CN112272785B - Antiglare film, method for producing same, and use thereof - Google Patents

Antiglare film, method for producing same, and use thereof Download PDF

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Publication number
CN112272785B
CN112272785B CN201980014768.5A CN201980014768A CN112272785B CN 112272785 B CN112272785 B CN 112272785B CN 201980014768 A CN201980014768 A CN 201980014768A CN 112272785 B CN112272785 B CN 112272785B
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meth
antiglare
acrylate
antiglare layer
polymer
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CN112272785A (en
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尾道浩
菅原庆峰
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Daicel Corp
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Daicel Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Abstract

The present invention relates to an antiglare film having an antiglare layer on a surface, wherein the surface of the antiglare layer has a concave-convex shape adjusted to a shape satisfying 2 or more of the following characteristics (1) to (3): (1) an arithmetic average roughness Ra of 0.05 to 0.25 μm; (2) The average length RSm of the roughness profile unit is 5-25 mu m; (3) The maximum section height Rt of the roughness profile is 0.1-1 μm. Further, the haze of the antiglare film is adjusted to 1 to 60%, and the 60 DEG gloss of the antiglare layer surface is adjusted to 0.1 to 70%. The antiglare film may have a dynamic friction coefficient of 3 or less on the surface of the antiglare layer measured under conditions of a load of 0.2N, a moving speed of 50 mm/sec, and an effective measurement distance of 50mm using a surface contact to which an artificial skin is attached. The antiglare film has both surface slidability by a finger and scratch resistance.

Description

Antiglare film, method for producing same, and use thereof
Technical Field
The present invention relates to an antiglare film which is suitable for preventing reflection of an external light source on a display surface of various display devices such as a liquid crystal display device (LCD) with a touch panel and an organic Electroluminescence (EL) display, has a good sliding touch by a finger, and is less likely to cause scratches due to friction, and is excellent in abrasion resistance, and a method for producing the same, and a use thereof.
Background
Antiglare films have been widely used as films for preventing external views from being reflected on the display surface of image display devices such as LCDs and organic EL displays and improving visibility. As a method for forming an antiglare film, a method of adding particles to a binder resin, a method of using phase separation of a plurality of resins, and the like are known.
Japanese patent No. 5846243 (patent document 1) discloses an optical laminate comprising a light-transmitting substrate and an antiglare layer provided on the light-transmitting substrate, wherein the outermost surface of the antiglare layer has an uneven shape, the average tilt angle of the uneven portion is defined as θa, the average roughness of the uneven portion is defined as Rz, the average spacing of the uneven portion is defined as Sm, the ratio of Rz to Sm is defined as the ratio ψ≡rz/Sm, the reference length is set to 0.25mm, θa and Rz are measured, the reference length is set to 0.80mm, and Sm is measured while satisfying that θa is 1.2 to 2.5 °, the ratio ψ is 0.016 to 0.121, the internal haze and the surface haze of the optical laminate are respectively 0 to 50% and 0.5 to 4.5%,
Japanese patent application laid-open No. 2015-125234 (patent document 2) discloses an antiglare film comprising an antiglare layer having a sea-island structure in which sea regions contain a first resin component and island regions contain a second resin component, and in which the second resin component contains aggregated fine particles, the antiglare film having a haze of 0.3 to 5%, an arithmetic average roughness Ra of the surface of the antiglare layer of 40 to 150nm, and an average interval Sm of the irregularities of 40 to 150 μm, formed on one surface of a transparent substrate.
Japanese patent application laid-open No. 2016-335574 (patent document 3) discloses an antiglare film comprising a transparent base material and an antiglare layer disposed on at least one surface of the transparent base material, wherein the surface of the antiglare layer opposite to the transparent base material is a concave-convex surface, the average spacing Sm of the concave-convex surfaces is 150 to 350 μm, the average tilt angle θa is 0.1 to 2.5 DEG, and the arithmetic average surface roughness Ra is 0.05 to 0.5 μm.
Japanese patent publication No. 6190581 (patent document 4) discloses an antiglare film comprising an antiglare layer having an elongated convex portion formed with phase separation of a plurality of resin components on the surface, the antiglare film having a haze of 10 to 40%, the elongated convex portion having a branched structure and a total length of 100 μm or more and being 1mm or more 2 The antiglare layer has 1 or more elongated projections on its surface, and the ratio of the length of the elongated projections having a branched structure to the length of the other projections is 100/0 to 70/30.
However, when the surface layer of these antiglare films is roughened to correspond to recent high-definition LCD and organic EL displays, the antiglare properties are increased, but the unevenness of the surface layer is also increased. Therefore, when friction occurs, force is concentrated on the portions having high irregularities, and there is a risk that chipping or particle falling occurs depending on the state of the irregularities, and scratch resistance is insufficient.
Prior art literature
Patent literature
Patent document 1: japanese patent publication No. 5846243 (claim 1)
Patent document 2: japanese patent application laid-open No. 2015-125234 (claims 1 and 2)
Patent document 3: japanese patent laid-open publication 2016-335574 (claim 1)
Patent document 4: japanese patent No. 6190581 (claims 1 and 3)
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide an antiglare film which satisfies antiglare properties, surface slidability with a finger, and scratch resistance at the same time, and a method for producing the same.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: the present invention has been completed by adjusting the uneven shape of the antiglare layer surface to a specific shape and adjusting the haze and the glossiness of the antiglare layer surface to specific ranges, whereby the antiglare property, the surface slidability with a finger, and the scratch resistance can be simultaneously satisfied.
That is, the antiglare film of the present invention is an antiglare film having an antiglare layer on the surface, the haze of which is 1 to 60%, the 60 ° gloss of the antiglare layer surface is 0.1 to 70%, and the uneven shape of the antiglare layer surface satisfies 2 or more of the following characteristics (1) to (3):
(1) The arithmetic average roughness Ra is 0.05-0.25 mu m;
(2) The average length RSm of the roughness profile unit is 5-25 mu m;
(3) The maximum section height Rt of the roughness profile is 0.1-1 μm.
