CN112442206B

CN112442206B - Laminated film

Info

Publication number: CN112442206B
Application number: CN202011380675.5A
Authority: CN
Inventors: 小野行弘
Original assignee: Dexerials Corp
Current assignee: Dexerials Corp
Priority date: 2015-05-27
Filing date: 2016-05-27
Publication date: 2023-08-18
Anticipated expiration: 2036-05-27
Also published as: CN112442205A; KR20240023690A; CN112442206A; CN112442205B; KR20190130683A; CN112415638A; TWI798788B; KR102393911B1; KR102635617B1; CN112415638B; HUE055516T2; KR20220062140A; TW202144170A; WO2016190415A1

Abstract

The present application relates to a laminated film, and provides a laminated film excellent in adhesion between an organic layer and an inorganic layer. The laminated film is provided with: a hard coat layer (10) having metal oxide particles (11) exposed on the surface thereof; and an adhesion layer (12) which is formed on the exposed surface of the metal oxide particles of the hard coat layer (10) and contains the same oxygen-deficient metal oxide or metal as the metal oxide particles (11), wherein the metal oxide particles (11) are Al ₂ O ₃ 、TiO ₂ 、ZrO ₂ 、CeO ₂ 、MgO、ZnO、Ta ₂ O ₅ 、Sb ₂ O ₃ 、SnO ₂ 、MnO ₂ . As a result, the adhesion layer (12) adheres strongly to the resin of the hard coat layer (10) and adheres more strongly to the exposed metal oxide particles (11), so that excellent adhesion can be obtained.

Description

Laminated film

The application is a divisional application of China patent application of which the application date is 2016, 5, 27 and the application number is 20160028850. X, and the name is laminated film and manufacturing method of the laminated film.

Technical Field

The present application relates to a laminated film having excellent adhesion between an organic layer and an inorganic layer, and a method for producing the laminated film. The present application claims priority based on japanese patent application No. japanese patent application publication No. 2015-107978, which was filed on even 27 th 5 of japan, and japanese patent application No. japanese patent application publication No. 2016-105680, which was filed on even 26 of 2016, which applications are incorporated herein by reference.

Background

An example of the laminated film is an antireflection film in which an AR (antireflection) layer by a dry process is formed on a hard coat layer having relatively high surface hardness (for example, see patent literature 1).

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

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 11-218603

Disclosure of Invention

Problems to be solved by the application

The present application has been made in view of such conventional practical situations, and provides a laminated film having excellent adhesion between an organic layer and an inorganic layer, and a method for producing the laminated film.

Means for solving the problems

The present inventors have conducted intensive studies and as a result found that: the adhesion between the organic layer and the inorganic layer is remarkably improved by exposing the metal oxide particles on the surface of the hard coat layer containing the metal oxide particles and forming an adhesion layer containing the same oxygen-deficient metal oxide or metal as the metal oxide particles on the surface.

That is, the laminated film of the present application is characterized by comprising: a hard coating layer with metal oxide particles exposed on the surface; and an adhesion layer which forms a film on the exposed surface of the metal oxide particles of the hard coat layer and contains an oxygen-deficient metal oxide having the same kind of metal as the metal oxide particles or a metal having the same kind of metal as the metal oxide particles.

The method for producing a laminated film according to the present application is characterized by comprising: an exposure step of exposing the metal oxide particles on the surface of the hard coat layer containing the metal oxide particles; and a film forming step of forming an adhesion layer on an exposed surface of the metal oxide particles of the hard coat layer, the adhesion layer including an oxygen deficient metal oxide having a metal of the same kind as the metal oxide particles or a metal of the same kind as the metal oxide particles.

Effects of the application

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

Drawings

Fig. 1 is a cross-sectional view schematically showing a hard coat layer in which metal oxide particles are exposed according to the present embodiment.

Fig. 2 is a cross-sectional view schematically showing a laminated film according to the present embodiment.

FIG. 3A cross-sectional view schematically showing an antireflection film to which the present application is applied.

Fig. 4 is a photograph showing an evaluation example of a cross-cut test (cross-cut test), in which fig. 4 (a) shows a case where peeling does not occur, fig. 4 (B) shows a case where peeling occurs partially, and fig. 4 (C) shows a case where peeling occurs entirely.

Fig. 5 (a) is a photograph of a TEM section of example 3, and fig. 5 (B) is a photograph of a TEM section of comparative example 1.

Symbol description

10 hard coat layers, 11 metal oxide particles, 12 adhesion layers, 20 functional layers, 30 base materials, 40 anti-reflection layers and 50 anti-fouling layers.

