CN112415638A - Method for producing laminated film - Google Patents
Method for producing laminated film Download PDFInfo
- Publication number
- CN112415638A CN112415638A CN202011380849.8A CN202011380849A CN112415638A CN 112415638 A CN112415638 A CN 112415638A CN 202011380849 A CN202011380849 A CN 202011380849A CN 112415638 A CN112415638 A CN 112415638A
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- hard coat
- oxide particles
- layer
- coat layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 118
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 98
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 98
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 230000002950 deficient Effects 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 118
- 238000011282 treatment Methods 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 239000011342 resin composition Substances 0.000 claims description 34
- 208000028659 discharge Diseases 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 9
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- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 239000005001 laminate film Substances 0.000 claims description 2
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- 238000012360 testing method Methods 0.000 description 49
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- 238000011156 evaluation Methods 0.000 description 28
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- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
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- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- PCLLJCFJFOBGDE-UHFFFAOYSA-N (5-bromo-2-chlorophenyl)methanamine Chemical compound NCC1=CC(Br)=CC=C1Cl PCLLJCFJFOBGDE-UHFFFAOYSA-N 0.000 description 1
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- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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Abstract
The present invention relates to a method for producing a laminated film, 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 particle of the hard coat layer, the adhesion layer containing an oxygen-deficient metal oxide having a metal of the same kind as the metal oxide particle or a metal of the same kind as the metal oxide particle; in the exposure step, the surface of the hard coat layer is etched, and the arithmetic mean roughness Ra of the surface of the hard coat layer after etching is 2nm to 12 nm. This allows the adhesion layer to firmly adhere to the resin of the hard coat layer and to more firmly adhere to the exposed metal oxide particles, thereby achieving excellent adhesion.
Description
The present application is a divisional application of the chinese patent application entitled "laminated film and method for manufacturing laminated film" filed as 2016, 5, 27, and having an application number of 201680028850. X.
Technical Field
The present invention relates to a laminated film having excellent adhesion between an organic layer and an inorganic layer, and a method for producing the laminated film. This application claims priority based on Japanese patent application No. Japanese laid-open at 2015, 5, month 27 and Japanese patent application No. Japanese laid-open at 2016, month 5, month 26 and Japanese patent application No. Japanese laid-open at 2016, month 26, which is hereby incorporated by reference into the present application.
Background
An example of the laminated film is an antireflection film in which an AR (Anti-reflection) layer is formed by a dry process on a hard coat layer having a relatively high surface hardness (see, for example, patent document 1).
However, since the hard coat layer is an organic layer and the AR layer is an inorganic layer, it is difficult to obtain excellent adhesion.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-218603
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-described conventional circumstances, 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 inventors of the present invention conducted extensive studies and found that: 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 kind of oxygen-deficient metal oxide or metal as the metal oxide particles on the surface, the adhesion between the organic layer and the inorganic layer is significantly improved.
That is, the laminated film of the present invention is characterized by comprising: a hard coat layer having metal oxide particles exposed on the surface thereof; and an adhesion layer formed on the exposed surface of the metal oxide particle of the hard coat layer and containing an oxygen-deficient metal oxide having the same kind of metal as the metal oxide particle or a metal having the same kind of metal as the metal oxide particle.
The method for producing a laminated film according to the present invention 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 on the exposed surface of the metal oxide particles of the hard coat layer, the adhesion layer containing 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.
Effects of the invention
According to the present invention, the adhesion layer is firmly attached to the resin of the hard coat layer and more firmly attached to the exposed metal oxide particles, and therefore, excellent adhesion can be obtained.
Drawings
Fig. 1 is a 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. 3 is a cross-sectional view schematically showing an antireflection film to which the present invention is applied.
Fig. 4 is a photograph showing an evaluation example of a cross-hatch test (cross-hatch test), fig. 4(a) shows a case where peeling does not occur, fig. 4(B) shows a case where peeling partially occurs, and fig. 4(C) shows a case where peeling occurs entirely.
FIG. 5 is a photograph of a TEM cross section of example 3, and FIG. 5(B) is a photograph of a TEM cross section of comparative example 1.