The antiglare film preferably satisfies all of the characteristics (1) to (3). The antiglare film may have a dynamic friction coefficient of 3 or less on the surface of the antiglare layer measured under conditions of a load of 0.2N, a moving speed of 50 mm/sec, and an effective measurement distance of 50mm, using a surface contact with an artificial skin. The antiglare layer may be a cured product of a curable composition containing one or more polymer components and one or more curable resin precursor components. The above polymer component may contain cellulose esters and/or (meth) acrylic polymers optionally having a polymerizable group. The cured resin precursor component may contain a urethane (meth) acrylate. The number of (meth) acryloyl groups in one molecule of the urethane (meth) acrylate may be 5 to 20. The cured resin precursor component may further contain a fluorine compound having a polymerizable group. The curable composition may further contain a filler.
The invention also includes a method for manufacturing the antiglare film, which comprises the following steps: an antiglare layer forming step of forming a concave-convex shape by phase separation by wet spinodal decomposition.
The invention also includes a display device provided with the antiglare film. The display device may be a liquid crystal display device with a touch panel or an organic EL display.
In the present specification and claims, (meth) acrylate includes both methacrylate and acrylate.
ADVANTAGEOUS EFFECTS OF INVENTION
In the present invention, the uneven shape of the antiglare layer surface is adjusted to a specific shape, and the haze and the glossiness of the antiglare layer surface are also adjusted to specific ranges, so that the antiglare property, the surface slidability with a finger, and the scratch resistance can be satisfied at the same time.
Detailed Description
[ antiglare layer ]
The antiglare film of the present invention is not limited to a material or structure of the antiglare layer, as long as the antiglare film has a specific surface shape and has an antiglare layer on the surface for exhibiting specific optical characteristics, but is formed of a transparent material having a fine uneven shape formed on the surface, and reflection of external view due to surface reflection can be suppressed by the uneven shape, thereby improving antiglare property.
The antiglare layer may be formed of a transparent material or any of an organic material and an inorganic material, but is preferably formed of a composition containing a resin component in view of productivity, handleability, and the like. As described above, the surface of the antiglare layer generally has an uneven shape, which is not particularly limited, and may be formed by physical processing, transfer using a mold, or the like, but in terms of productivity or the like, in the antiglare layer formed from a composition containing a resin component, fine uneven shapes formed from a phase separation structure of the resin component, or fine uneven shapes corresponding to the shape of particles may be used. Among these, in the cured product of the curable composition containing one or more curable resin precursor components, the rugged shape formed by the particle shape by the spinodal decomposition (wet spinodal decomposition) of the liquid phase, the rugged shape formed by the particle shape by containing particles (for example, thermoplastic resin particles such as polyamide particles, crosslinked poly (meth) acrylate particles, crosslinked polystyrene particles, crosslinked polymer particles such as crosslinked polyurethane particles, inorganic particles such as silica particles, and the like) is preferable, and the rugged shape formed by the wet spinodal decomposition is particularly preferable in terms of being easy to form irregular and regular rugged shape.
The antiglare layer having the concave-convex shape formed by wet spinodal decomposition may be a cured product of a curable composition containing one or more polymer components and one or more curable resin precursor components. Specifically, in the antiglare layer, phase separation by spinodal decomposition occurs with concentration during evaporation or removal of a solvent from a liquid phase of a composition (mixed liquid) containing one or more polymer components, one or more curable resin precursor components, and a solvent by drying or the like, and thus a phase separation structure having a relatively regular phase-to-phase distance can be formed. More specifically, the wet spinodal decomposition can be generally performed by applying the composition (homogeneous solution) to a support such as a base material layer and evaporating the solvent from the applied layer.
(Polymer component)
As the polymer component, a thermoplastic resin can be generally used. The thermoplastic resin is not particularly limited as long as it has high transparency and can be decomposed into the surface irregularities by spinodal decomposition, and examples thereof include: styrene-based resins, (meth) acrylic polymers, vinyl ester-based polymers, vinyl ether-based polymers, halogen-containing resins, polyolefins (including alicyclic polyolefins), polycarbonates, polyesters, polyamides, thermoplastic polyurethanes, polysulfone-based resins (polyethersulfone, polysulfone, etc.), polyphenylene ether-based resins (polymers of 2, 6-xylenol, etc.), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubbers or elastomers (diene-based rubbers such as polybutadiene, polyisoprene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylic rubber, urethane rubber, silicone rubber, etc.), and the like. These thermoplastic resins may be used alone or in combination of two or more.
Among these polymer components, styrene-based resins, (meth) acrylic polymers, vinyl acetate polymers, vinyl ether polymers, halogen-containing resins, alicyclic polyolefins, polycarbonates, polyesters, polyamides, cellulose derivatives, silicone-based resins, rubbers, elastomers, and the like are commonly used. As the polymer component, a polymer component which is amorphous and soluble in an organic solvent (particularly, a common solvent in which a plurality of polymer components and/or a cured resin precursor component can be dissolved) can be generally used. Particularly preferred are polymer components having high moldability, film-forming properties, transparency and weather resistance, for example, styrene resins, (meth) acrylic polymers, alicyclic polyolefins, polyesters, cellulose derivatives (cellulose esters and the like), and particularly preferred are (meth) acrylic polymers and cellulose esters.
As the (meth) acrylic polymer, a homopolymer or copolymer of a (meth) acrylic monomer, a copolymer of a (meth) acrylic monomer and a copolymerizable monomer, or the like can be used. Examples of the (meth) acrylic monomer include: (meth) acrylic acid; (meth) acrylic acid C such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate 1-10 Alkyl esters; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate; hydroxy alkyl (meth) acrylates such as hydroxy ethyl (meth) acrylate and hydroxy propyl (meth) acrylate; glycidyl (meth) acrylate; n, N-dialkylaminoalkyl (meth) acrylate; (meth) acrylonitrile; (meth) acrylic acid esters having alicyclic hydrocarbon groups such as tricyclodecane. Examples of the copolymerizable monomer include styrene monomers such as styrene, vinyl ester monomers, maleic anhydride, maleic acid, fumaric acid, and the like. These monomers may be used alone or in combination of two or more.
