JP2002292776A - Method for applying antistaining treatment to surface of matter and matter subjected to antistaining treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for applying antistaining treatment to the surface of the functional layer formed on the surface of matter lacking in flexibility like a panel material by transfer and the matter subjected to antistaining treatment. SOLUTION: In the method for applying antistaining treatment to the surface of the functional layer 2 formed on the surface of the matter 4 by transfer, the surface of the functional layer 2 to be subjected to antistaining treatment is coated with an antistaining agent coating solution containing a compound having at least a perfluoroalkyl group. The coated antistaining agent is subjected to fixing treatment and the unfixed excess antistaining agent is removed to form an antistaining treatment layer 5. Hydrophilizing treatment is preferably applied to the surface of the functional layer 2 to be preliminarily subjected to antistaining treatment. The compound is preferably a silicon compound having a hydrolyzable group other than the perfluoroalkyl group. As the functional layer, there are a reflection preventing layer, an anti-glare layer and a hard coat layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for antifouling a surface of a functional layer formed on a surface of an object by transfer and an object subjected to antifouling treatment.

In the present invention, the target object includes an object having poor flexibility or a support such as a plate material on which a functional coating layer having a uniform thickness is difficult to form, or an object such as glass or ceramics. . For example, CRT, LCD,
The surface of display elements such as screens for rear projectors, electroluminescent displays, and LED display panels require functional treatments such as anti-reflection treatment, anti-glare treatment, and hard coat treatment. Is required, and is a specific example of the target object in the present invention.

[0003]

2. Description of the Related Art Conventionally, antireflection processing has been performed on the surface of a display element such as a CRT by sputtering, spin coating, or the like. In some cases, anti-glare processing (also referred to as non-glare processing) is performed to prevent reflection of external light. By performing the anti-glare treatment, reflected light of external light can be scattered to reduce glare. Further, a hard coat treatment is performed to enhance the scratch resistance of the surface. The anti-reflection treatment and the anti-glare treatment may also serve as a hard coat treatment.

As described above, the surface of the display element is required to have a functional treatment such as an anti-reflection treatment, an anti-glare treatment, a hard coat treatment and the like. Antifouling treatment of the surface is required.

JP-A-6-308327 describes a method for modifying the surface of a polarizing plate, in which a composition containing a fluorinated silane compound having a specific structure or an oligomer or polymer thereof is reacted or adsorbed on the polarizing plate surface. It is described. In this method, a hard coat layer having an anti-glare effect is formed as a functional layer on a polarizing plate in advance by coating, and then an antifouling treatment is performed. However, when a functional layer such as a hard coat layer is formed on a plate material having poor flexibility by application, it is difficult to form a functional layer having a uniform thickness on the surface of the plate material.

In the coating method, when the support is flexible such as a film, a large-area functional layer can be easily formed. However, when the support is poor in flexibility, such as a plate material, the application is more difficult than in the case of the flexible support, and it is particularly difficult to control the film thickness uniformly. That is, in the case of a flexible film, the coater can be installed and the film can be moved and applied, and the control of the film thickness is easy. On the other hand, in the case of a plate material having poor flexibility, it is possible to move and apply the plate material if the area is small, but if the area is large, the accuracy of the film thickness due to movement or the like may be reduced by moving the plate material. Easy to get worse. There is also a method of moving the coater part,
If the flatness of the plate material is poor, the accuracy of the film thickness is poor.

In JP-A-2000-94584, a hard coat layer (b) is formed on one surface of a plastic film (a) directly or via another layer, and a hard coat layer (b) is formed directly or on another layer. A thin film coating layer (c) is formed from a silicon alkoxide-containing coating solution via a coating film, and an adhesive layer (d) is formed on the opposite surface of the plastic film (a) directly or via another layer. Has been described. Although the thin film coating layer (c) has antifouling properties, the plastic film (a) is present on the window to which the window film is adhered via the adhesive layer (d). Support film
Due to the presence of (a), surface hardness decreases, haze increases,
There are adverse effects such as a decrease in light transmittance and an increase in the total thickness of the surface coating. These adverse effects are important problems on the surface of a display element represented by a CRT.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for performing an antifouling treatment on the surface of a functional layer formed by transfer onto a surface of a poorly flexible object such as a plate material. Another object of the present invention is to provide an object subjected to an antifouling treatment in which a functional layer is provided on the surface of the object by transfer and an antifouling treatment layer is formed on the surface of the functional layer.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a method for treating a surface of a functional layer formed on a surface of an object by transfer, which comprises a compound having at least a perfluoroalkyl group. An antifouling treatment method comprising applying a coating solution to the surface of a functional layer to be subjected to antifouling treatment.

