KR20190130683A - Laminated thin film and method for producing laminated thin film - Google Patents

Abstract

The laminated thin film which is excellent in adhesiveness between an organic layer and an inorganic layer, and the manufacturing method of a laminated thin film are provided. The metal is formed on the hard coat layer 10 in which the metal oxide particles 11 are exposed on the surface, and on the metal oxide particle exposed surface of the hard coat layer 10, and has a metal in the same oxygen-deficient state as the metal oxide particles 11. The adhesion layer 12 which consists of an oxide or a metal is provided. Thereby, since the adhesion layer 12 adheres strongly with the resin of the hard-coat layer 10, and adheres more firmly with the exposed metal oxide particle 11, excellent adhesiveness can be obtained.

Description

Laminated thin film and the manufacturing method of laminated thin film {LAMINATED THIN FILM AND METHOD FOR PRODUCING LAMINATED THIN FILM}

The present invention relates to a laminated thin film excellent in adhesion between the organic layer and the inorganic layer, and a method for producing the laminated thin film. This application is priority based on Japanese Patent Application No. 2015-107978, filed May 27, 2015 in Japan, and Japanese Patent Application No. 2016-105680, filed May 26, 2016 in Japan. This application is hereby incorporated by reference herein.

As an example of a laminated thin film, the antireflection film which formed the AR (Anti-Reflective) layer by a dry process on the hard-coat layer with a relatively high surface hardness is mentioned (for example, refer patent document 1).

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

(Patent Document 1) JP 11-218603 A

The present invention has been proposed in view of such a conventional situation, and provides a laminated thin film excellent in adhesion between the organic layer and the inorganic layer, and a method of manufacturing the laminated thin film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventor exposes a metal oxide particle to the surface of the hard-coat layer containing a metal oxide particle, and the adhesion layer which consists of a metal oxide or metal of the oxygen-depletion state of the same kind as a metal oxide particle on that surface It was found that the adhesion between the organic layer and the inorganic layer was remarkably improved by forming a film.

That is, the laminated thin film which concerns on this invention is formed into the hard-coat layer by which metal oxide particle is exposed on the surface, and the oxygen deficiency which has the metal of the same kind as the said metal oxide particle by being formed into the metal oxide particle exposed surface of the said hard-coat layer. It is characterized by including the adhesion layer which consists of a metal of the state or the metal of the same kind with the said metal oxide particle.

Moreover, the manufacturing method of the laminated thin film which concerns on this invention is an exposure process which exposes a metal oxide particle to the surface of the hard-coat layer containing metal oxide particle, and the said metal on the metal oxide particle exposed surface of the said hard-coat layer. It is characterized by having the film-forming process of forming the adhesion layer which consists of a metal oxide of the oxygen deficiency state which has a metal of the same kind as an oxide particle, or a metal of the same kind with the said metal oxide particle.

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

FIG. 1: is sectional drawing which shows typically the hard-coat layer which the metal oxide particle which concerns on this embodiment was exposed.
2 is a cross-sectional view schematically showing the laminated thin film according to the present embodiment.
3 is a cross-sectional view schematically showing an antireflection film to which the present invention is applied.
4: is a photograph which shows the evaluation example of a cross hatch test, FIG. 4 (A) shows peeling in part, and FIG. 4 (B) shows peeling in part, and FIG. 4 (C) shows peeling in all Indicates if
FIG. 5A is a photograph of a TEM cross section of Example 3, and FIG. 5B is a photograph of a TEM cross section of Comparative Example 1. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail in the following order, referring drawings.

1. Laminated Thin Film

2. Anti-reflection film

3. Manufacturing method of laminated thin film

4. Examples

<1. Laminated Thin Films ＞

FIG. 1: is sectional drawing which shows typically the hard-coat layer which the metal oxide particle which concerns on this embodiment was exposed, and FIG. 2 is sectional drawing which shows typically the laminated thin film which concerns on this embodiment. The laminated thin film which concerns on this embodiment is formed into the hard-coat layer 10 which the metal oxide particle 11 is exposed to the surface, and the metal oxide particle exposed surface of the hard-coat layer 10, and is formed into a metal oxide particle 11 ) And an adhesion layer 12 made of a metal oxide or metal oxide particle 11 in the oxygen-deficient state having the same metal as the same metal. Moreover, it forms on the adhesion layer 12, and further includes the functional layer 20 which consists of an inorganic layer. According to such a structure, since the adhesion layer 12 adheres strongly to the resin of the hard coat layer 10 and adheres more firmly to the exposed metal oxide particles 11, the adhesion layer 12 adheres closely to the hard coat layer 10. The adhesiveness of the layer 12 can be improved, and the scratch resistance of a laminated thin film can be improved.