Detailed Description

Hereinafter, embodiments of the present application will be described in detail in the following order with reference to the drawings.

1. Laminated film

2. Antireflection film

3. Method for producing laminated film

4. Examples

< 1. Laminated film >

Fig. 1 is a cross-sectional view schematically showing the hard coat layer exposed with metal oxide particles according to the present embodiment, and fig. 2 is a cross-sectional view schematically showing the laminated film according to the present embodiment. The laminated film of the present embodiment includes: a hard coat layer 10 having metal oxide particles 11 exposed on the surface thereof; and an adhesion layer 12 which is formed on the exposed surface of the metal oxide particles of the hard coat layer 10 and contains an oxygen deficient metal oxide having the same metal as the metal oxide particles 11 or a metal having the same metal as the metal oxide particles 11. Further, the functional layer 20 is formed on the adhesion layer 12 and includes an inorganic layer. With such a configuration, the adhesion layer 12 adheres strongly to the resin of the hard coat layer 10 and further adheres strongly to the exposed metal oxide particles 11, so that the adhesion between the hard coat layer 10 and the adhesion layer 12 can be improved, and the scratch resistance of the laminated film can be improved.

[ hard coating ]

With respect to the hard coat layer 10, the metal oxide particles 11 are dispersed in the resin material, and the metal oxide particles 11 are exposed at the surface. Examples of the resin material of the hard coat layer 10 include ultraviolet curable resins, electron beam curable resins, thermosetting resins, thermoplastic resins, and two-component resins. Among them, an ultraviolet curable resin capable of efficiently forming the hard coat layer 10 by ultraviolet irradiation is preferably used.

Examples of the ultraviolet curable resin include acrylic, urethane, epoxy, polyester, amide, and silicone resins. Among them, for example, when the laminated film is used for optical applications, an acrylic type which can obtain high transparency is preferably used.

The acrylic ultraviolet curable resin is not particularly limited, and may be appropriately selected from difunctional or trifunctional or higher-functional acrylic monomers, oligomers, polymer components, and the like in view of hardness, adhesion, processability, and the like. Further, a photopolymerization initiator is blended into the ultraviolet curable resin.

Specific examples of the difunctional 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, and the like. Specific examples of the commercially available products include, for example, a product name "SR610" of sandomax (ltd).

Specific examples of the trifunctional or higher acrylate component include pentaerythritol triacrylate (PETA), 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO-modified triacrylate, epsilon-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), epsilon-caprolactone-modified tris (acryloxyethyl) acrylate, and the like. Specific examples of the commercially available products include, for example, a trade name "CN968" of sartomer, a trade name "SR444" of sartomer, and the like.

Specific examples of the photopolymerization initiator include an alkylbenzene-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and a titanocene-based photopolymerization initiator. Specific examples of the commercially available compounds include 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, basf Japan Co., ltd.), and the like.

In order to improve the smoothness, the acrylic ultraviolet curable resin preferably contains a leveling agent. Specific examples of the leveling agent include silicone leveling agents, fluorine leveling agents, and acrylic leveling agents, and one or two or more of these agents may be used. Among them, from the viewpoint of film coating properties, a silicone leveling agent is preferably used. Specific examples of the commercially available products include, for example, the product name "BYK337" (polyether modified polydimethylsiloxane) of japan, pick chemical.

The solvent used for the acrylic ultraviolet curable resin is not particularly limited as long as it satisfies the coatability of the resin composition, 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 cellosolve acetate, ethyl lactate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and the like, and one or two or more of these may be used. Among them, propylene glycol monomethyl ether acetate and butyl acetate are preferably used from the viewpoint of coatability. The acrylic ultraviolet curable resin may contain a functional imparting agent such as a hue adjuster, a colorant, an ultraviolet absorber, an antistatic agent, various thermoplastic resin materials, a refractive index adjusting resin, refractive index adjusting particles, and an adhesion imparting resin, other than the above.

The metal oxide particles 11 are particles of metal oxide, and the average particle diameter thereof is preferably 800nm or less, more preferably 20nm to 100 nm. If the average particle diameter of the metal oxide particles 11 is too large, it is difficult to use the laminated film for optical applications, and if the average particle diameter is too small, the adhesion between the hard coat layer 10 and the adhesion layer 12 is lowered. In the present specification, the average particle diameter means a value measured by the BET method.

The content of the metal oxide particles 11 is preferably 20 mass% or more and 50 mass% or less with respect to the total solid content of the resin composition of the hard coat layer 10. 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 large, the bendability or the like of the hard coat layer 10 is lowered. The solid component of the resin composition means all components except the solvent, and the liquid monomer component is also contained in the solid component.