According to the present invention, the antifouling agent coating solution is applied to the surface of the functional layer to be subjected to the antifouling treatment, and the applied antifouling agent is subjected to a fixing treatment. Remove,
The above antifouling treatment method for forming an antifouling treatment layer.

In the present invention, the surface of the functional layer to be subjected to antifouling treatment is preliminarily subjected to hydrophilic treatment, and then the antifouling agent coating solution is applied to the surface of the functional layer subjected to hydrophilization treatment. Processing method.

The present invention is the above-described antifouling treatment method, wherein the compound is a silicon compound having at least a perfluoroalkyl group and a hydrolyzable group. In the present invention, the functional layer may be an anti-reflection (AR) layer, an anti-glare (AG)
The antifouling treatment method described above, which is a layer or a hard coat layer. The present invention is the above antifouling treatment method, wherein the functional layer is composed of one or more layers, and the outermost layer of the functional layer contains silicone.

[0013] The present invention provides an antifouling treatment by applying a functional layer to the surface of an object by transfer and applying an antifouling agent coating solution containing a compound having at least a perfluoroalkyl group to the surface of the functional layer. This is an object on which a surface is subjected to antifouling treatment, on which a layer is formed. The present invention is the object whose surface is subjected to antifouling treatment, wherein the object is a display element.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view illustrating a layer configuration example of an antireflection film for transfer that can be used in the present invention. FIG.
FIG. 1 is a cross-sectional view showing an example of a layer configuration of an object having an antireflection layer to be subjected to an antifouling treatment provided on a surface by transfer in the present invention. The above-mentioned transfer means that the antireflection layer on the support is attached to another object via an adhesive layer. FIG. 3 is a cross-sectional view showing an example of the layer configuration of the object of the present invention whose surface has been subjected to antifouling treatment.

First, a transfer functional film that can be used when a functional layer is provided on the surface of an object by transfer will be described. The functional layer is selected from various types according to the purpose. For example, as the functional layer, antireflection (A
R) layer, anti-glare (AG) layer, hard coat layer and the like. Anti-reflection (AR) layer, anti-glare (A
The G) layer preferably also has a function as a hard coat layer.

The functional layer may be composed of one layer,
As shown in the example of the antireflection film for transfer, it may be composed of two or more layers. The layer that becomes the outermost layer of the functional layer after transfer to the target object should contain silicone so that the antifouling agent compound containing a silicon compound having a perfluoroalkyl group and a hydrolyzable group easily adheres or reacts. Is preferred.

The transfer functional film will be described by taking a transfer antireflection film as an example. In the anti-reflection film for transfer illustrated in FIG. 1, an anti-reflection layer is formed on a support (1).
(2) is provided, and an adhesive layer (3) is provided on the antireflection layer (2). The anti-reflection layer (2) is composed of two coating layers (2a) and (2b) having different refractive indices from each other, and the support (1) is closer than the layer (2a) closer to the support (1). Layer farther from
b) has a higher refractive index. When transferring the antireflection layer (2) from the support (1) to the surface of the object, the support (1) can be peeled off from the antireflection layer (2).

FIG. 1 shows an example in which the antireflection layer (2) is composed of two coating layers (2a) and (2b) having different refractive indexes. In the present invention, an antireflection film for transfer in which the antireflection layer (2) is composed of two or more coating layers having different refractive indices from each other may be used.

As described above, in the antireflection film for transfer used in the present invention, the two coating layers constituting the antireflection layer (2) are such that the coating layer close to the support (1) has a lower refractive index. , The upper coating layer has a higher refractive index. Whether the refractive index is high or low is a relative value when comparing the refractive indexes of two layers that are in contact with each other. With such a layer configuration of the antireflection layer (2), the support (1)
When the anti-reflection layer (2) is transferred from the
Support layer (1) is peeled off, coating layer having lower refractive index
(2a) is located on the outermost surface of the target object surface, and the antireflection effect is improved.

Further, in any of the two coating layers constituting the anti-reflection layer (2), by setting the physical film thickness d to less than 0.5 μm, the light of sunlight or lighting equipment can be prevented. The reflected light (wavelength λ) in the visible light region of 380 to 780 nm optically interferes to reduce the reflection intensity of the light, whereby an effect of preventing reflection of light in the visible light region is obtained. In particular, it is required that the wavelength having the lowest reflected light intensity be in the visible light region. At this time, the film thickness d is expressed by the following equation: d = kλ / (4 × n) (where k is 1 or 3).
= 1.35 to 2.5.