Examples of the (meth) acrylic polymer include: poly (meth) acrylate such as polymethyl methacrylate and methyl methacrylateEster- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylate copolymer, methyl methacrylate-acrylate- (meth) acrylic acid copolymer, (meth) acrylate-styrene copolymer (MS resin, etc.), and the like. Among these, poly (meth) acrylic acid C such as poly (meth) acrylic acid methyl ester is preferable 1-6 Alkyl esters, in particular, methyl methacrylate polymers containing methyl methacrylate as a main component (about 50 to 100% by mass, preferably about 70 to 100% by mass).
Examples of cellulose esters include: aliphatic organic acid esters (cellulose acetate such as cellulose diacetate and cellulose triacetate; cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, etc. C 1-6 Aliphatic carboxylic acid esters, etc.), aromatic organic acid esters (C such as cellulose phthalate and cellulose benzoate 7-12 Aromatic carboxylic acid esters), inorganic acid esters (e.g., cellulose phosphate, cellulose sulfate, etc.), and the like, and mixed acid esters such as acetic acid/cellulose nitrate may be used. These cellulose esters may be used singly or in combination of two or more. Among these, preferred are C such as diacetylcellulose, triacetylcellulose, cellulose acetate propionate, and cellulose acetate butyrate 2-4 Cellulose acetate, particularly preferably C acetate such as cellulose acetate propionate 3-4 Acid cellulose.
Polymer component [ especially (meth) acrylic Polymer]May be a polymer having a functional group participating in the curing reaction (or a functional group capable of reacting with the cured resin precursor component). The polymer may have a functional group in the main chain or may have a functional group in a side chain. The functional groups may be introduced into the main chain of the polymer by copolymerization, copolycondensation, or the like of the monomers, but are usually introduced into side chains. Examples of such functional groups include condensation groups, reactive groups (e.g., hydroxyl, acid anhydride, carboxyl, amino or imino groups, epoxy groups, glycidyl groups, isocyanate groups, etc.), and polymerizable groups [ e.g., C such as ethenyl, propenyl, isopropenyl, butenyl, allyl, etc.) 2-6 C such as alkenyl, ethynyl, propynyl, butynyl and the like 2-6 Alkynyl, ethylene fork, etc. C 2-6 Alkenylenes, or having these polymersGroups of the reactive group ((meth) acryl, etc.), etc]Etc. Among these functional groups, a polymerizable group is preferable.
Examples of the method for introducing the polymerizable group into the side chain include a method in which a thermoplastic resin having a functional group such as a reactive group or a condensation group is reacted with a polymerizable compound having a group reactive with the functional group.
Examples of the functional group in the thermoplastic resin having a functional group include a carboxyl group or an acid anhydride group thereof, a hydroxyl group, an amino group, an epoxy group, and the like.
In the case where the thermoplastic resin having a functional group is a thermoplastic resin having a carboxyl group or an acid anhydride group thereof, examples of the polymerizable compound having a group reactive with the functional group include: and polymerizable compounds having an epoxy group, a hydroxyl group, an amino group, an isocyanate group, and the like. Among these, a polymerizable compound having an epoxy group, for example, an epoxy ring C of (meth) acrylic acid such as cyclohexene (meth) acrylate, is commonly used 5-8 Alkenyl esters, glycidyl (meth) acrylate, allyl glycidyl ether, and the like.
As typical examples, a combination of a thermoplastic resin having a carboxyl group or an acid anhydride group thereof, an epoxy group-containing compound, particularly a (meth) acrylic polymer ((meth) acrylic acid- (meth) acrylate copolymer or the like), and an epoxy group-containing (meth) acrylate ((meth) epoxycycloalkenyl acrylate, glycidyl (meth) acrylate or the like) can be exemplified. Specifically, a polymer obtained by introducing a polymerizable unsaturated group into a part of the carboxyl group of a (meth) acrylic polymer, for example, a (meth) acrylic polymer (cyclome P, manufactured by the company cellophane) obtained by reacting a part of the carboxyl group of a (meth) acrylic acid- (meth) acrylate copolymer with an epoxy group of 3, 4-epoxycyclohexenylmethyl acrylate to introduce a polymerizable group (photopolymerizable unsaturated group) into a side chain thereof, or the like can be used.
The amount of the functional group (particularly polymerizable group) involved in the curing reaction to be introduced into the thermoplastic resin is, for example, about 0.001 to 10 moles, preferably about 0.01 to 5 moles, and more preferably about 0.02 to 3 moles, per 1kg of the thermoplastic resin.
These polymer components may be used in appropriate combination. That is, the polymer component may be composed of a variety of polymers. The various polymers may phase separate by wet spinodal decomposition. In addition, the various polymers may be mutually incompatible. In the case of combining plural kinds of polymers, the combination of the 1 st polymer and the 2 nd polymer is not particularly limited, and plural kinds of polymers which are mutually incompatible in the vicinity of the processing temperature, for example, two kinds of polymers which are mutually incompatible, may be appropriately used in combination. For example, in the case where the 1 st polymer is a (meth) acrylic polymer (e.g., polymethyl methacrylate, a (meth) acrylic polymer having a polymerizable group, etc.), the 2 nd polymer may be a cellulose ester (acetic acid C such as cellulose acetate propionate 3-4 Acid cellulose, etc.), polyesters (urethane-modified polyesters, etc.).
Further, from the viewpoint of scratch resistance after curing, it is preferable that at least one polymer among a plurality of polymers, for example, at least one polymer (at least one polymer in the case of combining the 1 st polymer and the 2 nd polymer) among mutually incompatible polymers is a polymer having a functional group (particularly, a polymerizable group) capable of reacting with a cured resin precursor component in a side chain.
The mass ratio of the 1 st polymer to the 2 nd polymer may be selected from, for example, the range of the former/latter=1/99 to 99/1, preferably about 10/90 to 97/3, and when the 1 st polymer is a (meth) acrylic polymer and the 2 nd polymer is a cellulose ester, the mass ratio of the former/latter=30/70 to 95/5, preferably about 50/50 to 90/10, more preferably about 60/40 to 85/15 (particularly preferably about 70/30 to 80/20). In the present invention, the surface shape and haze of the antiglare layer can be adjusted by adjusting the ratio of the two polymers, and Ra, RSm, and Rt, which are surface shapes, can be reduced or haze can be reduced by increasing the ratio of cellulose esters. The specific ratio of the two polymers may be appropriately selected depending on the type of the curable resin precursor component described later.