Description of the symbols
10 hard coat layer, 11 metal oxide particles, 12 adhesive layer, 20 functional layer, 30 base material, 40 anti-reflection layer, 50 antifouling layer.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. Laminated film
2. Anti-reflection film
3. Method for producing laminated film
4. Examples of the embodiments
< 1. laminated film >
Fig. 1 is a sectional view schematically showing a hard coat layer in which metal oxide particles are exposed according to the present embodiment, and fig. 2 is a sectional view schematically showing a laminated thin 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 formed on the exposed surface of the metal oxide particles of the hard coat layer 10 and containing an oxygen-deficient metal oxide having the same type of metal as the metal oxide particles 11 or a metal having the same type of metal as the metal oxide particles 11. The adhesive layer 12 further includes a functional layer 20 formed thereon and including an inorganic layer. With such a configuration, the adhesion layer 12 is firmly adhered to the resin of the hard coat layer 10 and further firmly adhered 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 abrasion resistance of the laminated film can be improved.
[ hard coating layer ]
With 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 an ultraviolet curable resin, an electron beam curable resin, a thermosetting resin, a thermoplastic resin, a two-liquid mixture resin, and the like. 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 these, when the laminated film is used for optical applications, for example, acrylic films which can obtain high transparency are preferably used.
The acrylic ultraviolet curable resin is not particularly limited, and may be appropriately selected from bifunctional, trifunctional, or higher multifunctional acrylic monomers, oligomers, and polymer components in consideration of hardness, adhesion, processability, and the like. Further, a photopolymerization initiator is blended in 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, cyclohexanedimethanol diacrylate, and the like. Specific examples of commercially available products include, for example, the trade name "SR 610" of sartomera (strain).
Specific examples of the trifunctional or higher acrylate component include pentaerythritol triacrylate (PETA), 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanurate triacrylate,. epsilon. -caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), and. epsilon. -caprolactone-modified tris (acryloyloxyethyl) acrylate. Specific examples of commercially available products include trade name "CN 968" of sartomer and trade name "SR 444" of sartomer.
Specific examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and a titanocene-based photopolymerization initiator. Specific examples of commercially available compounds include 1-hydroxycyclohexyl phenyl ketone (IRGACURE184, BASF Japan Co., Ltd.).
Further, the acrylic ultraviolet-curable resin preferably contains a leveling agent in order to improve smoothness. Specific examples of the leveling agent include a silicone-based leveling agent, a fluorine-based leveling agent, and an acrylic-based leveling agent, and one or two or more of these can be used. Among them, from the viewpoint of coating properties, an organic silicon leveling agent is preferably used. Specific examples of commercially available products include BYK337 (polyether-modified polydimethylsiloxane) which is a trade name of Nikk chemical Japan (Co., Ltd.).
The solvent used in the acrylic ultraviolet-curable resin is not particularly limited as long as it satisfies 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, and propylene glycol methyl ether, and one or two or more of these can 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 other functional agents than the above-mentioned ones, such as a hue adjusting agent, 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.
The metal oxide particles 11 are particles of a metal oxide, and the average particle diameter thereof is preferably 800nm or less, and 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 use, and if the average particle diameter is too small, the adhesion between the hard coat layer 10 and the adhesion layer 12 is reduced. In the present specification, the average particle diameter refers to a value measured by the BET method.
The content of the metal oxide particles 11 is preferably 20 mass% to 50 mass% 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 reduced, and if too large, the bending property of the hard coat layer 10 is reduced. The solid content of the resin composition means all components except the solvent, and the liquid monomer component is also included in the solid content.
Specific examples of the metal oxide particles 11 include SiO2(silica) and Al2O3(aluminum oxide), TiO2(titanium dioxide) ZrO2(zirconium dioxide), CeO2(cerium oxide), MgO (magnesium oxide), ZnO, Ta2O5、Sb2O3、SnO2、MnO2And the like. Among these, for example, when the laminated film is used for optical applications, silica which can obtain high transparency is preferably used. Specific examples of commercially available products include "IPA-ST-L" (silica sol) which is a trade name of Nissan chemical Co., Ltd. In addition, functional groups such as acryloyl groups and epoxy groups may be introduced into the surface of the metal oxide particles in order to improve adhesion and affinity with the resin.
