JPH10120444A - Composition for surface modifying membrane, surface modifying membrane, filter for displaying device and displaying device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for a surface modifying membrane excellent in uniform coating property on applying for a displaying device, etc., having a reflection preventing property and requiring an excellent fouling resistance, scratching resistance and processing resistance by dissolving a specific alkoxysilane compound in a fluorinated hydrocarbon solvent. SOLUTION: This composition for a surface modifying membrane is obtained by dissolving an alkoxysilane compound expressed by the formula: Rf [R1 -R2 -Si(OR3 )3 ]j and/or the formula: Rf [Si(OR3 )3 ]j [Rf is a fluoroalkylgroup or a perfluoropolyether group; R1 is a bivalent atom or group of atoms; R2 is a non-substituted or substituted bivalent hydrocarbon group; R3 is a non-substituted or substituted monovalent hydrocarbon group; (j) is 1 or 2] with a fluorinated hydrocarbon solvent. The fluorinated hydrocarbon solvent has preferably 70-240 deg.C boiling point. The concentration of the alkoxysilane compound in the composition is not especially limited, but e.g. approximately 1-200g/l is suitable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an excellent stain resistance,
Scratch resistance, a composition for a surface modified film applied to the surface of a display device or the like having an antireflection property required for processing resistance,
The present invention relates to a filter for a display device and a display device having such a surface modified film which can be used as a display device, a front panel of a CRT, or the like, which is formed by the method.

[0002]

2. Description of the Related Art When an object is viewed through a transparent material, it is troublesome that the reflected light is strong and the reflected image is clear. For example, a reflected image called a ghost or a flare occurs in a lens for spectacles, causing discomfort to the eyes. Or Further, in the case of a looking glass or the like, there is a problem that the contents are not clear due to the reflected light on the glass surface.

Conventionally, a method of coating a substance having a refractive index different from that of a substrate on a substrate by a vacuum deposition method or the like to prevent reflection has been performed. In this case, in order to maximize the antireflection effect, it is known that it is important to select the thickness of the substance covering the substrate.

For example, in the case of a single-layer film, it is necessary to select a substance having a lower refractive index than that of the base material to have an optical thickness of 1/4 or an odd multiple of the target light wavelength, that is, a minimum reflectance, that is, a maximum transmittance. It is known to give. Here, the optical film thickness is given by the product of the refractive index of the film forming material and the film thickness of the film. Furthermore, it is possible to form a multilayer antireflection film, and in this case, several proposals have been made regarding the selection of the film thickness (Optical Technology Contact Vol. 9,
No. 8, page 17 (1971)).

On the other hand, JP-A-58-46301, JP-A-59-49501, and JP-A-59-50401.
Japanese Patent Application Laid-Open Publication No. H11-176,086 describes a method of forming an antireflection film comprising a plurality of layers, which satisfies the above-mentioned optical film thickness condition, using a liquid composition. In recent years, optical articles having plastics as a base material having antireflection properties have been devised and put to practical use, taking advantage of advantages such as light weight and safety and easy handling. Many of them adopt a film configuration having silicon dioxide as a surface layer film.

[0006]

The antireflection film formed by the vapor deposition method is mainly composed of an inorganic oxide or an inorganic halide as a film-forming material. In a plastic substrate, the antireflection film has an essentially high surface hardness. On the other hand, there is a drawback that dirt such as hand marks, fingerprints, sweat, hair liquid, hair spray and the like are conspicuous and the dirt is difficult to remove. Further, there is a problem in that the surface is poor in slipperiness and the scratches become thicker. In addition, since wettability to water is large, raindrops and water droplets spread greatly when they adhere, and there is a problem in that an object appears distorted over a large area in an eyeglass lens or the like.

JP-A-58-46301, JP-A-5-46301
In order to impart a hard surface hardness also to the antireflection film described in JP-A-9-49501 and JP-A-59-50401, the outermost layer film contains 30% by weight or more of an inorganic substance typified by silica fine particles or the like. However, the antireflection film obtained from such a film composition has problems such as poor surface slip and easy damage due to abrasion of a cloth or the like.

Various surface treatment agents have been proposed and marketed for the purpose of resolving these problems, but all of them have a temporary function because they are dissolved by water or various solvents. There was no durability and poor durability. Further, JP-A-3-266801 reports that a fluorine-based resin layer is formed in order to impart water repellency. However, although these fluororesins certainly increase the water repellency, satisfactory results with respect to friction or wear have not been obtained.

