JP2016128927A - Laminated thin film and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film that offers superior adhesion between an organic layer and inorganic layer, and a manufacturing method therefor.SOLUTION: A laminated thin film includes a hard coat layer 10 having metal oxide particles 11 exposed on a surface thereof, and an adhesive layer 12 formed on the hard coat layer 10 to cover the surface with the exposed metal oxide particles and made of an oxygen-deficient metal oxide or metal of the same type as the metal oxide particles 11. This allows the adhesive layer 12 to be strongly adhered to resin of the hard coat layer 10, and to the exposed metal oxide particles 11 even more strongly, realizing superior adhesion thereby.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a laminated thin film having excellent adhesion between an organic layer and an inorganic layer, and a method for producing the laminated thin film.

  An example of a laminated thin film is an antireflection film in which an AR (Anti-Reflective) layer is formed on a hard coat layer having a relatively high surface hardness by a dry process (see, for example, Patent Document 1).

  However, since the hard coat layer is an organic layer and the AR layer is an inorganic layer, it is difficult to obtain excellent adhesion.

Japanese Patent Laid-Open No. 11-218603

  This invention is proposed in view of such a conventional situation, and provides the manufacturing method of the laminated thin film which is excellent in the adhesiveness between an organic layer and an inorganic layer, and a laminated thin film.

  As a result of intensive studies, the inventor has exposed metal oxide particles on the surface of the hard coat layer containing the metal oxide particles, and the surface of the metal oxide is in the same oxygen deficiency state as the metal oxide particles. Or it discovered that the adhesiveness between an organic layer and an inorganic layer improved remarkably by forming into a film the adhesion layer which consists of metals.

  That is, the laminated thin film according to the present invention is formed on the hard coat layer with the metal oxide particles exposed on the surface, and the metal oxide particle exposed surface of the hard coat layer, and is the same kind as the metal oxide particles. And an adhesion layer made of an oxygen-deficient metal oxide or metal.

  Further, the method for producing a laminated thin film according to the present invention includes an exposing step of exposing the metal oxide particles on the surface of the hard coat layer containing the metal oxide particles, and an exposed surface of the metal oxide particles of the hard coat layer. And a film forming step of forming an adhesion layer made of a metal oxide or metal of the same oxygen deficiency state as the metal oxide particles.

  According to the present invention, since the adhesion layer adheres strongly to the resin of the hard coat layer and adheres more strongly to the exposed metal oxide particles, excellent adhesion can be obtained.

FIG. 1 is a cross-sectional view schematically showing a hard coat layer with exposed metal oxide particles according to the present embodiment. FIG. 2 is a cross-sectional view schematically showing the laminated thin film according to the present embodiment. FIG. 3 is a cross-sectional view schematically showing an antireflection film to which the present invention is applied. FIG. 4 is a photograph showing an evaluation example of a cross-hatch test. FIG. 4A shows a case where no peeling occurs, FIG. 4B shows a case where some peeling occurs, and FIG. The case where peeling occurred in all cases is shown. 5A is a photograph of the TEM cross section of Example 3, and FIG. 5B is a photograph of the TEM cross section of Comparative Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. Laminated thin film 2. Antireflection film 3. Manufacturing method of laminated thin film Example

<1. Multilayer thin film>
FIG. 1 is a cross-sectional view schematically showing a hard coat layer from which metal oxide particles according to the present embodiment are exposed, and FIG. 2 is a cross-sectional view schematically showing a laminated thin film according to the present embodiment. is there. The laminated thin film according to the present embodiment is formed on the hard coat layer 10 with the metal oxide particles 11 exposed on the surface, and on the metal oxide particle exposed surface of the hard coat layer 10. And an adhesion layer 12 made of the same kind of oxygen-deficient metal oxide or metal. In addition, a functional layer 20 formed of an inorganic layer is further provided on the adhesion layer 12. According to such a configuration, the adhesion layer 12 strongly adheres to the resin of the hard coat layer 10 and more firmly adheres to the exposed metal oxide particles 11, so that the adhesion between the hard coat layer 10 and the adhesion layer 12 is achieved. And the scratch resistance of the laminated thin film can be improved.

