer is preferably in the range of 1 nm to 1000 nm.

  In the atmospheric pressure plasma treatment, a fluorine compound-containing layer can be formed by using a fluorine-containing organic compound as a source gas.

  As the fluorine-containing organic compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like is preferable.

Specifically, as the fluorine-containing organic compound, for example, a fluorocarbon compound such as carbon tetrafluoride, carbon hexafluoride, tetrafluoroethylene, hexafluoropropylene, and octafluorocyclobutane;
Fluorinated hydrocarbon compounds such as difluoromethane, tetrafluoroethane, propylene tetrafluoride, propylene trifluoride, and cyclobutane octafluoride;
Further, halides of fluorinated hydrocarbon compounds such as trichloromethane trichloride, dichloromethane monofluoride, cyclobutane dichloride, and fluorine-substituted products of organic compounds such as alcohols, acids, and ketones. Can do.

  These may be used alone or in combination. Examples of the fluorinated hydrocarbon gas include gases such as methane difluoride, ethane tetrafluoride, propylene tetrafluoride, and propylene trifluoride.

  Furthermore, it is possible to use halides of fluorinated hydrocarbon compounds such as trichloromethane trichloride, monochlorodifluoride methane, and cyclobutane dichloride tetrafluoride, and fluorine-substituted products of organic compounds such as alcohols, acids, and ketones. However, the present invention is not limited to these.

  Moreover, these compounds may have an ethylenically unsaturated group in the molecule. In addition, the above compounds may be used as a mixture.

  When a fluorine-containing organic compound is used as the reactive gas, the content of the fluorine-containing organic compound as the reactive gas in the reactive gas is from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment. It is preferable that it is 01-10 volume%, More preferably, it is 0.1-5 volume%.

  Further, when the fluorine-containing organic compound that is preferably used is a gas at normal temperature and pressure, it can be used as it is as a component of the reactive gas.

  Further, when the fluorine-containing organic compound is liquid or solid at normal temperature and pressure, it may be vaporized by vaporization means, for example, by heating, decompression, etc., or may be dissolved in an appropriate organic solvent. .

  Examples of silicon compounds useful as reactive gases include organometallic compounds such as dimethylsilane and tetramethylsilane, metal hydrides such as monosilane and disilane, metal halogens such as silane dichloride, silane trichloride, and silicon tetrafluoride. It is preferable to use a compound, an alkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, or the like, but is not limited thereto.

  Moreover, these can be used in combination as appropriate. Alternatively, another organic compound can be added to change or control the physical properties of the film.

  When a silicon compound is used as the reactive gas, the content of the silicon compound as the reactive gas in the reactive gas is 0.01 to 10 volumes from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment. %, Preferably 0.1 to 5% by volume.

  Although it does not specifically limit as an organometallic compound useful as a reactive gas, Al, As, Au, B, Bi, Sb, Ca, Cd, Cr, Co, Cu, Fe, Ga, Ge, Hg, In, Li Preferable organic metal compounds for forming metal compounds such as Mg, Mn, Mo, Na, Ni, Pb, Pt, Rh, Se, Si, Sn, Ti, Zr, Y, V, W, and Zn Can do.

  For example, in order to form a high refractive index layer of the antireflection layer, a titanium compound is preferable. Specifically, for example, an organic amino metal compound such as tetradimethylamino titanium, a metal hydrogen compound such as monotitanium and dititanium, Examples thereof include metal halogen compounds such as titanium chloride, titanium trichloride, and titanium tetrachloride, and metal alkoxides such as tetraethoxy titanium, tetraisopropoxy titanium, and tetrabutoxy titanium.

  The above silicon compounds and organometallic compounds are preferably metal hydrides and metal alkoxides from the viewpoint of handling, and are preferably used since metal alkoxides are not corrosive, do not generate harmful gases, and have little contamination in the process. It is done.

  When using an organometallic compound as the reactive gas, from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment, the content of the organometallic compound as the reactive gas in the reactive gas is 0.01 to Although it is preferable that it is 10 volume%, More preferably, it is 0.1-5 volume%.

  Further, in order to introduce a metal compound such as a silicon compound or a titanium compound into the discharge part, both can be used in a gas, liquid or solid state at normal temperature and pressure.