Further, the composition for a surface-modified film in which a fluorine-based compound is dissolved in a solvent has a problem in that the composition tends to be repelled into a spherical shape during the drying process of the solvent, and as a result, coating unevenness tends to occur. It was difficult to form a uniform film. The present invention has been made in view of such a situation, and is applied to a display device or the like having an antireflection property requiring excellent stain resistance, abrasion resistance, and processing resistance, and has excellent uniform coating properties. An object is to provide a composition for a surface-modified film.

Another object of the present invention is to provide a surface-modified film formed from the composition for a surface-modified film. It is still another object of the present invention to provide a filter for a display device having such a surface-modified film and being adhered to the display device or used as a front plate of the display device.

Still another object of the present invention is to provide a display device having such a display device filter.

[0012]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention described below. That is, the composition for a surface-modified film of the present invention is characterized in that an alkoxysilane compound represented by the following general formula (1) and / or (2) is dissolved in a fluorinated hydrocarbon solvent.

R _f ｛-R ₁ -R ₂ -Si (OR ₃ ) ₃ ｝ _j (1) R _f ｛Si (OR ₃ ) ₃ ｝ _j (2) (where R _f is fluoro An alkyl group or a perfluoropolyether group, R ₁ is a divalent atom or atomic group, R ₂
Represents an unsubstituted or substituted divalent hydrocarbon group, R ₃ represents an unsubstituted or substituted monovalent hydrocarbon group, and j is 1 or 2. The surface modified film of the present invention is a surface modified film obtained by dissolving an alkoxysilane compound represented by the general formula (1) and / or (2) on the surface of an inorganic base material using a fluorinated hydrocarbon solvent. It is characterized by being formed into a film using the composition.

In the filter for a display device of the present invention, the alkoxysilane compound represented by the above general formula (1) and / or (2) is coated on the surface of a single-layer or multilayer antireflection film provided on a plastic substrate. It is characterized by having a surface modified film formed using a composition for a surface modified film dissolved using a fluorinated hydrocarbon solvent.

In the display device of the present invention, the surface of a single-layer or multi-layer antireflection film provided on a plastic substrate is fluorinated with the alkoxysilane compound represented by the general formula (1) and / or (2). It is characterized by having a display device filter on which a surface modified film is formed using a composition for a surface modified film dissolved using a hydrocarbon-based solvent.

[0016]

In order to solve the above-mentioned problems in the prior art, the present inventors conducted surface treatment with a fluoroalkyl compound or a perfluoropolyether compound in the course of conducting various studies to reduce friction and abrasion.
Alternatively, it has been found that the stain resistance is improved. However, it was concluded that the surface treatment with this compound was very effective, but the effect was significantly reduced by chemical stability, for example, by solvent treatment. This is considered to be related to the interaction with SiO ₂ on the surface.

Thus, the present inventors have conducted further intensive studies and have found that a molecule represented by the general formula (1) or (2) contains a fluoroalkyl group or a perfluoropolyether group and an alkoxysilane group in one molecule. An attempt was made to solve the problem of abrasion resistance or contamination resistance of the surface of a display device or the like having antireflection properties by coating with a compound having the following.
In other words, an alkoxysilane structure is included in the molecular structure in order to have an interaction with the SiO ₂ surface, and a strong bond is formed on the surface. Therefore, problems such as solvent resistance, which have been unsatisfactory in the past, can be overcome.

However, the above general formulas (1) and (2)
The surface-modified film formed by dissolving the alkoxysilane compound represented by the formula in a hydrocarbon-based solvent or an alcohol-based solvent tends to cause coating unevenness, which causes stain resistance and visual inspection. It has been found that various properties such as poor appearance are adversely affected.

The inventors of the present invention have conducted intensive studies for the purpose of forming a uniform film on a surface-modified film formed with the alkoxysilane compound represented by the general formulas (1) and (2). . As a result, since the alkoxysilane compounds represented by the general formulas (1) and (2) are fluorine compounds, the composition in which such compounds are dissolved may be used in the course of drying the solvent, such as a hydrocarbon solvent or an alcohol solvent. Solvents with high surface energy (particularly their polar components) have the drawback that the composition is repelled on the surface to be coated and becomes spherical, resulting in uneven coating. It has been found that the composition can be uniformly applied to the application surface by using a fluorinated hydrocarbon solvent.