Specific examples of the metal oxide particles 11 include SiO ₂ (silica), al ₂ O ₃ (aluminum oxide), tiO ₂ (titanium dioxide), zrO ₂ (zirconium dioxide), ceO ₂ (cerium oxide), mgO (magnesium oxide), znO, ta ₂ O ₅ 、Sb ₂ O ₃ 、SnO ₂ 、MnO ₂ Etc. Among them, for example, when the laminated film is used for optical applications, silica which can obtain high transparency is preferably used. Specific examples of the commercially available products include those under the trade name "IPA-ST-L" (silica sol) of Nissan chemical Co., ltd. In order to improve the adhesion and affinity with the resin, functional groups such as acryl groups and epoxy groups may be introduced into the surface of the metal oxide particles.

As shown in fig. 1, metal oxide particles 11 are exposed and protrude 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, and for example, glow discharge treatment, plasma treatment, ion etching, alkali treatment, or the like can be used.

The average value of the protruding proportion 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, with respect to the average particle diameter. If the protruding proportion of the metal oxide particles 11 is too large, the metal oxide particles 11 are likely to peel off from the resin, and the adhesion between the hard coat layer 10 and the adhesion layer 12 is lowered, and if the protruding proportion is too small, the effect of improving the adhesion cannot be obtained.

The hard coat layer 10 is preferably formed by photopolymerization of an ultraviolet curable resin containing a urethane (meth) acrylate oligomer, a trifunctional or higher-functional (meth) acrylate monomer, a difunctional (meth) acrylate monomer, and a photopolymerization initiator. By using such a photocurable resin composition, a hard coat layer 10 having excellent hardness can be obtained.

[ sealing layer ]

The adhesion layer 12 is formed on the exposed surface of the metal oxide particles of the hard coat layer 10, and includes an oxygen deficient metal oxide having the same metal as the metal oxide particles 11 or a metal having the same metal as the metal oxide particles 11. As the oxygen-deficient metal oxide, siO may be mentioned _x 、AlO _x 、TiO _x 、ZrO _x 、CeO _x 、MgO _x 、ZnO _x 、TaO _x 、SbO _x 、SnO _x 、MnO _x Etc. Here, the oxygen-deficient metal oxide refers to a metal oxide in a state in which the number of oxygen atoms is insufficient compared with the stoichiometric composition. Further, as the metal, si, al, ti, zr, ce, mg, zn, ta, sb, sn, mn and the like can be given. For example, the metal oxide particles 11 are SiO ₂ In the case of (2), siO of the sealing layer 12 _x X in (2) is 0 or more and less than 2.0.

The oxidation degree and 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, the functional layer 20 is an Anti-Reflective layer (AR) and uses SiO ₂ In the case of the metal oxide particles 11, siO of the adhesion layer 12 _x X in (2) is preferably 0 to 1.9. The film thickness of the adhesion layer 12 is preferably less than 50% of the average particle diameter of the metal oxide particles 11 exposed on the surface of the hard coat layer 10, more preferably 1nm to 50nm, still more preferably 1nm to 30nm, and still more preferably 1nm to 10nm.

[ functional layer ]

The functional layer 20 is an inorganic layer formed on the adhesive layer 12. Examples of the functional layer 20 include an optical layer such as an antireflection layer, a retardation layer, and a polarizing layer. Such an optical layer is an inorganic layer formed by sputtering, for example, and therefore can have higher thermal dimensional stability than an organic layer.

In the laminated film having such a structure, the hard coat layer 10 and the adhesion layer 12 are firmly adhered by the metal oxide particles 11, and thus excellent adhesion can be obtained. In particular, by setting the average value of the protruding proportion of the metal oxide particles exposed on the surface of the hard coat layer 10 to 60% or less, more preferably 10% or more and 30% or less, excellent adhesion can be obtained even in the light resistance test using a xenon lamp.

< 2. Antireflection film >)

Next, an antireflection film will be described as an example of the laminated film. Fig. 3 is a cross-sectional view schematically showing an antireflection film to which the present application is applied. As shown in fig. 3, the antireflection film includes a base material 30; a hard coat layer 10 having metal oxide particles 11 exposed on the surface thereof; a sealing layer 12 which is formed on the exposed surface of the metal oxide particles of the hard coat layer 10 and contains an oxygen-deficient metal oxide or metal that is the same as the metal oxide particles 11; an anti-reflection layer 40; and an anti-fouling layer 50.