The polymer used to form the phase separation structure may include the thermoplastic resin and other polymers, in addition to the two incompatible polymers.
The glass transition temperature of the polymer component can be selected from the range of, for example, about-100℃to 250℃and preferably-50℃to 230℃and more preferably about 0℃to 200℃and, for example, about 50℃to 180 ℃. From the viewpoint of surface hardness, it is advantageous that the glass transition temperature is 50℃or higher (for example, about 70 to 200 ℃), preferably 100℃or higher (for example, about 100 to 170 ℃). The weight average molecular weight of the polymer component may be selected from, for example, 1000000 or less, preferably about 1000 to 500000.
(curing resin precursor component)
As the curable resin precursor component, a compound having a functional group that reacts by heat, active energy rays (ultraviolet rays, electron beams, etc.) or the like may be used, and various curable compounds that can be cured or crosslinked by heat, active energy rays, etc. to form a resin (particularly, cured or crosslinked resin) may be used. Examples of the curable resin precursor component include thermosetting compounds and resins [ low molecular weight compounds having an epoxy group, a polymerizable group, an isocyanate group, an alkoxysilyl group, a silanol group, and the like (for example, epoxy resins, unsaturated polyester resins, urethane resins, silicone resins, and the like) ]; a photocurable compound (a photocurable compound such as a photocurable monomer or oligomer) curable by an active light (ultraviolet ray or the like), and the photocurable compound may be an EB (electron beam) curable compound or the like. The photocurable compound such as a photocurable monomer, oligomer, or optionally a low molecular weight photocurable resin may be simply referred to as "photocurable resin".
The photocurable compound includes, for example, a monomer, an oligomer (or a resin, particularly a low molecular weight resin).
Examples of the monomer include: monofunctional monomers [ (meth) acrylic monomers such as (meth) acrylic acid esters, vinyl monomers such as vinyl pyrrolidone, (meth) acrylic acid isobornyl ester, (meth) acrylic acid adamantyl ester and the like, (meth) acrylic acid esters having a bridged cyclic hydrocarbon group ], polyfunctional monomers having at least 2 polymerizable unsaturated bonds [ alkylene glycol di (meth) acrylic acid esters such as ethylene glycol di (meth) acrylic acid esters, propylene glycol di (meth) acrylic acid esters, butylene glycol di (meth) acrylic acid esters, neopentyl glycol di (meth) acrylic acid esters, hexanediol di (meth) acrylic acid esters and the like; (poly) oxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and polyoxytetramethylene glycol di (meth) acrylate; di (meth) acrylates having a bridged cyclic hydrocarbon group such as tricyclodecane dimethanol di (meth) acrylate and adamantane di (meth) acrylate; and polyfunctional monomers having about 3 to 6 polymerizable unsaturated bonds such as glycerol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, di (trimethylol propane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among these monomers, polyfunctional (meth) acrylates having at least 2 (meth) acryloyl groups are commonly used.
Examples of the oligomer or resin include (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, and silicone (meth) acrylate of bisphenol a-alkylene oxide adduct.
These photocurable compounds may be used alone or in combination of two or more. Of these, a photocurable compound capable of being cured in a short time is preferable, for example, an ultraviolet curable compound (monomer, oligomer, optionally a low molecular weight resin, or the like), or an EB curable compound. In particular, the curable resin precursor which is advantageous for practical use is an ultraviolet curable resin. In particular, in the present invention, the photocurable compound preferably contains a urethane (meth) acrylate from the viewpoint of achieving both high antiglare property and suppression of the purpose of penetration.
The urethane (meth) acrylate may be a urethane (meth) acrylate obtained by reacting a (meth) acrylate having an active hydrogen atom with a polyisocyanate.
The polyisocyanate may be produced by reacting a polyol (for example, polyester, polyether polyester, etc.) with a polyisocyanate, or may be a urethane prepolymer having a free isocyanate group, but is preferably a polyisocyanate in view of scratch resistance.
Examples of the polyisocyanate include: aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, derivatives of polyisocyanates, and the like.
Examples of the aliphatic polyisocyanate include: c such as tetramethylene diisocyanate, hexamethylene Diisocyanate (HDI) and trimethylhexamethylene diisocyanate 2-16 Alkane diisocyanates, and the like. Examples of the alicyclic polyisocyanate include: 1, 4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), 4' -methylenebis (cyclohexyl isocyanate), hydrogenated xylylene diisocyanate, norbornane diisocyanate, and the like. Examples of the aromatic aliphatic polyisocyanate include: xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate, and the like. Examples of the aromatic polyisocyanate include: benzene diisocyanate, 1, 5-Naphthalene Diisocyanate (NDI), diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), 4 '-toluidine diisocyanate, 4' -diphenyl ether diisocyanate, and the like. Examples of the derivative of the polyisocyanate include: dimer, trimer and other polymers, biuret, allophanate, carbodiimide, uretdione and the like. These polyisocyanates may be used singly or in combination of two or more.
Among these polyisocyanates, diisocyanates or derivatives thereof having no yellowing are preferred from the viewpoint of both scratch resistance and optical properties, for example, aliphatic diisocyanates such as HDI, and non-yellowing modified diisocyanates such as alicyclic diisocyanates such as IPDI and hydrogenated XDI, or derivatives thereofThe substance is particularly preferably C such as HDI 4-12 Alkane diisocyanates (particularly preferably C 5-8 Alkane diisocyanates).
Examples of the (meth) acrylate having an active hydrogen atom include: hydroxy C (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate 2-6 Hydroxyalkoxy C (meth) acrylate such as alkyl ester and 2-hydroxy-3-methoxypropyl (meth) acrylate 2-6 Alkyl esters; and (meth) acrylic acid partial esters of polyhydric alcohols such as di (trimethylolethane) tri (meth) acrylate, di (trimethylolpropane) tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. These (meth) acrylates may be used singly or in combination of two or more. Among these, (meth) acrylic partial esters of polyhydric alcohols such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable from the viewpoint of scratch resistance.