It has also been found that the coating properties are greatly affected by the boiling point of the solvent. That is, the drying rate of the solvent is 7
At 0 ° C., it is usually said to be about 1 μm / s. In the case of a high boiling point solvent, the problem of drying after coating may remain. In the case of a low boiling point, there is a report that uneven coating is likely to occur due to convection during drying of the solvent. (IEEE Trans MAG., Vol.31, No6,1995, pp
2982-2984). As a result, among fluorocarbon solvents, by selecting a solvent having a boiling point in the range of 70 ° C. to 240 ° C., coating unevenness is suppressed as much as possible, and a uniform lubricating film having a uniform thickness is obtained. I found that I can get it.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail based on embodiments. FIG. 1 shows a sectional structure of a filter for a display device according to an embodiment of the present invention.

The filter 10 for a display device in the embodiment shown in FIG. 1 has an antireflection film 2 provided on one surface of a plastic substrate 1 and a surface modification film 3 formed on the upper surface thereof. The filter 10 according to the present embodiment includes:
For example, it is bonded to the surface of a panel 101 of a cathode ray tube (CRT) 100 shown in FIG. 2 via an adhesive layer. The adhesive for bonding the device 1 of the filter 10 to the panel 101 is not particularly limited, and various known adhesives can be used. Generally, an ultraviolet curable resin-based adhesive is used, and the cured layer of the adhesive is used. It is preferable that the refractive index be close to the refractive index of the panel, for example, the difference be within 0.8%. Specifically, for example, bisphenol A type epoxy (meth) acrylate having a molecular weight of 550 or more 10% by weight, urethane (meth) acrylate 20% by weight, hydroxyl group-containing mono (meth) acrylate 70% by weight,
A composition containing 3% of a photopolymerization initiator and about several% of other additives can be used.

In the present invention, the filter 1 shown in FIG.
The plastic substrate 1 is not particularly limited, and any substrate may be used as long as it is a substrate made of an organic polymer. However, optical properties such as transparency, refractive index, and dispersion, and furthermore, In view of various properties such as impact resistance, heat resistance and durability, in particular, polymethyl methacrylate, methyl methacrylate and other alkyl (meth) acrylates,
(Meth) acrylic resins such as copolymers with vinyl monomers such as styrene; polycarbonate, diethylene glycol bisallyl carbonate (CR-39)
(Brominated) bisphenol A type di (meth) acrylate homopolymer or copolymer, (brominated) bisphenol A mono (meth)
Thermosetting (meth) acrylic resins such as polymers and copolymers of urethane-modified monomers of acrylates;
Polyester, especially polyethylene terephthalate, polyethylene naphthalate and unsaturated polyester; acrylonitrile-styrene copolymer, polyvinyl chloride, polyurethane, epoxy resin and the like are preferable. It is also possible to use an aramid resin in consideration of heat resistance. In this case, the upper limit of the heating temperature is 200 ° C. or higher, and the temperature range is expected to be wide.

The surface of the plastic substrate as described above may be coated with a coating material such as a hard coat. It is possible to improve various physical properties such as hardness, chemical resistance, durability and dyeability.

In order to improve the hardness, it is possible to use a material to which various materials conventionally known as a plastic surface hardening film are applied, for example, Japanese Patent Publication No. 50-28092.
Gazette, Japanese Patent Publication No. 50-28446, Japanese Patent Publication No. 51-
24368, JP-A-52-112698,
The technology disclosed in Japanese Patent Publication No. 57-2735 can be applied. Further, an acrylic cross-linked product using a (meth) acrylic acid ester and a cross-linking agent such as pentaerythritol, or an organopolysiloxane-based product may be used. These can be used alone or in appropriate combination.

The antireflection film 2 formed on the plastic substrate 1 has a single-layer or multilayer structure, and various combinations are possible. In particular, in the case of a multilayer structure, the film configuration of the material forming the layer below the surface layer is required performance, for example, heat resistance, antireflection,
It can be determined appropriately based on experiments and the like according to the color of reflected light, durability, surface hardness and the like.

