TW201524761A - Glass laminate and liquid crystal display device - Google Patents

Abstract

This glass laminate (2) is configured by laminating glass (4), a phase difference layer (7), and a film (6) in the above order. The film (6) is a polymeric film in which carbon is substituted in at least one side chain of a glucose ring, and the surface of the film (6) opposite to the phase difference layer (7) undergoes hydrophilization and has antifogging properties.

Description

Glass laminate and liquid crystal display device

The present invention relates to a liquid crystal display device having a glass laminate having a laminated film on glass and a glass laminate.

In the car navigation system for vehicles, the touch panel is arranged in front of the liquid crystal display. The input method of the touch panel has been changed from the resistive film type to the electrostatic capacity mode in order to meet the demand for multi-touch as seen in smart phones in recent years. The capacitive touch panel is constructed by laminating a support and a touch sensor from the visual side.

In such a vehicle use, the touch panel is adapted to be adhered to the liquid crystal display and the adhesive layer, and is configured to perform the opposite direction through the gap layer. When the size of the liquid crystal display is 7 inches or more, when the size of the liquid crystal display is 7 inches or more, the touch panel and the liquid crystal display are easily entangled with air. Uniform bonding becomes difficult and the yield is easily reduced.

However, as described above, the configuration in which the touch panel is disposed through the gap layer between the liquid crystal display and the surface on the liquid crystal display side of the touch panel causes fogging. This is due to the lighting time of the liquid crystal display. The moisture in the void layer between the two is dew condensation due to a temperature difference between the touch panel and the liquid crystal display. In particular, in an in-vehicle environment, environmental fluctuations such as temperature changes are increased, and fog due to dew condensation as described above is likely to occur.

In addition, in order to protect the surface of the liquid crystal display, a transparent protective plate is disposed in the front surface of the liquid crystal display through the gap layer (see, for example, Patent Document 1). In such a configuration, the temperature difference in the illumination time of the liquid crystal display may be adhered to the surface of the transparent protective plate by the moisture in the void layer. However, in Patent Document 1, the liquid crystal display is protected by the transparent protective plate. The side surface forms a cellulose film having antifogging property to suppress adhesion of water droplets. Further, in Patent Document 2, for the purpose of preventing adhesion (anti-fog) of water droplets, an anti-fog layer is provided on the surface of the transparent support on the display side.

Even in the case of a liquid crystal display device (vehicle car navigation system) in which a touch panel is disposed through a liquid crystal display and a gap layer, as disclosed in Patent Document 1, it is considered that a layer having an anti-fog function is formed on the surface of the liquid crystal display side of the touch panel to prevent The fog caused by the adhesion of water droplets.

In addition, in recent years, the number of people who install polarized sunglasses has increased. However, when the screen of a car navigation system (liquid crystal display) is seen over polarized sunglasses, the screen looks dark or blurred due to the angle of view. . This is caused by the shift of the transmission axis of the polarizing plate disposed on the visual side of the liquid crystal display and the transmission axis of the polarizing film of the polarized sunglasses.

Therefore, for example, in Patent Document 2, visual inspection on a liquid crystal display Further, a λ/4 film is disposed on the outer side of the polarizing plate (opposite to the polarizing plate and the liquid crystal layer), and the linear polarized light transmitted through the polarizing plate is converted into a circularly polarized light by the λ/4 film, and when the polarized sunglasses are mounted, It is difficult to see a display image that is caused by the shift of the transmission axis.

Accordingly, the in-vehicle car navigation system having a gap layer between the touch panel and the liquid crystal display has an anti-fog function on the liquid crystal display side surface of the touch panel, and has a function of imparting a phase difference in the transmitted light. The layer is considered to have both visibility against fog attached to water droplets and display images when the polarized sunglasses are mounted.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2012-145632

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-83307

As a method of forming a film having an anti-fogging function and a phase difference function, for example, there is a method of alkali-treating (saponifying) a cellulose film to hydrophilize a surface. In order to exhibit the antifogging property by the saponification treatment, it is necessary to carry out the saponification treatment for a longer period of time than the saponification treatment when the cellulose film as the protective film is bonded to the polarizer. This is because the saponification treatment is weak in the same saponification treatment time as in the production of the polarizing plate, and it is difficult to exhibit antifogging property.

However, when the saponification treatment until the anti-fogging function is extended, a water absorbing layer (hydrophilized layer) having a large film thickness is formed on both surfaces of the cellulose film, and the moisture absorption amount (water content) of the cellulose film is greatly increased. Since the water is isotropic, when the water content of the cellulose film is increased, the retardation Ro in the in-plane direction of the cellulose film is greatly lowered.

According to this, the cellulose film having the anti-fog function and the phase difference function described above can prevent the fog from adhering due to water droplets, but the absorption of a large amount of moisture (by saponification treatment) retards the decrease of Ro, so that the polarized light cannot be improved. Visibility when installing sunglasses. Therefore, it is difficult to design a single-layer film having an anti-fogging function and a phase difference function.

The present invention has been made in view of the above problems, and an object thereof is to simultaneously exhibit the performance of an anti-fog function and enhance visibility when mounting polarized sunglasses, and to provide visibility even when the polarized sunglasses are not mounted. A glass laminate and a liquid crystal display device having the same.

The above object of the present invention is achieved by the following constitution. That is, the glass laminate system of the present invention is a glass laminate in which a glass, a retardation layer, and a film are laminated in this order, and the film is a polymer film of at least one or more substituted carbon in a side chain of a glucose ring, and the foregoing The surface on the opposite side of the phase difference layer has an antifogging property by hydrophilization treatment.

According to the above configuration, the visibility at the time of mounting the polarized sunglasses is improved by the phase difference layer. Moreover, since the anti-fog function is provided by the anti-fogging film, the visibility of the polarized sunglasses can be prevented from being lowered regardless of the attachment or non-mounting of the polarized sunglasses. Further, since the phase difference layer is covered with the antifogging film, the phase difference does not change even in a high humidity environment, and the visibility is improved.

1‧‧‧Liquid crystal display device

2‧‧‧glass laminate

3‧‧‧LCD display

4‧‧‧ glass

5‧‧‧Electrical Department

6‧‧‧film

7‧‧‧ phase difference layer

34‧‧‧Polar plate

S‧‧‧ void layer

Fig. 1 is a cross-sectional view showing a schematic configuration of a liquid crystal display device according to an embodiment of the present invention.

An embodiment of the present invention will be described below based on the drawings. In the present specification, when the numerical range is represented by A to B, the numerical range thereof is a value including the lower limit A and the upper limit B. Further, the present invention is not limited to the following.

[Liquid Crystal Display Device]

Fig. 1 is a cross-sectional view showing a schematic configuration of a liquid crystal display device 1 of the present embodiment. As shown in the figure, the liquid crystal display device 1 includes a glass laminate 2 and a liquid crystal display 3. The glass laminate 2 is disposed between the film 6 to be described later and the liquid crystal display 3 so as to be located in the voided layer S. The glass laminate 2 can be attached to the liquid crystal through an adhesive layer (not shown) around the void layer S. The display 3 can also be supported by the support member or the casing (none of which is shown) by the liquid crystal display 3 and the gap layer 3 being opposed to each other.

The liquid crystal display 3 has a liquid crystal panel 31 that displays an image, and a backlight 32 that illuminates the liquid crystal panel 31. The liquid crystal panel 31 has a liquid crystal element 33 in which a liquid crystal layer is sandwiched between a pair of substrates, and a polarizing plate 34‧35 which is disposed on the visual side (glass laminate 2 side) and the backlight 32 side with respect to the liquid crystal element 33, respectively. The polarizing plates 34.35 are arranged such that the transmission axes are perpendicular to each other.

The glass laminate 2 is formed on the glass 4, and is laminated in the order of the conductive portion 5, the retardation layer 7, and the film 6. The conductive portion 5 is, for example, a capacitive sensor of a capacitance type, and has a first electrode pattern 11 and an interlayer insulating layer 12 made of a transparent conductive film (for example, ITO) in this order from the glass 4 side. A second electrode pattern 13 composed of a transparent conductive film (for example, ITO). Further, the conductive portion 5 may form an electrode pattern on both sides of the glass if necessary. Further, it may have an anti-scattering film or an electromagnetic wave barrier layer.

The first electrode pattern 11 is formed on the glass 4 so as to extend in one direction (for example, the X direction). The interlayer insulating layer 12 is formed on the glass 4 as in the case of covering the first electrode pattern 11. The second electrode pattern 13 is formed to extend in a direction (for example, the Y direction) perpendicular to the extending direction of the first electrode pattern 11.

When the surface of the glass 4 is pressed by the finger, the first electrode pattern 11 is in contact with the second electrode pattern 13, and the capacitance between the first electrode pattern 11 and the second electrode pattern 13 is changed. By changing its electrostatic capacity The first electrode pattern 11 and the second electrode pattern 13 are detected, and the specific pressing position (coordinate) is detected.

Further, the conductive portion 5 can be formed by laminating the first electrode pattern 11 or the like on a transparent substrate different from the glass 4. In this case, the transparent substrate of the conductive portion 5 and the glass 4 may be, for example, adhered to an adhesive layer of an optical magnetic tape.

The phase difference layer 7 converts linearly polarized light into a layer close to a circularly polarized state. Therefore, the retardation Ro in the in-plane direction is preferably 40 nm or more and 200 nm or less, for example. Here, the retardation Ro in the in-plane direction of the phase difference layer 7 is defined by the following formula (i).

Formula (i): Ro=(nx-ny)×d

(In the formula, nx is the refractive index in the direction of the slow axis in the plane of the film, ny is the refractive index in the direction perpendicular to the slow axis in the film plane, and d is the thickness (nm) of the film).

The value of the retardation Ro can be measured, for example, using KOBRA-21ADH (Prince Measurement Machine (Unit)). Further, the retardation of Ro can be adjusted by the type of the resin, the type or amount of the additive such as a plasticizer, the film thickness of the film, the drawing conditions, and the like.

The retardation layer 7 may be a film or a layer formed by coating. For example, COP (cyclic olefin polymer) may be used as the film, and a liquid crystal compound or the like may be used for coating.