The support (1) is not particularly limited, and a flexible resin film is suitable. The resin film is lightweight and easy to handle. Examples of the resin film include a polyester film such as polyethylene terephthalate (PET), a polyolefin film such as polyethylene and polypropylene, a polycarbonate film, an acrylic film, a norbornene film (JS
R, Inc., Arton, etc.). In addition to the resin film, a cloth, paper, or the like can be used as the support.

The refractive index of the layer (2a) closer to the support (1) is:
For example, it is not less than 1.35 and less than 1.6. The physical thickness of the layer (2a) is preferably 0.05 μm or more and less than 0.5 μm, and more preferably 0.07 μm or more and 0.2 μm or less.

The layer (2a) is preferably, for example, a hard coat layer containing a resin as a main component. When the antireflection layer (2) is transferred from the support (1) to the surface of the target object, the hard coat layer is located on the outermost surface of the target object surface, and the antireflection effect and the scratch resistance effect can be obtained.

A hard coat layer formed using a silicone resin (for example, having a pencil hardness of more than 4H, preferably more than 5H) has low adhesion to a resin film such as PET, and is hardly adhered to the support (1). The hard coat layer can be easily peeled off. In the present invention, the support (1)
If the surface is treated with a release agent, the adhesion to the hard coat layer will be too low, causing problems such as peeling of the hard coat layer in the step of applying the layer (2b) thereon.

Therefore, in the present invention, it is preferable to improve the adhesion by subjecting the surface of the support (1) to a corona treatment or the like.
Further, instead of the corona treatment, an easy adhesive may be applied. For example, in the step of applying the layer (2b) on the layer (2a) by coating as described below, the coating liquid for forming the layer (2b) does not contain a binder resin, or if it contains a small amount, Preferably, the surface of the support (1) is subjected to a corona treatment. On the other hand, when the coating liquid contains a large amount of binder resin, the adhesiveness between the surface of the support (1) and the layer (2a) tends to be strong, so that the corona treatment may not be performed. The reason that the above tendency occurs is that the binder resin of the high refractive index layer penetrates the hard coat layer and reaches the support, and the binder resin and the support adhere to each other, whereby the hard coat layer and the support adhere. This is probably because they are increasing their sex. In the case where the treatment with the easy-to-adhesive agent or the corona treatment as described above is performed, the support (1) including the treated form is used.

The hard coat layer can be formed by applying a solution obtained by dissolving a hard coat agent in a solvent, if necessary, onto a support, drying and curing. The hard coating agent is not particularly limited, and various known hard coating agents can be used. For example, a thermosetting hard coat agent such as a silicone-based, acrylic-based, or melamine-based can be used.

Among these, silicone-based hard coat agents are excellent in that a hard coat layer having high hardness can be obtained. Further, the hard coat layer formed using the silicone-based hard coat agent is also preferable in that an antifouling agent compound containing a silicon compound having a perfluoroalkyl group and a hydrolyzable group easily adheres or reacts.

Also, radically polymerizable hard coating agents such as unsaturated polyester resin type and acrylic type, epoxy type,
An ultraviolet-curable hard coat agent such as a vinyl ether-based cationic polymerizable hard coat agent may be used. The UV-curable hard coat agent is preferable from the viewpoint of productivity such as curing reactivity. Among these, an acrylic radical polymerizable hard coat agent is preferable in consideration of curing reactivity and surface hardness.

The application of the hard coat agent may be performed by a known method such as a roll coater such as gravure or reverse roll, a Meyer bar, or a slit die coater. After application, it is dried in an appropriate temperature range and then cured. In the case of a thermosetting hard coat agent, an appropriate heat is applied, and for example, in the case of a silicone hard coat agent, 60 to 120 ° C.
Heat and cure for about 1 minute to 48 hours. In the case of a UV-curable hard coat agent, perform UV irradiation,
Let it cure. Ultraviolet irradiation is performed using a lamp such as a xenon lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp.
Irradiation on the order of cm ² is preferable.

The hard coat layer may contain an ultraviolet absorber. Various known UV absorbers may be used as the UV absorber. Examples thereof include a salicylic acid-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. The hard coat layer may further contain, if necessary, various known additives such as a light stabilizer such as a hindered amine light stabilizer, an antioxidant, an antistatic agent, and a flame retardant. UV absorbers and various additives
What is necessary is just to add and apply in a hard-coat agent.