As shown in fig. 1, the metal oxide particles 11 are exposed and protrude from the surface of the hard coat layer 10. The method of 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 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 with respect to the average particle diameter is preferably 60% or less, and 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 hard coat layer 10 and the adhesion layer 12 is reduced, whereas 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 (meth) acrylate monomer, a difunctional (meth) acrylate monomer, and a photopolymerization initiator. By using such a photocurable resin composition, the hard coat layer 10 having excellent hardness can be obtained.
[ bonding layer ]
The adhesion layer 12 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 kind of metal as the metal oxide particles 11 or a metal having the same kind of metal as the metal oxide particles 11. As the oxygen-deficient metal oxide, SiO is mentionedx、AlOx、TiOx、ZrOx、CeOx、MgOx、ZnOx、TaOx、SbOx、SnOx、MnOxAnd the like. Here, the oxygen-deficient metal oxide refers to a metal oxide in which the number of oxygen atoms is insufficient compared to the stoichiometric composition. Examples of the metal include Si, Al, Ti, Zr, Ce, Mg, Zn, Ta, Sb, Sn, and Mn. For example, the metal oxide particles 11 are SiO2In the case of (2), SiO of the adhesion layer 12xX in (2) is 0 or more and less than 2.0.
The oxidation degree and the film thickness of the adhesion layer 12 can be appropriately designed according to the functional layer 20 formed on the adhesion layer 12. For example, the functional layer 20 is an Anti-reflection layer (AR (Anti-Reflective) layer) and SiO (silicon oxide) is used2In the case of the metal oxide particles 11, the SiO of the adhesion layer 12xX in (2) is preferably 0 to 1.9. Further, the film thickness of the adhesion layer 12 is preferably smaller than that exposed on the surface of the hard coat layer 10The metal oxide particles 11 have an average particle diameter of 50%, specifically, preferably 1nm to 50nm, more preferably 1nm to 30nm, and still more preferably 1nm to 10 nm.
[ functional layer ]
The functional layer 20 is an inorganic layer formed on the adhesion layer 12. Examples of the functional layer 20 include optical layers such as an antireflection layer, a retardation layer, and a polarizing layer. Such an optical layer is an inorganic layer formed by sputtering, for example, and therefore can improve thermal dimensional stability as compared with an organic layer.
In the laminated film having such a configuration, the hard coat layer 10 and the adhesion layer 12 are firmly adhered to each other by the metal oxide particles 11, and therefore, excellent adhesion can be obtained. In particular, when the average value of the protruding ratio of the metal oxide particles exposed on the surface of the hard coat layer 10 with respect to the average particle diameter is 60% or less, more preferably 10% to 30%, 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 aforementioned laminated thin film. Fig. 3 is a cross-sectional view schematically showing an antireflection film to which the present invention is applied. As shown in fig. 3, the antireflection film includes a substrate 30; a hard coat layer 10 having metal oxide particles 11 exposed on the surface thereof; a bonding layer 12 formed on the exposed surface of the metal oxide particles of the hard coat layer 10 and containing an oxygen-deficient metal oxide or metal of the same type as the metal oxide particles 11; an antireflection layer 40; and an antifouling layer 50.
The substrate 30 is not particularly limited, and specific examples thereof include PET (Polyethylene terephthalate), a resin (COP) having an alicyclic structure in the main chain of a cycloolefin monomer, a resin (COC) obtained by addition polymerization of a cyclic olefin (e.g., norbornene) and an α -olefin (e.g., ethylene), TAC (triacetyl cellulose), and the like. The thickness of the substrate 30 varies depending on the kind and performance of the optical device to which it is applied, and is usually 25 to 200 μm, preferably 40 to 150 μm.
