JP4861710B2 - Manufacturing method of optical film, optical film, polarizing plate, and image display device - Google Patents

Description

  The present invention relates to an optical film manufacturing method, an optical film produced by the manufacturing method, a polarizing plate, and an image display device using these. More specifically, in an optical film obtained by coating an optical functional layer on a film substrate, there is little unevenness in drying, high-speed coating is possible, and a method for producing an optical film having high productivity, and the method. The present invention relates to the produced optical film, a polarizing plate, and an image display device using these.

  Optical functional films are generally applied to image display devices such as cathode ray tube display devices (CRT), plasma displays (PDP), electroluminescence displays (ELD), and liquid crystal display devices (LCD). . Examples of such an optical film include an optical compensation film, an antireflection film, an antiglare film, a surface protective film, and a polarizing plate.

  Since these optical films are used in an image display device that is directly visually observed, the film unevenness of the film is required to have a very strict quality of a low level that is hardly recognized visually. Furthermore, since a large-area film is used due to an increase in the screen size of the display, an optical film having a large area and no unevenness is required.

As a method for producing such an optical film, a method in which an optical functional layer is continuously applied to a film-like substrate is suitable in order to satisfy the above-mentioned required characteristics and to impart high productivity (patent) Reference 1). In particular, it is often performed by a drying method in which a solution containing a volatile solvent is applied and the volatile solvent in the optical function layer is volatilized and removed. In such a method of forming a coating layer by solution coating, unevenness often occurs due to coating and drying. In particular, when the coating layer is an optical functional layer, unevenness due to coating / drying directly changes the optical characteristics, so that a minute change in the dry state and a minute difference in film thickness are conspicuous as film unevenness. For this reason, the layer formation method which suppresses application | coating and drying nonuniformity, and the film with few application | coating and dry nonuniformity are desired.
Among these, for drying unevenness, after the coating layer is formed, the surface of the coating layer is sealed with a gas layer, and drying is performed while suppressing the drying air speed (Patent Document 2). There are known ways to keep the wind down.

JP-A-9-73081 JP-A-9-73016

  In optical film production, if a drying method that covers the surface of the coating layer and suppresses the wind is applied to suppress drying unevenness, drying of the volatile solvent is delayed, which is a major obstacle to high-speed coating to increase productivity. Become. Further, in order to prevent the occurrence of uneven coating during high speed coating, it is desirable to dilute the coating liquid to lower the viscosity, but this further tends to worsen the drying unevenness. Therefore, in order to achieve high-speed coating, a production method that can provide high surface quality with little drying unevenness and at the same time high-speed drying is desired.

The present invention has been made on the basis of the above-mentioned demands. Therefore, an object of the present invention is to provide a method for producing an optical film that can be dried at high speed, has no drying unevenness, and has excellent productivity. .
Another object of the present invention is to provide an optical film of excellent surface quality with high production efficiency and less unevenness by the manufacturing method.

  As a result of studying a method of drying at high speed without drying unevenness, the present inventor has controlled drying volatility and high-speed drying properties by controlling the volatility of volatile components in the coating liquid with respect to the air to be dried to a specific range. It has been found that both can be achieved. That is, the ratio R of the saturated vapor pressure (p) and atmospheric pressure (P) of the volatile solvent to the air to be dried is used as an index of the drying ability of the air. I found out that both sexes can be achieved. Furthermore, it has been found that by controlling the volatile solvent concentration (V) during the actual drying within a certain range with respect to R, drying unevenness can be particularly suppressed and high-speed drying can be achieved. Based on the result, the object of the present invention could be achieved by the optical film having the following constitution and the method for forming the optical film.

1. Optical having a coating step of coating a coating liquid containing at least one volatile component on a film substrate, and a drying step of volatilizing and removing volatile components from the coated coating liquid layer in the air the method of manufacturing a film, the saturated vapor pressure of the volatile solvent in the temperature of the drying step (p), the ratio R (= p / P) and the atmospheric pressure (P), and 0.05-1.5 ,
In the drying step, drying is performed at a ratio V / R of the volatile component volume fraction (V) of the coating solution in the vicinity of the coating film surface to R of 0.05 to 0.9. A method for producing a film.
2. 2. The method for producing an optical film as described in 1 above, wherein in the drying step, the surface of the coating film to be dried is covered with a plate, a wire mesh or a box and dried.
3. 3. The method for producing an optical film as described in 1 or 2 above, wherein the air supplied to the drying step contains a volatile component in the range of 1 to 50% of V.
4). The optical volume as described in any one of 1 to 3 above, wherein the volume fraction of volatile components other than the coating solution component contained in the air supplied to the drying step is 0.05 or less of the air A method for producing a film.
5. 5. The method for producing an optical film as described in any one of 1 to 4 above, wherein the volatile component comprises at least one selected from ketones, esters and alcohols.
6). 6. The method for producing an optical film as described in any one of 1 to 5 above, wherein an average drying rate of the volatile component in the drying step is 0.1 g / (m ² coating film) or more per ^second. .

7). An optical film produced by the method according to any one of 1 to 6 above.
8). 8. The optical film as described in 7 above, wherein the coating liquid contains a discotic compound.
9. 8. The optical film as described in 7 above, wherein the coating liquid contains translucent particles.
10. 10. The optical film as described in 9 above, wherein the layer coated with the coating solution is an antiglare layer.
11. 11. The optical film as described in any one of 7 to 10 above, which has an antireflection layer as an uppermost layer, and the antireflection layer is a low refractive index layer having a refractive index of 1.31 to 1.45.
1 2. A polarizing plate, wherein the protective film on at least one side of the polarizing film is the optical film described in any one of 7 to 11 above.
13. An image display device comprising at least one of the optical film described in 7 to 11 or the polarizing plate described in 12 above.
Although this invention is invention which concerns on said 1-13, hereafter, other matters are also described.

  According to the present invention, there is provided an optical film manufacturing method capable of manufacturing a high-quality optical film at a low cost with few coating failures such as drying unevenness. In addition, this manufacturing method provides an optical compensation film, an antireflection film, an antiglare film, a hard coat film, and other optical films having various functionalities that have little drying unevenness and excellent productivity. Furthermore, an image display device with excellent image quality can be manufactured using these optical films and polarizing plates using the optical films.

  Hereinafter, embodiments of the optical film according to the present invention will be described. In the present specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.

  The present invention can be widely used as a method for producing an optical film. Examples of the optical film include an optical compensation film, an antireflection film, an antiglare film, an antiglare antireflection film, a light diffusion film, a surface protective film, and a polarizing film. In particular, the production method of the present invention is suitable for an optical film used in an image display device. That is, in the present invention, a functional layer is provided by coating on a base film, and unevenness is suppressed with respect to an optical film imparting functions such as antireflection, antiglare, light scattering, surface hardness, and optical compensation. Excellent productivity is exhibited and it is preferably used. In these coating layers, a change in optical properties is often caused by a minute change in film thickness or a density change in contained particles, and unevenness is often easily seen visually. Further, since these films are used in an image display device and are directly observed through transmission and reflection, extremely strict quality is required against unevenness. The effect of the present invention is great for the optical film as described above.

[Coating liquid coating process and drying process]
Next, the coating liquid coating process and the drying process in the present invention will be described.
In the present invention, a coating liquid containing a volatile component is applied to a film-like substrate. The coating liquid containing the volatile component contains a component that forms a layer having characteristics such as an optical functional layer and a physical functional layer. In addition, before apply | coating this functional layer, another layer may be apply | coated and various surface treatments may be performed to the film surface.

The coating liquid used in the present invention needs to contain a volatile component. The volatile component is contained as a solvent that dissolves, disperses, and mixes the components contained in the coating solution and adjusts the viscosity, surface tension, and the like so that the properties of the solution are suitable for coating. Volatile components include common organic solvents (hydrocarbons, alcohols, ketones, esters, etc.), halogenated hydrocarbons (solvents containing chlorine, bromine, fluorine, etc.), and inorganic solvents such as water. It is done.
In addition, although the volatile component in this invention evaporates in the temperature which implements drying, shows the thing in which the content in a coating film reduces, The vapor pressure in the temperature to dry is about 1/1000 or more of atmospheric pressure Can be. As the volatile solvent in the present invention, those having a boiling point of 200 ° C. or less are preferable. In addition to the above volatile components, the optical functional layer of the present invention generally contains a non-volatile component for imparting functionality as described later. The sex component preferably has a vapor pressure at a drying temperature of less than about 1/1000 of the atmospheric pressure.

  Specific examples of the volatile solvent as described above include low-boiling solvents having a boiling point of 100 ° C. or lower, such as hexane (boiling point 68.7 ° C .: hereinafter omitted), heptane (98.4), cyclohexane ( 80.7), hydrocarbons such as benzene (80.1), dichloromethane (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5) Halogenated hydrocarbons such as trichloroethylene (87.2), ethers such as diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5), tetrahydrofuran (66), formic acid Esters such as ethyl (54.2), methyl acetate (57.8), ethyl acetate (77.1), isopropyl acetate (89), acetone (56.1) , Ketones such as 2-butanone (= methyl ethyl ketone: MEK, 79.6), methanol (64.5), ethanol (78.3), 2-propanol (82.4), 1-propanol (97.2) , Alcohols such as 2-butanol (99.5) and t-butanol (82.5), cyano compounds such as acetonitrile (81.6) and propionitrile (97.4), carbon disulfide (46. 2).

  Examples of the solvent having a boiling point of 100 ° C. or higher include, for example, octane (125.7 ° C., hereinafter “° C.” is omitted), toluene (110.6), xylene (138), tetrachloroethylene (121.2), and chlorobenzene. (131.7), dioxane (101.3), dibutyl ether (142.4), butyl acetate (126), isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (= methyl) Isobutyl ketone: MIBK, 115.9), 2-octanone (173), 1-butanol (117.7), iso-butanol (107.9), propylene glycol monomethyl ether (120), diacetone alcohol (168), N, N-dimethylformamide (153), N, N-dimethylacetamide (16 ), Dimethyl sulfoxide (189), water (100), and the like. However, the volatile solvent of the present invention is not limited to the above.

When using the above solvent in the coating solution, the solubility and reactivity of the components contained in the coating solution, the stability of the added particle components, etc., the solubility / diffusibility in the coating underlayer, and drying A suitable solvent can be selected as appropriate from the viewpoints of drying properties and viscosity adjustment in the process. From these points, ketones, esters, alcohols, hydrocarbons, and halogenated hydrocarbons are suitable. In the case of volatile solvents used for coating, consideration should be given to the safety of the human body, ecosystem, explosion-proof safety, greenhouse effect due to environmental release, ozone depletion, etc. Is required. From this point, it is preferable that the volatile solvent in the present invention in which ketones, esters, and alcohols are suitable is composed of these ketones, esters, and alcohols.
Of these solvents, ketones are particularly preferred. Among these, 2-butanone (MEK), 2-methyl-4-pentanone (MIBK), cyclohexanone and the like are particularly preferable solvents.

  In addition, the composition of the above solvent may be single or mixed, but it is also preferable to use a mixture of several kinds of solvents having different characteristics such as boiling point, solubility, and surface tension. It is particularly preferable to mix a solvent having a high boiling point in terms of imparting solubility of the coating liquid component, imparting dispersion stability, suppressing deterioration of drying unevenness due to rapid drying of the coating liquid, and suppressing increase in water content of the coating liquid.

When coating and drying the above-described coating solution using the volatile solvent of the present invention, it is preferable to control the volatility of the solvent under a condition for performing the drying within an appropriate range. As a measure of the volatility of the solvent in such a case, the vapor pressure of the solvent can be used. That is, as a relationship between the volatile solvent of the present invention and the air temperature condition for carrying out drying, the ratio R (= p) of the vapor pressure (p) of the volatile component at the drying temperature to the atmospheric pressure (P). / P) is preferably dried at a certain range. This R indicates the volume fraction when the volatile solvent is saturated under the drying conditions when R ≦ 1 or less. When R> 1, the saturated vapor pressure becomes larger than the atmospheric pressure, but it can be considered as a virtual saturated volume fraction in which the volatile solvent can volatilize to a volume fraction exceeding 1.
The vapor pressure at each temperature of the volatile component can be known from the Cox diagram showing the relationship between temperature and vapor pressure. That is, an equation relating to the relationship between vapor pressure (p) and temperature (T),
(Formula 1)
Log (p) = ab / (T)
Thus, it is possible to know the vapor pressure at a temperature, which is to obtain constants a and b obtained experimentally by each solvent. Such relationships and typical solvent temperature-vapor pressure relationships are described in general literature such as “Solvent Handbook” (edited by Asahara, Tokura et al., Kodansha Scientific).
In addition, the volatile component of this invention can also be used in mixture of several types. The vapor pressure at this time can be roughly estimated by weighted averaging of the vapor pressure of each component by the component ratio in a system where there is no interaction between solvents. However, some components to be mixed may deviate from a simple weighted average, but this can be obtained by experiments.

In the present invention, the value of R (= p / P) is preferably 0.05 to 1.5. Although the atmospheric pressure P varies depending on the weather or the like, P may be set to one atmospheric pressure (= 101.3 kPa) in drying at a normal atmospheric pressure.
When R is small, the solvent volatilizing ability with respect to the air to be dried is small, and a long drying time is required, which is not suitable for high-speed drying. On the other hand, if R exceeds 1.5, the boiling point of the solvent is greatly exceeded, which causes problems such as boiling of the solvent and drying unevenness due to rapid drying. The range of R is more preferably 0.06 to 1.0, and particularly preferably 0.07 to 0.7.

  In addition, when the drying is performed by volatilizing the solvent under such drying conditions, the solvent drying capacity (solvent saturated volume fraction in the air) indicated by R is calculated based on the saturated volume fraction. By carrying out actual drying with a low solvent volume fraction (V), it is possible to achieve drying that achieves both high speed drying and good drying unevenness. The solvent volume fraction (V) here is the same as the commonly used solvent concentration (volume%), but for comparison with R, the solvent ratio (0 to 1 when the volume of the whole air is 1). Number of ranges). It is desirable that the solvent volume fraction (V) can be measured in the vicinity of the coating surface to be actually dried, but in reality, it is defined by the solvent volume fraction in the range from just above the coating surface to about 5 cm above. can do. This solvent volume fraction can be known by collecting air near the coating surface when actually drying and measuring it by means of a solvent concentration meter, gas chromatography or the like. It can also be obtained by calculation from drying conditions, solvent characteristics, and the like. The solvent volume fraction V in the vicinity of the film surface is preferably in the range of 0.05 to 0.9 with respect to R. When this value is low, non-uniformity of drying properties occurs due to non-uniformity in the solvent volume fraction near the coating film surface, and non-uniform drying tends to occur. Moreover, when it becomes 0.8 or more, the drying promoting effect is small and it is not suitable for high-speed drying. This value is more preferably 0.07 to 0.6, and particularly preferably 0.10 to 0.5.

In order to control the air temperature, wind speed, and solvent concentration during drying as described above, air for drying is supplied and / or exhausted to a portion where a coating film containing a volatile solvent dries. Such a structure is preferable. At this time, in order to control the air supply and exhaust volume of the drying section to be constant, it is particularly preferable to cover the portion where the membrane surface is dried with a plate / box-like one to form a drying zone. . In such a drying zone, in order to rectify the flow of the drying air, it is preferable to cover the coating film surface with a plate or a metal net, or to cover the coating film surface with a box. An example of such a drying process is shown in FIGS. 1a and 1b. However, the present invention is not limited to this.
FIG. 1a is an example of a coating / drying process suitably used in the present invention. In this figure, the film-like support is conveyed from the delivery unit 1 and the coating solution is applied at the two coating units. Between these 1 and 2, you may perform a various process to a film as needed. In the coating film formed on the film at the application part 2, the volatile component is dried in a drying zone indicated by 31 to 36. At this time, air is sent from the air supply ports indicated by 41 to 46 to control the temperature, wind speed, solvent concentration, etc. of the drying zone. 41 to 46 may be exhaust ports, or an air supply port and an exhaust port may be provided. The zones 31 to 36 may be provided immediately after application or may be provided from a point after application for a while. After this drying, if necessary, volatilization of the residual solvent in the coating film or heat treatment zone 5 for performing heat treatment of the film, and 6 for performing active radiation curing such as UV can be performed. Thereafter, the coated film is wound up at 7.
FIG. 1b is another example of the drying process of the present invention. Here, in the drying zones 31 to 36, air can be sent from the air supply ports 41 to 46 in the direction perpendicular to the film surface, and the air hitting the coating film can be made uniform by the wire mesh 8 near the film surface for drying.

  When supplying and exhausting air for drying in this way, the shape of the volume of the drying zone, the structure of the drying chamber, the structure of the air supply and exhaust ports, etc., and the wire mesh on the part where the air blows on the membrane surface It is possible to control the flow of the air in the drying zone, the speed of the air toward the coating surface, and the uniform concentration of the solvent, etc. by means such as installing the air and controlling the amount of air supplied and exhausted. At this time, the wind speed hitting the film surface is not particularly limited as long as the range of the present invention is satisfied, but a range of 0.02 m / s to 2.0 m / s is preferable. More preferably, it is 0.05 m / s-1.5 m / s, Most preferably, it is 0.1-1.2 m / s.

  In carrying out the drying of the present invention, it is also preferable to contain a volatile solvent component in the supplied air in order to make the solvent concentration in the vicinity of the coating film surface as uniform as possible over the entire surface of the coated film. Thereby, the fall of the solvent density | concentration near the air supply opening at the time of drying can be suppressed, and the solvent density | concentration of the whole coating film can be made uniform. The solvent content in the supply air is preferably lower than the actual solvent concentration V on the film surface. A specifically preferable range is 1 to 50%, particularly preferably 1 to 30% of the film surface solvent concentration V.