The refractive index of the layer (2b) remote from the support (1) is:
For example, it is 1.6 or more and 2.5 or less. The physical thickness of the layer (2b) is preferably 0.05 μm or more and less than 0.5 μm, and more preferably 0.06 μm or more and 0.2 μm or less.

The layer (2b) is preferably a layer containing high refractive index fine particles. Examples of the high refractive index fine particles include tin oxide, indium oxide, antimony-doped tin oxide, tin-doped indium oxide, zinc oxide, and titanium oxide. The average particle size of these fine particles is 10 to 3
It is preferably 0 nm. Further, the refractive index may be adjusted by using a plurality of these materials.

The layer containing the high-refractive-index fine particles is provided by applying a liquid in which the high-refractive-index fine particles are dispersed in a solvent such as an organic solvent onto the layer (2a), and drying. At this time, a binder resin may or may not be used. When a binder resin is used, the amount of the binder resin is suitably 25% by weight or less, and preferably 20% by weight or less, based on the total of the binder resin and the fine particles.

In the anti-reflection film for transfer, as shown in FIG. 1, it is preferable that an adhesive layer (3) is applied and formed on the anti-reflection layer (2). By forming the adhesive layer, it becomes easy to transfer the antireflection layer (2) onto the target object via the adhesive layer. In the present invention, when the adhesive layer is not formed on the antireflection film, the adhesive layer may be provided in advance on the transfer target object. Of course, it is also preferable to form an adhesive layer (3) on the antireflection film and further provide an adhesive layer on the object to be transferred.

By coating the adhesive layer (3) on the antireflection layer (2), the adhesive is impregnated into the layer (2b) containing high refractive index fine particles, and the adhesive is applied to the layer (2b). To the layer (2a). Therefore, the dispersion of the high-refractive-index fine particles used in the formation of the high-refractive-index fine-particle-containing layer has a high film strength and a layer (2a ), A layer containing high refractive index fine particles having a strong adhesion to (1) is formed. This is an effect obtained because the thickness of the layer (2b) is as small as less than 0.5 μm as described above. This effect is obtained when the layer (2b) is 0.2
When the film thickness is less than μm, it becomes larger.

In the present invention, the adhesive layer (3) of the antireflection film and the adhesive layer previously provided on the object to be transferred include the antireflection layer (2) of the antireflection film and the surface of the object to be transferred. There are no particular limitations on the adhesive as long as it has an affinity for both and can strongly bond the two, and various known adhesives can be used. For example, acrylic adhesives, epoxy adhesives, isocyanate adhesives, silicone adhesives and the like can be mentioned. The adhesive may be curable by ultraviolet light or heat after being transferred to the transfer target object. Hot melt type may be used. The thickness of the adhesive layer (3) is 1 to 100 μm, preferably 5 to 20 μm.

As the adhesive used for the adhesive layer (3) of the anti-reflection film, an adhesive layer having a tacky feeling can be obtained only by applying an adhesive solution and drying, and after adhering on the object to be transferred. An adhesive that can obtain a very hard cured layer by ultraviolet curing the adhesive layer is preferable. Softening or deterioration of the adhesive layer after pasting on the transfer target object is not preferable.

Therefore, the present inventors also studied an adhesive satisfying such properties, and found that the following adhesive composition is suitable as the adhesive used for the adhesive layer of the functional film of the present invention. Was found. 1. The polymer resin component (P) having a glass transition temperature Tg of 30 ° C. or more and the curable low molecular component (M) are mixed in a weight ratio P /
An adhesive composition containing M = 8/2 to 2/8. 2. The adhesive composition according to 1, wherein the polymer resin component (P) is solid at room temperature and the curable low-molecular component (M) is liquid at room temperature. 3. The adhesive composition according to 1 or 2, wherein the polymer resin component (P) is an acrylic resin and the curable low molecular component (M) is an acrylic monomer. 4. The adhesive composition according to any one of the above items 1 to 3, further comprising a photopolymerization initiator. 5. The adhesive composition according to any one of the above items 1 to 4, which is cured by light irradiation.

Examples of the polymer resin component include acrylic resin 103B and 1BR-305 (manufactured by Taisei Kako Co., Ltd.). As the curable low molecular weight component, for example, KAYA
Examples include tri- or higher functional acrylic monomers such as RADGPO-303, KAYARAD TMPTA, and KAYARAD THE-330 (all manufactured by Nippon Kayaku Co., Ltd.). Various photopolymerization initiators can be used, for example, KAYACURE DETX-S
(Manufactured by Nippon Kayaku Co., Ltd.). Further, SD-3 containing a curable low molecular weight component and a photopolymerization initiator component was used.
18 (manufactured by Dainippon Ink and Chemicals, Inc.).

