WO2017057640A1 - 帯電防止ハードコートフィルム、偏光板、タッチパネル、液晶表示装置及び製造方法 - Google Patents
帯電防止ハードコートフィルム、偏光板、タッチパネル、液晶表示装置及び製造方法 Download PDFInfo
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- WO2017057640A1 WO2017057640A1 PCT/JP2016/078936 JP2016078936W WO2017057640A1 WO 2017057640 A1 WO2017057640 A1 WO 2017057640A1 JP 2016078936 W JP2016078936 W JP 2016078936W WO 2017057640 A1 WO2017057640 A1 WO 2017057640A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0073—Optical laminates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00865—Applying coatings; tinting; colouring
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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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
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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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
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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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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- 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
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
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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
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
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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
- G02F2202/00—Materials and properties
- G02F2202/16—Materials and properties conductive
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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
- G02F2202/00—Materials and properties
- G02F2202/22—Antistatic materials or arrangements
Definitions
- the present invention relates to an antistatic hard coat film, a polarizing plate, a touch panel, a liquid crystal display device, and a method for producing an antistatic hard coat film.
- Patent Document 1 An antistatic film having an antistatic function has been developed.
- Liquid crystal display devices have advantages such as high image quality, thinness, light weight, and low power consumption, and are widely used in televisions, personal computers, car navigators, and the like.
- a liquid crystal display device a liquid crystal cell is disposed between two polarizers (that is, an incident side polarizer and an output side polarizer) arranged so that transmission axes are orthogonal to each other, and a voltage is applied to the liquid crystal cell. The orientation of the liquid crystal molecules is changed to display an image on the screen.
- liquid crystal display devices having a touch panel have been widely used in portable terminals such as mobile phones and tablet personal computers.
- a user may touch the touch panel to accumulate charges on members constituting the liquid crystal display device. Charges accumulated in this way may disturb drive control of liquid crystal molecules in the liquid crystal cell. Therefore, in order to suppress the accumulation of charges as described above, it is conceivable to provide an antistatic film in the liquid crystal display device.
- the antistatic film is generally formed by coating an antistatic agent on a substrate, but depending on the type of conductive particles and binder contained in the antistatic agent, the pot life of the antistatic agent is short. There is a problem. If the pot life is short, the viscosity of the antistatic agent tends to increase. When the viscosity of the antistatic agent increases, there is a problem that the appearance of coating when the antistatic agent is coated on the substrate is deteriorated, and coating stripes are generated. Further, since the application stripe affects the thickness of the coating film, it has an effect on the surface resistance value, resulting in a large unevenness in driving the liquid crystal.
- the antistatic film described in Patent Document 1 has a problem that the base material is specified as a polyester film, and there are restrictions on the usage.
- the present invention was devised in view of the above-mentioned problems, and is an antistatic hard coat film having few streaks and a surface resistance value within a predetermined range, a polarizing plate provided with an antistatic hard coat film, a touch panel, a liquid crystal display device, And it aims at providing the manufacturing method of such an antistatic hard coat film.
- the present inventor has obtained a base film made of a thermoplastic resin containing a cycloolefin polymer, and conductive metal oxide fine particles provided on the base film.
- An antistatic hard coat film comprising an antistatic hard coat agent comprising an antistatic hard coat film comprising a surface resistance value in a predetermined range and a small number of streaks, and the present invention has been completed. . That is, the present invention is as follows.
- a base film made of a thermoplastic resin containing a cycloolefin polymer;
- An antistatic hard coat layer provided on the base film and containing conductive metal oxide fine particles,
- the surface resistance value of the antistatic hard coat layer is 1.0 ⁇ 10 6 ⁇ / ⁇ or more and 1.0 ⁇ 10 10 ⁇ / ⁇ or less,
- the antistatic hard coat film wherein the number of streaks having a length of 20 cm or more in the antistatic hard coat layer is 2 or less per 1330 mm ⁇ 500 mm of the antistatic hard coat layer.
- the antistatic hard coat layer is formed by applying a composition obtained by dissolving an antistatic hard coat agent containing the metal oxide fine particles in a particle aggregating solvent and a particle dispersible solvent onto the base film. Formed by The antistatic hard coat film according to [1], wherein the viscosity of the composition is 1 mPa ⁇ s or more and 6 mPa ⁇ s or less. [3] The antistatic hard coat film according to [1] or [2], wherein the metal oxide fine particles are antimony-doped tin oxide.
- the antistatic hard coat layer has a single layer structure, The antistatic hard coat film according to any one of [1] to [3], wherein the thickness of the antistatic hard coat layer is 10 ⁇ m or less.
- the base film is obliquely stretched, The antistatic hard coat film according to any one of [1] to [4], wherein the base film has a thickness of 50 ⁇ m or less.
- a polarizing plate comprising the antistatic hard coat film according to any one of [1] to [5] and a polarizer, wherein the polarizer and the substrate film are bonded.
- a touch panel comprising the polarizing plate according to [6] and a liquid crystal cell.
- a liquid crystal display device comprising the polarizing plate according to [6] and a liquid crystal cell.
- an antistatic hard coat film having few streaks and a surface resistance value in a predetermined range a method for producing the same, and a polarizing plate, a touch panel, and a liquid crystal display device provided with such an antistatic hard coat film are provided.
- FIG. 1 is a cross-sectional view schematically showing an example of the antistatic hard coat film of the present invention.
- FIG. 2 is a plan view schematically showing an example of the antistatic hard coat film of the present invention.
- a “long” film refers to a film having a length of at least 5 times the width, preferably 10 times or more, specifically, A film having such a length that it is wound up in a roll and stored or transported.
- the upper limit of the ratio of the length to the width is not particularly limited, but may be, for example, 100,000 times or more.
- nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the film and giving the maximum refractive index.
- ny represents the refractive index in the in-plane direction and orthogonal to the nx direction.
- nz represents the refractive index in the thickness direction.
- d represents the thickness of the film.
- the measurement wavelength is 550 nm unless otherwise specified.
- (meth) acrylate includes both “acrylate” and “methacrylate”
- (meth) acryloyl group includes both “acryloyl group” and “methacryloyl group”.
- the directions of the elements “parallel”, “vertical”, and “orthogonal” include errors within a range that does not impair the effects of the present invention, for example, ⁇ 5 °, unless otherwise specified. You may go out.
- the longitudinal direction of the long film is usually parallel to the film flow direction in the production line.
- polarizing plate and “1 ⁇ 4 wavelength plate” include not only a rigid member but also a flexible member such as a resin film.
- the angle formed by the optical axis of each film (the transmission axis of the polarizer, the slow axis of the retardation film, etc.) in the member having a plurality of films is determined from the thickness direction unless otherwise specified. Indicates the angle when viewed.
- the adhesive is not only a narrowly defined adhesive (an adhesive having a shear storage modulus of 1 MPa to 500 MPa at 23 ° C. after irradiation with energy rays or after heat treatment), A pressure-sensitive adhesive having a shear storage modulus at 23 ° C. of less than 1 MPa is also included.
- the slow axis of the film represents the slow axis in the plane of the film.
- the antistatic hard coat film of the present invention comprises a base film made of a thermoplastic resin containing a cycloolefin polymer, and an antistatic hard coat layer provided on the base film and containing conductive metal oxide fine particles.
- FIG. 1 is a cross-sectional view schematically showing an example of the antistatic hard coat film of the present invention.
- the antistatic hard coat film 100 of the present invention includes a base film 110 and an antistatic hard coat layer 120 provided on the base film 110.
- the antistatic hard coat layer 120 has a surface resistance value within a predetermined range.
- the number of stripes having a length of 20 cm or more within a predetermined range of the antistatic hard coat layer 120 of the present invention is 2 or less.
- the antistatic hard coat film 100 of the present invention has few streaks in a predetermined plane and a surface resistance value in a predetermined range.
- the surface 120U of the antistatic hard coat layer 120 in the antistatic hard coat film 100 may be exposed by being an outermost layer, and an arbitrary layer is provided on the antistatic hard coat layer 120. It may be.
- the base film may be a multilayer film having two or more layers.
- the base film used in the present invention is made of a thermoplastic resin containing a cycloolefin polymer.
- the cycloolefin polymer has an alicyclic structure in the structural unit.
- the cycloolefin polymer may have an alicyclic structure in the main chain, and may have an alicyclic structure in the side chain. Among these, from the viewpoint of mechanical strength and heat resistance, a polymer having an alicyclic structure in the main chain is preferable.
- alicyclic structure examples include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene, cycloalkyne) structure.
- cycloalkane saturated alicyclic hydrocarbon
- cycloalkene unsaturated alicyclic hydrocarbon
- cycloalkyne unsaturated alicyclic hydrocarbon
- a cycloalkane structure and a cycloalkene structure are preferable, and a cycloalkane structure is more preferable.
- the number of carbon atoms constituting the alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, particularly preferably per alicyclic structure. Is a range of 15 or less. By setting the number of carbon atoms constituting the alicyclic structure within this range, the mechanical strength, heat resistance, and moldability of the thermoplastic resin containing the polymer having the alicyclic structure are highly balanced.
- the proportion of structural units having an alicyclic structure can be appropriately selected depending on the purpose of use.
- the proportion of the structural unit having an alicyclic structure in the cycloolefin polymer is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
- the proportion of the structural unit having an alicyclic structure in the cycloolefin polymer is within this range, the transparency and heat resistance of the thermoplastic resin containing the cycloolefin polymer are improved.
- cycloolefin polymers examples include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, and hydrogenated products thereof.
- norbornene-based polymers are particularly suitable because of good moldability.
- a cycloolefin polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- Examples of the norbornene-based polymer include resins described in JP-A-3-14882, JP-A-3-122137, and JP-A-4-63807, specifically, norbornene-based monomers. Ring-opening polymers, hydrogenated products thereof, addition polymers of norbornene monomers, addition polymers of norbornene monomers and olefins, modified products of these polymers, and the like.
- a monomer having a norbornene structure may be referred to as a “norbornene monomer”.
- the ring-opening polymer of the norbornene monomer include a ring-opening homopolymer of one kind of monomer having a norbornene structure, a ring-opening copolymer of two or more kinds of monomers having a norbornene structure,
- a ring-opening copolymer with a norbornene-based monomer and another monomer that can be copolymerized therewith can be mentioned.
- examples of norbornene-based monomer addition polymers include addition homopolymers of one type of monomer having a norbornene structure, addition copolymers of two or more types of monomers having a norbornene structure, and , Norbornene monomers and addition copolymers with other monomers copolymerizable therewith.
- a hydrogenated product of a ring-opening polymer of a norbornene monomer is particularly suitable from the viewpoints of moldability, heat resistance, low moisture absorption, dimensional stability, lightness, and the like.
- norbornene monomers include norbornene, alkyl-substituted derivatives of norbornene, alkylidene-substituted derivatives of norbornene, aromatic-substituted derivatives of norbornene, and halogens, hydroxyl groups, ester groups, alkoxy groups, cyano of these substituted or unsubstituted olefins.
- polar group substitution products such as a group, an amide group, an imide group, and a silyl group.
- norbornene monomers include 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, and 5-butyl-2- Norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5- Examples include phenyl-5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, and 5-octadecyl-2-norbornene.
- the norbornene-based monomer includes, for example, a monomer obtained by adding one or more cyclopentadiene to norbornene; an alkyl-substituted derivative of this monomer; an alkylidene-substituted derivative of this monomer; Aromatic substituted derivatives; and these polar group-substituted products.
- Specific examples of such norbornene monomers include 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienooctahydro.
- the norbornene-based monomer includes, for example, a monomer having a polycyclic structure which is a multimer of cyclopentadiene; an alkyl-substituted derivative of this monomer; an alkylidene-substituted derivative of this monomer; Aromatic substituted derivatives; and these polar group-substituted products.
- Specific examples of such norbornene-based monomers include dicyclopentadiene and 2,3-dihydrodicyclopentadiene.
- Norbornene-based monomers include, for example, adducts of cyclopentadiene and tetrahydroindene; alkyl-substituted derivatives of this adduct; alkylidene-substituted derivatives of this adduct; aromatic-substituted derivatives of this adduct; And polar group substitution products.
- Specific examples of such norbornene monomers include 1,4-methano-1,4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2, 3,4,4a, 5,8,8a-octahydro-2,3-cyclopentadienonaphthalene and the like.
- Monomers having a norbornene structure can be used singly or in combination of two or more.
- X bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 2,5 ] decane- 7,9-diyl-ethylene structure
- the content of these structural units is 90% by weight or more based on the total structural units of the norbornene polymer
- the content ratio of X and the content of Y The ratio with respect to the ratio is preferably 100: 0 to 40:60 by weight ratio of X: Y.
- Examples of the monomer having the X structure as a structural unit include a norbornene-based monomer having a structure in which a five-membered ring is bonded to a norbornene ring. Specific examples thereof include tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and its derivatives (having substituents on the ring), 7,8 -Benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (common name: methanotetrahydrofluorene) and its derivatives.
- Examples of the monomer having the Y structure as a structural unit include, for example, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] deca-3,7-diene (common name: tetracyclododecene) and its derivatives (having a substituent in the ring).
- the norbornene-based monomer may be polymerized by a known method. If necessary, the norbornene-based monomer is a thermoplastic saturated norbornene-based resin by copolymerizing with another copolymerizable monomer or by hydrogenation. It can be set as a system polymer hydrogenated product. In addition, polymers and polymer hydrogenated products can be converted into ⁇ , ⁇ -unsaturated carboxylic acids and / or derivatives thereof, styrenic hydrocarbons, olefinic unsaturated bonds and organosilicon compounds having hydrolyzable groups, unsaturated You may modify
- the number average molecular weight of the cycloolefin polymer is a polystyrene conversion value measured by GPC (gel permeation chromatography) method using a toluene solvent, and is 10,000 to 200,000, preferably 15,000 to 100. 20,000, more preferably 20,000 to 50,000.