[Hard coat layer]

In the hard coat layer 10, the metal oxide particles 11 are dispersed in the resin material, and the metal oxide particles 11 are exposed on the surface. As a resin material of the hard-coat layer 10, ultraviolet curable resin, electron beam curable resin, thermosetting resin, thermoplastic resin, 2 liquid mixed resin, etc. are mentioned, for example. Among these, it is preferable to use the ultraviolet curable resin which can form the hard-coat layer 10 efficiently by ultraviolet irradiation.

As ultraviolet curable resin, an acryl type, a urethane type, an epoxy type, polyester type, an amide type, silicone type etc. are mentioned, for example. Among these, it is preferable to use the acryl system from which high transparency is obtained, for example, when making a laminated thin film into an optical use.

Acrylic ultraviolet curable resin is not specifically limited, From a bifunctional, trifunctional or more than trifunctional polyfunctional monomer, an oligomer, a polymer component, etc., it can select suitably and mix | blend in consideration of hardness, adhesiveness, workability, etc .. 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 -Decane diol 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, and the like. As a specific example available in the market, Sartomer Co., Ltd. brand name "SR610" etc. are mentioned, for example.

As a specific example of a trifunctional or more than trifunctional acrylate component, pentaerythritol triacrylate (PETA), 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO conversion triacrylate, (epsilon)- Caprolactone modified tris- (2-acryloxyethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), epsilon -caprolactone modified tris (acryloxyethyl) acrylate, and the like. As a specific example available on the market, the brand name "CN968" of a Satomer, the brand name "SR444" of a Satomer, etc. are mentioned, for example.

As a specific example of a photoinitiator, an alkylphenone type photoinitiator, an acylphosphine oxide type photoinitiator, a titanocene type photoinitiator, etc. are mentioned, for example. As a specific example available on the market, 1-hydroxycyclohexylphenyl ketone (IRGACURE184, BASF Japan Co., Ltd.), etc. are mentioned.

Moreover, it is preferable that acrylic ultraviolet curable resin contains a leveling agent in order to improve smoothness. As a specific example of a leveling agent, a silicone type leveling agent, a fluorine type leveling agent, an acryl type leveling agent, etc. are mentioned, These can use 1 type (s) or 2 or more types. Among these, it is preferable to use a silicone type leveling agent from a coating-film viewpoint. As a specific example available on the market, the brand name "BYK337" (polyether modified polydimethylsiloxane) etc. of Big Chemi Japan Co., Ltd. are mentioned, for example.

Moreover, if the solvent used for acrylic ultraviolet curable resin satisfy | fills the applicability | paintability of a resin composition, it will not specifically limit, It is preferable to select 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, and 2-hep Tanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, etc. are mentioned, These 1 type, or 2 or more types can be used. Among these, it is preferable to use propylene glycol monomethyl ether acetate and butyl acetate from a coatability viewpoint. Moreover, in addition to the above, acrylic ultraviolet curable resin can contain a function imparting agent, such as a color adjuster, a coloring agent, a ultraviolet absorber, an antistatic agent, various thermoplastic resin materials, refractive index adjusting resin, refractive index adjusting particle, and adhesiveness provision resin.

The metal oxide particle 11 consists of a metal oxide in the form of a particle | grain, It is preferable that the average particle diameter is 800 nm or less, More preferably, it is 20 nm or more and 100 nm or less. When the average particle diameter of the metal oxide particle 11 is too large, it becomes difficult to make a laminated thin film into an optical use, and when the average particle diameter is too small, the adhesiveness of the hard-coat layer 10 and the contact bonding layer 12 will fall. In addition, in this specification, an average particle diameter means the value measured by the 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. When there is too little content of the metal oxide particle 11, the adhesiveness of the hard-coat layer 10 and the contact bonding layer 12 will fall, and when too much, the flexibility of the hard-coat layer 10 etc. will fall. In addition, solid content of a resin composition is all components other than a solvent, and a liquid monomer component is 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 , Ta ₂ O ₅ , Sb ₂ O ₃ , SnO ₂ , MnO ₂ , and the like. Among these, it is preferable to use the silica from which high transparency is obtained, for example, when making a laminated thin film into an optical use. As a specific example available on the market, Nissan Chemical Co., Ltd. brand name "IPA-ST-L" (silica sol) etc. are mentioned, for example. Moreover, you may introduce 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, the metal oxide particles 11 are exposed and protrude on the surface of the hard coat layer 10. As an exposure method of the metal oxide particle 11, if the resin of the hard-coat layer 10 can be selectively etched as mentioned later, it will not specifically limit, For example, a glow discharge process, a plasma process, ion etching, Alkali treatment etc. can be used.