  In the case of gas, it can be introduced into the discharge part as it is, but in the case of liquid or solid, it can be used after being vaporized by vaporizing means such as heating, depressurization or ultrasonic irradiation.

  When metal compounds such as silicon compounds and titanium compounds are vaporized by heating, metal alkoxides that are liquid at room temperature and have a boiling point of 200 ° C. or less, such as tetraethoxysilane and tetraisopropoxytitanium, are used in the present invention. It is suitable for a method for forming a metal oxide thin film layer. The metal alkoxide may be used after diluted with an organic solvent. As the organic solvent, an organic solvent such as methanol, ethanol, n-hexane, or a mixed organic solvent thereof can be used.

  Furthermore, physical properties such as hardness and density of the thin film layer can be obtained by adding 0.1 to 10% by volume of oxygen, hydrogen, carbon dioxide, carbon monoxide, nitrogen, nitrogen dioxide, nitrogen monoxide, water, etc. in the reaction gas. Can be controlled.

  By the above method, an amorphous metal oxide layer such as silicon oxide or titanium oxide can be preferably produced.

  The cellulose ester film provided with the cured resin layer of the present invention is preferably used for, for example, an optical film having an antireflection layer obtained by laminating a low refractive index layer and a high refractive index layer, a conductive layer, an optical film having an antistatic layer, or the like. Can do.

  In the present invention, by providing a plurality of plasma discharge devices, a multilayer thin film can be continuously provided, and a multilayer laminate can be formed without unevenness of the thin film.

  For example, when producing an antireflection film having an antireflection layer on a cellulose ester film provided with the cured resin layer of the present invention, a high refractive index layer having a refractive index of 1.6 to 2.3 and a refractive index of 1.3 to A low refractive index layer of 1.5 can be continuously laminated on the surface of the cellulose ester film to produce efficiently.

  As the low refractive index layer, a fluorine-containing compound layer formed by plasma discharge treatment using a gas containing a fluorine-containing organic compound, or silicon oxide mainly formed by plasma discharge treatment using an organosilicon compound such as alkoxysilane is used. The high refractive index layer is preferably a metal oxide layer formed by plasma discharge treatment with a gas containing an organometallic compound, such as a layer having titanium oxide or zirconium oxide.

  Although there are thinning methods described above, the present invention is not limited to these methods, and the layer structure is not limited thereto. For example, an antifouling layer may be provided on the outermost surface by plasma discharge treatment in the presence of a fluorine-containing organic compound gas in the presence of atmospheric pressure or in the vicinity thereof.

  According to the above method, in the present invention, a multilayer thin film can be laminated, and a uniform antireflection film can be obtained without film thickness unevenness of each layer.

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

  The polarizing plate can be produced by a general method. A completely saponified polyvinyl alcohol aqueous solution is formed on at least one surface of a polarizing film prepared by immersing and stretching a hard coat film having an alkali saponification treatment on the back side of the cellulose ester film provided with the cured resin layer of the present invention in iodine solution It is preferable to stick together. The film may be used on the other surface, or another polarizing plate protective film may be used. The polarizing plate protective film used on the other surface of the optical film of the present invention preferably has an in-plane retardation Ro of 590 nm, a phase difference of 20 to 70 nm, and Rt of 100 to 400 nm. . These can be produced, for example, by the methods described in JP-A-2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the hard coat film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  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 optical 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.

  A conventional polarizing plate using a hard coat film is inferior in flatness, and when the reflected image is seen, fine wavy unevenness is recognized. According to a durability test at 60 ° C. and 90% RH, the wavy unevenness is observed. In contrast, the polarizing plate using the hard coat film of the present invention was excellent in flatness. Further, even in the durability test under the conditions of 60 ° C. and 90% RH, the wavy unevenness did not increase.

<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 optical film of the present invention is preferably used in reflective, transmissive, transflective LCDs, or LCDs of various drive systems such as TN, STN, OCB, HAN, VA, and IPS. In addition, the antireflection film in which the antireflection layer is formed on the optical film of the present invention has remarkably little color unevenness of the reflected light of the antireflection layer, and is excellent in flatness, plasma display, field emission display, organic EL display, inorganic It is also preferably used for various display devices such as EL displays and electronic paper. Especially in a large-screen display device with a 30-inch screen or more, a reflection image of a fluorescent lamp that appears to be distorted due to uneven color or undulation is not distorted like the reflection of a mirror. But there was an effect that eyes were not tired.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.