- the cycloolefin polymer has an unsaturated bond in the molecular structure, it can be made into a cycloolefin polymer by hydrogenation.
- the hydrogenation rate is 90% or more, preferably 95% or more, more preferably 99% or more, from the viewpoint of heat deterioration resistance, light deterioration resistance, and the like.
- the content of the cycloolefin polymer is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight.
- the thermoplastic resin containing a cycloolefin polymer used in the present invention may be an anti-aging agent such as phenolic or phosphorus-based, an anti-aging agent such as phenolic, an ultraviolet absorber, an aliphatic alcohol ester, Various additives such as lubricants such as partial esters and partial ethers of monohydric alcohols may be contained.
- the thermoplastic resin may contain a polymer other than the cycloolefin polymer as long as the object of the present invention is not impaired.
- the base film When the base film is a multilayer film including two or more layers, the base film includes a first surface layer, an intermediate layer including an ultraviolet absorber, and a second surface layer in this order in the thickness direction.
- a film is preferred. That is, the base film is composed of a first surface layer made of a thermoplastic resin containing a cycloolefin polymer, an intermediate layer made of a thermoplastic resin containing a cycloolefin polymer and an ultraviolet absorber, and a thermoplastic resin containing a cycloolefin polymer.
- the second surface layer is preferably provided in this order in the thickness direction. In such a multilayer film, the first surface layer and the second surface layer can suppress bleed-out of the ultraviolet absorber contained in the intermediate layer.
- the ultraviolet absorber examples include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and acrylonitrile-based ultraviolet absorbers, and among them, the ultraviolet absorption performance near 380 nm is excellent. Therefore, triazine-based ultraviolet absorbers are preferable. Two or more different types of ultraviolet absorbers may be used, or only one type may be used.
- a compound having a 1,3,5-triazine ring can be preferably used.
- 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-bis (2-hydroxy-4 -Butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine is preferably used.
- Teuvin 1577 manufactured by Ciba Specialty Chemicals
- benzotriazole ultraviolet absorbers examples include 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2 -(3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazole-2 -Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2- [5-chloro (2H)- Benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-te t-butylphenol, 2- (2H-benzotriazol-2-yl
- the content of the ultraviolet absorber in the thermoplastic resin containing the cycloolefin polymer is preferably 1 to 8% by weight, more preferably 3 to 6% by weight.
- the content of the ultraviolet absorber indicates the total amount of the ultraviolet absorber when a plurality of types of ultraviolet absorbers are used.
- the content of the ultraviolet absorber is less than the lower limit of the above range, the light transmittance at a wavelength of 200 nm to 370 nm is increased, and when the antistatic hard coat film is provided on the polarizing plate, the polarization degree of the polarizer may be lowered. There is.
- the content of the ultraviolet absorber exceeds the upper limit of the above range, the light transmittance on the short wavelength side may be reduced, and the yellowness of the antistatic hard coat film may be too strong. Therefore, by setting the content of the ultraviolet absorber in the above range, it has sufficient ultraviolet absorption performance and can suppress the deterioration of the color. Furthermore, by setting the content of the ultraviolet absorber in the above range, since a large amount of the ultraviolet absorber is not contained, it is possible to prevent the heat resistance of the resin composition from being lowered.
- the glass transition temperature of the cycloolefin polymer used in the present invention is preferably 80 ° C. or higher, more preferably 100 to 250 ° C.
- the base film made of a thermoplastic resin containing a cycloolefin polymer may be a film having an in-plane retardation of 10 nm or less and / or a retardation value in the thickness direction of ⁇ 10 nm to 10 nm, depending on the purpose.
- a film having the characteristics of a quarter wavelength plate having an in-plane retardation value of 120 to 150 nm with respect to transmitted light of 550 nm and a thickness direction retardation value of 60 to 225 nm may be used.
- the variation in retardation (Re) in the in-plane direction and the variation in retardation (Rth) in the thickness direction are preferably within 10 nm, more preferably within 5 nm, and particularly preferably within 2 nm.
- the thickness of the base film is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, particularly preferably 30 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less. By keeping the thickness of the base film within the above range, the antistatic film can be made thin. When the base film is a multilayer film having two or more layers, the total thickness is preferably within the above range.
- the base film can be produced by molding a thermoplastic resin containing a cycloolefin polymer into a film shape.
- a heat-melt molding method and a solution casting method can be used.
- the hot melt molding method can be classified into, for example, a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, and a stretch molding method.
- a melt extrusion molding method in order to obtain a base film excellent in mechanical strength and surface accuracy.
- a base film is a multilayer film provided with two or more layers, it is preferable to use a coextrusion method.
- the molding conditions are appropriately selected depending on the purpose of use and the molding method.
- the cylinder temperature is preferably set in the range of preferably 100 ° C. to 600 ° C., more preferably 150 ° C. to 350 ° C.
- the thickness of the unstretched film can be appropriately determined according to the purpose of use of the stretched film obtained.
- the thickness of the unstretched film is preferably 30 ⁇ m or more and 300 ⁇ m or less from the viewpoint of obtaining a uniform stretched film by a stable stretching process.
- the manufacturing method of a base film includes the process of extending
- the substrate film can exhibit optical properties such as retardation.
- the stretching treatment can be performed by any method depending on the retardation to be developed in the base film.
- a uniaxial stretching process that performs a stretching process only in one direction may be performed, or a biaxial stretching process that performs a stretching process in two different directions may be performed.
- a simultaneous biaxial stretching process in which stretching processes are performed simultaneously in two directions may be performed, and a sequential biaxial stretching process in which a stretching process is performed in one direction and then a stretching process is performed in another direction. May be performed.
- the stretching process includes a longitudinal stretching process for stretching in the film longitudinal direction, a transverse stretching process for stretching in the film width direction, and an oblique stretching process for stretching in an oblique direction that is neither parallel nor perpendicular to the film width direction. Any of these may be performed, and these may be performed in combination. Especially, in this invention, it is preferable to use the base film which performed the diagonal stretch process.
- the stretching method include a roll method, a float method, and a tenter method.
- the temperature at which the unstretched film is obliquely stretched is preferably between Tg ⁇ 30 ° C. and Tg + 60 ° C., more preferably Tg ⁇ 10 ° C. to Tg + 50, where Tg is the glass transition temperature of the thermoplastic resin containing the cycloolefin polymer. It is a temperature range of ° C.
- the draw ratio is usually 1.01 to 30 times, preferably 1.01 to 10 times, more preferably 1.01 to 5 times.
- the average thickness of the stretched film is preferably 20 ⁇ m or more and 250 ⁇ m or less, more preferably 23 ⁇ m or more and 188 ⁇ m or less from the viewpoint of mechanical strength and the like. Moreover, since the thickness unevenness in the width direction of the stretched film affects the availability of winding, it is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less.
- the glass transition temperature (Tg) of the thermoplastic resin containing the cycloolefin polymer is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, particularly Preferably it is 150 degreeC or more. If the Tg of the resin is too low, the heat resistance of the molded product is lowered. Although the upper limit of Tg in this case is not specifically limited, For example, it can be 200 degrees C or less.
- the thermoplastic resin has a glass transition temperature (Tg) of 120 ° C. or higher and a photoelastic coefficient of 10 ⁇ 10 ⁇ 10 ⁇ Pa ⁇ 1 or lower. Is preferably used. If the Tg is less than 120 ° C., the substrate film may be deformed by the drying process of the composition in which the antistatic hard coat agent is dissolved, the stress when curing the active energy ray, the temperature when laminating the conductive layer, and the like. Wrinkles may occur.
- Tg glass transition temperature
- the photoelastic coefficient exceeds 10 ⁇ 10 ⁇ 10 ⁇ Pa ⁇ 1 , the in-plane and thickness direction retardation values easily change due to tensile stress such as bonding, and partially optically isotropic. There is a risk of disappearing.
- the upper limit of Tg in this case is not specifically limited, For example, it can be 200 degrees C or less.
- the lower limit of the photoelastic coefficient in this case is not particularly limited, but may be, for example, 10 ⁇ 10 ⁇ 13 or more.
- the base film may be subjected to a surface treatment for the purpose of enhancing the adhesion with the antistatic hard coat layer.
- a surface treatment include plasma treatment, corona treatment, alkali treatment, and coating treatment.
- the use of corona treatment can strengthen the adhesion between the base film and the antistatic hard coat layer.
- the corona treatment condition is preferably 1 to 1000 W / m 2 / min as the irradiation amount of corona discharge electrons.
- the contact angle of the base film after corona treatment with respect to water is preferably 10 to 50 °.
- a composition in which the antistatic hard coat agent is dissolved immediately after the corona treatment is applied, a composition in which the antistatic hard coat agent is dissolved after neutralization may be applied, From the viewpoint of improving the appearance of the antistatic hard coat layer, it is preferable to apply a composition in which the antistatic hard coat agent is dissolved after neutralization.
- the antistatic hard coat layer is provided on the base film and includes conductive metal oxide fine particles.
- the antistatic hard coat layer may be provided indirectly on the base film through an arbitrary layer, but is usually provided directly on the surface of the base film.
- the metal oxide fine particles are aggregated so as to be linked in a chain to form a chain linked body, and a conductive path is formed by the chain linked body. Therefore, the antistatic hard coat film of the present invention can exhibit an antistatic function.
- the metal oxide which is a material of the metal oxide fine particles is not particularly limited, and a metal oxide having conductivity can be appropriately selected and used.
- metal oxides include tin oxide, antimony, tin oxide doped with fluorine or phosphorus, indium oxide, indium oxide doped with tin or fluorine, antimony oxide, and low-order titanium oxide, especially antimony.
- One of these may be used alone, or two or more of these may be used in combination at any ratio.
- the average particle diameter of the metal oxide fine particles is preferably 2 nm to 50 nm, more preferably 5 nm to 40 nm, and particularly preferably 4 nm to 10 nm. Further, these metal oxide fine particles are preferably connected in the form of 2 to 10 chains. By setting the average particle diameter of the metal oxide fine particles to 2 nm or more, the metal oxide fine particles having conductivity are suppressed from agglomerating in a granular form, and it is possible to obtain metal oxide fine particles having chain conductivity. It becomes. By setting the average particle diameter of the metal oxide fine particles to 50 nm or less, the transparency of the film obtained using the metal oxide fine particles can be improved and the haze can be reduced.
- the average particle diameter of the particles indicates a particle diameter at which the scattering intensity is maximum when it is assumed that the particle diameter distribution measured by the laser diffraction method shows a normal distribution.
- the metal oxide fine particles are preferably those obtained by treating the surface of the particles with a hydrolyzable organosilicon compound.
- the surface of the particle main body made of a metal oxide is usually modified with a hydrolyzate of an organosilicon compound. Therefore, hereinafter, the treatment of the surface of the metal oxide fine particles with the hydrolyzable organosilicon compound may be referred to as “modification treatment”.
- modification treatment metal oxide fine particles in which the particle surface is treated with a hydrolyzable organosilicon compound
- modified particles By performing such a modification treatment, the chain connection of the metal oxide fine particles can be strengthened, and the dispersibility of the metal oxide fine particles can be improved.
- Examples of the hydrolyzable organosilicon compound include an organosilicon compound represented by the following formula (1).
- R 1 a Si (OR 2 ) 4-a (1) (In the formula (1), R 1 and R 2 are each independently a group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an organic group having 1 to 10 carbon atoms. A represents an integer of 0 to 3.)
- examples of R 1 include a vinyl group, an acrylic group, and an alkyl group having 1 to 8 carbon atoms.
- examples of R 2 include a hydrogen atom, a vinyl group, an aryl group, an acrylic group, an alkyl group having 1 to 8 carbon atoms, and —CH 2 OC n H 2n + 1 (n is 1 to 4). Represents an integer of.
- an organosilicon compound in which “a” is 0 or 1 is preferable.
- the tetrafunctional organosilicon compound in which “a” is 0 in the formula (1) is effective in maintaining the connection of the metal oxide fine particles.
- the trifunctional organosilicon compound in which “a” is 1 in the formula (1) is a dispersion of metal oxide fine particles linked in a chain in a composition in which an antistatic hard coat agent is dissolved in a solvent. It is effective in improving the performance.
- the trifunctional or higher functional organosilicon compound in which “a” is 0 or 1 in the formula (1) usually has a high hydrolysis rate.
- the organosilicon compound represented by the formula (1) a tetrafunctional organosilicon compound in which “a” is 0 and a trifunctional organosilicon compound in which “a” is 1 are used in combination. preferable.
- the molar ratio of the tetrafunctional organosilicon compound to the trifunctional organosilicon compound is preferably 20/80 or more, more Preferably it is 30/70 or more, preferably 80/20 or less, more preferably 70/30 or less.
- the metal oxide fine particles can be efficiently linked in a chain form. Can do.
- the metal oxide fine particles are firmly connected in a chain form. can do.
- the connecting portion of the metal oxide fine particles has high activity, the tetrafunctional organosilicon compound having “a” of 0 is easily adsorbed to the connecting portion of the metal oxide fine particles.
- tetrafunctional organosilicon compounds are easily hydrolyzed, hydrolysis proceeds simultaneously with the mixing of alcohol, and a large amount of Si—OH is produced.