Further, in the present embodiment, the glass laminate 2 is formed by arranging the gap layer S between the liquid crystal display 3, the retardation axis of the retardation layer 7, and the polarizing plate on the glass laminate 2 side of the liquid crystal display 3. The angle of the absorption axis of 34 is desirably 10° or more and 80° or less.

In this case, the linearly polarized light emitted from the polarizing plate 34 of the liquid crystal display 3 is converted into circularly polarized light or rounded polarized light in the retardation layer 7, and the transmission axis of the polarized solar lens faces even in any direction (even with the polarizing plate 34). By shifting the direction of the transmission axis, the light component parallel to the transmission axis of the polarized sunglasses is directed to the observer's eye, so that the observer can visually recognize the displayed image, and the visibility of the polarized sunglasses can be surely improved.

[Details of the phase difference layer composed of a liquid crystal compound]

Next, details of the retardation layer 7 composed of the above liquid crystal compound will be described. For the retardation layer 7 composed of a liquid crystal compound, for example, a retardation layer obtained by forming a low molecular liquid crystal compound in a liquid crystal state after being aligned in a nematic direction and being fixed by photocrosslinking or thermal crosslinking can be used. Or a retardation layer obtained by forming a polymer liquid crystal compound in a liquid crystal state after being aligned in a nematic direction and fixing the alignment by cooling. In the case where the liquid crystal compound is used in the retardation layer 7, the retardation layer 7 is a layer in which the liquid crystal compound is fixed by polymerization or the like, and it is not necessary to display liquid crystallinity after the layer. The polymerizable liquid crystal compound may be a polyfunctional polymerizable liquid crystal or a monofunctional polymerizable liquid crystal compound. Further, the liquid crystalline compound may be a discotic liquid crystalline compound or a rod-like liquid crystalline compound.

In the retardation layer 7, it is preferable that the molecules of the liquid crystal compound are fixed in any of the alignment directions, the vertical alignment, the horizontal alignment, the mixed alignment, and the oblique alignment. In order to create a phase difference that is symmetrical to the viewing angle In the plate, the disc surface of the disc-shaped liquid crystal compound is substantially perpendicular to the plane of the layer, or the long axis of the rod-like liquid crystal compound is substantially horizontal with respect to the layer plane. The disc-shaped liquid crystal compound is substantially vertical, and means that the average value of the sandwich angle between the layer plane and the disk surface of the disc-type liquid crystal compound is in the range of 70 to 90. The angle is preferably from 80 to 90, more preferably from 85 to 90. Further, the rod-like liquid crystal compound is substantially horizontal, and means that the angle between the layer plane and the guide of the rod-like liquid crystal compound is in the range of 0 to 20°. The angle is preferably from 0 to 10, more preferably from 0 to 5 .

When the molecules of the liquid crystal compound are mixed to form a phase difference layer having a viewing angle dependency, the average tilt angle of the director of the liquid crystal compound is preferably 5 to 85°, more preferably 10 to 80°, and further Good for 15~75°.

The retardation layer 7 can be applied to the film 6 by a liquid crystal compound such as a rod-like liquid crystal compound or a disc-type liquid crystal compound, and a coating liquid containing a polymerization initiator or an alignment controlling agent or other additives as desired. form. It is preferred to form an alignment film on the film 6 to apply a coating liquid on the surface of the alignment film. Further, the retardation layer 7 may be formed of only one layer or a laminate of two or more layers.

(coating method)

The application of the above coating liquid can be carried out by a known method (for example, a bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method). Among them, it is preferably coated by a wire bar coating method, and the wire is coated. The number of rotations of the rod is preferably such that the following formula is satisfied.

0.6<(W×(R+2r)×π)/V<1.4

[W: number of rotations of the bar (rpm), R: diameter of the bar (m), r: diameter of the wire (m), V: transport speed of the support (m/min)]

The range of (W × (R + 2r) × π) / V is more preferably 0.7 to 1.3, still more preferably 0.8 to 1.2.

Further, it is preferable to use a die coating method, and in particular, a coating method using a slide coater or a slit coater is preferred.

(alignment film)

The retardation layer 7 is preferably applied to the surface of the alignment film by applying the coating liquid to form a molecular alignment of the liquid crystal compound. The alignment film is preferably used because it has a function of defining an alignment direction of a liquid crystal compound. However, when the liquid crystal compound is fixed in the alignment state after the alignment, the alignment film does not necessarily have to be a constituent element of the phase difference layer 7 because its function is realized. In other words, it is also possible to produce only the liquid crystalline compound layer on the alignment film fixed in the alignment state onto the film 6.

The alignment film may be subjected to a rubbing treatment such as an organic compound (preferably a polymer), an oblique vapor deposition of an inorganic compound, a formation of a layer having fine lines, or an organic compound by a Langmuir‧Blodgett method (LB film) (for example, ω - The means for accumulating the accumulation of tetracosanoic acid, dioctadecylmethylammonium chloride, and methyl stearate). Further, an alignment film which generates an alignment function by application of an electric field, application of a magnetic field, or light irradiation is also known. Among them, it is preferably formed by a rubbing treatment of a polymer.

The film 6 is a surface (on one side or both sides) of a polymer film of at least one or more carbon substituted with a glucose ring side chain, which is a hydrophilized antifogging film. Further, the surface portion of the film 6 which is hydrophilized is also referred to as a hydrophilized layer 6a, and the portion which is not hydrophilized may also be referred to as a non-hydrophilized layer 6b. In the film 6, the retardation Ro in the in-plane direction is several nm and there is almost no phase difference.

The film 6 is an antifogging film whose surface is hydrophilized. It is preferable that the change in the haze value before and after the contact with the vapor is small (for example, within 3%) with respect to the film 6. In this case, it can be said that the antifogging function of the film 6 after the contact with the vapor is suppressed is lowered.

Further, in the film 6, since the antifogging function after the contact with the vapor is suppressed, the adhesion to the water droplets on the surface of the film is suppressed. Therefore, since the polarized sunglasses are not mounted, the visibility of the display image can be improved even when viewed normally (the water droplets on the surface can suppress the deterioration of the visibility of the display image).

The hydrophilization treatment for imparting antifogging property can be carried out by light irradiation or saponification treatment. When light irradiation is performed, for example, light having a photon energy of 155 kcal/mol or more is irradiated onto the surface of the film 6 (polymer film). Further, when the saponification treatment is carried out, for example, the surface of the film 6 is subjected to alkali saponification treatment using an aqueous NaOH solution for 60 minutes, followed by washing with water and drying.

In the light irradiation treatment, uniform antifogging property can be imparted to the surface of the film 6, and sufficient antifogging property can be imparted by the thin hydrophilic layer as compared with the case where the hydrophilic layer is formed by saponification treatment. Further, since the light irradiation treatment can be performed on one side of the polymer film, the obtained film is obtained. 6 It is difficult to produce attachment, and it can be rolled up into strips. Further, at the time of winding, since it is not necessary to hold the protective film for preventing adhesion, the cost is also reduced.

The film 6 (polymer film) is desirably a cellulose ester film. By irradiating the cellulose ester film with light as described above, it is presumed that the ester group substituted by the side chain of the glucose ring is easily converted into a hydroxyl group because the hydrophilized layer 6a can be surely formed on the surface of the film 6 (it can be surely imparted antifogging property) Film 6). Further, since the cellulose ester itself is hygroscopic, water vapor generated by environmental changes may be enclosed inside the film 6 (non-hydrophilic layer 6b), and is preferable because an antifogging effect is obtained.

When the polymer film is a cellulose ester film, when the film is immersed in dichloromethane, the non-hydrophilized layer 6b is dissolved, and the hydrophilized layer 6a is not dissolved as a powder. From this, it can be said that the non-hydrophilic layer 6b is a methylene chloride-soluble layer, and the hydrophilized layer 6a is a methylene chloride-insoluble layer.

The film 6 is laminated on the glass 4 through the above-described conductive portion 5 and the retardation layer 7 serving as a touch sensor. Therefore, since the glass laminate 2 having the above-described configuration has both an anti-fog function and a touch sensor function, dew condensation due to temperature change is likely to occur, and it is effective to use the touch panel as a vehicle navigation system for vehicles.

[film detail]

Next, the details of the film 6 described above will be described.

(for hydrophilization treatment)

The surface of the film 6 (polymer film), as described above, is irradiated with light Or saponification treatment to carry out hydrophilization treatment. Usually, the light irradiation is performed on one side of the polymer film, and the saponification treatment is performed on both sides of the polymer film. Therefore, among the side chains of the polymer film on the surface of the film, a part of the substituent in which the carbon is substituted is substituted with an oxygen-containing polar group such as a hydroxyl group. By such a hydrophilization treatment, a moderate water absorption property is imparted to the surface of the film. The surface of the film which imparts water absorbency, for example, even if the water droplets adhere by rain or moisture in the air, the fogging value is increased by the formation of the hydration layer due to the expansion of the surface wetting, and the meaning is to ensure visibility. Mild.

The hydrophilization treatment in the present specification means, for example, a thioloxy group in a cellulose ester to be described later, or an alkoxy group in a cellulose ether, which is substituted with an oxygen-containing polar group such as a hydroxyl group, a carbonyl group or a carboxylic acid group. Treatment to replace the hydroxy group is particularly good. By the hydrophilization treatment, a hydrophilic group is introduced into the antifogging layer, and a layer excellent in hydrophilicity and water absorbability is obtained, and antifogging property is exhibited.

As a method of light irradiation, a treatment using vacuum ultraviolet rays or the like is used, for example, a method in which an excimer UV is irradiated by using a light source (excimer UV lamp) such as Ar, Kr, or Xe in a nitrogen atmosphere. The method of molecular UV), or (2) the method of using a low pressure mercury lamp. Among these, the hydrophilicity of the film in the depth direction is excellent, and the surface of the film can be sufficiently water-absorbent. From the viewpoint of easily obtaining a film having a small change in performance with time, it is preferred to irradiate the excimer UV. . Among them, it is particularly preferable to perform light irradiation using a light source of Xe.

It is preferable to appropriately adjust each of the light sources with the accumulated light amount by using the light irradiation of the light sources. Therefore, the film is prevented from being excessively hydrophilized. Following needle Explain the individual methods.