The high refractive index layer made of a dielectric material and the low refractive index layer having a lower refractive index than the high refractive index layer in the antireflection layer 40 are alternately formed by sputtering. As the dielectric material having a high refractive index, Nb is preferably used2O5Or TiO2As the low refractive index dielectric material, SiO is preferably used2。
The antifouling layer 50 is, for example, a coating layer of an alkoxysilane compound having a perfluoropolyether group. By coating an alkoxysilane compound having a perfluoropolyether group, water repellency is exhibited in which the water contact angle is 110 degrees or more, and the antifouling property can be improved.
The antireflection film having such a structure is excellent in scratch resistance, and therefore can be preferably used as a laminate film for a touch panel, for example. Further, such a laminated film for a touch panel is laminated on an image display element such as a liquid crystal display element or an organic EL display element, and thus can be suitably used as an image display and input device for a smartphone or a notebook computer.
< 3. method for producing laminated film
The method for manufacturing a laminated film of 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 on the exposed surface of the metal oxide particles of the hard coat layer, the adhesion layer containing the same kind of oxygen-deficient metal oxide or metal as the metal oxide particles. The exposure step and the film formation step are explained below.
[ exposing step ]
First, the metal oxide particles 11 and the ultraviolet curable resin composition containing the urethane (meth) acrylate oligomer, the trifunctional or higher (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 dispenser, for example.
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 microgravure coating method, a wire 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 missing angle wheel coating method, a blade coating method, and a spin coating method.
Next, the ultraviolet curable resin composition on the substrate is dried and photocured to form the hard coat layer 10. The drying conditions are not particularly limited, and natural drying may be employed, or artificial drying with adjustment of drying humidity, drying time, and the like may be employed. However, it is preferable that the coating film surface is not subjected to wind marks when the coating film surface is exposed to wind during drying. This is because, if the air wrinkles are generated, the coating appearance is deteriorated and the thickness of the surface is not uniform. As the light for curing the ultraviolet curable resin composition, energy rays such as gamma rays, alpha rays, and electron rays can be used 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 of 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 capable of large-area treatment is preferably used.
The glow discharge treatment is performed by a treatment apparatus in which two plate electrodes facing each other are disposed in a vacuum-dischargeable chamber, and a film is moved in parallel between the electrodes. The present processing apparatus may be provided in a film deposition apparatus.
The inside of the processing chamber is evacuated to, for example, 0.01Pa or less, and then an atmosphere gas is introduced. The pressure in the treatment chamber at this time is not particularly limited as long as it can maintain glow discharge, and is usually in the range of 0.1 to 100 Pa. As the atmosphere gas, an inert gas is mainly used, and hydrogen gas, oxygen gas, nitrogen gas, fluorine gas, chlorine gas, or the like can be used. Further, a mixed gas thereof may be used. Examples of the inert gas include helium, neon, argon, krypton, xenon, and radon. Among these, helium gas and argon gas are preferable from the viewpoint of availability, and argon gas is particularly preferable from the viewpoint of price.
After the introduction of the atmosphere gas, a voltage of several 100V is applied between the opposing electrodes to generate glow discharge. The film is continuously passed through the region where glow discharge occurs, and the film surface is modified by the ionized atmospheric gas.
The glow treatment can utilize the energy density (W/m) at the time of discharge2) And treatment time (min) to indicate strength. In the case of the continuous winding type apparatus, the processing time is a value obtained by dividing the length (m) of the processing region (the length in the direction along the film of the electrode) by the winding speed (m/min). The treatment intensity is the treatment time multiplied by the power density (W/m) at glow discharge2) The obtained value is represented by the following formula.
Treatment Strength (W.min/m)2) Power density (W/m)2) Length of processing area (m) ÷ speed of line transfer (m/min)
That is, by changing the input power and the traveling speed, films having different treatment strengths can be produced.
Intensity of glow discharge treatment (power X treatment time/treatment area, unit: W.min/m)2) Preferably 200 to 4150 W.min/m2More preferably 420 to 2100 W.min/m2. The greater the treatment strength, the more plasma is generated on the surface of the hard coat layer, and the projecting ratio of the metal oxide particles 11 becomes larger.