  In addition, if volatile components other than the volatile solvent component contained in the coating liquid are contained in the air to be dried of the present invention, drying is delayed and causes fluctuations in drying. It is preferable to reduce volatile components. Examples of the volatile component other than the coating liquid component include moisture in the air. Such a volatile component other than the coating liquid component is preferably 5% by volume or less in air, more preferably 3% by volume or less, still more preferably 1% by volume or less, and particularly preferably 0.5% by volume or less.

  The drying of the present invention is preferably applied when the content of volatile components in the coating film is high, the coating film has fluidity, and drying unevenness is likely to occur. The fluidity of the coating film varies depending on the properties of the coating solution, but when the volatile component concentration in the coating film is 0.1 or less, the fluidity hardly occurs. For this reason, it is preferable to apply the drying of this invention in the range whose volatile-component density | concentration in the coating film at the time of drying after application | coating is 0.99-0.1. More preferably, it is 0.98-0.15, Most preferably, it is 0.97-0.2. Further, the drying conditions of the present invention may be applied in a part of the drying time in which the volatile component concentration in the coating film becomes almost non-flowable after coating, and depends on the characteristics of the coating solution. It can select suitably according to the condition of the ease of generating the nonuniformity in drying time. In addition, you may apply conditions other than this invention within the drying time of a coating film. The drying of the present invention is preferably applied for a time of 10% or more of the coating film drying time. It is more preferable to apply to 30% or more time, and it is particularly preferable to apply to 50% or more time.

Moreover, the drying rate of the volatile solvent when the drying process of the present invention is applied is preferably 0.1 g / m ² or more per second on the average of the entire drying process, more preferably 0.3 g / m ^2. Or more, more preferably 0.5 g / m ² or more, and particularly preferably 0.7 g / m ² or more. If this drying speed is high, the drying can be completed without unevenness with a short drying process length, and the coating speed can be increased. The drying speed can be adjusted by the solvent type, the drying air speed, the drying temperature, etc. as described above.

In the above optical film of the present invention, the coating amount of the coating film is preferably 1 ml to 40 ml per 1 m ² , and particularly preferably 2 ml to 25 ml. The coating layer thickness of the optical functional layer is preferably 0.01 μm to 20 μm, and particularly preferably 0.05 μm to 10 μm.

[Process from delivery to application]
The optical film of the present invention is preferably applied in the coating step after continuously feeding the film-like substrate and pre-treating the film as necessary. Examples of the pretreatment of the film before coating include dust removal treatment, charge removal treatment, heat treatment, surface hydrophilization / hydrophobization treatment, alignment film alignment treatment, and the like. In addition, you may perform these processes before using a roll-shaped film in the application | coating process of this invention.
As the dust removal treatment, in order to remove foreign matters on the film, as a dry dust removal method, an adhesive roll, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571, JP-A-10-309553 The method described in Japanese Patent Application Laid-Open No. 7-333613 is used to spray ultrasonically vibrated compressed air as described in JP-A-7-333613. A method (such as New Ultra Cleaner, manufactured by Shinkosha Co., Ltd.) for peeling off and adhering deposits can be raised. In addition, as a wet dust removal method, a film is introduced into a cleaning tank, and a deposit is peeled off by an ultrasonic vibrator, or after a cleaning liquid is supplied to a film as described in Japanese Patent Publication No. 49-13020. , A method of blowing and sucking high-speed air, and a method in which a web is continuously rubbed with a roll wetted with a liquid described in Japanese Patent Application No. 11-215807, and then the liquid is jetted onto the rubbed surface. The method of washing can be used. Of these, methods using an adhesive roll or an ultrasonic dust remover are common.
The neutralization process is performed to increase the efficiency of dust removal and to suppress coating unevenness due to charging. As a charge removal method, a charge removal bar, a charge discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the web before and after dust removal and application is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.
The heat treatment of the film is performed for the purpose of improving the flatness of the base serving as the base material of the coating layer. As a heating method, a method using a heating roll, a method using insertion into a heating zone, and a heating method using an infrared heater or the like can be used.
The surface treatment of the film can be carried out for improving adhesion of the coating layer and wettability during coating. Such surface treatment includes alkali treatment (saponification treatment), chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone. Examples include oxidation treatment.
The alignment treatment of the alignment film is particularly preferably used when an optically anisotropic layer such as a liquid crystal layer is applied to the upper layer. At this time, it is desirable that an alignment film is formed on the film. As the alignment treatment of the alignment film, a rubbing treatment method using a cloth, a non-contact type alignment method such as optical alignment or magnetic alignment, or the like can be used.

[Coating process]
In the coating step, a coating layer can be applied and provided on the fed film by the method described below. However, it is not limited to the following description.
First, a coating solution containing components for forming each layer is prepared by using 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 or an extrusion coating method (US Pat. No. 2,681,294). The coating is formed on the transparent support according to the specification. Of these, wire bar coating, extrusion coating, and micro gravure coating are particularly preferred.

In the present invention, as the wire bar coating method and the extrusion coating method, the method described in JP-A-9-73081 can be preferably used.
Further, the micro gravure coating method applied to the present invention comprises a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm, and having a gravure pattern engraved on the entire circumference, below the support and on the support. The gravure roll is rotated in the reverse direction with respect to the conveying direction, and the surplus coating liquid is scraped off from the surface of the gravure roll by a doctor blade so that a fixed amount of the coating liquid is supported at a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred to the lower surface of the body and applied. As coating conditions by the micro gravure coating method, the number of gravure patterns engraved on the gravure roll is preferably 50 to 800 / inch, more preferably 100 to 300 / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5-200 micrometers is more preferable, It is preferable that the rotation speed of a gravure roll is 3-800 rpm, and it is more preferable that it is 5-200 rpm.
In addition, when performing application | coating, adjusting the temperature of a film-form base material (it may be described as a base) is also a preferable method in order to control applicability | paintability and drying property. This temperature adjustment is possible by roll contact, heater use, application room temperature adjustment, and the like.
Two or more layers may be applied simultaneously. The methods for simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).
In the coating of the present invention, the transport speed of the film-like support is preferably 0.5 to 200 m / min, more preferably 1 to 100 m / min, and particularly preferably 5 to 50 m / min.

[Heat treatment, actinic radiation curing process]
In the method for producing an optical film of the present invention, it is also preferable to perform treatment by heating as necessary after coating and drying. The heat treatment is performed for purposes such as treatment for aligning the liquid crystal layer, removal of residual volatile components, and thermosetting of the coating solution components. The temperature and time of the heat treatment at this time can be optimally set according to the characteristics of the coating film, the glass transition temperature of the film substrate to be applied, the thermal deformation characteristics, and the like. The general heat treatment temperature is in the range of 60 ° C. to 150 ° C., and the range of 80 ° C. to 140 ° C. is particularly preferable. The heat treatment time is preferably in the range of 10 seconds to 30 minutes, more preferably 20 seconds to 20 minutes, and particularly preferably 30 seconds to 15 minutes.
When the coating layer is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, it is preferable to perform curing by irradiating with an ionizing radiation. As the ionizing radiation, generally known methods such as ultraviolet irradiation, electron beam irradiation, and X-ray irradiation can be used. Of these methods, ultraviolet irradiation is particularly preferred. Ultraviolet irradiation can be carried out using various commercially available ultraviolet irradiation lamps such as mercury lamps and metal halide lamps. In addition, when implementing ultraviolet irradiation, it is also preferable to perform a crosslinking reaction or a polymerization reaction in the atmosphere where oxygen concentration was reduced. At this time, the oxygen concentration is preferably carried out in an atmosphere of 10% by volume or less. By forming in an atmosphere having an oxygen concentration of 10% by volume or less, a cured layer having excellent physical strength and chemical resistance can be formed. More preferably, it is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 2% by volume or less, particularly preferably an oxygen concentration. 1% by volume or less, most preferably 0.1% by volume or less.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

  Moreover, it is also preferable to control the temperature of the emitted coating film when cured with actinic radiation. As a method for controlling the temperature at the time of radiation irradiation of the coating film, there are a method for controlling the atmospheric temperature in the room where the active radiation is irradiated, a method in which a roll is installed on the side opposite to the irradiation side, and the method is controlled by the roll temperature. is there.

Subsequently, constituent materials necessary for the optical film will be described.
[Support]
As the support of the optical film of the present invention (sometimes referred to as a base material or a base), a film-like one can be used. A plastic film is particularly preferable.
The support preferably has a light transmittance of 80% or more. Examples of the polymer constituting the plastic film include cellulose acylate (eg, cellulose triacetate, cellulose diacetate, typically TAC-T80U, TD80U, TDY80U, etc. manufactured by Fuji Photo Film), polyamide, polycarbonate, polyester (eg, , Polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Corporation), polyacrylate, and the like. Of these, cellulose acylate, polyethylene terephthalate, norbornene resin, amorphous polyolefin and the like are preferable.
Of these, cellulose acylate is preferable, and a lower fatty acid ester of cellulose is more preferable. Lower fatty acid means a fatty acid having 6 or less carbon atoms. Particularly, the number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose acetate is particularly preferred. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used.

  Even in the case of polymers that are easily known to exhibit birefringence, such as polycarbonate and polysulfone, which are conventionally known, the birefringence can be developed by modifying the molecule as described in WO '00 / 26705. Can be used for the optical film of the present invention.

  When the optical film of the present invention is used for a polarizing plate protective film or a retardation film, cellulose acetate having an acetylation degree of 55.0 to 62.5% is preferably used as the polymer film. The acetylation degree is more preferably 57.0 to 62.0%.

The degree of acetylation means the mass of bound acetic acid per mass of glucopyranose unit. The degree of acetylation is determined by measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acetate is preferably 250 or more, and more preferably 290 or more. Cellulose acetate preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.0 to 1.65, and most preferably 1.0 to 1.6. preferable.

In cellulose acetate, the hydroxyl groups at the 2nd, 3rd and 6th positions of the glucose unit constituting cellulose are not evenly substituted, but the degree of substitution at the 6th position tends to be small. In the polymer film used in the present invention, it is preferable that the 6-position substitution degree of the glucose unit is the same as or more than the 2-position and 3-position.
The ratio of the substitution degree at the 6-position to the total substitution degree at the 2-, 3- and 6-positions of the glucose unit is preferably 30 to 40%, more preferably 31 to 40%, and more preferably 32 to Most preferably, it is 40%. The substitution degree at the 6-position is preferably 0.88 or more.
The degree of substitution at each position can be measured by NMR.
Cellulose acetate having a high degree of substitution at the 6-position is described in Synthesis Example 1 described in Paragraph Nos. 0043 to 0044, Synthesis Example 2 described in Paragraph Nos. 0048 to 0049, and Paragraph Nos. 0051 to 0052. It can be synthesized with reference to the method of Synthesis Example 3.

  As the cellulose acylate film, one composed of a single layer or a plurality of layers can be used. A single layer of triacetyl cellulose is prepared by drum casting or band casting disclosed in JP-A-7-11055 and the like. It can be prepared by the so-called co-casting method disclosed in Japanese Patent Publication No. 61-94725 and Japanese Patent Publication No. 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a web consisting of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. Co-cast a low-concentration dope on both sides of the cellulose ester dope, dry the film to some extent on the web, and peel off the film that has been given rigidity, Ide passed through a drying section by a variety of transport means is a method comprising removing the solvent.

  A typical solvent for dissolving cellulose acylate as described above is dichloromethane. However, from the viewpoint of the global environment and working environment, it is preferable that the solvent is substantially free of halogenated hydrocarbons such as dichloromethane. Therefore, a solvent that does not substantially contain dichloromethane is used for cooling and dissolving, which is a special dissolution method. It is also possible to form a film by dissolving by a method or a high temperature dissolution method. Such a cellulose acetate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, hereinafter published (Abbreviated as No. 2001-1745).

Also, a plasticizer for imparting flexibility to the cellulose acylate film, improving the light resistance of the film itself, or preventing deterioration of image display members such as polarizing plates, liquid crystal compounds for image display devices, and organic EL compounds. It is preferable to add a UV absorber, fine particles for imparting mechanical strength, improving dimensional stability, improving moisture resistance, imparting slipperiness, and the like. In addition, various other additives (for example, deterioration inhibitors (for example, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) depending on the application in each preparation step Etc.), an optical anisotropy adjusting agent, a release agent, an antistatic agent, an infrared absorber, etc.), which may be solid or oily. That is, the melting point and boiling point are not particularly limited. As the infrared absorbing dye, for example, those described in JP-A-2001-194522 are used.
These additives may be added at any stage in the dope preparation process, or may be performed by adding an additive to the final preparation process of the dope preparation process. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, when a cellulose acylate film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ. For example, it is described in Japanese Patent Application Laid-Open No. 2001-151902 and the like, but these are conventionally known techniques. Further, for these details, materials described in detail on pages 16 to 22 of the Japan Society for Invention and Innovation Technical Bulletin No. 2001-1745 (issued on March 15, 2001, Japan Society of Invention) are preferably used.

When generally used, the film thickness of the support of the optical film of the present invention is 20 to 200 μm, preferably 20 to 120 μm, and more preferably 30 to 90 μm. When the film thickness is in the above range, cutting of the support during production and generation of wrinkles are suppressed, the polarizing plate and the display device become thin, and further excellent in optical characteristics, cost, productivity, processing efficiency, and the like. .
The support used for the optical film of the present invention is preferably in the form of a long roll having a length of 100 to 5000 m and a width of 0.7 to 2 m. The optical film, the antireflection film, the polarizing plate protective film and the image display device of the present invention can be stably obtained with good optical characteristics such as thinning and weight reduction, and improving the transmittance and improving the contrast and display brightness. A wide and wide support can be handled with good handling properties without causing problems such as wrinkles.
Further, the fluctuation range of the film thickness of the support is within ± 3%, preferably within ± 2.5%, and more preferably within ± 1.5%. Within this variation, the variation in the thickness of the support is good without substantially affecting the coating property of the coating layer.

[Optical compensation film having optically anisotropic layer]
The optical compensation film, which is a typical form of the optical film of the present invention, will be described below. As an optical compensation film, for example, a film having an optically anisotropic layer made of a liquid crystal compound is known.
The optically anisotropic layer is preferably designed so as to compensate birefringence due to liquid crystal compound molecules in the liquid crystal cell in black display of the liquid crystal display device. The alignment state of the liquid crystal compound molecules in the liquid crystal cell in black display varies depending on the mode of the liquid crystal display device. The alignment state of the liquid crystal compound molecules in this liquid crystal cell is described in IDW'00, FMC 7-2, pages 411 to 414.
The optically anisotropic layer is formed directly from the liquid crystal compound on the support or from the liquid crystal compound via an alignment film. The alignment film preferably has a thickness of 10 μm or less.
The optically anisotropic layer can be formed by applying a liquid crystal compound and, if necessary, a coating liquid containing a polymerizable initiator and optional components on the alignment film. A preferred example of the alignment film of the present invention is described in JP-A-8-338913.

(Liquid crystal compound)
The liquid crystal compound used in the optically anisotropic layer may be a rod-like liquid crystal or a discotic liquid crystal, and these are high molecular liquid crystals or low molecular liquid crystals, and further, low molecular liquid crystals are crosslinked and no longer exhibit liquid crystallinity. Including. Most preferred is a discotic liquid crystal.

Examples of rod-like liquid crystalline molecules include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
The rod-like liquid crystalline molecule includes a metal complex. In addition, a liquid crystal polymer containing a rod-like liquid crystalline molecule in a repeating unit can also be used as the rod-like liquid crystalline molecule. In other words, the rod-like liquid crystal molecule may be bonded to a (liquid crystal) polymer.
For rod-like liquid crystalline molecules, see Chapter 4, Chapter 7 and Chapter 11 of the Chemistry of the Quarterly Chemistry Vol. 22 (1994) The Chemical Society of Japan, and the 142th Committee of the Japan Society for the Promotion of Science. Described in Chapter 3.
The birefringence of the rod-like liquid crystal molecule is preferably in the range of 0.001 to 0.7.
The rod-like liquid crystalline molecule preferably has a polymerizable group in order to fix its alignment state. The polymerizable group is preferably an unsaturated polymerizable group or an epoxy group, more preferably an unsaturated polymerizable group, and most preferably an ethylenically unsaturated polymerizable group. Preferable examples of the rod-like liquid crystal include those described in JP 2000-304932A.

<Discotic compound>
Discotic compounds include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, page 2655 (1994), and azacrown-based and phenylacetylene-based macrocycles.
Examples of the discotic compound include compounds having liquid crystallinity in which a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule. included. The molecule or the assembly of molecules is preferably a compound having rotational symmetry and imparting a certain orientation. However, the molecule itself is not limited to the above description as long as the molecule itself has negative uniaxiality and can give a certain orientation. In the optically anisotropic layer formed from the discotic liquid crystalline molecules, the compound finally contained in the optically anisotropic layer does not need to be a discotic liquid crystalline molecule. Also included are compounds having a group that reacts with heat or light and, as a result, polymerized or cross-linked by reaction with heat or light, resulting in a high molecular weight and loss of liquid crystallinity. Preferred examples of the discotic compound are described in JP-A-8-50206. Moreover, about superposition | polymerization of a discotic compound, Unexamined-Japanese-Patent No. 8-27284 has description.

  In order to fix the discotic compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic compound. However, when a polymerizable group is directly connected to the discotic core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, it is preferable to introduce a linking group between the discotic core and the polymerizable group. Specific examples of such discotic compounds are described in WO01 / 88574A1 pages 58 to 65.