(1) Method of irradiating excimer UV

The method of irradiating the excimer UV will be specifically described by taking a case where a xenon (Xe) lamp is used as an example. The Xe used in the xenon lamp is a rare gas, and the atomic system of the rare gas is not bonded as a component. However, an atom (excited atom) of a rare gas which is obtained by discharge or the like can be bonded to other atoms as a component. In the case of Xe, it becomes e+Xe → e+Xe ^*

Xe ^* + Xe + Xe → Xe ₂ ^* + Xe , the Xe ₂ ^* of the excited excimer molecule emits excimer UV of 172 nm when it migrates to the basal state.

To obtain excimer UV, a method of blocking discharge using a dielectric material is known. The dielectric material is a barrier discharge, and a gas space is disposed between the electrodes through a dielectric material (in the case of an excimer lamp, transparent quartz). By applying a high frequency and a high voltage of 10 kHz to the electrode, the gas space is similar to a thunder. Fine is called a discharge of a micro discharge.

Further, as a method of obtaining excimer UV with good efficiency, an electrodeless electric discharge is also known in addition to a dielectric material barrier discharge. The term "electrodeless electrical discharge" refers to a discharge that is combined by capacity, also known as RF discharge. The lamp and the electrode and their arrangement are basically the same as the dielectric material barrier discharge, and the high frequency applied between the two poles becomes several MHz. The electrodeless electrical boundary discharge thus produces a spatially and temporally identical discharge. Further, since the xenon lamp emits light at a single wavelength with a short wavelength of 172 nm UV, the xenon lamp is excellent in luminous efficiency.

Moreover, since the excimer lamp has high efficiency of light generation, it can be lit with a lower power input. In addition, since the excimer lamp does not emit light having a long wavelength due to the temperature rise factor, the energy of the single wavelength is irradiated in the ultraviolet region, and the increase in the surface temperature of the object to be irradiated is suppressed. Therefore, it is suitable for irradiation of a resin film which is susceptible to heat.

Excimer UV treatment is a treatment method in which light is irradiated by an excimer UV light source by a nitrogen purge or vacuum to reduce the oxygen concentration state (about less than 1%). A commercially available excimer illumination device by the oxtail motor (unit) or (share) M‧D. Excimer can be suitably used.

When Xe is used as the excimer lamp having a peak wavelength of the discharge gas of 165 nm to 175 nm, the cumulative amount of light is preferably 50 mJ or more and 1000 mJ or less, more preferably 100 mJ or more and 900 mJ or less, and more preferably 300 mJ or more and 600 mJ. the following. By performing light irradiation as the amount of accumulated light, the surface of the film is well hydrophilized, and exhibits sufficient water absorption performance. Moreover, such water absorption properties are difficult to change over time.

(2) Method of using low-pressure mercury lamp

Specific examples of the method of using the low-pressure mercury lamp include a method of using a low-pressure mercury lamp having a peak wavelength of 180 nm to 190 nm and a low-pressure mercury lamp having a peak wavelength of 250 nm to 260 nm. When a low-pressure mercury lamp having a peak wavelength of 180 nm to 190 nm and a low-pressure mercury lamp having a peak wavelength of 250 nm to 260 nm are used, it is preferable that the cumulative light amount of the peak wavelength is 1000 mJ or more and 10000 mJ or less, and more preferably 3000 mJ. Up to 9000 mJ or less, and more preferably 5,000 mJ or more and 8000 mJ or less. By performing light irradiation as the amount of accumulated light, the surface of the film is well hydrophilized, and exhibits sufficient water absorption performance. Moreover, such water absorption properties are difficult to change over time. Further, the anti-fog function is more easily obtained when the low-pressure mercury lamp is irradiated under nitrogen and vacuumed in the atmosphere. Further, the yellowing of the film can be controlled by cutting the wavelength of 254 nm with a filter.

For the method of using a low-pressure mercury lamp, for example, a commercially available low-pressure mercury lamp such as a oxtail motor can be used.

Further, in addition to the above light irradiation, corona discharge treatment or plasma treatment may be performed. The corona discharge treatment refers to a treatment in which discharge is performed between electrodes by applying a high voltage of 1 kV or more under atmospheric pressure. An oxygen-containing polar group (hydroxyl group, carbonyl group, carboxylic acid group, etc.) is generated on the surface of the film by corona discharge treatment, and the surface is hydrophilized. The corona discharge treatment can be carried out using a commercially available device such as Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Further, in the plasma treatment, the plasma-formed gas is irradiated onto the surface of the substrate, and the treatment of modifying the surface of the substrate includes a glow discharge treatment, a frame plasma treatment, and the like. For example, the method described in JP-A-6-123062, JP-A-H11-293011, JP-A-H11-005857, and the like can be used. By plasma treatment, an oxygen-containing polar group (hydroxyl group, carbonyl group, carboxylic acid group, etc.) is generated on the surface of the film to hydrophilize the surface. Further, in the glow discharge treatment, a film is placed between the opposing electrodes, and a plasma-exciting gas is introduced into the device. The high-frequency voltage is applied between the electrodes, and the plasma is excited by the plasma to perform glow discharge between the electrodes. Therefore, the surface of the film is treated and the hydrophilicity is improved.

(for polymer film)

The polymer film is a film in which at least one or more carbons of the glucose ring side chain are substituted.

Examples of the polymer film include a cellulose ester film, a cellulose ether film, and a cellulose ester ether film. Among these, a cellulose ester film is preferred from the viewpoint that the ester group which is easily substituted by the glucose ring side chain by the light of the light source is converted into a hydroxyl group to impart antifogging property to the film.

<Cellulose ester film>

The cellulose ester film contains a cellulose ester resin composition (hereinafter also referred to simply as cellulose ester) as a main component, and if necessary, a plasticizer, an ultraviolet absorber, a fine particle, a dye, a sugar ester compound, and a propylene which will be described later. A film of an additive such as a fluorene-based copolymer. In the present specification, the term "cellulose ester" means a part or all of the hydrogen atoms constituting the hydroxyl group (-OH) of the 2, 3, and 6 positions in the glucose unit of the β-1,4 bond. A cellulose halide resin substituted with a thiol group.

The cellulose ester is not particularly limited, and examples thereof include a hydrogen atom of a hydroxyl group of cellulose, and examples thereof include an ethyl group, a propyl group, a butyl group, an isobutyl group, a amyl group, a neopentyl group, a hexyl group, a decyl group, and a laurel. A cellulose ester resin substituted with an aliphatic fluorenyl group having 2 to 20 carbon atoms such as a mercapto group or a stearyl group. Among them, those having a carbon number of 2 to 4 are preferred, and more preferably an ethyl group, a propyl group or a butyl group. Still, the thiol group in the cellulose ester It can be a single type or a combination of a plurality of bases.

Specific preferred cellulose esters include cellulose phthalate resins such as cellulose triacetate, cellulose diacetate, cellulose acetate butyl ester, and cellulose acetate propionate. A cellulose halide resin such as cellulose triacetate, cellulose diacetate or cellulose ester propionate can be mentioned. These cellulose esters may be used singly or in combination of two or more. Among these, ethyl phthalocyanine is preferred.

The cellulose which is a raw material of the cellulose ester is not particularly limited, and examples thereof include cotton linters, wood pulp (derived from conifers, derived from broad-leaved trees), and kenaf. Further, the cellulose ester thus obtained can be used in combination at any ratio.

The cellulose ester can be produced by a known method. In general, the cellulose of the mixed raw material and a specific organic acid (acetic acid, propionic acid, etc.) and an acid anhydride (acetic anhydride, propionic anhydride, etc.), a catalyst (sulfuric acid, etc.), esterified cellulose, can be reacted to cellulose. The triester is completed. The three hydroxyl groups of the glucose unit in the triester can be substituted with a thiol group of an organic acid. When two kinds of organic acids are used at the same time, a cellulose ester of a mixed ester type such as cellulose acetate propionate or cellulose acetate butyl ester can be produced. Secondly, by hydrolyzing the cellulose triester, a cellulose ester having a desired degree of thiol substitution can be synthesized. Then, the steps of filtration, precipitation, water washing, dehydration, drying, and the like are carried out to finally prepare a cellulose ester.

More specifically, the cellulose ester can be synthesized by a method described in, for example, JP-A-H05-45804, JP-A-2005-281645, and JP-A-2003-270442. Again, as a city For the film to be sold, KC4UAW, KC6UAW, N-TAC KC4KR made by Konica Minolta ADVANCED LAYERS, and UZ-TAC and TD-80UL made by Fujifilm Co., Ltd. can be cited as materials. ) L20, L30, L40, L50 manufactured by Daicel, Ca398-3, Ca398-6, Ca398-10, Ca398-30, Ca394-60S, etc. manufactured by Eastman Chemical Co., Ltd., Japan.

The degree of substitution of the thiol group of the cellulose ester is preferably 2.0 or more from the viewpoint of antifogging property and production stability in the production step. Further, the degree of substitution of the fluorenyl group is preferably 3.0 or less from the viewpoint of durability of the film with time. In addition, the degree of substitution of the thiol group in the present specification means the average number of thiol groups per 1 glucose unit, and any one of the hydrogen atoms of the hydroxyl group of the 2, 3, and 6 positions of the 1 glucose unit is sulfhydryl. Replace the ratio. That is, the degree of substitution (the maximum degree of substitution) when the hydrogen atoms of the hydroxyl groups of the 2, 3, and 6 positions are all substituted by a thiol group is 3.0. The method for determining the degree of substitution of the thiol group can be carried out in accordance with ASTM D-817-91.

The weight average molecular weight (Mw) of the cellulose ester is preferably 75,000 or more, more preferably 80,000 or more, and more preferably from the viewpoint of improving heat resistance or strength (resistance to stretching or tearing) of the film. 85,000 or more. Further, the smaller the molecular weight, the absorption between the resin molecules due to the deformation force of the film over time, the wrinkles and peeling can be suppressed, and the weight average molecular weight (Mw) is preferably 300,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the cellulose ester, Mw/Mn, is preferably 2.0 to 3.5. This fiber The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the vitamin ester are determined by gel permeation chromatography (GPC), for example, by the following conditions.

Solvent: dichloromethane

Pipe column: Shodex K806, K805, K803G (connected to 3 tubes of Showa Denko (share) system)

Column temperature: 25 ° C

Sample concentration: 0.1% by mass

Detector: RI Model 504 (manufactured by GLS Science)

Pump: L6000 (made by Hitachi, Ltd.)