Example 1
<< Production of cellulose ester film >>
As shown below, dopes A1 to A6 were respectively prepared, and then cellulose ester films 1 to 9 described in Table 1 were prepared using each dope.

[Preparation of dope]
[Preparation of dope A1: cooling and dissolution]
The following materials were put into a sealed container, stirred at 30 ° C. for 20 minutes, and then the mixture was cooled to −75 ° C. (cooling rate: −2 ° C./min), and then heated to 45 ° C. to form a transparent dope. Obtained. The silicon dioxide fine particle dispersion shown below was added to this dope, mixed uniformly again, and subjected to a defoaming operation, and then the solution was added to Azumi Filter Paper No. Filtered twice using 244 to prepare Dope A1.

(Composition of dope A1)
Cellulose ester (cellulose acetate: acetyl substitution degree 2.8) 100 kg
350 kg of methyl acetate
100 kg of ethanol
Additive A (mixture) 11.5 kg
Silicon dioxide fine particle dispersion 15 kg
<Composition of silicon dioxide fine particle dispersion 1>
Silicon dioxide fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 0.3kg
1kg of ethanol
Methyl acetate 3.7kg
<Composition of additive A>
TPP (triphenyl phosphate) 8kg
BDP (biphenyl diphenyl phosphate) 3kg
E-4 0.5kg
[Preparation of dopes A2 to A4: cooling dissolution]
In the preparation of the dope A1, dopes A2 to A4 were obtained in the same manner except that the cellulose ester, additives, dissolution method, solvent, residual chlorine solvent amount and the like were changed as shown in Table 1.

  The details of each additive solution used for producing the dopes A2 to A4 are as follows.

<Composition of additive B>
EPEG (ethyl phthalyl ethyl glycolate) 5kg
E-3 5kg
E-4 1kg
<Composition of additive C>
EPEG (ethyl phthalyl ethyl glycolate) 5kg
E-3 5kg
E-1 1kg
<Composition of additive D>
TPP (triphenyl phosphate) 10kg
BDP (biphenyl diphenyl phosphate) 3kg
E-2 1kg
Moreover, the detail of the raw material which comprises the composition of each additive is shown below.

E-1: Tinuvin 171 (Ciba Specialty Chemicals Co., Ltd.)
E-2: Tinuvin 326 (Ciba Specialty Chemicals Co., Ltd.)
E-3: Trimethylolpropane tribenzoate

[Preparation of dope A5: room temperature dissolution]
The following materials were put into a sealed container, stirred at 30 ° C. for 20 minutes, then heated and completely dissolved while stirring.

  The dope is allowed to stand and the temperature is lowered to 30 ° C., 5 kg of the above-mentioned silicon dioxide fine particle dispersion is added thereto, mixed uniformly again, and subjected to defoaming operation. No. Filtered twice using 244 to prepare dope A5.

(Composition of dope A5)
Cellulose ester (cellulose acetate propionate acetyl group substitution degree 1.9
Propionyl substitution degree 0.7) 100kg
350 kg of methyl acetate
100 kg of ethanol
Additive A (mixture) 11.51 kg
Silicon dioxide fine particle dispersion 1 (supra) 5kg
[Preparation of dope A6: room temperature dissolution]
The following materials were put into a sealed container, stirred at 30 ° C. for 20 minutes, then heated and completely dissolved while stirring.

  The dope is allowed to stand and the temperature is lowered to 30 ° C., 5 kg of the above-mentioned silicon dioxide fine particle dispersion is added thereto, mixed uniformly again, and subjected to defoaming operation, and then the solution is Azumi filter paper manufactured by Azumi Filter Paper Co., Ltd. No. Filtered twice using 244 to prepare dope A6.