Various inorganic materials including silicon dioxide for forming these antireflection films can be formed by vacuum deposition,
There are various PVD (Physical Vapor Deposition) methods typified by ion plating and sputtering.
In order to obtain an antireflection film, as the inorganic substance (inorganic base material) suitable for the PVD method, in addition to SiO ₂ , for example, Al
₂ O ₃ , ZrO ₂ , TiO ₂ , Ta ₂ O ₅ , TaH
f ₂ , SiO, TiO, Ti ₂ O ₃ , HfO ₂ , Zn
O, In ₂ O ₃ / SnO ₂ , Y ₂ O ₃ , Yb ₂ O ₃ , S
Examples thereof include inorganic oxides such as b ₂ O ₃ , MgO, and CeO ₂ . It is preferable that the outermost surface layer of the antireflection film formed by such a PVD method is mainly composed of silicon dioxide. In the case of other than silicon dioxide, not only sufficient surface hardness cannot be obtained, but also the improvement of stain resistance and abrasion resistance aimed at by the present invention, and the durability of these properties may not be remarkably exhibited. Because there is. However, the present invention mainly relates to the configuration of the surface modified film covering the surface of such an antireflection film, and thus does not particularly limit the material of the outermost surface film of the antireflection film, It may be composed of something other than silicon dioxide.

The thickness of the outermost surface layer of the antireflection film should be determined according to the required performance other than the antireflection effect. It is preferable to select the optical film thickness of the surface layer to be １ ／ of the target light wavelength or an odd multiple thereof, from the viewpoint of giving a minimum reflectance, that is, a maximum transmittance.

On the other hand, the structure of the lower layer of the surface layer is not particularly limited. That is, although it is possible to form the surface layer directly on the substrate, it is possible to form a film having a higher refractive index than the surface layer on the substrate in order to make the antireflection effect more remarkable. Coating is effective. Some proposals have also been made regarding the selection of the film thickness and the refractive index of these multilayer antireflection films (for example,
Optical Technology Contact Vol.9 No.8 p.17 (1971)).

It is also possible to provide an inorganic light transmitting film such as a carbon sputter film or a carbon CVD film in the lower layer. In the present invention, the surface-modified film 3 covering the surface of the single-layer or multi-layer antireflection film 2 is a fluoroalkyl represented by the following general formulas (1) and / or (2). It is formed from a composition for a surface-modified film containing an alkoxysilane compound having a group or a perfluoropolyether group.

R _f ｛-R ₁ -R ₂ -Si (OR ₃ ) ₃ ｝ _j (1) R _f ｛Si (OR ₃ ) ₃ ｝ _j (2) (where R _f is fluoro An alkyl group or a perfluoropolyether group, R ₁ is a divalent atom or atomic group, R ₂
Represents an unsubstituted or substituted divalent hydrocarbon group, R ₃ represents an unsubstituted or substituted monovalent hydrocarbon group, and j is 1 or 2. ) The molecular structure of the perfluoropolyether group as R _f, is not particularly limited, but include perfluoropolyether group of various chain lengths, preferably C ₁
It is a monovalent or divalent perfluoropolyether having a perfluoroalkyloxy group of about to C ₃ as a repeating unit. Specific examples of the monovalent perfluoropolyether include the following.

[0032]

Embedded image

The following are examples of the divalent perfluoropolyether group.

[0034]

Embedded image

On the other hand, the molecular structure of the fluoroalkyl group as R _f is not particularly limited, and examples thereof include those in which a hydrogen atom of an alkyl group is substituted with a fluorine atom. Of which the molecular structure shown below is preferred.

F (CF ₂ ) _s (CH ₂ ) _t- (CH ₂ ) _t (CF ₂ ) _s (CH ₂ ) _t -In this formula, s is an integer of 6 to 12, and t is an integer of 20 or less. Show. In addition, among the compounds represented by the general formula (1) or (2), the alkoxysilane compound having a fluoroalkyl group is sufficient in terms of the solvent resistance, water contamination resistance, and the like as described above. In terms of abrasion resistance and frictional properties, it is inferior to the case of using an alkoxysilane compound having a perfluoropolyether group having excellent tribological properties in its molecular structure. is there.