The refractive index of the adhesive layer (3) used here is preferably close to the refractive index of the object to be transferred. If the difference between the two is large, strong reflected light may be generated at the interface between the two.

Further, the adhesive layer may be added by dispersing or dissolving pigments and dyes. The pigment may be selected from known scratch-resistant materials such as silica and inorganic materials for coloring.

When the adhesive layer (3) of the antireflection film is provided, a release film may be provided on the adhesive layer to protect the adhesive layer surface until use.

Although the anti-reflection film for transfer has been described above, other functional films for transfer can be similarly prepared. For example, when the functional layer is a hard coat layer, a hard coat layer may be used instead of the antireflection layer (2). The same hard coating agent as described above may be used. When the functional layer is an anti-glare (AG) layer, an anti-glare layer may be used instead of the anti-reflection layer (2). The anti-glare layer is
The support (1) can be formed by using a film having an anti-glare treatment surface, that is, a film having an uneven surface, and applying the same hard coat agent as described above on the uneven surface of the support film. Films having an anti-glare treated surface are usually sold under the name of matte film and the like. It is also possible to form a film having an anti-glare treated surface by applying a paint containing particles such as silica particles to the film. After the transfer to the target object, the uneven surface of the antiglare layer is exposed.

The functional layer of the above-described transfer functional film is attached to the surface of the object by transfer via an adhesive layer. When the functional layer is an anti-reflection layer, the object is an anti-reflection treated object having the layer configuration example shown in FIG.

FIG. 2 shows an adhesive layer (3) on the surface of the object (4).
FIG. 4 is a cross-sectional view showing an example of a layer configuration in which an antireflection layer (2) is provided via a layer. This adhesive layer (3) is derived from the adhesive layer (3) of the antireflection film for transfer and / or the adhesive layer previously formed on the target object (4).

The target object (4) is not particularly limited, and includes various objects. For example, an object having poor flexibility such as a plate material on which a coating layer having a uniform thickness is difficult to be formed, a support, an object such as glass or ceramics, and the like are included. For example, the surface of a CRT is required to be treated such as anti-reflection and hard coating, and the CRT is a specific example of the target object in the present invention.

To obtain an antireflection-treated object, the above-mentioned antireflection layer (2) of the antireflection film for transfer may be used as a support.
Transfer from (1) to target object (4). That is, through the adhesive layer of the antireflection film (if provided) and / or the adhesive layer on the target object so that the antireflection film is on the target object surface and the support (1) is on the outside, paste. Thereafter, the support (1) of the antireflection film is peeled off.

In the present invention, antifouling treatment is performed by applying an antifouling agent coating solution to the surface of the functional layer formed on the object surface by transfer. FIG. 3 is a sectional view showing an example of a layer configuration in which an antifouling treatment layer (5) is formed on the surface of an antireflection layer (2).

The antifouling agent coating solution contains a compound having at least a perfluoroalkyl group. By having a perfluoroalkyl group, the water and oil repellency of the antifouling treatment layer can be obtained. The antifouling compound is preferably a silicon compound having a hydrolyzable group in addition to the perfluoroalkyl group. Examples of the hydrolyzable group include an alkoxy group (for example, a methoxy group and an ethoxy group) and a silazane group. Having such a hydrolyzable group is preferable because it can easily adhere to or react with a hard coat layer formed using a silicone-based hard coat agent.
This is presumably because even though the silicone-based hard coat is cured to obtain a hardness, the curing reaction is not completely completed, and unreacted hydroxyl groups may remain.

In the present invention, the antifouling agent coating solution is applied to the surface of the functional layer to be subjected to the antifouling treatment, and the applied antifouling agent is subjected to a fixing treatment. It is good to remove and form an antifouling treatment layer.

The application of the antifouling agent coating solution can be carried out by various usual coating methods, for example, spraying, dipping, brushing,
Gauze coating, screen method, inkjet method, various roll coating methods, nozzle coating method and the like are performed. At this stage, an excessive amount of the antifouling agent coating liquid is usually applied.

The fixing treatment of the applied antifouling agent may be appropriately performed depending on the type of the antifouling compound and the type of the hard coat agent. For example, by leaving it at room temperature for about 0.5 to 48 hours, or at 50 to 150 ° C. for 0.1 to 6 hours.
This can be done by holding for 0 minutes. By the fixing treatment, the antifouling agent compound adheres to or reacts with the hard coat surface and is fixed.