(Composition of dope A6)
Cellulose ester (acetyl group substitution degree 2.8) 100 kg
400 kg of methylene chloride
40 kg of ethanol
Additive D (mixture) 14 kg
[Production of Cellulose Ester Film 1]
The dope A1 was cast on a stainless steel support having a surface temperature of 45 ° C. The film was dried with a drying air of 60 ° C., and after 60 seconds of casting, the film was peeled from the stainless steel support cooled to 10 ° C. The peeled film was stretched 1.1 times and 1.05 times in the transverse direction (TD) and longitudinal direction (MD) with a tenter, dried at 100 ° C., and gripped when the amount of residual chlorine solvent was 3%. The film was released and dried in a drying zone at 130 ° C. while being conveyed by a large number of rolls, and knurling was performed on both ends of the film with a width of 10 mm and a height of 7 μm to produce a cellulose ester film 1 having a thickness of 40 μm. The film width was 1.5 m and the winding length was 3000 m.

[Production of Cellulose Ester Films 2-9]
In producing the cellulose ester film 1, cellulose ester films 2 to 9 were produced in the same manner except that the dope shown in Table 1 was used instead of the dope A1.

  The residual chlorine solvent amount shown in Table 1 was measured according to the following method.

  The residual amount of the chlorinated solvent was determined by gas chromatography connected to a headspace sampler as described below.

  Specifically, each collected cellulose ester film is put into a vial, and heat treatment is performed at 110 ° C. for 3 hours to collect volatile components, and then the chlorine-based volatile components are analyzed by gas chromatography. The amount of solvent was determined.

  Here, the amount of chlorine-based solvent in the volatile component was defined as ag, the mass after the heat treatment of the cellulose ester film was defined as bg, and the residual amount of the chlorine-based solvent was determined by the following equation.

Chlorinated solvent residual amount (% by mass) = (a / b) × 100 (%)
The measurement conditions for gas chromatography are as follows.

  Gas chromatography 5890 type SERISII manufactured by Hewlett-Packard Company and headspace sampler HP7694 type were used, and the measurement was performed under the following measurement conditions.

Headspace sampler heating conditions: 120 ° C, 20 minutes GC introduction temperature: 150 ° C
Temperature rise: 40 ° C, hold for 5 minutes → 100 ° C (8 ° C / min)
Column: J-W DB-WAX (inner diameter 0.32 mm, length 30 m)
"Coating of tree fat layer"
The surface of the cellulose ester film 1 was hydrophilized by alkali saponification. That is, after 1 minute in 1 mol / L sodium hydroxide 50 ° C., neutralization, the cellulose ester film was alkali-saponified and washed with water, micro gravure coating liquid for the lower Bark fat layer (ultraviolet curing resin layer) applied using a coater, after drying at 90 ° C., using a UV lamp to cure the coated layer at dose 0.1 J / cm ^2, to form a tree fat layer with a thickness of 6 [mu] m, hard invention Coat film 1 was obtained.

<Tree fat layer coating solution>
Polymerizable compound: Exemplified compound A3-1 35 parts by weight Photopolymerization initiator: The following compound 2 parts by weight Water 40 parts by weight Trietheramine was added as appropriate to adjust the pH to 8.5. The coating solutions were prepared trees fat layer coating solution was filtered through a polypropylene filter having a pore size of 0.4 .mu.m.

Furthermore, in preparation of the said hard coat film, except changing the solvent composition (water and organic-solvent composition) of a resin layer coating liquid and a cellulose-ester film as shown in Table 2, hard coat films 2-21 Was made.

<< Evaluation of hard coat film >>
About each hard coat film produced as mentioned above, flatness index | exponent, flatness: visual observation, adhesiveness, and long-term storage property were evaluated on condition of the following.

  First, a method for evaluating a sample manufactured according to the present invention will be described.

[Flatness index: Evaluation of minute irregularities]
Laser displacement meter: Keyence Co., Ltd., Model: LT-8100, Resolution: 0.2 μm, Scan with a laser displacement meter in the width direction, measure fine undulations on the surface, and flatness of the optical film evaluated.

  The measuring method is that the film is placed on a flat and horizontal table, both ends of the width are fixed to the table with tape, and the measuring camera is set in parallel with the table on a moving rail made by Sigma Kogyo Co., Ltd. The sample film was set to have a distance of 25 mm, scanned at a moving speed of 5 cm / min, measured, and the obtained values were ranked according to the following criteria. The value obtained by the measurement is the state and size of minute irregularities on the film surface.

