WO2013146482A1 - ハードコーティング組成物および高屈折率アンチブロッキング層形成組成物 - Google Patents
ハードコーティング組成物および高屈折率アンチブロッキング層形成組成物 Download PDFInfo
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- WO2013146482A1 WO2013146482A1 PCT/JP2013/057891 JP2013057891W WO2013146482A1 WO 2013146482 A1 WO2013146482 A1 WO 2013146482A1 JP 2013057891 W JP2013057891 W JP 2013057891W WO 2013146482 A1 WO2013146482 A1 WO 2013146482A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/36—Chemically modified polycondensates by etherifying
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/13338—Input devices, e.g. touch panels
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a hard coating composition that provides a hard coat layer having high visibility and good hardness, and also has extensibility.
- the present invention also provides a high refractive index antiblocking layer forming composition, an antiblocking film obtained by coating the high refractive index antiblocking layer forming composition, and a transparent conductive material on at least one surface of the antiblocking film.
- the present invention relates to a transparent conductive laminate having a layer formed thereon.
- Liquid crystal display devices have advantages such as thinness, light weight, and low power consumption, and are used in various fields such as computers, word processors, televisions, mobile phones, and portable information terminal devices.
- touch panels having a mechanism for operating devices by holding down the display on the screen are rapidly spreading.
- a touch panel has, for example, a mobile phone such as a smartphone, a tablet PC, a personal digital assistant device, a bank ATM, a vending machine, a personal digital assistant (PDA), a copying machine, a facsimile machine, and a game machine due to its excellent operability.
- PDA personal digital assistant
- a transparent conductive laminate having a transparent conductive layer provided on a transparent substrate is generally used.
- ITO indium-tin oxide
- a film such as a PET film or a polycarbonate film is often used from the viewpoint of high transparency and price.
- These base films may be provided with a transparent hard coat layer for the purpose of improving scratch resistance and durability.
- production of this interference fringe brings about the fall of visibility.
- interference fringes depends on the refractive index difference between the transparent substrate film and the transparent hard coat layer and the extremely slight variation in the film thickness of the transparent hard coat layer.
- the generation of such interference fringes is theoretically eliminated by completely eliminating variations in the film thickness of the transparent hard coat layer.
- such means are unrealistic in the current technology and are extremely difficult to implement.
- JP 2009-265590 A discloses a hard coating agent using fine particles of metal oxide such as zirconia, titanium oxide, ITO, ATO, ZnO, tin oxide, and zinc antimonate as a high refractive index agent. Describes a method of adjusting the refractive index of the hard coat layer by blending into the hard coat layer.
- a high refractive index agent such as a metal oxide
- Patent Document 2 describes a transparent hard coat layer-containing film having excellent visibility. And this patent document 2 has a reference about a high refractive index layer.
- the high refractive index layer in Patent Document 2 is formed by vapor deposition or sputtering of a metal oxide such as ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 , ITO, or the like. It is formed by dispersing in a binder resin (such as [0007] paragraph).
- Patent Document 3 describes a coating material that is formed in a layer on a transparent base body and has no noticeable interference fringes.
- This coating material is characterized in that the attenuation coefficient is adjusted by blending fine particles and / or pigments.
- various metals, metal oxides, metal nitrides, metal carbides are listed as fine particles, and azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, quinophthalone pigments are used as pigments. Pigments are mentioned (such as [0021] paragraph).
- Patent Documents 1 to 3 disclose means for preventing generation of interference fringes and improving visibility. However, all of these Patent Documents 1 to 3 differ from the present invention in that a high refractive index agent such as a metal oxide is used.
- Patent Document 4 describes an optical laminate in which the high refractive index hard coat layer contains a bromine-based resin (claim 1 and the like). This optical laminate is described as having improved optical characteristics, light resistance, hardware performance, and the like. On the other hand, the present invention does not use a brominated resin in increasing the refractive index of the hard coat layer, and the configuration of the invention is different from this invention.
- Patent Document 5 JP-A-2008-239673
- Patent Document 5 describes a transparent crosslinked film obtained by curing and crosslinking a vinyl ester composition, a polyfunctional acrylate and a composition containing a (meth) acrylate having a fluorene skeleton. (Claim 1).
- This transparent crosslinked film is characterized by excellent surface hardness and no interference fringes.
- the test is performed under the condition of a film thickness of 50 ⁇ m. This film thickness is very high compared with the film thickness generally used in the field of hard coat layers. Therefore, there is a cost disadvantage.
- production suppression effect in the crosslinked film obtained by the composition described in this patent document 5 has not reached the level currently calculated
- an object of the present invention is to provide a hard coating composition that forms a hard coat layer having high visibility and good hardness and also having extensibility.
- the present invention can also provide a technique that can effectively prevent defects such as adhesion between layered materials such as a resin film, that is, a blocking phenomenon, without adversely affecting the visibility.
- the present invention (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule
- a hard coating composition comprising an acrylate compound, 60 to 85 parts by mass of phenol novolac acrylate (A) and 15 to 30 parts by mass of (meth) acrylate (B) with respect to 100 parts by mass of the resin component contained in the hard coating composition, A hard coating composition is provided, which solves the above problems.
- the phenol novolac acrylate (A) is represented by the following formula (I)
- R 1 is H or CH 2 OH
- R 2 is H or OH
- n is 2 to 5
- m is 0 to 5.
- the (meth) acrylate (B) is more preferably an aromatic group-containing (meth) acrylate having a refractive index in the range of 1.56 to 1.64.
- the total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide is more preferably 0.0001% by mass or less in the composition.
- the hard coat coating composition further comprises a component (C) a fluorene skeleton-containing (meth) acrylate having 2 or more (meth) acrylate groups, May include
- the phenol novolac acrylate (A) is 40 to 70 parts by mass
- the (meth) acrylate (B) is 10 to 30 parts by mass
- the contained (meth) acrylate (C) is preferably contained in an amount of 15 to 40 parts by mass.
- the fluorene skeleton-containing (meth) acrylate (C) is represented by the following formula (II)
- each R 3 is independently H or CH 3 ;
- A is independently, -OCH 2 CH 2 -, - OCH 2 CH 2 CH 2 -, - OCH (CH 3) CH 2 — Or —OCH 2 CH (CH 3 ) —, and each R is independently H or CH 3 .
- the present invention also provides A transparent polymer substrate, and A hard coat layer formed by coating the hard coating composition on a substrate; A hard coat film having The hard coat layer has a refractive index of 1.565 to 1.620, A hard coat film is also provided.
- the thickness of the hard coat layer is more preferably 0.05 to 10 ⁇ m.
- the hard coat film is The substrate is a PET film having a thickness of 20 to 300 ⁇ m, More preferably, the hard coat film is characterized in that no crack is generated in the hard coat layer when the film is stretched 15% in the MD direction at 20 ° C. under the condition of a pulling speed of 5 mm / sec.
- the hard coat film is
- the base material is a polycarbonate film having a thickness of 30 to 200 ⁇ m, More preferably, the hard coat film is characterized in that cracks do not occur in any of the hard coat layer and the substrate when bent at 180 ° under the conditions of 25 ° C. and 60 degrees / second.
- the present invention also provides a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of the hard coat film. More preferably, the transparent conductive layer is a crystalline layer containing indium oxide, and the thickness of the transparent conductive layer is 5 to 50 nm.
- a metal oxide layer is present between the hard coat layer and the transparent conductive layer, and the thickness of the metal oxide layer is 0.5 to 5.0 nm.
- the present invention also provides a touch panel having the transparent conductive laminate.
- a high refractive index anti-blocking layer-forming composition comprising a first component and a second component,
- the first component is an unsaturated double bond-containing acrylic copolymer
- the second component is (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Including acrylate,
- the phenol novolac acrylate (A) is contained in an amount of 60 to 85 parts by mass and the (meth) acrylate (B) in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component.
- the difference ⁇ SP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 4,
- the first component and the second component cause layer separation, and an antiblocking layer having fine irregularities on the surface is formed.
- a high-refractive index anti-blocking layer forming composition is provided, which solves the above problems.
- the phenol novolac acrylate (A) is represented by the following formula (I)
- R 1 is H or CH 2 OH
- R 2 is H or OH
- n is 2 to 5
- m is 0 to 5.
- the (meth) acrylate (B) is preferably an aromatic group-containing (meth) acrylate having a refractive index in the range of 1.56 to 1.64.
- the total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide is 0.0001% by mass or less in the composition. preferable.
- the present invention also provides A transparent polymer substrate, and An anti-blocking layer formed by coating the substrate with the high refractive index anti-blocking layer forming composition, An anti-blocking film having The anti-blocking layer has a refractive index of 1.565 to 1.620, and The anti-blocking layer has an arithmetic average roughness (Ra) of 0.001 to 0.09 ⁇ m and a ten-point average roughness (Rz) of 0.01 to 0.5 ⁇ m.
- Ra arithmetic average roughness
- Rz ten-point average roughness
- the thickness of the anti-blocking layer is preferably 0.05 to 10 ⁇ m.
- the substrate is a PET film having a thickness of 20 to 300 ⁇ m
- Examples of the anti-blocking film include those characterized in that no cracks are generated in the anti-blocking layer when the film is stretched 15% in the MD direction at 20 ° C. under a pulling speed of 5 m / min.
- the base material is a polycarbonate film having a thickness of 30 to 200 ⁇ m
- Examples of the anti-blocking film include those characterized in that cracks do not occur in either the anti-blocking layer or the substrate when bent 180 ° under the conditions of 25 ° C. and 60 degrees / second.
- the anti-blocking film preferably has a total light transmittance of 88% or more and a haze value of 2% or less.
- the present invention further provides a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of the anti-blocking film.
- the transparent conductive layer is a crystalline layer containing indium oxide and the thickness of the transparent conductive layer is 5 to 50 nm.
- a metal oxide layer exists between the anti-blocking layer and the transparent conductive layer, and the thickness of the metal oxide layer is 0.5 to 5.0 nm.
- the present invention also provides a touch panel having the transparent conductive laminate.
- the hard coating composition of the present invention provides a transparent hard coat layer provided on a transparent polymer substrate.
- the transparent hard coat layer formed by the hard coating composition of the present invention is characterized by having good hardness and high visibility and extensibility.
- the transparent hard coat layer formed by the hard coating composition of the present invention has a high refractive index. Therefore, even when the transparent hard coat layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.
- the hard coating composition of the present invention is further characterized by having a high refractive index even without containing a high refractive index agent such as a metal oxide. Therefore, the obtained transparent hard coat layer is characterized by having high extensibility in addition to high hardness and refractive index.
- a fluorene skeleton-containing (meth) acrylate having two or more (meth) acrylate groups is blended as the component (C). You can also. When the component (C) is blended, the refractive index can be set higher.
- the hard coating composition of the present invention even when a transparent hard coat layer is formed on a base film having a high refractive index such as a PET film or a polycarbonate film, it has high visibility and good hardness. In addition, there is an advantage that a hard coat layer having extensibility is provided.
- the anti-blocking layer-forming composition of the present invention can provide an anti-blocking layer that is a resin layer having irregularities on the surface, simply by photocuring after coating on a substrate and drying as necessary. .
- the obtained anti-blocking film has high hardness and is hardly damaged.
- no particulate matter having an average particle diameter of more than 0.5 ⁇ m is used, there is an advantage that visibility and optical characteristics are not impaired.
- the anti-blocking film obtained by coating the anti-blocking layer forming composition of the present invention exhibits an effect that a blocking phenomenon (for example, interlayer adhesion) does not occur even when a plurality of the anti-blocking films are overlapped.
- a blocking phenomenon for example, difficulty of peeling from a winding roll
- the obtained anti-blocking layer has a high refractive index and also has excellent extensibility. Due to this feature, the occurrence of interference fringes can be suppressed, and there is an advantage that extremely high visibility is achieved.
- 4 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Example E1.
- 6 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Comparative Example E10.
- 4 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Example F1.
- the hard coating composition of the present invention comprises: (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Contains acrylate compounds.
- the phenol novolac acrylate (A) is contained in an amount of 40 to 90 parts by mass and the (meth) acrylate (B) is contained in an amount of 10 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
- the hard coating composition of the present invention comprises (A) a phenol novolac acrylate having 2 or more acrylate groups.
- the hard coating composition contains the phenol novolac acrylate (A)
- the resulting hard coat layer becomes a high refractive index layer that is transparent and has high hardness. Thereby, generation
- Phenol novolac acrylate (A) is represented by the following formula (I)
- R 1 is H or CH 2 OH
- R 2 is H or OH
- n is 2 to 5
- m is 0 to 5.
- n is preferably 2 to 4
- m is preferably 0 to 3
- more preferably n is 2 to 4
- m is more preferably 0 to 1.
- the weight average molecular weight of the phenol novolac acrylate (A) is preferably 400 to 2500, more preferably 450 to 2000.
- the hydroxyl value of the phenol novolak acrylate (A) is preferably 100 to 180 mgKOH / g, more preferably 120 to 160 mgKOH / g.
- the weight average molecular weight of each component can be measured by a gel permeation chromatography method.
- a high-speed GPC device such as HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.
- HLC-8220GPC manufactured by Tosoh Corporation
- 2 g of a test sample was weighed and treated in a vacuum dryer at 40 ° C. for 2 hours to remove moisture, and then a THF solution. And a measurement is performed under the conditions of a column injection amount: 10 ⁇ l and a flow rate: 0.35 ml / min.
- the phenol novolac acrylate (A) is provided on the condition that it is contained in an amount of 60 to 85 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
- the amount of the phenol novolac acrylate (A) is less than 60 parts by mass and when the amount of the phenol novolac acrylate (A) exceeds 85 parts by mass, the hardness of the resulting hard coat layer is low. There is a bug.
- (B) Aromatic group-containing mono- or poly (meth) acrylate compound having 1 to 2 mol of alkylene oxide structure of 2 or 3 carbon atoms in the molecule.