The substrate 30 is not particularly limited, and specific examples thereof include PET (polyethylene terephthalate ), a resin (COP) having an alicyclic structure in a main chain having a cycloolefin as a monomer, a resin (COC) obtained by addition polymerization of a cyclic olefin (for example, norbornene) and an α -olefin (for example, ethylene), TAC (triacetylcellulose), and the like. The thickness of the base material 30 varies depending on the type and performance of the optical device to which it is applied, and is usually 25 to 200. Mu.m, preferably 40 to 150. Mu.m.

The hard coat layer 10 and the adhesive layer 12 are similar to the laminated film described above. In the antireflection film to which the present application is applied, it is preferable that the metal oxide particles 11 of the hard coat layer 10 are SiO ₂ The sealing layer 12 is SiO _x (x is 0.5 to 1.9). The thickness of the hard coat layer 10 is usually 0.5 to 20. Mu.m, preferably 1 to 15. Mu.m, and the thickness of the adhesion layer 12 is preferably 10nm or less.

The high refractive index layers and the low refractive index layers having a lower refractive index than the high refractive index layers of the anti-reflection layer 40 formed of the dielectric are alternately formed by sputtering. As the dielectric having a high refractive index, nb is preferably used ₂ O ₅ Or TiO ₂ As the low refractive index dielectric, siO is preferably used ₂ 。

The stain-proofing layer 50 is, for example, a coating layer of an alkoxysilane compound having a perfluoropolyether group. Coating an alkoxysilane compound having a perfluoropolyether group results in exhibiting hydrophobicity with a water contact angle of 110 degrees or more, and can improve antifouling properties.

The antireflection film having such a structure is excellent in scratch resistance, and therefore can be preferably used as a laminated film for a touch panel, for example. Further, such a laminated film for a touch panel can be preferably used as an image display or input device for a smart phone or a notebook computer by laminating the laminated film on an image display element such as a liquid crystal display element or an organic EL display element.

< 3 > method for producing laminated film

The method for producing a laminated film according to the present embodiment includes: an exposure step of exposing the metal oxide particles on the surface of the hard coat layer containing the metal oxide particles; and a film forming step of forming an adhesion layer containing an oxygen deficient metal oxide or metal of the same kind as the metal oxide particles on the exposed surface of the metal oxide particles of the hard coat layer. The exposure step and the film formation step will be described below.

[ exposing step ]

First, for example, the metal oxide particles 11 and the ultraviolet curable resin composition containing the urethane (meth) acrylate oligomer, the trifunctional or higher-functional (meth) acrylate monomer, the difunctional (meth) acrylate monomer, and the photopolymerization initiator are uniformly mixed by a conventional method using a stirrer such as a disperser, and then prepared.

Next, the ultraviolet curable resin composition is coated on the substrate. The coating method is not particularly limited, and a known method can be used. Examples of known coating methods include a micro gravure coating method, a bar coating method, a direct gravure coating method, a die coating method, a dip coating method, a spray coating method, a reverse roll coating method, a curtain coating method, a corner-gap coating method, a blade coating method, and a spin coating method.

Next, the ultraviolet curable resin composition on the substrate is dried and photo-cured to form the hard coat layer 10. The drying conditions are not particularly limited, and may be natural drying or artificial drying in which drying humidity, drying time, or the like is adjusted. However, it is preferable that the surface of the coating film is not subject to wind when it is dried. This is because if wind streaks occur, deterioration of the coating appearance and uneven thickness of the surface properties occur. In addition, energy rays such as gamma rays, alpha rays, and electron rays may be used as light for curing the ultraviolet-curable resin composition, in addition to ultraviolet rays.

Next, the surface of the hard coat layer 10 is etched to expose the metal oxide particles 11 as shown in fig. 1. 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, and for example, glow discharge treatment, plasma treatment, ion etching, alkali treatment, or the like can be used. Among them, glow discharge treatment which can be performed over a large area is preferably used.

The glow discharge treatment is performed by a treatment apparatus in which two flat electrodes are disposed in opposition in a vacuum-capable chamber, and the film is moved in parallel between the electrodes. The present processing apparatus may be provided in a film forming apparatus.

The process chamber is evacuated to a vacuum of, for example, 0.01Pa or less, and then an atmosphere gas is introduced. The pressure in the processing chamber at this time is not particularly limited as long as the glow discharge can be maintained, and is usually in the range of 0.1 to 100 Pa. As the atmosphere gas, an inert gas is mainly used, and hydrogen, oxygen, nitrogen, fluorine, chlorine, and the like can be used. In addition, the mixture of these may be used. Examples of the inert gas include helium, neon, argon, krypton, xenon, and radon. Among them, helium and argon are preferable from the viewpoint of easiness of obtaining, and argon is particularly preferable in terms of price.