[Hard coat layer]
In the hard coat layer 10, metal oxide particles 11 are dispersed in a resin material, and the metal oxide particles 11 are exposed on the surface. Examples of the resin material of the hard coat layer 10 include an ultraviolet curable resin, an electron beam curable resin, a thermosetting resin, a thermoplastic resin, and a two-component mixed resin. Among these, it is preferable to use an ultraviolet curable resin capable of efficiently forming the hard coat layer 10 by ultraviolet irradiation.

  Examples of the ultraviolet curable resin include acrylic, urethane, epoxy, polyester, amide, and silicone. Among these, for example, when a laminated thin film is used as an optical application, it is preferable to use an acrylic system that provides high transparency.

  The acrylic ultraviolet curable resin is not particularly limited, and is in view of hardness, adhesion, workability, etc. from a bifunctional, trifunctional or higher polyfunctional acrylic monomer, oligomer, polymer component, etc. It can be properly selected and blended. Moreover, a photoinitiator is mix | blended with ultraviolet curable resin.

  Specific examples of the bifunctional acrylate component include polyethylene glycol (600) diacrylate, dimethylol-tricyclodecane diacrylate, bisphenol AEO-modified diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, Propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) Diacrylate, cyclohexane dimethanol diacrylate, etc. are mentioned. Specific examples that can be obtained on the market include the trade name “SR610” of Sartomer Co., Ltd.

  Specific examples of the tri- or higher functional acrylate component include pentaerythritol triacrylate (PETA), 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-converted triacrylate, ε-caprolactone-modified tris- (2-acrylic). Roxyethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), ε-caprolactone-modified tris (acryloxyethyl) acrylate and the like. Specific examples that can be obtained in the market include Sartomer's trade name “CN968”, Sartomer's trade name “SR444”, and the like.

  Specific examples of the photopolymerization initiator include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and the like. Specific examples that can be obtained on the market include 1-hydroxycyclohexyl phenyl ketone (IRGACURE184, BASF Japan Ltd.).

  The acrylic ultraviolet curable resin preferably contains a leveling agent in order to improve smoothness. Specific examples of the leveling agent include a silicone leveling agent, a fluorine leveling agent, and an acrylic leveling agent, and one or more of these can be used. Among these, it is preferable to use a silicone leveling agent from the viewpoint of coating properties. Specific examples that can be obtained on the market include, for example, the trade name “BYK337” (polyether-modified polydimethylsiloxane) of Big Chemie Japan Co., Ltd.

  The solvent used in the acrylic ultraviolet curable resin is not particularly limited as long as the application property of the resin composition is satisfied, but is preferably selected in consideration of safety. Specific examples of the solvent include propylene glycol monomethyl ether acetate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples thereof include ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol methyl ether, and one or more of these can be used. Among these, it is preferable to use propylene glycol monomethyl ether acetate and butyl acetate from the viewpoint of coatability. In addition to the above, acrylic UV curable resins include hue adjusters, colorants, UV absorbers, antistatic agents, various thermoplastic resin materials, refractive index adjusting resins, refractive index adjusting particles, and adhesion imparting. Functionality imparting agents such as resins can be contained.

  The metal oxide particles 11 are formed by forming metal oxide particles, and the average particle diameter is preferably 800 nm or less, more preferably 20 nm or more and 100 nm or less. If the average particle diameter of the metal oxide particles 11 is too large, it will be difficult to make the laminated thin film into an optical application. If the average particle diameter is too small, the adhesion between the hard coat layer 10 and the adhesion layer 12 will be reduced. In addition, in this specification, an average particle diameter means the value measured by BET method.

  Moreover, it is preferable that content of the metal oxide particle 11 is 20 mass% or more and 50 mass% or less with respect to the whole solid content of the resin composition of the hard-coat layer 10. FIG. If the content of the metal oxide particles 11 is too small, the adhesion between the hard coat layer 10 and the adhesion layer 12 is lowered, and if too much, the flexibility of the hard coat layer 10 is lowered. In addition, solid content of a resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

Specific examples of the metal oxide particles 11 include SiO ₂ (silica), Al ₂ O ₃ (alumina), TiO ₂ (titania), ZrO ₂ (zirconia), CeO ₂ (ceria), MgO (magnesia), ZnO, Examples include Ta ₂ O ₅ , Sb ₂ O ₃ , SnO ₂ , and MnO ₂ . Among these, for example, when a laminated thin film is used for optical purposes, it is preferable to use silica that can provide high transparency. As a specific example which can be obtained on the market, for example, trade name “IPA-ST-L” (silica sol) of Nissan Chemical Co., Ltd. can be cited. Moreover, you may introduce | transduce functional groups, such as an acryl group and an epoxy group, on the surface of a metal oxide particle in order to improve adhesiveness and affinity with resin.