- the hard coating composition of the present invention comprises (B) 2 or 3 carbon atoms. And an aromatic group-containing mono- or poly (meth) acrylate having 1 to 2 mol of an alkylene oxide structure in the molecule.
- the (meth) acrylate (B) preferably has a viscosity of less than 300 mPa ⁇ s and a refractive index in the range of 1.56 to 1.64.
- the viscosity of component (B) it is possible to design the viscosity of component (B) to be less than 300 mPa ⁇ s by including 1-2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Become. Further, in the (meth) acrylate of the component (B), when the alkylene oxide structure having 2 or 3 carbon atoms is contained in the molecule in an amount of 1 to 2 mol, the extensibility of the obtained hard coat layer is improved.
- examples of the “alkylene structure having 2 or 3 carbon atoms” include an ethylene oxide structure and a propylene oxide structure.
- Component (B) (meth) acrylate is further characterized by having an aromatic group.
- a high refractive index such as a refractive index in the range of 1.56 to 1.64 is achieved.
- Examples of the aromatic group-containing (meth) acrylate that can be preferably used as the component (B) in the present invention include, for example, an alkyleneoxylated phenol (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule.
- Examples include acrylate, alkyleneoxylated orthophenylphenol (meth) acrylate, alkyleneoxylated metaphenylphenol (meth) acrylate, alkyleneoxylated paraphenylphenol (meth) acrylate, and alkyleneoxylated cumylphenol (meth) acrylate.
- (meth) acrylate having two aromatic groups is more preferable in that it has a high refractive index.
- the refractive index of component (B) can be measured with an Abbe refractometer by a method based on JIS K0062.
- the viscosity of the component (B) is preferably less than 300 mPa ⁇ s.
- the viscosity of component (B) is more preferably in the range of 1 to 300 mPa ⁇ s, still more preferably in the range of 1 to 200 mPa ⁇ s.
- the viscosity of component (B) can be measured with a B-type viscometer (TVB-22L, manufactured by Toki Sangyo Co., Ltd.).
- B-type viscometer examples include TVB-22L (manufactured by Toki Sangyo Co., Ltd.).
- Component (B) preferably has a weight average molecular weight in the range of 150 to 600, and more preferably in the range of 200 to 400.
- the component (B) is contained in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
- the (meth) acrylate (B) is contained in the hard coating composition in the above mass range, there is an advantage that the obtained hard coat layer has high hardness and high refractive index.
- the amount of the component (B) is less than 15 parts by mass and when the amount of the component (B) exceeds 30 parts by mass, there is a problem that the hardness of the obtained hard coat layer is lowered.
- (C) A fluorene skeleton-containing (meth) acrylate having two or more (meth) acrylate groups
- skeleton containing (meth) acrylate (C) which has the (meth) acrylate group beyond it is mentioned. Since the fluorene skeleton-containing (meth) acrylate (C) has a high refractive index, there is an advantage that the refractive index of the obtained hard coat layer can be set high.
- each R 3 is independently H or CH 3 ;
- A is independently, -OCH 2 CH 2 -, - OCH 2 CH 2 CH 2 -, - OCH (CH 3) CH 2 — Or —OCH 2 CH (CH 3 ) —, and each R is independently H or CH 3 .
- a more preferred example of the fluorene skeleton-containing (meth) acrylate (C) is an acrylate monomer represented by the following formula (II) -1.
- (II) -1 [In the above formula (II) -1, each R represents a hydrogen atom or a methyl group, and m and n each independently represents an integer of 1 to 5. ]
- fluorene skeleton-containing (meth) acrylate (C) a commercially available product may be used.
- the commercially available fluorene skeleton-containing (meth) acrylate (C) include the NK ester series marketed by Shin-Nakamura Chemical Co., Ltd. and the Ogsol EA series marketed by Osaka Gas Chemical Co., Ltd.
- the phenol novolac acrylate (A) is 40 to 70 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
- Parts, (meth) acrylate (B) is contained in an amount of 10 to 30 parts by mass
- fluorene skeleton-containing (meth) acrylate (C) is contained in an amount of 15 to 40 parts by mass.
- the phenol novolac acrylate (A) is 40 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition. It is necessary to contain ⁇ 70 parts by mass.
- the amount of the phenol novolac acrylate (A) is less than 40 parts by mass and when the amount of the phenol novolac acrylate (A) exceeds 70 parts by mass, the hardness of the obtained hard coat layer is low. There is a bug.
- the (meth) acrylate of the component (B) is based on 100 parts by mass of the resin component contained in the hard coating composition. It is necessary to contain 10 to 30 parts by mass.
- the (meth) acrylate (B) is contained in the hard coating composition in the above mass range, there is an advantage that the obtained hard coat layer has high hardness and high refractive index.
- the amount of the component (B) is less than 10 parts by mass and when the amount of the component (B) exceeds 30 parts by mass, there is a problem that the hardness of the obtained hard coat layer is lowered.
- the component (C) When the fluorene skeleton-containing (meth) acrylate of the component (C) is contained in the hard coat coating composition, the component (C) is contained in 15 to 40 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition. On condition that When the amount of the component (C) exceeds 40 parts by mass, the hardness of the obtained hard coat layer may be lowered.
- the hard coating composition of the present invention may contain other (meth) acrylates in addition to the components (A) and (B) and, if necessary, the component (C).
- examples of such (meth) acrylates include polyfunctional (meth) acrylate monomers and / or oligomer compounds. These polyfunctional (meth) acrylate monomers and / or oligomer compounds have a high hardness due to a curing reaction based on the reaction of (meth) acryloyl groups by irradiation with active energy rays after the hard coating composition is applied. There is an advantage that a hard coat layer can be obtained.
- the polyfunctional (meth) acrylate monomer and / or oligomer compound preferably has three or more (meth) acryloyl groups.
- three or more (meth) acryloyl groups there is an advantage that a hard coat layer having high hardness can be obtained after irradiation with active energy rays.
- polyfunctional (meth) acrylate monomer and / or oligomer compound include, for example, hydroxypropylated trimethylolpropane triacrylate, isocyanuric acid ethylene oxide modified diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and trimethylolpropane triacrylate.
- examples thereof include acrylate, tris (acryloxyethyl) isocyanurate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and oligomers thereof. These monomers or oligomers may be used alone or in combination of two or more.
- the hard coating composition contains other (meth) acrylates, it is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition. More preferably, it is in the range of parts by mass.
- the hard coating composition of the present invention such as a photopolymerization initiator preferably contains a photopolymerization initiator. Due to the presence of the photopolymerization initiator, the resin component is favorably polymerized by irradiation with active energy rays such as ultraviolet rays.
- photopolymerization initiators include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and oxime ester polymerization initiators.
- alkylphenone photopolymerization initiators examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane.
- acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
- titanocene photopolymerization initiators include bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium Is mentioned.
- Examples of the oxime ester polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy And ethoxy) ethyl ester.
- These photoinitiators may be used individually by 1 type, and may use 2 or more types together.
- a preferable amount of the photopolymerization initiator is 100 parts by mass of the above components (A) and (B), and if necessary, the component (C) and other (meth) acrylates (these are collectively referred to as “resin component”).
- the amount is 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass.
- the hard coating composition used in the present invention may contain a solvent.
- the solvent is not particularly limited, and can be appropriately selected in consideration of the components contained in the composition, the type of base material to be coated, the coating method of the composition, and the like.
- Specific examples of the solvent that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol.
- Ether solvents such as dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate and ethylene glycol diacetate; dimethylformamide, Amide solvents such as diethylformamide and N-methylpyrrolidone; methyl Cellosolve, ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, alcohol solvents such as propanol; and the like; dichloromethane, halogenated solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.
- the hard coating composition of the present invention can contain various additives as required.
- additives include conventional additives such as antistatic agents, plasticizers, surfactants, and antioxidants.
- the hard coating composition of the present invention does not need to contain a high refractive index agent composed of a metal oxide such as ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 or indium-tin oxide due to the above configuration. It is characterized in that a hard coat layer having a high refractive index can be formed. Therefore, the hard coating composition of the present invention does not contain a high refractive index agent such as a metal oxide selected from the group consisting of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide. Is preferred.
- the hard coating composition preferably has a total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide of 0.0001% by mass or less in the composition. . This is because when a high refractive index agent such as a metal oxide is present in the hard coat layer, the stretchability and the bending resistance are generally inferior as compared with the layer containing only the resin component.
- the present invention further provides a hard coat film formed using the above hard coating composition.
- This hard coat film has a transparent polymer base material and a hard coat layer formed by coating the base material with the hard coating composition.
- the hard coat layer in the present invention is characterized by having a high refractive index of 1.565 to 1.620.
- a PET film or a polycarbonate film is preferably used as the transparent polymer substrate.
- the PET film and the polycarbonate film are suitably used as a base film for a film having a transparent conductive layer constituting a touch panel from the viewpoints of high film strength and transparency and low cost.
- these films generally have a high refractive index of 1.5 or more. Since the refractive index of these films is higher than the refractive index of the resin component constituting the normally used hard coat film, the difference in refractive index with the hard coat layer increases, and the frequency of occurrence of interference fringes increases. There's a problem.
- the interference fringes refer to iris-like reflection caused by interference of light reflected at each interface in a multilayer body composed of a transparent film and a transparent coat layer. This interference fringe tends to appear prominently under irradiation of a three-wavelength fluorescent lamp.
- the three-wavelength light-emitting fluorescent lamp is a fluorescent lamp characterized by a strong emission intensity at a specific wavelength, which is characterized by the fact that things can be clearly seen.
- the hard coating composition of the present invention is characterized in that a hard coat layer having a high refractive index can be formed. Therefore, even if a transparent hard coat layer is formed on a transparent substrate film such as a PET film or a polycarbonate film, there is a feature that no interference fringes are generated.
- the hard coating composition of the present invention may be applied to a base film other than the PET film or the polycarbonate film.
- a base film include triacetyl cellulose (TAC) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, and polysulfone.
- TAC triacetyl cellulose
- diacetylene cellulose film acetate butyrate cellulose film
- polyether sulfone film polyacrylic resin film, polyurethane resin film, polyester film, and polysulfone.
- examples thereof include a film, a polyether film, a polymethylpentene film, a polyether ketone film, and a (meth) acrylonitrile film.
- the thickness of the transparent polymer substrate can be appropriately selected according to the use, but is generally about 20 to 300 ⁇ m.
- the hard coat layer is formed by applying the above hard coating composition on a transparent polymer substrate.
- the coating method of the hard coating composition can be selected as appropriate according to the situation of the hard coating composition and the painting process. For example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method It can be applied by a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294).
- the thickness of the hard coat layer is not particularly limited and can be set in a timely manner in consideration of various factors.
- the hard coating composition can be applied so as to obtain a hard coat layer of 0.01 to 20 ⁇ m.
- a hard coat layer is formed by curing the coating film obtained by applying the coating composition.
- This curing can be performed by irradiation using a light source that emits an active energy ray having a wavelength as required.
- a light source that emits an active energy ray having a wavelength as required.
- the active energy ray to be irradiated for example, light having an exposure dose of 0.1 to 1.5 J / cm 2 , preferably 0.3 to 1.5 J / cm 2 can be used.
- the wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like.
- the hard coat film of the present invention is characterized in that a high refractive index of 1.565 to 1.620 of the hard coat layer is achieved without using a high refractive index agent.
- the refractive index of the hard coat layer can be measured in accordance with JIS K7142 using, for example, an Abbe refractometer.
- the hard coat film of the present invention preferably has a total light transmittance of 85% or more, more preferably 90% or more. Further, the hard coat film of the present invention preferably has a haze of 2% or less, more preferably 1% or less.
- ZnO since the TiO 2, CeO 2, SnO 2 , be free of high refractive index such as ZrO 2 high refractive index has been achieved, need to include such a high refractive index agent There is no. Therefore, it is possible to achieve a high total light transmittance and a low haze value as described above.
- the total light transmittance (T t (%)) is calculated by the following equation by measuring the incident light intensity (T 0 ) with respect to the hard coat film and the total transmitted light intensity (T 1 ) transmitted through the hard coat film. .
- the haze is calculated from the following formula in accordance with JIS K7105.
- H Haze (cloudiness value) (%)
- T d Diffuse transmittance (%)
- T t Total light transmittance (%)
- the total light transmittance and the haze value can be measured using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
- the hard coat layer formed using the hard coating composition of the present invention is characterized by having high extensibility in addition to high hardness and refractive index. Therefore, the hard coat film in this invention can be used suitably in preparation of the film which has a transparent conductive layer which comprises a touchscreen etc., for example.
- a transparent conductive layer and an optical interference layer for controlling the reflectance by optical interference can be used in combination in an appropriate order as required.
- the order in which the transparent conductive layer, the optical interference layer, and the hard coat layer are laminated is not particularly limited as long as the function expected to be exhibited is achieved according to the application.
- the transparent conductive layer is A
- the optical interference layer is B
- the hard coat layer that is the subject of the present invention is C
- the transparent polymer substrate is D
- the subject is not subject to the present invention.
- a / B / C / D / E, A / B / C / D / C, A / B / B / C / D / E, A / B / B / C / D / C, A / C / D / E / B, A / C / D / C / B, A / C / D / E / B, A / C / D / C / B, A / C / D / E / B / B, A / C / D / C / B / B, etc. can do.
- the optical interference layer described above refers to a layer that prevents or suppresses reflected light by appropriately combining a high refractive index layer and a low refractive index layer.
- the optical interference layer is composed of at least one high refractive index layer and at least one low refractive index layer. Two or more combination units of the high refractive index layer and the low refractive index layer may be used.
- the thickness of the optical interference layer is preferably 30 nm to 150 nm, and more preferably 50 nm to 150 nm.
- the optical interference layer can be formed by either a wet method or a dry method.
- a wet method such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, etc., spray method, dipping method, etc., dry method such as PVD method such as sputtering method, vacuum deposition method, ion plating method, etc. Printing method, CVD method, etc. can be applied.
- a transparent conductive laminate constituting a touch panel or the like is generally a film having a transparent conductive layer.
