JP2001147303A - Method for producing functional film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve adhesion of an dirt-proof, film to the surface of an antireflection film in a method for producing a functional film. SOLUTION: In order to produce a functional film 10, a film-forming step S1 is first carried out. In the step S1, an antireflection film 14 is formed continuously on the surface of a resin substrate 11 wound in to a roll shape, while allowing the substrate 11 to run in a hermetically sealed atmosphere, and the substrate 11 is rewound into a roll shape. An exposure step S2 is then carried out. In the step S2, the wound substrate 11 is rewound in an open atmosphere, and the surface of the formed antireflection film 14 is activated naturally by exposure to the air. A coating step S4 in which the activated surface of the antireflection film 14 is coated with a coating solution containing an dirt-proof material, and the coating solution is dried to form an dirt-proof film 15 is carried out. After the preparation of the coating solution and before the coating, an aging step S3 is carried out so that the reactivity of the coating solution is enhanced, and the fixation of the antifouling film 15 on the surface of the antireflection film 14 is promoted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention mainly relates to a cathode ray tube (C)
(RT) relates to a method for producing a functional film to be attached to a panel glass surface.

[0002]

2. Description of the Related Art Generally, in a display device such as a cathode ray tube (CRT), a functional film is attached to the surface of a panel on which an image is displayed via an adhesive or an adhesive such as an ultraviolet curable resin. Have been. This functional film is formed by appropriately combining films having various functions such as an explosion-proof auxiliary effect, an antistatic effect, a transmittance adjusting effect, an antireflection effect, and an antifouling effect on a resin base material serving as a base material. As one example, a laminate formed by laminating a hard coat film, a transparent conductive film, an antireflection film, and an antifouling film on a resin substrate is known.

Here, the antifouling film is made of a fluorine-based resin in which dirt such as fingerprints does not easily adhere to the surface thereof, and the dirt once adhered can be easily removed by dry wiping or water wiping. A coating solution formed by adding a perfluoro group-containing phosphoric acid ester as a catalyst to a solution containing a perfluoro group-containing silicon-based material as a solute is coated on an antireflection film, and further dried. It is formed by doing.

[0004] Thus, a hard coat film on a resin substrate,
The functional film obtained by forming the transparent conductive film, antireflection film and antifouling film is wound up and stored in a roll immediately after the formation of the outermost antifouling film, and is withdrawn from this roll when used. Then, it is adhered to the surface to be adhered, for example, the surface of a panel glass of a CRT via an adhesive (ultraviolet curable resin) or an adhesive.

As a method of attaching such a functional film to the panel glass surface, first, as shown in FIG. 5, an ultraviolet curable resin 7a is applied to the surface of the panel glass 1. Next, the other end of the functional film 10 is placed on the ultraviolet-curable resin 7a while one end of the functional film 10 is held by the film grip 304 so as to float above the ultraviolet-curable resin 7a. Then, while moving the pressure roll 305 from the other end toward the one end side on the functional film 10, the film gripper 304 is lowered, and the one end side is gradually brought into contact with the ultraviolet curable resin 7 a, whereby the functional film 10 1
0 is placed on the ultraviolet curing resin 7a. afterwards,
By irradiating the functional film 10 with ultraviolet light, the ultraviolet curable resin 7a is cured, whereby the functional film 10 is attached to the panel glass 1.

[0006]

When a functional film is adhered to the panel glass surface with an adhesive made of an ultraviolet-curable resin, for example, if the adhered surface is contaminated, the ultraviolet-curable resin is cured by irradiation with ultraviolet light. Even if it does, this functional film will easily peel off from the panel glass surface. Then, when the functional film is peeled off as described above, a process such as re-adhering the functional film is required, and as a result, there is an inconvenience that the cost of the cathode ray tube using the functional film is increased.

In some cases, the functional film 10 is attached to the surface of the panel glass 1 using an adhesive instead of the ultraviolet curing resin 7a. In particular, when affixing to the panel glass surface using an adhesive, for example, after shipping the obtained CRT product, if the functional film is peeled off for reprocessing as recycling, the adhesive remains on the panel glass surface,
It becomes difficult to reuse this. If the reuse becomes difficult in this way, there arises an inconvenience that the cost of a cathode ray tube using this functional film is increased.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method of manufacturing a functional film in which panel glass can be reused to reduce the cost of a cathode ray tube. .