It is preferable that the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particle 11 exposed on the hard-coat layer 10 surface is 60% or less, More preferably, it is 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 from the resin, the adhesion between the hard coat layer 10 and the adhesion layer 12 is lowered, and the protruding ratio is too small. The effect of improving adhesiveness is not obtained.

Moreover, the hard-coat layer 10 is a ultraviolet curable resin containing a urethane (meth) acrylate oligomer, a trifunctional or more (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a photoinitiator. It is preferable to carry out photopolymerization. By using such a photocurable resin composition, the hard-coat layer 10 which has the outstanding hardness can be obtained.

[Adhesive layer]

The adhesion layer 12 is formed on the exposed surface of the metal oxide particles of the hard coat layer 10, and is the same as the metal oxide or metal oxide particles 11 in the oxygen-deficient state having the same metal as the metal oxide particles 11. Made of metal. Examples of the metal oxides in the oxygen deficient state include SiO _x , AlO _x , TiO _x , ZrO _x , CeO _x , MgO _x , ZnO _x , TaO _x , SbO _x , SnO _x , MnO _x , and the like. Here, the metal oxide of an oxygen deficiency state means the metal oxide of the state in which oxygen water is lacking rather than stoichiometric composition. Moreover, Si, Al, Ti, Zr, Ce, Mg, Zn, Ta, Sb, Sn, Mn etc. are mentioned as a metal. For example, the x has a range from 0 (inclusive) to 2.0 in, SiO _x of the adhesive layer 12 when the metal oxide particles 11 is an SiO _2.

The oxidation degree and film thickness of the adhesion layer 12 can be designed suitably according to the functional layer 20 formed into a film 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. It is preferable that it is 1.9 or more. In addition, the film thickness of the adhesion layer 12 is preferably smaller than 50% of the average particle diameter of the metal oxide particles 11 exposed on the surface of the hard coat layer 10, specifically, 1 nm to 50 nm. It is preferable that it is 1 nm-30 nm, and it is still more preferable that it is 1 nm-10 nm.

[Functional layer]

The functional layer 20 is an inorganic layer formed on the adhesion layer 12. As the functional layer 20, optical layers, such as an antireflection layer, a phase difference layer, and a polarizing layer, are mentioned, for example. Since such an optical layer is an inorganic layer formed by sputtering, for example, thermal dimensional stability can be improved compared with an organic layer.

Since the hard coat layer 10 and the adhesion layer 12 are firmly adhere | attached by the metal oxide particle 11, the laminated thin film which consists of such a structure can obtain the outstanding adhesiveness. In particular, when the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particle exposed to the hard-coat layer 10 surface is 60% or less, More preferably, it is 10% or more and 30% or less, and it is the inside of a xenon lamp. Excellent adhesiveness can also be obtained also in a light test.

<2. Antireflection Film

Next, an antireflection film will be described as an example of the above-described laminated thin film. 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 includes a substrate 30, a hard coat layer 10 on which metal oxide particles 11 are exposed on the surface, and a metal oxide particle exposed surface of the hard coat layer 10. It is formed into a film, and the adhesion layer 12 which consists of a metal oxide or metal of the oxygen-depleted state of the same kind as the metal oxide particle 11, the antireflection layer 40, and the antifouling layer 50 is provided.

Although the base material 30 is not specifically limited, Specifically, PET (Polyethylene terephthalate), resin (COP) which has alicyclic structure in the main chain which uses a cycloolefin as a monomer, and cyclic olefin (for example, norbornene) Resin (COC) obtained by addition polymerization of alpha-olefin (for example, ethylene), TAC (triacetyl cellulose), etc. are mentioned. Although the thickness of the base material 30 differs according to the kind and performance of the optical apparatus to which it is applied, it is 25-200 micrometers normally, Preferably it is 40-150 micrometers.

The hard coat layer 10 and the adhesion layer 12 are the same as the laminated thin film mentioned above. In the antireflection film to which the present invention is applied, it is preferable that 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). Moreover, it is preferable that the thickness of the hard-coat layer 10 is 0.5-20 micrometers normally, Preferably it is 1-15 micrometers, and the film thickness of the contact bonding layer 12 is 10 nm or less.

In the antireflection layer 40, a high refractive index layer made of a dielectric material and a low refractive index layer having a lower refractive index than the high refractive index layer are alternately formed by sputtering. As the high refractive index dielectric, Nb ₂ O ₅ or TiO ₂ is used. As the low refractive index dielectric, SiO ₂ is preferably used.