  The optically anisotropic layer is generally formed by applying a solution obtained by dissolving a discotic compound and other compounds (eg, plasticizer, surfactant, polymer, etc.) in a solvent onto the alignment film, drying, and then discotic nematic. It is obtained by heating to the phase formation temperature and then cooling while maintaining the orientation state (discotic nematic phase). Alternatively, the optically anisotropic layer is formed by applying a solution obtained by dissolving a discotic compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) in a solvent onto the alignment film, drying, and then discotic It is obtained by heating to the nematic phase formation temperature, polymerizing (by irradiation with UV light or the like), and further cooling.

  The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic compound is preferably 70 to 300 ° C, and more preferably 70 to 170 ° C.

  The plasticizer, surfactant, and polymerizable monomer used together with the discotic compound are preferably compatible with the discotic compound and can change the tilt angle of the discotic compound or do not inhibit the orientation. Among the additive components, addition of a polymerizable monomer (eg, a compound having a vinyl group, a vinyloxy group, an acryloyl group and a methacryloyl group) is preferable. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic compound. In addition, when a monomer having 4 or more polymerizable reactive functional groups is mixed and used, the adhesion between the alignment film and the optically anisotropic layer can be improved.

In the optically anisotropic layer, an appropriate polymer may be used together with the discotic compound, and the polymer has a certain degree of compatibility with the discotic compound and can change the tilt angle of the discotic compound. Is preferred.
A cellulose ester can be mentioned as an example of a preferable polymer. Preferred examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. The amount of the polymer added is preferably in the range of 0.1 to 10% by mass and preferably in the range of 0.1 to 8% by mass with respect to the discotic compound so as not to inhibit the orientation of the discotic compound. It is more preferable that it is in the range of 0.1 to 5% by mass.

  The orientation in the film thickness direction of the optically anisotropic layer of the discotic compound is preferably a hybrid orientation. In the hybrid orientation, the angle between the major axis (disk surface) of the discotic compound and the surface of the support, that is, the inclination angle, increases with increasing distance from the surface of the polarizing film in the depth direction of the optically anisotropic layer or is decreasing. The angle preferably decreases with increasing distance. Further, the change in the inclination angle can be continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, or intermittent change including increase and decrease. . The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. Even if a region where the angle does not change is included, it may be increased or decreased as a whole. However, it is preferred that the tilt angle changes continuously.

  The average direction of the major axis (disk surface) of the discotic compound (average of the major axis direction of each molecule) is generally determined by selecting the discotic compound or the material of the alignment film, or by selecting the rubbing treatment method. Can be adjusted. Moreover, the major axis (disk surface) direction of the discotic compound on the surface side (air side) can be generally adjusted by selecting the type of additive used together with the discotic compound or the discotic compound. Examples of the additive used together with the discotic compound include a plasticizer, a surfactant, a polymerizable monomer and a polymer. The degree of change in the orientation direction of the major axis can also be adjusted by selecting liquid crystalline molecules and additives as described above.

  The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and most preferably 0.7 to 5 μm. However, depending on the mode of the liquid crystal cell, it may be thick (3 to 10 μm) in order to obtain high optical anisotropy.

(Fixing the alignment state of liquid crystalline molecules)
The aligned liquid crystalline molecules can be fixed while maintaining the alignment state. The immobilization is preferably performed by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).

The amount of the photopolymerization initiator used is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.5 to 5% by mass, based on the solid content of the coating solution.
It is preferable to use ultraviolet rays for light irradiation for polymerization of liquid crystalline molecules.
The irradiation energy ^is preferably in the range of ^{20mJ / cm 2 ~50J / cm 2} 2, more preferably in the range of 20~5000mJ / cm ^2, further in the range of 100 to 800 mJ / cm ² preferable. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.
A protective layer may be provided on the optically anisotropic layer.

(Alignment film)
The alignment film is usually used because it has the function of defining the alignment direction of the liquid crystal molecules. It is not necessarily essential as a component of the invention. For example, it is possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizer.

  The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field or light irradiation is also known.

The alignment film is particularly preferably formed by polymer rubbing treatment. In principle, the polymer used for the alignment film has a molecular structure having a function of aligning liquid crystal molecules.
In the present invention, in addition to the function of aligning liquid crystal molecules, a crosslinkable function having a function of aligning a side chain having a crosslinkable functional group (eg, a double bond) to the main chain or aligning liquid crystal molecules. It is preferred to introduce the group into the side chain.
As the polymer used in the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.

Examples of such polymers include methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols and modified polyvinyl alcohols described in JP-A-8-338913, paragraph [0022], poly (N- Methylol acrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like. Most preferred are polyvinyl alcohol and modified polyvinyl alcohol.
Specific examples of the alignment film forming composition such as the modified polyvinyl alcohol compound and the crosslinking agent include those described in JP-A Nos. 2000-155216 and 2002-62426.
The thickness of the alignment film is preferably in the range of 0.1 to 10 μm.

[Anti-glare film, light diffusion film, anti-reflection film]
Another preferred embodiment of the optical film of the present invention includes an antiglare film that controls light transmission by scattering due to particles and surface irregularities, a light diffusing film, and surface reflectivity by optical interference of a coating layer. There is an anti-reflective film to control.

(Anti-glare film)
The anti-glare film is a film that scatters light incident on the film by unevenness formed on the surface and suppresses reflection, and is preferably used to suppress reflection of a light source such as a fluorescent lamp on an image display device. It is done. Such an antiglare layer can be formed by methods such as imparting irregularities by adding matte particles, or imparting surface irregularities by phase separation of the coating layer. Moreover, a hard coat property can be imparted to the antiglare property imparting layer, a light scattering property can be imparted, or a function such as a high refractive index can be imparted.

(Light diffusion film)
The light diffusing film scatters the light emitted from the image display device to make it uniform, or in combination with an optical compensation film, enlarges the viewing angle of the liquid crystal display device (especially the downward viewing angle) and changes the viewing angle in the viewing direction. However, it can be used for the purpose of reducing contrast, gradation or black-and-white reversal, or suppressing hue change.
It was confirmed that the scattered light intensity distribution measured with a goniophotometer correlates with the viewing angle improvement effect for the viewing angle improvement effect. That is, as the light emitted from the backlight is diffused by the effect of internal scattering of the translucent fine particles contained in the light diffusion film installed on the surface of the polarizing plate on the viewing side, the viewing angle characteristics are improved. However, if it is diffused too much, backscattering will increase and the front luminance will decrease, or the scattering will be too great and the image clarity will deteriorate. Therefore, it is necessary to control the scattered light intensity distribution within a certain range. Therefore, as a result of intensive studies, in order to achieve the desired visual characteristics, the scattered light intensity at 30 °, which correlates particularly with the visual angle improvement effect, is 0.01 with respect to the light intensity at the output angle 0 ° of the scattered light profile. % To 0.2% is preferable, 0.02% to 0.15% is more preferable, and 0.03% to 0.1% is particularly preferable.
The scattered light profile can be measured using the automatic variable angle photometer GP-5 manufactured by Murakami Color Research Laboratory Co., Ltd. for the created light scattering film.

  The light diffusion layer of the present invention is formed from a binder, an inorganic filler, a translucent fine particle and the like. It is also preferable to impart characteristics such as hard coat properties and high refractive index to the light diffusion layer.

(Antireflection film)
A basic configuration of an antireflection film which is one embodiment of the optical film of the present invention will be described with reference to the drawings. In the present specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.
The cross-sectional view schematically shown in FIG. 2A is an example of the antireflection film of the present invention. The antireflection film 1 has a layer structure in the order of a transparent support 2 and three types of functional layers (a hard coat layer 3, an antiglare hard coat layer 4, and a low refractive index layer 5). Matt particles 6 are dispersed in the antiglare hard coat layer 4. In the present invention, the functional layer such as the hard coat layer 3 and the antiglare hard coat layer 4 may be a hard coat layer having such an antiglare property or a hard coat layer having no antiglare property. A light diffusion layer may be used. Moreover, as shown to Fig.2 (a), you may divide into several layers for every function, and may have several functions with a single layer. Of the functional layers, the low refractive index layer 5 is coated on the outermost layer.
Further, the low refractive index layer preferably satisfies the following mathematical formula (2) from the viewpoint of reducing the reflectance.
Formula (2)
(M / 4) × 0.7 <n ₁ d ₁ <(m / 4) × 1.3
In the formula, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling the said Numerical formula (2) means that m (positive odd number, usually 1) which satisfy | fills Numerical formula (2) exists in the said wavelength range.
In addition, it is preferable that the refractive index of parts other than the mat | matte particle | grains 6 of the glare-proof hard-coat layer 4 exists in the range of 1.50-2.00, and the refractive index of the low refractive index layer 5 is 1.35-1. A range of 49 is preferred.

The cross-sectional view schematically shown in FIG. 2 (b) is an example of the antireflection film of the present invention. The antireflection film 1 includes a transparent support 2, each functional layer (hard coat layer 3, medium refractive index). Layer 7, high refractive index layer 8), low refractive index layer (outermost layer) 5. The transparent support 2, the medium refractive index layer 7, the high refractive index layer 8, and the low refractive index layer 5 have refractive indexes that satisfy the following relationship.
Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer In the layer structure as shown in FIG. As described in the above, it is more excellent that the medium refractive index layer satisfies the following formula (3), the high refractive index layer satisfies the following formula (4), and the low refractive index layer satisfies the following formula (5). It is preferable at the point which can produce the antireflection film which has prevention performance.

Formula (3)
(Hλ / 4) × 0.7 <n ₁ d ₁ <(hλ / 4) × 1.3
In Formula (3), h is a positive integer (generally 1, 2 or 3), n ₁ is the refractive index of the medium refractive index layer, and d ₁ is the layer thickness (nm) of the medium refractive index layer. It is. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.
Formula (4)
(Iλ / 4) × 0.7 <n ₂ d ₂ <(iλ / 4) × 1.3
In formula (4), i is a positive integer (generally 1, 2 or 3), n ₂ is the refractive index of the high refractive index layer, and d ₂ is the layer thickness (nm) of the high refractive index layer. It is. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

Formula (5)
(Jλ / 4) × 0.7 <n ₃ d ₃ <(jλ / 4) × 1.3
In Equation (5), j is a positive odd number (generally 1), n ₃ is the refractive index of the low refractive index layer, and d ₃ is the layer thickness (nm) of the low refractive index layer. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

In the layer configuration as shown in FIG. 2B, the medium refractive index layer satisfies the following formula (6), the high refractive index layer satisfies the following formula (7), and the low refractive index layer satisfies the following formula (8). Is particularly preferred. Here, λ is 500 nm, h is 1, i is 2, and j is 1.
Formula (6)
(Hλ / 4) × 0.80 <n ₁ d ₁ <(hλ / 4) × 1.00
Formula (7)
(Iλ / 4) × 0.75 <n ₂ d ₂ <(iλ / 4) × 0.95
Formula (8)
(Jλ / 4) × 0.95 <n ₃ d ₃ <(jλ / 4) × 1.05

  The high refractive index, medium refractive index, and low refractive index described here refer to the relative refractive index between layers. Moreover, in FIG.2 (b), the high refractive index layer is used as a light interference layer, and the antireflection film which has the very outstanding antireflection performance can be produced.

Next, each functional layer of the present invention and materials constituting the functional layer will be described.
[Hard coat layer]
As the hard coat layer, a so-called smooth hard coat layer that is not anti-glare and imparts physical strength to the antireflection film is also preferably used, and is provided on the surface of the transparent support. In particular, the transparent support and the antiglare hard coat layer, the transparent support and the light diffusion layer, and the transparent support and the high refractive index layer are preferably provided.

  The binder of the hard coat layer is added in an amount of 30 to 95% by mass based on the solid content of the coating composition of the layer.

The hard coat layer preferably contains inorganic fine particles having an average primary particle size of 200 nm or less. The average particle diameter here is a mass average diameter. By setting the average particle size of the primary particles to 200 nm or less, a hard coat layer that does not impair the transparency can be formed.
The inorganic fine particles have functions of increasing the hardness of the hard coat layer and suppressing curing shrinkage of the coating layer. It is also added for the purpose of controlling the refractive index of the hard coat layer.
As inorganic fine particles, in addition to the inorganic fine particles exemplified in the high refractive index layer, silicon dioxide, aluminum oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, titanium dioxide, zirconium oxide, tin oxide, ITO, zinc oxide, etc. Fine particles. Preferred are silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, tin oxide, ITO, and zinc oxide.

The preferable average particle diameter of the primary particles of the inorganic fine particles is 5 to 200 nm, more preferably 10 to 150 nm, still more preferably 20 to 100 nm, and particularly preferably 20 to 50 nm.
In the hard coat layer, the inorganic fine particles are preferably dispersed as finely as possible.
The particle size of the inorganic fine particles in the hard coat layer is preferably 5 to 300 nm, more preferably 10 to 200 nm, more preferably 20 to 150 nm, and particularly preferably 20 to 80 nm in terms of average particle diameter.

  The content of the inorganic fine particles in the hard coat layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the total mass of the hard coat layer.

  The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 0.5 to 7 μm, and particularly preferably 0.7 to 5 μm.

The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.
Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.
The hard coat layer is preferably formed by applying a coating composition for forming a hard coat layer on the surface of the transparent support.

[Anti-glare, light-scattering hard coat layer]
The hard coat layer imparting antiglare properties and light scattering properties of the present invention will be described below.
The antiglare hard coat layer is formed from a binder for imparting hard coat properties, matte particles for imparting antiglare properties, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength. Is done.

The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer (binder precursor) is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
Particularly preferable examples of such a binder component include actinic radiation curable resins such as polyfunctional monomers and polyfunctional oligomers having radically polymerizable or cationically polymerizable groups.

  Examples of the radical polymerizable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. It is preferable to contain a polyfunctional monomer containing two or more radically polymerizable groups in the molecule.

  The radical polymerizable polyfunctional monomer is preferably selected from compounds having at least two terminal ethylenically unsaturated bonds. Preferably, it is a compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule. Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention. These can have chemical forms such as, for example, monomers, prepolymers (ie, dimers, trimers and oligomers) or mixtures thereof, and copolymers thereof.

  As these actinic radiation curable resins, preferably, a resin having an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as polybutadiene resins, polythiol polyene resins, and polyhydric alcohols (hereinafter, acrylate and methacrylate are referred to as (meth) acrylates). Can be mentioned. Specific examples of the polyfunctional monomer include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and hexanediol. (Meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Mixture of enterythritol hexa (meth) acrylate and penta (meth) acrylate, 1,6 hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4- Examples include cyclohexane diacrylate, 1,2,3-cyclohexanetetra (meth) acrylate, polyurethane polyacrylate, polyester polyacrylate, and the like. In addition, vinylbenzene and derivatives thereof (eg, 1,4-vinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-vinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, And methylene bisacrylamide) and methacrylamide. It is also preferable to mix a monofunctional monomer such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, vinyltoluene, or N-vinylpyrrolidone. Two or more of these monomers may be used in combination.

  Examples of the actinic radiation curable resin include a polymerizable ester compound (monoester or polyester) of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, paragraph No. [0026] of JP-A-2001-139663. ] To [0027]. Further, for example, vinyl methacrylate, allyl methacrylate, allyl acrylate, aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-2-226149. Those having an aromatic skeleton described above, and those having an amino group described in JP-A-1-165613 are also preferably used. In addition, it has a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule (Japanese Patent Publication No. 48-41708), urethane acrylates (Japanese Patent Publication No. 2-16765), and an ethylene oxide skeleton. Urethane compounds (JP-B-62-39418, etc.), polyester acrylates (JP-B-52-30490, etc.)), and the light described in Journal of Japan Adhesion Association, Vol. 20 (7), 300-308 (1984) Curable monomers and oligomers can also be used.

  As these actinic radiation curable resins, commercially available products such as Nippon Kayaku Co., Ltd., Osaka Organic Chemical Co., Ltd., Dainippon Ink Chemical, Toa Gosei, Mitsubishi Chemical, etc. can be used. .

  Two or more of these actinic radiation curable resins may be used in combination. Of these, particularly preferred are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate and penta (meth) acrylate. A mixture of trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like.

  In order to increase the refractive index of the binder, the monomer structure may contain an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms. preferable.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. It can be cured by a polymerization reaction to form an antireflection film.

As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (p. 159, issuer: Kazuhiro Takasato, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Nippon Ciba-Geigy Co., Ltd.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p-nitrobenzenediazonium Etc.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. It can be cured to form a hard coat layer.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.
Further, a polymer having no crosslinkable functional group may be added to the hard coat layer for the purpose of adjusting the coating viscosity, adjusting the coating film hardness, imparting the stability of the particles, and imparting the cohesiveness.

  The binder of the antiglare hard coat layer is added in an amount of 20 to 95% by mass based on the solid content of the coating composition of the layer.

For the purpose of imparting antiglare properties, the antiglare hard coat layer is a matte particle having an average particle size of 1 to 10 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin, for the purpose of imparting antiglare properties. Contains particles.
As specific examples of the mat particles, particles of inorganic compounds such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
As the shape of the mat particle, either a true sphere or an indefinite shape can be used.

  Two or more kinds of mat particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare originates from the fact that the pixels are enlarged or reduced due to unevenness existing on the film surface (contributing to anti-glare properties) and lose uniformity of brightness, but with a particle size smaller than that of mat particles that provide anti-glare properties. It can be greatly improved by using mat particles having a different refractive index from the binder.

  Furthermore, the particle size distribution of the mat particles is most preferably monodisperse, and the particle sizes of the particles are preferably closer to each other. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. Or less, more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a matting agent having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

The mat particles are contained in the antiglare hard coat layer so that the amount of mat particles in the formed antiglare hard coat layer is preferably 10 to 2000 mg / m ² , more preferably 100 to 1400 mg / m ^2. Is done.
The particle size distribution of the matte particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

In order to increase the refractive index of the antiglare hard coat layer, in addition to the above mat particles, at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin and antimony is used. It is preferable to contain an inorganic filler made of an oxide and having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
Conversely, in order to increase the difference in refractive index from the matte particles, an anti-glare hard coat layer using high-refractive index matte particles uses silicon oxide to keep the refractive index of the layer low. Is also preferable. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler used in the antiglare hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO _2. It is done. TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the antiglare hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of binder and inorganic filler of the antiglare hard coat layer according to the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

  The film thickness of the antiglare hard coat layer is preferably 0.5 to 20 μm, more preferably 1 to 15 μm, and further preferably 1.2 to 10 μm.