Flow rate: 1.0ml/min

Calibration curve: A calibration curve of 13 samples up to a standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1000000 to 500 was used. 13 samples were used at almost equal intervals.

<Cellulose ether film>

The cellulose ether film is composed of a cellulose ether resin composition (hereinafter simply referred to as cellulose ether) as a main component, and if necessary, a plasticizer, an ultraviolet absorber, a fine particle, a dye, a sugar ester compound, and an acrylonitrile which will be described later. A film of an additive such as a base copolymer.

The cellulose ether used in the present embodiment is preferably one in which a hydroxyl group of cellulose is substituted with an alkoxy group having 4 or less carbon atoms. Specifically, the hydroxyl group of cellulose is substituted by any one of a methoxy group, an ethoxy group, a propoxy group, and a butoxy group or a plurality of alkoxy groups. Especially the hydroxyl group of cellulose The oxy group and the ethoxy group are preferably substituted by a single or plural alkoxy group. Among them, ethyl cellulose having an ethoxy group substitution degree of 1.8 or more and 2.8 or less, more preferably 1.8 or more and 2.5 or less can be suitably used. The degree of substitution can be quantified by the method described in ASTM D4794-94.

When the degree of substitution is less than 1.8, the water absorption rate of the film increases, except that it is limited to the type of the solvent to be dissolved alone. The tendency of the dimensional stability of the film to decrease. Further, even if the degree of substitution exceeds 2.8, it is not limited to the type of solvent to be dissolved, and the resin itself tends to be expensive.

The cellulose ether can be produced by a method known per se. For example, cellulose can be used as an alkali cellulose treated with a strong caustic soda solution by reacting it with methyl chloride or ethyl chloride and by etherification.

The weight average molecular weight (Mw) of the cellulose ether is preferably from 100,000 to 400,000, more preferably from 130,000 to 300,000, still more preferably from 150,000 to 250,000. When the Mw is more than 400,000, not only the solubility of the solvent is lowered, but also the viscosity of the resulting solution is too high, and it is not suitable for the solvent casting method, the thermoforming is difficult, and the problem of the transparency of the film is lowered. Further, when Mw is less than 100,000, the mechanical strength of the obtained film tends to be lowered.

As the cellulose ether, a cellulose ether produced from a single raw material can be used, and a cellulose ether having two or more different raw materials can be used in combination.

[Method for Producing Film]

Next, a method of producing the film 6 having antifogging property will be described. Here, as a polymer film, a case where a cellulose ester film is used will be described as an example, but the case of using another polymer film may be the same. Manufacturing.

The film 6 can be obtained by (a) a step of forming a film of a cellulose ester by a solution flow method or a melt casting method (film forming step), and (b) a step of hydrophilizing a surface of the film formed film. Manufacturing. Further, the film 6 can be produced by hydrophilization treatment using the commercially available polymer film by the above step (b).

(a) Film forming step

First, the cellulose ester is formed into a film by a solution flow method or a melt casting method. Hereinafter, the film forming method will be described by way of an example in which the solution flowing method is used. However, the melt flowing method can also be carried out by referring to a conventionally known method. When the film is formed by the solution flow method, the film forming step preferably comprises (i) a dopant preparation step, (ii) a doping flow extension step, (iii) a drying step 1, (iv) a peeling step, and (v) pulling. The step of stretching, (vi) drying step 2, and (vii) film winding step.

(i) dopant modulation step

The dopant preparation step is a step of dissolving a cellulose ester and an additive described later in a solvent to prepare a dopant. The concentration of the cellulose ester in the dopant is preferably such that the drying load after casting to the metal support can be reduced. However, when the concentration of the cellulose ester is too high, the load at the time of filtration is increased, and the filtration accuracy is deteriorated. The concentration of these is, for example, 10 to 35% by mass, preferably 15 to 25% by mass.

The solvent used in the preparation of the dopant may be used alone or in combination. More than one species. It is preferred to use a solvent for dissolving a cellulose ester alone (good solvent), a single swelling cellulose ester or a mixed insoluble solvent (lean solvent) in terms of production efficiency. As a good solvent, dichloromethane or methyl acetate is preferable, and as a poor solvent, for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone or the like is preferably used. Further, the dopant is preferably in the form of 0.01 to 2% by mass of water.

As the solvent used for the dissolution of the cellulose ester, the solvent removed from the film by drying is recovered in the film forming step, and the reusable can be used.

When the above-described dopant is prepared, a general method can be used for the method of dissolving the cellulose ester. Further, by combining heating and pressurization, it can be heated to a temperature higher than the boiling point of normal pressure.

Next, it is preferred to filter the above-obtained dopant by using a suitable filter material such as filter paper. Therefore, impurities in the dopant can be removed and reduced. As the filter material, a filter material having an absolute filtration accuracy of 0.008 mm or less is preferable, and a filter material of 0.001 to 0.008 mm is more preferable, and a filter material of 0.003 to 0.006 mm is more preferable. The filter medium is not particularly limited, but a well-known filter medium can be used.

(ii) Doping flow extension step

The doping flow extension step is the step of casting (casting) the doping stream onto the endless metal support. The metal support is preferably a mirror-finished surface, and is preferably a cylinder which is plated with a stainless steel belt or a casting. The casting range can be 1~4m. Metal support The surface temperature may be a temperature of -50 ° C or more and less than the boiling point of the solvent, preferably 0 to 40 ° C, more preferably 5 to 30 ° C.

The method of regulating the temperature of the metal support is particularly limited, but there is a method of blowing hot air or cold air, or a method of bringing warm water into contact with the back side of the metal support. It is preferable that the temperature of the metal support becomes a short period of time because the warm water is efficiently transmitted by the warm water. When using hot air, there is a case where a higher temperature wind is used.

(iii) Drying step 1

The drying step 1 is a step of drying the cast dopant as a screen. The surface temperature of the metal support is the same as the doping flow extension step. The higher the temperature, the better the drying speed of the stencil is accelerated, but when it is too high, the stencil is foamed or the planarity is deteriorated.

(iv) stripping step

The stripping step is a step of stripping the screen from the metal support. In order to show that the film after film formation has good planarity, the amount of residual solvent when the stencil is peeled off from the metal support is preferably from 10 to 150% by mass, more preferably from 20 to 40% by mass or from 60 to 130% by mass. More preferably, it is 20 to 30% by mass or 70 to 120% by mass.

Further, in the present specification, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(M - N) / N} × 100

(In the formula, M is the stencil or film in the manufacture or after the manufacture The quality of the sample taken at the time point, N is the mass of the sample taken at any time during or after manufacture of the stencil or film at 115 ° C for 1 hour)

(v) drawing step

The drawing step is a step of drawing the web which has just been peeled off from the metal support in at least one direction. By performing the drawing treatment, the alignment of the molecules in the film can be regulated. The drawn film may be a two-axis drawn film, but a one-axis drawn film is preferred. However, the drawing step is not essential, and the cellulose ester film may be an undrawn film.

It is preferable to perform the pull delay to draw 1.05 to 1.50 times in the lateral direction (TD direction). By performing the drawing treatment in accordance with such a draw ratio, the resin molecules are aligned, and the expansion and contraction of the alignment direction with time is suppressed, and the film is elasticized. According to this, even when the thickness of the film is small, high antifogging property is maintained, and excellent workability is imparted while suppressing occurrence of wrinkles with time.

In addition to or instead of this, the longitudinal direction (MD direction) may be drawn at a draw ratio of 1.01 to 1.50 times. The drawing in the transverse direction (TD direction) and the longitudinal direction (MD direction) may be performed sequentially or simultaneously.

The amount of residual solvent in the pull-delay film is preferably from 1 to 50% by mass, more preferably from 3 to 45% by mass. When such a residual solvent amount, it is easy to combine both the production efficiency and the transparency of the film.

The drawing method is not particularly limited. As the drawing method, for example, a plurality of rolls can be cited to give a difference in the peripheral speed, and the difference in the peripheral speed of the rolls is utilized therebetween. For the method of drawing in the MD direction, the two ends of the screen are fixed by a clamp or a needle, and the gap between the jaws or the needle is diffused to the direction of the MD direction, and the same direction is diffused to the lateral direction to the TD direction. The method, the MD/TD direction simultaneously diffuses the MD/TD in both directions, and the like.

Also, the drawing method can be inclined drawing. The oblique drawing means that the repeating direction of the film intersects with the winding direction, and the one end side of the transverse direction of the film is transported earlier than the other end side, and the film is stretched in the oblique direction with respect to the lateral direction. .

The drawing temperature is preferably 120 ° C or more and 200 ° C or less, more preferably 150 ° C or more and 200 ° C or less, and still more preferably 150 ° C or more and 190 ° C or less.

It is preferred that the film be heat-fixed after drawing. The heat is fixed at a temperature higher than the final drawing temperature in the TD direction, and is preferably in the range of from 0.5 to 300 seconds in a temperature range of from Tg to 20 °C. In this case, it is preferable to perform heat fixation while sequentially dividing the temperature into a range of 1 to 100 ° C in a region where the temperature is divided into two or more. Further, the Tg (glass transition temperature) of the film is controlled by the ratio of the material type of the thin film and the material of the film, and can be determined by the method described in JIS K7121:1987.

(vi) drying step 2

The drying step 2 is a step of further drying the drawn film. In the drying step 2, the film is preferably dried in an amount of 1% by mass or less based on the amount of the residual solvent, more preferably 0.1% by mass or less, still more preferably 0% to 0.01% by mass or less.

(vii) film winding step

The film winding step is a step of winding up the dried stencil (polished cellulose ester film). In the winding of the film, the film having a good dimensional stability can be obtained by setting the residual solvent range to 0.4% by mass or less.

(b) Hydrophilization treatment step

The step of re-copying the cellulose ester film of the film to impart antifogging property to the surface of the film by hydrophilization treatment. Since the details of this step are as described above, the description thereof will be omitted.