- the transparent conductive layer is not particularly limited, but is a crystalline layer containing indium oxide, more specifically indium such as ITO (indium-tin oxide) and IZO (indium-zinc oxide).
- ITO indium-tin oxide
- IZO indium-zinc oxide
- a crystalline layer is preferably used.
- a method for forming the transparent conductive layer there are a PVD method such as a sputtering method, a vacuum deposition method, and an ion plating method, a coating method, a printing method, and a CVD method, and the PVD method or the CVD method is preferable.
- the hard coat layer provided using the hard coating composition of the present invention is characterized by having high visibility and good hardness and high extensibility. Due to the high extensibility of the obtained hard coat layer, even when the base film is locally thermally expanded by heating in the stage of providing the transparent conductive layer, the hard coat layer follows well, As a result, there is an advantage that defects such as film warp do not occur.
- the transparent polymer substrate on which the hard coating composition is applied is a hard coat film having a thickness of 20 to 300 ⁇ m
- this hard coat film When the film is stretched by 15% in the MD direction at 20 ° C. under the condition of a pulling speed of 5 mm / sec, there is a state in which no crack is generated in the hard coat layer.
- the thickness of the hard coat layer is, for example, 0.05 to 10 ⁇ m.
- the production of a polymer base film is performed by winding a resin base material in a molten state in a roll shape while being perpendicular to the vertical direction (winding direction: MD direction) and the horizontal direction (TD direction: MD direction).
- the film is produced by a biaxial stretching method in which a film having a uniform thickness is produced.
- high stress remains in the MD direction. Therefore, the obtained film tends to cause thermal expansion / shrinkage particularly in the MD direction.
- Generation of cracks (film cracks) and the like can be effectively verified by performing a test in which the obtained hard coat film is stretched in the MD direction, which is the direction wound during the production of the polymer base film. There is an advantage.
- the transparent polymer substrate constituting the hard coat film is a polycarbonate film
- the elongation performance of the formed hard coat layer can be evaluated by verifying the bending resistance of the hard coat film.
- Polycarbonate is a material with excellent physical properties such as heat resistance and impact resistance, but especially in the case of a polycarbonate film with a thin film thickness, cracks may occur due to stress such as bending.
- a polycarbonate film having a thin film thickness is used as a base film, when the hard coat layer formed on the base film has high extensibility, by providing the hard coat layer, It becomes possible to prevent the occurrence of cracks.
- the hard coat layer formed by the hard coating composition of the present invention has high extensibility.
- the hard coat film using a polycarbonate having a thin film thickness as a base film there is an advantage that toughness against bending stress can be improved. More specifically, when the transparent polymer substrate to which the hard coating composition is applied is a hard coat film which is a polycarbonate film having a thickness of 30 to 200 ⁇ m, the hard coat film is treated at 25 ° C. and 60 degrees / degree. Even when it is bent 180 ° under the second condition, there is a state in which no crack occurs in either the hard coat layer or the substrate.
- the thickness of the hard coat layer may be 0.05 to 10 ⁇ m.
- the hard coat layer formed using the hard coating composition of the present invention is characterized by having good hardness and high visibility and extensibility.
- the transparent hard coat layer formed by the hard coating composition of the present invention has a high refractive index. Therefore, even when the transparent hard coat layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.
- the hard coat layer in the present invention can be suitably used in a film having a transparent conductive layer constituting a touch panel electrode.
- the high refractive index antiblocking layer forming composition of the present invention comprises a first component and a second component.
- the first component is an unsaturated double bond-containing acrylic copolymer.
- the second component includes (A) a phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule.
- the phenol novolac acrylate (A) is contained in an amount of 60 to 85 parts by mass and the (meth) acrylate (B) in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component.
- the difference ⁇ SP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 4, and the first component and the second component contained in the composition
- This high refractive index anti-blocking layer forming composition is characterized in that after coating, the first component and the second component cause layer separation, and an anti-blocking layer having fine irregularities on the surface is formed.
- an unsaturated double bond-containing acrylic copolymer is used as the first component.
- An unsaturated double bond-containing acrylic copolymer is, for example, a resin obtained by copolymerizing a (meth) acrylic monomer and another monomer having an ethylenically unsaturated double bond, a (meth) acrylic monomer and another ethylenically unsaturated Acrylic acid or glycidyl acrylate for resins reacted with monomers having double bonds and epoxy groups, resins made by reacting (meth) acrylic monomers with other monomers having ethylenically unsaturated double bonds and isocyanate groups, etc. And those having an unsaturated double bond and other functional groups added thereto.
- the unsaturated double bond-containing acrylic copolymers may be used alone, or two or more thereof may be mixed and used.
- the unsaturated double bond-containing acrylic copolymer preferably has a weight average molecular weight of 2,000 to 100,000, more preferably 5,000 to 50,000.
- the second component is: (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Acrylate, including.
- a phenol novolak acrylate having 2 or more acrylate groups and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Acrylate, including.
- the phenol novolac acrylate (A) is provided on the condition that it is contained in an amount of 60 to 85 parts by mass with respect to 100 parts by mass of the second component.
- the amount of the phenol novolac acrylate (A) is less than 60 parts by mass and when the amount of the phenol novolac acrylate (A) exceeds 85 parts by mass, the hardness of the obtained anti-blocking layer is low. There is a bug.
- (B) Aromatic group-containing mono- or poly (meth) acrylate compound having 1 to 2 mol of alkylene oxide structure of 2 or 3 carbon atoms in the molecule.
- This component (B) is a component of component (B) of the hard coat coating composition. The description is omitted because it is an aromatic group-containing mono- or poly (meth) acrylate compound having the same alkylene oxide structure having 2 or 3 carbon atoms in the molecule and having 1 to 2 mol in the molecule.
- the component (B) is included in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component contained in the high refractive index antiblocking layer forming composition.
- the obtained anti-blocking layer has an advantage of high hardness and high refractive index.
- the amount of the component (B) is less than 15 parts by mass and when the amount of the component (B) exceeds 30 parts by mass, there is a problem that the hardness of the obtained anti-blocking layer is lowered.
- the second component in the high refractive index anti-blocking layer forming composition of the present invention may contain other (meth) acrylates in addition to the components (A) and (B). Omitted Such (meth) acrylates are the same as "other (meth) acrylates" according to the hard coating composition.
- the second component contained in the high-refractive index anti-blocking layer forming composition contains other (meth) acrylates
- 100 parts by mass of the second component contained in the high-refractive index anti-blocking layer forming composition The range is preferably 1 to 30 parts by mass, and more preferably 1 to 25 parts by mass.
- High refractive index antiblocking layer forming composition is composed of a first component and a second component, and addition of a solvent, a photopolymerization initiator, a catalyst, a photosensitizer and the like as required. It is prepared by mixing the agent.
- phase separation is caused by the difference in SP value between the first component and the second component.
- the difference ( ⁇ SP) between the SP value of the first component and the SP value of the second component is within the range of 1 to 4.
- the compatibility of the resins with each other is low, whereby the first component and the second component are applied after application of the anti-blocking layer forming composition. It is thought that phase separation is brought about.
- the ⁇ SP is more preferably in the range of 2.0 to 3.5.
- the SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility.
- solubility parameter is a measure of solubility.
- the SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller.
- the SP value can be measured by the following method [References: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].
- Measurement temperature 20 ° C
- Sample Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
- solvent Good solvent: Dioxane, acetone, etc. Poor solvent: n-hexane, ion-exchanged water, etc.
- Muddy point measurement The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.
- the SP value ⁇ of the resin is given by the following equation.
- the high refractive index antiblocking layer-forming composition of the present invention may further contain components such as various solvents, photopolymerization initiators and additives in addition to the first component and the second component.
- Preferred organic solvents when the first component and the second component are the above combinations include, for example, ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol
- An ether solvent such as anisole, phenetol propylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether;
- One of these solvents may be used alone, or two or more organic solvents may be mixed and used.
- a solvent for example, 1 to 9900 parts by mass, preferably 10 to 900 parts by mass are added to 100 parts by mass of the total amount of the first component and the second component (collectively referred to as “resin component”). Can do.
- the high refractive index anti-blocking layer forming composition preferably contains a photopolymerization initiator.
- the photopolymerization initiator include 2-hydroxy-2methyl-1phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Can be mentioned.
- a preferable amount of the photopolymerization initiator is 0.01 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin component.
- the high refractive index anti-blocking layer forming composition may contain conventional additives such as an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, if necessary.
- additives such as an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, if necessary.
- the amount is preferably 0.01 to 20 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin component.
- the high refractive index anti-blocking layer forming composition can form a resin layer having irregularities without using resin particles or the like by using the first component and the second component as described above. There is. Therefore, it is preferable that the anti-blocking layer forming composition does not contain resin particles.
- the anti-blocking layer forming composition may contain at least one or more inorganic particles, organic particles, or a composite thereof, if necessary. These particles are not particularly added for the purpose of forming irregularities on the surface, but are added to form more uniform and fine irregularities by controlling phase separation and precipitation. These particles have an average particle size of 0.5 ⁇ m or less, preferably 0.01 to 0.3 ⁇ m. When it exceeds 0.5 ⁇ m, the transparency slightly decreases.
- inorganic particles include silica, alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO There may be mentioned at least one selected from the group consisting of (antimony oxide / tin oxide), tin oxide, indium oxide and antimony oxide.
- organic particles include at least one selected from the group consisting of acrylic, olefin, polyether, polyester, urethane, polyester, silicone, polysilane, polyimide, and fluorine particles.
- the anti-blocking layer having fine irregularities on the surface can be formed by coating the high refractive index anti-blocking layer forming composition and then curing the composition.
- the coating method of the anti-blocking layer forming composition include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and extrusion coating.
- the thickness of the anti-blocking layer include an embodiment having a thickness of 0.01 to 20 ⁇ m.
- the high refractive index antiblocking layer-forming composition After coating the high refractive index antiblocking layer-forming composition, it can be phase separated and cured by irradiating light.
- the light to be irradiated for example, light having an exposure amount of 0.1 to 3.5 J / cm 2 , preferably 0.5 to 1.5 J / cm 2 can be used.
- the wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing will occur.
- Anti-blocking film This invention further provides the anti-blocking film formed using the said high refractive index anti-blocking layer forming composition.
- This anti-blocking film has a transparent polymer base material and an anti-blocking layer formed by coating the high refractive index anti-blocking layer forming composition on the base material.
- the anti-blocking layer in the present invention is characterized by having a high refractive index of 1.565 to 1.620 in addition to having an excellent anti-blocking performance.
- a PET film or a polycarbonate film is preferably used as the transparent polymer substrate.
- the PET film and the polycarbonate film are suitably used as a base film for a film having a transparent conductive layer constituting a touch panel from the viewpoints of high film strength and transparency and low cost.
- these films generally have a high refractive index of 1.5 or more. Since the refractive index of these films is higher than the refractive index of the resin component constituting the commonly used anti-blocking film, the difference in refractive index with the anti-blocking layer increases, and the frequency of occurrence of interference fringes increases. There's a problem.
- the interference fringes refer to iris-like reflection caused by interference of light reflected at each interface in a multilayer body composed of a transparent film and a transparent coat layer. This interference fringe tends to appear prominently under irradiation of a three-wavelength fluorescent lamp.
- the three-wavelength light-emitting fluorescent lamp is a fluorescent lamp characterized by a strong emission intensity at a specific wavelength, which is characterized by the fact that things can be clearly seen.
- the high refractive index anti-blocking layer forming composition of the present invention is characterized in that an anti-blocking layer having a high refractive index can be formed. Therefore, even if an antiblocking layer is formed on a transparent substrate film such as a PET film or a polycarbonate film, there is a feature that no interference fringes are generated.
- the high refractive index anti-blocking layer forming composition of the present invention may be applied to a substrate film other than the PET film or the polycarbonate film.
- a base film include triacetyl cellulose (TAC) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, and polysulfone.
- TAC triacetyl cellulose
- diacetylene cellulose film acetate butyrate cellulose film
- polyether sulfone film polyacrylic resin film
- polyurethane resin film polyester film
- polysulfone examples thereof include a film, a polyether film, a polymethylpentene film, a polyether ketone film, and a (meth) acrylonitrile film.
- the thickness of the transparent polymer substrate can be appropriately selected according to the use, but is generally about 20 to 300 ⁇ m.
- the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention has fine irregularities.
- the arithmetic average roughness (Ra) of the surface roughness curve of the anti-blocking layer is preferably less than 0.1 ⁇ m, more preferably 0.001 to 0.09 ⁇ m, and 0.002 to 0.00. Particularly preferred is 08 ⁇ m.
- the arithmetic average roughness (Ra) of the roughness curve is a parameter defined in JIS B 0601-2001.
- the arithmetic average roughness (Ra) of the surface roughness curve of the anti-blocking layer is 0.1 ⁇ m or more, problems such as generation of glare and whitening of the coating film may occur. If the value of Ra is less than the particularly preferable range, a blocking phenomenon occurs, which is not preferable.
- JIS B 0601-2001 is a Japanese industrial standard and is a standard based on ISO 4288.
- Arithmetic average roughness (Ra) of the roughness curve is a sample of only the reference length in the direction of the average line from the roughness curve, the X axis in the direction of the average line of this extracted portion, and Y in the direction of the vertical magnification.
- y f (x)
- ⁇ m micrometers
- the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention preferably has an Rz of 0.5 ⁇ m or less.
- Rz is the ten-point average roughness of the roughness curve, and is a parameter defined in JIS B0601-2001.
- Rz is more preferably 0.3 ⁇ m or less, and further preferably 0.2 ⁇ m or less.
- the lower limit is preferably 0.01 ⁇ m.
- the arithmetic average roughness (Ra) and ten-point average roughness (Rz) of the surface roughness curve of the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention are, for example, manufactured by Kosaka Laboratory Ltd. Can be measured according to JIS B 0601-2001 using a high-precision fine shape measuring instrument or a color 3D laser microscope manufactured by Keyence Corporation.