[0009]

The following means have been taken in order to achieve the above-mentioned object of the present invention. In other words, the method for producing a functional film according to the present invention is such that an antireflection film is continuously formed on the surface of the resin substrate while the resin substrate wound in a roll shape is run in a closed atmosphere, and the roll is rolled again. A film forming step of winding into a shape, and an exposing step of exposing the formed antireflection film to the atmosphere and naturally activating the surface by rewinding the wound resin substrate in an open atmosphere, Applying a coating solution containing an antifouling substance to the surface of the activated antireflection film and drying the coating solution to form an antifouling film; and performing a coating process on the surface of the antireflection film. Is characterized by improving the adhesiveness. Specifically, in the film forming step, an optical multilayer film including an SiO ₂ layer as an uppermost layer is formed as the antireflection film, and in the exposing step, the surface of the SiO ₂ layer is formed by allowing moisture in the air to act on the SiO ₂ layer. In the coating step, a coating liquid obtained by adding a perfluoro group-containing phosphoric acid ester as a catalyst to a solution containing a perfluoro group-containing silicon-based antifouling substance as a solute is applied.
Preferably, in the exposing step, the resin base material is rolled at a speed of 5 m / min to 10 m / min in an open atmosphere adjusted to a temperature of 25 ° C. ± 3 ° C. and a humidity of 60% ± 5%. In some cases, the coating step enhances the reactivity of the coating liquid by performing aging after preparing the coating liquid and before coating, whereby the antifouling film reacts with the surface of the antireflection film. Promotes immobilization.

The present invention also provides a film forming step of continuously forming an antireflection film on the surface of the resin base material while running the resin base material wound in a roll shape, and winding the roll back again. A coating step of continuously applying a coating solution containing an antifouling substance to the surface of the antireflection film while running the wound resin substrate again, and drying to form an antifouling film. In the production method, after the coating solution is prepared, aging is performed before coating to increase the reactivity of the coating solution, thereby performing an aging step of promoting the fixation of the antifouling film to the antireflection film. It is characterized by the following. Specifically, the coating step is performed by using a solution containing a silicon-based contaminant containing a perfluoro group as a solute,
A coating liquid containing a perfluoro group-containing phosphate ester as a catalyst is applied. In this case, the aging step is performed at a temperature of 25 ° C. ± 3 ° C. and a humidity of 60% ± 5%.
The coating liquid is allowed to stand in the atmosphere of the above for up to one hour.

The inventor of the present invention has conducted intensive studies on the fact that the adhesive remains on the surface of the panel glass.
The cause is that when the functional film is wound up in a roll and stored, the antifouling film is formed on the back surface of the resin substrate of the functional film (the surface opposite to the surface on which the antireflection film, the antifouling film, etc. are formed). Some believe that there is a so-called set-off.
That is, since the antifouling film is difficult to adhere to the dirt and the like, if the antifouling film is set off on the back surface of the resin base material that is in contact with the adhesive, the set off portion also has an antifouling film. Acts in the same manner as described above, and the adhesion to the pressure-sensitive adhesive becomes weak. Therefore,
When the functional film is peeled off, the adhesive remains on the panel glass side instead of the resin film. Therefore, in the method for manufacturing a functional film of the present invention, the resin substrate roll after the antireflection film is formed by sputtering or the like is wound at least once in the air. The environment at that time is, for example, a temperature of about 25 ° C. and a humidity of about 60%. Due to this exposure to the air, moisture adheres to the surface of the antireflection film and is chemically activated. By applying the coating liquid to the naturally activated surface, the adhesiveness is improved, and it is possible to prevent the set-off of the antifouling film described above. Before coating the coating liquid on the antireflection film, the coating liquid is aged in a liquid pan of a roll coater. Thereby, the reactivity of the coating liquid increases, and the coating liquid is quickly fixed to the surface of the antireflection film. For this reason, even if the resin substrate is wound up after coating, the antifouling film is not transferred to the back surface of the resin substrate.

[0012]

Embodiments of the present invention will be described below in detail with reference to the drawings. 1A and 1B show a method for producing a functional film according to the present invention, wherein FIG. 1A is a cross-sectional view of the functional film, and FIG.
In (A), reference numeral 10 denotes a functional film. The functional film 10 includes a hard coat film 12, an antireflection film (including a transparent conductive film) 14 as a functional film on a resin substrate 11,
In this embodiment, the antifouling film 15 is laminated in this order, and is adhered to the surface of the panel glass 1 of the cathode ray tube via the adhesive 7 and used. As shown in the figure, the functional film 10 has the back surface of the resin substrate 11 adhered to the surface of the panel glass 1, and the antifouling film 15 is located at the outermost layer. I have.