The average value of the protruding proportion of the metal oxide particles 11 with respect to the average particle diameter is preferably 60% or less, and 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 reduced, whereas 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 surface after etching is preferably 2nm to 12nm, more preferably 4nm to 8 nm. If the arithmetic average roughness Ra of the hard coat layer 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 easily peel off from the hard coat layer 10.
[ film Forming Process ]
In the film formation step, the adhesion layer 12 containing the oxygen-deficient metal oxide or metal of the same type 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, when a SiOx film is formed, reactive sputtering using a silicon target in a mixed gas atmosphere of oxygen and argon is preferably used. Further, since the functional layer 20 such as an antireflection layer, a retardation layer, and a polarizing layer formed on the adhesion layer 12 can be formed by sputtering, 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 adhesion layer 12 to the resin of the hard coat layer 10 can be obtained, and a larger adhesion force of the adhesion layer 12 to the metal oxide particles 11 can be obtained, so that excellent adhesion can be obtained.
Examples
< 4. example >
In this example, an antireflection film was produced, and adhesion between the hard coat layer and the AR layer was evaluated by a cross cut test. The present invention is not limited to these examples.
< 4.1 first embodiment >
In the first example, the effect of the protruding ratio of the filler on the hard coating surface on the adhesion was examined. Calculation of the protrusion height and protrusion ratio of the filler on the surface of the hard coat layer, measurement of the surface roughness Ra of the hard coat layer, and evaluation of the anti-reflection film cross cut test 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) to measure the minimum and maximum values of the protrusion height of the filler on the surface of the hard coat layer. Then, the minimum value (%) and the maximum value (%) of the protrusion ratio with respect to the average particle size of the filler were calculated by dividing the minimum value and the maximum value of the protrusion height of the filler by the average particle size of the filler, respectively. The average (%) of the protrusion ratio with respect to the average particle size of the filler was calculated from the lowest value (%) and the highest value (%) of the protrusion ratio with respect to the average particle size of the filler.
[ measurement of surface roughness Ra of hard coat layer ]
The arithmetic Force microscope (Atomic Force microscope: AFM) was used to measure the arithmetic average roughness Ra of the hard coat surface.
[ evaluation of lattice test ]
100 divisions (squares (liter) of 1mm × 1mm were formed on the surface of the antireflection film. Then, the surface state of the initial cross section was observed and evaluated. After the alcohol wet wipe sliding test, the surface state of the scribed surface was observed and evaluated. Further, after an alcohol wet wipe slip test was performed after putting into an environment of 90 ℃ to dry (low humidity) -500 hours, the surface state of the crosshatched surface was observed and evaluated. In addition, after the wet tissue sliding test is carried out after the environment with the temperature of 60-95-500 h of humidity is put into the wet tissue sliding test chamber, the surface state of the grid surface is observed and evaluated. Further, an alcohol wet wipe slip test was performed after putting xenon irradiation (xenon arc lamp, 7.5kW) for 60 hours, and then the surface state of the scribed surface was observed. In the alcohol wet wipe sliding test, the wet wipe coated with ethanol was applied with a load of 250g/cm to the scribed surface2The pressure was applied to the antireflection film, and the film was slid 500 times in a reciprocating manner at a distance of 10 cm.
In 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 off as shown in fig. 4(a), the case where a part of the cross cut peeled off as shown in fig. 4(B) was Δ, and the case where all the cross cuts peeled off as shown in fig. 4(C) was 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% based on the total solid content of the resin composition. The resin composition was prepared by dissolving silica particles, an acrylic ester, a leveling agent, and a photopolymerization initiator in a solvent as shown in table 1.
[ Table 1]
The photocurable resin composition was applied to a PET film using a PET film as a substrate by a bar coater, and then the resin composition was photopolymerized to form a hard coat layer having a thickness of 5 μm.
Next, the treatment intensity of the glow discharge treatment was 8300 W.min/m2And the surface treatment of the hard coat is performed. Table 2 shows the protrusion height of the filler, the protrusion ratio of the filler, and the surface roughness Ra of the hard coat surface of example 1.