- the trifunctional organosilicon compound in which “a” is 1 has low solubility in water, and when mixed with alcohol, it dissolves in water and proceeds with hydrolysis. Therefore, it is considered that the trifunctional organosilicon compound reacts later with the Si—OH of the tetrafunctional organosilicon compound that has been previously adsorbed and hydrolyzed on the connecting portion of the metal oxide fine particles. Therefore, when a tetrafunctional organosilicon compound and a trifunctional organosilicon compound are used in combination, the tetrafunctional organosilicon compound is not mixed with the aqueous dispersion of metal oxide fine particles at the same time. After mixing the organosilicon compound with an aqueous dispersion of metal oxide fine particles, it is preferable to mix an alcohol and a trifunctional organosilicon compound.
- hydrolyzable organosilicon compounds include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, and ethyltrimethoxy.
- modified particles metal oxide fine particles whose particle surfaces are treated with a hydrolyzable organosilicon compound
- the modified particles are produced in the state of a dispersion.
- an aqueous dispersion of metal oxide fine particles to be treated is prepared.
- the concentration of the metal oxide fine particles in the aqueous dispersion is preferably 1% by weight or more, more preferably 10% by weight or more, and preferably 40% by weight or less.
- the pH of the aqueous dispersion is preferably adjusted to 2 or more, more preferably 2.5 or more, and preferably 4 or less.
- the pH of the aqueous dispersion is preferably adjusted to 2 or more, more preferably 2.5 or more, and preferably 4 or less.
- Examples of the method for adjusting the pH include an ion exchange treatment method using an ion exchange resin and a method of mixing an acid.
- the ion exchange resin an H-type cation exchange resin is preferable.
- the pH of the aqueous dispersion can be shifted to acidic by ion exchange treatment. Further, if the pH is not sufficiently lowered only by the ion exchange resin treatment, an acid may be mixed in the aqueous dispersion as necessary.
- deionization treatment is also performed during the ion exchange treatment, so that the metal oxide fine particles are easily aligned in a chain shape.
- the solid content concentration of the aqueous dispersion is preferably 10% by weight or more, more preferably 15% by weight or more, and preferably 40% by weight or less, more preferably 35% by weight or less. adjust.
- the hydrolyzable organosilicon compound can be uniformly adsorbed on the metal oxide fine particles.
- aqueous dispersion of metal oxide fine particles prepared as described above and a hydrolyzable organosilicon compound are mixed.
- hydrolyzable organosilicon compound include compounds represented by the above formula (1).
- the amount of the hydrolyzable organosilicon compound can be appropriately set according to factors such as the type of the organosilicon compound and the particle diameter of the metal oxide fine particles.
- the weight ratio of the metal oxide fine particles to the hydrolyzable organosilicon compound is preferably 0.01 or more, more preferably 0.02 or more, preferably 0.5. Below, more preferably 0.3 or less. When two or more types of organosilicon compounds are used, it is preferable that the total amount of the organosilicon compounds satisfies the weight ratio range.
- the weight ratio By making the weight ratio equal to or greater than the lower limit of the above range, it is possible to suppress the breakage of the chain-linked metal oxide fine particles in the composition in which the antistatic hard coat agent is dissolved.
- An antistatic hard coat film having an antistatic function is obtained.
- the dispersibility of the metal oxide fine particles in the composition in which the antistatic hard coat agent is dissolved is improved, the viscosity of the composition in which the antistatic hard coat agent is dissolved is lowered, or the antistatic hard coat is reduced. Since the composition with the agent dissolved therein can be improved in stability over time, the haze of the antistatic hard coat layer can be reduced.
- the layer of the hydrolyzate of the organosilicon compound that modifies the surface of the metal oxide fine particles can be suppressed by making the weight ratio not more than the upper limit of the above range, the antistatic hard coat layer The surface resistance value can be reduced.
- the step of hydrolyzing the hydrolyzable organosilicon compound is performed by mixing an aqueous dispersion of metal oxide fine particles and alcohol. This step is usually performed after the step of mixing the aqueous dispersion of metal oxide fine particles and the hydrolyzable organosilicon compound.
- a tetrafunctional organosilicon compound and a trifunctional organosilicon compound are used in combination, after the tetrafunctional organosilicon compound is mixed with an aqueous dispersion of metal oxide fine particles, It is preferable to mix the trifunctional organosilicon compound with the aqueous dispersion of metal oxide fine particles simultaneously with or after mixing the alcohol with the aqueous dispersion and mixing the aqueous dispersion of metal oxide fine particles with the alcohol. .
- alcohol examples include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, and butanol. These alcohols may be used alone or in combination of two or more in any ratio. Further, an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, or propylene glycol monoethyl ether may be used in combination with the alcohol.
- an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, or propylene glycol monoethyl ether may be used in combination with the alcohol.
- the amount of the alcohol is such that the solid content concentration of the aqueous dispersion of metal oxide fine particles after mixing with the alcohol (total solid content including the organosilicon compound.
- the organosilicon compound is converted to silica) is within the desired range. It is preferable to adjust.
- the desired range of the solid content concentration of the aqueous dispersion is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less.
- the temperature during hydrolysis is preferably 30 ° C or higher, more preferably 40 ° C or higher.
- the upper limit of the temperature during hydrolysis is usually not more than the boiling point (approximately 100 ° C.) of the solvent used.
- an acid may be mixed with the aqueous dispersion of metal oxide fine particles as a hydrolysis catalyst.
- the acid include hydrochloric acid, nitric acid, acetic acid, and phosphoric acid.
- an acid may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- a preferred specific example of the operation in hydrolyzing the organosilicon compound is as follows. First, a tetrafunctional organosilicon compound in which “a” is 0 in formula (1) is mixed with an aqueous dispersion of metal oxide fine particles, and this aqueous dispersion and alcohol are mixed to obtain a tetrafunctional organic compound. Hydrolysis of the silicon compound is performed. Thereafter, the aqueous dispersion is cooled to room temperature and mixed with the alcohol again if necessary. Thereafter, the trifunctional organosilicon compound in which “a” is 1 in the formula (1) is mixed with the aqueous dispersion, and the temperature is raised to a temperature suitable for the hydrolysis described above for hydrolysis.
- the chain connection of metal oxide fine particles can be maintained by the hydrolyzate of the tetrafunctional organosilicon compound. Furthermore, since the bonding of the hydrolyzate of the trifunctional organosilicon compound to the surface of the metal oxide fine particles is promoted, the dispersibility of the metal oxide fine particles can be improved.
- the surface of the metal oxide fine particles can be modified with the hydrolyzate of the organosilicon compound to obtain modified particles.
- the modified particles are obtained in the form of a dispersion dispersed in a solvent such as water.
- This modified particle dispersion can be used as it is for the preparation of a composition in which the antistatic hard coat agent is dissolved, but may be subjected to a washing treatment or a deionization treatment as necessary. By reducing the ion concentration by deionization treatment, a modified particle dispersion having excellent stability can be obtained.
- This deionization treatment can be performed using, for example, an ion exchange resin such as a cation exchange resin, an anion exchange resin, or both ion exchange resins. Moreover, as a washing process, it can carry out using an ultrafiltration membrane method.
- an ion exchange resin such as a cation exchange resin, an anion exchange resin, or both ion exchange resins.
- a washing process it can carry out using an ultrafiltration membrane method.
- the obtained dispersion of modified particles may be used after solvent replacement, if necessary.
- solvent substitution is performed, dispersibility in a binder polymer and a polar solvent described later is improved. Therefore, the coating property of the composition obtained by dissolving the antistatic hard coat agent with a solvent can be improved. Therefore, the smoothness of the surface of the antistatic hard coat layer can be improved, and the appearance of defects such as streaks and unevenness in the antistatic hard coat layer can be suppressed. Further, the scratch resistance, transparency and adhesion of the antistatic hard coat layer can be improved, and the haze can be reduced. Moreover, the manufacturing reliability of the antistatic hard coat film can be improved.
- the obtained dispersion of modified particles may be mixed with water if necessary.
- the number of modified particles connected usually increases, and the conductivity of the resulting antistatic hard coat layer is improved.
- the above-mentioned conductive metal oxide fine particles are usually linked in a chain form in a dispersion containing the metal oxide fine particles or an antistatic hard coat agent. Since such connection is maintained in the antistatic hard coat layer, a conductive path is formed in the antistatic hard coat layer by the connected metal oxide fine particles. Therefore, it is speculated that the antistatic hard coat layer can exhibit excellent antistatic properties.
- the metal oxide fine particles are not aggregated in a granular form but are aggregated so as to be linked in a chain form, the metal oxide fine particles are difficult to form an aggregate that is large enough to cause visible light scattering. Therefore, it is presumed that the haze of the antistatic hard coat layer containing such metal oxide fine particles can be lowered.
- the present invention is not limited to the above estimation.
- the average number of linked metal oxide fine particles is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 or more.
- the antistatic performance of the antistatic hard coat layer can be enhanced by setting the average number of metal oxide fine particles connected to the lower limit value or more.
- the upper limit of the average number of connections of the metal oxide fine particles is preferably 20 or less, more preferably 10 or less. By making the average number of metal oxide fine particles connected to the upper limit or less, chain-connected metal oxide fine particles can be easily produced.
- the average number of connections of the metal oxide fine particles can be measured by the following method.
- a photograph of the chain-like connected body of metal oxide fine particles is taken with a transmission electron microscope. From this photograph, the number of links in each chain linked body is determined for 100 chain linked bodies of metal oxide fine particles. And the average value of the connection number of each chain
- the amount of metal oxide fine particles is preferably 3% by weight or more, more preferably 5% by weight or more, particularly preferably 10% by weight or more, preferably 80% by weight or less, more preferably It is 70% by weight or less, particularly preferably 50% by weight or less.
- the amount of the metal oxide fine particles is preferably 3% by weight or more, more preferably 5% by weight or more, particularly preferably 10% by weight or more, preferably 80% by weight or less, more preferably It is 70% by weight or less, particularly preferably 50% by weight or less.
- the antistatic hard coat layer usually contains a binder polymer in addition to the metal oxide fine particles. With the binder polymer, the metal oxide fine particles can be held in the antistatic hard coat layer.
- the binder polymer a polymer obtained by polymerizing a polymerizable monomer containing 50% by weight or more of a compound having 3 or more (meth) acryloyl groups in one molecule is preferable.
- a polymer obtained by polymerizing a polymerizable monomer containing 50% by weight or more of a compound having 3 or more (meth) acryloyl groups in one molecule is preferable.
- Examples of the compound having three or more (meth) acryloyl groups in one molecule include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( And (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
- the compound which has 3 or more (meth) acryloyl groups in 1 molecule may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- a combination of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate These combinations may be used as a polymerizable monomer for obtaining a binder polymer.
- a polymerizable monomer containing a total of 80% by weight or more of a compound having four (meth) acryloyl groups in one molecule, a compound having five, and a compound having six. is preferably used.
- any monomer compound may be used in combination with a compound having three or more (meth) acryloyl groups in one molecule as described above.
- optional monomer compounds include trifunctional or tetrafunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.
- Isocyanates such as isophorone diisocyanate; ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, diallyl phthalate, trimethylolpropane triacrylate, glycerin diallyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate
- Polyfunctional unsaturated monomers such as bisphenoxyethanol full orange acrylate, 2-propenoic acid [5,5 ′-(9-fluorene-9-ylidene) bis (1,1′-biphenyl) -2- (polyoxyethylene) ester], 2-propenoic acid [5,5′-4- ( 1,1′biphenylyl) methylenebis (1,1′-biphenyl) -2- (polyoxyethylene) ester] and other compounds having an aromatic ring and a (meth) acryloyl group; and methyl (meth) acrylate,
- the compound having a carboxyl group and a polymerizable carbon-carbon double bond when a compound having a carboxyl group and a polymerizable carbon-carbon double bond is used in an amount of 0.01 wt% to 5 wt% in the total amount of the polymerizable monomer, It is preferable because the surface resistance value of the prevention hard coat layer can be effectively reduced.
- the compound having a carboxyl group and a polymerizable carbon-carbon double bond include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, muconic acid, half of maleic anhydride and monoalcohol.
- Esters compounds in which a part of hydroxyl groups in acrylates having hydroxyl groups such as dipentaerythritol pentaacrylate and pentaerythritol triacrylate are added to the carbon-carbon double bond of acrylic acid; and dipentaerythritol pentaacrylate and pentaerythritol A compound obtained by reacting a hydroxyl group in an acrylate having a hydroxyl group such as triacrylate with a dicarboxylic acid or a carboxylic anhydride. One of these may be used alone, or two or more of these may be used in combination at any ratio.
- the acid value of the polymerizable monomer containing 50% by weight or more of a compound having 3 or more (meth) acryloyl groups in one molecule is preferably 0.01 mgKOH / g to 0.5 mgKOH / g.
- the acid value of the polymerizable monomer is measured using bromothymol blue as an indicator according to JIS K0070 (Test method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products). Yes.
- the amount of the binder polymer is preferably 10% by weight or more, more preferably 15% by weight or more, particularly preferably 20% by weight or more, and most preferably 50% by weight or more. Is 100% by weight or less, more preferably 95% by weight or less, and particularly preferably 90% by weight or less.
- the amount of the binder polymer within the above range, the adhesion between the antistatic hard coat layer and the base film can be improved, and the dispersibility of the metal oxide fine particles in the antistatic hard coat layer can be improved. Can be made.
- the thickness of the antistatic hard coat layer can be made uniform.
- the antistatic hard coat layer may contain an optional component other than the metal oxide fine particles and the binder polymer as long as the effects of the present invention are not significantly impaired.
- arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- An antistatic hard coat film is formed by coating a base film with a composition in which an antistatic hard coat agent containing metal oxide fine particles is dissolved in a solvent (hereinafter, also simply referred to as “composition”). It can be manufactured by a manufacturing method including a step of forming a hard coat layer.
- composition in which an antistatic hard coat agent containing metal oxide fine particles is dissolved in a solvent
- the layer of the composition in which the antistatic hard coat agent is dissolved in a solvent at the time of coating is usually in a fluid state, after the composition is coated on the substrate film, It is preferable to perform the process of hardening the film
- this antistatic hard coat film a polymer obtained by polymerizing a polymerizable monomer containing 50% by weight or more of a compound having 3 or more (meth) acryloyl groups in one molecule is provided.
- a preferred method for producing an antistatic hard coat film comprising an antistatic hard coat layer contained as a binder polymer will be described.
- an antistatic hard coat agent is prepared.
- this antistatic hard coat agent in this example, a material containing metal oxide fine particles and a polymerizable monomer for obtaining a binder polymer is used.
- the polymerizable monomer a polymerizable monomer containing 50% by weight or more of a compound having 3 or more (meth) acryloyl groups in one molecule is used.
- the polymerizable monomer can be polymerized by irradiation with active energy rays such as ultraviolet rays. Therefore, the antistatic hard coat agent preferably contains a photopolymerization initiator.
- photopolymerization initiators include benzoin derivatives, benzyl ketals, ⁇ -hydroxyacetophenones, ⁇ -aminoacetophenones, acyl phosphine oxides, and o-acyl oximes.
- photopolymerization initiators examples include combinations of benzophenone / amine, Michlerketone / benzophenone, and thioxanthone / amine (trade names: Irgacure, Darocur, etc., manufactured by Ciba Geigy).
- a photoinitiator may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- the amount of the photopolymerization initiator is preferably 1 part by weight or more, more preferably 2 parts by weight or more, particularly preferably 2.5 parts by weight or more, preferably 20 parts by weight or more with respect to 100 parts by weight of the polymerizable monomer.
- the amount is not more than parts by weight, more preferably not more than 10 parts by weight, particularly preferably not more than 5 parts by weight.
- a solvent capable of dissolving the cycloolefin polymer and easily volatilizing is preferable.
- the particle aggregating solvent refers to a solvent that facilitates aggregation of metal oxide fine particles. Even if the antistatic hard coat agent is dissolved and applied, the surface resistance value of the antistatic hard coat layer is kept within a predetermined range. It can be stored.
- the particle aggregating solvent include ketone-based solvents, specifically, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK).
- a particle-dispersible solvent is a solvent that facilitates dispersion of metal oxide fine particles.
- a particle-dispersible solvent in the composition, aggregation of metal oxide fine particles is suppressed, and as a result, thickening is prevented.
- production of a coating stripe etc. can be suppressed.
- the particle dispersible solvent include alcohol, and particularly alcohol having a boiling point of less than 100 ° C.
- the alcohol include methanol, ethanol, mixed ethanol, n-propanol, and isopropanol. Among them, mixed ethanol is preferable.
- the minimum of the boiling point of this alcohol is not specifically limited, For example, it may be 40 degreeC or more.
- Mixed ethanol represents a mixed solvent containing ethanol as a main component and further containing alcohol other than ethanol and optionally water.
- alcohols other than ethanol include methanol, n-propanol, isopropanol, and butanol. Of these, methanol and n-propanol are preferred.
- One type of alcohol other than ethanol may be used alone, or two or more types may be used in combination at any ratio.
- the main component means that the content ratio exceeds 50%.
- the mixing ratio (weight ratio) of ethanol and alcohol other than ethanol in the mixed ethanol is preferably 70:30 to 96: 4, more preferably 80:20 to 90:10, and still more preferably 84:16 to 87. : 13.
- the mixing ratio (weight ratio) of the particle-aggregating solvent and the particle-dispersing solvent is preferably 50:50 to 85:15, more preferably 55:45 to 75: 25, more preferably 60:40 to 70:30.
- the high boiling point solvent is a solvent other than the particle aggregating solvent and having a boiling point of 100 ° C. or higher.
- high boiling point solvents include diacetone alcohol, acetylacetone, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether.
- the upper limit of the boiling point of this solvent is not specifically limited, For example, it can be 200 degrees C or less.
- the mixing ratio (weight ratio) of the particle aggregating solvent and the high boiling point solvent is preferably 67:33 to 95: 5, more preferably 80:20 to 91: 9, More preferably, it is 82:18 to 85:15.
- the mixing ratio (weight ratio) of the particle-dispersing solvent and the high-boiling solvent is (particle-dispersing solvent: high-boiling solvent), preferably 60:40 to 85:15, more preferably 65:35 to 80:20, More preferably, it is 70:30 to 75:25.
- the amount of the solvent is preferably set so that the solid content concentration of the composition falls within a desired range.
- the solid content concentration of the composition is preferably 0.01% by weight or more, more preferably 1% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less.
- the concentration of the resin in the composition is preferably in the range of 1 to 5% by weight, more preferably 0.2 to 39.6% by weight, based on the resin. If it exists in this range, adhesiveness with a base film will be high, and the thickness of the film to form can be made uniform.
- the thickness of the coating is not too thin and not too thick, it can form a coating with sufficient antistatic performance, is excellent in transparency, has a low haze, In addition, there are no cracks in the coating and no warpage in the substrate. Furthermore, since the viscosity of the composition does not increase, the coating property is excellent, and the flatness of the surface does not deteriorate or the stripe unevenness does not occur.
- the viscosity of the composition is preferably 1 mPa ⁇ s or more, more preferably 1.2 mPa ⁇ s or more, further preferably 1.3 mPa ⁇ s or more, preferably 6 mPa ⁇ s or less, more preferably 6.5 mPa ⁇ s. s or less, more preferably 5.5 mPa ⁇ s or less, and particularly preferably 3 mPa ⁇ s or less.
- the viscosity of the composition can be measured by the method described later.
- the antistatic hard coat agent may contain any component that the antistatic hard coat layer can contain.
- the antistatic hard coat agent can be obtained by mixing each component contained in the antistatic hard coat agent with an appropriate mixing device.
- An example of the mixing device is a homomixer.
- a composition in which the antistatic hard coat agent is dissolved in a solvent is applied onto the base film to form a film of the composition on the base film. Then, if necessary, after removing the solvent by drying, the film of the composition is cured by irradiating active energy rays such as ultraviolet rays to polymerize the polymerizable monomer, and the antistatic hard coat layer is formed. obtain.
- Examples of the coating method include, for example, a slot coater, a spin coater, a roll coater, a curtain coater, and screen printing.
- the heating temperature for removing the solvent, the processing time for each step, and the like are appropriately set according to the material, the type of the solvent, the thickness of the coating, and the like.
- the coating of the composition is preferably performed in an environment with a predetermined relative humidity.
- the specific relative humidity during the coating is preferably 40% RH or more, more preferably 45% RH or more, still more preferably 50% RH or more, particularly preferably 52% RH or more, preferably 65%. RH or less, more preferably 60% RH or less, still more preferably 58% RH or less, and particularly preferably 57% RH or less.
- the relative humidity of the environment at the time of coating is set to be equal to or higher than the lower limit of the above range, discharge due to charging of the base film and coating unevenness due to uneven charging can be suppressed.
- fine-particles can be suppressed by making the relative humidity of the environment at the time of application below the upper limit of the said range, the tear of an antistatic hard-coat layer and the nonuniformity of a haze can be suppressed.
- the significance of setting the relative humidity of the environment at the time of coating to be equal to or lower than the upper limit of the above range will be specifically described.
- the volatilization of the solvent immediately after application removes heat from the substrate by the amount of heat of vaporization of the solvent, resulting in a surface of the paint film. Condensation may occur. Such a phenomenon is called “brushing”, and the portion where the brushing occurs may be whitened.
- the aggregation of the metal oxide fine particles contained in the film of the composition may proceed excessively in the portion where the brushing occurs. There is sex.
- the antistatic hard coat layer may be torn or the haze of the antistatic hard coat layer may be uneven.
- the effect of brushing as described above is likely to occur in a portion where the area of the film of the composition in which the antistatic hard coat agent is dissolved is in contact with the outside air. This is because if the area that comes into contact with the outside air is large, the cooling starts quickly, and therefore condensation tends to occur.
- the film of the composition has a large area and touches the outside air to start cooling quickly. Therefore, the film of the composition is easily cooled and condensation is likely to occur. Therefore, in the vicinity of the edge of the film of this composition, the antistatic hard coat layer is particularly susceptible to tearing and haze unevenness due to the effect of the brushing.
- the relative humidity of the environment during coating is less than or equal to the upper limit of the above range, the occurrence of brushing as described above is suppressed. Therefore, tearing of the antistatic hard coat layer and uneven haze can be easily suppressed in the entire layer including the vicinity of the end portion of the antistatic hard coat layer.
- aggregation of conductive particles due to brushing is suppressed, and tearing of the antistatic hard coat layer and haze unevenness are suppressed. This is significant in that a uniform antistatic hard coat layer can be realized.
- the solvent is removed from the film of the composition by drying as necessary.
- the temperature and pressure at the time of drying can be appropriately set according to conditions such as the material type of the antistatic hard coat layer, the type of solvent, and the thickness of the antistatic hard coat layer.
- active energy rays are irradiated to the film of the composition.
- the film of the composition in which the polymerizable monomer is polymerized and the antistatic hard coat agent is dissolved is cured, so that an antistatic hard coat layer containing metal oxide fine particles and a binder polymer is obtained.
- Irradiation conditions such as the wavelength and irradiation amount of the active energy ray can be appropriately set according to conditions such as the type of the material of the antistatic hard coat layer and the thickness of the antistatic hard coat layer.
- FIG. 2 is a plan view schematically showing an example of the antistatic hard coat film of the present invention.
- the antistatic hard coat layer 120 included in the antistatic hard coat film 100 of the present invention is formed by coating the base film 110 with a composition in which an antistatic hard coat agent is dissolved in a solvent. Even in this case, the influence of excessive aggregation of the metal oxide fine particles due to brushing can be suppressed. Therefore, the antistatic hard coat layer 120 can reduce the number of tears in the regions 121 and 122 near both ends in the coating width direction X of the antistatic hard coat layer 120.
- the coating width direction X of the antistatic hard coat layer 120 is the in-plane direction of the antistatic hard coat layer 120, and the composition was applied to form the antistatic hard coat layer 120. This is a direction perpendicular to the coating direction Y in the process.
- the coating width direction X usually indicates a direction parallel to the width direction of the base film 110.
- the regions 121 and 122 in the vicinity of both ends in the coating width direction X of the antistatic hard coat layer 120 are both regions within 50 mm from the ends 120L and 120R in the coating width direction X of the antistatic hard coat layer 120. Indicates.
- the above-mentioned regions 121 and 122 indicate regions having a width W 121 and W 122 of 50 mm continuous from the end portions 120L and 120R in the coating width direction X of the antistatic hard coat layer 120.
- brushing during application of the composition generally tends to occur near the edge of the film of the composition.
- the vicinity of the end of the film of the composition corresponds to the regions 121 and 122 in the vicinity of both ends in the coating width direction X of the antistatic hard coat layer 120, the antistatic hard coat layer in these regions 121 and 122.
- 120 tears There is a tendency for 120 tears to occur.
- the number of tears can be reduced in the regions 121 and 122 where tearing is likely to occur.
- the number of tears of the antistatic hard coat layer 120 having an area of 5 mm 2 or more in the regions 121 and 122 within 50 mm from the end in the coating width direction X of the antistatic hard coat layer 120 is the above-mentioned both. It is preferably less than 10, more preferably 5 or less, particularly preferably 2 or less per 1 m of the length of the regions 121 and 122. Thereby, since haze value can be made small in the whole antistatic hard coat film, transparency of an antistatic hard coat film can be improved. Further, the surface resistance value of the antistatic hard coat layer can fall within a predetermined range for the entire antistatic hard coat film.
- the number of tears of the antistatic hard coat layer 120 can be measured by the following method.
- the regions 121 and 122 within 50 mm from the end in the coating width direction X of the antistatic hard coat layer 120 are observed with a microscope. And the area of a tear is measured within a microscope visual field. At this time, if the tear has an area of 5 mm 2 or more, it is counted as one tear. This operation is performed within a range of 1 m in the coating direction Y of the regions 121 and 122, and the number of tears per 1 m in the length of both the regions 121 and 122 is measured.
- the antistatic hard coat layer may have a multilayer structure comprising two or more layers, but preferably has a single layer structure consisting of only one layer.
- the antistatic hard coat layer has a single layer structure, the antistatic hard coat layer can be easily produced, and the thickness of the antistatic hard coat film can be reduced.
- the thickness of the antistatic hard coat layer is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, still more preferably 1.5 ⁇ m or more, particularly preferably 2.0 ⁇ m or more, preferably 10 ⁇ m or less, more preferably It is 8 ⁇ m or less, more preferably 7 ⁇ m or less, and particularly preferably 6 ⁇ m or less.
- the thickness of the antistatic hard coat layer can be measured with an interference film thickness meter (“F20 film thickness measurement system” manufactured by Filmetrics).
- the ratio of the thickness of the antistatic hard coat layer to the thickness of the base film is preferably 1/50 or more, more preferably 1/35 or more, and particularly preferably 1/25. It is above, Preferably it is 1/2 or less, More preferably, it is 1/3 or less, Most preferably, it is 1/4 or less.