- the anti-blocking layer formed by the high-refractive index anti-blocking layer forming composition of the present invention has an irregular, fine and dense uneven shape, and therefore exhibits excellent anti-blocking properties.
- the anti-blocking layer in the present invention is also advantageous in that the sharpness of an image displayed by a light source such as a liquid crystal module is not deteriorated.
- the pitch of light rays emitted from the liquid crystal has become finer. Therefore, in order to maintain image clarity, a finer and denser uneven shape is required.
- the anti-blocking layer in the present invention has an advantage that it has a fine and dense concavo-convex shape and is not accompanied by a decrease in image sharpness such as a decrease in contrast and a decrease in luminance.
- the anti-blocking layer in the present invention is characterized in that the refractive index of the anti-blocking layer is as high as 1.565 to 1.620 without using a high refractive index agent.
- the refractive index of the anti-blocking layer can be measured using an Abbe refractometer according to JIS K7142.
- the anti-blocking film of the present invention preferably has a total light transmittance of 85% or more, and more preferably 90% or more. Further, the anti-blocking film of the present invention preferably has a haze of 2% or less, more preferably 1% or less.
- ZnO since the TiO 2, CeO 2, SnO 2 , be free of high refractive index such as ZrO 2 high refractive index has been achieved, need to include such a high refractive index agent There is no. Therefore, it is possible to achieve a high total light transmittance and a low haze value as described above.
- the high refractive index anti-blocking layer forming composition has a total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide of 0.0001% by mass or less in the composition. Is preferred. This is because when a high refractive index agent such as a metal oxide is present in the anti-blocking layer, the extensibility and the bending resistance are generally inferior as compared with the resin-only layer.
- the total light transmittance (T t (%)) is calculated by the following equation by measuring the incident light intensity (T 0 ) with respect to the anti-blocking film and the total transmitted light intensity (T 1 ) transmitted through the anti-blocking film. .
- the haze is calculated from the following formula in accordance with JIS K7105.
- H Haze (cloudiness value) (%)
- T d Diffuse transmittance (%)
- T t Total light transmittance (%)
- the total light transmittance and the haze value can be measured using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
- the anti-blocking layer formed using the high refractive index anti-blocking layer forming composition of the present invention is characterized by having high extensibility in addition to high hardness and refractive index. Therefore, the anti-blocking film in this invention can be used suitably in preparation of the film which has a transparent conductive layer which comprises a touchscreen etc., for example.
- a transparent conductive layer and an optical interference layer for controlling the reflectance by optical interference can be used in combination in an appropriate order as necessary depending on the application.
- the order in which the transparent conductive layer, the optical interference layer, and the high-refractive index anti-blocking layer are stacked is not particularly limited as long as it fulfills a function expected to appear depending on the application.
- the transparent conductive layer is A
- the optical interference layer is B
- the high refractive index antiblocking layer to be the subject of the present invention is C
- the transparent polymer base material is D
- the present invention when the order of lamination is used as a substrate for a touch panel, the transparent conductive layer is A, the optical interference layer is B, the high refractive index antiblocking layer to be the subject of the present invention is C, the transparent polymer base material is D, and the present invention.
- the optical interference layer described above refers to a layer that prevents or suppresses reflected light by appropriately combining a high refractive index layer and a low refractive index layer.
- the optical interference layer is composed of at least one high refractive index layer and at least one low refractive index layer. Two or more combination units of the high refractive index layer and the low refractive index layer may be used.
- the thickness of the optical interference layer is preferably 30 nm to 150 nm, and more preferably 50 nm to 150 nm.
- the optical interference layer can be formed by either a wet method or a dry method.
- a wet method such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, etc., spray method, dipping method, etc., dry method such as PVD method such as sputtering method, vacuum deposition method, ion plating method, etc.
- a printing method, a CVD method, or the like can be applied.
- a transparent conductive laminate constituting a touch panel or the like is generally a film having a transparent conductive layer.
- the transparent conductive layer is not particularly limited, but is a crystalline layer containing indium oxide, and more specifically, mainly composed of indium such as ITO (indium-tin oxide) and IZO (indium-zinc oxide).
- ITO indium-tin oxide
- IZO indium-zinc oxide
- a crystalline layer is preferably used.
- a method for forming the transparent conductive layer there are a PVD method such as a sputtering method, a vacuum deposition method, and an ion plating method, a coating method, a printing method, and a CVD method, and the PVD method or the CVD method is preferable.
- the transparent conductive layer of the transparent conductive laminate, the anti-blocking layer and the base film may be twisted based on the difference in thermal shrinkage and thermal expansion between the two.
- the anti-blocking layer provided using the high refractive index anti-blocking layer forming composition of the present invention is characterized by having high visibility and good hardness and high extensibility.
- the resulting antiblocking layer has high extensibility, so that the antiblocking layer follows well even when the base film is locally thermally expanded by heating in the stage of providing the transparent conductive layer, etc. As a result, there is an advantage that defects such as film warp do not occur.
- the anti-blocking film in which the transparent polymer substrate on which the high refractive index anti-blocking layer forming composition is coated is a PET film having a thickness of 20 to 300 ⁇ m
- the thickness of the anti-blocking layer is, for example, 0.05 to 10 ⁇ m.
- the production of a polymer base film is performed by winding a resin base material in a molten state in a roll shape while being perpendicular to the vertical direction (winding direction: MD direction) and the horizontal direction (TD direction: MD direction).
- the film is produced by a biaxial stretching method in which a film having a uniform thickness is produced.
- high stress remains in the MD direction. Therefore, the obtained film tends to cause thermal expansion / shrinkage particularly in the MD direction.
- Generation of cracks (film cracks) and the like can be effectively verified by performing a test in which the obtained anti-blocking film is stretched in the MD direction, which is the direction wound during the production of the polymer base film. There is an advantage.
- extension performance of the formed antiblocking layer can be evaluated by verifying the bending resistance of an antiblocking film.
- Polycarbonate is a material with excellent physical properties such as heat resistance and impact resistance, but especially in the case of a polycarbonate film with a thin film thickness, cracks may occur due to stress such as bending. .
- a polycarbonate film having a thin film thickness is used as a base film in this way, when the extensibility of the anti-blocking layer formed on the base film is high, by providing an anti-blocking layer, It becomes possible to prevent the occurrence of cracks.
- the antiblocking layer formed by the high refractive index antiblocking layer forming composition of the present invention has high extensibility. Therefore, there is an advantage that the toughness against bending stress can be improved in an anti-blocking film using a polycarbonate having a thin film thickness as a base film. More specifically, when the transparent polymer base material on which the high refractive index antiblocking layer forming composition is coated is an antiblocking film which is a polycarbonate film having a thickness of 30 to 200 ⁇ m, Even when it is bent 180 ° under the conditions of 60 ° C. and 60 ° C., there is a state in which no cracks are generated in either the antiblocking layer or the substrate.
- the thickness of the anti-blocking layer is, for example, 0.05 to 10 ⁇ m.
- the anti-blocking layer formed using the high refractive index anti-blocking layer forming composition of the present invention is characterized by having good anti-blocking performance and hardness, and high visibility and extensibility.
- the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention has a high refractive index. Therefore, even when the anti-blocking layer in the present invention is provided on a substrate film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.
- the antiblocking layer in this invention can be used suitably especially in the film which has a transparent conductive layer which comprises a touchscreen electrode.
- phenol novolac type epoxy resin solution Metoquinone 1000 ppm and triphenylphosphine 2000 ppm are added to 100 parts by weight of the solid content of the obtained phenol novolac type epoxy resin, and acrylic acid is added dropwise at 100 ° C. until the acid value becomes 1 mgKOH / g or less.
- a phenol novolac type epoxy acrylate (1) was obtained.
- the obtained phenol novolak epoxy acrylate (1) had a weight average molecular weight of 950, a hydroxyl value of 140 mgKOH / g, and a refractive index of 1.572.
- the SP value was 12.7.
- Example E1 As the component (A), the phenol novolac type epoxy acrylate (1) obtained in Production Example 1 is used, and as the component (B), ethoxylated orthophenylphenol acrylate (acrylate having 1 mol of ethoxy structure in the molecule, viscosity at 25 ° C.
- a hard coating composition was prepared using 130 mPa ⁇ s and a refractive index of 1.577). The raw materials shown in Table 1 were sequentially mixed at the solid content mass shown in Table 1 and stirred to obtain a hard coating composition.
- the viscosity measurement of the ethoxylated orthophenylphenol acrylate of the component (B) was obtained by collecting 100 ml of the ethoxylated orthophenylphenol acrylate of the component (B) as a test sample in a glass container and adjusting the temperature to 20 ° C. Using a viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.) and M1Rotor, the measurement was performed at a rotation speed of 60 rpm. The refractive index of component (B) was measured using an Abbe refractometer by a method based on JIS K0062.
- the obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light using an ultraviolet irradiator (manufactured by Fusion) to obtain a PET film and a hard coat film having a 6.5 ⁇ m thick hard coat layer.
- KEFW Teijin DuPont 188 ⁇ m optical PET film
- the obtained hard coating composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 9. After coating, it was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain a hard coat film having a polycarbonate film and a hard coat layer having a thickness of 5.0 ⁇ m.
- Example E2 to E5 The hard coating composition was changed in the same manner as in Example E1 except that the type and amount of component (A) were changed to those described in Table 1 and pentaerythritol triacrylate was used as the other (meth) acrylates. A product was prepared. Using the obtained hard coating composition, two types of hard coat films were obtained in the same manner as in Example E1.
- Comparative Examples E6 and E10 With the formulation shown in Table 2, hard coating compositions were prepared as in the examples.
- the obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 13. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light using an ultraviolet irradiator (manufactured by Fusion) to obtain a PET film and a hard coat film having a 6.5 ⁇ m thick hard coat layer. Further, the obtained hard coating composition was dropped onto a 100 ⁇ m optical PC film (Pure Ace) manufactured by Teijin Chemicals and coated using a bar coater # 10. After coating, it was dried at 70 ° C.
- Comparative Examples E8, E12, E13 With the formulation shown in Table 2, hard coating compositions were prepared as in the examples. The obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 20. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion). In the case of using the hard coating composition of Comparative Example E12, a hard coat film having a PET film and a hard coat layer having a film thickness of 6.5 ⁇ m was obtained.
- KEFW Teijin DuPont 188 ⁇ m optical PET film
- the coating composition was not cured and a hard coat layer could not be provided. Further, the obtained hard coating composition was dropped onto a 100 ⁇ m optical PC film (Pure Ace) manufactured by Teijin Chemicals and coated using a bar coater # 14. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion). When the hard coating composition of Comparative Example E12 was used, a hard coat film having a polycarbonate film and a hard coat layer having a thickness of 5.0 ⁇ m was obtained. On the other hand, when the hard coating compositions of Comparative Examples E8 and E13 were used, the coating composition was not cured and a hard coat layer could not be provided.
- an ITO layer was formed, and a transparent conductive laminate to be a movable electrode substrate was produced.
- the thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150 ⁇ / ⁇ .
- the interference fringes of the obtained transparent conductive laminate were not visually recognized.
- nD 1.3 to 1.7 manufactured by Atago Co., Ltd.
- nD 1.3 to 1.7 manufactured by Atago Co., Ltd.
- nD 1.3 to 1.7 manufactured by Atago Co., Ltd.
- One drop of the intermediate solution was dropped on the sample with a dropper, and the secondary prism was closed.
- the condition is that air does not enter the intermediate liquid layer.
- Lamp light was incident on the sub-prism, the measurement knob was turned while looking through the eyepiece, the boundary of the light and darkness of the refractive field was adjusted to the intersection, the value of the scale field was read to 4 digits after the decimal point, and the refractive index was measured.
- the hardness was measured using a pencil scratch coating film hardness tester (Model P, pressure load 100 g to 1 kg, manufactured by Toyo Seiki Seisakusho).
- a pencil for pencil scratch test (manufactured by the Japan Paint Inspection Association) manufactured by Mitsubishi Uni was used and adjusted with abrasive paper (3MP-1000) so that the tip of the lead had a smooth and circular cross section.
- the pencil was fixed so that the scratch angle was 45 °, and the test was performed under the condition of a load of 750 g. For each test, the test was repeated five times while shifting the test location while smoothing the core. The presence or absence of dents on the surface of the coating film was confirmed visually based on the following evaluation criteria.
- the hardness of the PET film used in the preparation of the hard coat films of Examples and Comparative Examples is HB to F, and the hardness of the polycarbonate (PC) film is 5B to 4B. Therefore, in a hard coat film having a PET film and a hard coat layer, if the hardness is H or more, the hardness is increased by two or more stages, and it is determined that the hard coat layer has sufficient hardness. . Further, in a hard coat film having a polycarbonate film and a hard coat layer, if the hardness is 3B or more, the hardness is increased by two or more steps, and it is determined that the hard coat layer has sufficient hardness. .
- the elongation was measured using an autograph (AG-1S manufactured by Shimadzu Corporation).
- a test sample is cut out to 10 mm ⁇ 150 mm, and is sandwiched between upper and lower chucks of the measuring instrument in a direction in which the longitudinal direction of the sample is extended.
- a sample sample was stretched at a speed of 2 cm / sec under room temperature (20 ° C.) conditions, an elongation rate at which no breakage / crack occurred was obtained.
- Interference fringe evaluation method Interference fringes (appearance evaluation) The test piece was bonded to a 100 ⁇ 100 mm black acrylic plate using an optical film adhesive so that the coated surface was on the surface. A sample is placed at a distance of 10 cm vertically from the fluorescent tube of a stand-type three-wavelength fluorescent lamp (SLH-399 manufactured by TWINBARD) and visually observed. Visual observation was performed and judged based on the following evaluation criteria.
- ⁇ Interference fringes (interference patterns) are not visually recognized under a three-wavelength fluorescent lamp, but slightly visible under sunlight
- ⁇ Interference fringes (interference patterns) are slightly visible
- ⁇ Interference fringes (interference patterns) Clearly visible
- the light transmittance of the test piece was measured with an ultraviolet-visible spectrophotometer (UV-2450, manufactured by Shimadzu Corporation)
- UV-2450 ultraviolet-visible spectrophotometer
- the transmittance amplitude in the range of 500 to 750 nm was determined based on the following evaluation criteria.