[Additives included in the film]

Next, an additive which can contain the film (polymer film) used in the present embodiment will be described. For the purpose of further improving the performance of the antifogging film, the film used in the embodiment may include, for example, (a) a plasticizer, (b) a UV absorber, (c) a microparticle, (d) a dye, (e) a sugar ester compound and (f) an acrylonitrile-based copolymer. Preferably, it comprises at least one of (a) a plasticizer, (b) an ultraviolet absorber, and (c) fine particles, and more preferably contains (a) a plasticizer, (b) a UV absorber, and (c) fine particles. All.

(a) Plasticizer

The polymer film preferably contains a plasticizer for the purpose of improving mechanical strength or water resistance. As the plasticizer, a polyester compound is preferred.

The polyester compound is not particularly limited, and for example, a polymer obtained by a condensation reaction of a dicarboxylic acid or an ester-forming derivative thereof with a glycol, and having a terminal hydroxyl group (hereinafter referred to as "polyester plural" can be used. An alcohol") or a polymer in which a hydroxyl group at the terminal of the polyester polyol is blocked with a monocarboxylic acid (hereinafter referred to as "end-terminated polyester"). In the present specification, the ester-forming derivative means an ester of a dicarboxylic acid, a dicarboxylic acid chloride, or an anhydride of a dicarboxylic acid.

By using the above polyester polyol or end-capped polyester, the peeling or wrinkling of the film over time is further suppressed. Although the reason for obtaining such an effect is not clear, it is presumed that the above-mentioned compound is dispersed in the direction of the surface of the film during film formation, and the deformation stress is dispersed in the thickness direction in order to prevent the peeling and wrinkling of the film over time. .

Specific examples of the polyester compound include the ester compounds represented by the following general formula (A).

B-(G-A)n-G-B‧‧‧(A)

(wherein B is a hydroxyl group, a benzene monocarboxylic acid residue or an aliphatic monocarboxylic acid residue, and G is an alkylene glycol residue having a carbon number of 2 to 18 or an aryl glycol residue having a carbon number of 6 to 12. a base or a carbon number of 4 to 12 oxyalkylene glycol residues, A is a C 4 to 12 alkyl dicarboxylic acid residue or a carbon number 6 to 16 aryl dicarboxylic acid residue, n is An integer greater than 1).

In the above general formula (A), a compound in which B is a hydroxyl group corresponds to a polyester polyol, and a compound in which B is a benzene monocarboxylic acid residue or an aliphatic monocarboxylic acid residue corresponds to a terminal terminated polyester. Polyester compound represented by general formula (A) The substance is obtained by the same reaction as the usual polyester-based plasticizer.

The aliphatic monocarboxylic acid component of the polyester compound represented by the general formula (A) is preferably, for example, an aliphatic monocarboxylic acid having 3 or less carbon atoms, and examples thereof include acetic acid, propionic acid, and butyric acid (butyric acid). One type or a mixture of two or more types is used.

The benzene monocarboxylic acid component of the polyester compound represented by the general formula (A) is, for example, benzoic acid, p-tert-butylbenzoic acid, o-benzoic acid, m-benzoic acid, p-benzoic acid, dimethylbenzoic acid, or B. The benzoic acid, the n-propyl benzoic acid, the aminobenzoic acid, the ethoxylated benzoic acid, the aliphatic acid, etc. may be used alone or in combination of two or more. In particular, it is preferred to include benzoic acid or para-benzoic acid.

The alkylene glycol component having a carbon number of 2 to 18 as the polyester compound represented by the general formula (A) is ethylene glycol, 1,2-propanediol (1,2-propanediol), and 1,3-propane. Glycol (1,3-propanediol), 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl1,3-propanediol, 1,4- Butylene glycol, 2,3-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-cyclopentane Glycol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3 propanediol (3,3-dimethylol heptane), 3-methyl-1,5-pentanediol 1,6-di Alcohol, 2,2,4-trimethyl1,3-pentanediol, 2-ethyl1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-anthracene Alkanediol, 1,10-decanediol, 1,12-octadecanediol, etc. These glycols are one type or a mixture of two or more types. Among them, preferred are ethylene glycol, diethylene glycol, 1,2-propylene glycol, 2-methyl1,3-propanediol, and more preferably ethylene glycol. Alcohol, diethylene glycol, 1,2-propanediol. In particular, the alkylene glycol having 2 to 12 carbon atoms is preferred because it has excellent compatibility with the resin constituting the film. More preferably, the alkylene glycol having a carbon number of 2 to 6 is more preferably an alkylene glycol having a carbon number of 2 to 4.

The oxygen-lowering glycol component having 4 to 12 carbon atoms of the polyester compound represented by the general formula (A) is, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol or tripropylene glycol. The glycol may be used alone or as a mixture of two or more.

The aryl glycol having 6 to 12 carbon atoms of the polyester compound represented by the general formula (A) is, for example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or cyclohexanediethanol. A cyclic glycol such as 1,4-benzenedimethanol, which may be used alone or as a mixture of two or more kinds.

The alkylene dicarboxylic acid component having a carbon number of 4 to 12 as the polyester compound represented by the general formula (A), for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, and sebacic acid And azelaic acid, dodecanedicarboxylic acid, etc., and these are used as one type or as a mixture of 2 or more types.

The aryldicarboxylic acid component having 6 to 16 carbon atoms of the polyester compound represented by the general formula (A) is phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 1 , 4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,6-onion two Carboxylic acid, etc. The above aryl dicarboxylic acid may have a substituent in the aromatic ring. Examples of the substituent include a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group, and an aryl group having 6 to 12 carbon atoms.

In general formula (A), when B is a hydroxyl group, that is, a polyester compound When the material is a polyester polyol, A is preferably an aryl dicarboxylic acid residue having 10 to 16 carbon atoms. For example, a dicarboxylic acid having an aromatic ring structure such as a benzene ring structure, a naphthalene ring structure or an onion ring structure can be used. Specific examples of the aryldicarboxylic acid component include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, and 2,6-. Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,6-onion dicarboxylic acid. Preferred are 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, more preferably It is 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and particularly preferably 2,6-naphthalene dicarboxylic acid. These may be used alone or in combination of two or more.

The polyester polyol preferably has a carbon number of the dicarboxylic acid used as a raw material in an average range of 10 to 16. When the average number of carbon atoms of the dicarboxylic acid is 10 or more, the dimensional stability of the film is excellent, and when the average carbon number is 16 or less, the compatibility with the resin constituting the film is excellent, and the transparency of the obtained film is remarkably excellent. The dicarboxylic acid preferably has an average carbon number of 10 to 14, and more preferably has an average carbon number of 10 to 12.

When the average carbon number of the dicarboxylic acid of the polyester polyol is a single dicarboxylic acid polymerized polyester polyol, the number of carbon atoms of the dicarboxylic acid is used, but two or more kinds of dicarboxylic acid are polymerized and polymerized. In the case of an ester polyol, it means the sum of the product of the carbon number of the individual dicarboxylic acid and the molar fraction of the dicarboxylic acid.

When the average carbon number is 10 to 16, an aryl dicarboxylic acid having 10 to 16 carbon atoms as described above and a dicarboxylic acid other than the above may be used in combination. The dicarboxylic acid to be used in combination is preferably a dicarboxylic acid having 4 to 9 carbon atoms, and examples thereof include succinic acid, glutaric acid, adipic acid, maleic acid, and o-benzene. Dicarboxylic acid, isophthalic acid, terephthalic acid or such esterates, acid chlorides, acid anhydrides.

Hereinafter, specific examples of the carbon number of the polyester polyol of 10 to 16 dicarboxylic acids are shown, but the present embodiment is not limited thereto.

(1) 2,6-naphthalenedicarboxylic acid

(2) 2,3-naphthalene dicarboxylic acid

(3) 2,6-onion dicarboxylic acid

(4) 2,6-naphthalenedicarboxylic acid: succinic acid (75:25~99:1 molar ratio)

(5) 2,6-naphthalenedicarboxylic acid: terephthalic acid (50:50~99:1 molar ratio)

(6) 2,3-naphthalenedicarboxylic acid: succinic acid (75:25~99:1 molar ratio)

(7) 2,3-naphthalenedicarboxylic acid: terephthalic acid (50:50~99:1 molar ratio)

(8) 2,6-onion dicarboxylic acid: succinic acid (50:50~99:1 molar ratio)

(9) 2,6-onion dicarboxylic acid: terephthalic acid (25:75~99:1 molar ratio)

(10) 2,6-naphthalenedicarboxylic acid: adipic acid (67:33~99:1 molar ratio)

(11) 2,3-naphthalenedicarboxylic acid: adipic acid (67:33~99:1 molar ratio)

(12) 2,6-onion dicarboxylic acid: adipic acid (40:60~99:1 molar ratio)

As the polyester compound usable in the present embodiment, in addition to the above-mentioned polyester polyol, it is preferred to use an octanol-water partition coefficient (logP(B)) from the viewpoint of water solubility or alignment of the compound. It is a compound of 0 or more and less than 7.

Polyester polyol, if necessary in the presence of esterification catalyst The dicarboxylic acid or the ester-forming derivative (corresponding to the component of the general formula (A) A) and the glycol (corresponding to the component of the general formula (A) G), for example, The esterification reaction is carried out in a temperature range of 180 to 250 ° C for 10 to 25 hours by a conventionally known method.

In the esterification reaction, a solvent such as toluene or xylene may be used, but a method in which glycol is used as a solvent-free or raw material as a solvent is preferred.

As the esterification catalyst, for example, tetraisopropyl titanate, tetrabutyl titanate, p-toluenesulfonic acid, dibutyltin oxide or the like can be used. The esterification catalyst is preferably used in an amount of 0.01 to 0.5 parts by mass based on 100 parts by mass of the total amount of the dicarboxylic acid or the ester-forming derivative.

The molar ratio of the dicarboxylic acid or the ester-forming derivative to the glycol, the terminal group of the polyester must be the molar ratio of the hydroxyl group, thus forming a derivative with respect to the dicarboxylic acid or the ester The substance is 1 mole, and the glycol is 1.1 to 10 moles. Preferably, it is 1 to 8 moles relative to the dicarboxylic acid or the ester-forming derivative, and the glycol is 1.5 to 7 moles, more preferably 1 mole relative to the dicarboxylic acid or the ester-forming derivative. , glycol is 2 to 5 moles.