Excessive antifouling agent not fixed is removed. The removal may be performed by, for example, dry wiping with a cloth, rinsing with water or various solvents (for example, alcohol such as ethanol), or wiping. The fixed antifouling agent compound forms an ultrathin antifouling treatment layer. The antifouling treatment layer only has to perform the antifouling function. In principle, if one molecule layer is formed, the antifouling function is sufficiently exhibited. Therefore, it is as thin as possible (eg, 0.01 μm
The following is preferable because the function of the functional layer provided on the surface of the target object is not impaired. For example, adverse effects such as a decrease in antireflection function, a decrease in surface hardness, and an increase in haze do not occur.

In the present invention, it is also preferable that the surface of the functional layer to be subjected to the antifouling treatment is previously subjected to a hydrophilic treatment, and then the antifouling agent coating solution is applied to the surface of the functional layer which has been subjected to the hydrophilic treatment. Hydrophilic treatment is a type of treatment that improves the wettability of water on the surface.By performing the hydrophilic treatment, the wettability of a coating solution having a hydrophilic group such as a hydroxyl group is improved. It adheres well to the surface, and the adhesion strength is improved because the surface is uniformly covered. For example, in the plasma treatment, it is considered that a change occurs in molecular bonding on the surface, and a hydrophilic group such as a hydroxyl group is generated on the surface, so that the affinity for a coating solution having a hydrophilic group is improved. In addition, removal of stains such as non-hydrophilic groups such as organic substances attached to the surface may also make the surface hydrophilic. In particular, hydrolyzing an antifouling compound having a hydrolyzable group generates a hydroxyl group in the molecule, and therefore, it is effective to apply a hydrophilic treatment to the surface to be subjected to the antifouling treatment. In addition, silicone is more structurally acrylic than acrylic resin.
When the hydrophilic treatment is performed, molecular bonds on the surface are changed, and the surface is easily hydrophilized. As a result, the reactivity between the hard coat layer formed using the silicone-based hard coat agent and the antifouling agent compound having a hydrolyzable group is preferably increased.

The hydrophilization treatment is not particularly limited, and examples thereof include a plasma treatment, a corona treatment, an ultraviolet irradiation treatment, a flame (flame) treatment, a heated air method, and an acid treatment method. The plasma treatment, corona treatment, and ultraviolet irradiation treatment are also preferably performed in air, nitrogen, an inert gas, reduced pressure, or other various gases. However, for example, in the case of plasma treatment, the surface may be hydrophobized depending on the atmosphere in which plasma irradiation is performed, and further, such hydrophobicity and functional surface may be damaged depending on the intensity and time of plasma irradiation, For example, there is a possibility that the function of the functional layer may be impaired, such as a decrease in the antireflection function, a decrease in the surface hardness, an increase in the haze, a crack, a crack, and the like.

The degree of the hydrophilic treatment is not particularly limited, but the contact angle of the outermost surface with pure water is preferably 50.
° or less, more preferably 30 ° or less, even more preferably 10 ° or less, the antifouling agent adapts well to the surface, and evenly covers the surface, so that the antifouling treatment performance is improved and the better antifouling Property is obtained. Further, since the antifouling agent reacts more with the surface, the antifouling treatment effect is further maintained.

FIG. 4 is a diagram for explaining the interference of reflected light on an object subjected to the antifouling treatment and the antireflection treatment of the present invention as shown in FIG. In FIG.
On the surface of the object (4) on which the antireflection layer (2) is transferred and the antifouling treatment layer (5) is provided, three or more interfaces including the antireflection layer (2), ie, antifouling treatment Interface between layer (5) and layer (2a) (referred to as interface I), interface between layer (2a) and layer (2b) (interface II)
), And an interface (referred to as interface III) between the layer (2b) and the adhesive layer (3) is formed. The incident light (Li) is reflected at any of these interfaces (I, II, III), and the reflected light (L)
_{r I, Lr II, Lr III} ) occurs. In the present invention, these reflected lights interfere with each other in the visible light region and cancel each other. As a result, an excellent anti-reflection effect can be obtained. Since the antifouling treatment layer (5) has a very small thickness of 0.01 μm or less, the antifouling treatment layer is not recognized as one layer for light having a wavelength in the visible light region. For this reason, the reflection which contributes to the anti-reflection function is reflected light (Lr _I , Lr _II ,
Lr _III ) only, and as a result, the antireflection performance does not change even if antifouling treatment is performed.

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

Example 1 As shown in FIG.
(1) Low refractive index layer (2a), high refractive index layer (2b) and adhesive layer on top
An antireflection film for transfer having (3) in this order was prepared.