A: Unevenness due to film deformation is less than 0.5 μm ○: Unevenness due to film deformation is less than 0.5 to 1.0 μm Δ: Unevenness due to film deformation is less than 1.0 to 3.0 μm ×: Due to film deformation Concavity and convexity are 3.0 μm or more
Cut each sample into a size of 90cm in width and 100cm in length, and arrange five 50W fluorescent lamps at a height of 1.5m so that the sample stage can be illuminated from a 45 ° angle. Each film sample was placed, the irregularities that appeared to be reflected on the optical film surface were visually observed, and the flatness was visually evaluated according to the following criteria. By this method, it is possible to determine “tsun” and “wrinkle”.

◎: All five fluorescent lamps look straight ○: Some fluorescent lamps appear to be bent slightly △: Fluorescent lamps appear to be slightly bent overall ×: Fluorescent lamps appear to swell greatly [Evaluation of adhesion]
A cross-cut test based on JIS K 5400 was performed. Vertical In specific 1mm intervals tree fat layer coated surface on the horizontal put eleven cuts were made 100 pieces of cross-cut of 1mm square. A cellophane tape was affixed on this, peeled off quickly at an angle of 90 degrees, and the state of the grids remaining without peeling was visually observed, and the adhesion was evaluated according to the following criteria.

◎: Peeling is hardly observed and adhesion is very good. ○: Slight peeling is observed but adhesion is good. Δ: Slight peeling is observed, but there is no practical problem. Peeling is noticeable and has practical problems [Evaluation of long-term storage]
The optical film wound up in a roll is covered with a polyethylene sheet to prevent dust adhesion, and is stored as it is for one month in a warehouse at 40 ° C. and 70 to 80% RH. The flatness of the film after long-term storage was evaluated.

  The results obtained as described above are shown in Table 3.

As is clear from the results in Table 3, the films 1 to 4, 6 to 9, 11 to 16, and 20 of the present invention are on the cellulose ester film substrate in which the residual amount of the chlorinated solvent is less than 0.01% by mass. In addition, by forming a resin layer with a resin layer coating composition containing 30% by mass or more of water with respect to the total amount of solvent, each characteristic is compared with Comparative Examples Films 5, 10, 17 to 19, 21 It turns out that it is excellent.

Example 2
Using cellulose ester film 1 produced in Example 1, prior to applying the tree fat layer performs corona discharge treatment or ultraviolet irradiation treatment to the cellulose ester film under the following conditions, by coating the tree fat layer. The coating compositions of the tree fat layer solvent composition using the resin layer coating composition was changed as shown in Table 4, to prepare a hard coat film 22-27.

Corona discharge treatment: The cellulose ester film was treated using a corona discharge treatment apparatus described in JP-A-10-296856 under the condition of 8 W / m ² · min.

Ultraviolet irradiation treatment: The cellulose ester film was irradiated with a low-pressure mercury lamp for 30 seconds and treated with a light amount of 300 mJ / cm ² .

  Adhesiveness was evaluated according to the method described in Example 1 for the obtained hard coat films 22 to 27, and the results obtained are shown in Table 4.

  As is apparent from the results in Table 4, it can be seen that the adhesion between the hard coat film and the substrate is further improved by performing the surface activation treatment.

Example 3
<< Preparation of antireflection film >>
An antireflection layer was formed on the hard coat films 1 to 27 produced above.

  The following medium refractive index layer coating solution is applied onto the hard coat films 1 to 27 using a wire bar coater, dried at 70 ° C., and then irradiated with ultraviolet rays to cure the coating layer, and the medium refractive index layer. (Refractive index 1.72 and film thickness 80 nm) was formed. On top of that, the following coating solution for a high refractive index layer was applied using a wire bar coater, dried at 70 ° C., then irradiated with ultraviolet rays to cure the coating layer, and a high refractive index layer (refractive index 1.9). , A film thickness of 70 nm) was formed. Furthermore, the following coating solution for a low refractive index layer is applied using a wire bar coater, dried at 70 ° C., and cured by heat treatment to form a low refractive index layer (refractive index 1.45, film thickness 95 nm). An antireflection film 1 to 27 having a visible light reflectance of 0.5% or less was formed.