The number of (meth) acryloyl groups (the number of functional groups) in the urethane (meth) acrylate per molecule may be 2 or more (bifunctional or more), for example, about 2 to 30, preferably about 3 to 25 (for example, about 5 to 20), and more preferably about 8 to 18 (particularly preferably about 9 to 15). When the number of the functional groups is too small, scratch resistance may be lowered.
The weight average molecular weight of the urethane (meth) acrylate is not particularly limited, and in Gel Permeation Chromatography (GPC), it may be 5000 or less (for example, 500 to 5000) in terms of polystyrene, and may be, for example, 550 to 4000, preferably 600 to 3000, and more preferably 800 to 2000 (particularly preferably 1000 to 1500). If the molecular weight is too large, the scratch resistance may be lowered.
From the viewpoint of enabling surface modification, the photocurable compound preferably contains a fluorine-containing curable compound (a fluorine atom-containing precursor component or a fluorine-containing compound having a polymerizable group) in addition to the urethane (meth) acrylate.
Examples of the fluorine-containing curable compound include fluorides of the above monomer and oligomer, for example, fluoroalkyl (meth) acrylate [ e.g., perfluorooctyl ethyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like ], fluoro (poly) oxyalkylene glycol di (meth) acrylate [ e.g., fluoroethylene glycol di (meth) acrylate, fluoropolyethylene glycol di (meth) acrylate, fluoropropylene glycol di (meth) acrylate, and the like ], fluorine-containing epoxy resins, fluorine-containing urethane resins, and the like. Among these, a fluoropolyether compound having a (meth) acryloyl group is preferable. The fluorine-containing curable compound may be a commercially available fluorine-based polymerizable leveling agent.
The proportion of the fluorine-containing curable compound is, for example, 0.1 to 5 parts by mass, preferably 0.2 to 4 parts by mass, more preferably 0.3 to 3 parts by mass (particularly preferably 0.5 to 2 parts by mass) per 100 parts by mass of the curable composition (total solid content). When the proportion of the fluorine-containing curable compound is too small, the effect of promoting phase separation may be reduced, and when the proportion is too large, the scratch resistance may be reduced.
Depending on the kind of the curable resin precursor component, the curable composition may further contain a filler in order to improve antiglare property and scratch resistance.
The filler may contain, for example, inorganic particles such as silica particles, titania particles, zirconia particles, and alumina particles, and organic particles such as crosslinked (meth) acrylic polymer particles and crosslinked styrene resin particles. These fillers may be used alone or in combination of two or more.
Among these fillers, silica particles are preferable in view of excellent optical properties and easy formation of irregularities by spinodal decomposition, which can achieve both transparency and antiglare properties. The silica particles are preferably solid silica particles in view of improving the transparency of the antiglare film.
The shape of the filler may be anisotropic, but is preferably isotropic, and particularly preferably spherical. The average particle diameter of the filler is, for example, about 0.1 to 10. Mu.m, preferably about 0.5 to 5. Mu.m, more preferably about 0.8 to 3. Mu.m, particularly preferably about 1 to 2. Mu.m.
The proportion of the filler is, for example, about 1 to 50 parts by mass, preferably about 2 to 40 parts by mass, and more preferably about 3 to 30 parts by mass, per 100 parts by mass of the curable composition (total solid content).
The curable resin precursor component may further contain a curing agent according to the kind thereof. For example, the thermosetting resin may contain a curing agent such as an amine or a polycarboxylic acid, and the photocurable resin may contain a photopolymerization initiator. Examples of the photopolymerization initiator include usual components such as acetophenones, benzophenones, benzils, benzoins, benzophenones, thioxanthones, and acylphosphinoxides. The proportion of the curing agent such as a photopolymerization initiator is 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably about 1 to 8% by mass, relative to the entire cured resin precursor component.
The cured resin precursor component may further contain a curing accelerator. For example, the photocurable resin may contain tertiary amines (dialkylaminobenzoates and the like), phosphine photopolymerization accelerators and the like as photocuring accelerators.
(combination of Polymer component and cured resin precursor component)
In the present invention, at least two components of the polymer component and the cured resin precursor component are used in combination so as to be phase-separated from each other at around the processing temperature. Examples of the combination in which phase separation occurs include: (a) A combination of multiple polymer components that are mutually incompatible with each other and phase separated; (b) A combination of polymer components that are incompatible with the cured resin precursor components and phase separate; (c) Combinations of various cured resin precursor components that are mutually incompatible and phase separated from each other, and the like. Among these combinations, (a) a combination of a plurality of polymer components with each other and (b) a combination of a polymer component with a cured resin precursor component are generally preferred, and (a) a combination of a plurality of polymer components with each other is particularly preferred. When the compatibility of both the components in which phase separation occurs is high, the components do not effectively undergo phase separation during the drying process for evaporating the solvent, and the function as an antiglare layer is lowered.
The polymer component and the cured resin precursor component are generally incompatible with each other. In the case where the polymer component is incompatible with the cured resin precursor component and phase separation occurs, a plurality of polymer components may be used as the polymer component. In the case where multiple polymer components are used, at least one of the polymer components may be incompatible with the cured resin precursor components, and the other polymer components may be compatible with the cured resin precursor components described above. In addition, a combination of two polymer components which are mutually incompatible with the curable resin precursor component (particularly, a monomer or oligomer having a plurality of curable functional groups) may be used.
In the case where the polymer component is composed of a plurality of polymer components that are mutually incompatible to cause phase separation, the cured resin precursor component may be used in combination with at least one polymer component of the plurality of polymers that are mutually compatible at around the processing temperature. That is, for example, in the case where the 1 st polymer and the 2 nd polymer constitute a plurality of mutually incompatible polymer components, the cured resin precursor component may be compatible with either the 1 st polymer or the 2 nd polymer, or may be compatible with both polymer components, but more preferably, only one polymer component is compatible. In the case of compatibility with the two polymer components, the phase is separated into at least two phases of a mixture containing the 1 st polymer and the cured resin precursor component as main components and a mixture containing the 2 nd polymer and the cured resin precursor component as main components.