  As shown in FIG. 1, metal oxide particles 11 are exposed and protruded from the surface of the hard coat layer 10. The method for exposing the metal oxide particles 11 is not particularly limited as long as the resin of the hard coat layer 10 can be selectively etched as will be described later. For example, glow discharge treatment, plasma treatment, ion etching, alkali treatment is performed. Etc. can be used.

  The average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles 11 exposed on the surface of the hard coat layer 10 is preferably 60% or less, more preferably 10% or more and 30% or less. If the protruding ratio of the metal oxide particles 11 is too large, the metal oxide particles 11 are easily peeled off from the resin, and the adhesion between the hard coat layer 10 and the adhesion layer 12 is lowered. If the protruding ratio is too small, the adhesion is decreased. Improvement effect cannot be obtained.

  The hard coat layer 10 is made of an ultraviolet curable resin containing a urethane (meth) acrylate oligomer, a tri- or higher-functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a photopolymerization initiator. Photopolymerization is preferred. By using such a photocurable resin composition, the hard coat layer 10 having excellent hardness can be obtained.

[Adhesion layer]
The adhesion layer 12 is formed on the exposed surface of the metal oxide particles of the hard coat layer 10 and is made of the same type of oxygen-deficient metal oxide or metal as the metal oxide particles 11. Examples of the oxygen-deficient metal oxide include SiO _x , AlO _x , TiO _x , ZrO _x , CeO _x , MgO _x , ZnO _x , TaO _x , SbO _x , SnO _x , and MnO _x . Here, the metal oxide in an oxygen deficient state refers to a metal oxide in which the number of oxygens is insufficient compared to the stoichiometric composition. Examples of the metal include Si, Al, Ti, Zr, Ce, Mg, Zn, Ta, Sb, Sn, and Mn. For example, when the metal oxide particles 11 are SiO ₂ , _x in SiO _x of the adhesion layer 12 is 0 or more and less than 2.0.

The degree of oxidation and the film thickness of the adhesion layer 12 can be appropriately designed according to the functional layer 20 formed on the adhesion layer 12. For example, when the functional layer 20 is an antireflection layer (AR (Anti-Reflective) layer) and SiO ₂ is used as the metal oxide particles 11, _x in SiO _x of the adhesion layer 12 is 0 or more and 1.9 or less. It is preferable that

[Functional layer]
The functional layer 20 is an inorganic layer formed on the adhesion layer 12. Examples of the functional layer 20 include optical layers such as an antireflection layer, a retardation layer, and a polarizing layer. Since such an optical layer is an inorganic layer formed by sputtering, for example, thermal dimensional stability can be improved as compared with an organic layer.

  In the laminated thin film having such a configuration, the hard coat layer 10 and the adhesion layer 12 are firmly attached by the metal oxide particles 11, so that excellent adhesion can be obtained. In particular, when the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles exposed on the surface of the hard coat layer 10 is 60% or less, more preferably 10% or more and 30% or less, the light resistance in the xenon lamp is reduced. Even in the property test, excellent adhesion can be obtained.

<2. Antireflection film>
Next, an antireflection film will be described as an example of the laminated thin film described above. FIG. 3 is a cross-sectional view schematically showing an antireflection film to which the present invention is applied. As shown in FIG. 3, the antireflection film is formed on the base material 30, the hard coat layer 10 with the metal oxide particles 11 exposed on the surface, and the metal oxide particle exposed surface of the hard coat layer 10. And an adhesion layer 12 made of a metal oxide or metal in the same oxygen deficiency state as the metal oxide particles 11, an antireflection layer 40, and an antifouling layer 50.