In addition, the hard coat layer, the antiglare layer, and the light scattering layer of the present invention have an organosilicon compound represented by the following general formula 1 (generally known as silane coupling), or a hydrolyzate thereof and a portion thereof. It is also preferred that a condensate is included. In addition, it is a well-known fact that the organosilicon compound represented by the general formula 1 is easily hydrolyzed and subsequently undergoes a dehydration condensation reaction.
General formula 1
R _m Si (X) _n
(R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M + n is 4, and m and n are each an integer of 0 or more. M is 0-3.)

  In the above general formula 1, R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. For example, each group such as methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl, etc. Is mentioned. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

  The substituent contained in R is not particularly limited, but may be a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl). Each group such as t-butyl), aryl group (phenyl group, naphthyl group, etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group, etc.), acyloxy group (acetoxy, acryloyloxy, methacryloyloxy, etc.) Each group), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (phenoxycarbonyl group etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-) Each group such as N-octylcarbamoyl), acylamino group ( Sechiruamino, benzoylamino, acrylamino, each group) such as methacrylic amino and the like. These substituents may be further substituted. When there are a plurality of R, at least one is preferably a substituted alkyl group or a substituted aryl group.

X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I, etc.) ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m + n is 4, and m and n are each an integer of 0 or more. m is 0-3, preferably 1, 2, and particularly preferably 1.

When a plurality of R or X are present, the plurality of R or X may be the same or different.
When there are a plurality of R, it is preferable that at least one is a substituted alkyl group or a substituted aryl group.

  Among the organosilane compounds represented by the general formula 1, an organosilane compound having a vinyl polymerizable substituent such as a methacryloyloxy group or an acryloyloxy group is particularly preferable. Specific examples include those described in paragraph numbers [0026] to [0028] of JP-A-2004-42278.

  The hydrolyzate and / or partial condensate of the organosilane compound may be produced by water content in the coating solution, progress of reaction, etc., or is prepared by treating the organosilane compound in the presence of a catalyst in advance. In some cases. For hydrolysis and condensation, examples of the catalyst include acids, bases, and organometallic compounds. In the present invention, it is also preferable to use a material obtained by condensing an organosilane compound in advance.

  In addition, for the coating solution according to the present invention, in order to improve coating properties, uniform drying, and impart high-speed coating suitability, either or both of a fluorine-based component and a silicone-based component having a surfactant activity are added. It is also preferable to add it to the coating composition. These surface active components may be added for surface wettability, antifouling property, dustproof property, chargeability adjustment and the like.

  Preferable examples of the silicone compound include those having a substituent at the end of the compound chain and / or the side chain, containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. Can be mentioned.

  Although there is no restriction | limiting in particular in the molecular weight of a silicone type compound, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular also in silicone atom content of a silicone type compound, It is preferable that it is 18.0 mass% or more, It is especially preferable that it is 25.0-37.8 mass%, 30.0-37. Most preferably, it is 0.0 mass%.

  Examples of preferable silicone compounds include, but are not limited to, those described in paragraph No. [0068] of JP-A-2004-42278.

A compound containing a fluoroalkyl group is also preferred as an additive. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain [eg, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.], but branched structures [eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.], an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group). , A perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C). ₄ F ₈ H, - _{H 2 CH 2 OCH 2 CH 2} C 8 F 17, -CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited and is used. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferable fluorine-based compounds include “R-2020”, “M-2020”, “R-3833”, “M-3833” [trade name: manufactured by Daikin Chemical Industries, Ltd.]; -171, F-172, F-179A, F-780-F, defender MCF-300 [trade name: manufactured by Dainippon Ink, Inc.] and the like, but are not limited thereto.

  Of the above additives, it is particularly preferable to contain a fluoroalkyl group-containing copolymer in the coating composition. This fluoroalkyl group-containing copolymer is preferable because an effect of improving surface defects such as coating unevenness and drying unevenness of the optical film appears with a smaller addition amount.

  Further, when a coating film of a low refractive index layer is further formed on the coating layer, the additive preferably has a substituent that contributes to bond formation or compatibility. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.

  Furthermore, by selecting the structure of the following fluoroalkyl group-containing copolymer, the copolymer unevenly distributed on the surface of the functional layer is extracted into the upper solvent when the upper layer (for example, a low refractive index layer) is applied, thereby preventing the antireflection of the present invention. When the film is formed, it is also preferable not to exist on the functional layer surface (functional layer interface). Moreover, adjusting the addition amount of the fluoroaliphatic group-containing copolymer is also effective in improving the above effect.

  Specifically, such a method includes adding a fluoroaliphatic group-containing copolymer containing 10% by mass or more of a polymer unit of a fluoroaliphatic group-containing monomer in the coating solution, and then adding the fluoroaliphatic group-containing copolymer. In order to segregate the surface (conforms to the uneven distribution and consent) and to obtain adhesion with the upper layer, a solvent of a coating solution for forming the upper layer is applied on the functional layer containing the fluoroaliphatic group-containing copolymer. In this method, the surface free energy of the functional layer is changed by 1 mN / m or more by drying, particularly 3 mN / m or more.

Furthermore, the fluoroalkyl group-containing copolymer (sometimes abbreviated as “fluorine polymer”) has a perfluoroalkyl group having 4 or more carbon atoms or a CF ₂ H-group having 4 or more carbon atoms in the side chain. It is preferable to use a copolymer having a fluoroalkyl group.
Among them, an acrylic resin, a methacrylic resin, and a copolymer thereof containing a repeating unit (polymerized unit) corresponding to the monomer described in (i) below and a repeating unit (polymerized unit) corresponding to the monomer described in (ii) below. Copolymers with possible vinyl monomers are useful. Such monomers include Polymer Handbook 2nd edition, J. MoI. Brandrup, Wiley lnterscience (1975), Chapter 2, pages 1-483 can be used.
Specifically, for example, one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. And the like.
Such compounds are the following compounds.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula 2

In the general formula 2, R ¹ represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, more preferably an oxygen atom or —N (R ¹² ) —, and still more preferably an oxygen atom. R ¹² represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. R _f represents —CF ₃ or —CF ₂ H.
M in General Formula 2 represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1.
N in the general formula 2 represents an integer of 1 to 17, more preferably 4 to 11, and still more preferably 6 to 7. R _f is preferably —CF ₂ H.
Further, two or more kinds of polymer units derived from the fluoroalkyl group-containing monomer represented by the general formula 2 may be contained in the fluorine-based polymer as a constituent component.

(Ii) A monomer represented by the following general formula 3 copolymerizable with the above (i):

In the general formula 3, R ¹³ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, more preferably an oxygen atom or —N (R ¹⁵ ) —, and still more preferably an oxygen atom. R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.
R ¹⁴ is a linear, branched, or cyclic alkyl group having 1 to 60 carbon atoms that may have a substituent, or an aromatic group that may have a substituent (for example, a phenyl group or a naphthyl group). ). The alkyl group may include a poly (alkyleneoxy) group. A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group having 5 to 40 carbon atoms, or an aromatic group having 6 to 18 carbon atoms is more preferable. Alkyl groups including 8 linear, branched, or cyclic alkyl groups and poly (alkyleneoxy) groups having 5 to 30 carbon atoms are highly preferred. The poly (alkyleneoxy) group will be described below.

Poly (alkyleneoxy) groups can be represented by (OR) x, R is an alkylene group having 2 to 4 carbon atoms, such as _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH It is preferably (CH ₃ ) CH ₂ — or —CH (CH ₃ ) CH (CH ₃ ) —. x represents 2-30, 2-20 are preferable and 4-15 are more preferable.
The oxyalkylene units in the poly (oxyalkylene) group may be the same as in the poly (oxypropylene) group, or two or more different oxyalkylene units may be randomly distributed. It may be a linear or branched oxypropylene or oxyethylene unit, or may be present as a linear or branched block of oxypropylene units and a block of oxyethylene units.
The poly (oxyalkylene) chain may also include those linked by one or more chain bonds (for example, —CONH—Ph—NHCO—, —S—, etc .: Ph represents a phenylene group). If the chain bond has a valence of 3 or more, this provides a means for obtaining branched oxyalkylene units. When this copolymer is used in the present invention, the molecular weight of the poly (oxyalkylene) group is suitably from 250 to 3,000.
Poly (oxyalkylene) acrylates and methacrylates are commercially available hydroxypoly (oxyalkylene) materials such as “Pluronic” (Asahi Denka Kogyo Co., Ltd.), Adeka Polyether (Asahi Denka Kogyo Co., Ltd.) ) "Carbowax (Glyco-Products)", "Triton" (Toriton (Rohm and Haas)) and PEG (Daiichi Kogyo Seiyaku Co., Ltd.) It can be produced by a known method by reacting with acrylic acid, methacrylic acid, acrylic chloride, methacryl chloride or acrylic acid anhydride, etc. Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula 2 used in the production of the fluoropolymer used in the present invention is 10% by mass or more based on the total amount of the monomer of the fluoropolymer, Preferably it is 50 mass% or more, More preferably, it is 70-100 mass%, More preferably, it is the range of 80-100 mass%.

The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 6,000 to 80,000, and still more preferably 8,000 to 60,000.
Here, the mass average molecular weight and the molecular weight are converted to polystyrene by GTH analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation), and solvent THF and differential refractometer detection. Is the molecular weight. The molecular weight was calculated from the peak area of 300 or more components.

  Furthermore, the preferable addition amount of the fluorine-based polymer used in the present invention is 0.001 to 5 mass with respect to the mass of the coating solution from the viewpoint of expression of the effect due to the addition, drying, and suppression of occurrence of surface failure. %, Preferably 0.005 to 3% by mass, and more preferably 0.01 to 1% by mass.

  Hereinafter, examples of specific structures of the fluorine-based polymer according to the present invention are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

(High refractive index layer)
In the antireflection film of the present invention, a high refractive index layer can be preferably used in order to impart better antireflection performance.

(Inorganic fine particles mainly composed of titanium dioxide)
The high refractive index layer used in the present invention contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium. The main component means a component having the largest content (mass%) among the components constituting the particles.
The refractive index of the high refractive index layer used in the present invention is a refractive index of 1.55 to 2.40, which is a so-called high refractive index layer or a medium refractive index layer, but in the following specification, This layer may be collectively referred to as a high refractive index layer.
The inorganic fine particles mainly composed of titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. 80 is most preferred.
The mass average diameter of primary particles of inorganic fine particles mainly composed of titanium dioxide is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.
The crystal structure of the inorganic fine particles containing titanium dioxide as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

By containing at least one element selected from Co, Al and Zr in the inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, and the weather resistance of the high refractive index layer of the present invention Can be improved.
In particular, the preferred element is Co. It is also preferable to use two or more types in combination.
The content of Co, Al or Zr with respect to Ti is preferably 0.05 to 30% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.2 to 7% by mass with respect to Ti. %, Particularly preferably 0.3 to 5% by mass, most preferably 0.5 to 3% by mass.
Co, Al, and Zr can be present in at least one of the inside and the surface of the inorganic fine particles mainly composed of titanium dioxide, but are preferably present inside the inorganic fine particles mainly composed of titanium dioxide. Most preferably it is present both inside and on the surface.
There are various methods for causing Co, Al, and Zr to exist (for example, dope) in the inorganic fine particles mainly composed of titanium dioxide. For example, the ion implantation method (18 (5), 262-268, 1998; Yasushi Aoki), JP-A-11-263620, JP-T-11-512336, European Patent Application No. 0335773. And a technique described in JP-A-5-330825.
Techniques for introducing Co, Al, and Zr in the process of forming inorganic fine particles containing titanium dioxide as a main component (for example, Japanese Patent Application Laid-Open No. 11-512336, European Patent Application Publication No. 0335773, Japanese Patent Application Laid-Open No. Hei 5- No. 330308) is particularly preferable.
Co, Al, and Zr are also preferably present as oxides.
The inorganic fine particles containing titanium dioxide as the main component can further contain other elements depending on the purpose. Other elements may be included as impurities. Examples of other elements include Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Mg, Si, P, and S.

The inorganic fine particles mainly composed of titanium dioxide used in the present invention may be surface-treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.) and inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) ₃ Etc.), zirconium-containing inorganic compounds (such as ZrO ₂ and Zr (OH) ₄ ), silicon-containing inorganic compounds (such as SiO ₂ ), and iron-containing inorganic compounds (such as Fe ₂ O ₃ ). .
An inorganic compound containing cobalt, an inorganic compound containing aluminum, and an inorganic compound containing zirconium are particularly preferable, and an inorganic compound containing cobalt, Al (OH) _{3, and} Zr (OH) ₄ are most preferable.
Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. In particular, the surface treatment is preferably performed with at least one of the silane coupling agent (organosilane compound) represented by the general formula 1, a partial hydrolyzate thereof, and a condensate thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium, and throat tetraisopropoxy titanium, and preneact (KR-TTS, KR-46B, KR-55, KR-41B, etc .; Ajinomoto Co., Inc. ))).
Examples of the organic compound used for the surface treatment include polyols, alkanolamines, and other organic compounds having an anionic group, and particularly preferable are organic compounds having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. is there.
Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.
The organic compound used for the surface treatment preferably further has a crosslinked or polymerizable functional group. Crosslinking or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) capable of addition reaction with radical species, cationic polymerizable groups (epoxy groups). , An oxatanyl group, a vinyloxy group, etc.), a polycondensation reactive group (hydrolyzable silyl group, etc., N-methylol group) and the like, and a group having an ethylenically unsaturated group is preferable.

Two or more kinds of these surface treatments can be used in combination. It is particularly preferable to use an inorganic compound containing aluminum and an inorganic compound containing zirconium in combination.
The inorganic fine particles mainly composed of titanium dioxide of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

  The shape of the inorganic fine particles mainly composed of titanium dioxide contained in the high refractive index layer is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape, and particularly preferably an indefinite shape or a spindle shape. is there.

<Dispersant>
A dispersant can be used to disperse the inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer of the present invention.
In order to disperse the inorganic fine particles mainly composed of titanium dioxide of the present invention, it is particularly preferable to use a dispersant having an anionic group.
As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (and a sulfo group), a phosphoric acid group (and a phosphono group), or a sulfonamide group, or a salt thereof is effective. A sulfonic acid group, a phosphoric acid group and a salt thereof are preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersant per molecule may be one or more.
A plurality of anionic groups may be contained for the purpose of further improving the dispersibility of the inorganic fine particles. The average number is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.
A preferred dispersant used for dispersion of inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer of the present invention has an anionic group and a crosslinkable or polymerizable functional group, and the crosslinkable or polymerizable functional group. In the side chain.
The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is preferably 1000 or more. . The more preferable mass average molecular weight (Mw) of the dispersant is 2,000 to 1,000,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000.

  As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The average number of anionic groups contained in the dispersant per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

The dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain has the anionic group in the side chain or terminal.
Particularly preferred dispersants are those having an anionic group in the side chain. In the dispersant having an anionic group in the side chain, the composition of the anionic group-containing repeating unit is in the range of 10 ^{−4 to} 100 mol%, preferably 1 to 50 mol%, particularly preferably 5 in the total repeating units. ˜20 mol%.

  Examples of the cross-linkable or polymerizable functional group include ethylenically unsaturated groups (for example, (meth) acryl group, allyl group, styryl group, vinyloxy group, etc.) capable of addition reaction / polymerization reaction with radical species, cationic polymerizable group (epoxy) Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups), and the like. Preferred are groups having an ethylenically unsaturated group.

  The average number of cross-linkable or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the crosslinking or polymerizable functional group contained in the dispersant may contain a plurality of types in one molecule.

In the preferred dispersant for use in the present invention, examples of the repeating unit having an ethylenically unsaturated group in the side chain include poly-1,2-butadiene and poly-1,2-isoprene structures or (meth) acrylic acid. An ester or amide repeating unit to which a specific residue (the R group of —COOR or —CONHR) is bonded can be used. Examples of the specific residue (R _{group), - (CH 2) n} -CR 21 = CR 22 R 23, - (CH 2 O) n-CH 2 CR 21 = CR 22 R 23, - (CH _{2 CH 2 O) n-CH} 2 CR 21 = CR 22 R 23, - (CH 2) n-NH-CO-O-CH 2 CR 21 = CR 22 R 23, - (CH 2) nO-CO- CR ²¹ = CR ²² R ²³ and — (CH ₂ CH ₂ O) ₂ —X (R ^{21 to} R ²³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, An aryloxy group, R ²¹ and R ²² or R ²³ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue) Can be mentioned. Specific examples of R of the ester residue include —CH ₂ CH═CH ₂ (corresponding to an allyl (meth) acrylate polymer described in JP-A No. 64-17047), —CH ₂ CH ₂ O—CH ₂ CH _{= CH 2, -CH 2 CH 2} OCOCH = CH 2, -CH 2 CH 2 OCOC (CH 3) = CH 2, -CH 2 C (CH 3) = CH 2, -CH 2 CH = CH-C 6 H _{5, -CH 2 CH 2 OCOCH =} CH-C 6 H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and -CH ₂ CH ₂ OX (X is a dicyclopentadienyl residue) is included It is. Specific examples of R of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (Y is a 1-cyclohexenyl residue) and —CH ₂ CH ₂ —OCO—CH═CH ₂ , _{-CH 2 CH 2 -OCO-C (} CH 3) = CH 2 are included.