Although the terminal group of the above polyester polyol is a hydroxyl group, the polyester polyol also contains a compound which is a carboxyl terminal of a by-product. However, in the carboxyl terminal of the polyester polyol, the content is preferably lower because of lowering the humidity stability. Specifically, the acid value is preferably 5.0 mgKOH/g or less, more preferably 1.0 mgKOH/g or less, still more preferably 0.5 mgKOH/g or less. However, the term "acid value" as used herein refers to the amount of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample (the carboxyl group present in the sample). number. The acid value can be measured in accordance with JIS K0070:1992.

The polyester polyol is preferably in a range of a hydroxyl group (hydroxyl group) (OHV) of 35 mg/g or more and 220 mg/g or less. Here, the hydroxy (hydroxyl) valence refers to the number of milligrams of potassium hydroxide necessary for neutralizing the hydroxy group-bonded acetic acid when the hydroxyl group contained in 1 g of the acetylated sample is used. The hydroxy (hydroxyl) valence is an acetylation group using a hydroxyl group in a sample of acetic anhydride, and the unused acetic acid is titrated with a potassium hydroxide solution, which is obtained from the difference between the titration value of the initial acetic anhydride.

The polyester polyol preferably has a hydroxyl group content of 70% or more. When the hydroxyl group content is small, there is a tendency to lower the compatibility of the polyester polyol with the resin constituting the film. Therefore, the hydroxyl group content is preferably 70% or more, more preferably 90% or more, still more preferably 99% or more. In the present embodiment, the compound having a hydroxyl group content of 50% or less is not included in the polyester polyol because one of the terminal groups is substituted with a group other than a hydroxyl group.

The aforementioned hydroxyl group content can be determined by the following formula (B).

Y/X×100=hydroxyl content (%)‧‧‧(B)

X: hydroxyl value (OHV) of the aforementioned polyester polyol

Y: 1 (number average molecular weight (Mn)) × 56 × 2 × 1000

The polyester polyol preferably has a number average molecular weight in the range of 300 to 3,000, more preferably a number average molecular weight of 350 to 2,000.

Further, the polyester polyol of the present embodiment preferably has a molecular weight dispersion of 1.0 to 3.0, more preferably 1.0 to 2.0. When the degree of dispersion is within the above range, it is easy to obtain a polyester having excellent compatibility with a resin constituting the film. Alcohol.

Further, the polyester polyol preferably contains 50% or more of a component having a molecular weight of 300 to 1800. By setting the number average molecular weight to the above range, the compatibility can be greatly improved.

The end-capped polyester may be at least one of the two terminal groups B as a monocarboxylic acid residue. That is, one of the two terminal groups B is a hydroxyl group, and the other may be a monocarboxylic acid residue. Preferably, both of the terminal groups B are preferably monocarboxylic acid residues.

As the terminal group B, the above-mentioned benzene monocarboxylic acid residue or aliphatic monocarboxylic acid residue can be used, and a benzene monocarboxylic acid residue can be preferably used. That is, the terminal group B is preferably an aromatic terminal polyester.

The terminal end-capped polyester may be a glycol (a component corresponding to G of the general formula (A)), a dicarboxylic acid or an ester-forming derivative (a composition equivalent to the general formula (A) A). And a monocarboxylic acid or such an ester-forming derivative (a component corresponding to B of the general formula (A)) is obtained by an esterification reaction, and for example, JP-A-2011-52205, JP-A-2008 It is synthesized by the publication of Japanese Patent Laid-Open No. 2008-88292, and the like.

The ester compound of the present embodiment has a mixture of a molecular weight and a molecular structure at the time of synthesis. Among the components of the present embodiment, for example, it is preferred that at least one of the components of the general formula (A) has benzene. A polyester compound of a formic acid residue and an adipic acid residue.

The end-capped polyester preferably has a number average molecular weight of from 300 to 1,500, more preferably from 400 to 1,000. Also, the acid value is 0.5 mgKOH/g. The hydroxyl group (hydroxyl group) has a valence of 25 mgKOH/g or less, more preferably an acid value of 0.3 mgKOH/g or less, and a hydroxyl group (hydroxyl group) of 15 mgKOH/g or less.

Hereinafter, the specific compound which can be used for the ester type compound represented by the general formula (A) of this embodiment is shown, but this embodiment is not limited to this.

In the film of the present embodiment, the polyester compound is preferably contained in an amount of 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass, based on the entire film (100% by mass). Further, as the other plasticizer, materials such as those described in [0102] to [0155] of International Publication No. 10/026832 can be suitably used.

(b) UV absorber

The film of this embodiment may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of enhancing the durability of the film by absorbing ultraviolet rays of 400 nm or less. The ultraviolet absorber is added at a transmittance of 370 nm at a wavelength of 10% or less, preferably 5% or less, more preferably 2% or less.

The ultraviolet absorber is not particularly limited, and examples thereof include an oxydiphenyl ketone compound, a benzotriazole compound, a salicylate compound, a diphenyl ketone compound, a cyanoacrylate compound, and the like. A azine compound, a nickel stear salt compound, an inorganic powder or the like. Among these, a benzotriazole-based ultraviolet absorber, a diphenylketone-based ultraviolet absorber, and a triazine-based ultraviolet absorber are preferably used, and a benzotriazole-based ultraviolet absorber or diphenylketone is more preferably used. It is a UV absorber. Specifically, for example, 5-chloro-2-(3,5-di-sec-butyl-2-hydroxyphenyl)-2H-benzotriazole, (2-2H-benzene) is preferably used. And triazol-2-yl)-6-(linear and side chain dodecyl)-4-methylphenol, 2-hydroxy-4-benzyloxydiphenyl ketone, 2,4-benzyloxy Phenyl ketone and the like are commercially available as Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin of Tinuvin 328, Tinuvin 928, etc. (above is Ciba Japan K.K.). Other, it is preferred to use a disk-shaped compound having a compound of 1,3,5-triazine ring or the like as an ultraviolet absorber.

The cellulose ester solution of the present embodiment preferably contains two or more kinds of ultraviolet absorbers. Further, as the ultraviolet absorber, a polymer ultraviolet absorber is preferably used, and a polymer type ultraviolet absorber described in JP-A-6-148430 is particularly preferably used.

As a method of adding the ultraviolet absorber, an ultraviolet absorber may be dissolved in an alcohol such as methanol, ethanol or butanol or an organic solvent such as dichloromethane, methyl acetate, acetone or dioxane or a mixed solvent thereof. A method of adding to a dopant or directly adding to a dopant composition. In this case, if it is not dissolved in an organic solvent like an inorganic powder, it is preferable to use a dissolver or a sand mixer in an organic solvent and a cellulose ester, and to add it to the dopant after dispersion.

The amount of the ultraviolet absorber to be used is not the same as the type and use condition of the ultraviolet absorber. However, when the film has a dry film thickness of 30 to 200 μm, it is preferably 0.5 to 10% by mass, more preferably 0.6. ~4% by mass.

(c) microparticles

The film preferably contains fine particles from the viewpoint of slidability and storage stability. Examples of the fine particles include, as an inorganic compound, cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, calcium citrate hydrate, and citric acid. Aluminum, magnesium citrate and calcium phosphate. Although the microparticles contain ruthenium, it is preferable to reduce the turbidity, especially ruthenium dioxide.

For cerium oxide, it is preferred that the hydrophobicized person has both slidability and haze value. Of the four stanol groups, preferably two or more are substituted with a hydrophobic substituent, and more preferably three or more. The hydrophobic substituent is preferably a methyl group.

The average primary particle diameter of the cerium oxide is preferably 20 nm or less, more preferably 10 nm or less. In addition, the average primary particle diameter of the fine particles was observed by a transmission electron microscope (magnification: 500,000 to 2,000,000 times), and 100 particles were observed, and the particle diameter was measured to have an average value, which was used as the primary average particle diameter.

As the fine particles of cerium oxide, for example, those commercially available under the trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (all manufactured by Japan Aerosil Co., Ltd.) can be used.

Examples of the polymer fine particles include a decyl alkane resin, a fluororesin, and an acrylic resin. It is preferable to use a decane resin, especially a network having a three-dimensional network structure, for example, TOSPEARL103, the same 105, the same 108, the same 120, the same 145, the same 3120, and the same 240 (the above is Toshiba 矽) The brand name of the oxyalkylene (stock) system is commercially available.

Among them, Aerosil 200V, Aerosil R972V, and Aerosil R812 are preferable because the effect of lowering the friction coefficient while maintaining the film at a low haze value, and it is preferable to use Aerosil R812.

The amount of the fine particles added is preferably 0.01 parts by mass to 5.0 parts by mass based on 100 parts by mass of the cellulose ester. When the amount of addition is large, the coefficient of friction is excellent, and when the amount of addition is small, the amount of aggregates is reduced.

In the film of the present embodiment, the dynamic friction coefficient of at least one side surface is preferably 0.2 to 1.0.

(d) Dyes

In the film, a dye for adjusting the color odor can be added within a range that does not impair the effects of the embodiment. In the film, for example, in order to suppress the yellow taste of the film, a cyan dye may be added. As a preferable dye, an anthraquinone type dye is mentioned.

(e) sugar ester compound

Examples of the sugar ester compound used in the present embodiment include glucose, galactose, mannose, fructose, xylose, or arabinose, lactose, sucrose, canetetraose, 1F-fructose-based canetetraose, and water. Sucrase, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose or canetriose. Other examples include gentiobiose, gentian trisaccharide, gentian tetrasaccharide, xylotriose, and galactosyl sucrose.

Among these compounds, a compound having both a rutose structure and a furanose structure is particularly preferred. Specifically, sucrose, canetriose, canetetraose, 1F-fructose-based canetetraose, stachyose, etc. are preferred, and sucrose is preferred.

The whole or a part of the hydroxyl group in the sucrose structure or the furanose structure is not particularly limited as long as the monocarboxylic acid used for the esterification, but a well-known aliphatic monocarboxylic acid or alicyclic monocarboxylic acid can be used. , aromatic monocarboxylic acid, and the like. The carboxylic acid to be used may be used alone or in combination of two or more.