The antifouling layer 50 is a coating layer of the alkoxysilane compound which has a perfluoropolyether group, for example. By coating the alkoxysilane compound which has a perfluoro polyether group, a water contact angle shows water repellency of 110 degree or more, and antifouling property can be improved.

Since the antireflection film which consists of such a structure is excellent in scratch resistance, it can be used suitably as a laminated film for touch panels, for example. Moreover, by laminating such a laminated film for touch panels on image display elements, such as a liquid crystal display element and an organic electroluminescent display element, it can apply suitably as an image display / input device of a smartphone or a personal computer.

<3. Manufacturing Method of Laminated Thin Film>

The manufacturing method of the laminated thin film which concerns on this embodiment is an exposure process which exposes a metal oxide particle to the surface of the hard-coat layer containing metal oxide particle, and the said metal oxide on the metal oxide particle exposed surface of the said hard-coat layer. It has a film-forming process which forms the adhesion layer which consists of a metal oxide or a metal of the oxygen-deficient state of the same kind as particle | grains. Hereinafter, an exposure process and a film-forming process are demonstrated.

[Exposure process]

First, the metal oxide particle 11, a urethane (meth) acrylate oligomer, a trifunctional or more (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a photoinitiator are contained, for example. The ultraviolet curable 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 apply | coated on a base material. The coating method is not particularly limited, and a known method can be used. As a well-known coating method, for example, the microgravure coating method, the wire bar coating method, the direct gravure coating method, the die coating method, the dip method, the spray coating method, the reverse roll coating method, the curtain coating method, the comma coating method, the knife A coating method, a spin coating method, etc. are mentioned.

Next, the hard coat layer 10 is formed by drying and photocuring the ultraviolet curable resin composition on a base material. Drying conditions are not specifically limited, Natural drying may be sufficient, and artificial drying which adjusts drying humidity, drying time, etc. may be sufficient. However, in the case of blowing air to the surface of the paint during drying, it is preferable that the rubbing does not occur on the surface of the coating film. This is because when a rumor occurs, the appearance of the coating is deteriorated and the thickness variation of the surface property occurs. As light for curing the ultraviolet curable resin composition, energy rays such as gamma rays, alpha rays, and electron beams can be applied in addition to ultraviolet rays.

Next, the surface of the hard coat layer 10 is etched and the metal oxide particles 11 are exposed as shown in FIG. 1. As an exposure method of the metal oxide particle 11, if resin of the hard-coat layer 10 can be selectively etched, it will not specifically limit, For example, glow discharge treatment, plasma treatment, ion etching, alkali treatment, etc. Can be used. Among these, it is preferable to use the glow discharge process which can process a large area.

A glow discharge process arrange | positions two flat electrodes which oppose in the tank which can be evacuated by vacuum, and performs it with the processing apparatus which a film runs in parallel between the electrodes. In addition, this processing apparatus may be provided in the film-forming apparatus.

Atmospheric gas is introduced after exhausting the inside of the processing chamber by, for example, 0.01 kPa or less. The pressure in the processing chamber at this time is not particularly limited as long as the glow discharge can be maintained, but is usually in the range of 0.1 to 100 kPa. Although an inert gas is mainly used as an atmospheric gas, hydrogen, oxygen, nitrogen, fluorine, chlorine gas, etc. may be sufficient. Moreover, the gas which mixed these may be sufficient. Examples of the inert gas include helium, neon, argon, krypton, xenon, radon, and the like. Among these, helium gas and argon gas are preferable from the ease of acquisition, and argon gas is preferable especially in terms of price.

After the introduction of the atmosphere gas, glow discharge occurs by applying a voltage of several hundred V between the opposing electrodes. The film is continuously passed through the area where the glow discharge has occurred, and the film surface is modified by the atmospheric gas ionized.

The glow treatment can exhibit its strength and weakness by the energy density (W / m 2) and the treatment time (min) at the time of discharge. Moreover, in the case of a continuous winding type apparatus, processing time becomes the value which divided length m of a process area | region (length in the direction along the film of an electrode) by winding speed (m / min). The processing intensity is obtained by multiplying the processing time by the power density (W / m 2) at the time of glow discharge and represented by the following formula.

Treatment intensity (W · min / ㎡) = power density (W / ㎡) × treatment area length (m) ÷ feed rate (m / min)

That is, the film which differs in processing strength can be manufactured by changing input power and transmission speed.