The divalent atom or atomic group as R ₁ in the general formula (1) is not particularly limited, but is usually an atom or atomic group such as COO, CONH, and S. R ₂ in the general formula (1) is an unsubstituted or substituted divalent hydrocarbon group, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, and the number of carbon atoms is not particularly limited. .

R ₃ is an unsubstituted or substituted monovalent hydrocarbon group constituting an alkoxy group. The number of carbon atoms is not particularly limited, but is, for example, about C _{1 to} C ₅ , for example, methyl. And alkyl groups such as an ethyl group, a propyl group and an isopropyl group. In the above R _{1 to} R ₃ , as long as the flexibility or the fluctuation property of the carbon atom chain is not impaired, the carbon atom chain may partially have a cyclic structure such as an unsaturated bond, a characteristic group, or an aromatic ring. Further, it may have a short-chain branched chain or a side chain.

The molecular weight of the alkoxy compound represented by the general formula (1) or (2) is not particularly limited.
500 in terms of number average molecular weight in terms of stability, ease of handling, etc.
Those having a molecular weight of about 10,000 to 10,000, more preferably about 500 to 4000 are used. Further, the thickness of the surface-modified film formed of such a compound is not particularly limited, either. 1nm ~
It is desirable that the thickness be 100 nm, more preferably 10 nm or less, specifically, about 0.5 nm to 5 nm.

As the coating method, various methods used in a normal coating operation can be applied. From the viewpoint of uniformity of the antireflection effect and control of the reflection interference color, spin coating, dipping coating,
Curtain flow coating and the like are preferably used. Further, from the viewpoint of workability, a method of impregnating a material such as paper or cloth with a liquid and performing coating and casting is also preferably used.

In such a coating operation, the compound represented by the general formula (1) or (2) is usually diluted in a volatile solvent and used as a composition for a surface-modified film. The solvent used is not particularly limited, but in consideration of the stability of the composition, the wettability of the outermost surface layer of the antireflection film to be coated, typically the silicon dioxide film, volatility, etc. Should be determined. In the present invention, a fluorinated hydrocarbon solvent is used from the viewpoint of uniform coating properties of the coating film.

The fluorinated hydrocarbon-based solvent is a compound in which part or all of the hydrogen atoms of a hydrocarbon-based solvent such as an aliphatic hydrocarbon, a cyclic hydrocarbon, and ether are substituted with a fluorine atom. For example, perfluoroheptane (boiling point 80 ° C.), perfluorooctane (boiling point 102 ° C.), trade names SV-110 (boiling point 110 ° C.), SV-13 manufactured by Autodigmont, Inc.
Examples thereof include perfluoropolyethers having a boiling point of 135 ° C. and perfluoroalkanes such as FC series manufactured by Sumitomo 3M. Among these fluorinated hydrocarbon solvents, as a solvent for dissolving the fluorine compounds of the above general formulas (1) and (2), in order to obtain an organic film having a uniform thickness and a uniform thickness, the solvent has a boiling point of 70%. It is preferable to select those having a temperature range of -240 ° C and use one of these alone or in combination of two or more. If the boiling point is too low, drying may occur during transfer during gravure printing, for example, resulting in coating unevenness. On the other hand, if the boiling point is too high, drying may not be carried out properly and the coating form may not be improved.

The degree of dilution with a diluting solvent when preparing the composition for a surface-modified film containing the compound represented by the general formula (1) and / or (2) is not particularly limited, For example, it is appropriate to adjust the concentration to about 1 to 200 g / L. In this case, if necessary, an alcohol-based solvent, a hydrocarbon-based solvent, or the like may be mixed with the fluorinated hydrocarbon-based solvent as a solvent.

Further, an acid or a base as a reaction catalyst can be added to the coating solution, if necessary. As the acid catalyst, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acid clay, iron oxide, boric acid, trifluoroacetic acid and the like can be used. As the base catalyst, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. An alkali metal hydroxide or the like can be used. The addition amount of these catalysts is preferably about 0.001 to 1 mmol / L. In addition to these acids and bases, phosphate ester-based catalysts,
Alternatively, a carbonyl compound such as acetylacetone can be added to enhance its catalytic effect. By adding the catalyst in this way, the general formula (1)
The interaction involving the bonding reaction between the silano group of the compound represented by (2) and SiO ₂ on the surface of the antireflection film proceeds well without heating. For this reason, in a thin film material on SiO ₂ , excellent demands for durability can be expected despite the strict requirements for durability due to its film thickness. The addition amount of such a carbonyl compound can be about 0.1 to 100 mmol / L.