- ⁇ The difference between the maximum value and the minimum value of the transmittance is less than 0.5%
- ⁇ The difference between the maximum value and the minimum value of the transmittance is 0.5% or more and less than 1.0%
- ⁇ The maximum value and the minimum value of the transmittance Difference in value is 1.0% or more
- I-184 1-hydroxycyclohexyl phenyl ketone, photopolymerization initiator bisphenol A EO-modified diacrylate: manufactured by Toagosei Co., Ltd., Aronix M-211B, bisphenol A EO (2 mol) -modified diacrylate
- high refractive index filler 1 zirconia ZRMIBK30WT % (Zirconium oxide, manufactured by CIK Nanotech)
- High refractive index filler 2 Titania TiMIBK15WT% (titanium oxide, manufactured by CIK Nanotech)
- Bifunctional urethane acrylate NV100: CN-9893 (manufactured by Sartomer) Indicates.
- Comparative Examples E1 and E2 are examples in which the amount of component (B) is outside the scope of the present invention. In these cases, there was a problem that the hardness of the obtained film was lowered.
- Comparative Example E3 is an example using a diacrylate having a bisphenol A skeleton instead of the component (A). In Comparative Example 3, the refractive index of the obtained film was lowered, and the occurrence of interference fringes was confirmed. There was also a problem that the hardness was lowered.
- Comparative Example E4 is an example using acryloylmorpholine instead of component (B). Also in this comparative example E4, the refractive index of the obtained film was lowered, and the occurrence of interference fringes was confirmed. Moreover, the extensibility was also inferior. Comparative Examples E5 to E8 are examples in which zirconia oxide or titanium oxide, which is a high refractive index agent, is used instead of using components (A) and (B). In these comparative examples, while the hardness was good, the extensibility was greatly inferior. The composition of Comparative Example E8 was not cured. Comparative Examples E9 to E13 are examples using bifunctional urethane acrylate for the purpose of imparting extensibility to the hard coat layer. In these comparative examples, although there was an example in which the extensibility was somewhat improved, the balance between hardness and refractive index was poor. Note that the composition of Comparative Example E13 did not cure.
- the hard coating compositions of Comparative Examples E5 to E13 contain a high refractive index filler.
- the refractive index itself of the obtained hard coat layer is certainly high.
- interference fringes are confirmed in any of the hard coat layers obtained in these comparative examples.
- the reason why the interference fringes were confirmed in these comparative examples is that the resin component forming the hard coat layer has a low refractive index, while a high refractive index filler having a high refractive index is mixed in the resin component. This is probably because of this.
- FIG. 1 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Example E1.
- FIG. 2 is a graph showing the transmission spectrum (transmittance (%)) in the wavelength range of 400 to 800 nm of the hard coat layer obtained using the hard coating composition of Comparative Example E10.
- the hard coat layer obtained using the hard coating composition of the present invention has a very small amplitude width in the transmission spectrum and optical blurring in the visible wavelength range. Can be understood.
- the hard coat layer obtained using the hard coating composition of Comparative Example E10 has a large amplitude width in the transmission spectrum and a large optical blur in the visible wavelength range. Also from these transmission spectrum results, the technical effect of the present invention can be understood for confirmation.
- the viscosity measurement of the ethoxylated orthophenylphenol acrylate of the component (B) was obtained by collecting 100 ml of the ethoxylated orthophenylphenol acrylate of the component (B) as a test sample in a glass container and adjusting the temperature to 20 ° C. Using a viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.) and M1Rotor, the measurement was performed at a rotation speed of 60 rpm. The refractive index of component (B) was measured using an Abbe refractometer by a method based on JIS K0062.
- the obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light using an ultraviolet irradiator (manufactured by Fusion) to obtain a PET film and a hard coat film having a 6.5 ⁇ m thick hard coat layer.
- KEFW Teijin DuPont 188 ⁇ m optical PET film
- the obtained hard coating composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 9. After coating, it was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain a hard coat film having a polycarbonate film and a hard coat layer having a thickness of 5.0 ⁇ m.
- Example F2 to F4 The hard coating composition was changed in the same manner as in Example 1 except that the type and amount of component (A) were changed to those shown in Table 3 and pentaerythritol triacrylate was used as the other (meth) acrylates. A product was prepared. Using the obtained hard coating composition, two types of hard coat films were obtained in the same manner as in Example 1. In Example F4, Ogsol EA-F5503 (manufactured by Osaka Gas Chemical Co., Ltd.) was used as the component (C).
- Comparative Examples F1 and F2 With the formulation shown in Table 4 , hard coating compositions were prepared as in the examples. Using the obtained hard coating composition, two types of hard coat films were obtained in the same manner as in Example F1.
- an ITO layer was formed, and a transparent conductive laminate to be a movable electrode substrate was produced.
- the thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150 ⁇ / ⁇ .
- the interference fringes of the obtained transparent conductive laminate were not visually recognized.
- Example E6 The same evaluation as in Example E6 was performed on the hard coat films obtained in Examples F1 to F4 and Comparative Examples F1 and F2. The evaluation results are shown in Table 3 and Table 4.
- I-184 1-hydroxycyclohexyl phenyl ketone, a photopolymerization initiator.
- any of the hard coating films having a hard coat layer formed using the hard coating compositions of Examples F1 to F4 had no generation of interference fringes and had a high refractive index and good hardness. . Furthermore, the obtained hard coating film had high extensibility and bending resistance.
- Comparative Example F1 is an example in which the amount of component (A) and component (C) is less than the range in the present invention. In Comparative Example F1, the film extensibility and flex resistance were inferior.
- Comparative Example F2 is an example in which the amount of component (A) is less than the range in the present invention and the amount of component (C) exceeds the range in the present invention. In Comparative Example F2, there was a problem that the hardness of the obtained film was lowered. From the results of these Examples and Comparative Examples, it can be seen that an excellent interference fringe suppressing effect is achieved in the hard coat layer obtained by the present invention.
- FIG. 3 is a graph showing a transmission spectrum (transmittance (%)) in the wavelength range of 400 to 800 nm of the hard coat layer obtained using the hard coating composition of Example F1.
- the hard coat layer obtained by using the hard coating composition of the present invention has a very small amplitude width in the transmission spectrum and small optical blur in the visible wavelength range. Understandable. Also from these transmission spectrum results, the technical effect of the present invention can be understood for confirmation.
- Example G1 As the first component, the unsaturated double bond-containing acrylic copolymer (I) obtained in Production Example 3 was used.
- the component (A) of the second component the phenol novolac type epoxy acrylate (1) obtained in Production Example 1 is used, and as the component (B), ethoxylated orthophenylphenol acrylate (acrylate having 1 mol of ethoxy structure in the molecule,
- An anti-blocking layer forming composition was prepared using a viscosity at 25 ° C. of 130 mPa ⁇ s, a refractive index of 1.577, and an SP value of 10.6).
- the raw materials shown in Table 1 were sequentially mixed at the solid content mass shown in Table 5 and stirred to obtain an anti-blocking layer forming composition.
- the viscosity measurement of the ethoxylated orthophenylphenol acrylate of the component (B) was obtained by collecting 100 ml of the ethoxylated orthophenylphenol acrylate of the component (B) as a test sample in a glass container and adjusting the temperature to 20 ° C. Using a viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.) and M1Rotor, the measurement was performed at a rotation speed of 60 rpm. The refractive index of component (B) was measured using an Abbe refractometer by a method based on JIS K0062.
- the SP value of the second component was calculated as a weight average with respect to the SP value and content of each component such as the component (A), the component (B), and other components contained in the second component.
- the obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a PET film and an antiblocking layer having a thickness of 6.5 ⁇ m.
- the obtained anti-blocking layer-forming composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 9. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays using an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a polycarbonate film and an antiblocking layer having a thickness of 5.0 ⁇ m.
- Examples G2 to G5 The type and amount of component (A) were changed to those described in Table 5 and pentaerythritol triacrylate (SP value: 12.7) was used as another (meth) acrylate contained in the second component. Except for the above, an anti-blocking layer forming composition was prepared in the same manner as in Example G1. Two types of anti-blocking films were obtained using the obtained anti-blocking layer-forming composition in the same manner as in Example G1.
- an anti-blocking layer forming composition was prepared in the same manner as Example G1.
- the obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 13. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a PET film and an antiblocking layer having a thickness of 6.5 ⁇ m.
- the obtained anti-blocking layer forming composition was dropped onto a 100 ⁇ m optical PC film (Pure Ace) manufactured by Teijin Chemicals and coated using a bar coater # 10. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays using an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a polycarbonate film and an antiblocking layer having a thickness of 5.0 ⁇ m.
- an anti-blocking layer forming composition was prepared in the same manner as Example G1.
- the obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 16. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a PET film and an antiblocking layer having a thickness of 6.5 ⁇ m.
- the obtained anti-blocking layer forming composition was dropped on a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays using an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a polycarbonate film and an antiblocking layer having a thickness of 5.0 ⁇ m.
- Comparative Examples G8, G12, G13 With the formulation shown in Table 6, an anti-blocking layer forming composition was prepared in the same manner as Example G1. The obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 20. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion). In the case of using the anti-blocking layer forming composition of Comparative Example G12, an anti-blocking film having a PET film and an anti-blocking layer with a film thickness of 6.5 ⁇ m was obtained.
- KEFW Teijin DuPont 188 ⁇ m optical PET film
- the coating composition was not cured and an anti-blocking layer could not be provided. Further, the obtained anti-blocking layer forming composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 14. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion).
- an ITO layer was formed, and a transparent conductive laminate to be a movable electrode substrate was produced.
- the thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150 ⁇ / ⁇ .
- the interference fringes of the obtained transparent conductive laminate were not visually recognized.
- Example E1 The same evaluation as in Example E1 was performed on the antiblocking films obtained in Examples G1 to G5 and Comparative Examples G1 to G13. Anti-blocking (AB) performance was also evaluated as described below. The evaluation results are shown in Table 5 and Table 6.
- I-184 1-hydroxycyclohexyl phenyl ketone, photopolymerization initiator bisphenol A EO modified diacrylate: manufactured by Toagosei Co., Ltd., Aronix M-211B, bisphenol A EO (2 mol) modified diacrylate, SP value 11.3
- Acryloylmorpholine SP value 11.9
- Bifunctional urethane acrylate NV100: CN-9893 (manufactured by Sartomer), SP value 11.1
- High refractive index filler 1 Zirconia ZRMIBK30WT% (zirconium oxide, manufactured by CIK Nanotech)
- High refractive index filler 2 Titania TiMIBK15WT% (titanium oxide, manufactured by CIK Nanotech) Indicates.
- the anti-booking film having an anti-blocking layer formed using the anti-blocking layer forming composition of the example has a good anti-blocking performance, no generation of interference fringes, and a high refractive index, It had good hardness. Furthermore, the obtained anti-booking film had high extensibility and bending resistance.
- Comparative Examples G1 and G2 are examples in which the amount of component (B) is outside the scope of the present invention. In these cases, there was a problem that the hardness of the obtained film was lowered.
- Comparative Example G3 is an example in which diacrylate having a bisphenol A skeleton is used instead of component (A). In Comparative Example G3, the refractive index of the obtained film was lowered, and generation of interference fringes was confirmed.
- Comparative Example G4 is an example using acryloylmorpholine instead of component (B). Also in this comparative example G4, the refractive index of the obtained film was lowered, and the occurrence of interference fringes was confirmed. Moreover, the extensibility was also inferior. Comparative Examples G5 to G8 are examples in which zirconia oxide or titanium oxide, which is a high refractive index agent, is used instead of using components (A) and (B). In these comparative examples, while the hardness was good, the antiblocking property and the extensibility were greatly inferior. Note that the composition of Comparative Example G8 was not cured.
- Comparative Examples G9 to G13 are examples using bifunctional urethane acrylate for the purpose of imparting extensibility to the anti-blocking layer.
- the anti-blocking property was inferior, and although the extensibility was somewhat improved, the balance between the hardness and the refractive index was poor.
- the composition of Comparative Example G13 was not cured.
- the anti-blocking layer forming compositions of Comparative Examples G5 to G13 contain a high refractive index filler. By including the high refractive index filler, the refractive index itself of the obtained anti-blocking layer is certainly high.
- the anti-blocking layers obtained in these comparative examples are confirmed to have interference fringes.
- the reason why interference fringes have been confirmed in these comparative examples is that the resin component forming the anti-blocking layer has a low refractive index, while a high refractive index filler having a high refractive index is mixed in the resin component. This is probably because of this. For this reason, even if the refractive index itself of the anti-blocking layer is increased, the resin component having a low refractive index has an adverse effect, and it is considered that an excellent interference fringe generation suppressing effect cannot be obtained.
- the transparent hard coat layer formed by the hard coating composition of the present invention is characterized by having good hardness and high visibility and extensibility.
- the transparent hard coat layer formed by the hard coating composition of the present invention has a high refractive index. Therefore, even when the transparent hard coat layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, interference fringes are not generated and high extensibility is achieved. There is an advantage that.
- the anti-blocking layer formed by the anti-blocking layer-forming composition of the present invention is characterized by having excellent anti-blocking performance and good hardness, high visibility and extensibility.
- the anti-blocking layer formed by the anti-blocking layer forming composition of the present invention is further characterized by having a high refractive index. Therefore, even when the anti-blocking layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.