  The substrate 30 is not particularly limited, and specific examples thereof include PET (Polyethylene terephthalate), a resin (COP) having a cycloolefin as a main chain and an alicyclic structure in the main chain, a cyclic olefin (for example, norbornenes) and α. -Resin (COC) obtained by addition polymerization with olefin (for example, ethylene), TAC (triacetyl cellulose), etc. are mentioned. The thickness of the substrate 30 varies depending on the type and performance of the optical device to which it is applied, but is usually 25 to 200 μm, preferably 40 to 150 μm.

The hard coat layer 10 and the adhesion layer 12 are the same as the laminated thin film described above. In the antireflection film to which the present invention is applied, the metal oxide particles 11 of the hard coat layer 10 are SiO ₂ , and the adhesion layer 12 is SiO _x (x is 0.5 or more and 1.9 or less). preferable. Further, the thickness of the hard coat layer 10 is usually 0.5 to 20 μm, preferably 1 to 15 μm, and the film thickness of the adhesion layer 12 is preferably 10 nm or less.

The antireflection layer 40 is formed by alternately forming a high refractive index layer made of a dielectric and a low refractive index layer having a lower refractive index than the high refractive index layer by sputtering. The dielectric of high refractive index _Nb 2 _{O 5} or TiO _2, SiO ₂ is preferably used as the dielectric of low refractive index.

  The antifouling layer 50 is, for example, a coating layer of an alkoxysilane compound having a perfluoropolyether group. By coating with an alkoxysilane compound having a perfluoropolyether group, the water contact angle is 110 ° or more and water repellency can be exhibited, and the antifouling property can be improved.

  Since the antireflection film which consists of such a structure is excellent in abrasion resistance, it can be preferably utilized, for example as a laminated film for touch panels. Furthermore, by laminating such a laminated film for a touch panel on an image display element such as a liquid crystal display element or an organic EL display element, it can be preferably applied as an image display / input device for a smartphone or a personal computer.

<3. Manufacturing method of laminated thin film>
The method for producing a laminated thin film according to the present embodiment includes an exposure step of exposing metal oxide particles on the surface of a hard coat layer containing metal oxide particles, and a metal oxide particle exposed surface of the hard coat layer. And a film forming step of forming an adhesion layer made of a metal oxide or metal of the same oxygen deficiency state as the metal oxide particles. Hereinafter, the exposure process and the film forming process will be described.

[Exposure process]
First, for example, ultraviolet curing containing metal oxide particles 11, a urethane (meth) acrylate oligomer, a tri- or higher-functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a photopolymerization initiator. The mold resin composition is uniformly mixed and adjusted according to a conventional method using a stirrer such as a disper.

  Next, an ultraviolet curable resin composition is applied onto the substrate. The coating method is not particularly limited, and a known method can be used. Known coating methods include, for example, micro gravure coating method, wire bar coating method, direct gravure coating method, die coating method, dip method, spray coating method, reverse roll coating method, curtain coating method, comma coating method, knife coating method. And spin coating method.

  Next, the hard coat layer 10 is formed by drying and photocuring the ultraviolet curable resin composition on the substrate. The drying conditions are not particularly limited, and may be natural drying or artificial drying that adjusts drying humidity, drying time, and the like. However, when wind is applied to the surface of the paint at the time of drying, it is preferable not to generate a wind pattern on the surface of the coating film. This is because, when a wind pattern is generated, the coating appearance is deteriorated and the surface thickness is uneven. In addition to ultraviolet rays, energy rays such as gamma rays, alpha rays, and electron beams can be applied as the light for curing the ultraviolet curable resin composition.

  Next, the surface of the hard coat layer 10 is etched to expose the metal oxide particles 11 as shown in FIG. The method for exposing the metal oxide particles 11 is not particularly limited as long as the resin of the hard coat layer 10 can be selectively etched. For example, glow discharge treatment, plasma treatment, ion etching, alkali treatment, or the like is used. Can do. Among these, it is preferable to use a glow discharge treatment capable of a large area treatment.

  The glow discharge treatment is performed in a treatment apparatus in which two flat plate electrodes facing each other are placed in a tank that can be evacuated to vacuum, and a film runs in parallel between the electrodes. In addition, this processing apparatus may be installed in the film-forming apparatus.