In the case where the compatibility of the plurality of polymer components selected is high, the polymer components are not effectively phase-separated from each other during the drying process for evaporating the solvent, and the function as an antiglare layer is lowered. The phase separation of the various polymer components can be readily determined by the following operations: a uniform solution was prepared using a solvent which was a good solvent for both components, and whether or not the remaining solid components were cloudy was confirmed by visual observation during the slow evaporation of the solvent.
In addition, the refractive indices of the cured or crosslinked resin produced by curing the polymer component and the cured resin precursor component are generally different from each other. The refractive indices of the plurality of polymer components (polymer 1 and polymer 2) are also different from each other. The difference in refractive index between the polymer component and the cured or crosslinked resin and the difference in refractive index between the plurality of polymer components (polymer 1 and polymer 2) may be, for example, about 0.01 to 0.2, preferably about 0.05 to 0.15.
The ratio (mass ratio) of the polymer component to the cured resin precursor component is not particularly limited, and may be selected from, for example, a range of about 1/99 to 95/5, for example, about 2/98 to 90/10 (for example, 3/97 to 50/50), preferably about 5/95 to 40/60, more preferably about 10/90 to 30/70 (particularly preferably about 15/85 to 25/75). When the proportion of the polymer component is too small, there is a possibility that the antiglare property is lowered, whereas when the proportion is too large, there is a possibility that the scratch resistance is lowered.
(other Components)
The antiglare layer formed from the cured product of the curable composition may contain various additives such as: leveling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants, water-soluble polymers, fillers, crosslinking agents, coupling agents, colorants, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, tackifiers, defoamers, and the like. The proportion of the additive is, for example, about 0.01 to 10 mass% (particularly preferably about 0.1 to 5 mass%) relative to the entire antiglare layer.
(thickness of antiglare layer)
The thickness (average thickness) of the antiglare layer is, for example, about 1 to 20. Mu.m, preferably about 2 to 10. Mu.m, more preferably about 3 to 8. Mu.m, particularly preferably about 5 to 7. Mu.m. In the present specification and claims, the average thickness of the antiglare layer can be obtained by measuring 10 arbitrary points using an optical film thickness measuring instrument and calculating an average value.
[ substrate layer ]
The antiglare film of the present invention may be formed by the antiglare layer alone, or may be formed by a base layer and an antiglare layer formed on at least one surface of the base layer. Among these, it is preferable to laminate an antiglare layer on one side (only one side) of the base material layer from the viewpoints of handling properties, mechanical properties, productivity, and the like.
The base material layer may be formed of a transparent material. The transparent material may be selected according to the application, or may be an inorganic material such as glass, but is usually an organic material in terms of strength, moldability, and the like. Examples of the organic material include: cellulose derivatives, polyesters, polyamides, polyimides, polycarbonates, (meth) acrylic polymers, and the like. Among these, cellulose esters, polyesters, polycarbonates and the like are commonly used, and polyesters and polycarbonates are preferable.
Examples of the polyester include polyalkylene arylates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of the polycarbonate include bisphenol type polycarbonate.
Among these, poly-C such as PET and PEN is preferable in view of excellent balance of mechanical properties, transparency and the like 6-10 Aromatic acid C 2-4 Alkylene esters, bisphenol a type polycarbonates.
The base material layer may contain a conventional additive exemplified as one of the antiglare layers. The proportion of the additive is also the same as that of the antiglare layer.
The base material layer may be a uniaxially or biaxially stretched film, but may be an unstretched film in view of low birefringence and excellent optical isotropy.
The substrate layer may be subjected to a surface treatment (for example, corona discharge treatment, flame treatment, plasma treatment, ozone irradiation treatment, ultraviolet irradiation treatment, or the like), or may have an easily adhesive layer.
The thickness (average thickness) of the base material layer is, for example, 5 to 2000. Mu.m, preferably 15 to 1000. Mu.m, and more preferably about 20 to 500. Mu.m.
[ Properties of antiglare film ]
The antiglare film of the present invention can satisfy antiglare properties, surface slidability with a finger, and scratch resistance at the same time by having a given surface shape. Specifically, the arithmetic average roughness Ra of the antiglare layer surface is, for example, about 0.03 to 0.3 μm, preferably about 0.05 to 0.3 μm (for example, about 0.06 to 0.3 μm), more preferably about 0.07 to 0.25 μm (particularly preferably about 0.08 to 0.2 μm). When Ra is too small, there is a risk of deterioration of antiglare properties, whereas when Ra is too large, there is a risk of deterioration of scratch resistance.
The average length RSm of the roughness profile unit of the antiglare layer surface is, for example, about 3 to 35 μm, preferably 5 to 25 μm, more preferably 8 to 25 μm (particularly preferably 10 to 25 μm). If RSm is too small, the antiglare property may be lowered, whereas if RSm is too large, scratch resistance and slipping property by a finger may be lowered.
The maximum section height Rt of the roughness profile of the antiglare layer surface is, for example, about 0.05 to 2 μm (for example, 0.1 to 1.5 μm), preferably 0.3 to 1 μm, more preferably 0.4 to 0.9 μm (particularly preferably 0.5 to 0.8 μm). When Rt is too small, there is a risk of deterioration of antiglare properties, whereas when Rt is too large, there is a risk of deterioration of scratch resistance.
The antiglare layer surface may have 2 or more characteristics among Ra, RSm, and Rt as long as the above range is satisfied, but it is preferable that all the characteristics satisfy the above range in terms of being capable of highly satisfying antiglare properties, surface slidability with a finger, and scratch resistance.
In the present specification and claims, the arithmetic average roughness Ra, the average length RSm of the roughness profile unit, and the maximum section height Rt of the roughness profile can be obtained by measuring the roughness of the antiglare layer surface according to JIS B0601 using a noncontact surface/layer section shape measuring system [ vertscan2.0", manufactured by rhombic systems, inc.