- the surface resistance value of the antistatic hard coat layer is usually 1.0 ⁇ 10 6 ⁇ / ⁇ or more, preferably 1.0 ⁇ 10 7 ⁇ / ⁇ or more, more preferably 1.0 ⁇ 10 8 ⁇ / ⁇ or more. Yes, usually 1.0 ⁇ 10 10 ⁇ / ⁇ or less, preferably 5.0 ⁇ 10 9 ⁇ / ⁇ or less, more preferably 1.0 ⁇ 10 9 ⁇ / ⁇ or less.
- the antistatic hard coat layer has such a surface resistance value, the antistatic property of the antistatic hard coat film can be enhanced.
- the surface resistance value can be measured using Hirester UX MCP-HT800 (manufactured by Mitsubishi Chemical Analytical Co.) in accordance with JIS K6911.
- the number of stripes having a length of 20 cm or more in the antistatic hard coat layer is usually 2 or less, preferably 1 or less, and more preferably 0 per 1330 mm ⁇ 500 mm of the antistatic hard coat layer.
- the number of stripes having a length of 20 cm or more is cut out of a sample film having a dimension of 1330 mm ⁇ 500 mm and a side of 500 mm parallel to the application direction of the composition in which an antistatic hard coat agent is dissolved in a solvent,
- the sample film can be measured by visually observing the antistatic hard coat layer side.
- the refractive index of the antistatic hard coat layer is preferably 1.500 or more, more preferably 1.510 or more, further preferably 1.515 or more, particularly preferably 1.520 or more, preferably 1.550 or less. More preferably, it is 1.540 or less, More preferably, it is 1.535 or less, Most preferably, it is 1.530 or less.
- the refractive index of the antistatic hard coat layer is subjected to Cauchy fitting based on values measured at a wavelength of 407 nm, a wavelength of 532 nm, and a wavelength of 633 nm with a refractive index film thickness measuring device (“Prism Coupler” manufactured by Metricon). It is a numerical value obtained at a wavelength of 550 nm.
- the water contact angle on the surface of the antistatic hard coat layer is preferably 70 ° to 90 °.
- the adhesive repelling can be suppressed when the antistatic hard coat film is adhered with an adhesive. Therefore, for example, when the space between the polarizing plate provided with the antistatic hard coat film and the touch panel is filled with an interlayer adhesive during the manufacture of the liquid crystal display device, repelling between the interlayer adhesive and the polarizing plate can be suppressed.
- the water contact angle can be measured in accordance with JIS R3257 ⁇ / 2 method.
- the antistatic hard coat layer in the present invention functions not only as an antistatic ability but also as a hard coat layer.
- the JIS pencil hardness of the antistatic hard coat layer is preferably B or more, more preferably HB or more, and particularly preferably H or more.
- the antistatic hard coat layer can also function as a hard coat layer, so that the scratch resistance of the antistatic hard coat film can be improved.
- JIS pencil hardness is determined by tilting a pencil of various hardness by 45 °, applying a load of 500 g from above, scratching the surface of the layer, and starting scratching. Hardness.
- the antistatic hard coat layer has a scratch resistance when the surface of the antistatic hard coat layer of the antistatic hard coat film is applied to steel wool # 0000 with a load of 10 gf to 50 gf to 100 gf to 500 gf applied to 1 cm 2 square of steel wool.
- the surface state after the reciprocation is visually observed to obtain a load in which no scratch is recognized.
- the load in which no scratch is observed is preferably 10 gf or more, more preferably 50 gf or more, and particularly preferably 100 gf or more.
- the antistatic hard coat film of the present invention can be provided with an arbitrary layer in combination with the base film and the antistatic hard coat layer.
- the antistatic hard coat film may include an antireflection layer on the antistatic hard coat layer.
- the antistatic hard coat film may be provided with an easy adhesion layer on the surface of the base film opposite to the antistatic hard coat layer.
- the haze value of the antistatic hard coat film is usually 1.0% or less, preferably 0.75% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.
- the antistatic hard coat film has a haze value in such a range, in the liquid crystal display device provided with this antistatic hard coat film, it is possible to suppress a decrease in image visibility due to haze, and a clear image can be obtained. Can be displayed.
- the haze value of the antistatic hard coat film can be measured using a haze meter (“Haze Guard II” manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K7136.
- the transmission hue L * of the antistatic hard coat film is preferably 94 or more, more preferably 94.5 or more, still more preferably 94.7 or more, particularly preferably 95.0 or more, preferably 97 or less, more preferably Is 96.5 or less, more preferably 96.3 or less, and particularly preferably 96.0 or less.
- the transmitted hue L * is a coordinate L * in the L * a * b * color system.
- the transmitted hue L * of the antistatic hard coat film can be measured by a spectrophotometer (“V-7200” manufactured by JASCO Corporation) using a C light source.
- the total light transmittance of the antistatic hard coat film is preferably 85% or more, more preferably 86% or more, and particularly preferably 88% or more.
- the total light transmittance of the antistatic hard coat film can be measured in the wavelength range of 380 nm to 780 nm using an ultraviolet / visible spectrometer.
- the thickness of the antistatic hard coat film is from 10 ⁇ m to 100 ⁇ m, more preferably from 20 ⁇ m to 60 ⁇ m. By setting the thickness of the antistatic hard coat film in the above range, there is an advantage that the polarizing plate can be made thin.
- the thickness of the antistatic hard coat film can be measured using a contact-type film thickness meter (ABS Digimatic Indicator, manufactured by Mitutoyo Corporation).
- the antistatic hard coat film has a light transmittance at a wavelength of 380 nm of 10% or less, preferably 5% or less, more preferably 1% or less at a wavelength of 380 nm. Further, the light transmittance at a wavelength of 280 to 370 nm is 1.5% or less, and the light transmittance at a wavelength of 280 to 370 nm is 1% or less. In the present invention, when the light transmittance at a wavelength of 380 nm exceeds 10%, the polarizer changes due to ultraviolet rays, and the degree of polarization decreases. The said light transmittance can be measured using a spectrophotometer based on JISK0115.
- the light transmittance at wavelengths of 280 to 370 nm and 380 nm is in the above range, coloring of the polarizer and a decrease in the degree of polarization can be suppressed when used by being attached to the polarizer.
- the light transmittance can be measured using an ultraviolet-visible near-infrared spectrophotometer (V-7200, manufactured by JASCO Corporation).
- the antistatic hard coat film has an in-plane retardation at a wavelength of 550 nm of 85 nm to 120 nm, more preferably 90 nm to 110 nm.
- the retardation of the antistatic hard coat film is within the above range, the screen is not darkened depending on the orientation even when the liquid crystal display device is used using polarized sunglasses.
- the antistatic hard coat film may be a long film or a single film. Usually, from the viewpoint of increasing production efficiency, the antistatic hard coat film is produced as a long film. When a sheet antistatic hard coat film is produced, the sheet antistatic hard coat film is usually produced by cutting a long antistatic hard coat film into a desired shape.
- the antistatic hard coat film of the present invention is preferably provided on a polarizing plate.
- the polarizing plate provided with the antistatic hard coat film of the present invention usually comprises an antistatic hard coat film and a polarizer, and the polarizer and the substrate film are bonded.
- Any polarizer can be used.
- a polarizer what is obtained by carrying out an extending
- the polarizing plate may include an arbitrary polarizing plate protective film, a polarizer and an antistatic hard coat film in this order.
- an arbitrary polarizing plate protective film an optically isotropic isotropic film may be used, or a retardation film having a desired retardation may be used.
- the retardation film exhibits an optical compensation function to improve the viewing angle dependency and compensate for the light leakage phenomenon of the polarizer when obliquely viewed. The viewing angle characteristics can be improved.
- a retardation film for example, a longitudinal uniaxially stretched film, a laterally uniaxially stretched film, a longitudinally and laterally biaxially stretched film, a retardation film obtained by polymerizing a liquid crystalline compound, and the like can be used.
- the retardation film include a uniaxially or biaxially stretched thermoplastic resin film made of a thermoplastic resin such as a cycloolefin resin.
- Specific examples of commercially available thermoplastic resin films include “Zeonor Film” manufactured by ZEON Corporation; “Essina” and “SCA40” manufactured by Sekisui Chemical Co., Ltd .; “Arton Film” manufactured by JSR Corporation, and the like. .
- the bonding method of the polarizer and the substrate film is not particularly limited, and may be bonded by an adhesive layer, or may be directly bonded by a method such as plasma treatment on the member surface.
- the adhesive will be described later.
- the antistatic hard coat film of the present invention is preferably provided in a liquid crystal display device.
- a liquid crystal display device provided with the antistatic hard coat film of the present invention usually comprises a liquid crystal cell, a polarizer provided on the viewing side of the liquid crystal cell, and an antistatic hard coat film provided on the viewing side of the polarizer.
- the antistatic hard coat film is provided so as to include a base film and an antistatic hard coat layer in the order closer to the polarizer.
- a liquid crystal cell As an example of a suitable liquid crystal display device, a liquid crystal cell, an arbitrary polarizing plate protective film, a polarizer, and an antistatic hard coat film are arranged from the liquid crystal cell side toward the viewing side (the side on which the user views the image).
- a liquid crystal display device provided in order is mentioned.
- the liquid crystal display device controls driving of liquid crystal molecules in the liquid crystal cell while maintaining a clear image displayed by the liquid crystal display device. Can be stabilized.
- the base film of the antistatic hard coat film is made of a thermoplastic resin containing a cycloolefin polymer, heat resistance and moisture resistance are improved as compared with a conventional liquid crystal display device having a polarizing plate protective film made of a material such as triacetyl cellulose. Can be improved.
- such an antistatic hard coat film does not require the use of a water-based adhesive at the time of bonding, it is possible to suppress deterioration in quality in a durability test under high temperature and high humidity.
- the liquid crystal is obtained from the ultraviolet rays that are exposed when manufacturing the liquid crystal display device and the ultraviolet rays that are exposed when using the liquid crystal display device. Components such as cells and polarizers can be protected.
- the liquid crystal cell an arbitrary one such as a TN method, a VA method, an IPS method, or the like can be used.
- the IPS liquid crystal cell is preferable because the display color of the liquid crystal display does not change when the viewing angle changes.
- an in-cell type liquid crystal cell may be used to reduce the thickness of the entire liquid crystal display device.
- a cover glass on the outermost surface on the viewing side.
- the viewing side refers to the side on which the viewer of the displayed image is located when using the liquid crystal display device.
- the antistatic hard coat film is usually provided so that the base film is closer to the liquid crystal cell than the antistatic hard coat layer.
- the slow axis of the base film of the antistatic hard coat film is a predetermined angle with respect to the transmission axis of the polarizer. It is preferable to arrange so as to form ⁇ .
- the angle ⁇ is preferably 40 ° or more, more preferably 43 ° or more, preferably 50 ° or less, more preferably 48 ° or less, and particularly preferably 45 ° ⁇ 1 °. An angle within the range.
- polarized light that passes through the liquid crystal cell and the polarizer and passes through the antistatic hard coat film can be converted into circularly polarized light or elliptically polarized light, so the user of the liquid crystal display device wears polarized sunglasses. Even in the state, the display content can be made visible.
- Components of the liquid crystal display device such as a liquid crystal cell, a polarizing plate protective film, a polarizer, and an antistatic hard coat film may be bonded and integrated.
- a polarizing plate protective film, a polarizer, and an antistatic hard coat film may be bonded to form a single polarizing plate.
- the polarizing plate may be fixed to the liquid crystal cell by bonding the polarizing plate and the liquid crystal cell.
- the said structural member may be bonded together by the suitable adhesive bond layer, and may be bonded together directly by methods, such as plasma treatment of the member surface.
- any adhesive can be used, for example, rubber-based, fluorine-based, acrylic-based, polyvinyl alcohol-based, polyurethane-based, silicone-based, polyester-based, polyamide-based, polyether-based, epoxy-based adhesives, etc. Can be used. Moreover, these adhesives may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- an ultraviolet curable adhesive layer such as an acrylic adhesive layer is provided between the polarizer and the antistatic film, and the polarizer and the antistatic film are connected by the ultraviolet curable adhesive layer. It is preferable to bond them together.
- the thickness of the adhesive layer is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less.
- the thickness of the coating film was measured using an interference type film thickness meter (F20 film thickness measurement system, manufactured by Filmetrics).
- the thickness of the base film was measured using a contact-type film thickness meter (ABS Digimatic Indicator, manufactured by Mitutoyo Corporation).
- the film was cut into a rectangle of 1330 mm ⁇ 500 mm to obtain a sample film. At this time, the side of 500 mm was cut out so as to be parallel to the coating direction.
- the streaks are observed by visually observing the antistatic hard coat layer side of the sample film under Polarion Light (manufactured by C's Sea Co., Ltd.), observing the presence or absence of streaks, and the length of the streaks. The case of this or less was determined as “2”, and the case of 3 or more streaks of 20 cm or more was determined as “1”.
- Example 1 (1-1. Production of base film) A diagonally stretched film of cycloolefin polymer was prepared as a base film.
- This base film is a long film of cycloolefin polymer (thickness 40 ⁇ m, trade name “Zeonor film ZF14-040”, manufactured by Nippon Zeon Co., Ltd., hereinafter abbreviated as “ZNR”). It was a stretched film stretched at a stretch ratio of 1.5 times in a direction of 45 °, and the thickness was 25 ⁇ m.
- composition (B1) in which antistatic hard coat agent is dissolved Metal oxide fine particles were produced by the following method. 130 parts by weight of potassium stannate and 30 parts by weight of antimony potassium tartrate were dissolved in 400 parts by weight of pure water to obtain a solution. This solution was added to 1,000 parts by weight of pure water in which 1.0 part by weight of ammonium nitrate and 12 parts by weight of 15% by weight aqueous ammonia were dissolved, and then hydrolyzed while stirring at 60 ° C. for 12 hours. During this hydrolysis, a 10% by weight nitric acid solution was added to keep the pH at 9.0.