It is preferable that it is 200-4150 W * min / m <2>, and, as for the process intensity (power x processing time / processing area, unit: W * min / m <2>) of a glow discharge process, it is more preferable that it is 420-2100 W * min / m <2>. . The greater the processing strength, the more plasma is generated on the surface of the hard coat layer, and the greater the protruding ratio of the metal oxide particles 11.

It is preferable that the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particle 11 is 60% or less, More preferably, it is 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 from the resin, and the adhesion between the organic layer and the inorganic layer is lowered. If the protruding ratio is too small, the effect of improving the adhesion is not obtained. .

Moreover, it is preferable that arithmetic mean roughness Ra of the hard-coat layer surface after an etching is 2 nm or more and 12 nm or less, and it is more preferable that they are 4 nm or more and 8 nm or less. If the arithmetic mean roughness Ra on the surface of the hard coat layer is too small, the protruding ratio of the metal oxide particles 11 is not sufficient, and if the arithmetic mean roughness Ra is too large, the metal oxide particles 11 are removed from the hard coat layer 10. ) Tends to be easily peeled off.

[Film forming process]

In the film-forming process, the adhesion layer 12 which consists of a metal oxide or metal of the oxygen-deficient state of the same kind as the metal oxide particle 11 is formed into the metal oxide particle exposed surface of the hard-coat layer 10. As a film-forming method of the contact bonding 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 to use reactive sputtering by the mixed gas atmosphere of oxygen gas and argon gas. Moreover, since functional layers 20, such as an anti-reflection layer, a phase difference layer, and a polarizing layer, which are formed on the adhesion layer 12, can also be formed by sputtering, productivity can be improved.

Thus, by forming the adhesion layer 12 on the hard-coat layer 10 which exposed the metal oxide particle, in addition to the big adhesion of resin of the adhesion layer 12 and the hard-coat layer 10, the adhesion layer 12 ) And even greater adhesion between the metal oxide particles 11 can be obtained.

Example

<4. Example>

In the present Example, the antireflection film was produced and the adhesiveness of a hard-coat layer and AR layer was evaluated by the cross hatch test. In addition, this invention is not limited to these Examples.

<4.1 first embodiment>

In Example 1, the influence on the adhesiveness of the protrusion ratio of the filler on the hard-coat layer surface was verified. The calculation of the protrusion height and the protrusion ratio of the filler on the hard coat layer surface, the measurement of the surface roughness (Ra) of the hard coat layer, and the 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]

The cross section of the antireflection film was observed using a transmission electron microscope (TEM), and the minimum and maximum values of the protrusion height of the filler on the surface of the hard coat layer were measured. And the average particle diameter of the filler was divided about each of the minimum value and the highest value of the protrusion height of a filler, and the minimum value (%) and the maximum value (%) of the protrusion ratio with respect to the average particle diameter of a filler were computed. Moreover, the average value (%) of the protrusion ratio with respect to the average particle diameter of a filler was computed from the minimum value (%) and maximum value (%) of the protrusion ratio with respect to the average particle diameter of a filler.

[Measurement of Surface Roughness (Ra) of the Hard Coat Layer]

Arithmetic mean roughness (Ra) of the surface of the hard coat layer was measured using Atomic Force Microscopy (AFM).

[Evaluation of cross hatch examination]

100 cross hatches (eyes) of 1 mm x 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 crosshatch surface was observed and evaluated. Moreover, after performing the alcohol wipe sliding test after the environment introduction of the temperature of 90 degreeC-Dry (low humidity) -time 500 h, the surface state of the crosshatch surface was observed and evaluated. Moreover, after performing the alcohol wipe sliding test after the environment introduction of the temperature of 60 degreeC-humidity 95% -time 500 h, the surface state of the crosshatch surface was observed and evaluated. Moreover, after carrying out the alcohol wipe sliding test after the environment input of xenon irradiation (xenon arc lamp, 7.5 kW) -time 60 h, the surface state of the cross hatch surface was observed. In addition, the alcohol wipe sliding test was performed by pushing the wipe which apply | coated ethyl alcohol to the crosshatch surface at 250 g / cm <2> of loads to the antireflection film, and sliding the distance of 10 cm back and forth 500 times.

Evaluation of the cross hatch test, as a result of observing the surface state of the cross hatch surface, when the peeling does not occur in the cross hatch as shown in Fig. 4 (A), peeled to a part of the cross hatch as shown in Fig. 4 (B). (Triangle | delta) and the case where peeling generate | occur | produced in all the cross hatches like FIG.

EXAMPLE 1

The content of the silica particle with an average particle diameter of 50 nm prepared the photocurable resin composition which is 28 mass% with respect to the solid content whole of a resin composition. As shown in Table 1, the resin composition was prepared by dissolving a silica particle, an acrylate, a leveling agent, and a photoinitiator in a solvent.