The surface of the antiglare layer is excellent in slidability with a finger, and the dynamic friction coefficient of the surface of the antiglare layer measured under conditions of a load of 0.2N, a moving speed of 50 mm/sec, and an effective measurement distance of 50mm can be about 3 or less (e.g., 0.01 to 1), for example, 0.1 to 3, preferably 0.15 to 2.5, and more preferably 0.2 to 2 (particularly preferably 0.3 to 2), using a surface contact with an artificial skin. If the coefficient of dynamic friction is too high, there is a risk that the sliding properties of the finger will be reduced.
In the present specification and claims, the coefficient of dynamic friction can be measured using a dynamic friction meter, and in detail, the coefficient of dynamic friction can be measured by a method described in examples described later.
The antiglare layer surface is excellent in scratch resistance, and when the antiglare layer surface is reciprocated 10 times at room temperature (20 to 25 ℃) with steel wool #0000 at a speed of 50 mm/sec at a distance of 5cm, the maximum load without generating scratches may be 50g load or more (for example, 50 to 2000g load), for example, 100g load or more, preferably 200g load or more, further preferably 500g load or more (particularly preferably 800g load or more).
In the present specification and claims, the scratch resistance can be evaluated by the method described in examples described below.
The antiglare film of the present invention has high transparency and excellent visibility. The haze of the antiglare film is about 1 to 60%, preferably 2 to 50%, more preferably 3 to 40% (particularly preferably 5 to 30%). When the haze is too low, there is a possibility that the antiglare property is lowered, whereas when it is too high, there is a possibility that the visibility is lowered.
In the present specification and claims, haze can be measured by setting the antiglare layer surface to the light receiver side using a haze meter (trade name "NDH-5000W" manufactured by japan electric color industry co.) in accordance with JIS K7163.
The antiglare film has a total light transmittance of, for example, 70% or more (for example, 70 to 100%), preferably 80 to 99%, more preferably 85 to 98% (particularly preferably 90 to 95%). If the total light transmittance is too low, there is a possibility that the transparency is lowered.
In the present specification and claims, the total light transmittance can be measured in accordance with JIS K7361 using a haze meter (NDH-5000W, manufactured by japan electric color industry co.).
The 60 ° glossiness of the antiglare layer surface is about 1 to 70%, preferably about 10 to 68%, and more preferably about 15 to 65%. In applications where transparency is important, the 60 ° gloss may be, for example, about 30 to 70%, preferably about 50 to 68%, and more preferably about 60 to 65%. In the application where the antiglare property is important, the 60 ° glossiness may be, for example, 5 to 60%, preferably 10 to 50%, and more preferably about 20 to 30%. If the 60 ° gloss is too small, there is a possibility that visibility is lowered, whereas if it is too large, there is a possibility that antiglare property is lowered.
In the present specification and claims, 60 ° gloss can be measured in accordance with JIS K8741 using a gloss meter (TQC corporation "polyglos KT-GL 0030").
The antiglare film of the present invention may be combined with an adhesive layer, a low refractive index layer, an antireflection layer, or the like, which are conventional functional layers, in addition to the antiglare layer and the base material layer.
[ method for producing antiglare film ]
The method for producing the antiglare film of the present invention is not particularly limited, and may be appropriately selected depending on the kind of material, and may be formed by physical processing, transfer using a mold, or the like, but from the viewpoint of productivity or the like, a method of producing the antiglare film by a curing step of curing the curable composition by heat or active energy rays is preferable, and from the viewpoint of producing a regular surface roughness and easily forming an antiglare layer having the surface roughness of the present invention, it is preferable to include an antiglare layer forming step of forming the roughness by phase separation by wet spinodal decomposition.
In the antiglare layer forming step, the surface may be roughened by phase separation during drying of the liquid composition for forming the antiglare layer by wet spinodal decomposition. In the case of using a curable composition containing one or more polymer components and one or more curable resin precursor components as a liquid composition for forming an antiglare layer in a wet manner, the following method may be employed: the curable composition is applied to a support and dried, at least two components selected from the group consisting of a polymer component and a cured resin precursor component are phase-separated by wet spinodal decomposition, and the phase-separated curable composition is cured by heat or active energy rays.
In the case where the antiglare film is formed by the antiglare layer alone, the support may be a support that can be peeled off the antiglare layer, but a base layer is preferable in terms of mechanical properties and the like.
The curable composition may contain a solvent. The solvent may be used in accordance with the above polymer components before curing the resinThe type and solubility of the bulk component may be selected so long as the solvent is one that at least uniformly dissolves the solid components (e.g., various polymer components and cured resin precursor components, reaction initiator, and other additives). In particular, the phase separation structure can also be controlled by adjusting the solubility of the solvent to the polymer component and the cured resin precursor. Examples of such solvents include: ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (di
Figure BDA0002644023680000161
Alkanes, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (methylene chloride, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves [ methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether (1-methoxy-2-propanol), etc ]Cellosolve acetate, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc. The solvent may be a mixed solvent. />
Among these solvents, a solvent containing a ketone such as methyl ethyl ketone is preferable, a mixed solvent of a ketone, an alcohol (aliphatic alcohol such as butanol) and/or an ester (aliphatic carboxylic acid ester such as butyl acetate) is more preferable, and a ketone (particularly, di-C) is most preferable 1-4 Alkyl ketones) with alcohols (especially C 1-6 Alkanol). The proportion of the alcohol and/or ester (total amount in the case of mixing both) in the mixed solvent is, for example, about 1 to 150 parts by mass (for example, 3 to 100 parts by mass), preferably about 5 to 100 parts by mass, and more preferably about 10 to 30 parts by mass (particularly preferably about 15 to 20 parts by mass) relative to 100 parts by mass of the ketone. In the present invention, by appropriately combining the solvents, phase separation by spinodal decomposition can be adjusted, and a concave-convex shape which can satisfy visibility, transparency, and antiglare property can be formed.
The concentration of the solute (polymer component, cured resin precursor component, reaction initiator, and other additives) in the mixed solution may be selected within a range that does not impair the phase separation, the flow property, and the coatability, and is, for example, about 1 to 80 mass%, preferably about 10 to 70 mass%, and more preferably about 20 to 50 mass% (particularly preferably about 30 to 40 mass%).