After the introduction of the atmosphere gas, a glow discharge was generated by applying a voltage of several 100V between the opposing electrodes. The film is continuously passed through a region where glow discharge occurs, whereby the film surface is modified by the ionized atmosphere gas.

The glow treatment can utilize energy density (W/m) ² ) And processing time (min) to indicate strength. In the case of the continuous winding apparatus, the processing time is a value obtained by dividing the length (m) of the processing region (length in the film direction of the electrode) by the winding speed (m/min). The treatment intensity is the treatment time multiplied by the power density (W/m) at the time of glow discharge ² ) The obtained value is represented by the following formula.

Treatment strength (W.min/m) ² ) =power density (W/m) ² ) X treatment area length (m)/(travel speed (m/min))

That is, by changing the input power and the traveling speed, films having different treatment strengths can be produced.

Treatment intensity of glow discharge treatment (power X treatment time/treatment area, unit: W.min/m) ² ) Preferably 200 to 4150 W.min/m ² More preferably 420 to 2100 W.min/m ² . The greater the treatment strength, the more plasma is generated on the hard coat layer surface, and the greater the protruding proportion of the metal oxide particles 11 becomes.

The average value of the protruding proportion of the metal oxide particles 11 to the average particle diameter is preferably 60% or less, more preferably 10% or more and 30% or less. If the protruding proportion of the metal oxide particles 11 is too large, the metal oxide particles 11 are likely to peel off from the resin, and the adhesion between the organic layer and the inorganic layer is lowered, and if the protruding proportion is too small, the effect of improving the adhesion cannot be obtained.

The arithmetic average roughness Ra of the hard coat layer surface after etching is preferably 2nm to 12nm, more preferably 4nm to 8 nm. If the arithmetic average roughness Ra of the hard coat surface is too small, the protruding proportion of the metal oxide particles 11 is insufficient, and if the arithmetic average roughness Ra is too large, the metal oxide particles 11 tend to be easily peeled off from the hard coat layer 10.

[ film Forming Process ]

In the film forming step, an adhesion layer 12 containing an oxygen deficient metal oxide or metal of the same kind as the metal oxide particles 11 is formed on the exposed surface of the metal oxide particles of the hard coat layer 10. As a method for forming the adhesion layer 12, sputtering using a target is preferably used. For example, in the case of forming a SiOx film, it is preferable to use a silicon target, and reactive sputtering using a mixed gas atmosphere of oxygen and argon is used. Further, the functional layer 20 such as an antireflection layer, a retardation layer, and a polarizing layer formed on the adhesive layer 12 can be formed by sputtering, and thus productivity can be improved.

By forming the adhesion layer 12 on the hard coat layer 10 in which the metal oxide particles are exposed in this manner, a large adhesion force of the resin of the adhesion layer 12 and the hard coat layer 10 can be obtained, and a larger adhesion force of the adhesion layer 12 and the metal oxide particles 11 can be obtained, so that excellent adhesion can be obtained.

Examples

< 4. Examples >

In this example, an antireflection film was produced, and adhesion between the hard coat layer and the AR layer was evaluated by a dicing test. The present application is not limited to these examples.

< 4.1 first embodiment >

In the first example, the effect of the protruding proportion of the filler on the hard coat layer surface on the adhesion was verified. Calculation of the protrusion height and the 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-cut test of the antireflection film were performed as follows.

[ calculation of the protrusion height and the protrusion ratio of the filler on the hard coating surface ]

The cross section of the antireflection film was observed using a transmission electron microscope (Transmission Electron Microscope: TEM), and the minimum and maximum protruding heights of the filler on the surface of the hard coat layer were measured. Then, the minimum value (%) and the maximum value (%) of the protrusion ratio with respect to the average particle diameter of the filler are calculated by dividing the minimum value and the maximum value of the protrusion height of the filler by the average particle diameter of the filler, respectively. Further, the average value (%) of the protruding proportion with respect to the average particle diameter of the filler is calculated from the minimum value (%) and the maximum value (%) of the protruding proportion with respect to the average particle diameter of the filler.

[ measurement of surface roughness Ra of hard coating layer ]

The arithmetic average roughness Ra of the hard coat surface was measured by using an atomic force microscope (Atomic Force Microscopy: AFM).