(Preparation of medium refractive index layer / high refractive index layer / low refractive index layer)
<Preparation of titanium dioxide dispersion>
Titanium dioxide (primary particle mass average particle size: 50 nm, refractive index: 2.70) 30 parts by mass, anionic diacrylate monomer (PM21, manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass, cationic methacrylate monomer ( DMAEA (manufactured by Kojin Co., Ltd.) 0.3 parts by mass and methyl ethyl ketone 65.2 parts by mass were dispersed by a sand grinder to prepare a titanium dioxide dispersion.

<Preparation of coating solution for middle refractive index layer>
In 151.9 g of cyclohexanone and 37.0 g of methyl ethyl ketone, 0.14 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.04 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved. Further, 6.1 g of the above titanium dioxide dispersion and 2.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer. When this coating solution was applied to a cellulose ester film and dried and the refractive index after UV curing was measured, a medium refractive index layer having a refractive index of 1.72 was obtained.

<Preparation of coating solution for high refractive index layer>
In 1152.8 g of cyclohexanone and 37.2 g of methyl ethyl ketone, 0.06 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.02 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved. Furthermore, the ratio of the above titanium dioxide dispersion and the titanium dioxide dispersion of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) is increased, and the refractive index of the high refractive index layer is increased. The amount was adjusted so as to be a ratio, and the mixture was stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer. When this coating solution was applied to a cellulose ester film, dried and the refractive index after UV curing was measured, a high refractive index layer having a refractive index of 1.9 was obtained.

<Preparation of coating solution for low refractive index layer>
200 g of methanol dispersion of silica fine particles with an average particle size of 15 nm (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.), 3 g of silane coupling agent (KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 g of 0.1 mol / L hydrochloric acid After stirring at room temperature for 5 hours, the mixture was allowed to stand at room temperature for 3 days to prepare a dispersion of silica fine particles treated with silane coupling. To 35.04 g of the dispersion, 58.35 g of isopropyl alcohol and 39.34 g of diacetone alcohol were added. Further, 1.02 g of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.51 g of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 772.85 g of isopropyl alcohol were added. Furthermore, 25.6 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was added and dissolved. 67.23 g of the resulting solution was added to the above dispersion, a mixture of isopropyl alcohol and diacetone alcohol. The mixture was stirred for 20 minutes at room temperature and filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a low refractive index layer. When this coating solution was applied to a cellulose ester film and dried, and the refractive index after UV curing was measured, the refractive index was 1.45.

<Production of polarizing plate>
Polarizers 1 to 27 were prepared according to the following procedure using each of the prepared antireflection films.

  A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Subsequently, according to the following processes 1-5, the polarizing film, each antireflection film, and the cellulose ester film of the back side were bonded together, and the polarizing plate was produced. As the polarizing plate protective film on the back surface side, a cellulose ester film having a retardation (measured at 590 nm, in-plane retardation Ro = 43 nm, retardation in the thickness direction Rt = 135 nm) was used as a polarizing plate.

  Step 1: Soaked in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizer.

  On the other hand, the surface of the anti-reflection layer side of the hard coat film on which the anti-reflection layer was formed was subjected to the saponification treatment while applying a peelable polyethylene film and protecting it from alkali.

  Step 2: The 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: Gently wipe off the excess adhesive adhering to the polarizing film in Step 2 and place it on the cellulose ester film treated in Step 1, so that the antireflection layer of the hard coat film is on the outside Laminated and placed.

Step 4: Excess adhesive and bubbles were removed from the end of the laminate of the antireflection film, the polarizing film, and the cellulose ester film sample laminated in Step 3 with a hand roller and bonded together. The pressure of the hand roller was 20 to 30 N / cm ² and the roller speed was about 2 m / min.

  Process 5: The sample which bonded the polarizing film produced in the process 4, the cellulose-ester film, and the antireflection film in the 80 degreeC dryer was dried for 2 minutes, and the polarizing plate was produced. Polarizing plates 1 to 27 were prepared using antireflection films 1 to 27, respectively.