After using PET film as a base material and apply | coating the said photocurable resin composition on the PET film with the bar coater, the resin composition was photopolymerized and the hard-coat layer of thickness 5micrometer was formed.

Next, the surface treatment of the hard coat layer was performed with the processing intensity of the glow discharge treatment being 8300 W · min / m 2. In Table 2, the protrusion height of the filler on the hard-coat layer surface in Example 1, the protrusion ratio of a filler, and surface roughness Ra are shown.

After the glow discharge treatment, an adhesion layer made of SiO _x having a thickness of 10 nm was 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 was formed on the adhesion layer. Was formed. Furthermore, the antifouling layer of thickness 10nm which consists of the alkoxysilane compound which has a perfluoropolyether group was formed on AR layer, and the antireflection film of Example 1 was manufactured. The reflectance of this antireflection film was 0.5% or less, and the water contact angle was 110 degrees or more. In Table 2, evaluation of the cross hatch test of the antireflection film in Example 1 is shown.

EXAMPLE 2

An anti-reflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed at a treatment intensity of the glow discharge treatment of 4200 W · min / m 2. In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in Example 2, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

EXAMPLE 3

An anti-reflection 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 treatment intensity of the glow discharge treatment being 2100 W · min / m 2. In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in Example 3, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

EXAMPLE 4

An antireflection film was produced in the same manner as in Example 1 except that the hard coat layer was subjected to surface treatment with a treatment intensity of the glow discharge treatment being 830 W · min / m 2. In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in Example 4, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

EXAMPLE 5

An antireflection film was produced in the same manner as in Example 1 except that the hard coat layer was subjected to surface treatment with a treatment intensity of the glow discharge treatment being 420 W · min / m 2. In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in Example 5, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

EXAMPLE 6

An antireflection film was produced in the same manner as in Example 1 except that the hard coat layer was subjected to surface treatment with a treatment intensity of the glow discharge treatment being 200 W · min / m 2. In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in Example 6, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

EXAMPLE 7

The surface treatment of the hard coat layer was carried out with the treatment intensity of the glow discharge treatment being 420 W · min / m 2, and after the glow discharge treatment, the adhesion layer made of Si having a thickness of 10 nm was formed by sputtering. In the same manner as in Example 1, an antireflection film was produced. In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in Example 7, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

[Comparative Example 1]

Except not having performed a glow discharge process, it carried out similarly to Example 1, and manufactured the antireflection film. In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in the comparative example 1, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

[Comparative example 2]

An anti-reflection film was produced in the same manner as in Example 1 except that the silica composition was not blended with the resin composition, and the surface treatment of the hard coat layer was performed at a treatment intensity of the glow discharge treatment of 830 W · min / m 2. It was. In Table 2, evaluation of the surface roughness (Ra) in the comparative example 2 and the cross hatch test of an antireflection film is shown.

[Comparative Example 3]

An antireflection film was produced in the same manner as in Example 1 except that the hard coat layer was subjected to the surface treatment of the glow discharge treatment at 830 W · min / m 2, and SiO ₂ was deposited as the adhesion layer. . In Table 2, evaluation of the protrusion height of the filler on the hard-coat layer surface in the comparative example 3, the protrusion ratio of a filler, surface roughness (Ra), and the cross hatch test of an antireflection film is shown.

When silica particle was not exposed like the comparative example 1, peeling generate | occur | produced in the whole cross hatch in the sliding test by alcohol wipe. Moreover, when surface treatment was performed without mix | blending silica particle like the comparative example 2, peeling generate | occur | produced in all the cross hatches in the sliding test by alcohol wipe similarly to the comparative example 1. Further, in the same way as in Comparative Example 1 when the deposition of SiO ₂ as an adhesive layer as in Comparative Example 3, in the sliding test by an alcohol wipe, the peeling occurred in all the cross-hatch.

On the other hand, in the sliding test by alcohol wipe, the adhesiveness improvement was seen by exposing a silica particle like Example 1-7. 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 Comparative Example 1 shown to FIG. 5 (B) are compared, in Example 3, the interface of a hard-coat layer and an adhesion layer While it is circular in shape by exposure of this silica particle, it turns out that exposure of a silica particle contributes to the improvement of adhesiveness also in being linear in Comparative Example 1.

Moreover, when the average value of the protrusion ratio with respect to the average particle diameter of a metal oxide particle was 60% or less, especially 10% or more and 30% or less, the outstanding evaluation result was obtained in the sliding test by alcohol wipe.