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Abstract
Description
(A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレート、および
(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート化合物
を含む、ハードコーティング組成物であって、
ハードコーティング組成物中に含まれる樹脂成分100質量部に対して、フェノールノボラック型アクリレート(A)は60~85質量部および(メタ)アクリレート(B)は15~30質量部含まれる、
ハードコーティング組成物、を提供するものであり、これにより上記課題が解決される。
で示される化合物であるのがより好ましい。
を含んでもよく、
その場合、ハードコーティング組成物中に含まれる樹脂成分100質量部に対して、フェノールノボラック型アクリレート(A)は40~70質量部、(メタ)アクリレート(B)は10~30質量部およびフルオレン骨格含有(メタ)アクリレート(C)は15~40質量部で含まれるのが好ましい。
R4は、-A-OC(O)CR=CH2であって、Aはそれぞれ独立して、-OCH2CH2-、-OCH2CH2CH2-、-OCH(CH3)CH2-または-OCH2CH(CH3)-であり、Rはそれぞれ独立してHまたはCH3である。]
で示される化合物であるのがより好ましい。
透明高分子基材、および、
上記ハードコーティング組成物を、基材に塗装することによって形成されるハードコート層、
を有するハードコートフィルムであって、
ハードコート層は、1.565~1.620の屈折率を有する、
ハードコートフィルム、も提供する。
基材が、厚さ20~300μmのPETフィルムであり、
ハードコートフィルムは、20℃において引っ張り速度5mm/秒の条件においてフィルムをMD方向に15%引き伸ばした際、上記ハードコート層にクラックが発生しないことを特徴とするものがより好ましい。
基材が、厚さ30~200μmのポリカーボネートフィルムであり、
ハードコートフィルムは、25℃および60度/秒の条件において180°折り曲げた際、上記ハードコート層および基材の何れにおいてもクラックが発生しないことを特徴とするものもより好ましい。
第1成分および第2成分を含む、高屈折率アンチブロッキング層形成組成物であって、
第1成分が、不飽和二重結合含有アクリル共重合体であり、
第2成分が、
(A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレート、および
(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート
を含み、
第2成分100質量部に対して、フェノールノボラック型アクリレート(A)は60~85質量部および(メタ)アクリレート(B)は15~30質量部含まれており、
第1成分のSP値(SP1)および第2成分のSP値(SP2)の差△SPが1~4の範囲内であり、
組成物中に含まれる第1成分および第2成分の質量比は、第1成分:第2成分=0.5:99.5~20:80であり、
高屈折率アンチブロッキング層形成組成物を塗装した後に、第1成分および第2成分が層分離を生じ、表面に微細な凹凸を有するアンチブロッキング層が形成される、
高屈折率アンチブロッキング層形成組成物、を提供するものであり、これにより上記課題が解決される。
で示される化合物であるのが好ましい。
透明高分子基材、および、
上記高屈折率アンチブロッキング層形成組成物を、基材に塗装することによって形成されるアンチブロッキング層、
を有するアンチブロッキングフィルムであって、
アンチブロッキング層は、1.565~1.620の屈折率を有し、かつ、
アンチブロッキング層は、算術平均粗さ(Ra)が0.001~0.09μmであり、十点平均粗さ(Rz)が0.01~0.5μmである、
アンチブロッキングフィルム、も提供する。
基材が、厚さ20~300μmのPETフィルムであり、
アンチブロッキングフィルムは、20℃において引っ張り速度5m/分の条件においてフィルムをMD方向に15%引き伸ばした際、アンチブロッキング層にクラックが発生しないことを特徴とするものが挙げられる。
基材が、厚さ30~200μmのポリカーボネートフィルムであり、
アンチブロッキングフィルムは、25℃および60度/秒の条件において180°折り曲げた際、アンチブロッキング層および基材の何れにおいてもクラックが発生しないことを特徴とするものが挙げられる。
本発明のハードコーティング組成物は、
(A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレート、および
(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート化合物
を含む。そして上記ハードコーティング組成物中に含まれる樹脂成分100質量部に対して、フェノールノボラック型アクリレート(A)は40~90質量部および(メタ)アクリレート(B)は10~30質量部含まれる。
本発明のハードコーティング組成物は、(A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレートを含む。ハードコーティング組成物がフェノールノボラック型アクリレート(A)を含むことによって、得られるハードコート層が、透明であり、かつ、高い硬度を有する高屈折率層となる。これにより、干渉縞の発生を効果的に防ぐことができる。
で示される、フェノールノボラック型アクリレートであるのが好ましい。上記式(I)中、nは2~4でありmは0~3であるであるのがより好ましく、nは2~4でありmは0~1であるのがさらに好ましい。
本発明のハードコーティング組成物は、(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレートを含む。この(メタ)アクリレート(B)は、粘度300mPa・s未満であり、かつ屈折率が1.56~1.64の範囲内であるのが好ましい。
本発明のハードコーティング組成物の1態様として、上記成分(A)および(B)に加えて、2またはそれ以上の(メタ)アクリレート基を有する、フルオレン骨格含有(メタ)アクリレート(C)をさらに含む態様が挙げられる。フルオレン骨格含有(メタ)アクリレート(C)は高屈折率を有するため、得られるハードコート層の屈折率を高く設定することができるという利点がある。
R4は、-A-OC(O)CR=CH2であって、Aはそれぞれ独立して、-OCH2CH2-、-OCH2CH2CH2-、-OCH(CH3)CH2-または-OCH2CH(CH3)-であり、Rはそれぞれ独立してHまたはCH3である。]
で示される、アクリレートモノマーが挙げられる。
[上記式(II)-1中、各Rは水素原子またはメチル基を示し、mおよびnは、それぞれ独立して、1~5の整数を示す。]
本発明のハードコーティング組成物は、上記成分(A)および(B)、必要に応じて成分(C)に加えて、他の(メタ)アクリレート類を含んでもよい。このような(メタ)アクリレート類として、例えば、多官能(メタ)アクリレートモノマーおよび/またはオリゴマー化合物が挙げられる。これらの多官能(メタ)アクリレートモノマーおよび/またはオリゴマー化合物は、ハードコーティング組成物を塗装した後の活性エネルギー線の照射により、(メタ)アクリロイル基の反応に基づく硬化反応が生じ、高硬度を有するハードコート層が得られるという利点がある。
本発明のハードコーティング組成物は光重合開始剤を含むのが好ましい。光重合開始剤が存在することによって、紫外線などの活性エネルギー線照射により樹脂成分が良好に重合することとなる。光重合開始剤の例として、例えば、アルキルフェノン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤、チタノセン系光重合開始剤、オキシムエステル系重合開始剤などが挙げられる。アルキルフェノン系光重合開始剤として、例えば2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノンなどが挙げられる。アシルフォスフィンオキサイド系光重合開始剤として、例えば2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイドなどが挙げられる。チタノセン系光重合開始剤として、例えば、ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウムなどが挙げられる。オキシムエステル系重合開始剤として、例えば、1.2-オクタンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(0-アセチルオキシム)、オキシフェニル酢酸、2-[2-オキソ-2-フェニルアセトキシエトキシ]エチルエステル、2-(2-ヒドロキシエトキシ)エチルエステルなどが挙げられる。これらの光重合開始剤は、1種を単独で用いてもよく、また2種以上を併用してもよい。
本発明はさらに、上記ハードコーティング組成物を用いて形成されるハードコートフィルムも提供する。このハードコートフィルムは、透明高分子基材、および、上記ハードコーティング組成物を、基材に塗装することによって形成されるハードコート層、を有する。そして本発明におけるハードコート層は、1.565~1.620という高い屈折率を有することを特徴とする。
本件発明においては、ZnO、TiO2、CeO2、SnO2、ZrO2などの高屈折率剤を含まなくても高屈折率化が達成されているため、このような高屈折率剤を含める必要がない。そのため、上記のように高い全光線透過率および低いヘイズ値を達成することが可能となる。
本発明の高屈折率アンチブロッキング層形成組成物は、第1成分および第2成分を含む。上記第1成分は、不飽和二重結合含有アクリル共重合体である。上記第2成分は、(A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレート、および(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート、を含む。そして、第2成分100質量部に対して、フェノールノボラック型アクリレート(A)は60~85質量部および(メタ)アクリレート(B)は15~30質量部含まれることを条件とする。さらに、上記第1成分のSP値(SP1)および第2成分のSP値(SP2)の差△SPが1~4の範囲内であり、組成物中に含まれる第1成分および第2成分の質量比は、第1成分:第2成分=0.5:99.5~20:80であることを条件とする。この高屈折率アンチブロッキング層形成組成物は、塗装した後に、第1成分および第2成分が層分離を生じ、表面に微細な凹凸を有するアンチブロッキング層が形成されることを特徴とする。
第1成分として、不飽和二重結合含有アクリル共重合体が用いられる。不飽和二重結合含有アクリル共重合体は、例えば(メタ)アクリルモノマーと他のエチレン性不飽和二重結合を有するモノマーとを共重合した樹脂、(メタ)アクリルモノマーと他のエチレン性不飽和二重結合およびエポキシ基を有するモノマーとを反応させた樹脂、(メタ)アクリルモノマーと他のエチレン性不飽和二重結合およびイソシアネート基を有するモノマーとを反応させた樹脂などにアクリル酸やグリシジルアクリレートなどの不飽和二重結合を有しかつ他の官能基を有する成分を付加させたものなどが挙げられる。これらの不飽和二重結合含有アクリル共重合体は1種を単独で用いてもよく、また2種以上を混合して用いてもよい。この不飽和二重結合含有アクリル共重合体は、重量平均分子量で2000~100000であるのが好ましく、5000~50000であるのがより好ましい。
第2成分は、
(A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレート、および
(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート、
を含む。以下、各成分(A)および(B)について詳述する。
この成分(A)は、ハードコートコーティング組成物の成分(A)と同じ2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレートであるので、記載を省略する。
この成分(B)はハードコートコーティング組成物の成分(B)と同じ、炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート化合物なので記載を省略する。
本発明の高屈折率アンチブロッキング層形成組成物における第2成分は、上記成分(A)および(B)に加えて、他の(メタ)アクリレート類を含んでもよい。このような(メタ)アクリレート類はハードコートコーティング組成物に記載の「他の(メタ)アクリレート類」と同じであるので省略する。
上記高屈折率アンチブロッキング層形成組成物は、第1成分および第2成分、そして必要に応じた溶媒、光重合開始剤、触媒、光増感剤などの添加剤を混合することにより調製される。本発明の高屈折率アンチブロッキング層形成組成物中における第1成分と第2成分との比率は、第1成分:第2成分=0.5:99.5~20:80である。この比率は、第1成分:第2成分=1:99~20:80がより好ましく、1:99~15:85であるのがさらに好ましい。
サンプル:樹脂0.5gを100mlビーカーに秤量し、良溶媒10mlをホールピペットを用いて加え、マグネティックスターラーにより溶解する。
溶媒:
良溶媒…ジオキサン、アセトンなど
貧溶媒…n-ヘキサン、イオン交換水など
濁点測定:50mlビュレットを用いて貧溶媒を滴下し、濁りが生じた点を滴下量とする。
φi:濁点における各溶媒の体積分率
δi:溶媒のSP値
ml:低SP貧溶媒混合系
mh:高SP貧溶媒混合系
本発明はさらに、上記高屈折率アンチブロッキング層形成組成物を用いて形成されるアンチブロッキングフィルムも提供する。このアンチブロッキングフィルムは、透明高分子基材、および、上記高屈折率アンチブロッキング層形成組成物を、基材に塗装することによって形成されるアンチブロッキング層、を有する。そして本発明におけるアンチブロッキング層は、優れたアンチブロッキング性能を有することに加えて、1.565~1.620という高い屈折率を有することも特徴とする。
本件発明においては、ZnO、TiO2、CeO2、SnO2、ZrO2などの高屈折率剤を含まなくても高屈折率化が達成されているため、このような高屈折率剤を含める必要がない。そのため、上記のように高い全光線透過率および低いヘイズ値を達成することが可能となる。より詳しくは、上記高屈折率アンチブロッキング層形成組成物は、ZnO、TiO2、CeO2、SnO2、ZrO2およびインジウム-スズ酸化物の総含有量が組成物中の0.0001質量%以下であるのが好ましい。金属酸化物などの高屈折率剤が、アンチブロッキング層中に存在する場合は、樹脂成分のみの層と比較して、一般に伸長性および耐屈曲性が劣ることとなるためである。
攪拌装置、温度計、滴下漏斗および還流装置のついた反応装置に、フェノールノボラック樹脂(重量平均分子量700~900、エポキシ当量150~200)150gおよびエピクロルヒドリン550gを混合し、100℃、100~200mgの減圧条件下にて48.5%の水酸化ナトリウム水溶液110gを2時間かけて滴下した。反応終了後、温度を室温まで冷却し過剰の水酸化ナトリウム水溶液を酸で中和、減圧下にて加熱し過剰のエピクロルヒドリンを除去した後、生成物をメチルイソブチルケトンに溶解させ、水洗濾別により副生成塩を除去してフェノールノボラック型のエポキシ樹脂溶液を得た。
得られたフェノールノボラック型のエポキシ樹脂の固形分100重量部に対し、メトキノン1000ppm、トリフェニルホスフィン2000ppmを加え、100℃にてアクリル酸を滴下し、酸価が1mgKOH/g以下になるまで反応させフェノールノボラック型エポキシアクリレート(1)を得た。
得られたフェノールノボラック型エポキシアクリレート(1)は、重量平均分子量が950であり、水酸基価は140mgKOH/g、屈折率は1.572であった。また、SP値は12.7であった。