The functional film shown in (A) is manufactured according to the process shown in (B). First, a film forming step S1 is performed, and while the resin substrate 11 wound into a roll shape is run in a closed atmosphere, an antireflection film 14 is continuously formed on the surface of the resin substrate 11 by sputtering or the like, and the roll is again formed. And roll it up. Note that a hard coat film 12 made of acrylic resin or the like is previously applied to the surface of a resin base material 11 made of PET or the like. Next, an exposure step S2 is performed, and the anti-reflection film 14 is exposed to the air to naturally activate the surface by rewinding the resin substrate 11 wound in a roll shape in an open atmosphere. Thereafter, a coating step S4 is performed through an aging step S3. In the coating step S4, a coating liquid containing an antifouling substance is applied to the surface of the naturally activated antireflection film 14 and dried to form the antifouling film 15. By performing the natural activation in the exposure step S2 in advance, the adhesion of the antifouling film 15 to the surface of the antireflection film 14 can be improved. The aging step S3 inserted before the post-coating step S4 of the exposure step S2 increases the reactivity of the coating liquid by preparing the coating liquid and performing aging before coating, thereby preventing the reflection. This is performed to promote the immobilization of the antifouling film 15 on the surface of the film 14.

Preferably, in the film forming step S1, an optical multilayer film including an SiO ₂ layer as the uppermost layer is formed as the antireflection film 14. In the exposure step S2, moisture in the air acts on the SiO ₂ layer to naturally activate the surface. Coating process S4
Applies a coating solution obtained by adding a perfluoro group-containing phosphate as a catalyst to a solution containing a silicon-based antifouling substance containing a perfluoro group as a solute. In this case, in the exposure step S2, the roll-shaped resin substrate 11 is heated at a rate of, for example, 5 m / min to 10 m / min in an open atmosphere where the temperature is adjusted to 25 ° C. ± 3 ° C. and the humidity is adjusted to 60% ± 5%. To rewind. Similarly, in the aging step S3, when the temperature is 2
The coating is performed by leaving the coating liquid in an atmosphere at 5 ° C. ± 3 ° C. and a humidity of 60% ± 5% for a maximum of one hour.

The antifouling film used for the functional film is a fluororesin. After the coating liquid containing such an antifouling substance is applied, the fluororesin is chemically bonded to the surface of the antireflection film 14, whereby the water repellent and antifouling property is exhibited. In the coating liquid application step, the coating liquid is applied, dried, and wound into a roll. Therefore, if the fluororesin is not chemically bonded to the surface of the antireflection film 14 made of SiO ₂ or the like, the fluororesin is transferred to the back surface of the resin substrate 11. When the functional film 10 with the fluororesin transferred to the back surface is attached to a CRT, the film is easily peeled off, and at the same time, the adhesive 7 used for the attachment is C
It remains on the RT side.

From the results of the chemical investigation, it was found that water was involved in the chemical bonding at the interface between the antireflection film 14 and the antifouling film 15. Since the antireflection film 14 is formed in a high vacuum by sputtering or the like, the adsorption of moisture on the surface during the film formation stage is very small. Therefore, before applying the coating liquid, the roll of the resin substrate 11 on which the anti-reflection film 14 is formed is wound in the atmosphere. In particular,
The roll-shaped resin substrate 11 is set on a roll unwinder, and is wound up by another roll winder. This is because the anti-reflection film 14
The purpose is to adsorb moisture to the surface of the surface. The conditions are, as described above, a temperature of 25 ° C. ± 3 ° C. and a humidity of 60%.
± 5% is appropriate and the winding speed is 5m / min to 10m
/ Min is appropriate. As a result, moisture is adsorbed on the SiO ₂ layer located on the surface of the antireflection film 14 and is naturally activated.

Thus, the exposure step S2 aims at activating the surface of the antireflection film 14, while the aging step S3 aims at increasing the reactivity on the coating liquid side.
Before coating, the coating solution is aged in the liquid pan for 30 to 60 minutes. The environmental conditions are the same as in the exposure step S2. Chemical reactivity can be enhanced by introducing atmospheric moisture into the coating liquid. However, if aging is excessively performed, the coating liquid itself rapidly deteriorates and does not chemically react with the surface of the antireflection film 14, so that the aging time is limited to 60 minutes.