Preferred examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanecarboxylic acid, and eleven. Alkanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pentadecanoic acid, stearic acid, decanoic acid, icosonic acid, behenic acid, tetracosane Saturated fatty acids such as acid, wax acid, heptacosanoic acid, montanic acid, tridecanoic acid, tridecanoic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linoleic acid, peanut oleic acid, An unsaturated fatty acid such as octenoic acid.

Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and the like.

The preferred aromatic monocarboxylic acid is exemplified by a benzene ring of a benzoic acid such as benzoic acid or benzoic acid, an alkyl group, an alkoxy aromatic monocarboxylic acid, cinnamic acid, a benzylic acid or a biphenylcarboxylic acid. An aromatic monocarboxylic acid having two or more benzene rings, such as naphthalenecarboxylic acid or tetrahydronaphthalenecarboxylic acid, or a derivative thereof. Specific examples thereof include xylene acid, dimethylbenzoic acid, mesitylene acid, 2,3,4-trimethylbenzoic acid (prehnitylic acid), and γ-isotrimethyl benzoic acid (Isodurylic acid). Dirylic acid, Mesitoic acid, α-isotrimethylbenzene acid, fennel acid, α-benzoic acid, Hydroatropic acid, Atropic acid, hydrogenated cinnamon Acid, salicylic acid, o-anisic acid, m-anisic acid, p-anisic acid, miscellaneous Creosotic acid, o-high salicylic acid, m-high salicylic acid, p-high salicylic acid, o-catecholic acid, beta-thalatinic acid, vanillic acid, isovanillonic acid, anthraquinone Resin, o-cucurbit acid, gallic acid, asaronic acid, mandelic acid, Homoanisic Acid, Homovanillic acid, Homoveratric acid , o-high lauric acid, Phthalonic acid, and Coumalic acidd. Among them, benzoic acid and naphthyl acid are particularly preferred.

The oligosaccharide ester compound can be suitably used as a "compound having at least one of 1 to 12 sucrose structure or furanose structure" which will be described later.

The oligosaccharide is produced by an enzyme such as amylase such as starch or sucrose. Examples of the oligosaccharide which can be used in the present embodiment include malto-oligosaccharide, isomaltoligosaccharide, fructooligosaccharide, and galacto. Oligosaccharides, xylooligosaccharides.

In addition, the ester compound is a compound which condenses at least one of a caramel structure or a furanose structure represented by the following general formula (B) in one or more and twelve or less. In the general formula (B), R ₁₁ to R ₁₅ and R ₂₁ to R ₂₅ represent a fluorenyl group or a hydrogen atom having 2 to 22 carbon atoms, m and n each represent an integer of 0 to 12, and m + n represents 1 to 12, respectively. Integer.

R ₁₁ to R ₁₅ and R ₂₁ to R ₂₅ are preferably a benzamidine group or a hydrogen atom. The benzamidine group may further have a substituent R ₂₆ , and examples of R ₂₆ include an alkyl group, an alkenyl group, an alkoxy group, and a phenyl group. Further, the alkyl group, the alkenyl group, and the phenyl group may have a substituent. Oligosaccharides can also be produced in the same phase as the ester compound.

More specifically, the sugar ester compound is exemplified by a compound represented by the general formula (1).

In the formula, R ₁ to R ₈ represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms. R ₁ to R ₈ may be the same or different.

In the following, the compound represented by the general formula (1) (compound 1-1 to compound 1-23) is specifically shown, but it is not limited thereto. Further, when the average degree of substitution in the following table is less than 8.0, any one of R ₁ to R ₈ represents a hydrogen atom.

(f) propylene fluorenyl copolymer

The film of the present embodiment may contain an acrylonitrile-based polymer having a weight average molecular weight of 500 or more and 30,000 or less. In particular, it is preferred that the ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule and the ethylenically unsaturated monomer Xb having a hydrophilic group having no aromatic ring in the molecule are obtained. The polymer X having a weight average molecular weight of 5,000 or more and 30,000 or less is more preferably an ethylenically unsaturated monomer Xa which does not have an aromatic ring and a hydrophilic group in the molecule, and a hydrophilic group which does not have an aromatic ring in the molecule. The weight of the ethylenically unsaturated monomer Xb The polymer X having a weight average molecular weight of 5,000 or more and 30,000 or less and the polymer Y having a weight average molecular weight of 500 or more and 3,000 or less obtained by polymerizing the ethylenically unsaturated monomer YA having no aromatic ring.

The acrylonitrile-based copolymer may be added in an amount of from 1 to 30 parts by mass based on 100 parts by mass of the cellulose ester.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In the examples, the expression "parts" or "%" is used, unless otherwise stated, "mass parts" or "% by mass".

(cellulose ester resin)

As the cellulose ester resin, the following are prepared.

DAC: cellulose diacetate (acetamyl substitution degree 2.45, Mw 300,000)

(cellulose ester film)

As the cellulose ester film, the following are prepared.

6UA (Konica Minolta (share) system)

6TD (Fuji Film Co., Ltd.)

(COP film)

As the COP film, the following are prepared.

Cyclic olefin polymer film (ZF14 Japan Zeon Co., Ltd.)

(rod compound)

As the rod-like compound forming the alignment film, the following ones are prepared.

(liquid crystal compound)

As the liquid crystalline compound, the following ones are prepared.

<Example 1> (hydrophilization treatment)

On one side of the above cellulose ester film (6UA), excimer light was irradiated onto the hydrophilized surface at an intensity of 500 mJ/cm ² to prepare an antifogging film. The reforming treatment device having the excimer light source and the upgrading treatment conditions are as follows.

<Modification processing device>

(shares) M‧D‧COM excimer irradiation device MODEL: MECL-M-1-200

Wavelength: 172nm

Enclosed lamp gas: Xe

<Modification processing conditions>

Excimer light intensity: 130mW/cm ² (172nm)

Distance between sample and light source: 2mm

Oxygen concentration in the irradiation device: 0.3%

Next, an alignment film was formed on the surface opposite to the surface of the cellulose ester film (6UA) which was subjected to the hydrophilization treatment, and a retardation layer was formed thereon using a liquid crystal compound. The method of forming the alignment film and the retardation layer is as follows.

(Formation of alignment film)

On the surface opposite to the surface on which the cellulose ester film (6UA) was hydrophilized, the alignment film coating liquid having the following composition was applied by a bar coater at 20 ml/m ² . The film was dried by hot air at 60 ° C for 60 seconds, and further dried by hot air at 100 ° C for 120 seconds to form a film. Next, the formed film was subjected to a rubbing treatment in a direction of 20° with respect to the longitudinal direction of the film to form an alignment film.

<Alignment film coating liquid>

(formation of phase difference layer)

On the alignment film, the phase difference layer coating liquid having the following structure was applied as a wire bar. This was heated in a thermostat at 125 ° C for 3 minutes to align the rod-like liquid crystalline compound. Next, a 120 W/cm high pressure mercury lamp was used to irradiate the UV crosslinked rod-like liquid crystalline compound for 30 seconds. The temperature at the time of UV hardening was set to 80 ° C to obtain a retardation layer. The thickness of the phase difference layer was 2.0 μm. Then, let cool to room temperature.

<phase difference layer coating liquid>

Further, the glass laminate of Example 1 was obtained by laminating the surface on the retardation layer side with the glass plate using an adhesive.

<Example 2>

In the first embodiment, in place of the light irradiation treatment, both sides of the cellulose ester film (6UA) were hydrophilized by a saponification treatment, and the above-mentioned COP film was bonded to either surface instead of the rod-like liquid crystal compound to form a retardation layer. A glass laminate of Example 2 was obtained in the same manner as in Example 1 except the above.

<Saponification conditions>

A cellulose ester film (6 UA) prepared by immersing 2 (2N) of a NaOH aqueous solution at 55 ° C for 1 hour was washed with water and dried to prepare an antifogging film.

<Example 3>

In Example 1, in the replacement light irradiation treatment, both surfaces of the hydrophilized cellulose ester film (6UA) were subjected to saponification treatment, the angle of friction at the time of formation of the alignment film was changed to 60°, and the retardation layer Ro was adjusted to 100 nm. A glass laminate of Example 3 was obtained in the same manner as in Example 1 except the above.

<Example 4>

In Example 1, the angle of friction at the time of formation of the alignment film was changed to 55°, and the phase difference layer was changed by the film thickness, and Ro was adjusted to 70 nm. In addition to this The glass laminate of Example 4 was obtained in the same manner as in Example 1.

<Example 5>

In the first embodiment, instead of 6UA, the cellulose ester film of 6TD was used instead of the light irradiation treatment, and both sides of the cellulose ester film (6TD) were hydrophilized by the saponification treatment, and the friction at the formation of the alignment film was changed by the film thickness. The angle was adjusted to a retardation layer of 45°, and Ro was adjusted to 30 nm. A glass laminate of Example 5 was obtained in the same manner as in Example 1 except the above.

<Comparative Example 1> (Production of cellulose ester film A1) <Microparticle Dispersion 1>

The mixture was stirred and mixed for 50 minutes with a dissolver, and then dispersed with Manton Gaulin.

<Microparticle Addition Liquid 1>

The fine particle dispersion 1 was slowly added while thoroughly stirring in a dissolution tank to which methylene chloride was added. Further, in the attritor, the particle size of the secondary particles is dispersed to a specific size. This was filtered with Finemet NF manufactured by Nippon Seisaku Co., Ltd. to prepare a fine particle addition liquid 1.

<Main dopant A>

The main dopant A having the following constitution is prepared. First, dichloromethane and ethanol were added to the pressure dissolution tank. This is carried out by stirring the cellulose acetate while adding the solvent to the pressure dissolution tank. Heat this and stir until completely dissolved. The main dopant A was prepared by filtering the filter paper No. 244 made of an Anion filter paper.

Next, the dopant was uniformly cast on the stainless steel belt support at a temperature of 33 ° C and a width of 1500 mm using an endless belt casting device. The temperature of the stainless steel belt is controlled to 30 °C. Further, on the stainless steel belt support, the amount of the residual solvent in the cast (cast) film was evaporated to 75% by mass, and then peeled off from the stainless steel belt support at a peeling tension of 130 N/m.