[ evaluation of cross-hatch test ]

100 1mm×1mm cross cuts (checks (raised mesh)) are formed on the surface of the antireflection film. Then, the surface state of the cross-cut surface at the initial stage was observed and evaluated. After the alcohol wet wipe sliding test, the surface state of the cross-cut surface was observed and evaluated. After the test was carried out in an environment of 90℃to drying (low humidity) for 500 hours, the sliding test of the alcohol wet tissue was carried out, and then the surface state of the cross-cut surface was observed and evaluated.In addition, after the test was carried out in an environment of 60℃to 95% humidity for 500 hours, the sliding test of the alcohol wet tissue was carried out, and then the surface state of the cross cut surface was observed and evaluated. Further, after an alcohol wet wipe sliding test was performed after an environment of xenon irradiation (xenon arc lamp, 7.5 kW) for 60 hours was input, the surface state of the cross-cut surface was observed. In the alcohol wet wipe sliding test, the wet wipe coated with alcohol was subjected to a load of 250g/cm on the cross-cut surface ² Pressing against the antireflection film was performed by reciprocating 500 times at a distance of 10 cm.

Regarding the evaluation of the cross-cut test, the surface state of the cross-cut surface was observed, and as a result, the case where the cross-cut did not peel as in fig. 4 (a) was defined as "o", the case where a part of the cross-cut did peel as in fig. 4 (B) was defined as "Δ", and the case where all the cross-cuts peeled as in fig. 4 (C) was defined as "x".

Example 1

A photocurable resin composition was prepared in which the content of silica particles having an average particle diameter of 50nm was 28 mass% relative to the total solid content of the resin composition. The resin compositions were prepared by dissolving silica particles, acrylate, leveling agent and photopolymerization initiator in a solvent as shown in table 1.

TABLE 1

The photocurable resin composition was applied onto a PET film using a bar coater using a PET film as a base material, and then the resin composition was photopolymerized to form a hard coat layer having a thickness of 5. Mu.m.

Next, the treatment intensity of the glow discharge treatment was set at 8300 W.min/m ² And surface treatment of the hard coat layer is performed. The protrusion height of the filler, the protrusion ratio of the filler, and the surface roughness Ra of the hard coat layer surface of example 1 are shown in table 2.

After glow discharge treatment, a film thickness of 10nm containing SiO was obtained by sputtering _x An adhesion layer comprising Nb is formed on the adhesion layer ₂ O ₅ Film, siO ₂ Film, nb ₂ O ₅ Film and SiO ₂ AR layer of film. Further, an antifouling layer having a thickness of 10nm and containing an alkoxysilane compound having a perfluoropolyether group was formed on the AR layer, and an antireflection film of example 1 was produced. The reflectance of the antireflection film is 0.5% or less, and the water contact angle is 110 degrees or more. Table 2 shows evaluation of the cross-cut test of the antireflection film of example 1.

Example 2

The treatment intensity of the glow discharge treatment was 4200 W.min/m ² An antireflection film was produced in the same manner as in example 1, except that the hard coat layer was subjected to surface treatment. Table 2 shows the evaluation of the protrusion height of the filler, the protrusion ratio of the filler, the surface roughness Ra, and the cross-cut test of the antireflection film on the hard coat layer surface of example 2.

Example 3

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

Example 4

The treatment intensity of the glow discharge treatment was 830 W.min/m ² An antireflection film was produced in the same manner as in example 1, except that the hard coat layer was subjected to surface treatment. Table 2 shows the evaluation of the protrusion height of the filler, the protrusion ratio of the filler, the surface roughness Ra, and the cross-cut test of the antireflection film on the hard coat layer surface of example 4.

Example 5

The treatment intensity of the glow discharge treatment was 420 W.min/m ² An antireflection film was produced in the same manner as in example 1, except that the hard coat layer was subjected to surface treatment. Table 2 shows the protrusion height and the protrusion ratio of the filler on the hard coat layer surface of example 5Examples, evaluation of surface roughness Ra and evaluation of a cross-cut test of an antireflection film.

Example 6

The treatment intensity of the glow discharge treatment was set to 200 W.min/m ² An antireflection film was produced in the same manner as in example 1, except that the hard coat layer was subjected to surface treatment. Table 2 shows the evaluation of the protrusion height of the filler, the protrusion ratio of the filler, the surface roughness Ra, and the cross-cut test of the antireflection film on the hard coat layer surface of example 6.

Example 7

The treatment intensity of the glow discharge treatment was 420 W.min/m 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, and an adhesion layer containing Si was formed by sputtering after the glow discharge treatment, wherein the film thickness was 10nm. Table 2 shows the evaluation of the protrusion height of the filler, the protrusion ratio of the filler, the surface roughness Ra, and the cross-cut test of the antireflection film on the hard coat layer surface of example 7.

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, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-cut test of the antireflection film on the hard coat layer surface of comparative example 1.