After glow discharge treatment, the resultant was formed into a film thickness of 10nm by sputtering and containing SiOxThe adhesion layer of (2) is formed by film-forming Nb-containing2O5Film, SiO2Film, Nb2O5Film and SiO2An AR layer of the film. Further, an anti-fouling layer having a thickness of 10nm and containing an alkoxysilane compound having a perfluoropolyether group was formed on the AR layer to prepare an anti-reflection film of example 1. The anti-reflection film has a reflectance of 0.5% or less and a water contact angle of 110 degrees or more. Table 2 shows evaluation of the anti-reflection film of example 1 in the cross cut test.
[ example 2]
The treatment intensity of the glow discharge treatment was 4200 W.min/m2An antireflection film was produced in the same manner as in example 1, except that the surface treatment of the hard coat layer was performed. Hardness of example 2 is shown in Table 2The protrusion height of the filler on the coating surface, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the anti-reflection film by the cross cut test.
[ example 3]
The treatment intensity of the glow discharge treatment was 2100 W.min/m2An antireflection film was produced in the same manner as in example 1, except that the surface treatment of the hard coat layer was 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 anti-reflection film in the cross cut test on the hard coat surface in example 3.
[ example 4]
The treatment intensity of the glow discharge treatment was set to 830 W.min/m2An antireflection film was produced in the same manner as in example 1, except that the surface treatment of the hard coat layer was 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 anti-reflection film in the cross cut test on the hard coat surface in example 4.
[ example 5]
The treatment intensity of the glow discharge treatment was set to 420 W.min/m2An antireflection film was produced in the same manner as in example 1, except that the surface treatment of the hard coat layer was 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 anti-reflection film in the cross cut test on the hard coat surface in example 5.
[ example 6]
The treatment intensity of the glow discharge treatment was set to 200 W.min/m2An antireflection film was produced in the same manner as in example 1, except that the surface treatment of the hard coat layer was 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 anti-reflection film in the cross cut test on the hard coat surface in example 6.
[ example 7]
The treatment intensity of the glow discharge treatment was set to 420 W.min/m2An antireflection film was produced in the same manner as in example 1, except that the surface treatment of the hard coat layer and the glow discharge treatment were carried out, and then the adhesion layer containing Si with a film thickness of 10nm was formed by sputtering. Table 2 shows the resultsThe hard coat layer surface of example 7 was evaluated for the protrusion height of the filler, the protrusion ratio of the filler, the surface roughness Ra, and the anti-reflection film in the cross cut test.
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 anti-reflection film in the cross cut test on the hard coat layer surface of comparative example 1.
Comparative example 2
The resin composition does not contain silica particles, and the treatment strength of glow discharge treatment is set to 830 W.min/m2An antireflection film was produced in the same manner as in example 1, except that the surface treatment of the hard coat layer was performed. Table 2 shows the surface roughness Ra of comparative example 2 and the evaluation of the anti-reflection film by the cross cut test.
Comparative example 3
The treatment intensity of the glow discharge treatment was set to 830 W.min/m2To perform surface treatment of the hard coat layer, and SiO2An antireflection film was produced in the same manner as in example 1, except that an adhesion layer was formed. Table 2 shows the protrusion height of the filler, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the anti-reflection film in the cross cut test on the hard coat layer surface in comparative example 3.
[ Table 2]
When the silica particles were not exposed as in comparative example 1, peeling occurred in all of the divisions in the sliding test using the alcohol wet wipe. In addition, in the case of performing the surface treatment without blending the silica particles as in comparative example 2, peeling was generated on all the divisions in the sliding test with the alcohol wet wipe as in comparative example 1. In addition, SiO was added as in comparative example 32When the adhesive layer was formed, the entire area of the cut was peeled off in the sliding test using the alcohol wet wipe as in comparative example 1.