In applying the composition for a surface-modified film according to the present invention, it is preferable that the surface of the antireflection film to be applied be cleaned. Furthermore, degreasing with an organic solvent, steam cleaning with a fluorine-based gas, and the like are applied. It is also an effective means to perform various pretreatments for the purpose of improving adhesion and durability, and particularly preferably used methods include activating gas treatment, chemical treatment with an acid, alkali, or the like.

The composition for a surface-modified film of the present invention forms a surface-modified film capable of imparting abrasion resistance in addition to contamination resistance, abrasion resistance and processing resistance, particularly to a silicon oxide surface. can do. Therefore, the filter for a display device on which the surface modified film of the present invention has been formed is less likely to be stained than a normal antireflection film, and the stain is less noticeable. Furthermore, it has the advantage that dirt can be easily removed, or the surface slides well, so that it is not easily scratched. In addition to these properties, it has durability with respect to abrasion.

The present invention is not limited to the above-described embodiment, but can be variously modified within the scope of the present invention. For example, in the above-described embodiment, the filter 10 is used by bonding to the panel 101 of the CRT 100 shown in FIG. 2. However, the filter 10 according to the present invention does not necessarily need to be used by bonding to the surface of the panel 101. Instead, a filter of a type that can be detachably attached to the front surface of the panel 101 may be used.

The panel of the display device to which the filter 10 is attached is not limited to a panel having a curvature such as a CRT, but also a panel of a flat display device such as a liquid crystal display device or a plasma display. Panel of the display device. The filter according to the present invention may be attached to the panel of these display devices with an adhesive or the like, or may be detachably attached. When the filter is detachably mounted, a frame is attached to the outer periphery of the filter according to the present invention, and the filter according to the present invention is stretched over the frame.

The multilayer structure of the filter according to the present invention is not limited to the embodiment shown in FIG. 1, and various multilayer structures are conceivable. Further, the composition for a surface-modified film of the present invention,
In addition to the above, the present invention can be applied to, for example, a direct glass panel or a plastic lens, and has a wide range of application.

[0050]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" indicates parts by weight.

Example 1 (1) Preparation of Antireflection Film A transparent polyethylene terephthalate (PET) film having a thickness of 100 μm was used as a substrate. One side of this PET film is previously subjected to a hard coat treatment for securing surface hardness, and a 120 nm-thick ITO is pre-deposited thereon by a vacuum deposition method as an anti-reflection film. SiO ₂ was formed by vapor deposition to a thickness of 70 nm. In addition, the hard coat treatment referred to here generally applies an acrylic cross-linkable resin material, cross-links and cures it with ultraviolet rays or electron beams, or applies a silicon-based, melamine-based, epoxy-based resin material, It is performed by heat curing. (2) Preparation of a coating composition containing an alkoxysilane compound having a perfluoropolyether group (lubricant) 2 g of an alkoxysilane compound having a perfluoropolyether group (compound 1 in Table 1 having a molecular weight of about 1000)
Perfluoroheptane with a boiling point of 80 ° C (Sumitomo 3M,
The product was dissolved in a solvent (1) in Table 2 under the trade name PF-5070 and filtered through a membrane filter to obtain a coating composition. (3) Coating and drying The coating composition prepared in (2) is dip-coated on the surface of the antireflection film obtained in (1) at a pulling rate of 5 cm / min, and then air-dried to have antireflection properties. An optical article was obtained. No temperature operation was performed in the coating and drying steps. (4) Performance Evaluation The performance of the obtained optical article was evaluated by conducting a test according to the following method. Table 3 shows the test results of the following evaluation items (a) to (e). In order to check the solvent resistance, the same test was performed again after washing with ethanol. Table 3 shows the obtained results.

(A) Stain resistance test 5 ml of tap water was dripped on the filter surface, left for 48 hours in a room temperature atmosphere (25 ° C. ± 2 ° C.), and the remaining state of water scale after wiping with a cloth was visually observed. And observed. The case where scale was successfully removed was defined as good, and the case where scale was not removed was defined as poor.

(B) Surface Slipperiness The degree of scratching when the surface was scratched with a pencil (hardness: 3H) was evaluated. The criteria are as follows. ：: Not caught at all.