FIG. 2 is a graph showing the expression time of the water repellent and antifouling properties of the antifouling film. In the graph, the elapsed time is plotted on the horizontal axis, and the contact angle is plotted on the vertical axis as a measure of the water repellency.
The contact angle indicates the contact angle of pure water dropped on the antifouling film, and the larger the value, the higher the water repellency. In the graph, curve A represents the case of the antifouling film formed through the exposure step and the aging step according to the present invention, and curve B represents the case of the conventional antifouling film. As is clear from the graph, the water repellency of the present invention is shorter in the present invention, indicating that the surface of the antireflection film reacts quickly with the coating liquid. This prevents the antifouling film applied on the surface of the antireflection film from being transferred to the back surface during the process of winding the resin substrate into a roll. On the other hand, conventionally, there is no means for promoting the reaction such as an exposure step and an aging step after the formation of the anti-reflection film. The transfer amount of the antifouling film to the back surface of the film increases.

Referring to FIG. 3, the film forming step S shown in FIG.
1 will be specifically described. (A) shows a sputtering apparatus used for forming an antireflection film. (B) shows a specific configuration example of the antireflection film 14 formed on the resin substrate 11 on which the hard coat film 12 is formed in advance. As shown, the antireflection film 14 is made of an optical multilayer film,
The first layer (SiO ₂ ) 141 and the second layer (IT
O) 142, third layer (SiO ₂ ) 143, fourth layer (IT
O) 144 and a fifth layer (SiO ₂ ) 145 are stacked. SiO ₂ functions as a low refractive layer, and ITO functions as a high refractive layer. In addition, ITO is a composite oxide of indium and tin and has conductivity, and also has an antistatic effect. The anti-reflection film 14 is provided so as to reduce reflection of external light and display a preferable image. As described above, the anti-reflection film 14 includes an optical multilayer film in which thin film materials having different refractive indexes are alternately laminated. Is formed. Here, the antireflection film 14 is configured so that SiO ₂ is located on the outermost surface.

The sputtering apparatus for forming the antireflection film 14 includes a first sputtering chamber 104 and a second sputtering chamber 106 as shown in FIG. The first sputtering chamber 104 is provided with a sputtering target / cathode assembly 110 and a reactive gas supply port 112. Similarly, a sputtering target / cathode assembly 111 and a reactive gas supply port 113 are provided in the second sputtering chamber 106. Here, the sputtering target of the first sputtering chamber 104 is a silicon single crystal, and the target of the second sputtering chamber 106 is metal indium to which tin is added. The sputtering gas is argon, and the reactive gas supplied to each of the sputtering chambers 104 and 106 is oxygen.

In order to form the anti-reflection film 14 with the sputtering apparatus having the above-described configuration, first, the resin substrate 11 is supplied from the film unwinder 102 to the first sputtering chamber 104 along the cooling roll 103, One layer (SiO
₂ ) Form. Subsequently, the second sputtering chamber 106
To form a second layer (ITO). Further, after the reflectance after the second layer is formed is measured by the detector 107, the film is wound by the film winder 108. Next, the material wound up by the winding machine 108 is fed out in reverse, and the third layer is formed in the first sputtering chamber 104 along the cooling roll 103 (the second sputtering chamber 106 simply passes). After measuring the reflectance after the formation of the third layer in 109, the film is rewound to the unwinder 102. Along the cooling roll 103 from the unwinder 102 again (the first sputtering chamber 104 simply passes), the fourth layer is formed in the second sputtering chamber 106, and the reflectance after the fourth layer is formed is measured by the detector 107. After winding machine 1
Take up to 08. Rewinding roll 108 from winder 108 again
Along 03, a fifth layer is formed in the first sputtering chamber 104 (the second sputtering chamber 106 simply passes),
After measuring the reflectance after the fifth layer is formed by the detector 109, the film is wound around the unwinder 102.

FIG. 4 is a schematic diagram specifically showing the coating step shown in FIG. As shown in the figure, a pair of rollers 218 on a coating tank 217 storing a coating liquid 216 is applied to the resin substrate 11 on which the antireflection film 14 is formed.
The coating liquid 216 is applied between the a and 218b, and the applied coating liquid 216 is dried by passing the resin substrate 11 through a drier 219 to form an antifouling film made of a fluororesin. Thereafter, the functional film 10 produced by forming the antifouling film is formed.
Is rolled out of the dryer 219 and stored until ready for use. The roller 218a is made of a chrome-plated metal roll, the roller 218b is made of rubber or a soft resin, and the lower roller 218a is made of
Since the lower portion is arranged so as to be immersed in the coating liquid 216, the coating liquid 216 is applied to the lower surface (the surface on which the antireflection film is formed) of the resin base material 11 passed therethrough. Has become. In the present invention, since the exposure step S2 and the aging step S3 shown in FIG. 1 are performed before performing the coating step, the adhesion of the antifouling film to the antireflection film is increased, and the function of the dryer 219 is performed. When the film 10 is wound into a roll, the antifouling film is not transferred to the back surface.