On the other hand, as in examples 1 to 7, the improvement of the adhesion was observed in the sliding test with the alcohol wet wipe by exposing the silica particles. Further, comparing the photograph of the TEM cross section of example 3 shown in fig. 5(a) with the photograph of the TEM cross section of comparative example 1 shown in fig. 5(B), it is also understood that the exposure of the silica particles contributes to the improvement of the adhesion because the interface between the hard coat layer and the adhesion layer in example 3 has an arc shape due to the exposure of the silica particles, whereas the interface is linear in comparative example 1.
In addition, since the average value of the protruding ratio of the metal oxide particles with respect to the average particle diameter is 60% or less, particularly 10% to 30%, 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 amount of the filler added in the hard coat layer on the adhesion was examined. Further, the effect of the kind of filler and the adhesion layer of the hard coat layer on the adhesion was verified. Further, surface treatment methods other than glow discharge treatment will be discussed. The evaluation of the anti-reflection film in the cross cut test 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 in which the content of silica particles (trade name: MEK-ST-Z, manufactured by nippon chemical industries, ltd.) having an average particle diameter of 100nm was 28 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of example 8 in the cross cut test.
[ example 9]
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, manufactured by nippon chemical industries, ltd.) having an average particle diameter of 20nm was 28 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of example 9 in the cross cut test.
[ example 10]
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-Z, manufactured by nippon chemical industries, ltd.) having an average particle diameter of 100nm was 20 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of example 10 in the cross cut test.
[ 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, manufactured by nippon chemical industries, ltd.) having an average particle diameter of 20nm was 50 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of example 11 in the cross cut test.
[ example 12]
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, japan chemical corporation) having an average particle diameter of 50nm was 20 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of example 12 in the cross cut test.
[ 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, japan chemical corporation) having an average particle diameter of 50nm was 50 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of example 13 in the cross cut test.
Comparative example 4
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, japan chemical corporation) having an average particle diameter of 50nm was 10 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of comparative example 4 in the cross cut test.
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 (trade name: SSX-101, waterlogging chemical industry, ltd.) having an average particle diameter of 1 μm was 3 mass% based on the total solid content of the resin composition, as shown in table 3. Table 3 shows evaluation of the anti-reflection film of comparative example 5 in the cross cut test.
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 anti-reflection film of comparative example 6 in the cross cut test.
Comparative example 7
An antireflection film was produced in the same manner as in example 4, except that, as shown in table 3, 5% NaOH, 25 ℃ and 30 seconds alkali treatment were performed instead of the glow discharge treatment. Table 3 shows evaluation of the anti-reflection film of comparative example 7 in the cross cut test.
[ example 14]
An antireflection film was produced in the same manner as in example 4, except that alkali treatment was performed at 45 ℃ for 2 minutes instead of glow discharge treatment with 5% NaOH as shown in Table 3. Table 3 shows evaluation of the anti-reflection film of example 14 in the cross cut test.
[ example 15]
An antireflection film was produced in the same manner as in example 4, except that alkali treatment was performed at 45 ℃ for 5 minutes instead of glow discharge treatment as shown in table 3 with 5% NaOH. Table 3 shows evaluation of the anti-reflection film of example 15 in the cross cut test.
[ Table 3]
When the amount of the silica particles added was small as in comparative example 4, peeling occurred in all the divisions in the sliding test using the alcohol wet wipe. In addition, in the case of using acrylic particles instead of silica particles as in comparative example 5, peeling occurred in all of the divisions in the sliding test with an alcohol wet wipe as in comparative example 4.
On the other hand, as in examples 8 to 15, when silica particles having an average particle diameter of 20nm or more and 100nm or less were contained in a range of 20 mass% to 50 mass% with respect to the total solid content of the resin composition, improvement of adhesion was observed in the sliding test with an alcohol wet wipe. In particular, as in examples 10 and 11, when the average particle diameter of the silica particles is 20nm or more and 100nm or less and the content of the silica particles is 50 mass% or more and 20 mass% or more of the total solid content of the resin composition, excellent adhesion was obtained in the alcohol wet wipe sliding test after the xenon irradiation (xenon arc lamp, 7.5kW) was put into the environment for 60 hours.