<4.2 Second Example>

In Example 2, the influence on the adhesiveness of the average particle diameter and addition amount of the filler of a hard-coat layer was verified. Moreover, the influence on the adhesiveness of the kind of the filler of a hard-coat layer, and an adhesion layer was verified. Moreover, the surface treatment methods other than a glow discharge treatment were examined. In addition, evaluation of the cross hatch test of the antireflection film was performed similarly to the 1st Example.

EXAMPLE 8

As shown in Table 3, content of the silica particle (brand name: MEK-ST-Z, Nissan Chemical Industry Co., Ltd.) of an average particle diameter of 100 nm is a photocurable resin composition which is 28 mass% with respect to the whole solid content of a resin composition. Except having prepared, it carried out similarly to Example 4, and manufactured the anti-reflection film. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 8 is shown.

EXAMPLE 9

As shown in Table 3, content of the silica particle (brand name: MEK-ST-40, Nissan Chemical Industry Co., Ltd.) of 20 nm of average particle diameters is 28 mass% with respect to the solid content of the resin composition, Except having prepared, it carried out similarly to Example 4, and manufactured the anti-reflection film. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 9 is shown.

EXAMPLE 10

As shown in Table 3, content of the silica particle (brand name: MEK-ST-Z, Nissan Chemical Industries, Ltd.) of an average particle diameter of 100 nm is the photocurable resin composition which is 20 mass% with respect to the solid content of the resin composition. Except having prepared, it carried out similarly to Example 4, and manufactured the anti-reflection film. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 10 is shown.

EXAMPLE 11

As shown in Table 3, content of the silica particle (brand name: MEK-ST-40, Nissan Chemical Industries, Ltd.) of 20 nm of average particle diameters is 50 mass% with respect to the whole solid content of a resin composition, The photocurable resin composition Except having prepared, it carried out similarly to Example 4, and manufactured the anti-reflection film. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 11 is shown.

EXAMPLE 12

As shown in Table 3, content of the silica particle (IPA-ST-L, Nissan Chemical Co., Ltd.) of an average particle diameter of 50 nm prepared the photocurable resin composition which is 20 mass% with respect to the whole solid content of a resin composition. Except for the above, an antireflection film was produced in the same manner as in Example 4. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 12 is shown.

EXAMPLE 13

As shown in Table 3, content of the silica particle (IPA-ST-L, Nissan Chemical Co., Ltd.) of 50 nm of average particle diameter prepared the photocurable resin composition which is 50 mass% with respect to the solid content whole of a resin composition. Except for the above, an antireflection film was produced in the same manner as in Example 4. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 13 is shown.

[Comparative example 4]

As shown in Table 3, content of the silica particle (IPA-ST-L, Nissan Chemical Co., Ltd.) of an average particle diameter of 50 nm prepared the photocurable resin composition which is 10 mass% with respect to the solid content whole of a resin composition. Except for the above, an antireflection film was produced in the same manner as in Example 4. In Table 3, evaluation of the cross hatch test of the antireflection film in the comparative example 4 is shown.

[Comparative Example 5]

As shown in Table 3, the photocurable resin composition whose content of the acrylic particle (brand name: SSX-101, Sekisui Chemical Co., Ltd.) of an average particle diameter of 1 micrometer is 3 mass% with respect to the solid content whole of a resin composition. Except having prepared, it carried out similarly to Example 4, and manufactured the antireflection film. In Table 3, evaluation of the cross hatch test of the antireflection film in the comparative example 5 is shown.

[Comparative Example 6]

As shown in Table 3, it carried out similarly to Example 4 except having performed the corona treatment instead of the glow discharge treatment, and produced the antireflection film. In Table 3, evaluation of the cross hatch test of the antireflection film in the comparative example 6 is shown.

[Comparative Example 7]

As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that the alkali treatment was performed for 5% NaOH, 25 ° C, and 30 seconds instead of the glow discharge treatment. In Table 3, evaluation of the cross hatch test of the antireflection film in the comparative example 7 is shown.

EXAMPLE 14

As shown in Table 3, the antireflection film was produced like Example 4 except having performed 5% NaOH, 45 degreeC, and alkali treatment for 2 minutes instead of the glow discharge process. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 14 is shown.

EXAMPLE 15

As shown in Table 3, the antireflection film was produced like Example 4 except having performed 5% NaOH, 45 degreeC, and alkali treatment for 5 minutes instead of the glow discharge process. In Table 3, evaluation of the cross hatch test of the antireflection film in Example 15 is shown.