Comparative example 2

The resin composition was not blended with silica particles, and the treatment strength of the glow discharge treatment was 830 W.min/m ² An antireflection film was produced in the same manner as in example 1, except that the hard coat layer was subjected to surface treatment. Table 2 shows the evaluation of the surface roughness Ra and the cross-cut test of the antireflection film of comparative example 2.

Comparative example 3

The treatment intensity of the glow discharge treatment was 830 W.min/m ² To carry out surface treatment of the hard coat layer and to carry out SiO ₂ An antireflection film was produced in the same manner as in example 1, except that the film was formed as an adhesive layer. Table 2 shows the protrusion height of the filler, the protrusion ratio of the filler, and the surface roughness Ra of the hard coat layer surface of comparative example 3Evaluation of the cross-cut test of the antireflection film.

TABLE 2

In the case where the silica particles were not exposed as in comparative example 1, all the scratches were peeled off in the sliding test using the alcohol wet pad. In the case where the surface treatment was performed without adding silica particles as in comparative example 2, the entire cross-cuts were peeled off in the sliding test using the alcohol wet wipe as in comparative example 1. Further, siO was used as in comparative example 3 ₂ In the case of film formation as an adhesive layer, all the scratches were peeled off in the sliding test using an alcohol wet wipe, as in comparative example 1.

On the other hand, as in examples 1 to 7, the silica particles were exposed, and thus the improvement of the adhesion was observed in the sliding test using the alcohol wet tissue. In addition, it is also known that the exposure of the silica particles contributes to the improvement of the adhesion by comparing the photograph of the TEM section of example 3 shown in fig. 5 (a) with the photograph of the TEM section of comparative example 1 shown in fig. 5 (B), in which the interface between the hard coat layer and the adhesion layer has a circular arc shape due to the exposure of the silica particles, whereas the interface has a linear shape in comparative example 1.

Further, since the average value of the protruding proportion of the metal oxide particles to the average particle diameter is 60% or less, particularly 10% or more and 30% or less, excellent evaluation results can be obtained in the sliding test using the alcohol wet wipe.

< 4.2 second embodiment >

In the second example, the influence of the average particle diameter and the addition amount of the filler of the hard coat layer on the adhesion was verified. In addition, the influence of the types of the filler and the adhesion layer of the hard coat layer on the adhesion was examined. Further, a surface treatment method other than glow discharge treatment will be discussed. The evaluation of the cross-cut test of the antireflection film was performed in the same manner as in the first example.

Example 8

An antireflection film was produced in the same manner as in example 4 except that a photocurable resin composition was prepared as shown in Table 3, the content of silica particles (trade name: MEK-ST-Z, nissan chemical Co., ltd.) having an average particle diameter of 100nm being 28% by mass relative to the total solid content of the resin composition. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 8.

Example 9

An antireflection film was produced in the same manner as in example 4 except that a photocurable resin composition was prepared as shown in Table 3, the content of silica particles (trade name: MEK-ST-40, nissan chemical Co., ltd.) having an average particle diameter of 20nm being 28% by mass relative to the total solid content of the resin composition. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 9.

Example 10

An antireflection film was produced in the same manner as in example 4 except that a photocurable resin composition was prepared as shown in Table 3, the content of silica particles (trade name: MEK-ST-Z, nissan chemical Co., ltd.) having an average particle diameter of 100nm being 20% by mass relative to the total solid content of the resin composition. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 10.

Example 11

An antireflection film was produced in the same manner as in example 4 except that a photocurable resin composition was prepared in which the content of silica particles (trade name: MEK-ST-40, nissan chemical Co., ltd.) having an average particle diameter of 20nm was 50% by mass relative to the total solid content of the resin composition as shown in Table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 11.

Example 12

An antireflection film was produced in the same manner as in example 4 except that a photocurable resin composition having a content of silica particles (IPA-ST-L, manufactured by daily chemical Co., ltd.) having an average particle diameter of 50nm of 20 mass% relative to the total solid content of the resin composition was prepared as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 12.

Example 13

An antireflection film was produced in the same manner as in example 4 except that a photocurable resin composition was prepared in which the content of silica particles (IPA-ST-L, manufactured by daily chemical Co., ltd.) having an average particle diameter of 50nm was 50 mass% relative to the total solid content of the resin composition as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 13.

Comparative example 4

An antireflection film was produced in the same manner as in example 4 except that a photocurable resin composition having a silica particle (IPA-ST-L, manufactured by daily chemical Co., ltd.) having an average particle diameter of 50nm in an amount of 10 mass% relative to the total solid content of the resin composition was prepared as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of comparative example 4.