  After the processing chamber is evacuated to a vacuum of, for example, 0.01 Pa or less, an atmospheric gas is introduced. The pressure in the processing chamber at this time is not particularly limited as long as glow discharge can be maintained, but is usually in the range of 0.1 to 100 Pa. As the atmospheric gas, an inert gas is mainly used, but hydrogen, oxygen, nitrogen, fluorine, chlorine gas, or the like may be used. Moreover, these mixed gas may be sufficient. Examples of the inert gas include helium, neon, argon, krypton, xenon, and radon. Among these, helium gas and argon gas are preferable from the viewpoint of availability, and argon gas is particularly preferable in terms of cost.

  After introducing the atmospheric gas, a glow discharge is generated by applying a voltage of several hundred volts between the opposing electrodes. The film is continuously passed through the region where the glow discharge is generated, whereby the film surface is reformed by the atmosphere gas ionized.

The intensity of the glow treatment can be shown by the energy density (W / m ² ) at the time of discharge and the treatment time (min). In the case of a continuous winding type apparatus, the processing time is a value obtained by dividing the length of the processing region (m) (the length of the electrode in the direction along the film) by the winding speed (m / min). . The treatment intensity is obtained by multiplying the power density (W / m ² ) at the time of glow discharge by the treatment time, and is represented by the following formula.
Processing intensity (W · min / m ² ) = Power density (W / m ² ) × Processing area length (m) ÷ Feed rate (m / min)

  That is, films with different processing strengths can be created by changing the input power / feed rate.

Processing the intensity of the glow discharge treatment (electric power × treatment time / process area, unit: W · min / ^{m 2)} is preferably 200~4150W · min / ^{m 2,} is 420~2100W · min / ^{m 2} It is more preferable. As the treatment strength increases, more plasma is generated on the surface of the hard coat layer, and the protrusion ratio of the metal oxide particles 11 increases.

  The average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles 11 is preferably 60% or less, more preferably 10% or more and 30% or less. When the protruding ratio of the metal oxide particles 11 is too large, the metal oxide particles 11 are easily peeled off from the resin, the adhesion between the organic layer and the inorganic layer is lowered, and when the protruding ratio is too small, the effect of improving the adhesion is achieved. Cannot be obtained.

  Further, the arithmetic average roughness Ra of the hard coat layer surface after etching is preferably 2 nm or more and 12 nm or less, and more preferably 4 nm or more and 8 nm or less. When the arithmetic average roughness Ra of the hard coat layer surface is too small, the protruding ratio of the metal oxide particles 11 is not sufficient, and when the arithmetic average roughness Ra is too large, the metal oxide particles 11 are easily peeled off from the hard coat layer 10. There is a tendency.

[Film formation process]
In the film forming step, an adhesion layer 12 made of a metal oxide or metal of the same oxygen deficiency state as the metal oxide particles 11 is formed on the metal oxide particle exposed surface of the hard coat layer 10. As a method for forming the adhesion layer 12, it is preferable to use sputtering using a target. For example, when forming a SiOx film, it is preferable to use a silicon target and reactive sputtering in a mixed gas atmosphere of oxygen gas and argon gas. In addition, since the functional layer 20 such as an antireflection layer, a retardation layer, or a polarizing layer formed on the adhesion layer 12 can also be formed by sputtering, productivity can be improved.

  By forming the adhesion layer 12 on the hard coat layer 10 from which the metal oxide particles are exposed in this way, in addition to the large adhesion between the adhesion layer 12 and the resin of the hard coat layer 10, the adhesion layer 12 and the metal Since even greater adhesion with the oxide particles 11 is obtained, excellent adhesion can be obtained.

<4. Example>
In this example, an antireflection film was produced, and the adhesion between the hard coat layer and the AR layer was evaluated by a cross hatch test. The present invention is not limited to these examples.

<4.1 First Example>
In the first example, the influence of the protrusion ratio of the filler on the surface of the hard coat layer on the adhesion was verified. Calculation of the protrusion height and protrusion ratio of the filler on the surface of the hard coat layer, measurement of the surface roughness Ra of the hard coat layer, and evaluation of the cross-hatch test of the antireflection film were performed as follows.