攪拌装置、温度計、滴下漏斗および還流装置のついた反応装置に、フェノールノボラック樹脂(重量平均分子量900~1100、エポキシ当量150~200)150gおよびエピクロルヒドリン550gを混合し、100℃、100~200mgの減圧条件下にて48.5%の水酸化ナトリウム水溶液110gを2時間かけて滴下した。反応終了後、温度を室温まで冷却し過剰の水酸化ナトリウム水溶液を酸で中和、減圧下にて加熱し過剰のエピクロルヒドリンを除去した後、生成物をメチルイソブチルケトンに溶解させ、水洗濾別により副生成塩を除去してフェノールノボラック型のエポキシ樹脂溶液を得た。
得られたフェノールノボラック型のエポキシ樹脂の固形分100重量部に対し、メトキノン1000ppm、トリフェニルホスフィン2000ppmを加え、100℃にてアクリル酸を滴下し、酸価が1mgKOH/g以下になるまで反応させフェノールノボラック型エポキシアクリレート(2)を得た。
得られたフェノールノボラック型エポキシアクリレート(2)は、重量平均分子量が1200であり、水酸基価は137mgKOH/g、屈折率は1.571であった。また、SP値は12.6であった。
成分(A)として、製造例1で得られたフェノールノボラック型エポキシアクリレート(1)を、成分(B)として、エトキシ化オルトフェニルフェノールアクリレート(エトキシ構造を分子中に1mol有するアクリレート、25℃における粘度130mPa・s、屈折率1.577)を用いてハードコーティング組成物を調製した。表1に示された原料を、表1に示された固形分質量で順次混合し、撹拌して、ハードコーティング組成物を得た。
なお、成分(B)のエトキシ化オルトフェニルフェノールアクリレートの粘度測定は、試験サンプルとして成分(B)のエトキシ化オルトフェニルフェノールアクリレート100mlをガラス容器に採取し、20℃に温度調整した後、B型粘度計(TVB-22L 東機産業株式会社製)およびM1Rotorを用いて、60rpmの回転速度にて測定した。
また、成分(B)の屈折率は、JIS K0062に準拠した方法により、アッベ屈折率計を用いて測定した。
塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、PETフィルムおよび膜厚6.5μmのハードコート層を有するハードコートフィルムを得た。
塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、ポリカーボネートフィルムおよび膜厚5.0μmのハードコート層を有するハードコートフィルムを得た。
成分(A)の種類および量を表1に記載されたものに変更し、他の(メタ)アクリレート類としてペンタエリスリトールトリアクリレートを用いたこと以外は、実施例E1と同様にして、ハードコーティング組成物を調製した。得られたハードコーティング組成物を用いて、実施例E1と同様にして2種類のハードコートフィルムを得た。
表2に示された配合により、ハードコーティング組成物を、実施例と同様にして調製した。得られたハードコーティング組成物を用いて、実施例E1と同様にして2種類のハードコートフィルムを得た。
表2に示された配合により、ハードコーティング組成物を、実施例と同様にして調製した。
得られたハードコーティング組成物を、帝人デュポン製188μm光学用PETフィルム(KEFW)に滴下し、バーコーター#13を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、PETフィルムおよび膜厚6.5μmのハードコート層を有するハードコートフィルムを得た。
また、得られたハードコーティング組成物を、帝人化成製100μm光学用PCフィルム(ピュアエース)に滴下し、バーコーター#10を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、ポリカーボネートフィルムおよび膜厚5.0μmのハードコート層を有するハードコートフィルムを得た。
表2に示された配合により、ハードコーティング組成物を、実施例と同様にして調製した。
得られたハードコーティング組成物を、帝人デュポン製188μm光学用PETフィルム(KEFW)に滴下し、バーコーター#16を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、PETフィルムおよび膜厚6.5μmのハードコート層を有するハードコートフィルムを得た。
また、得られたハードコーティング組成物を、帝人化成製100μm光学用PCフィルム(ピュアエース)に滴下し、バーコーター#12を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、ポリカーボネートフィルムおよび膜厚5.0μmのハードコート層を有するハードコートフィルムを得た。
表2に示された配合により、ハードコーティング組成物を、実施例と同様にして調製した。
得られたハードコーティング組成物を、帝人デュポン製188μm光学用PETフィルム(KEFW)に滴下し、バーコーター#20を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射した。比較例E12のハードコーティング組成物を用いた場合においては、PETフィルムおよび膜厚6.5μmのハードコート層を有するハードコートフィルムを得た。一方で、比較例E8およびE13のハードコーティング組成物を用いた場合においては、コーティング組成物が硬化せず、ハードコート層を設けることができなかった。
また、得られたハードコーティング組成物を、帝人化成製100μm光学用PCフィルム(ピュアエース)に滴下し、バーコーター#14を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射した。比較例E12のハードコーティング組成物を用いた場合においては、ポリカーボネートフィルムおよび膜厚5.0μmのハードコート層を有するハードコートフィルムを得た。一方で、比較例E8およびE13のハードコーティング組成物を用いた場合においては、コーティング組成物が硬化せず、ハードコート層を設けることができなかった。
実施例E1で得られたハードコートフィルムを用い、さらにこの硬化樹脂層上に、酸化インジウムと酸化錫が重量比95:5の組成で充填密度98%の酸化インジウム-酸化錫ターゲットを用いるスパッタリング法によって、ITO層を形成し、可動電極基板となる透明導電性積層体を作製した。形成されたITO層の膜厚は約30nm、製膜後の表面抵抗値は約150Ω/□であった。得られた透明導電性積層体の干渉縞は視認されなかった。
アッベ屈折計(アタゴ社製2T 測定範囲 nD=1.3~1.7)を用いて下記方法にて測定した。
主プリズムに、中間液(モノブロモナフタレンなど)をスポイドで1滴を落とし、測定するサンプルを置いた。サンプル上に中間液をスポイドで1滴を落とし、副プリズムを閉じた。ここで、中間液層に空気が入らないことを条件とした。
副プリズムにランプ光を入射させ、接眼鏡をのぞきながら測定つまみを回して、屈折視野の明暗の境を交点に合わせ、目盛視野の値を小数点以下4桁まで読み取り、屈折率を測定した。
鉛筆引掻塗膜硬さ試験機(東洋精機製作所製 型式P 加圧荷重100g~1kg)を用いて測定した。
三菱ユニ製 鉛筆引かき値試験用鉛筆(日本塗料検査協会検査済みのもの)を使用し、芯の先端が平滑で円形の断面になるように研磨紙(3M P-1000)にて調整した。試料を測定台に設置後、引掻角度が45°になるよう鉛筆を固定し、荷重750gの条件で試験を行った。試験毎に、芯を平滑にしながら、試験場所をずらして5回試験を繰り返した。
塗膜表面に凹みの発生有無下記評価基準に基づき、目視で確認した。
例えば2Hの鉛筆を用いた試験の場合、
凹みの発生が1本も無い場合、2Hと判断した。
凹みの発生が1~2本の場合、鉛筆の硬度を1段階下げて評価し、1段階下げて凹みの発生が1本も無い場合は硬度の評価は中間領域(H~2H等)と判断した。
凹みの発生が3本以上の場合は、H以下と判断し、1段階下げての評価を同様に実施した。
そのため、PETフィルムおよびハードコート層を有するハードコートフィルムにおいては、硬度がH以上であれば、硬度が2段階以上高くなっており、ハードコート層が十分な硬度を有していると判断される。
また、ポリカーボネートフィルムおよびハードコート層を有するハードコートフィルムにおいては、硬度が3B以上であれば、硬度が2段階以上高くなっており、ハードコート層が十分な硬度を有していると判断される。
オートグラフ(島津製作所製 AG-1S)を用いて測定を行った。
試験サンプルを10mm×150mmに切り出し、サンプル長手方向を伸張させる向きにて測定機器の上下のチャックに挟む。室温(20℃)条件下にて、試料サンプルを2cm/secの速さで伸張させた際、破断・クラックの発生しない伸張率を求めた。
試料を50mm×50mmに調整し、試料を180°折り曲げた時の評価を行った。下記の評価基準に基づき、目視にて行った。
○ : 塗膜・基材にクラックは生じない。
△ : 塗膜にのみクラック発生が確認できる。
× : 塗膜・基材共にクラック発生が確認できる。
干渉縞(外観評価)
試験片を100×100mmの黒色アクリル板に光学フィルム用粘着剤を用い塗工面が表面にくるように貼り合せた。スタンド式3波長蛍光灯(TWINBARD製 SLH-399型)の蛍光管から垂直下10cmの距離にサンプルを設置して目視観察をし、評価結果が○以上のサンプルについては、更に太陽光下での目視観察を実施し、下記の評価基準に基づき、判定した。
◎ : 干渉縞(干渉模様)が3波長蛍光灯下でも太陽光下でも視認されない。
○ : 3波長蛍光灯下で干渉縞(干渉模様)が視認されないが太陽光下では僅かに視認される
△ : 干渉縞(干渉模様)が僅かに視認される
× : 干渉縞(干渉模様)がはっきりと視認される
試験片の光線透過率を紫外可視分光光度計(島津製作所製UV-2450)によって測定し、
500~750nmの範囲における透過率の振幅に対し、下記評価基準に基づき、判定した。
○ : 透過率の最大値と最小値の差が0.5%未満
△ : 透過率の最大値と最小値の差が0.5%以上1.0%未満
× : 透過率の最大値と最小値の差が1.0%以上
I-184:1-ヒドロキシシクロヘキシルフェニルケトン、光重合開始剤
ビスフェノールA EO変性ジアクリレート:東亜合成株式会社製、アロニックスM-211B、ビスフェノールA EO(2mol)変性ジアクリレート
高屈折率フィラー1:ジルコニア ZRMIBK30WT%(酸化ジルコニウム、CIKナノテック社製)
高屈折率フィラー2:チタニア TiMIBK15WT%(酸化チタン、(CIKナノテック社製)
2官能ウレタンアクリレート:NV100:CN-9893(サートマー社製)
を示す。
比較例E1およびE2は、成分(B)の量が本発明の範囲外である例である。これらの場合は、何れも、得られるフィルムの硬度が低くなる不具合があった。
比較例E3は、成分(A)の代わりに、ビスフェノールA骨格を有するジアクリレートを用いた例である。この比較例3では、得られるフィルムの屈折率が低くなり、干渉縞の発生が確認された。また、硬度が低くなる不具合があった。
比較例E4は、成分(B)の代わりに、アクリロイルモルフォリンを用いた例である。この比較例E4でもまた、得られるフィルムの屈折率が低くなり、干渉縞の発生が確認された。また、伸長性も劣っていた。
比較例E5~E8は、成分(A)および(B)を用いる代わりに、高屈折率剤である酸化ジルコニアまたは酸化チタンを用いた例である。これらの比較例では、硬度は良好である一方で、伸長性が大きく劣っていた。なお比較例E8の組成物は硬化しなかった。
比較例E9~E13は、ハードコート層に伸長性を付与することを目的として、2官能ウレタンアクリレートを用いた例である。これらの比較例では、伸長性が多少向上した例もあるものの、硬度および屈折率のバランスが悪くなった。なお比較例E13の組成物は硬化しなかった。
また、これらの実施例および比較例の結果からも、本発明によって得られるハードコート層において、優れた干渉縞抑制効果が達成されていることがわかる。
成分(A)として、製造例1で得られたフェノールノボラック型エポキシアクリレート(1)を、成分(B)として、エトキシ化オルトフェニルフェノールアクリレート(エトキシ構造を分子中に1mol有するアクリレート、25℃における粘度130mPa・s、屈折率1.577)を、成分(C)として、オグソールEA-0200(下記式(II)-1において各Rが水素原子であり、m+n=2である、フルオレン骨格含有アクリレート、大阪ガスケミカル社製)
なお、成分(B)のエトキシ化オルトフェニルフェノールアクリレートの粘度測定は、試験サンプルとして成分(B)のエトキシ化オルトフェニルフェノールアクリレート100mlをガラス容器に採取し、20℃に温度調整した後、B型粘度計(TVB-22L 東機産業株式会社製)およびM1Rotorを用いて、60rpmの回転速度にて測定した。
また、成分(B)の屈折率は、JIS K0062に準拠した方法により、アッベ屈折率計を用いて測定した。
塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、PETフィルムおよび膜厚6.5μmのハードコート層を有するハードコートフィルムを得た。
塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、ポリカーボネートフィルムおよび膜厚5.0μmのハードコート層を有するハードコートフィルムを得た。
成分(A)の種類および量を表3に記載されたものに変更し、他の(メタ)アクリレート類としてペンタエリスリトールトリアクリレートを用いたこと以外は、実施例1と同様にして、ハードコーティング組成物を調製した。得られたハードコーティング組成物を用いて、実施例1と同様にして2種類のハードコートフィルムを得た。
なお、実施例F4では、成分(C)として、オグソールEA-F5503(大阪ガスケミカル社製)を用いた。
表4に示された配合により、ハードコーティング組成物を、実施例と同様にして調製した。得られたハードコーティング組成物を用いて、実施例F1と同様にして2種類のハードコートフィルムを得た。
実施例F1で得られたハードコートフィルムを用い、さらにこの硬化樹脂層上に、酸化インジウムと酸化錫が重量比95:5の組成で充填密度98%の酸化インジウム-酸化錫ターゲットを用いるスパッタリング法によって、ITO層を形成し、可動電極基板となる透明導電性積層体を作製した。形成されたITO層の膜厚は約30nm、製膜後の表面抵抗値は約150Ω/□であった。得られた透明導電性積層体の干渉縞は視認されなかった。
I-184:1-ヒドロキシシクロヘキシルフェニルケトン、光重合開始剤
を示す。
比較例F1は、成分(A)および成分(C)の量が本発明における範囲より少ない例である。この比較例F1では、フィルムの伸長性および耐屈曲性が劣っていた。
比較例F2は、成分(A)の量が本発明における範囲より少なく、成分(C)の量が本発明における範囲を超える例である。この比較例F2では、得られるフィルムの硬度が低くなる不具合があった。
これらの実施例および比較例の結果からも、本発明によって得られるハードコート層において、優れた干渉縞抑制効果が達成されていることがわかる。
イソボロニルメタクリレート187.2g、メチルメタクリレート2.8g、メタクリル酸10.0gからなる混合物を混合した。この混合物を、攪拌羽根、窒素導入管、冷却管および滴下漏斗を備えた1000ml反応容器中の、窒素雰囲気下で110℃に加温したプロピレングリコールモノメチルエーテル360gにターシャリーブチルペルオキシ-2-エチルヘキサエート2.0gを含むプロピレングリコールモノメチルエーテルの80.0g溶液と同時に3時間かけて等速滴下し、その後、1時間、110℃で反応させた。
第1成分として、製造例3で得られた不飽和二重結合含有アクリル共重合体(I)を用いた。第2成分の成分(A)として、製造例1で得られたフェノールノボラック型エポキシアクリレート(1)を、成分(B)として、エトキシ化オルトフェニルフェノールアクリレート(エトキシ構造を分子中に1mol有するアクリレート、25℃における粘度130mPa・s、屈折率1.577、SP値10.6)を用いてアンチブロッキング層形成組成物を調製した。表1に示された原料を、表5に示された固形分質量で順次混合し、撹拌して、アンチブロッキング層形成組成物を得た。
また、成分(B)の屈折率は、JIS K0062に準拠した方法により、アッベ屈折率計を用いて測定した。
塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、PETフィルムおよび膜厚6.5μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。
塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、ポリカーボネートフィルムおよび膜厚5.0μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。
成分(A)の種類および量を表5に記載されたものに変更し、第2成分に含まれる他の(メタ)アクリレート類としてペンタエリスリトールトリアクリレート(SP値:12.7)を用いたこと以外は、実施例G1と同様にして、アンチブロッキング層形成組成物を調製した。得られたアンチブロッキング層形成組成物を用いて、実施例G1と同様にして2種類のアンチブロッキングフィルムを得た。
表6に示された配合により、アンチブロッキング層形成組成物を、実施例と同様にして調製した。得られたアンチブロッキング層形成組成物を用いて、実施例G1と同様にして2種類のアンチブロッキングフィルムを得た。
表6に示された配合により、アンチブロッキング層形成組成物を、実施例G1と同様にして調製した。
得られたアンチブロッキング層形成組成物を、帝人デュポン製188μm光学用PETフィルム(KEFW)に滴下し、バーコーター#13を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、PETフィルムおよび膜厚6.5μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。
また、得られたアンチブロッキング層形成組成物を、帝人化成製100μm光学用PCフィルム(ピュアエース)に滴下し、バーコーター#10を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、ポリカーボネートフィルムおよび膜厚5.0μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。
表6に示された配合により、アンチブロッキング層形成組成物を、実施例G1と同様にして調製した。
得られたアンチブロッキング層形成組成物を、帝人デュポン製188μm光学用PETフィルム(KEFW)に滴下し、バーコーター#16を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、PETフィルムおよび膜厚6.5μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。
また、得られたアンチブロッキング層形成組成物を、帝人化成製100μm光学用PCフィルム(ピュアエース)に滴下し、バーコーター#12を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射し、ポリカーボネートフィルムおよび膜厚5.0μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。
表6に示された配合により、アンチブロッキング層形成組成物を、実施例G1と同様にして調製した。
得られたアンチブロッキング層形成組成物を、帝人デュポン製188μm光学用PETフィルム(KEFW)に滴下し、バーコーター#20を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射した。比較例G12のアンチブロッキング層形成組成物を用いた場合においては、PETフィルムおよび膜厚6.5μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。一方で、比較例G8およびG13のアンチブロッキング層形成組成物を用いた場合においては、コーティング組成物が硬化せず、アンチブロッキング層を設けることができなかった。
また、得られたアンチブロッキング層形成組成物を、帝人化成製100μm光学用PCフィルム(ピュアエース)に滴下し、バーコーター#14を用いて塗工した。塗工後、70℃にて1分間乾燥させ、紫外線照射機(Fusion製)にて350mJの紫外線を照射した。比較例12のアンチブロッキング層形成組成物を用いた場合においては、ポリカーボネートフィルムおよび膜厚5.0μmのアンチブロッキング層を有するアンチブロッキングフィルムを得た。一方で、比較例G8およびG13のアンチブロッキング層形成組成物を用いた場合においては、コーティング組成物が硬化せず、アンチブロッキング層を設けることができなかった。
実施例G1で得られたアンチブロッキングフィルムを用い、さらにこの硬化樹脂層上に、酸化インジウムと酸化錫が重量比95:5の組成で充填密度98%の酸化インジウム-酸化錫ターゲットを用いるスパッタリング法によって、ITO層を形成し、可動電極基板となる透明導電性積層体を作製した。形成されたITO層の膜厚は約30nm、製膜後の表面抵抗値は約150Ω/□であった。得られた透明導電性積層体の干渉縞は視認されなかった。
実施例および比較例で得られたアンチブロッキングフィルムを、2×5cmの大きさに切り出し、塗工面をPETフィルム(易接着層未塗布)面に重ね合わせ、ガラス板に挟んで200gf/cm2条件にて、室温で24時間放置した。その後、ブロッキング現象(AB性)を、下記基準により目視評価した。
○ : アンチブロッキング性あり
× : アンチブロッキング性なし
I-184:1-ヒドロキシシクロヘキシルフェニルケトン、光重合開始剤
ビスフェノールA EO変性ジアクリレート:東亜合成株式会社製、アロニックスM-211B、ビスフェノールA EO(2mol)変性ジアクリレート、SP値11.3
アクリロイルモルフォリン:SP値11.9
2官能ウレタンアクリレート:NV100:CN-9893(サートマー社製)、SP値11.1
高屈折率フィラー1:ジルコニア ZRMIBK30WT%(酸化ジルコニウム、CIKナノテック社製)
高屈折率フィラー2:チタニア TiMIBK15WT%(酸化チタン、(CIKナノテック社製)
を示す。
比較例G1およびG2は、成分(B)の量が本発明の範囲外である例である。これらの場合は、何れも、得られるフィルムの硬度が低くなる不具合があった。
比較例G3は、成分(A)の代わりに、ビスフェノールA骨格を有するジアクリレートを用いた例である。この比較例G3では、得られるフィルムの屈折率が低くなり、干渉縞の発生が確認された。また、硬度が低くなる不具合があった。
比較例G4は、成分(B)の代わりに、アクリロイルモルフォリンを用いた例である。この比較例G4でもまた、得られるフィルムの屈折率が低くなり、干渉縞の発生が確認された。また、伸長性も劣っていた。
比較例G5~G8は、成分(A)および(B)を用いる代わりに、高屈折率剤である酸化ジルコニアまたは酸化チタンを用いた例である。これらの比較例では、硬度は良好である一方で、アンチブロッキング性および伸長性が大きく劣っていた。なお比較例G8の組成物は硬化しなかった。
比較例G9~G13は、アンチブロッキング層に伸長性を付与することを目的として、2官能ウレタンアクリレートを用いた例である。これらの比較例では、アンチブロッキング性が劣っていた、また、伸長性が多少向上した例もあるものの、硬度および屈折率のバランスが悪くなった。なお比較例G13の組成物は硬化しなかった。
Claims (27)
- (A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレート、および
(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート、
を含み、
ハードコーティング組成物中に含まれる樹脂成分100質量部に対して、フェノールノボラック型アクリレート(A)は60~85質量部および(メタ)アクリレート(B)は15~30質量部含まれるハードコーティング組成物。 - 前記(メタ)アクリレート(B)は、屈折率が1.56~1.64の範囲内である、芳香族基含有(メタ)アクリレートである、請求項1または2に記載のハードコーティング組成物。
- 成分(A)および(B)の他に、さらに
(C)2またはそれ以上の(メタ)アクリレート基を有する、フルオレン骨格含有(メタ)アクリレート、
を含む、ハードコーティング組成物であって、
ハードコーティング組成物中に含まれる樹脂成分100質量部に対して、フェノールノボラック型アクリレート(A)は40~70質量部、(メタ)アクリレート(B)は10~30質量部およびフルオレン骨格含有(メタ)アクリレート(C)は15~40質量部含まれる、
請求項1記載のハードコーティング組成物。 - ZnO、TiO2、CeO2、SnO2、ZrO2およびインジウム-スズ酸化物の総含有量が組成物中の0.0001質量%以下である、請求項1~5いずれかに記載のハードコーティング組成物。
- 透明高分子基材、および、
請求項1~6いずれかに記載のハードコーティング組成物を、基材に塗装することによって形成されるハードコート層、
を有するハードコートフィルムであって、
ハードコート層は、1.565~1.620の屈折率を有する、
ハードコートフィルム。 - 前記ハードコート層の厚さが0.05~10μmである、請求項7記載のハードコートフィルム。
- 前記基材が、厚さ20~300μmのPETフィルムであり、
ハードコートフィルムは、20℃において引っ張り速度5mm/秒の条件においてフィルムをMD方向に15%引き伸ばした際、前記ハードコート層にクラックが発生しないことを特徴とする、
請求項7または8記載のハードコートフィルム。 - 前記基材が、厚さ30~200μmのポリカーボネートフィルムであり、
ハードコートフィルムは、25℃および60度/秒の条件において180°折り曲げた際、前記ハードコート層および基材の何れにおいてもクラックが発生しないことを特徴とする、
請求項7または8記載のハードコートフィルム。 - 請求項7~10いずれかに記載のハードコートフィルムの少なくとも一方の面上に透明導電層が形成された、透明導電性積層体。
- 前記透明導電層が酸化インジウムを含む結晶質層であり、かつ、透明導電層の厚さが5~50nmである、請求項11記載の透明導電性積層体。
- 前記ハードコート層および透明導電層の間に金属酸化物層が存在し、金属酸化物層の厚さが0.5~5.0nmである、請求項11または12記載の透明導電性積層体。
- 請求項11~13いずれかに記載の透明導電性積層体を有するタッチパネル。
- 第1成分および第2成分を含む、高屈折率アンチブロッキング層形成組成物であって、
第1成分が、不飽和二重結合含有アクリル共重合体であり、
第2成分が、
(A)2またはそれ以上のアクリレート基を有する、フェノールノボラック型アクリレート、および
(B)炭素数2または3のアルキレンオキシド構造を分子中に1~2mol有する、芳香族基含有モノまたはポリ(メタ)アクリレート
を含み、
第2成分100質量部に対して、フェノールノボラック型アクリレート(A)は60~85質量部および(メタ)アクリレート(B)は15~30質量部含まれており、
第1成分のSP値(SP1)および第2成分のSP値(SP2)の差△SPが1~4の範囲内であり、
組成物中に含まれる第1成分および第2成分の質量比は、第1成分:第2成分=0.5:99.5~20:80であり、
高屈折率アンチブロッキング層形成組成物を塗装した後に、第1成分および第2成分が層分離を生じ、表面に微細な凹凸を有するアンチブロッキング層が形成される、
高屈折率アンチブロッキング層形成組成物。 - 前記(メタ)アクリレート(B)は、屈折率が1.56~1.64の範囲内である、芳香族基含有(メタ)アクリレートである、請求項15または16に記載の高屈折率アンチブロッキング層形成組成物。
- ZnO、TiO2、CeO2、SnO2、ZrO2およびインジウム-スズ酸化物の総含有量が組成物中の0.0001質量%以下である、請求項15~17いずれかに記載の高屈折率アンチブロッキング層形成組成物。
- 透明高分子基材、および、
請求項15~18いずれかに記載の高屈折率アンチブロッキング層形成組成物を、基材に塗装することによって形成されるアンチブロッキング層、
を有するアンチブロッキングフィルムであって、
アンチブロッキング層は、1.565~1.620の屈折率を有し、かつ、
アンチブロッキング層は、算術平均粗さ(Ra)が0.001~0.09μmであり、十点平均粗さ(Rz)が0.01~0.5μmである、
アンチブロッキングフィルム。 - 前記アンチブロッキング層の厚さが0.05~10μmである、請求項19記載のアンチブロッキングフィルム。
- 基材が、厚さ20~300μmのPETフィルムであり、
アンチブロッキングフィルムは、20℃において引っ張り速度5m/分の条件においてフィルムをMD方向に15%引き伸ばした際、アンチブロッキング層にクラックが発生しないことを特徴とする、
請求項19または20記載のアンチブロッキングフィルム。 - 基材が、厚さ30~200μmのポリカーボネートフィルムであり、
アンチブロッキングフィルムは、25℃および60度/秒の条件において180°折り曲げた際、アンチブロッキング層および基材の何れにおいてもクラックが発生しないことを特徴とする、
請求項19または20記載のアンチブロッキングフィルム。 - 前記アンチブロッキングフィルムは、全光線透過率が88%以上であり、かつ、ヘイズ値が2%以下である、請求項19~22いずれかに記載のアンチブロッキングフィルム。
- 請求項19~13いずれかに記載のアンチブロッキングフィルムの少なくとも一方の面上に透明導電層が形成された、透明導電性積層体。
- 前記透明導電層が酸化インジウムを含む結晶質層であり、かつ、透明導電層の厚さが5~50nmである、請求項24記載の透明導電性積層体。
- 前記アンチブロッキング層および透明導電層の間に金属酸化物層が存在し、金属酸化物層の厚さが0.5~5.0nmである、請求項24または25記載の透明導電性積層体。
- 請求項24~26いずれかに記載の透明導電性積層体を有するタッチパネル。
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CN104756199B (zh) * | 2012-03-30 | 2017-03-01 | 帝人株式会社 | 透明导电层压材料 |
JP5490955B1 (ja) | 2013-09-30 | 2014-05-14 | 帝人株式会社 | 導電性積層体およびそれを用いるタッチパネル |
JP5490954B1 (ja) | 2013-09-30 | 2014-05-14 | 日本ビー・ケミカル株式会社 | 導電性積層体およびそれを用いるタッチパネル |
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KR102241216B1 (ko) | 2016-10-07 | 2021-04-15 | 니폰 페인트 오토모티브 코팅스 가부시키가이샤 | 광학 적층 부재 |
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- 2013-03-19 WO PCT/JP2013/057891 patent/WO2013146482A1/ja active Application Filing
- 2013-03-19 KR KR1020147030463A patent/KR102066759B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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CN104487524B (zh) | 2016-11-16 |
CN104487524A (zh) | 2015-04-01 |
KR102066759B1 (ko) | 2020-01-15 |
US9938426B2 (en) | 2018-04-10 |
US20150049261A1 (en) | 2015-02-19 |
TW201400561A (zh) | 2014-01-01 |
KR20140143212A (ko) | 2014-12-15 |
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