Comparative example 5

An antireflection film was produced in the same manner as in example 4, except that a photocurable resin composition was prepared in which the content of acrylic particles having an average particle diameter of 1 μm (trade name: SSX-101, product of water deposition industry) was 3% by mass relative to the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of comparative example 5.

Comparative example 6

An antireflection film was produced in the same manner as in example 4, except that corona treatment was performed instead of glow discharge treatment as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of comparative example 6.

Comparative example 7

An antireflection film was produced in the same manner as in example 4, except that 5% naoh, 25 ℃ and 30 seconds of alkali treatment were used instead of the glow discharge treatment as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of comparative example 7.

Example 14

An antireflection film was produced in the same manner as in example 4, except that 5% naoh, 45 ℃ and alkali treatment was performed for 2 minutes instead of glow discharge treatment as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 14.

Example 15

An antireflection film was produced in the same manner as in example 4, except that 5% naoh, 45 ℃ and alkali treatment was performed for 5 minutes instead of glow discharge treatment as shown in table 3. Table 3 shows evaluation of the cross-cut test of the antireflection film of example 15.

TABLE 3

When the amount of silica particles added was small as in comparative example 4, all the scratches were peeled off in the sliding test using an alcohol wet wipe. In addition, when acrylic particles were used instead of silica particles as in comparative example 5, all the cross cuts were peeled off in the sliding test using an alcohol wet wipe as in comparative example 4.

On the other hand, in the case where silica particles having an average particle diameter of 20nm to 100nm were contained in the range of 20 mass% to 50 mass% with respect to the total solid content of the resin composition as in examples 8 to 15, the improvement of the adhesion was observed in the sliding test using the alcohol wet tissue. In particular, when the content of silica particles is 50 mass% or more and 20 mass% or less of the total solid content of the resin composition in terms of the average particle diameter of the silica particles being 20nm or more and 100nm or less as in examples 10 and 11, excellent adhesion can be obtained in the alcohol wet wipe sliding test after the exposure to xenon (xenon arc lamp, 7.5 kW) for 60 hours.

In addition, when corona treatment was performed as a surface treatment as in comparative example 6, peeling occurred in all the cross cuts in the sliding test using an alcohol wet wipe. In addition, when alkali treatment was performed at 25 ℃ for 30 seconds with 5% naoh as the surface treatment as in comparative example 7, peeling was also generated in all the cross-cuts in the sliding test using the alcohol wet wipe.

On the other hand, in the case of alkali treatment by heating as in examples 14 and 15, improvement of adhesion was observed in the sliding test using the alcohol wet tissue. In the case of heating and alkali treatment, the sliding test using the alcohol wet wipe was evaluated less than the case of glow discharge treatment. This is considered because the alkali treatment is a wet treatment, and the shape of the interface between the hard coat layer and the adhesion layer due to the exposure of the silica particles is linear.

Claims

1. A laminated film is provided with:

a hard coating layer with metal oxide particles exposed on the surface; and

a film-forming layer which is formed on the exposed surface of the metal oxide particles of the hard coat layer and which contains an oxygen-deficient metal oxide having a metal of the same kind as the metal oxide particles or an adhesion layer of a metal of the same kind as the metal oxide particles;

the metal oxide particles are Al ₂ O ₃ 、TiO ₂ 、ZrO ₂ 、CeO ₂ 、MgO、ZnO、Ta ₂ O ₅ 、Sb ₂ O ₃ 、SnO ₂ 、MnO ₂ ，

The average value of the protruding proportion of the metal oxide particles exposed on the surface of the hard coat layer with respect to the average particle diameter is 60% or less,

the metal oxide particles have an average particle diameter of 20nm to 100nm, and the metal oxide particles are contained in an amount of 20 mass% to 50 mass% relative to the total solid content of the resin composition of the hard coat layer.

2. The laminated film according to claim 1, wherein the average value of the protruding proportion of the metal oxide particles exposed on the surface of the hard coat layer with respect to the average particle diameter is 10% to 30%.

3. The laminated film according to claim 1, wherein the film thickness of the sealing layer is less than 50% of the average particle diameter of the metal oxide particles exposed on the surface of the hard coat layer.

4. The laminated film according to any one of claims 1 to 3, further comprising, on the sealing layer: and an antireflection layer in which high refractive index layers and low refractive index layers having a lower refractive index than the high refractive index layers are alternately laminated.

5. The laminated film according to any one of claims 1 to 3, wherein the hard coat layer is obtained by photopolymerization of an ultraviolet curable resin containing a urethane (meth) acrylate oligomer, a trifunctional or higher (meth) acrylate monomer, a difunctional (meth) acrylate monomer, and a photopolymerization initiator.