  In the dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growth radical of a polymerization process of a polymerizable compound) is added to the unsaturated bond group, and the polymer compound is directly or between molecules. Addition polymerization is carried out through the polymerization chain, and a crosslink is formed between the molecules to cure. Alternatively, atoms in the molecule (for example, hydrogen atoms on carbon atoms adjacent to the unsaturated bond group) are extracted by free radicals to form polymer radicals that are bonded together to form a bridge between the molecules. Harden.

The cross-linkable or polymerizable functional group-containing unit may constitute all repeating units other than the anionic group-containing repeating unit, preferably 5 to 50 mol% of the total cross-linking or repeating unit, particularly Preferably it is 5-30 mol%.
A preferable dispersant of the present invention may be a copolymer with an appropriate monomer other than a monomer having a crosslinkable or polymerizable functional group or an anionic group. Although it does not specifically limit regarding a copolymerization component, It selects from various viewpoints, such as dispersion stability, compatibility with another monomer component, and the intensity | strength of a formed film. Preferred examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.
The preferred dispersant form of the present invention is not particularly limited, but is preferably a block copolymer or a random copolymer, and particularly preferably a random copolymer from the viewpoint of cost and synthetic ease.
As the above dispersant, compounds of (Chemical Formula 1) to (Chemical Formula 6) of JP-A No. 2004-29705 can be used.

  The amount of the dispersant used relative to the inorganic fine particles is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass, and most preferably 5 to 20% by mass. Two or more dispersants may be used in combination.

<Composition of high refractive index layer and coating method>
The inorganic fine particles mainly composed of titanium dioxide used for the high refractive index layer are used for forming the high refractive index layer in a dispersion state.
In the dispersion of the inorganic fine particles, it is dispersed in a dispersion medium in the presence of the dispersant.
As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media 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), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred.
Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and toluene.

The inorganic fine particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. 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 inorganic fine particles are preferably made as fine as possible in the dispersion medium, and the mass average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm.
By refining the inorganic fine particles to 200 nm or less, a high refractive index layer that does not impair the transparency can be formed.

  The high-refractive index layer used in the present invention is preferably added to the dispersion liquid in which the inorganic fine particles are dispersed in the dispersion medium as described above, preferably a binder precursor necessary for matrix formation (of the antiglare hard coat layer described above). The same as the binder precursor), a photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer, and the coating composition for forming a high refractive index layer is coated on a transparent support, and ionized. It is preferably formed by curing by a crosslinking reaction or a polymerization reaction of a radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

Furthermore, it is preferable to cause the binder of the high refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the application of the layer.
The binder of the high refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer undergo a crosslinking or polymerization reaction, and the binder is anionic. The base is incorporated. Furthermore, the binder of the high refractive index layer has a function in which the anionic group maintains the dispersed state of the inorganic fine particles, and the cross-linked or polymerized structure imparts a film forming ability to the binder to contain the inorganic fine particles. Improves physical strength, chemical resistance, and weather resistance.

It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
As the radical photopolymerization initiator, the same antiglare hard coat layer as described above can be used.

In the high refractive index layer, the binder preferably further has a silanol group. When the binder further has a silanol group, the physical strength, chemical resistance, and weather resistance of the high refractive index layer are further improved.
For example, the silanol group may be obtained by applying the silane coupling agent represented by the general formula 1 having a crosslinkable or polymerizable functional group, a partial hydrolyzate thereof, or a condensate thereof to the above coating composition for forming a high refractive index layer. Then, the coating composition is applied onto a transparent support, and the above-mentioned dispersant, polyfunctional monomer or polyfunctional oligomer, the silane coupling agent represented by the general formula 1, the partial hydrolyzate thereof, or the condensation thereof The product can be introduced into the binder by crosslinking reaction or polymerization reaction.

In the high refractive index layer, the binder preferably has an amino group or a quaternary ammonium group.
For the binder of the high refractive index layer having an amino group or quaternary ammonium group, for example, a monomer having a crosslinkable or polymerizable functional group and an amino group or quaternary ammonium group is added to the coating composition for forming the above high refractive index layer. And it can form by apply | coating a coating composition on a transparent support body, carrying out a crosslinking reaction or a polymerization reaction with said dispersing agent, a polyfunctional monomer, and a polyfunctional oligomer.

  A monomer having an amino group or a quaternary ammonium group functions as a dispersion aid for inorganic fine particles in the coating composition. Furthermore, after coating, a dispersant, a polyfunctional monomer or a polyfunctional oligomer is crosslinked or polymerized to form a binder, thereby maintaining good dispersibility of the inorganic fine particles in the high refractive index layer, physical strength, resistance A high refractive index layer excellent in chemical properties and weather resistance can be produced.

Preferable monomers having an amino group or a quaternary ammonium group include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, hydroxypropyltrimethylammonium chloride (meth) acrylate, dimethyl And allyl ammonium chloride.
It is preferable that the usage-amount with respect to the dispersing agent of the monomer which has an amino group or a quaternary ammonium group is 1-40 mass%, More preferably, it is 3-30 mass%, Most preferably, it is 3-20 mass%. If the binder is formed by crosslinking or polymerization reaction simultaneously with or after the application of the high refractive index layer, these monomers can be effectively functioned before the application of the high refractive index layer.

  The crosslinked or polymerized binder has a structure in which the main chain of the polymer is crosslinked or polymerized. Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

  The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked or polymerized structure.

The anionic group is preferably bonded to the main chain as a side chain of the binder via a linking group.
The linking group that binds the anionic group and the main chain of the binder is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked or polymerized structure chemically bonds (preferably covalently bonds) two or more main chains. In the crosslinked or polymerized structure, it is preferable to covalently bond three or more main chains. The crosslinked or polymerized structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof. .

  The binder is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked or polymerized structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96 mol%, more preferably 4 to 94 mol%, and most preferably 6 to 92 mol%. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked or polymerized structure in the copolymer is preferably 4 to 98 mol%, more preferably 6 to 96 mol%, and most preferably 8 to 94 mol%.

The repeating unit of the binder may have both an anionic group and a crosslinked or polymerized structure. The binder may contain other repeating units (repeating units having neither an anionic group nor a crosslinked or polymerized structure).
Other repeating units are preferably repeating units having a silanol group, an amino group or a quaternary ammonium group.

  In the repeating unit having a silanol group, the silanol group is directly bonded to the main chain of the binder or is bonded to the main chain via a linking group. The silanol group is preferably bonded to the main chain as a side chain via a linking group. The linking group that connects the silanol group and the main chain of the binder is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. When the binder contains a repeating unit having a silanol group, the ratio is preferably 2 to 98 mol%, more preferably 4 to 96 mol%, and most preferably 6 to 94 mol%.

  In the repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the binder or bonded to the main chain via a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or the quaternary ammonium group to the main chain of the binder is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the binder includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.1 to 32 mol%, more preferably 0.5 to 30 mol%, and more preferably 1 to 28 mol. % Is most preferred.

In addition, even if the silanol group, the amino group, and the quaternary ammonium group are contained in the repeating unit having an anionic group or the repeating unit having a crosslinked or polymerized structure, the same effect can be obtained.
The crosslinked or polymerized binder is preferably formed by applying a coating composition for forming a high refractive index layer on a transparent support and performing crosslinking or polymerization reaction simultaneously with or after coating.

  The binder of the high refractive index layer is added in an amount of 5 to 80% by mass based on the solid content of the coating composition of the layer.

The inorganic fine particles have a function of suppressing curing shrinkage as well as an effect of controlling the refractive index of the high refractive index layer.
In the high refractive index layer, the inorganic fine particles are preferably dispersed as finely as possible, and the mass average diameter is 1 to 200 nm. The mass average diameter of the inorganic fine particles in the high refractive index layer is preferably 5 to 150 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm.
By refining the inorganic fine particles to 200 nm or less, a high refractive index layer that does not impair the transparency can be formed.

The content of the inorganic fine particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more inorganic fine particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. A binder obtained by a crosslinking or polymerization reaction such as an ionizing radiation curable compound can also be preferably used.
In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably It is 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

In addition to the above components (inorganic fine particles, polymerization initiators, photosensitizers, etc.), the high refractive index layer includes resins, surfactants, antistatic agents, coupling agents, thickeners, anti-coloring agents, and coloring. Agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, conductive metal particles, etc. It can also be added.
The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

The strength of the high refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.
Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.
The haze of the high refractive index layer is preferably as low as possible when it does not contain particles that impart an antiglare function. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The high refractive index layer is preferably constructed directly on the transparent support or via another layer.

(Low refractive index layer)
The low refractive index layer preferably used in the antireflection film of the present invention will be described below.
The refractive index of the low refractive index layer in the present invention is preferably in the range of 1.31 to 1.48 for the purpose of imparting antireflection properties. The low refractive index layer in the present invention is preferably constructed as an outermost layer having scratch resistance and antifouling properties.

(Material for forming cured film of low refractive index layer)
The low refractive index layer of the present invention preferably contains a fluorine-containing polymer as a low refractive index binder. The fluoropolymer is preferably a fluoropolymer that is crosslinked by heat or ionizing radiation.
Further, the above-mentioned low refractive index layer is a conventionally known silicone and / or fluorine-containing compound as means for realizing a low refractive index and effectively imparting slipperiness to the surface and greatly improving the scratch resistance. It is preferable to appropriately apply the material for forming a cured film into which is introduced. More preferably, it contains a fluorine-containing compound. In particular, the low refractive index layer in the present invention is composed mainly of a thermosetting and / or light or radiation (for example, ionizing radiation) curable crosslinkable fluorine-containing compound and is composed of a cured fluorine-containing polymer. Is preferred.

  Therefore, in the present invention, the low refractive index layer is produced in the presence of the above-mentioned inorganic fine particles and an acid catalyst, and the hydrolyzate of the organosilane represented by the general formula (1) described above and again shown below. And / or a partially condensed product thereof, and a cured film formed by applying and curing a curable low refractive index layer-forming composition containing at least one fluorine-containing polymer having a curable reactive group. It is preferable.

Formula _{1: R m Si (X)} n
(R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M + n is 4, and m and n are each an integer of 0 or more. M is 0-3.)

The composition for forming a low refractive index layer further contains a polyfunctional polymerizable compound containing at least two polymerizable groups selected from radical polymerizable groups and / or cationic polymerizable groups and a polymerization initiator. It is also preferable.
In addition, an inorganic filler for improving the film strength can be used in the low refractive index layer of the present invention. The low refractive index layer preferably contains at least one hollow structure inorganic fine particle having a refractive index of 1.17 to 1.37. The inorganic fine particles preferably have an average particle size of 30% to 100% of the thickness of the low refractive index layer. If the average particle diameter of the inorganic fine particles is in the range of 30% to 100% of the thickness of the low refractive index layer, the strength of the low refractive index layer film is sufficiently exhibited, which is preferable. In addition, by using inorganic fine particles having such a refractive index in the low refractive index layer, while suppressing an increase in the refractive index of the layer itself, there are also restrictions such as a long-time thermosetting and a saponification treatment for providing a polarizing film. Without both, a low refractive index and high film strength can be achieved at the same time.
Hereinafter, the curable composition for forming a low refractive index layer will be described in detail.

(Composition for forming a low refractive index layer)
<Fluoropolymer>
As described above, the low refractive index layer in the present invention is composed of a fluorine-containing polymer formed and cured mainly of a thermosetting and / or light or radiation (for example, ionizing radiation) curable fluorine-containing compound. It is preferable.

  In the present invention, “mainly containing a fluorine-containing compound” means that the fluorine-containing compound contained in the low refractive index layer is 50% by mass or more based on the total mass of the low refractive index layer. More preferably, it is contained in an amount of at least mass%.

  The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47. Moreover, it is preferable that a fluorine-containing compound contains a fluorine atom in 35-80 mass%.

  Examples of the fluorine-containing compound include a fluorine-containing polymer, a fluorine-containing surfactant, a fluorine-containing ether, and a fluorine-containing silane compound. Specifically, for example, paragraph numbers [0018] to [0026] of JP-A-9-222503, paragraph numbers [0019] to [0030] of JP-A-11-38202, paragraph number [0018] of JP-A-2001-40284 [0027] to [0028], and the compounds described in paragraph Nos. [0030] to [0047] of 2004-45462.

In particular, the fluorine-containing polymer preferably used for the low refractive index layer includes hydrolysis and dehydration condensation of a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). In addition to the above-mentioned products, there can be mentioned fluorine-containing copolymers having a fluorine-containing monomer unit and a constituent unit for imparting crosslinking reactivity as constituent components.
Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole. Etc.), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical), M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

The fluorine-containing polymer used for the low-refractive index layer includes a repeating structural unit containing a fluorine atom, a repeating structural unit containing a crosslinkable or polymerizable functional group, and a co-polymer consisting of a repeating structural unit composed of other substituents. Coalescence is preferred. That is, a copolymer of a fluorinated monomer and a monomer for imparting a crosslinkable group, that is, a fluorinated polymer having a curable reactive group that is a crosslinkable or polymerizable functional group is preferred, and other monomers are also co-polymerized. A polymerized fluorine-containing polymer may be used.
The crosslinkable or polymerizable functional group may be any conventionally known functional group.

  Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. These compounds having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  Examples of the polymerizable functional group include a radical polymerizable group and a cationic polymerizable group. Preferably, radically polymerizable groups [for example, (meth) acryloyl group, styryl group, vinyloxy group, etc.] and cationically polymerizable groups (for example, epoxy group, thioepoxy group, oxetanyl group, etc.) are mentioned.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. Such a repeating structural unit is preferably a repeating structural unit formed by a hydrocarbon-based copolymer component for solvent solubilization, and a fluorine-based polymer in which such a structural unit is introduced in an amount of about 50% by mass in the whole polymer. preferable. In this case, it is also preferable to combine with a silicone compound.

  Other monomers that may be copolymerized are not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate) , 2-ethylhexyl acrylate), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), Vinyl ethers (such as methyl vinyl ether), vinyl esters (such as vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamides (such as Nt-butylacrylamide, N-cyclohexylacrylamide), methacrylamido Kind, and acrylonitrile derivatives.

  The silicone compound preferably copolymerized is a compound having a polysiloxane structure, which contains a curable functional group or a polymerizable functional group in the polymer chain, and is crosslinked in the low refractive index layer film. Those having a structure are preferred. Examples thereof include reactive silicones such as “Silaplane” [manufactured by Chisso Corporation], and compounds containing silanol groups at both ends of the polysiloxane structure described in JP-A-11-258403.

  Crosslinking or polymerization reaction of a fluorine-containing polymer having a crosslinkable or polymerizable group is carried out by irradiating light or heating a curable composition for forming a low refractive index layer, which is the outermost layer, simultaneously with or after coating. It is preferable. In this case, examples of the polymerization initiator that can be used include the same as those described for the high refractive index layer.

  When the polymerization reaction is performed by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination. Examples include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The low refractive index layer is a sol-gel cured film formed by curing an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent in the presence of a catalyst in a condensation reaction. Are also preferably used.

  For example, polyfluoroalkyl group-containing silane compounds or partially hydrolyzed condensates thereof (compounds described in JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, etc.), JP-A-9-157582 Perfluoroalkyl group-containing silane coupling agents described in Japanese Patent Publication No. JP-A-2000-117902, and silyl compounds containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (JP 2000-117902 A, JP 2001-48590 A, And the like described in JP-A-2002-53804).

  Examples of the catalyst to be used in combination include conventionally known compounds, and those described in the above documents are preferably exemplified.

  As the fluorine-containing polymer having a curable reactive group particularly useful in the present invention, a copolymer of a perfluoro compound selected from perfluoroolefin, perfluorocycloolefin, and non-conjugated perfluorodiene and vinyl ethers or vinyl esters. Is mentioned. In particular, it preferably has a group capable of undergoing crosslinking reaction alone [a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group]. These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymerized units of the polymer.

  As a preferred form of the copolymer used for the low refractive index layer, one having the following general formula 4 can be mentioned.

In General Formula 4, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred examples include *-(CH ₂ ) ₂ -O-**, *-(CH ₂ ) ₂ -NH-**, *-(CH ₂ ) ₄ -O-**, *-(CH ₂ ) ₆ -O-**, *-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O-**, * -CONH- (CH ₂ ) ₃ -O-**, * -CH ₂ CH (OH ) CH ₂ -O-**, * -CH ₂ CH ₂ OCONH (CH ₂ ) ₃ -O-** (* represents the linking site on the polymer main chain side, ** represents the linking on the (meth) acryloyl group side) Represents a part). m represents 0 or 1;

  In General Formula 4, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the general formula 4, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each structural component, x represents 30 to 60, y represents 5 to 70, and z represents a value satisfying 0 to 65, respectively. Preferably, x is 35 to 55, y is 30 to 60, and z is 0 to 20, particularly preferably x is 40 to 55, y is 40 to 55, and z is 0 to 10.

  As a particularly preferred form of the copolymer used for the low refractive index layer, the general formula 5 can be mentioned.

In general formula 5, X, x, and y have the same meaning as in general formula 4, and the preferred ranges are also the same.
n represents an integer of 2 to 10, preferably 2 to 6, and particularly preferably 2 to 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 4 is applicable.
z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 to 65 and 0 to 65. z1 is preferably 0 to 30, and z2 is preferably 0 to 10, z1 is preferably 0 to 10, and z2 is particularly preferably 0 to 5.

  For the copolymer represented by the general formula 4 or 5, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized.

  Specific examples of the compound include compounds described in paragraph numbers “0043” to “0047” of JP-A-2004-45462. However, the present invention is not limited to these.