- the precipitate produced by hydrolysis was filtered and washed, and then dispersed again in water to prepare a hydroxide dispersion of an antimony-doped tin oxide precursor having a solid content of 20% by weight.
- the dispersion was spray dried at a temperature of 100 ° C.
- the obtained powder was heat-treated at 550 ° C. for 2 hours in an air atmosphere to obtain an antimony-doped tin oxide powder.
- a sol was prepared by dispersing 60 parts by weight of this powder in 140 parts by weight of a 4.3% by weight aqueous potassium hydroxide solution and pulverizing it with a sand mill for 3 hours while maintaining the dispersion at 30 ° C.
- the sol obtained above is dealkalized with an ion exchange resin until the pH is 3.0, and then pure water is added to form metal oxide fine particles composed of antimony-doped tin fine particles having a solid content of 20% by weight ( An aqueous dispersion of 1) was prepared.
- the pH of this aqueous dispersion of metal oxide fine particles was 3.3.
- the average particle size of the metal oxide fine particles (1) was 9 nm.
- the temperature of 100 parts by weight of the aqueous dispersion of the metal oxide fine particles (1) obtained was adjusted to 25 ° C., and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .; normal ethyl silicate, SiO 2 concentration 28).
- a mixed solvent of ethanol 85.5% by weight, normal propyl alcohol 9.6% by weight, and methanol 4.9% by weight (hereinafter referred to as mixed ethanol 2 and A dispersion of chain metal oxide fine particles (1) coated with silica and having a solid content of 19.4% by weight was prepared.
- the average number of connected fine particles constituting the chain metal oxide fine particles (1) was 5. This average number of connections is a value obtained by taking a transmission electron micrograph of chain metal oxide fine particles, obtaining the number of connections for 100 chain metal oxide fine particles, and rounding the average value. It is.
- UV-curable polymerizable monomer composition (R1) was prepared.
- the solid content concentration of the polymerizable monomer composition (R1) was 100%.
- a mixture (PE3A / PE4A) of 222 parts by weight of isophorone diisocyanate, pentaerythritol triacrylate (hereinafter abbreviated as “PE3A”) and pentaerythritol tetraacrylate (hereinafter abbreviated as “PE4A”). 75/25 (weight ratio)) 795 parts by weight of polyfunctional urethane acrylate (U1) which is a urethane-reactive acrylate was prepared. The concentration of the solid content of this polyfunctional urethane acrylate (U1) was 100%.
- These composition (R1) and polyfunctional urethane acrylate (U1) were used as a monomer composition which gives a binder polymer.
- composition (B1) was prepared, a mixed solution of 47.11 parts by weight of methyl ethyl ketone, 6.18 parts by weight of the above mixed ethanol 2 and 9.28 parts by weight of diacetone alcohol was added for dilution. B2) was obtained. It was 1.5 mPa * s when the viscosity of the composition (B2) was measured by the above-mentioned measuring method.
- the surface opposite to the masking film of the obliquely stretched film obtained in (1-1) was subjected to corona treatment (output 0.4 kW, discharge amount 200 W ⁇ min / m 2 ).
- the composition (B2) prepared above was applied to the surface subjected to the corona treatment using a die coater so that the thickness of the antistatic hard coat layer obtained after curing was 3.0 ⁇ m.
- a film (B2) was formed.
- the composition (B2) was applied in an environment with a relative humidity of 50%.
- the film of the composition (B2) was dried at 60 ° C. for 2 minutes, and then cured by irradiation with 250 mJ / cm 2 of light with a high-pressure mercury lamp to obtain an antistatic hard coat layer.
- the obtained antistatic hard coat film was wound into a roll with a winding tension of 200 N.
- the surface resistance value and streaks of the antistatic hard coat layer in the antistatic hard coat film thus obtained were evaluated by the method described above.
- a polarizer was prepared by doping a resin film (PVA (polyvinyl alcohol) film) with iodine and stretching it in one direction. Further, the antistatic hard coat film was pulled out from the roll of the antistatic hard coat film, and the masking film was peeled off to expose the surface of the base film opposite to the antistatic hard coat layer. And the surface of the exposed base film and the one surface of the polarizer were bonded together with an ultraviolet curable acrylic adhesive. At this time, the slow axis of the substrate film was at an angle of 45 ° with respect to the transmission axis of the polarizer.
- PVA polyvinyl alcohol
- a cycloolefin film subjected to lateral uniaxial stretching was bonded as a polarizing plate protective film with an ultraviolet curable acrylic adhesive.
- the slow axis of the cycloolefin film was parallel to the transmission axis of the polarizer.
- the polarizing plate is provided with a polarizing plate protective film, an adhesive layer, a polarizer, an adhesive layer, a base film, and an antistatic hard coat layer in this order in the thickness direction by irradiating ultraviolet rays to cure the adhesive. I got a plate.
- a liquid crystal display device was manufactured by incorporating the polarizing plate prepared as described above into a liquid crystal panel including an in-cell type liquid crystal cell including a touch sensor. At this time, the direction of the polarizing plate was set so that the surface on the antistatic hard coat layer side was directed to the viewing side. The evaluation of the visibility of the image of the liquid crystal display device thus obtained and the evaluation of the stability of the liquid crystal drive were performed by the methods described above.
- Example 2 In Example 1, the base film was changed to a laterally uniaxially stretched film of cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd., Tg 126 ° C.). Except for the above, the production and evaluation of an antistatic hard coat film and the production and evaluation of a liquid crystal display device were carried out in the same manner as in Example 1.
- Example 3 In Example 1, the thickness of the base film was changed from 25 ⁇ m to 47 ⁇ m. Except for the above, the production and evaluation of an antistatic hard coat film and the production and evaluation of a liquid crystal display device were carried out in the same manner as in Example 1.
- Example 4 In Example 1, the coating thickness of the composition (B2) was changed from 3 ⁇ m to 10 ⁇ m. Except for the above, the production and evaluation of an antistatic hard coat film and the production and evaluation of a liquid crystal display device were carried out in the same manner as in Example 1.
- Example 5 After the composition (B1) was prepared, 53.21 parts by weight of methyl isobutyl ketone was used instead of 47.11 parts by weight of methyl ethyl ketone, and 6.18 parts by weight of mixed ethanol 2 was added without dilution. Otherwise, in the same manner as (1-2) in Example 1, a composition (B3) having a solid content concentration of 20% was obtained. Production and evaluation of an antistatic hard coat film and production and evaluation of a liquid crystal display device were carried out in the same manner as in Example 1 except that the composition (B3) was used instead of the composition (B2). In addition, the viscosity of the composition (B3) was 3.0 mPa ⁇ s.
- Example 6 38.0 parts by weight of methyl ethyl ketone, 5.1 parts by weight of mixed ethanol 2 and 7.6 parts by weight of diacetone alcohol were added to the composition (B1) obtained in (1-2) of Example 1 to obtain a solid. A composition (B4) having a partial concentration of 23% was obtained. Production and evaluation of an antistatic hard coat film and production and evaluation of a liquid crystal display device were carried out in the same manner as in Example 1 except that the composition (B4) was used instead of the composition (B2). The composition (B4) had a viscosity of 8.0 mPa ⁇ s.
- Example 7 (7-1. Production of base film) A diagonally stretched film of cycloolefin polymer was prepared as a base film. This base film was obtained by stretching a long film of cycloolefin polymer (thickness 70 ⁇ m, trade name “Zeonor film ZF14-070”) in a direction of 45 ° with respect to the short direction of the film at a draw ratio of 1.5 times. It was a stretched film and the thickness was 47 ⁇ m.
- composition (B8) in which antistatic hard coat agent is dissolved A mixed solution is obtained by sufficiently mixing 7.2 parts by weight of the polymerizable monomer composition (R1), 0.8 parts by weight of the polyfunctional urethane acrylate (U1), and 0.4 parts by weight of the photopolymerization initiator. It was. In this mixed solution, 28.76 parts by weight of the dispersion of metal oxide particles (1) (containing 38.2% by weight of solids, that is, 11.33 parts by weight, 17.43 parts by weight of mixed ethanol 2 other than the solids) And 0.5 parts by weight of a leveling agent were added and mixed uniformly to obtain a liquid composition (B7) having active energy ray curability.
- composition (R1), polyfunctional urethane acrylate (U1), photopolymerization initiator, chain metal oxide particles (1), and leveling agent are the same as those used in (1-2) of Example 1. A thing was used.
- the prepared composition (B7) was diluted by adding a mixed solution of 47.11 parts by weight of methyl ethyl ketone, 6.18 parts by weight of the mixed ethanol 2 and 9.28 parts by weight of diacetone alcohol, and the composition (B8 ) It was 5 mPa * s when the viscosity of the composition (B8) was measured by the above-mentioned measuring method.
- composition (B6) was obtained in the same manner as (1-2) of Example 1 except that the dispersion of the chain metal oxide particles (1) was not added. Production and evaluation of an antistatic hard coat film and production and evaluation of a liquid crystal display device were carried out in the same manner as in Example 1 except that the composition (B6) was used in place of the composition (B2).
- MEK represents methyl ethyl ketone
- MIBK represents methyl isobutyl ketone
- EtOH represents mixed ethanol
- IPA represents isopropyl alcohol
- DAA represents diacetone alcohol
- ATO antimony-doped tin oxide
- ZNR represents an obliquely stretched film manufactured using a trade name “Zeonor Film ZF14-040” or a trade name “Zeonor Film ZF14-070”).
- Example 2 is inferior in image visibility evaluation to other examples. This shows that the image visibility of a liquid crystal display device improves that a base film is a diagonally stretched film.
- Example 3 since a substrate film having a thickness greater than that of Example 1 was used, in-plane retardation was increased. For this reason, although a slight color change was observed in the image of the liquid crystal display device, there was no practical harm in use.
- Example 4 since the antistatic hard coat layer having a thickness larger than that of the antistatic hard coat layer of Example 1 was used, the haze value was increased. For this reason, the visibility of the image of the liquid crystal display device was slightly lowered, but there was no actual harm in use.
- Example 5 the mixing ratio of the particle-aggregating solvent and the particle-dispersing solvent, the mixing ratio of the particle-aggregating solvent and the high-boiling solvent, and the mixing ratio of the particle-dispersing solvent and the high-boiling solvent are outside the more preferable ranges.
- a composition (B3) was used. As a result, the liquid crystal drive was slightly uneven due to charging, but there was no actual damage in use.
- Example 6 since the composition (B4) having a higher viscosity than the composition (B1) was used, the coating was poor and five 5 cm stripes were generated.