(Formation of Low Refractive Index Layer) Silicone Hard Coat Solution KP-854 (Shin-Etsu Chemical Co., Ltd.) 100
400 parts by weight of ethanol was added to parts by weight to obtain a coating solution for a low refractive index layer. Apply this coating solution to a 75 μm thick PET film
(1) Apply on top, dry, cure at 100 ° C for 2 hours,
A low refractive index layer (2a) having a thickness of 0.09 μm was formed.

(Formation of high refractive index layer) Average particle size is about 30 n
75 parts by weight of ethanol dispersion of ultrafine tin oxide particles having a solid content of 15% by weight (manufactured by C-I Kasei Co., Ltd.) and ethanol dispersion of ultra-fine titanium oxide particles having an average particle size of about 30 nm (C-I Kasei Corporation) Made, solid content concentration 15% by weight)
115 parts by weight of ethanol was added to 25 parts by weight of the mixture to obtain a coating solution for a high refractive index layer. The obtained coating solution was applied on the low refractive index layer (2a) and dried to form a high refractive index layer (2b) having a thickness of 0.09 μm.

(Formation of Adhesive Layer) Acrylic Resin UVHC
-1101 (GE Toshiba Silicone) 100 parts by weight,
71 parts by weight of 1BR-305 (manufactured by Taisei Kako, solid content concentration: 39.5% by weight) and 24 of methyl ethyl ketone (MEK)
5 parts by weight were added to obtain an adhesive layer coating solution. This coating solution is applied on the high refractive index layer (2b), dried, and
A thick adhesive layer (3) was formed. When the adhesive layer was touched with a finger, there was a tacky feeling. Thus, an antireflection film was obtained.

(Application of Antireflection Layer to Polycarbonate Plate of Target Object) A polycarbonate plate having a thickness of 2 mm was used as a target object. Apply the obtained antireflection film to the adhesive layer
(3) was attached with a laminator such that it was in contact with one surface of the polycarbonate plate. Irradiation of ultraviolet light to adhesive layer
(3) was cured. The support PET film (1) was peeled off. The adhesive layer (3) was very strong. Thus, as shown in FIG. 2, the antireflection layers (2: 2a, 2b) were provided on the polycarbonate plate (4) via the adhesive layer (3). The other surface of the polycarbonate plate was similarly provided with an antireflection layer. The contact angle of pure water on the surface of the low refractive index layer (2a) was 61 °.

(Anti-fouling treatment) On the surface of the low refractive index layer (2a), which is the outermost layer of the antireflection layer (2), a fluorine-based silicone coating agent X24-9271 (manufactured by Shin-Etsu Chemical Co., Ltd.) using a cotton swab. , KP-801M improved product, containing perfluoroalkyl group and hydrolyzable group) and dried. This was placed in an atmosphere at 100 ° C. for 5 minutes to react the surface of the low refractive index layer (2a) with the fluorine-based silicone coating agent. Then, excess fluorine-based silicone coating agent on the low refractive index layer (2a) was wiped off with a cloth soaked in ethanol to form an antifouling treatment layer (5).

Example 2 In Example 1, after the antireflection layer (2: 2a, 2b) was applied and before the fluorine-based silicone coating agent was applied, a plasma irradiator (manufactured by Keyence Corporation, ST- 7000) so that the contact angle of pure water on the surface of the low refractive index layer (2a) becomes 30 °. Thereafter, in the same manner as in Example 1, a fluorine-based silicone coating agent was applied to the surface of the low refractive index layer (2a) to form an antifouling treatment layer (5).

Example 3 In Example 2, the contact angle of pure water on the surface of the low refractive index layer (2a) was adjusted to 5 to 10 ° using a plasma irradiator (ST-7000, manufactured by Keyence Corporation). A hydrophilic treatment was performed so that Thereafter, in the same manner as in Example 1, a fluorine-based silicone coating agent was applied to the surface of the low refractive index layer (2a) to form an antifouling treatment layer (5).

(Evaluation of antifouling property) Each sample obtained in Examples 1 to 3 was evaluated as follows. As a comparative example, a sample not subjected to the antifouling treatment in Example 1 was evaluated. Antifouling treatment layer of samples of Examples 1 to 3
(5) Characters were written on the surface and the antireflection layer of the comparative example, on which the antifouling treatment was not performed, by oil-based magic, respectively. The letters were wiped dry with a cloth. In all of the samples of Examples 1 to 3, the characters could be completely wiped off. In the sample of the comparative example, characters could hardly be wiped off.