  The copolymer used for the low refractive index layer is synthesized by synthesizing precursors such as a hydroxyl group-containing polymer by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. Then, it can be carried out by introducing a (meth) acryloyl group by the polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to carry out the polymerization in the range of 50 to 100 ° C.

The reaction pressure can be selected as appropriate, but it is usually 1-100 kg / cm ² , particularly about 1-30 kg / cm ² . The reaction time is about 5 to 30 hours.

  As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.

  The fluorine-containing polymer of the low refractive index layer is added in an amount of 20 to 95% by mass based on the solid content of the coating composition of the layer.

Next, the inorganic fine particles that can be contained in the low refractive index layer of the present invention are described below.
As the inorganic fine particles used in the low refractive index layer, particles such as silicon dioxide (silica) and fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride) are preferable. Particularly preferred are silicon dioxide (silica) particles.
The amount of the inorganic fine particles is ^{preferably 1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . When the blending amount is in the above range, the scratch resistance is excellent, the occurrence of fine irregularities on the surface of the low refractive index layer is reduced, and the appearance such as black tightening and the integrated reflectance are improved.
Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost. The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to further reduce the increase in the refractive index of the low refractive index layer, it is preferable to use hollow inorganic fine particles, and the hollow inorganic fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1. .35, more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the inorganic component of the outer shell forming the hollow inorganic particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x calculated from the following formula (9) is preferably 10 to 60%, more preferably 20 to 60. %, Most preferably 30-60%.
Equation (9): x = (4πa 3/3) / (4πb 3/3) × 100
If the hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the low refractive index is less than 1.17. Rate particles are not used.
The refractive index of these hollow inorganic particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  The void ratio of the hollow particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.

  The average particle diameter of the hollow particles is preferably 30% or more and 100% or less, more preferably 35% or more and 80% or less, and particularly preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the hollow particles is preferably in the range of 30 nm to 100 nm, more preferably 35 nm to 80 nm, and particularly preferably 40 nm to 60 nm. When the average particle size is in the above range, the strength of the film is sufficiently expressed, which is preferable.

(Inorganic fine particles of small size)
In addition, at least one kind of inorganic fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (hereinafter sometimes referred to as “small size particles”) is used as the above-mentioned inorganic fine particles having a larger particle size. (Hereinafter, sometimes referred to as “large size particles”) is preferably used together. The small size particles may not have a hollow structure.
The small size particles are preferable because they can exist in the gaps between the large size particles, and can contribute as a retaining agent for the large size particles. Moreover, it is preferable also in terms of raw material costs.

  When the low refractive index layer is 100 nm, the average particle size of the small size particles is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm.

  5-100 mass parts is preferable with respect to 100 mass parts of large size particles (preferably hollow particles), and more preferably 10-80 mass parts.

  Specific compounds constituting the small size particles include the same compounds as exemplified for the hollow particles. Particularly preferred is an oxide of silicon.

The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape.
(Dispersion of inorganic fine particles)
Any of the inorganic fine particles described above may be used in the dispersion or in the curable composition for forming a low refractive index layer in order to stabilize dispersion, or to increase the affinity and binding properties with the binder component. A physical surface treatment such as a plasma discharge treatment or a corona discharge treatment, or a chemical surface treatment with a surfactant or a coupling agent may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (for example, a titanium coupling agent or a silane coupling agent) is preferably used. Of these, treatment with a silane coupling agent is particularly preferred. As the silane coupling agent, those represented by the general formula (1) can also be preferably used.

The above coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in order to perform surface treatment in advance before the preparation of the coating liquid for forming the curable low refractive index layer. It is preferable to add it as an additive at the time of preparation to be contained in the layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

  The blending ratio of the inorganic fine particles is preferably 5 to 90 parts by mass with respect to 100 parts by mass of the composition for forming a low refractive index layer from the viewpoint of transparency, strength, etc. of the low refractive index layer film. More preferably, it is set to -60 mass parts. Moreover, when mix | blending a hollow particle and another particle, 5-95 mass parts is preferable, and, as for the hollow particle in all the particles, More preferably, it is 10-90 mass parts, Most preferably, it is 30-80 mass parts.

(Organosilane compound)
At least one of the functional layers constituting the antireflection film of the present invention includes at least one component of an organosilane compound, a hydrolyzate thereof and a partial condensate thereof, a so-called sol, in the coating liquid forming the layer. It is preferable in terms of scratch resistance to contain a component (hereinafter sometimes referred to as such). In particular, the low refractive index layer preferably contains a sol component in order to achieve both antireflection ability and scratch resistance, and the hard coat layer also preferably contains a sol component. This sol component is condensed by a drying and heating process after coating the coating solution to form a cured product, which becomes a binder for the layer. Moreover, when this hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.
As the organosilane compound, an organosilane hydrolyzate and / or a partial condensate thereof represented by the general formula (1) is particularly preferable.

The hydrolyzate and / or partial condensate of the organosilane compound particularly preferred in the present invention is generally produced by treating the organosilane compound in the presence of a catalyst. Examples of the catalyst include acids, bases, organometallic compounds, and the like, and specific examples include the same as described in the high refractive index layer sol-gel reaction.
The hydrolysis reaction of organosilane and the subsequent condensation reaction are generally carried out in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

The organosilane hydrolysis / condensation reaction can be carried out in the absence of a solvent or in a solvent, but an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, Ketones and esters are preferred.
The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating liquid or a part of the coating liquid, and those that do not impair solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms.
Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of solid content in the reaction is not particularly limited, but is usually in the range of 1% to 90%, preferably in the range of 20% to 70%.

0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane, in the presence or absence of the above solvent, and in the presence of a catalyst. It is carried out by stirring at 25 to 100 ° C.
In the present invention, (wherein, ^{R 3} represents an alkyl group having 1 to 10 carbon atoms) Formula ^R 3 OH alcohol of the general formula ^R 4 COCH ₂ COR ⁵ (formula represented by, ^{R 4} is carbon From Zr, Ti, or Al having a ligand represented by a compound represented by an alkyl group having 1 to 10 carbon atoms, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) Hydrolysis is preferably performed by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a selected metal as a central metal.

Metal chelate compounds (wherein, ^{R 3} represents an alkyl group having 1 to 10 carbon atoms) Formula ^R 3 OH alcohol and ^R 4 COCH ₂ COR ⁵ (wherein represented by, ^{R 4} is C 1 -C To 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a metal as a central metal can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has a general formula of Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred, and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. If it is less than 0.01% by mass, the condensation reaction of the organosilane compound is slow, and the durability of the coating film may be deteriorated. On the other hand, if it exceeds 50% by mass, the hydrolyzate and / or partial condensate of the organosilane compound And the storage stability of the composition containing the metal chelate compound may be deteriorated, which is not preferable.

  In addition to the composition containing the sol component and the metal chelate compound, a β-diketone compound and / or a β-ketoester compound is added to the coating liquid for the hard coat layer or the low refractive index layer used in the present invention. Is preferred. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention, and acts as a stability improver for the composition used in the present invention. Is. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition may be inferior, which is not preferable.

The content of the hydrolyzate and / or partial condensate of the organosilane compound is preferably small for the surface layer that is a relatively thin film and large for the lower layer that is a thick film. In the case of a surface layer such as a low refractive index layer, the total solid content of the content layer (addition layer) is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and 1 to 10% by mass. Most preferred.
The amount added to the layers other than the low refractive index layer is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and more preferably 0.05 to 10 mass% of the total solid content of the containing layer (addition layer). More preferably, it is 0.1 to 5% by mass.
In the present invention, first, a composition containing a hydrolyzate and / or partial condensate of the organosilane compound and a metal chelate compound is prepared, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto is prepared. It is preferable to coat by coating it in at least one coating solution of a hard coat layer or a low refractive index layer.

  5-100 mass% is preferable, the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer has more preferable 5-40 mass%, 8-35 mass% is still more preferable, 10-30 mass % Is particularly preferred. If the amount used is too small, it is difficult to obtain the effect of the present invention. However, if the amount used is less than or equal to the upper limit value, the refractive index increases too much, or the shape and surface shape of the low refractive index layer film deteriorate. Therefore, it is preferable to use an appropriate amount within the above range because the excellent effects of the present invention can be exhibited.

(Polyfunctional polymerizable compound)
As described above, a polyfunctional polymerizable compound can be further added to the curable composition for forming the low refractive index layer.

  As the polyfunctional polymerizable compound, any of radical polymerizable functional group and / or cationic polymerizable functional group may contain two or more polymerizable groups. Examples of the radical polymerizable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group is preferable. It is preferable to contain a polyfunctional monomer containing two or more radically polymerizable groups in the molecule.

  As the cationically polymerizable compound used in the present invention, any compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator can be used. Examples thereof include an epoxy compound, a cyclic thioether compound, a cyclic ether compound, a spiro orthoester compound, a vinyl hydrocarbon compound, and a vinyl ether compound. In the present invention, one or more of the above cationic polymerizable organic compounds may be used. Specific contents of these radical polymerizable compounds and cationic polymerizable compounds include those similar to the polyfunctional monomers and oligomers described in the high refractive index layer.

  The radical polymerizable compound and the cationic polymerizable compound described above are preferably contained in a mass ratio of radical polymerizable compound: cation polymerizable compound in a ratio of 90:10 to 20:80, and 80:20 to More preferably, it is contained at a ratio of 30:70. Moreover, it is preferable that the compounding quantity of the said polyfunctional polymerizable compound containing a radically polymerizable compound and a cationically polymerizable compound shall be 0.1-20 mass parts with respect to 100 mass parts of said fluoropolymers.

(Other additives)
In addition to the components described above, the low refractive index layer in the present invention is provided with an anti-fouling property of a known silicone compound or fluorine compound for the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like. It is preferable that a soiling agent, a slipping agent and the like are appropriately added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the curable composition for forming the low refractive index layer, more preferably 0.05 to It is a case where it is added in the range of 10% by mass, and particularly preferably 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the end of the compound chain and / or the side chain, containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. Can be mentioned.

  Although there is no restriction | limiting in particular in the molecular weight of a silicone type compound, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular also in silicone atom content of a silicone type compound, It is preferable that it is 18.0 mass% or more, It is especially preferable that it is 25.0-37.8 mass%, 30.0-37. Most preferably, it is 0.0 mass%.

  Examples of preferable silicone compounds include, but are not limited to, those described in paragraph No. [0068] of JP-A-2004-42278.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain [eg, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.], but branched structures [eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.], an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group). , A perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C). ₄ F ₈ H, - _{H 2 CH 2 OCH 2 CH 2} C 8 F 17, -CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  The fluorine-based compound preferably further has a substituent that contributes to bond formation or compatibility with the film of the low refractive index layer. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.

  The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited and is used. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferable fluorine-based compounds include “R-2020”, “M-2020”, “R-3833”, “M-3833” [trade name: manufactured by Daikin Chemical Industries, Ltd.]; "F-171", "Megafuck F-172", "Megafuck F-179A", "Defenser MCF-300" [trade name: manufactured by Dainippon Ink, Ltd.] It is not something.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a dustproof agent, an antistatic agent, and the like such as known cationic surfactants or polyoxyalkylene compounds can be added as appropriate. As for these dustproof agent and antistatic agent, the structural unit may be included as a part of the function in the above-described silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the curable composition, more preferably in the range of 0.05 to 10% by mass. This is the case.

  The low refractive index layer may also contain microvoids. Specific examples include the contents described in JP-A-9-222502, JP-A-9-288201, JP-A-11-6902, and the like.

  Furthermore, in the present invention, organic fine particles can also be used. Examples of the organic fine particles include compounds described in paragraphs [0020] to [0038] of JP-A No. 11-3820, and the shape thereof is The same as the above-mentioned inorganic fine particles.

  The thickness of the low refractive index layer is preferably 0.03 to 0.2 μm, more preferably 0.05 to 0.15 μm.

(Properties of low refractive index layer)
The low refractive index layer in the present invention preferably has a surface energy of 26 mN / m or less, more preferably 15 to 25.8 mN / m. It is preferable from the viewpoint of antifouling property to make the surface energy within this range.

  In addition, the low refractive index layer exhibits antifouling effect if it is a cured film made of a fluoropolymer containing a thermosetting or light or radiation (for example, ionizing radiation) curable crosslinkable fluorine compound. Therefore, it is preferable. In particular, if the fluorine-based compound contained in the low refractive index layer that is the outermost layer is 50% by mass or more with respect to the total mass of the outermost layer, the entire surface of the low refractive index layer film has uniform and stable characteristics. This is preferable.

  The surface energy of a solid can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” (issued by Realize 1989.12.10). In the case of the film of the present invention, it is preferable to use a contact angle method. Specifically, two types of solutions having known surface energies are dropped on the protective film surface of the polarizing plate, and the tangent line drawn on the droplet and the film surface are crossed at the intersection of the surface of the droplet and the film surface. The surface angle of the film is defined as the contact angle, and the surface energy of the film can be calculated by calculation. The contact angle of the outermost layer surface with water is preferably 90 ° or more, more preferably 95 ° or more, and particularly preferably 100 ° or more.

  The dynamic friction coefficient on the surface of the low refractive index layer is preferably 0.25 or less, more preferably 0.05 to 0.25, and particularly preferably 0.03 to 0.15. The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless steel hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless steel hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min. .

  The hardness of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K-5400. The scratch resistance of the low refractive index layer is preferably as the wear amount in the Taber test according to JIS K-6902 is smaller.

[Polarizing plate / Polarizing film]
The optical film of the present invention is preferable because it can remarkably exhibit its function by being bonded to a polarizing plate or used as a protective film for a polarizing plate.
The polarizing plate is mainly composed of a polarizing film and two protective films sandwiching it from both sides. The optical film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides.

As the polarizing film, a known polarizing film may be used, or a polarizing film cut out from a long polarizing film roll whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. The polarizing film is preferably a coating-type polarizing film having a use size typified by those manufactured by Optiva, or a polarizing film made of a binder and iodine or a dichroic dye.
In the latter case, iodine and dichroic dye in the polarizing film exhibit a deflection performance by being oriented in the binder. It is preferable that the iodine and the dichroic dye are aligned along the binder molecule, or the dichroic dye is aligned in one direction by self-assembly such as liquid crystal.
Currently used polarizers are made by immersing a stretched polymer binder in a solution of iodine or dichroic dye in a bath and allowing iodine or dichroic dye to penetrate into the binder. Is common.
In general-purpose polarizing films, iodine or dichroic dye is distributed about 4 μm (about 8 μm on both sides) from the polymer surface, and a thickness of at least 10 μm is necessary to obtain sufficient polarization performance. The penetrability can be controlled by the solution concentration of iodine or dichroic dye, the temperature of the bath, and the immersion time.
As described above, the lower limit of the binder thickness is preferably 10 μm. On the other hand, the upper limit of the thickness is not particularly limited, but the thinner the better, from the viewpoint of suppressing the light leakage phenomenon that occurs when the polarizing plate is used in a liquid crystal display device. In the case of the polarizing plate used in the present invention, it is preferably not more than currently used polarized light (about 30 μm), more preferably 25 μm or less, and further preferably 20 μm or less. When the thickness is 20 μm or less, the light leakage phenomenon is not observed on a 17-inch liquid crystal display device.

The binder of the polarizing film may be cross-linked. As the crosslinked binder, a polymer that can be crosslinked per se can be used. A polarizing film can be formed by reacting a polymer having a functional group or a binder obtained by introducing a functional group into a polymer between the binders by light, heat, or pH change.
Moreover, you may introduce | transduce a crosslinked structure into a polymer with a crosslinking agent. The introduction of the crosslinked structure can be formed by introducing a bonding group derived from the crosslinking agent between the binders using a crosslinking agent that is a highly reactive compound and crosslinking between the binders.
Crosslinking is generally carried out by applying a coating solution containing a polymer or a mixture of a polymer and a crosslinking agent on a transparent support and then heating. Since it is only necessary to ensure durability at the final product stage, the crosslinking treatment may be performed at any stage until the final polarizing plate is obtained.

  As the binder for the polarizing film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used. Examples of polymers include polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, polystyrene, gelatin, polyvinyl alcohol, modified polyvinyl alcohol, poly (N-methylolacrylamide), polyvinyltoluene, chlorosulfonated polyethylene, nitrocellulose, chlorinated Polyolefin (eg, polyvinyl chloride), polyester, polyimide, polyvinyl acetate, polyethylene, carboxymethyl cellulose, polypropylene, polycarbonate and copolymers thereof (eg, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, styrene) / Vinyl toluene copolymer, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer). Water-soluble polymers (eg, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol) are preferred, gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred, and polyvinyl alcohol and modified polyvinyl alcohol are most preferred. .

The saponification degree of polyvinyl alcohol and modified polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%, and most preferably 95 to 100%. The polymerization degree of polyvinyl alcohol is preferably 100 to 5000.
Modified polyvinyl alcohol is obtained by introducing a modifying group into polyvinyl alcohol by copolymerization modification, chain transfer modification or block polymerization modification. In the copolymerization modification, COONa, Si (OH) ₃ , N (CH ₃ ) ₃ .Cl, C ₉ H ₁₉ COO, SO ₃ Na, C 12 H ₂₅ can be introduced as modifying groups. In chain transfer modification, COONa, SH, or SC ₁₂ H ₂₅ can be introduced as a modifying group. The degree of polymerization of the modified polyvinyl alcohol is preferably 100 to 3000. The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127.
Unmodified polyvinyl alcohol and alkylthio-modified polyvinyl alcohol having a saponification degree of 85 to 95% are particularly preferred.
Two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

When a large amount of the crosslinking agent for the binder is added, the heat and humidity resistance of the polarizing film can be improved. However, when 50 mass% or more of a crosslinking agent is added to the binder, the orientation of iodine or the dichroic dye is lowered. The addition amount of the crosslinking agent is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass with respect to the binder.
The binder contains some crosslinking agent that has not reacted even after the crosslinking reaction has been completed. However, the amount of the remaining crosslinking agent is preferably 1.0% by mass or less in the binder, and more preferably 0.5% by mass or less. When the crosslinking agent is contained in the binder layer in an amount exceeding 1.0% by mass, there may be a problem in durability. That is, when a polarizing film having a large amount of residual crosslinking agent is incorporated in a liquid crystal display device and used for a long time or left in a high-temperature and high-humidity atmosphere for a long time, the degree of polarization may decrease.
The crosslinking agent is described in US Reissue Patent 23297. Boron compounds (eg, boric acid, borax) can also be used as a crosslinking agent.