When the addition amount of silica particle was small like the comparative example 4, peeling generate | occur | produced in the whole cross hatch in the sliding test by alcohol wipe. Moreover, when acrylic particle was used instead of silica particle like the comparative example 5, peeling generate | occur | produced in all the cross hatches in the sliding test by alcohol wipe similarly to the comparative example 4.

On the other hand, when the silica particle whose average particle diameter is 20 nm or more and 100 nm or less is contained in 20 mass% or more and 50 mass% or less with respect to the whole solid content of a resin composition like Examples 8-15, the sliding test by alcohol wipes WHEREIN: The improvement of adhesiveness was seen. In particular, when content of a silica particle is 50 mass% or less 20 mass% or more of the whole solid content of a resin composition with respect to the average particle diameter of 20 nm-100 nm of a silica particle like Example 10, 11, xenon irradiation (xenon arc Excellent adhesion was obtained in the alcohol wipe sliding test after the lamp was charged with an environment of 7.5 kW) -hour 60 h.

Moreover, when corona treatment was performed as a surface treatment like the comparative example 6, peeling generate | occur | produced in all the cross hatches in the sliding test by alcohol wipe. Moreover, also when the alkali treatment for 5% NaOH, 25 degreeC, and 30 second was performed as a surface treatment like the comparative example 7, in the sliding test by alcohol wipe, peeling generate | occur | produced in all the cross hatches.

On the other hand, when the alkali treatment was heated and carried out as in Examples 14 and 15, in the sliding test by the alcohol wipe, an improvement in adhesion was observed. Moreover, when the alkali process was heated and performed, evaluation of the sliding test by alcohol wipe was bad compared with the case where the glow discharge process was performed. This is considered to be because the alkali treatment is a wet treatment, and the shape due to exposure of the silica particles at the interface between the hard coat layer and the adhesive layer has become a straight line.

10: hard coat layer
11: metal oxide particles
12: adhesion layer
20: functional layer
30: description
40: antireflection layer
50: antifouling layer

Claims (12)

A hard coat layer formed by exposing metal oxide particles to a surface thereof;
It is formed on the metal oxide particle exposed surface of the said hard-coat layer, and is provided with the contact | adhesion layer which consists of a metal oxide of the oxygen deficiency state which has a metal of the same kind as the said metal oxide particle, or a metal of the same kind as the said metal oxide particle,
Arithmetic mean roughness Ra of the said hard-coat layer surface is 2 nm or more and 12 nm or less, The laminated thin film. The method of claim 1,
The laminated thin film whose average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particle exposed on the said hard-coat layer surface is 60% or less. The method of claim 1,
The laminated thin film whose average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particle exposed to the said hard-coat layer surface is 10% or more and 30% or less. The method according to any one of claims 1 to 3,
The laminated thin film whose average particle diameter of the said metal oxide particle is 20 nm or more and 100 nm or less. The method according to any one of claims 1 to 3,
Laminated thin film whose content of the said metal oxide particle is 20 mass% or more and 50 mass% or less with respect to the whole solid content of the resin composition of the said hard-coat layer. The method according to any one of claims 1 to 3,
The laminated thin film whose content of the said metal oxide particle is 50 mass% or less 20 mass% or more of the whole solid content of a resin composition with respect to the average particle diameter of 20 nm or more and 100 nm or less of the said metal oxide particle. The method according to any one of claims 1 to 3,
The laminated thin film whose film thickness of the said contact layer is smaller than 50% of the average particle diameter of the metal oxide particle exposed on the said hard-coat layer surface. The method according to any one of claims 1 to 3,
The metal oxide particles are made of SiO ₂ ,
The adhesion layer is made of _{SiO x (0 ≤ x <2} ), multi-layered thin film. The method according to any one of claims 1 to 3,
A laminated thin film 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 laminated on the adhesion layer. The method according to any one of claims 1 to 3,
The hard coat layer is formed by photopolymerizing a urethane (meth) acrylate oligomer, a trifunctional or higher (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and an ultraviolet curable resin containing a photoinitiator, Laminated thin film. An exposure step of exposing the metal oxide particles to the surface of the hard coat layer containing the metal oxide particles;
It has a film-forming process which forms the adhesion layer which consists of a metal oxide of the oxygen deficiency state which has a metal of the same kind as the said metal oxide particle, or a metal of the same kind as the said metal oxide particle, on the metal oxide particle exposed surface of the said hard-coat layer,
Arithmetic mean roughness Ra of the said hard-coat layer surface is 2 nm or more and 12 nm or less, The manufacturing method of the laminated thin film. The method of claim 11,
The said exposure process WHEREIN: The manufacturing method of the laminated thin film which exposes a metal oxide particle by a glow discharge process.

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