Δ: If it is strengthened, it will be caught. X: Even if weakened, it is caught. (C) Abrasion resistance test The surface of the optical article was rubbed 30 times with steel wool # 0000 under a load of 200 g under a load of 200 g, and the surface was evaluated for scratches.
The criteria are as follows.

○: Not attached at all. Δ: Fine scratches are formed. X: The scratch is remarkable. (D) Difficulty of attaching dirt The difficulty of attaching dirt was visually evaluated. The criteria are as follows.

○: Not noticeable even if attached. Δ: attached, but easily removable. X: The appearance after attachment is conspicuous. (E) Contact angle The contact angle between water and methylene iodide was measured. The measurement is
This was performed using CA-A manufactured by Kyowa Interface Chemical Co., Ltd. Measurement
The value of the contact angle is the residual rate of the surface-modified film or water.
Or as a measure of oil contamination.
You. Also, to check the stability to solvents,
The values before and after washing with ethanol were measured.Example 2 Having a perfluoropolyether group in Example 1.
Preparation of an alkoxysilane compound-containing coating composition
In the above, solvent 2 was used instead of solvent 1 in Table 2.
Outside, an optical article was obtained in the same manner as in Example 1, and
Performance evaluation was performed. Table 3 shows the obtained results.Examples 3 to 7 In Example 1, only the solvents shown in Table 3 were used.
Outside, an optical article was obtained in the same manner as in Example 1, and
Performance evaluation was performed. Table 3 shows the obtained results.Examples 8 and 9 Having a perfluoropolyether group in Example 1.
Preparation of an alkoxysilane compound-containing coating composition
, The compound of Table 1 as an alkoxysilane compound
Example 2 or 3 was used, except that solvent 3 in Table 2 was used.
An optical article was obtained in the same manner as in Example 1, and its performance was evaluated.
Done. Table 3 shows the obtained results. Comparative Example 1 Having a perfluoropolyether group in Example 1.
Preparation of an alkoxysilane compound-containing coating composition
, A perfluoroalkane having a boiling point of 42 ° C. (Sumitomo
3M, trade name FC-84, using solvent 8) in Table 2
An optical article was obtained in the same manner as in Example 1 except for
The performance was evaluated. Table 3 shows the obtained results.Comparative Example 2 Having a perfluoropolyether group in Example 1.
Preparation of an alkoxysilane compound-containing coating composition
, A perfluoroalkane having a boiling point of 56 ° C (Sumitomo
3M, trade name FC-72, using solvent 9) in Table 2.
An optical article was obtained in the same manner as in Example 1 except for
The performance was evaluated. Table 3 shows the obtained results.Comparative Example 3 Having a perfluoropolyether group in Example 1.
Preparation of an alkoxysilane compound-containing coating composition
, A perfluoroalkane having a boiling point of 253 ° C.
Tomo 3M, trade name FC-71, solvent 10 in Table 2)
Except for using it, an optical article was prepared in the same manner as in Example 1.
The performance was evaluated. Table 3 shows the obtained results.
You.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

From the results in Table 3, it can be seen that by preparing a composition using a fluorinated hydrocarbon solvent, particularly a fluorinated hydrocarbon solvent having a boiling point of 70 to 240 ° C., the coating properties are improved and the coating unevenness is improved. It is observed to decrease.

[0061]

As described above, the composition for a surface-modified film according to the present invention is obtained by dissolving the alkoxysilane compound of the above formula (1) and / or (2) in a fluorinated hydrocarbon solvent,
The paintability is improved.

The surface modified film according to the present invention is formed on the inorganic film using the composition. Further, in the filter for a display device according to the present invention, the surface of a single-layer or multi-layer antireflection film provided on a plastic substrate is covered with the surface-modified film.

Therefore, the composition for a surface modified film, the surface modified film, the filter for a display device and the display device having the same according to the present invention have the following effects. (1) It is hard to be stained by fingerprints, hand marks, and the like, and hardly noticeable. These effects are permanently maintained. (2) It can be easily removed even if it is dried due to adhesion of scale and the like. (3) Good surface slipperiness. (4) Dirt such as dust hardly adheres, and the usability is good. (5) There is durability against abrasion. (6) The drying temperature after application can be reduced to a low temperature of 50 ° C. or less. (7) Since the coating unevenness can be reduced, the yield is improved, the appearance is beautiful, and there is no discomfort.