As the dichroic dye, an azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye is used. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (eg, sulfo, amino, hydroxyl).
Examples of dichroic dyes include C.I. I. Direct Yellow 12, C.I. I. Direct Orange 39, C.I. I. Direct Orange 72, C.I. I. Direct Red 39, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I. I. Direct Violet 48, C.I. I. Direct Blue 67, C.I. I. Direct Blue 90, C.I. I. Direct Green 59, C.I. I. Acid Red 37 is included. As for the dichroic dyes, those described in JP-A-1-161202, 1-172906, 1-172907, 1-183602, 1-248105, 1-265205, 7-261024 are used. There are descriptions in each publication.
The dichroic dye is used as a free acid or an alkali metal salt, ammonium salt or amine salt. By blending two or more kinds of dichroic dyes, polarizing films having various hues can be produced. A polarizing film using a compound (pigment) that exhibits a black color when the polarization axes are orthogonal to each other, or a polarizing film or a polarizing plate in which various dichroic molecules are blended so as to exhibit a black color, have both a single-plate transmittance and a polarizability. It is excellent and preferable.

  In order to increase the contrast ratio of the liquid crystal display device, the transmittance of the polarizing plate is preferably higher and the degree of polarization is preferably higher. The transmittance of the polarizing plate is preferably in the range of 30 to 50%, more preferably in the range of 35 to 50%, and in the range of 40 to 50% in the light having a wavelength of 550 nm (of the polarizing plate). Most preferably, the maximum value of the single plate transmittance is 50%. The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.

  It is also possible to arrange the polarizing film and the optically anisotropic layer, or the polarizing film and the alignment film via an adhesive. As the adhesive, a polyvinyl alcohol resin (including a modified polyvinyl alcohol with an acetoacetyl group, a sulfonic acid group, a carboxyl group, or an oxyalkylene group) or an aqueous boron compound solution can be used. Of these, polyvinyl alcohol resins are preferred. The thickness of the adhesive layer is preferably in the range of 0.01 to 10 μm after drying, and particularly preferably in the range of 0.05 to 5 μm.

(Manufacture of polarizing plates)
From the viewpoint of yield, the polarizing film is stretched by tilting the binder at an angle of 10 to 80 degrees with respect to the longitudinal direction (MD direction) of the polarizing film (stretching method), or rubbed (rubbing method). It is preferable to dye with a dichroic dye. The tilt angle is preferably stretched so as to match the angle formed between the transmission axis of the two polarizing plates bonded to both sides of the liquid crystal cell constituting the LCD and the vertical or horizontal direction of the liquid crystal cell.
A normal inclination angle is 45 °. However, recently, liquid crystal display devices that are not necessarily 45 ° have been developed for transmissive, reflective, and transflective LCDs, and it is preferable that the stretching direction can be arbitrarily adjusted in accordance with the design of the LCD.

In the stretching method, the stretching ratio is preferably 2.5 to 30.0 times, and more preferably 3.0 to 10.0 times. Stretching can be performed by dry stretching in air. Moreover, you may implement wet extending | stretching in the state immersed in water. The stretch ratio of dry stretching is preferably 2.5 to 5.0 times, and the stretch ratio of wet stretching is preferably 3.0 to 10.0 times. The stretching step may be performed in several steps including oblique stretching. By dividing into several times, it is possible to stretch more uniformly even at high magnification. Before the oblique stretching, a slight stretching (a degree to prevent shrinkage in the width direction) may be performed horizontally or vertically.
Diagonal stretching can be performed by performing tenter stretching in biaxial stretching by different stretching operations. The biaxial stretching is the same as the stretching method performed in normal film formation. In biaxial stretching, stretching is performed at different speeds on the left and right, so that the thickness of the binder film before stretching needs to be different on the left and right. For this purpose, in casting film formation, the die solution can be tapered to make a difference between the left and right in the flow rate of the binder solution.
As described above, a binder film that is obliquely stretched by 10 to 80 degrees with respect to the MD direction of the polarizing film is manufactured.
The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

In the rubbing method, a rubbing treatment method widely adopted as a liquid crystal alignment treatment process of LCD can be applied. That is, orientation is obtained by rubbing the surface of the film in a certain direction using paper, gauze, felt, rubber, nylon, or polyester fiber. Generally, it is carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are planted on average. It is preferable to carry out using a rubbing roll in which the roundness, cylindricity, and deflection (eccentricity) of the roll itself are all 30 μm or less. The wrap angle of the film on the rubbing roll is preferably 0.1 to 90 °. However, as described in JP-A-8-160430, a stable rubbing treatment can be obtained by winding 360 ° or more.
When rubbing a long film, it is preferable to transport the film at a speed of 1 to 100 m / min with a constant tension by a transport device. The rubbing roll is preferably rotatable in the horizontal direction with respect to the film traveling direction for setting an arbitrary rubbing angle. It is preferable to select an appropriate rubbing angle in the range of 0 to 60 °. When used in a liquid crystal display device, the angle is preferably 40 to 50 °. 45 ° is particularly preferred.

(Polarizing plate protective film)
In the polarizing plate of the present invention, the film on the side in contact with the liquid crystal cell is preferably an optical compensation film having an optical compensation layer comprising an optical anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film. However, in terms of widening the viewing angle, an optical compensation layer made of a compound having a discotic structural unit described in JP-A-2001-100042 is provided. An optical compensation film characterized in that the angle formed by the discotic compound and the support is changed in the depth direction of the layer is preferable.
The angle preferably increases as the distance from the support surface side of the optically anisotropic layer increases.
The manufacturing cost of a polarizing plate can be reduced because the optical compensation film of the present invention also serves as a polarizing plate protective film.

  In the present invention, when a film (such as an antireflection film, an antiglare film, or a light diffusing film) imparting surface reflectivity and surface hardness, represented by an antireflection film, is used for an image display device, an adhesive layer is provided on one side. It is preferable to arrange on the outermost surface of the display, for example. When the transparent support is triacetylcellulose, triacetylcellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film.

When the antireflection film of the present invention is disposed on the outermost surface of a display by providing an adhesive layer on one side, or is used as it is as a protective film for a polarizing plate, it is a transparent support for sufficient adhesion. It is preferable to carry out a saponification treatment after an outermost layer mainly composed of a fluoropolymer is formed thereon. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a deflection film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so it is difficult for dust to enter between the deflection film and the antireflection film when bonded to the deflection film, thus preventing point defects due to dust. It is valid.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the surface of the antireflection film is saponified, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, the method (2) is superior.
(1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the formation of the antireflection layer on the transparent support, the alkaline liquid is applied to the surface of the antireflection film opposite to the surface on which the antireflection film is formed, and is heated, washed and / or washed. By summing, only the back surface of the film is saponified.
By using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate excellent in scratch resistance, antifouling property and the like can be obtained.

  In the polarizing plate of the present invention, it is particularly preferable to provide an antireflection film, an antiglare film and a light scattering film on the outermost surface side of the image surface device, and to provide an optical compensation film on the side in contact with the image display device. A combination of an antireflection film and an optical compensation film is particularly preferable.

(Image display device)
The optical film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). The anti-reflection and anti-glare film of the present invention is used by adhering the transparent support side to the image display surface of the image display device for surface protection and anti-surface reflection.

The antireflection film of the present invention, when used as one side of the surface protective film of the polarizing film, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of a mode such as a curry compensate bend cell (OCB).
Further, among the present invention, the optical compensation film can be preferably used for a liquid crystal display device. In that case, it becomes more preferable by using the optically anisotropic layer shown below.

A preferred form of the optically anisotropic layer in each liquid crystal mode will be described below.
(TN mode liquid crystal display)
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.
The alignment state in the liquid crystal cell in the TN mode black display is an alignment state in which the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie in the vicinity of the cell substrate.

The rod-like liquid crystalline molecules in the center of the cell are compensated with discotic liquid crystalline molecules of homeotropic orientation (horizontal orientation in which the disc surface lies down) or (transparent) support, and the rod-like liquid crystalline properties in the vicinity of the cell substrate The molecule can be compensated by a discotic liquid crystalline molecule having a hybrid orientation (an orientation in which the inclination of the major axis changes with the distance from the polarizing film).
The rod-like liquid crystalline molecules in the center of the cell are compensated with rod-like liquid crystalline molecules of homogeneous orientation (horizontal orientation in which the major axis lies) or (transparent) support, and the rod-like liquid crystalline properties in the vicinity of the cell substrate The molecule can be compensated by a discotic liquid crystal molecule of hybrid orientation.

Homeotropic alignment liquid crystal molecules are aligned in a state where the angle between the long axis average alignment direction of the liquid crystal molecules and the plane of the polarizing film is 85 to 95 °.
The liquid crystal molecules of homogeneous alignment are aligned with the angle between the average alignment direction of the long axes of the liquid crystal molecules and the plane of the polarizing film being less than 5 °.
In the hybrid alignment liquid crystal molecules, the angle between the average alignment direction of the long axes of the liquid crystal molecules and the plane of the polarizing film is preferably larger than 15 °, and more preferably 15 ° to 85 °.

(Transparent) An optically anisotropic layer in which the support or discotic compound is homeotropically oriented, an optically anisotropic layer in which rod-like liquid crystalline molecules are homogeneously oriented, and a homeotropically oriented discotic compound and The optically anisotropic layer comprising a homogeneously aligned rod-like liquid crystal molecule mixture preferably has an Rth retardation value of 40 nm to 200 nm and an Re retardation value of 0 to 70 nm. The Rth retardation value (Rth) is a value defined by the following formula (I), and the Re retardation value (Re) is a value defined by the following formula (II).
(I) Rth = {(nx + ny) / 2−nz} × d
(II) Re = (nx−ny) × d
[In formulas (I) and (II), nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, and nz is the film refractive index. The refractive index in the thickness direction. And d is the thickness of the film].
Regarding the discotic liquid crystalline molecular layer having homeotropic alignment (horizontal alignment) and the rod-like liquid crystalline molecular layer having homogeneous alignment (horizontal alignment), JP-A-12-304931 and JP-A-12-304932 describe each of them. Are listed. Japanese Patent Application Laid-Open No. 8-50206 discloses a disk-like liquid crystal molecular layer having a hybrid orientation.

(OCB mode liquid crystal display)
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between an upper portion and a lower portion of the liquid crystal cell. Liquid crystal display devices using a bend alignment mode liquid crystal cell are disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is called an OCB (Optically Compensatory Bend) liquid crystal mode.
Similarly to the TN mode, the liquid crystal cell in the OCB mode is in a black display, and the alignment state in the liquid crystal cell is such that the rod-like liquid crystal molecules rise in the center of the cell and the rod-like liquid crystal molecules lie in the vicinity of the cell substrate. .

  Since the TN mode and the alignment of the liquid crystal are the same in black display, the preferred mode is the same for the TN mode. However, since the OCB mode has a larger range in which the liquid crystal compound rises in the center of the cell than the TN mode, the optically anisotropic layer in which the discotic compound is homeotropically aligned, or the rod-like liquid crystal molecule It is necessary to slightly adjust the retardation value of the optically anisotropic layer that is homogeneously oriented. Specifically, the optically anisotropic layer in which the discotic compound on the (transparent) support is homeotropically oriented, or the optically anisotropic layer in which the rod-like liquid crystalline molecules are homogeneously oriented is Rth retardation. The value is preferably 150 nm to 500 nm, and the Re retardation value is preferably 20 to 70 nm.

(VA mode liquid crystal display device)
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening the viewing angle ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

In the black display of the VA mode liquid crystal display device, since most of the rod-like liquid crystalline molecules in the liquid crystal cell are in an upright state, the optically anisotropic layer in which the discotic compound is homeotropically aligned, or The liquid crystal compound is compensated by the optically anisotropic layer in which the rod-like liquid crystalline molecules are homogeneously oriented, and separately, the rod-like liquid crystalline molecules are homogeneously oriented, the average orientation direction of the major axis of the rod-like liquid crystalline molecules and the transmission axis of the polarizing film It is preferable to compensate the viewing angle dependency of the polarizing plate with an optically anisotropic layer having an angle with the direction of less than 5 °.
(Transparent) The optically anisotropic layer in which the support or the discotic compound is homeotropically oriented, or the optically anisotropic layer in which the rod-like liquid crystalline molecules are homogeneously oriented has an Rth retardation value of 150 nm to 500 nm. And the Re retardation value is preferably 20 to 70 nm.

(Other liquid crystal display devices)
The ECB mode and STN mode liquid crystal display devices can be optically compensated in the same way as described above.
In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

  In particular, for a TN mode or IPS mode liquid crystal display device, as described in JP-A-2001-100043, an optical compensation film having a viewing angle expansion effect is used as a protective film having two polarizing films on both sides. Among them, by using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle expansion effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

Hereinafter, the present invention will be specifically described in detail based on examples, but the present invention is not limited thereto.
[Example 1]
(1-1) Preparation of light diffusive film-coated sample (preparation of coating solution for light diffusion layer)
285 g of commercially available zirconia-containing UV curable hard coat solution (Desolite Z7404, manufactured by JSR Corporation, solid content concentration of about 61%, solid content of ZrO ₂ content of about 70%, polymerizable monomer, polymerization initiator contained) 85 g of a mixture of pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) is mixed, and 28 g of a silane coupling agent (KBM-5103, Shin-Etsu Chemical Co., Ltd.) is mixed and stirred. did. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.
Further, a 30% methyl isobutyl ketone dispersion of classified strengthened crosslinked PMMA particles (refractive index: 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 3.0 μm was added to this solution at 10,000 rpm with a Polytron disperser. 35 g of a dispersion dispersed for 20 minutes was added, and then a 30% methyl isobutyl ketone dispersion of silica particles having an average particle diameter of 1.5 μm (refractive index: 1.46, Seahosta KE-P150, manufactured by Nippon Shokubai Co., Ltd.) was added to Polytron. 90 g of a dispersion dispersed for 30 minutes at 10,000 rpm in a disperser was added. Then, the coating solution was prepared by diluting with methyl isobutyl ketone and methyl ethyl ketone so that the required solvent composition was obtained. At this time, the non-volatile content concentration of each coating solution was about 50% by mass.
Further, in the same manner, the solvent composition of the additive was changed as necessary to prepare a coating solution containing IPA and ethyl acetate, and coating solutions A1 to A4 shown in Table 1 were prepared. In Table 1, the value of R was calculated from the results obtained by determining the vapor pressure at each temperature of each solvent from the solvent handbook. In the case of a mixed solvent, the vapor pressure was obtained as a weighted average from the mass ratio of each component. V was obtained by measuring the solvent concentration in the vicinity of the actual film surface with a gas concentration meter.

(Production of light diffusive film)
A triacetyl cellulose film TD-80U (manufactured by Fuji Photo Film) was unwound as a support in the form of a roll, and the coating liquid A for optical functional layer had a gravure pattern of 135 lines / inch and a depth of 60 μm and a diameter of 50 mm. The coating was performed using a gravure roll and a doctor blade, and after the coating, the solvent was evaporated and dried in the drying step having the structure shown in FIG. 1a. In FIG. 1 a, the drying zones 31 to 36 are box-shaped having a width of 150 cm, a length of 100 cm, and a depth of 6 cm, and a # 200 wire mesh is installed on the coating film surface portion (referred to as a drying step a). Air for drying was supplied to the drying zone from air supply ports 41 to 46 installed on one side in the width direction of the drying zone. The supply air was supplied after adjusting the air at 25 ° C. and 60% RH (absolute humidity 0.012) to the temperature shown in Table 1. Using such a drying step, coating was performed under the coating and drying conditions shown in Table 1. Then, after heating in a heat treatment zone of 10 m at 100 ° C., using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm, the irradiation intensity is 400 mW / cm ² and the irradiation amount is 150 mJ / cm ² . Ultraviolet rays were irradiated in an atmosphere having an oxygen concentration of 0.1% to cure the wound coating layer. After curing, the thickness of the optical functional layer was about 3.4 μm. Further, the coating amount of the coating solution at this time was about 10 ml / m ² .

(1-2) Preparation of antiglare film-coated sample (Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM5103 (trade name); manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. Thereafter, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1800, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating solution for antiglare hard coat layer)
50 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 38.5 g of a mixed solvent of MIBK / cyclohexanone. Furthermore, 2 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
Further, a 30% MIBK dispersion of polystyrene particles having an average particle size of 3.5 μm (refractive index: 1.60, SX-350, manufactured by Soken Chemical Co., Ltd.) dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser is 1 13.3 g of a 30% MIBK dispersion of acrylic-styrene particles (refractive index of 1.55, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 3.5 g was added. Finally, 0.75 g of fluorine-based polymer (FP-8) and silane coupling agent sol liquid a20 g were added to prepare a coating liquid B1. The solvent composition of this coating solution was such that the MIBK / cyclohexanone ratio was 7/3. At this time, the concentration of nonvolatile components in the liquid was about 45% by mass.
In the same manner, MIBK was replaced with toluene, and a coating solution B2 having a toluene / cyclohexanone ratio of 7/3 was prepared.