[Calculation of protrusion height and protrusion ratio of filler on hard coat layer surface]
Using a transmission electron microscope (TEM), the cross section of the antireflection film was observed to measure the minimum and maximum protrusion heights of the filler on the hard coat layer surface. Then, the average particle size of the filler was divided with respect to the minimum value and the maximum value of the protrusion height of the filler, and the minimum value (%) and the maximum value (%) of the protrusion ratio with respect to the average particle size of the filler were calculated. . Moreover, the average value (%) of the protrusion ratio with respect to the average particle diameter of the filler was calculated from the minimum value (%) and the maximum value (%) of the protrusion ratio with respect to the average particle diameter of the filler.

[Measurement of surface roughness Ra of hard coat layer]
The arithmetic average roughness Ra of the hard coat layer surface was measured using an atomic force microscope (AFM).

[Evaluation of cross-hatch test]
100 cross hatches of 1 mm × 1 mm were formed on the surface of the antireflection film. And the surface state of the cross hatch surface in the initial stage was observed and evaluated. Moreover, after performing the alcohol wipe sliding test, the surface state of the cross hatch surface was observed and evaluated. Further, after an alcohol wipe sliding test was performed after the environment was introduced at a temperature of 90 ° C.-Dry (low humidity) -time of 500 h, the surface state of the cross hatch surface was observed and evaluated. Further, after an alcohol wipe sliding test was performed after the environment was introduced at a temperature of 60 ° C., a humidity of 95%, and a time of 500 hours, the surface state of the cross hatch surface was observed and evaluated. Further, after an alcohol wipe sliding test was performed after the xenon irradiation (xenon arc lamp, 7.5 kW) -time 60 h was applied, the surface state of the cross hatch surface was observed. The alcohol wipe sliding test was performed by pressing a wipe coated with ethyl alcohol against the anti-reflection film with a load of 250 g / cm ² against the cross hatch surface, and sliding it back and forth 500 times a distance of 10 cm.

  As a result of observing the surface state of the cross-hatch surface, the cross-hatch test was evaluated when the cross-hatch surface did not peel as shown in FIG. 4 (A), and the cross-hatch test as shown in FIG. 4 (B). The case where peeling occurred in the part was Δ, and the case where peeling occurred in the entire cross hatch as shown in FIG.

[Example 1]
A photocurable resin composition in which the content of silica particles having an average particle diameter of 50 nm was 28% by mass with respect to the entire solid content of the resin composition was prepared. As shown in Table 1, the resin composition was prepared by dissolving silica particles, acrylate, leveling agent, and photopolymerization initiator in a solvent.

  A PET film was used as a substrate, and the photocurable resin composition was applied onto the PET film with a bar coater, and then the resin composition was photopolymerized to form a hard coat layer having a thickness of 5 μm.

Next, the surface treatment of the hard coat layer was performed at a glow discharge treatment strength of 8300 W · min / m ² . Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 1, the protrusion ratio of the filler, and the surface roughness Ra.

After the glow discharge treatment, an adhesion layer made of SiO _{x having a} thickness of 10 nm is formed by sputtering, and an AR layer made of an Nb ₂ O ₅ film, an SiO ₂ film, an Nb ₂ O ₅ film, and an SiO ₂ film on the adhesion layer Was deposited. Further, an antifouling layer having a thickness of 10 nm made of an alkoxysilane compound having a perfluoropolyether group was formed on the AR layer, and the antireflection film of Example 1 was produced. The reflectance of this antireflection film was 0.5% or less, and the water contact angle was 110 degrees or more. Table 2 shows the evaluation of the cross-hatch test of the antireflection film in Example 1.

[Example 2]
An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity set to 4200 W · min / m ² . Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 2, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

[Example 3]
An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity set to 2100 W · min / m ² . Table 2 shows the protrusion height of the filler on the hard coat layer surface in Example 3, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

[Example 4]
An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity of 830 W · min / m ² . Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 4, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

[Example 5]
An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with a glow discharge treatment intensity of 420 W · min / m ² . Table 2 shows the protrusion height of the filler on the hard coat layer surface in Example 5, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

[Example 6]
An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity of 200 W · min / m ² . Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 6, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

[Example 7]
Except that the surface treatment of the hard coat layer was performed with the treatment intensity of the glow discharge treatment being 420 W · min / m ² and that the adhesion layer made of Si having a thickness of 10 nm was formed by sputtering after the glow discharge treatment. An antireflection film was produced in the same manner as in Example 1. Table 2 shows the protrusion height of the filler on the hard coat layer surface in Example 7, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

[Comparative Example 1]
An antireflection film was produced in the same manner as in Example 1 except that the glow discharge treatment was not performed. Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Comparative Example 1, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

[Comparative Example 2]
Reflection was carried out in the same manner as in Example 1 except that no silica particles were blended in the resin composition and that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity set to 830 W · min / m ^2. A prevention film was prepared. Table 2 shows the surface roughness Ra in Comparative Example 2 and the evaluation of the cross-hatch test of the antireflection film.