[Brief description of the drawings]

FIG. 1 is a drawing showing a cross-sectional structure of a filter for a display device according to an embodiment of the present invention.

FIG. 2 is a schematic perspective view of a CRT according to one embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Plastic base material, 2 ... Anti-reflection film, 3 ... Surface modification film, 10 ... Filter, 100 ... CRT, 1
01 ... Panel

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G09F 9/00 G02B 1/10 A

Claims (9)

[Claims] 1. A composition for a surface-modified film, comprising an alkoxysilane compound represented by the following general formula (1) and / or (2) dissolved in a fluorinated hydrocarbon solvent. R _f ｛-R ₁ -R ₂ -Si (OR ₃ ) ₃ ｝ _j (1) R _f ｛Si (OR ₃ ) ₃ ｝ _j (2) (where R _f is a fluoroalkyl group or A perfluoropolyether group, R ₁ is a divalent atom or atomic group, R ₂
Represents an unsubstituted or substituted divalent hydrocarbon group, R ₃ represents an unsubstituted or substituted monovalent hydrocarbon group, and j is 1 or 2. ) 2. The fluorinated hydrocarbon solvent having a boiling point of 70
The composition for a surface-modified film according to claim 1, wherein the composition has a temperature of from -240 ° C. 3. The composition for a surface-modified film according to claim 1, wherein the concentration of the alkoxysilane compound represented by the formula (1) and / or (2) is 1 to 200 g / L. 4. A composition for a surface-modified film in which an alkoxysilane compound represented by the following general formula (1) and / or (2) is dissolved on a surface of an inorganic base material using a fluorinated hydrocarbon solvent. A surface modified film characterized by being formed into a film. R _f ｛-R ₁ -R ₂ -Si (OR ₃ ) ₃ ｝ _j (1) R _f ｛Si (OR ₃ ) ₃ ｝ _j (2) (where R _f is a fluoroalkyl group or A perfluoropolyether group, R ₁ is a divalent atom or atomic group, R ₂
Represents an unsubstituted or substituted divalent hydrocarbon group, R ₃ represents an unsubstituted or substituted monovalent hydrocarbon group, and j is 1 or 2. ) 5. The fluorinated hydrocarbon solvent having a boiling point of 70
The surface modified film according to claim 4, wherein the temperature is from -240C. 6. The surface of a single-layer or multi-layer antireflection film provided on a plastic substrate has the following general formula (1) and / or
Or a filter for a display device having a surface-modified film formed by using a composition for a surface-modified film in which the alkoxysilane compound represented by (2) is dissolved using a fluorinated hydrocarbon-based solvent. . R _f ｛-R ₁ -R ₂ -Si (OR ₃ ) ₃ ｝ _j (1) R _f ｛Si (OR ₃ ) ₃ ｝ _j (2) (where R _f is a fluoroalkyl group or A perfluoropolyether group, R ₁ is a divalent atom or atomic group, R ₂
Represents an unsubstituted or substituted divalent hydrocarbon group, R ₃ represents an unsubstituted or substituted monovalent hydrocarbon group, and j is 1 or 2. ) 7. The fluorinated hydrocarbon solvent having a boiling point of 70
The display device filter according to claim 6, wherein the temperature is from 240 to 240 ° C. 8. The filter for a display device according to claim 6, wherein the surface layer of the antireflection film on which the surface modification film is formed is mainly composed of silicon oxide. 9. The surface of a single-layer or multi-layer antireflection film provided on a plastic substrate has the following general formula (1) and / or
Or a display device filter on which a surface-modified film is formed using a composition for a surface-modified film in which the alkoxysilane compound represented by (2) is dissolved using a fluorohydrocarbon-based solvent. Display device. R _f ｛-R ₁ -R ₂ -Si (OR ₃ ) ₃ ｝ _j (1) R _f ｛Si (OR ₃ ) ₃ ｝ _j (2) (where R _f is a fluoroalkyl group or A perfluoropolyether group, R ₁ is a divalent atom or atomic group, R ₂
Represents an unsubstituted or substituted divalent hydrocarbon group, R ₃ represents an unsubstituted or substituted monovalent hydrocarbon group, and j is 1 or 2. )