The peeled cellulose ester film was stretched by 15% in the transverse direction using a tentering machine while applying heat of 160 °C. The amount of residual solvent at the start of drawing was 15% by mass. Next, the drying is terminated while the dry area is conveyed by a plurality of rolls. The drying temperature was 130 ° C and the transport tension was 100 N/m. After drying, the film was cut into a width of 1.5 m, and knurling having a width of 10 mm and a height of 10 μm was applied to both ends of the film, and wound into a roll to obtain a cellulose ester film A1 having a dried film thickness of 40 μm. The roll length is 5000m.

The retardation Ro of the in-plane direction of the cellulose ester film A1 was 50 nm as measured by the following measurement method. Further, the slow axis axis is the same as the drawing process direction in the lateral direction.

(Measurement of retardation) <direction of the slow phase axis>

The Abbe refractometer (1T) was used to measure the average refractive index of the film sample in the surface at a temperature of 23 ° C and a relative humidity of 55% RH in a wavelength of 590 nm, thereby obtaining the direction of the slow axis.

<Measurement of retardation>

The retardation Ro in the in-plane direction was measured using an automatic birefringence meter KOBRA-21ADH (Prince Measurement Machine (Unit)). Shang, Ro is shown in the following formula.

Formula (i): Ro = (nx - ny) × d (nm)

Here, d is the thickness (nm) of the film, nx is the refractive index in the direction of the slow axis, and ny is the refractive index in the direction perpendicular to the axis of the film and the slow axis.

The glass laminate of Comparative Example 1 was obtained by adhering one surface of the cellulose ester film A1 described above to a glass plate using an adhesive.

<Comparative Example 2>

In Example 2, the glass laminate of Comparative Example 2 was obtained by omitting the retardation layer.

<Comparative Example 3>

The both surfaces of the cellulose ester film A1 were subjected to a hydrophilization treatment by saponification treatment, and the glass laminate of Comparative Example 3 was obtained by laminating one surface thereof with a glass plate using an adhesive. Further, a phase difference increasing agent was added to the cellulose ester film A1, and Ro was adjusted to 140 nm.

<Evaluation method> (Visibility when installing polarized sunglasses)

The visibility when the image was observed by installing polarized sunglasses was evaluated as follows.

First, a polarizing plate (a polarizing plate on the visual side of the liquid crystal display) is placed on a lighting device (Schaukasten), and the produced glass laminate is attached to a polarizing plate. The angle between the absorption axis of the polarizing plate and the slow axis of the glass laminate was as shown in Table 1. Further, in the lighting device, when the polarized sunglasses were attached, the angle was observed while changing the angle, and the visibility was evaluated based on the following evaluation criteria.

<Evaluation criteria>

◎: The brightness of the angle was not changed even if the angle of observation was changed.

○: When the angle of observation is changed, the brightness changes but is still sufficiently bright.

△: When the angle of observation is changed, the brightness changes and there is a slightly darkened angle.

×: When the angle of observation is changed, the brightness changes and there is an angle that is completely darkened.

The evaluation of the above visibility is supplemented. When the glass laminate has a desired Ro, the linear polarized light transmitted through the polarizing plate is converted into circularly polarized light or rounded polarized light by the glass laminated body, and the polarized sunglasses are transmitted through the light (light leakage is generated). Accordingly, the evaluation in this case is either ◎, ○, or Δ. Further, when the glass laminate does not have a desired Ro, the linearly polarized light transmitted through the polarizing plate cannot be converted into circularly polarized light or rounded polarized light by the glass laminate, and is blocked by polarized sunglasses. Therefore, the evaluation becomes ×.

(Fog after vapor irradiation and its visibility)

The produced glass laminate was continuously irradiated with steam at a specific time of 40 ° C (any one of 60 seconds, 45 seconds, 20 seconds, and 5 seconds) at 23 ° C and 55% RH. Further, the change in the haze value (haze) before the vapor irradiation and the visibility at the time of mounting the polarized sunglasses with respect to the vapor irradiation were investigated. The measurement of the haze value was carried out using a haze meter NDH2000 (manufactured by Nippon Denshoku Co., Ltd.). Further, the haze after the vapor irradiation was evaluated based on the following evaluation criteria. In addition, the evaluation criteria of the visibility when the polarized sunglasses are installed are the same as described above.

<Evaluation criteria>

◎: The change in the haze value after 60 seconds of irradiation was within 3%.

○: The change in the haze value after irradiation for 45 seconds was within 3%.

△: The change in the haze value after the irradiation for 20 seconds was within 3%.

×: The change in the haze value after 5 seconds of irradiation was 10% or more.

The evaluation results of the examples and comparative examples are shown in Table 1.

As a result of Table 1, the visibility of the polarized sunglasses which were not irradiated with the vapor state was only × in Comparative Example 2, and it was said that the visibility was not suitable for the polarized sunglasses. In addition, any of ◎, ○, and △ can be said to have no problem in visibility of polarized sunglasses. This is because there is no retardation layer in Comparative Example 2, and the linearly polarized light transmitted through the polarizing plate is blocked by polarized sunglasses by the glass laminate being not converted into circularly polarized light or rounded polarized light. Further, Examples 1 to 5 have a retardation layer, and in Comparative Examples 1 and 3, since the cellulose ester film A1 itself has Ro, linearly polarized light transmitted through the polarizing plate can be converted into circularly polarized light or rounded polarized light by the glass laminate. Therefore, the polarized sunglasses are transmitted through the light.

Next, in the haze after the vapor irradiation, Comparative Examples 1 and 3 were ×, and it can be said that the reduction in the antifogging function after the vapor irradiation was not suppressed. In addition to this, it is ◎ or ○, and it can be said that the reduction of the anti-fog function after the vapor irradiation is suppressed. This is considered to be because the anti-fog function is not provided in Comparative Example 1, and a water-absorbing layer (hydrophilized layer) having a large film thickness is formed on both surfaces of the cellulose ester film A1 by saponification treatment in Comparative Example 3, and the film is greatly increased. The moisture absorption (water content), which absorbs a large amount of moisture by vapor irradiation, lowers the retardation of Ro. Further, in Examples 1 and 4, since there was no hydrophilization treatment by light irradiation, there was no suspense in which the retardation Ro was lowered due to water absorption. Further, in Examples 2, 3, and 5 and Comparative Example 2, since the cellulose ester film having no phase difference function was used, there was no concept of retarding Ro.

Next, for the visibility of the polarized sunglasses after the vapor irradiation, only the comparative example 2 is ×, and it can be said that it is not suitable for the visibility of the polarized sunglasses. In addition, it is any one of ◎, ○, △, which can be said to be partial There is no problem with the visibility of light sunglasses. This is because there is no phase difference layer in the original comparative example 2. Further, in Examples 1 to 5, since the retardation layer was covered with the cellulose ester film, there was no suspense in which the retardation of Ro was lowered. Further, in Comparative Examples 1 and 3, it is considered that although a large amount of moisture is absorbed by vapor irradiation to lower the retardation Ro, the degree is not reduced to the function of converting into circularly polarized light or rounded polarized light.

From the above, the result of the evaluation is that when the glass laminates of Examples 1 to 5 are disposed through the liquid crystal display and the void layer, the performance of the anti-fog function can be simultaneously achieved and the visibility of the polarized sunglasses can be improved, and It is said that the reduction of the anti-fog function after the suppression of the vapor irradiation can also improve the visibility of the polarized sunglasses when they are not mounted.

The glass laminate and the liquid crystal display device of the present embodiment described above can be expressed as follows.

A glass laminate which is a glass laminate in which a glass, a retardation layer, and a film are laminated in this order, wherein the film is a polymer film in which at least one carbon of a glucose ring side chain is substituted. The surface on the opposite side to the aforementioned retardation layer has a hydrophilization-treated antifogging property.

2. The glass laminate according to the above 1, wherein the polymer film is a cellulose ester film.

3. The glass laminate according to the above 1 or 2, wherein the retardation layer is a liquid crystalline compound.

4. The glass laminate according to any one of the above 1 to 3, wherein the phase difference layer and the film are provided as touch sensing The conductive part of the device.

The glass laminate according to any one of the above 1 to 4, wherein a phosphoric acid-based plasticizer is not added to the film.

A liquid crystal display device comprising the glass laminate according to any one of the above 1 to 5, and a liquid crystal display, wherein the glass laminate system is disposed such that a gap layer is provided between the film and the liquid crystal display.

7. The liquid crystal display device according to the above aspect, wherein a phase of the slow axis of the retardation layer and an absorption axis of the polarizing plate on the glass laminate side of the liquid crystal display are 10 or more and 80 or less. .

[Industrial availability]

The glass lamination system of the present invention is first used in front of a liquid crystal display such as a car navigation system, and the touch panel disposed through the gap layer can be used as a protective plate for various display devices such as an information display used outdoors.

1‧‧‧Liquid crystal display device

2‧‧‧glass laminate

3‧‧‧LCD display

4‧‧‧ glass

5‧‧‧Electrical Department

6‧‧‧film

6a‧‧‧Hydrophilic layer

6b‧‧‧non-hydrophilic layer

7‧‧‧ phase difference layer

11‧‧‧1st electrode pattern

12‧‧‧Interlayer insulation

13‧‧‧2nd electrode pattern

31‧‧‧LCD panel

32‧‧‧ Backlight

33‧‧‧Liquid crystal components

34, 35‧‧‧ polarizing plate

S‧‧‧ void layer

Claims (7)

A glass laminate which is a glass laminate in which a glass, a retardation layer, and a film are laminated in this order, wherein the film is a polymer film in which at least one or more carbons of a glucose ring side chain are substituted. And the surface on the opposite side to the aforementioned retardation layer has a hydrophilization-treated antifogging property. The glass laminate of claim 1, wherein the polymer film is a cellulose ester film. The glass laminate of claim 1, wherein the phase difference layer is a liquid crystalline compound. The glass laminate according to claim 1, wherein a conductive portion serving as a touch sensor is provided between the retardation layer and the thin film. The glass laminate of claim 1, wherein a phosphate-based plasticizer is not added to the film. A liquid crystal display device comprising the glass laminate according to any one of claims 1 to 5, and a liquid crystal display, wherein the glass laminate system is disposed such that a gap layer is provided between the film and the liquid crystal display. The liquid crystal display device according to claim 6, wherein the retardation axis of the retardation layer and the absorption axis of the polarizing plate on the glass laminate side of the liquid crystal display are 10° or more and 80° or less.