(Preparation of antiglare film)
A triacetyl cellulose film TDY-80U (manufactured by Fuji Photo Film) is unwound as a support in the form of a roll, and an anti-glare hard coat layer coating solution B1 or B2 is used using an extrusion coater described in JP-A-9-73081. And applied. Thereafter, in the drying step (a), the volatile solvent is dried with the coating liquid, coating speed, and drying conditions shown in Table 2 by the same drying step (b) except that the length of the drying zone 31 to 36 is 200 cm. went. Then, after heating in a heat treatment zone of 10 m at 100 ° C., an ultraviolet ray with an irradiation intensity of 200 mW / cm ² and an irradiation amount of 80 mJ / cm ² was further oxygenated using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). The coating layer was cured by being irradiated in an atmosphere having a concentration of 0.1% and wound up. After curing, the thickness of the optical functional layer was about 7 μm. Further, the coating amount as a coating solution at this time was about 20 ml / m ² .

(1-3) Evaluation of coated sample, result (evaluation of coated surface)
The coated surface was evaluated for the above coated products. As an evaluation, a method of observing the prepared film through transmission of a fluorescent light source of three wavelengths and a polarizing plate blackened with a black sheet or crossed Nicol on the back surface are attached, and a three-wave fluorescent lamp and an artificial solar light source (CIE) Inspection with reflected light of standard light source type C) was performed, and both results were combined into an evaluation value.
Although transmission evaluation is judged severely as evaluation of a coated product, A to C are acceptable in reflection evaluation as an optical film.
The above evaluation results were determined as described above.
A: Unevenness is hardly visible.
B: Slight unevenness is visible, but there is no particular problem.
C: Unevenness is visible but acceptable.
D: Unevenness is visible and is not acceptable.
E: Unevenness is quite strong.
Hereinafter, Example Samples 1, 5, 21, 24, and 27 shall be read as Reference Example Samples 1, 5, 21, 24, and 27, respectively.

(1-4) Evaluation result of coated product Table 1 shows the evaluation result of the light scattering film coated product of the present invention. The solvent ratio and the solvent type are changed with respect to Comparative Examples Samples 1 and 2 having a small R, and the samples of Examples 1 to 9 in which R is within the scope of the present invention show a good surface shape. In Examples 6 and 7, even when the coating speed was increased, a good surface shape was obtained. In Example 1 where V / R was 0.9 or more and Example 5 where V / R was 0.05 or less, the drying unevenness slightly deteriorated, but was within an allowable range. In addition, in Examples 10 to 12 in which the temperature was raised in the drying zones 34 to 36 and the drying of the present invention was performed, good surface shapes were obtained. However, the surface shape of Comparative Sample 3 with high temperature and R exceeding 1.5 deteriorated. Among these, Example 7 and Example 10 are particularly preferable samples with good drying unevenness and good productivity.
The evaluation results of the antiglare film-coated product of the present invention are shown in Table 2. By applying the drying conditions of the present invention, a good surface shape was obtained. Moreover, it is especially favorable when implemented in the range of V / R of 0.10-0.5. Moreover, from the handling property and safety | security of a coating liquid, the coating liquid B-1 which does not use toluene is more preferable. Of these anti-glare films, the example sample 25 is a sample with good drying unevenness and good productivity.
In Example 3, 7, the drying zone weighed volatile solvent content of the coating film of the outlet, each dried per second when obtaining the average drying rate of the portion ^{0.06g / m 2, 0.11g / m} 2 Met.

[Example 2]
(2-1) Preparation of optical compensation film sample (preparation of polymer substrate)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

(Cellulose acetate solution composition)
Cellulose acetate with 60.9% acetylation (from linter material) 80 parts by weight Cellulose acetate with 60.8% acetylation (from linter material) 20 parts by mass Triphenyl phosphate (plasticizer) 7.8 parts by mass Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass Methylene chloride (first solvent) 300 parts by mass Methanol (second solvent) 54 parts by mass 1-butanol (third solvent) 11 parts by mass

In a separate mixing tank, 4 parts by mass of cellulose acetate having an acetylation degree of 60.9% (based on linter), 16 parts by mass of the following retardation increasing agent, silica fine particles (particle size 20 nm, Mohs hardness about 7) 0.5 parts by mass, 87 parts by mass of methylene chloride and 13 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution.
A dope was prepared by mixing 36 parts by mass of the retardation increasing agent solution with 464 parts by mass of the cellulose acetate solution and stirring sufficiently. The addition amount of the retardation increasing agent was 5.0 parts by mass with respect to 100 parts by mass of cellulose acetate.

The obtained dope was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried for 1 minute, and after the film having a residual solvent amount of 43% by mass was peeled off, the width of the film was 28 in the width direction using a tenter with 140 ° C. dry air. % Stretched. Then, it dried with 135 degreeC dry air for 20 minutes, and manufactured the polymer base material (PK-1) whose residual solvent amount is 0.3 mass%.
The obtained polymer substrate (PK-1) had a width of 1340 mm and a thickness of 92 μm. The polymer substrate was wound up in a roll shape with a length of 3900 m. When the retardation value (Re) at a wavelength of 590 nm was measured using an ellipsometer (M-150, manufactured by JASCO Corporation), it was 43 nm. Moreover, it was 175 nm when the retardation value (Rth) in wavelength 590nm was measured.
The produced polymer substrate (PK-1) was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, neutralized with sulfuric acid, washed with pure water and dried. The surface energy of this PK-1 was determined by the contact angle method and found to be 63 mN / m.
On this PK-1, an alignment film coating solution having the following composition was applied at a coating amount of 28 ml / m ² with a # 16 wire bar coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.

(Orientation film coating solution composition)
Modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde (crosslinking agent) 0.5 parts by weight

  The alignment film was rubbed in the direction of 45 ° with the slow axis (measured at a wavelength of 632.8 nm) of the polymer substrate (PK-1).

(Formation of optically anisotropic layer)
On the alignment film, 91.0 parts by mass of the following discotic liquid crystalline molecules, 9.0 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyrate ( CAB531-1, manufactured by Eastman Chemical Co., Ltd.) 1.5 parts by mass, photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Co.), sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass, fluorosurfactant MegaFac F-780-F solution 1.25 parts by mass were dissolved in 135 parts by mass of methyl ethyl ketone. Thereafter, methyl ethyl ketone was appropriately added to prepare a coating liquid C having a specific gravity of 0.905 and a solid content concentration of about 30%.

This coating solution C is continuously applied onto the alignment film with a # 4 wire bar at a coating solution coating amount of about 7 ml / m ² , and after coating, the solvent is volatilized and dried in a drying process as shown in FIG. 1a. Carried out. In FIG. 1a, the drying zones 31 to 36 have a box shape with a width of 150 cm, a length of 30 cm, and a depth of 6 cm, and are supplied with air for drying from one side in the width direction and exhausted from the other side. is there. At this time, the air to be dried flows from the air supply side to the exhaust side, but the shape of the air supply / exhaust port and the drying zone are adjusted so that the air flows uniformly. It should be noted that a wire mesh or the like is not provided near the coating film surface (this is referred to as a drying process c). In such a drying process, drying was performed under the coating and drying conditions shown in Table 3. After drying, the discotic liquid crystalline compound was aligned by heating at 130 ° C. for 2 minutes. Next, UV irradiation was performed for 1 minute using a 120 W / cm high-pressure mercury lamp at 100 ° C. to polymerize the discotic liquid crystalline compound. Then, it stood to cool to room temperature. In this way, an optical compensation sheet with an optically anisotropic layer was produced.

(2-2) Evaluation of coated surface shape The coated surface shape was evaluated for the above coated samples. As an evaluation, the prepared film was placed with the polarizing plate in a crossed Nicol arrangement, and the unevenness of the obtained optical compensation sheet was observed from the front and the direction inclined from the normal to 60 °. Sensory evaluation was performed as shown in FIG. As an optical film, A to C are within an allowable range.
A: Unevenness is hardly visible.
B: Slight unevenness is visible, but there is no particular problem.
C: Unevenness is visible but acceptable.
D: Unevenness is visible and is not acceptable.
E: Unevenness is quite strong.

(2-3) Creation and evaluation results of coated product Table 3 shows the evaluation results of the coated product of the optical compensation film of the present invention. Any of the samples is a sample within the specified range of the present invention and exhibits a relatively good surface shape. Among them, Examples 31 to 35 are strongly dried on the supply side when the wind speed is high. Unevenness occurred. On the other hand, in Examples 36 to 40 containing MEK solvent gas in the supply air, unevenness on the supply side was not easily generated even when the wind speed of the film surface was increased, and a good surface shape was obtained. In Examples 41 and 42, the coating speed was increased under the condition where the film surface wind speed was high, but a good surface shape was maintained. In Examples 43 to 46, the surface shape is good when the absolute humidity of the supply air is lower. Among these, the samples of Examples 41 and 46 are particularly preferable samples with high coating speed and little drying unevenness.
In Examples 39, 41, and 42, the volatile solvent content of the coating film at the exit of the drying zone was measured, and the average drying speed in the drying zone was determined to be 0.4, 0.6, 0.00 per second, respectively. It was 9 g / m ² .

(Example 3)
(3-1) Preparation of antireflection film A low refractive index layer was applied to Example Samples 7, 10, and 25 of the present invention.
(Preparation of coating solution for low refractive index layer)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.
<Coating solution composition D for low refractive index layer>
Opstar JN7228A 100 parts by mass (thermally crosslinkable fluorine-containing polymer composition: manufactured by JSR Corporation)
MEK-ST 4.3 parts by mass (silica dispersion, average particle size 15 nm: manufactured by Nissan Chemical Co., Ltd.)
MEK-ST different particle size 5.1 parts by mass (silica dispersion average particle size 45 nm: manufactured by Nissan Chemical Co., Ltd.)
Sol liquid a 2.2 parts by mass MEK 15.0 parts by mass Cyclohexanone 3.6 parts by mass

  Further, instead of the heat-crosslinkable fluorine-containing polymer JN7228A used in the coating solution for the low refractive index layer, a heat-crosslinkable fluorine-containing polymer having a refractive index of 1.44 (JTA-113, solid content concentration 6%, JSR Corporation The coating solution E using (made)) was also prepared in the same manner.

(Coating of low refractive index layer)
The light diffusive or anti-glare hard coat films of Example Samples 7, 10, and 25 were unwound again, and the low refractive index layer coating solution shown in Table 4 was a gravure pattern with 200 lines / inch and a depth of 30 μm. Using a microgravure roll having a diameter of 50 mm and a doctor blade, coating was performed under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 20 m / min. At this time, in the drying step C, drying was performed under the same conditions as in Example Sample 31. After drying, heating at 120 ° C. for 150 seconds, followed by heating at 140 ° C. for 8 minutes, and then using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm The ultraviolet ray of ² was irradiated with an oxygen concentration of 0.1% under a nitrogen purge to form a low refractive index layer having a thickness of 100 nm to prepare an antireflection film and wound up.
In this manner, Example Samples 7D, 10D, and 25D coated with the low refractive index layer coating liquid D and Example Samples 7E, 10E, and 25E coated with the low refractive index layer coating liquid E were prepared.

(Saponification treatment of antireflection film)
The antireflection film was subjected to the following treatment.
A 1.5 mol / l aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C. In this way, a saponified antireflection film was produced.

(3-2) Evaluation of antireflection film About these obtained antireflection films, the following items were evaluated.
<1> Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. For the results, an integrating sphere average reflectance of 450 to 650 nm was used.

<2> Steel Wool Scratch Resistance Evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., grade No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move.
Travel distance (one way): 13cm
Rubbing speed: 13cm / second,
Load: 500 g / cm ²
Tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
Δ × ˜ ×: There is a scratch that can be seen at first glance.

<3> Evaluation of resistance to rubbing with a cotton swab A cotton swab is fixed to the rubbing tip of a rubbing tester, and the sample is fixed with clips on the top and bottom of a smooth dish. A rubbing test was performed by applying a load of 500 g and changing the number of rubbing. The rubbing conditions are as follows.
Rubbing distance (one way): 1cm,
Rubbing speed: About 2 reciprocations / second The sample after rubbing was observed, and the rubbing resistance was evaluated as follows based on the number of times film peeling occurred.
×: Film peeling after 0-10 round trips × Δ: Film peeling after 10-30 round trips Δ: Film peeling after 30-50 round trips ○ △: Film peeling after 50-100 round trips ○: Film peeling after 100-150 round trips ◎: 150 No film peeling even when reciprocating

  The results are shown in Table 4. According to the present invention, an antireflection film having excellent surface uniformity and high scratch resistance can be obtained with high productivity.

[Example 4]
Preparation of polarizing plate using optical compensation film (preparation of polarizer)
PVA having an average polymerization degree of 4000 and a saponification degree of 99.8 mol% was dissolved in water to obtain a 4.0% aqueous solution. This solution was band-cast using a die having a taper and dried to form a film so that the width before stretching was 110 mm, the thickness was 120 μm at the left end, and 135 μm at the right end.
The film was peeled off from the band, and obliquely stretched in the 45 ° direction in a dry state, and immersed in an aqueous solution of 0.5 g / L iodine and 50 g / L potassium iodide for 1 minute at 30 ° C., and then 100 g boric acid. / L, immersed in an aqueous solution of 60 g / L of potassium iodide at 70 ° C. for 5 minutes, further washed with water at 20 ° C. for 10 seconds and then dried at 80 ° C. for 5 minutes to obtain an iodine-based polarizer (HF-01 ) The polarizer had a width of 660 mm and a thickness of 20 μm on both the left and right sides.

(Preparation of polarizing plate)
The optical compensation film of Example Sample 41 is subjected to saponification treatment, and using a polyvinyl alcohol-based adhesive on the polymer substrate (PK-1) surface of the optical compensation film on one side of the polarizer (HF-01). Pasted. Moreover, the saponification process was performed to the 80-micrometer-thick triacetylcellulose film (TD-80U: Fuji Photo Film Co., Ltd. product), and it affixed on the other side of the polarizer using the polyvinyl alcohol-type adhesive agent.
The transmission axis of the polarizer and the slow axis of the polymer substrate (PK-1) were arranged in parallel. The transmission axis of the polarizer and the slow axis of the triacetyl cellulose film were arranged so as to be orthogonal to each other. In this way, a polarizing plate HB-1 was produced.
Similarly, a polarizing plate HB-2 using the saponified antireflection film Example 7E and HB-3 using Example 25E were prepared.

  The thus prepared polarizing plate HB-1 is a liquid crystal display device (Sumitomo 3M which is a polarization separation film having a polarization selection layer) mounted with a transmission type TN liquid crystal display device in an optimal arrangement with the optical compensation sheet facing the liquid crystal cell side. When the D-BEF manufactured by Co., Ltd. was replaced with the polarizing plate on the viewing side of the D-BEF between the backlight and the liquid crystal cell, there was no unevenness and a good polarizing plate could be created. Further, by using HB-2, the effect of further widening the viewing angle was obtained. By using HB-3, a display device with extremely low display quality and extremely high display quality was obtained.

It is the aspect of the application | coating and drying process preferably used by this invention. (A) is an example thereof. Moreover, (b) is another example. (A) is a cross-sectional schematic diagram which shows the typical layer structure of an anti-glare antireflection film. (B) is a cross-sectional schematic diagram which shows the typical layer structure of the antireflection film excellent in the antireflection performance.

Explanation of symbols

(Reference numerals in FIGS. 1a and 1b)
DESCRIPTION OF SYMBOLS 1 Sending part 2 Application | coating part 31-36 Drying zone 41-46 Supply (exhaust) vent of a drying zone 5 Heat processing part 6 Active radiation irradiation part 7 Winding part 8 Wire mesh (code | symbol of FIG. 2)
DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Hard coat layer 4 Anti-glare hard coat layer 5 Low refractive index layer 6 Fine particle 7 Middle refractive index layer 8 High refractive index layer

Claims (13)

Optical having a coating step of coating a coating liquid containing at least one volatile component on a film substrate, and a drying step of volatilizing and removing volatile components from the coated coating liquid layer in the air the method of manufacturing a film, the saturated vapor pressure of the volatile solvent in the temperature of the drying step (p), the ratio R (= p / P) and the atmospheric pressure (P), and 0.05-1.5 ,
In the drying step, drying is performed under a ratio V / R of the volatile solvent component volume fraction (V) of the coating solution in the air in the vicinity of the coating surface to 0.05 to 0.9. A method for producing an optical film. 2. The method for producing an optical film according to claim 1, wherein in the drying step, the coated film surface to be dried is covered with a plate, a metal mesh, or a box and dried.   The method for producing an optical film according to claim 1 or 2, wherein the air supplied to the drying step contains a volatile component in a range of 1 to 50% of V.   The volume fraction of volatile components other than the coating liquid component contained in the air supplied to the drying step is 0.05 or less of the air, according to any one of claims 1 to 3. Manufacturing method of optical film.   The method for producing an optical film according to claim 1, wherein the volatile component comprises at least one selected from ketones, esters, and alcohols. 6. The optical film according to claim 1, wherein an average drying rate of the volatile component in the drying step is 0.1 g / (m ² coating film) or more per ^second. Method. Optical film characterized by being manufactured by a method according to any one of claims 1-6. The optical film according to claim 7 , wherein a discotic compound is contained in the coating solution. The optical film according to claim 7 , wherein the coating liquid contains translucent particles. The optical film according to claim 9 , wherein the layer coated with the coating solution is an antiglare imparting layer.   The optical film according to any one of claims 7 to 10, wherein the optical film has an antireflection layer as an uppermost layer, and the antireflection layer is a low refractive index layer having a refractive index of 1.31 to 1.45.   A polarizing plate, wherein the protective film on at least one side of the polarizing film is the optical film according to claim 7.   An image display device comprising at least one of the optical film according to claim 7 or the polarizing plate according to claim 12.

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