[Comparative Example 3]
An antireflection film was prepared in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with a glow discharge treatment intensity of 830 W · min / m ² and SiO ₂ was formed as an adhesion layer. Produced. Table 2 shows the protrusion height of the filler on the hard coat layer surface in Comparative Example 3, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.

When the silica particles were not exposed as in Comparative Example 1, peeling occurred on the entire cross hatch in the sliding test using an alcohol wipe. Further, when the surface treatment was performed without blending silica particles as in Comparative Example 2, all the cross hatches were peeled off in the sliding test with alcohol wipes as in Comparative Example 1. Further, when SiO ₂ was formed as an adhesion layer as in Comparative Example 3, as in Comparative Example 1, peeling occurred in the entire cross hatch in the sliding test using alcohol wipe.

  On the other hand, when silica particles were exposed as in Examples 1 to 7, adhesion was improved in a sliding test using an alcohol wipe. Moreover, when the photograph of the TEM cross section of Example 3 shown to FIG. 5 (A) and the photograph of the TEM cross section of the comparative example 1 shown to FIG. 5 (B) are compared, in Example 3, a hard-coat layer, an adhesion layer, and It can be seen that the exposure of the silica particles contributes to the improvement of the adhesion, since the interface of this is a circular arc shape due to the exposure of the silica particles, but is a linear shape in Comparative Example 1.

  Moreover, when the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles is 60% or less, particularly 10% or more and 30% or less, an excellent evaluation result can be obtained in a sliding test using an alcohol wipe. It was.

<4.2 Second Embodiment>
In the second example, the influence of the average particle diameter of the filler of the hard coat layer and the addition amount on the adhesion was verified. Moreover, it verified about the influence on the adhesiveness of the filler of a hard-coat layer, and the kind of contact | adherence layer. In addition, surface treatment methods other than glow discharge treatment were studied. The evaluation of the anti-reflection film cross-hatch test was performed in the same manner as in the first example.

[Example 8]
As shown in Table 3, the content of silica particles having an average particle diameter of 100 nm (trade name: MEK-ST-Z, Nissan Chemical Industries, Ltd.) is 33% by mass with respect to the entire solid content of the resin composition. An antireflection film was produced in the same manner as in Example 4 except that a photocurable resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 8.

[Example 9]
As shown in Table 3, the content of silica particles having an average particle diameter of 20 nm (trade name: MEK-ST-40, Nissan Chemical Industries, Ltd.) is 33% by mass with respect to the entire solid content of the resin composition. An antireflection film was produced in the same manner as in Example 4 except that a photocurable resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 9.

[Example 10]
As shown in Table 3, the content of silica particles having an average particle diameter of 50 nm (IPA-ST-L, Nissan Chemical Co., Ltd.) is 20% by mass with respect to the entire solid content of the resin composition. An antireflection film was produced in the same manner as in Example 4 except that the resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 10.

[Example 11]
As shown in Table 3, the content of silica particles having an average particle diameter of 50 nm (IPA-ST-L, Nissan Chemical Co., Ltd.) is 50% by mass with respect to the entire solid content of the resin composition. An antireflection film was produced in the same manner as in Example 4 except that the resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 11.

[Comparative Example 4]
As shown in Table 3, the content of silica particles having an average particle diameter of 50 nm (IPA-ST-L, Nissan Chemical Co., Ltd.) is 10% by mass with respect to the entire solid content of the resin composition. An antireflection film was produced in the same manner as in Example 4 except that the resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Comparative Example 4.

[Comparative Example 5]
As shown in Table 3, light having an average particle size of 1 μm acrylic particles (trade name: SSX-101, Sekisui Chemical Co., Ltd.) is 3% by mass with respect to the total solid content of the resin composition. An antireflection film was produced in the same manner as in Example 4 except that a curable resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Comparative Example 5.