(Production of liquid crystal display device)
A liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plates on both sides of the 15-inch display VL-150SD manufactured by Fujitsu were previously peeled off, and the produced polarizing plates 1 to 22 were each stuck to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices 1 to 27 were respectively produced.

[Evaluation of visibility]
Each liquid crystal display device thus obtained was allowed to stand for 100 hours under conditions of 60 ° C. and 90% RH, then returned to 23 ° C. and 55% RH, and visibility was evaluated according to the following method.

  For the evaluation of visibility, the liquid crystal panel (liquid crystal display device) was visually observed, and the visibility in the oblique direction was evaluated according to the following criteria.

◎: Reflection image has no color irregularity, black appears to be clear and clear, and no white spots in the image are observed ○: Reflection image has no color irregularity, black appears to be crisp and clear, but slightly △: Some uneven color in the reflected image is observed, little black color is observed, the sharpness is slightly low, and there is white defect in the image ×: The color unevenness in the reflected image is remarkable, There are no black spots, the sharpness is low, and the white spots of the image are worrisome. In the present invention, ◯ and ◎ are practical.

  Table 5 shows the results obtained as described above.

  As is clear from the results in Table 5, it can be seen that the liquid crystal display device using the optical film of the present invention is superior in visibility to the comparative example.

  Separately, the viewing angle was measured in each liquid crystal display device by EZ-contrast manufactured by ELDIM. The viewing angle was expressed in the range of the tilt angle from the normal direction with respect to the panel surface where the contrast ratio at the time of white display and black display of the liquid crystal cell is 10 or more. As a result, it was confirmed that the liquid crystal display device of the present invention incorporating the polarizing plate produced using the optical film of the present invention has a viewing angle of 160 ° or more when measured from an oblique 45 ° direction. Moreover, even if there was a reflection of a fluorescent lamp from an oblique direction, the black color appeared to appear, there was no uneven color of the reflected light, and the eyes did not get tired. On the other hand, in the comparative liquid crystal display devices 5, 10, 17 to 19, and 21, black from an oblique direction does not appear due to fine wavy unevenness, and color unevenness is recognized in the reflected image in the antireflection layer. In addition, the visibility was inferior, and the effect of improving visibility by expanding the viewing angle had declined.

It is a figure which shows an example of the plasma discharge processing apparatus used in order to form the surface treatment or metal oxide layer which concerns on this invention. It is a figure which shows an example of the plasma discharge processing apparatus which has a rotating electrode useful for forming the surface treatment or metal oxide thin film layer concerning this invention, and a fixed electrode.

Explanation of symbols

F Optical film G Reaction gas G 'Exhaust gas 10A, 10B, 110 Rotating electrode 11A, 11B, 11C, 11D U-turn roll 20, 21 Guide roll 30 Reactive gas supply unit 40, 140 Gas exhaust port 50, 150 Discharge unit 51 Rectifier plate 80, 180 Power supply 81, 82, 181, 182 Voltage supply means 111 Fixed electrode 120, 121 Guide roll 122, 123 Nip roll 124, 125 Partition plate 130 Air supply pipe 131 Reactive gas generator 190 Plasma discharge treatment vessel

Claims (5)

A coating composition comprising at least a resin and a solvent composed of water and an organic solvent, having a solid content of 10 to 70% by mass and a water content of 30% by mass or more in the solvent. The film layer is applied to a cellulose ester film substrate that is biaxially stretched after film formation and has a residual amount of chlorinated solvent of less than 0.01% by mass, and is further cured by actinic radiation to form a resin layer. A method for producing an optical film, comprising: providing an optical film . 2. The method for producing an optical film according to claim 1, wherein a cellulose ester solution containing substantially no chlorinated solvent is used in carrying out the solution casting film forming method . Before SL cellulose ester film base, method for producing an optical film according to claim 1, characterized in that the film formed as a film by solution casting with cellulose ester solution prepared in cooling dissolution method. The said cellulose-ester film base material is surface-modified before apply | coating the said coating composition, The manufacturing method of the optical film of any one of Claims 1-3 characterized by the above-mentioned . Before Symbol surface modification treatment, corona discharge treatment, ultraviolet irradiation treatment, a manufacturing method of an optical film according to claim 4, wherein the plasma discharge treatment, or an alkali saponification treatment.

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