(Measurement of contact angle of pure water) Using CA-D manufactured by Kyowa Interface Science Co., Ltd., temperature 20 ° C., relative humidity 60
%, The contact angle of pure water on the surface of the antifouling layer (5) of each of the samples obtained in Examples 1 to 3 was measured. The contact angle of pure water before antifouling treatment was also measured under the same conditions. As shown in Table 1, the anti-fouling treatment increased the contact angle. As in Examples 2 and 3, by performing the hydrophilization treatment before the antifouling treatment, the contact angle was further increased, and the antifouling treatment effect was enhanced.

(Evaluation of Antireflection Effect) Each sample was evaluated as follows. Combining the spectrophotometer V-570 (manufactured by JASCO Corporation) with an integrating sphere (manufactured by JASCO Corporation), 550
The reflected light having a wavelength of nm and the transmitted light having a wavelength of 550 nm were measured. As shown in Table 1, all samples were 550
It exhibited high transmittance and low reflectance at a wavelength of nm.
That is, even when the antifouling treatment was performed, an excellent antireflection effect was obtained.

[0069]

[Table 1]

[0070]

According to the present invention, there is provided a method for performing an antifouling treatment on the surface of a functional layer formed by transfer on a surface of a poorly flexible object such as a plate material. An antifouling treated object provided by transfer and having an antifouling treatment layer formed on the surface of the functional layer is provided. In particular, the present invention is suitable for a case where a functional layer having a uniform thickness is applied to the surface of a display element by transfer and the surface of the functional layer is subjected to antifouling treatment.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a layer configuration example of an antireflection film for transfer that can be used in the present invention.

FIG. 2 is a cross-sectional view illustrating an example of a layer configuration of an object in which an antireflection layer to be subjected to antifouling treatment is provided on a surface by transfer in the present invention.

FIG. 3 is a cross-sectional view showing an example of a layer configuration of an object whose surface is subjected to an antifouling treatment according to the present invention.

FIG. 4 is a diagram for explaining interference of reflected light on an object subjected to antifouling processing and antireflection processing according to the present invention.

[Explanation of symbols]

 (1): support (2): antireflection layer (2a): layer closer to the support; low refractive index layer (2b): layer far from the support; high refractive index layer (3): adhesion Agent layer (4): Target object (5): Antifouling treatment layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G09F 9/00 313 G02B 1/10 A (72) Inventor Takahiro Yamauchi 1-13-1 Nihonbashi, Chuo-ku, Tokyo No. F-term in TDK Corporation (Reference) 2K009 AA05 AA15 BB24 CC03 CC26 CC42 DD02 DD06 EE05 4F100 AA21 AA28 AH05D AK25G AK45 AK52 AK52C AR00B AR00C AR00D AT00A BA02 BA03 BA04 BA07 BA10B12 J04 GB10 EC04 J10 GBC JN06C JN18 5G435 AA08 AA09 AA11 AA17 GG43 HH03 HH05 HH18 KK05 KK07

Claims (8)

[Claims] An antifouling treatment for a surface of a functional layer formed on a surface of an object by transfer, wherein an antifouling agent coating solution containing a compound having at least a perfluoroalkyl group is subjected to an antifouling treatment. An antifouling treatment method comprising applying the composition to the surface of a functional layer to be treated. 2. An antifouling agent coating solution is applied to the surface of the functional layer to be subjected to antifouling treatment, and the applied antifouling agent is subjected to a fixing treatment to remove an unfixed excess antifouling agent. The antifouling treatment method according to claim 1, wherein an antifouling treatment layer is formed. 3. The method according to claim 1, wherein the surface of the functional layer to be subjected to the antifouling treatment is previously subjected to a hydrophilic treatment, and then the antifouling agent coating solution is applied to the surface of the functional layer subjected to the hydrophilic treatment. The antifouling treatment method described in the above. 4. The antifouling treatment method according to claim 1, wherein the compound is a silicon compound having at least a perfluoroalkyl group and a hydrolyzable group. 5. The antifouling treatment method according to claim 1, wherein the functional layer is an antireflection (AR) layer, an antiglare (AG) layer, or a hard coat layer. 6. The antifouling treatment according to claim 1, wherein the functional layer is composed of one or more layers, and the outermost layer of the functional layer contains silicone. Method. 7. An antifouling treatment layer is provided by transfer on a surface of an object, and an antifouling agent coating solution containing a compound having at least a perfluoroalkyl group is applied to the surface of the functional layer to form an antifouling treatment layer. An object that has been formed and whose surface has been subjected to antifouling treatment. 8. The surface-treated object according to claim 7, wherein the object is used for a display element.