[Comparative Example 6]
As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that the corona treatment was performed instead of the glow discharge treatment. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Comparative Example 6.

[Comparative Example 7]
As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that 5% NaOH, 25 ° C., and 30 seconds of alkali treatment were performed instead of the glow discharge treatment. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Comparative Example 7.

[Example 12]
As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that 5% NaOH, 45 ° C., and 2 minutes of alkali treatment were performed instead of the glow discharge treatment. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 12.

[Example 13]
As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that 5% NaOH, 45 ° C., and 5 minutes of alkali treatment were performed instead of the glow discharge treatment. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 13.

  When the addition amount of silica particles was small as in Comparative Example 4, peeling occurred in the entire cross hatch in the sliding test using alcohol wipe. Further, when acrylic particles were used instead of silica particles as in Comparative Example 5, as in Comparative Example 4, in the sliding test with alcohol wipe, peeling occurred on the entire cross hatch.

On the other hand, when silica particles having an average particle diameter of 20 nm or more and 100 nm or less are contained in the range of 20% by mass or more and 50% by mass or less with respect to the entire solid content of the resin composition as in Examples 8 to 11, alcohol wipes In the sliding test, the improvement in adhesion was observed.

  Further, when the corona treatment was performed as the surface treatment as in Comparative Example 6, peeling occurred on the entire cross hatch in the sliding test using the alcohol wipe. In addition, as in Comparative Example 7, when the surface treatment was performed with an alkali treatment of 5% NaOH, 25 ° C., and 30 seconds, peeling occurred on the entire cross hatch in the sliding test using an alcohol wipe.

  On the other hand, when the alkali treatment was carried out as in Examples 12 and 13, an improvement in adhesion was observed in a sliding test using an alcohol wipe. In addition, when the alkali treatment was performed with warming, the evaluation of the sliding test with an alcohol wipe was worse than when the glow discharge treatment was performed. This is probably because the alkali treatment is a wet treatment, and the shape of the exposed silica particles at the interface between the hard coat layer and the adhesion layer is linear.

DESCRIPTION OF SYMBOLS 10 Hard coat layer, 11 Metal oxide particle, 12 Adhesion layer, 20 Functional layer, 30 Base material, 40 Antireflection layer, 50 Antifouling layer

Claims (10)

A hard coat layer in which metal oxide particles are exposed on the surface;
A laminated thin film comprising: a metal oxide particle exposed surface of the hard coat layer, and an adhesion layer made of a metal oxide or metal of the same oxygen deficiency state as the metal oxide particles.   2. The laminated thin film according to claim 1, wherein the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles exposed on the surface of the hard coat layer is 60% or less.   2. The laminated thin film according to claim 1, wherein the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles exposed on the surface of the hard coat layer is 10% or more and 30% or less.   The laminated thin film according to any one of claims 1 to 3, wherein an average particle diameter of the metal oxide particles is 20 nm or more and 100 nm or less.   5. The laminated thin film according to claim 1, wherein the content of the metal oxide particles is 20% by mass or more and 50% by mass or less based on the entire solid content of the resin composition of the hard coat layer. . The metal oxide particles are made of SiO ₂ ;
The laminated thin film according to claim 1, wherein the adhesion layer is made of SiO _x (0 ≦ x <2).   The antireflection layer according to any one of claims 1 to 6, further comprising an antireflection layer in which a high refractive index layer and a low refractive index layer having a lower refractive index than the high refractive index layer are alternately stacked on the adhesion layer. Laminated thin film.   The hard coat layer photopolymerizes an ultraviolet curable resin containing a urethane (meth) acrylate oligomer, a tri- or higher-functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a photopolymerization initiator. The laminated thin film according to claim 1, wherein the laminated thin film is formed. An exposure step of exposing the metal oxide particles on the surface of the hard coat layer containing the metal oxide particles;
A film forming step of forming an adhesion layer made of a metal oxide or metal of the same kind as that of the metal oxide particles on the exposed surface of the metal oxide particles of the hard coat layer. The method for producing a laminated thin film according to claim 9, wherein in the exposing step, the metal oxide particles are exposed by glow discharge treatment.