In addition, when the surface treatment was performed by corona treatment as in comparative example 6, peeling occurred in all of the divisions in the sliding test using the alcohol wet wipe. In addition, in the case of performing the alkali treatment of 5% NaOH, 25 ℃ and 30 seconds as the surface treatment as in comparative example 7, peeling was caused in all the divisions 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 with an alcohol wet wipe. Further, when the alkali treatment is performed by heating, the evaluation of the slip test using the alcohol wet wipe is inferior to that in the case of performing the glow discharge treatment. This is considered to be 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 becomes linear.
Claims (11)
1. A method for manufacturing a laminated film, 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 particle of the hard coat layer, the adhesion layer containing an oxygen-deficient metal oxide having a metal of the same kind as the metal oxide particle or a metal of the same kind as the metal oxide particle,
in the exposure step, the surface of the hard coat layer is etched, and the arithmetic mean roughness Ra of the surface of the hard coat layer after etching is 2nm to 12 nm.
2. The method for producing a laminated film according to claim 1, wherein an average value of a protruding proportion of the metal oxide particles exposed on the surface of the hard coat layer with respect to an average particle diameter is 60% or less.
3. The method for producing a laminated film according to claim 1, wherein an 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% or more and 30% or less.
4. The method for producing a laminated film according to any one of claims 1 to 3, wherein the average particle diameter of the metal oxide particles is 20nm or more and 100nm or less.
5. The method of producing a laminated film according to any one of claims 1 to 3, wherein a content of the metal oxide particles is 20 mass% or more and 50 mass% or less with respect to a total solid content of a resin composition of the hard coat layer.
6. The method for producing a laminated film according to any one of claims 1 to 3, wherein the metal oxide particles have an average particle diameter of 20nm or more and 100nm or less, and the content of the metal oxide particles is 50 mass% or less and 20 mass% or more of the total solid content of the resin composition.
7. The method of producing a laminated thin film according to any one of claims 1 to 3, wherein a film thickness of the adhesion layer is less than 50% of an average particle diameter of the metal oxide particles exposed on the surface of the hard coat layer.
8. The method for producing a laminated film according to any one of claims 1 to 3, wherein the metal oxide particles comprise SiO2The bonding layer comprises SiOxWherein x is more than or equal to 0 and less than 2.
9. The method of manufacturing a laminated film according to any one of claims 1 to 3, further forming, on the adhesion layer: and 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.
10. The method for producing a laminate film according to any one of claims 1 to 3, wherein the hard coat layer is formed 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.
11. The method of manufacturing a laminated thin film according to claim 1, wherein in the exposing step, the metal oxide particles are exposed by glow discharge treatment.
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| PCT/JP2016/065724 WO2016190415A1 (en) | 2015-05-27 | 2016-05-27 | Laminated thin film and method for producing laminated thin film |
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| JP7320862B2 (en) * | 2018-11-09 | 2023-08-04 | 深▲せん▼市元子科技有限公司 | Membrane and manufacturing process |
| JP7057865B2 (en) | 2019-11-26 | 2022-04-20 | 日東電工株式会社 | Anti-reflection film and its manufacturing method, and image display device |
| CN115803194A (en) * | 2020-07-13 | 2023-03-14 | 日东电工株式会社 | Optical film with antifouling layer |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN112442205A (en) | 2021-03-05 |
| CN112442205B (en) | 2023-08-22 |
| KR102393911B1 (en) | 2022-05-03 |
| TW202144170A (en) | 2021-12-01 |
| KR20220062140A (en) | 2022-05-13 |
| KR20240023690A (en) | 2024-02-22 |
| HUE055516T2 (en) | 2021-12-28 |
| CN112442206B (en) | 2023-08-18 |
| CN112442206A (en) | 2021-03-05 |
| CN112415638B (en) | 2023-06-06 |
| WO2016190415A1 (en) | 2016-12-01 |
| KR20190130683A (en) | 2019-11-22 |
| TWI798788B (en) | 2023-04-11 |
| KR102635617B1 (en) | 2024-02-08 |
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