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Abstract
Description
すなわち、本発明は下記のとおりである。
〔1〕 シクロオレフィンポリマーを含む熱可塑性樹脂からなる基材フィルムと、
前記基材フィルム上に設けられ、導電性を有する金属酸化物微粒子を含む帯電防止ハードコート層と、を備え、
前記帯電防止ハードコート層の表面抵抗値が、1.0×106Ω/□以上1.0×1010Ω/□以下であり、
前記帯電防止ハードコート層の、長さが20cm以上のスジの本数が、前記帯電防止ハードコート層の1330mm×500mm当たり2本以下である、帯電防止ハードコートフィルム。
〔2〕 前記帯電防止ハードコート層は、前記金属酸化物微粒子を含む帯電防止ハードコート剤を、粒子凝集性溶媒及び粒子分散性溶媒に溶解させた組成物を、前記基材フィルム上に塗工することにより形成され、
前記組成物の粘度が1mPa・s以上6mPa・s以下である、〔1〕に記載の帯電防止ハードコートフィルム。
〔3〕 前記金属酸化物微粒子は、アンチモンドープ酸化スズである、〔1〕又は〔2〕に記載の帯電防止ハードコートフィルム。
〔4〕 前記帯電防止ハードコート層が、単層構造を有し、
前記帯電防止ハードコート層の厚みが、10μm以下である、〔1〕~〔3〕のいずれか1項に記載の帯電防止ハードコートフィルム。
〔5〕 前記基材フィルムは、斜め延伸されたものであり、
前記基材フィルムの厚みが、50μm以下である、〔1〕~〔4〕のいずれか1項に記載の帯電防止ハードコートフィルム。
〔6〕 〔1〕~〔5〕のいずれか1項に記載の帯電防止ハードコートフィルムと、偏光子とを備え、前記偏光子と前記基材フィルムとが接合されている、偏光板。
〔7〕 〔6〕に記載の偏光板と、液晶セルとを備える、タッチパネル。
〔8〕 前記液晶セルが、IPS方式の液晶セルである、〔7〕に記載のタッチパネル。
〔9〕 視認側の最表面にカバーガラスを有する、〔7〕又は〔8〕に記載のタッチパネル。
〔10〕 〔6〕に記載の偏光板と、液晶セルとを備える、液晶表示装置。
〔11〕 〔1〕~〔5〕のいずれか1項に記載の帯電防止ハードコートフィルムの製造方法であって、
導電性を有する金属酸化物微粒子を含む帯電防止ハードコート剤を、粒子凝集性溶媒及び粒子分散性溶媒に溶解させた組成物を、基材フィルム上に塗工し、帯電防止ハードコート層を形成することを含み、
前記組成物の粘度が1mPa・s以上6mPa・s以下である、帯電防止ハードコートフィルムの製造方法。
本発明の帯電防止ハードコートフィルムは、シクロオレフィンポリマーを含む熱可塑性樹脂からなる基材フィルムと、基材フィルム上に設けられ、導電性を有する金属酸化物微粒子を含む帯電防止ハードコート層とを備える。
図1は、本発明の帯電防止ハードコートフィルムの一例を模式的に示す断面図である。
図1に示すように、本発明の帯電防止ハードコートフィルム100は、基材フィルム110と、この基材フィルム110上に設けられた帯電防止ハードコート層120とを備える。また、帯電防止ハードコート層120は、所定範囲の表面抵抗値を有する。さらに、本発明の帯電防止ハードコート層120の所定範囲内における長さが20cm以上のスジの本数が2本以下である。このような構成を有することにより、本発明の帯電防止ハードコートフィルム100は、所定の面内でのスジが少なく、所定範囲の表面抵抗値を有する。この際、帯電防止ハードコートフィルム100において帯電防止ハードコート層120は、最外層となることでその表面120Uが露出していてもよく、当該帯電防止ハードコート層120上に任意の層が設けられていてもよい。また、基材フィルムは、2以上の層を備える複層フィルムであってもよい。
本発明で用いる基材フィルムは、シクロオレフィンポリマーを含む熱可塑性樹脂からなる。シクロオレフィンポリマーは、構造単位に脂環式構造を有する。シクロオレフィンポリマーは、主鎖に脂環式構造を有していてもよく、側鎖に脂環式構造を有していてもよい。中でも、機械的強度及び耐熱性の観点から、主鎖に脂環式構造を有する重合体が好ましい。
ノルボルネン構造を有する単量体は1種単独で、あるいは2種以上を組み合わせて用いることができる。
基材フィルムは、シクロオレフィンポリマーを含む熱可塑性樹脂をフィルム状に成形することにより製造しうる。成形方法の例としては、加熱溶融成形法、及び溶液流延法を用いうる。中でも、フィルム中の揮発性成分を低減させる観点から、加熱溶融成形法を用いることが好ましい。加熱溶融成形法は、さらに詳細には、例えば溶融押出成形法、プレス成形法、インフレーション法、射出成形法、ブロー成形法、延伸成形法などに分類できる。これらの中で、機械的強度および表面精度などに優れる基材フィルムを得るためには、溶融押出成形法を用いるのが好ましい。
また、基材フィルムが、2以上の層を備える複層フィルムである場合には、共押出法を用いることが好ましい。
帯電防止ハードコート層は、基材フィルム上に設けられ、導電性を有する金属酸化物微粒子を含む。この際、帯電防止ハードコート層は、任意の層を介して基材フィルム上に間接的に設けられていてもよいが、通常は、基材フィルムの表面に直接設けられている。帯電防止ハードコート層においては、金属酸化物微粒子が鎖状に連結するように凝集して鎖状連結体を形成しており、この鎖状連結体によって導電パスが形成されている。そのため、本発明の帯電防止ハードコートフィルムは、帯電防止機能を発揮できる。
金属酸化物微粒子の材料である金属酸化物は、特に限定されず、導電性を有する金属酸化物を適宜選択して用いうる。金属酸化物の例としては酸化スズ、アンチモン、フッ素またはリンがドーピングされた酸化スズ、酸化インジウム、スズまたはフッ素がドーピングされた酸化インジウム、酸化アンチモン、及び低次酸化チタンが挙げられ、特に、アンチモンがドーピングされた酸化スズ(アンチモンドープ酸化スズ)、アンチモンがドーピングされた酸化インジウムが好ましく、アンチモンがドーピングされた酸化スズがより好ましい。これらは1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
R1 aSi(OR2)4-a (1)
(式(1)において、R1及びR2は、それぞれ独立して、水素原子、ハロゲン原子、炭素原子数1~10の炭化水素基、及び、炭素原子数1~10の有機基からなる群より選ばれる基を表し、aは、0~3の整数を表す。)
また、式(1)において、R2の例は、水素原子、ビニル基、アリール基、アクリル基、炭素原子数1~8のアルキル基、及び-CH2OCnH2n+1(nは1~4の整数を表す。)が挙げられる。
したがって、四官能の有機ケイ素化合物と三官能の有機ケイ素化合物とを組み合わせて用いる場合には、これらの有機ケイ素化合物を同時に金属酸化物微粒子の水分散液と混合するのではなく、まず、四官能の有機ケイ素化合物を金属酸化物微粒子の水分散液と混合したのち、アルコールを混合するとともに三官能の有機ケイ素化合物を混合することが好ましい。
また、通常、イオン交換処理の際には、脱イオン処理も行われるので、金属酸化物微粒子は鎖状に配向し易くなる。
まず、式(1)において「a」が0である四官能の有機ケイ素化合物を、金属酸化物微粒子の水分散液と混合し、この水分散液とアルコールとを混合して、四官能の有機ケイ素化合物の加水分解を行う。その後、水分散液を室温に冷却し、必要に応じて再び前記アルコールと混合する。その後、式(1)において「a」が1である三官能の有機ケイ素化合物を前記の水分散液と混合し、前述の加水分解に適した温度に昇温して、加水分解を行う。これにより、四官能の有機ケイ素化合物の加水分解物によって、金属酸化物微粒子の鎖状の連結を維持することができる。さらに、三官能の有機ケイ素化合物の加水分解物の金属酸化物微粒子の表面への結合が促進されるので、金属酸化物微粒子の分散性を向上させることができる。
金属酸化物微粒子の鎖状連結体の写真を、透過型電子顕微鏡によって撮影する。この写真から、金属酸化物微粒子の鎖状連結体100個について、それぞれの鎖状連結体における連結数を求める。そして、各鎖状連結体の連結数の平均値を計算し、小数点以下1桁を四捨五入して、金属酸化物微粒子の平均連結数を得る。
帯電防止ハードコート層は、金属酸化物微粒子に加えて、通常、バインダ重合体を含む。バインダ重合体により、金属酸化物微粒子を帯電防止ハードコート層に保持することができる。
重合性単量体の酸価は、JIS K0070(化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化物の試験方法)により、指示薬にブロモチモールブルーを用いて測定しうる。
帯電防止ハードコート層は、本発明の効果を著しく損なわない限り、金属酸化物微粒子及びバインダ重合体以外に任意の成分を含みうる。また、任意の成分は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
帯電防止ハードコートフィルムは、金属酸化物微粒子を含む帯電防止ハードコート剤を溶媒に溶解させた組成物(以下、単に「組成物」ともいう)を基材フィルム上に塗工して、帯電防止ハードコート層を形成する工程を含む製造方法により製造しうる。また、塗工時点において帯電防止ハードコート剤を溶媒に溶解させた組成物の層は、通常流体状であるので、前記組成物を基材フィルム上に塗工した後には、塗工された帯電防止ハードコート剤を溶媒で溶解させた組成物の膜を硬化させる工程を行うことが好ましい。以下、この帯電防止ハードコートフィルムの製造方法の例として、(メタ)アクリロイル基を1分子中に3個以上有する化合物を50重量%以上含む重合性単量体を重合して得られる重合体をバインダ重合体として含む帯電防止ハードコート層を備える帯電防止ハードコートフィルムの好ましい製造方法を説明する。
粒子分散性溶媒と高沸点溶媒との混合比率(重量比)としては(粒子分散性溶媒:高沸点溶媒)、好ましくは60:40~85:15、より好ましくは65:35~80:20、さらに好ましくは70:30~75:25である。
混合比率を上記の範囲内に収めることで、帯電防止ハードコート剤を溶媒で溶解させた組成物の液安定性が上昇し、ポットライフを長くすることができるとともに、表面抵抗値を所定の範囲内に収めることができる。
一般に、溶媒を含む塗料を基材上に塗工して塗料膜を形成した場合、塗工直後の溶媒の揮発により、基材から溶媒の気化熱の分だけ熱が奪われ、塗料膜の表面に結露が生じることがある。このような現象は「ブラッシング」と呼ばれ、このブラッシングが生じた部分では見た目が白化することがある。
また、前記のようなブラッシングの影響は、帯電防止ハードコート剤を溶解させた組成物の膜が外気に触れる面積が広い部分において生じやすい。これは、外気に触れる面積が大きいと、冷却が早く始まり、そのため結露が生じやすいからである。
通常、組成物の膜の端部近傍においては、組成物の膜の上面だけでなく、端面においても外気に触れる。そのため、この組成物の膜の端部近傍においては、組成物の膜は大面積で外気に触れて早く冷却が開始されるので、冷えやすく、結露が生じやすい。したがって、この組成物の膜の端部近傍では、前記のブラッシングの影響を受けて、帯電防止ハードコート層の断裂及びヘイズのムラが特に生じやすい。
図2は、本発明の帯電防止ハードコートフィルムの一例を模式的に示す平面図である。
前述したように、本発明の帯電防止ハードコートフィルム100が備える帯電防止ハードコート層120は、帯電防止ハードコート剤を溶媒に溶解させた組成物を基材フィルム110上に塗工して形成した場合であっても、ブラッシングによる金属酸化物微粒子の過剰な凝集の影響を抑制できる。そのため、この帯電防止ハードコート層120は、帯電防止ハードコート層120の塗工幅方向Xの両端部近傍の領域121及び122における断裂の数を少なくできる。
ここで、帯電防止ハードコート層120の塗工幅方向Xとは、帯電防止ハードコート層120の面内方向であって、帯電防止ハードコート層120を形成するために前記組成物を塗工した工程における塗工方向Yに垂直な方向である。基材フィルム110が長尺のフィルムである場合、この塗工幅方向Xは、通常、基材フィルム110の幅方向に平行な方向を示す。
また、帯電防止ハードコート層120の塗工幅方向Xの両端部近傍の領域121及び122とは、帯電防止ハードコート層120の塗工幅方向Xの端部120L及び120Rから50mm以内の両領域を示す。即ち、前記の領域121及び122とは、帯電防止ハードコート層120の塗工幅方向Xの端部120L及び120Rから連続する、幅W121及びW122が50mmの領域を示す。
前述のように、組成物の塗工時のブラッシングは、一般に、組成物の膜の端部近傍において生じやすい。この組成物の膜の端部の近傍は、帯電防止ハードコート層120の塗工幅方向Xの両端部近傍の領域121及び122に相当するから、この領域121及び122において、帯電防止ハードコート層120の断裂が生じやすい傾向がある。しかし、上述したように、組成物の塗工環境において相対湿度を適切に調整することにより、このように断裂が生じやすい領域121及び122において、断裂の数を少なくできる。
顕微鏡により、帯電防止ハードコート層120の塗工幅方向Xの端部から50mm以内の領域121及び122を観察する。そして、顕微鏡視野内で、断裂の面積を測定する。このとき、断裂が5mm2以上の面積を有していれば、1個の断裂としてカウントする。この操作を、前記の領域121及び122の塗工方向Yでの長さ1mの範囲で行い、両領域121及び122の長さ1m当たりの断裂の数を測定する。
帯電防止ハードコート層の厚みは、干渉式膜厚計(フィルメトリクス社製「F20膜厚測定システム」)にて測定しうる。
帯電防止ハードコート層の表面抵抗値は、通常1.0×106Ω/□以上、好ましくは1.0×107Ω/□以上、より好ましくは1.0×108Ω/□以上であり、通常1.0×1010Ω/□以下、好ましくは5.0×109Ω/□以下、より好ましくは1.0×109Ω/□以下である。帯電防止ハードコート層がこのような表面抵抗値を有することにより、帯電防止ハードコートフィルムの帯電防止性を高めることができる。そのため、帯電防止ハードコートフィルムをインセルタイプのタッチパネルを備える液晶表示装置に組み込んだ場合に、タッチパネルの操作時における帯電による液晶駆動のムラの発生を抑制することができる。
表面抵抗値は、JIS K6911に準拠して、ハイレスターUX MCP-HT800(三菱化学アナリック社製)を用いて測定しうる。
長さが20cm以上のスジの本数は、寸法が1330mm×500mmであって、且つ500mmの辺が帯電防止ハードコート剤を溶媒に溶解させた組成物の塗布方向と平行である試料フィルムを切り取り、この試料フィルムの帯電防止ハードコート層側を目視で観察する方法で測定しうる。
帯電防止ハードコート層の屈折率は、屈折率膜厚測定装置(Metricon社製「プリズムカプラ」)にて波長407nm、波長532nm、及び波長633nmの3波長で測定した値を元にコーシーフィッティングを行い求めた、波長550nmでの数値である。