[0023]

As described above, according to the present invention,
Before applying the coating liquid containing the antifouling substance, by performing roll rewinding and aging of the coating liquid, the reactivity between the coating liquid and the antireflection film surface is improved, and the water repellent and antifouling performance is exhibited. Can be shortened. Since the expression time is shortened, after the coating liquid is applied and dried, the chemical reaction at the interface between the antifouling film and the antireflection film progresses to some extent before being wound into a roll, and the antifouling film is transferred to the back of the functional film. The amount is reduced. As a result, it is possible to improve the adhesiveness when the functional film is attached to a CRT or the like, and to prevent a problem that the adhesive remains on the CRT side instead of the film side.

[Brief description of the drawings]

FIG. 1 is a schematic view illustrating a method for producing a functional film according to the present invention.

FIG. 2 is a graph showing a water repellency developing time of a functional film manufactured according to the present invention.

FIG. 3 is a schematic view showing a film forming step included in the method for producing a functional film according to the present invention.

FIG. 4 is a schematic view showing a coating step included in the method for producing a functional film according to the present invention.

FIG. 5 is an explanatory view showing a method for attaching a functional film.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Panel glass, 7 ... Adhesive, 10 ... Functional film, 11 ... Resin base material, 12 ... Hard coat film, 14 ... Anti-reflection film, 15 ... Anti-reflection Soil, S
1 ... film forming step, S2 ... exposure step, S3 ... aging step, S4 ... coating step

Claims (7)

[Claims] A film forming step of continuously forming an antireflection film on the surface of the resin substrate while running the resin substrate wound in a roll shape in a closed atmosphere, and winding the film back into a roll shape; An exposing step of exposing the formed anti-reflection film to the atmosphere to naturally activate the surface thereof by rewinding the wound resin substrate in an open atmosphere; and the activated anti-reflection film. Applying a coating solution containing an antifouling substance to the surface of the antireflection film and drying the coating liquid to form an antifouling film, thereby improving the adhesion of the antifouling film to the surface of the antireflection film. Characteristic method for producing functional films. 2. The film forming step includes forming an optical multilayer film including an SiO ₂ layer as an uppermost layer as the anti-reflection film, and the exposing step includes applying atmospheric moisture to the SiO ₂ layer to form a surface thereof. The coating step comprises applying a coating solution obtained by adding a perfluoro group-containing phosphate as a catalyst to a solution containing a perfluoro group-containing silicon-based antifouling substance as a solute. The method for producing a functional film according to claim 1, wherein: 3. The exposing step comprises winding the resin base material at a speed of 5 m / min to 10 m / min in an open atmosphere adjusted to a temperature of 25 ° C. ± 3 ° C. and a humidity of 60% ± 5%. 3. The method for producing a functional film according to claim 2, wherein the method is changed. 4. In the coating step, after the coating liquid is prepared, aging is performed before coating to increase the reactivity of the coating liquid, whereby the antifouling film with respect to the surface of the antireflection film is formed. The method for producing a functional film according to claim 2, wherein fixation of the film is promoted. 5. A film forming step of continuously forming an antireflection film on the surface of the resin base material while running the resin base material wound in a roll shape, and winding the film back into a roll shape. A process of continuously applying a coating solution containing an antifouling substance to the surface of the antireflection film while running the resin substrate again and drying to form an antifouling film. Performing aging before preparing the coating solution after coating to increase the reactivity of the coating solution, thereby performing an aging step to promote the fixation of the antifouling film to the antireflection film. Method of manufacturing functional films. 6. The coating step includes applying a coating liquid obtained by adding a perfluoro group-containing phosphate as a catalyst to a solution containing a perfluoro group-containing silicon-based contaminant as a solute. The method for producing a functional film according to claim 5, characterized in that: 7. The aging step is performed at a temperature of 25 ° C. ±
7. The method for producing a functional film according to claim 6, wherein the coating liquid is allowed to stand in an atmosphere at 3 [deg.] C. and a humidity of 60% ± 5% for up to one hour.