帯電防止ハードコート層のJIS鉛筆硬度は、好ましくはB以上、より好ましくはHB以上、特に好ましくはH以上である。帯電防止ハードコート層のJIS鉛筆硬度を高めることにより、帯電防止ハードコート層をハードコート層としても機能させることができるので、帯電防止ハードコートフィルムの耐擦傷性を向上させることができる。ここで、JIS鉛筆硬度は、JIS K5600-5-4に準拠して、各種硬度の鉛筆を45°傾けて、上から500g重の荷重を掛けて層の表面を引っ掻き、傷が付きはじめる鉛筆の硬さである。
キズが認められない荷重は、好ましくは10gf以上、より好ましくは50gf以上、特に好ましくは100gf以上である。帯電防止ハードコート層の耐擦傷性を高めることで、偏光板化などの加工工程での不用意な外的要因によるキズ付きを抑制することができる。
本発明の帯電防止ハードコートフィルムは、基材フィルム及び帯電防止ハードコート層に組み合わせて、任意の層を備えうる。
例えば、帯電防止ハードコートフィルムは、帯電防止ハードコート層上に反射防止層を備えていてもよい。
また、帯電防止ハードコートフィルムは、帯電防止ハードコート層とは反対側の基材フィルムの面に、易接着層を備えていてもよい。
帯電防止ハードコートフィルムのヘイズ値は、具体的には、通常1.0%以下、好ましく0.75%以下、より好ましくは0.5%以下、特に好ましくは0.3%以下である。帯電防止ハードコートフィルムがこのような範囲のヘイズ値を有することにより、この帯電防止ハードコートフィルムを備えた液晶表示装置において、ヘイズによる画像視認性の低下を抑制することができ、鮮明な画像を表示することができる。
帯電防止ハードコートフィルムのヘイズ値は、JIS K7136に準拠して、ヘイズメーター(東洋精機社製「ヘイズガードII」)を用いて測定しうる。
前記の透過色相L*は、L*a*b*表色系における座標L*である。帯電防止ハードコートフィルムの透過色相L*は、分光光度計(日本分光社製「V-7200」)により、C光源を用いて測定しうる。
帯電防止ハードコートフィルムの全光線透過率は、紫外・可視分光計を用いて、波長380nm~780nmの範囲で測定しうる。
帯電防止ハードコートフィルムの厚みは、接触式膜厚計(ABSデジマチックインジケータ、ミツトヨ社製)を用いて測定しうる。
光線透過率は、紫外可視近赤外分光光度計(V-7200、日本分光製)を用いて測定しうる。
本発明の帯電防止ハードコートフィルムは、偏光板に設けることが好ましい。本発明の帯電防止ハードコートフィルムを備える偏光板は、通常、帯電防止ハードコートフィルムと、偏光子とを備え、前記偏光子と前記基材フィルムとが接合されている。
本発明の帯電防止ハードコートフィルムは、液晶表示装置に設けることが好ましい。本発明の帯電防止ハードコートフィルムを備える液晶表示装置は、通常、液晶セルと、液晶セルの視認側に設けられた偏光子と、偏光子の視認側に設けられた帯電防止ハードコートフィルムとを備える。また、この際、帯電防止ハードコートフィルムは、偏光子に近い順に、基材フィルム及び帯電防止ハードコート層を備えるように設けることが好ましい。好適な液晶表示装置の一例としては、液晶セル側から視認側(使用者が画像を視認する側)に向かって、液晶セル、任意の偏光板保護フィルム、偏光子及び帯電防止ハードコートフィルムをこの順に備える液晶表示装置が挙げられる。
(表面抵抗値の測定方法)
フィルムを100mm×100mmのサイズに切り取り、試料フィルムを得た。試料フィルムの帯電防止ハードコート層上にプローブを固定し、ハイレスターUX MCP-HT800(三菱化学アナリック社製)を用いて、JIS K6911に準拠するように、試料フィルムの帯電防止ハードコート層を有する側の面の表面抵抗値を測定した。帯電防止ハードコート層の測定箇所を変えて合計5か所測定し、それらの平均値を表面抵抗値とした。測定条件は出力500Wで10秒間とした。
帯電防止ハードコート剤を溶媒で溶解させた組成物の粘度は、測定用セルに組成物を15mL入れ、音叉型振動式粘度計(SVシリーズ、エーアンドディー社製)を用いて測定した。
塗膜の厚みは、干渉式膜厚計(F20膜厚測定システム、フィルメトリクス社製)を用いて測定した。
基材フィルムの厚みは、接触式膜厚計(ABSデジマチックインジケータ、ミツトヨ社製)を用いて測定した。
フィルムを1330mm×500mmの長方形に切り取り、試料フィルムを得た。このとき、500mmの辺が塗布方向と平行となるように切り取った。スジの観察は、試料フィルムの帯電防止ハードコート層側をポラリオンライト(シーズシー社製)の下で目視にて行い、スジの有無、スジの長さを観察し、さらに20cm以上のスジが2本以下の場合を「2」と判定し、20cm以上のスジが3本以上の場合を「1」と判定した。
液晶表示装置の表示面に画像を表示させた状態で、表示面を、正面から偏光サングラスを通して観察した。観察は、表示面に垂直な回転軸を中心にして表示面を45°ずつ回転して、8つの設置方向で行った。
このとき、いずれの設置方向でも画像の色味が変化せず、画像がクリアに視認できる場合には、画像の視認性が特に良好であるとして「3」と判定した。また、若干、画像がぼやけたり、設置方向によって画像の色味が変化したりした場合には、画像の視認性が良好であるとして「2」と判定した。さらに、画像にひどいぼやけ、設置方向による色味変化、又は、表示ムラが見られた場合には、画像の視認性が不良であるとして「1」と判定した。
液晶表示装置のタッチパネルを操作した。このとき、液晶駆動の乱れが発生することなく画像が視認できる場合には、液晶駆動の安定性が特に良好であるとして「3」と判定した。また、まれに液晶駆動の乱れが発生する場合には、液晶駆動の安定性が良好であるとして「2」と判定した。さらに、画像が乱れて表示ムラが見られる場合には、液晶駆動の安定性が不良であるとして「1」と評価した。
(1-1.基材フィルムの製造)
基材フィルムとして、シクロオレフィンポリマーの斜め延伸フィルムを用意した。この基材フィルムは、シクロオレフィンポリマー(厚み40μm、商品名「ゼオノアフィルムZF14-040」、日本ゼオン株式会社製、以下「ZNR」と略記することがある。)の長尺フィルムを、フィルム短尺方向に対して45°の方向に、延伸倍率1.5倍で延伸した延伸フィルムであり、厚みは25μmであった。
金属酸化物微粒子を、以下の方法により製造した。
錫酸カリウム130重量部及び酒石アンチモニルカリウム30重量部を純水400重量部に溶解し、溶液を得た。この溶液を、硝酸アンモニウム1.0重量部及び15重量%アンモニア水12重量部を溶解した純水1,000重量部中に添加した後、60℃で12時間、攪拌しながら加水分解を行った。この加水分解の際に、10重量%硝酸溶液を添加してpH9.0に保った。
(1-1)で得た斜め延伸フィルムのマスキングフィルムとは反対側の面に、コロナ処理(出力0.4kW、放電量200W・min/m2)を施した。このコロナ処理を施された面に、上記で作製した組成物(B2)を、硬化後に得られる帯電防止ハードコート層の厚みが3.0μmとなるようにダイコーターを用いて塗布し、組成物(B2)の膜を形成した。組成物(B2)の塗布は、相対湿度50%の環境において行った。
こうして得られた帯電防止ハードコートフィルムにおける帯電防止ハードコート層の表面抵抗値及びスジの評価を、上述した方法によって行った。
樹脂フィルム(PVA(ポリビニルアルコール)フィルム)にヨウ素をドープして一方向に延伸して製造された偏光子を用意した。また、前記の帯電防止ハードコートフィルムのロールから帯電防止ハードコートフィルムを引き出し、マスキングフィルムを剥離して、帯電防止ハードコート層とは反対側の基材フィルムの面を露出させた。そして、露出した基材フィルムの面と、前記の偏光子の片面とを、紫外線硬化型のアクリル接着剤で貼り合わせた。この際、基材フィルムの遅相軸は、偏光子の透過軸に対して45°の角度をなすようにした。
タッチセンサーを備える、インセルタイプの液晶セルを含む液晶パネルに、前記のように作製した偏光板を組み込んで、液晶表示装置を製造した。この際、偏光板の向きは、帯電防止ハードコート層側の面が視認側に向くように設定した。
こうして得られた液晶表示装置の画像の視認性の評価及び液晶駆動の安定性の評価を上述した方法によって行った。
実施例1において、基材フィルムをシクロオレフィンポリマーの横一軸延伸フィルム(日本ゼオン株式会社製、Tg126℃)に変えた。以上の事項以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
実施例1において、基材フィルムの厚みを25μmから47μmと変えた。以上の事項以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
実施例1において、組成物(B2)の塗工厚みを3μmから10μmに変えた。以上の事項以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
組成物(B1)を調液後、メチルエチルケトン47.11重量部に代えてメチルイソブチルケトン53.21重量部を用い、且つ、ミックスエタノール2の6.18重量部を添加せずに希釈した。他は、実施例1の(1-2)と同様にして、固形分濃度が20%の、組成物(B3)を得た。
組成物(B2)に代えて組成物(B3)を用いた以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
なお、組成物(B3)の粘度は3.0mPa・sであった。
実施例1の(1-2)において得た組成物(B1)に、メチルエチルケトンを38.0重量部、ミックスエタノール2を5.1重量部、及びダイアセトンアルコールを7.6重量部加え、固形分濃度が23%の組成物(B4)を得た。
組成物(B2)に代えて組成物(B4)を用いた以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
なお、組成物(B4)の粘度は8.0mPa・sであった。
(7-1.基材フィルムの製造)
基材フィルムとして、シクロオレフィンポリマーの斜め延伸フィルムを用意した。この基材フィルムは、シクロオレフィンポリマー(厚み70μm、商品名「ゼオノアフィルムZF14-070」)の長尺フィルムを、フィルム短尺方向に対して45°の方向に、延伸倍率1.5倍で延伸した延伸フィルムであり、厚みは47μmであった。
重合性単量体の組成物(R1)7.2重量部、多官能ウレタンアクリレート(U1)0.8重量部、及び光重合開始剤0.4重量部を十分混合して、混合液を得た。
この混合液に、金属酸化物粒子(1)の分散液28.76重量部(固形分38.2重量%、即ち11.33部含有。固形分以外はミックスエタノール2を17.43重量部)、及び、レベリング剤0.5重量部を加え、均一に混合して、活性エネルギー線硬化性を有する液状組成物(B7)を得た。
組成物(R1)、多官能ウレタンアクリレート(U1)、光重合開始剤、鎖状の金属酸化物粒子(1)及びレベリング剤としては、実施例1の(1-2)で使用したものと同じものを用いた。
調製した組成物(B7)に、メチルエチルケトン47.11重量部、前記のミックスエタノール2を6.18重量部、ダイアセトンアルコール9.28重量部の混合溶液を加えて希釈を行い、組成物(B8)を得た。組成物(B8)の粘度を上述の測定方法で測定したところ、5mPa・sであった。
(1-1)で得た斜め延伸フィルムに代えて(7-1)で得た斜め延伸フィルムを用い、組成物(B2)に代えて組成物(B8)を用い、硬化後に得られる帯電防止ハードコート層の厚みが1.5μmとなるように塗布厚みを変更した。以上の事項以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
メチルエチルケトンの量を30.2重量部、ミックスエタノール2の量を4.0重量部、及びダイアセトンアルコールの量を6.04重量部に変えた他は、実施例1の(1-2)と同様にして、固形分濃度が26%の、帯電防止ハードコート剤を溶解させた組成物(B5)を得た。
組成物(B2)に代えて組成物(B5)を用いた以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
組成物(B5)の粘度は15mPa・sであった。
鎖状の金属酸化物粒子(1)の分散液を添加しなかった他は、実施例1の(1-2)と同様にして、組成物(B6)を得た。
組成物(B2)に代えて組成物(B6)を用いた以外は実施例1と同様にして帯電防止ハードコートフィルムの製造及び評価、並びに液晶表示装置の製造及び評価を行った。
110 基材フィルム
120 帯電防止層
120L、120R 帯電防止層の塗工幅方向Xの端部
120U 帯電防止層の表面
121、122 帯電防止層の塗工幅方向Xの両端部近傍の領域
Claims (11)
- シクロオレフィンポリマーを含む熱可塑性樹脂からなる基材フィルムと、
前記基材フィルム上に設けられ、導電性を有する金属酸化物微粒子を含む帯電防止ハードコート層と、を備え、
前記帯電防止ハードコート層の表面抵抗値が、1.0×106Ω/□以上1.0×1010Ω/□以下であり、
前記帯電防止ハードコート層の、長さが20cm以上のスジの本数が、前記帯電防止ハードコート層の1330mm×500mm当たり2本以下である、帯電防止ハードコートフィルム。 - 前記帯電防止ハードコート層は、前記金属酸化物微粒子を含む帯電防止ハードコート剤を、粒子凝集性溶媒及び粒子分散性溶媒に溶解させた組成物を、前記基材フィルム上に塗工することにより形成され、
前記組成物の粘度が1mPa・s以上6mPa・s以下である、請求項1に記載の帯電防止ハードコートフィルム。 - 前記金属酸化物微粒子は、アンチモンドープ酸化スズである、請求項1又は2に記載の帯電防止ハードコートフィルム。
- 前記帯電防止ハードコート層が、単層構造を有し、
前記帯電防止ハードコート層の厚みが、10μm以下である、請求項1~3のいずれか1項に記載の帯電防止ハードコートフィルム。 - 前記基材フィルムは、斜め延伸されたものであり、
前記基材フィルムの厚みが、50μm以下である、請求項1~4のいずれか1項に記載の帯電防止ハードコートフィルム。 - 請求項1~5のいずれか1項に記載の帯電防止ハードコートフィルムと、偏光子とを備え、前記偏光子と前記基材フィルムとが接合されている、偏光板。
- 請求項6に記載の偏光板と、液晶セルとを備える、タッチパネル。
- 前記液晶セルが、IPS方式の液晶セルである、請求項7に記載のタッチパネル。
- 視認側の最表面にカバーガラスを有する、請求項7又は8に記載のタッチパネル。
- 請求項6に記載の偏光板と、液晶セルとを備える、液晶表示装置。
- 請求項1~5のいずれか1項に記載の帯電防止ハードコートフィルムの製造方法であって、
導電性を有する金属酸化物微粒子を含む帯電防止ハードコート剤を、粒子凝集性溶媒及び粒子分散性溶媒に溶解させた組成物を、基材フィルム上に塗工し、帯電防止ハードコート層を形成することを含み、
前記組成物の粘度が1mPa・s以上6mPa・s以下である、帯電防止ハードコートフィルムの製造方法。
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