Examples of the coating method include a usual method such as a roll coating method, an air knife coating method, a blade coating method, a bar coating method, a reverse coating method, a wire bar coating method, a corner-bar coating method, a dip/squeeze (dip squeeze) coating method, a die coating method, a gravure coating method, a micro gravure coating method, a screen coating method, a dip coating method, a spray coating method, and a spin coating method. Among these methods, a bar coating method, a gravure coating method, and the like are commonly used. The coating liquid may be applied as many times as necessary.
After casting or coating the above-mentioned mixture, phase separation by spinodal decomposition can be induced by evaporating the solvent at a temperature near or lower than the boiling point of the solvent (for example, a temperature lower than the boiling point of the solvent by about 1 to 120 ℃, preferably 5 to 50 ℃, particularly preferably about 10 to 50 ℃). The solvent may be evaporated by drying, for example, at a temperature of about 30 to 200 ℃ (e.g., 30 to 150 ℃), preferably 40 to 120 ℃, more preferably 50 to 90 ℃ (particularly preferably 60 to 85 ℃) corresponding to the boiling point of the solvent.
By spinodal decomposition accompanied by such evaporation of the solvent, the average distance between domains of the phase separation structure can be given order or periodicity.
The phase separation structure formed by spinodal decomposition can be immediately immobilized by finally curing the curable composition after drying by active light (ultraviolet rays, electron beams, etc.), heat, or the like. The curable composition may be cured by a combination of heat, light, and the like depending on the kind of the curable resin precursor component.
The heating temperature may be selected from a suitable range, for example, about 50 to 150 ℃. The light irradiation may be selected according to the kind of the photocurable component or the like, and ultraviolet rays, electron beams, or the like are generally used. The usual light source is usually an ultraviolet irradiation device.
As light sources, e.g. in ultraviolet lightIn the case of the wire, deep UV lamp, low pressure mercury lamp, high pressure mercury lamp, ultra-high pressure mercury lamp, halogen lamp, laser light source (light source such as helium-cadmium laser, excimer laser) and the like can be used. The irradiation light amount (irradiation energy) varies depending on the thickness of the coating film, and is, for example, 10 to 10000mJ/cm 2 Preferably 20 to 5000mJ/cm 2 More preferably 30 to 3000mJ/cm 2 Left and right. The illumination may be performed in an inert gas atmosphere, if necessary.
[ display device ]
The antiglare film of the present invention can be used for various display devices such as a Liquid Crystal Display (LCD) and an organic EL display because of its high antiglare property and scratch resistance, and is useful as a display device with a touch panel, particularly a high-definition LCD with a touch panel and an organic EL display because of its excellent surface slidability with a finger.
Specifically, the LCD may be a reflective LCD that illuminates a display unit including a liquid crystal cell with external light, or may be a transmissive LCD that includes a backlight unit for illuminating the display unit. In the reflective LCD, incident light from the outside may be introduced through the display unit, and the transmitted light transmitted through the display unit may be reflected by the reflective member, thereby illuminating the display unit. In the reflective LCD, the antiglare film of the present invention may be disposed in an optical path located in front of the reflective member. For example, the antiglare film of the present invention may be disposed or laminated on a front surface (a front surface on the viewing side) of a display unit or the like, and in particular, may be disposed on a front surface of an LCD having a collimated backlight unit and not having a prism sheet.
In a transmissive LCD, a backlight unit may include a light guide plate (e.g., a light guide plate having a wedge-shaped cross section) for allowing light from a light source (e.g., a tubular light source such as a cold cathode tube, a point light source such as a light emitting diode) to enter from one side and exit from an exit surface on the front surface. Further, a prism sheet may be disposed on the front surface side of the light guide plate, if necessary. A reflecting member for reflecting light from the light source toward the light exit surface is generally disposed on the back surface of the light guide plate. In such a transmissive LCD, the antiglare film of the present invention may be disposed in an optical path located in front of the light source, and for example, the antiglare film may be disposed or laminated on the front surface or the like of the display unit.
In an organic EL display, a light-emitting element is formed in each pixel of an organic EL, and the light-emitting element is generally formed of a metal or other negative electrode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, an ITO or other positive electrode, a glass plate, or a transparent plastic plate or other substrate. In the organic EL display, the antiglare film of the present invention may be disposed in an optical path.
In addition, the antiglare film of the present invention can be used as an after-market oriented protective or protective film for preventing damage to an LCD, organic EL display including a touch panel.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The raw materials used in examples and comparative examples were evaluated as follows, and the antiglare films obtained were evaluated by the following methods.
[ raw materials ]
Acrylic resin having a polymerizable group: a compound obtained by adding 3, 4-epoxycyclohexenyl methyl acrylate to a part of carboxyl groups of a (meth) acrylic acid- (meth) acrylic acid ester copolymer, "CYCLOMER P (ACA) 320M", manufactured by Kagaku Kogyo Co., ltd., solid content 40% by mass
Cellulose acetate propionate: "CAP-482-20", from EASTMAN corporation, degree of acetylation=2.5%, degree of propionylation=46%, number average molecular weight 75000 in terms of polystyrene
Urethane acrylate a: 10-functional aliphatic urethane acrylate, average molecular weight 1200, manufactured by Daicel Ornex Co., ltd. "KRM8452"
Urethane acrylate B: 9-functional aliphatic urethane acrylate, average molecular weight 1800, KRM8904, manufactured by Daicel Ornex Co., ltd "
Urethane acrylate C:15 functional urethane acrylate, theoretical molecular weight 2300, "U-15HA" from Xinzhongcun chemical industry Co., ltd "
Urethane acrylate D:15 functional urethane acrylate, "U-53H", new Zhongcun chemical industry Co., ltd "
Fluorine-containing ultraviolet-reactive surface modifier: DIC Co., ltd. "MEGAFAC RS-75"
Acrylic coating liquid containing silica: acrylic ultraviolet curable Compound containing silica particles, "Z-757-4RL" manufactured by Aike Industrial Co., ltd., solid content of 43 wt%
And (3) a photoinitiator: IRGACURE 907, manufactured by BASF JAPAN Co., ltd "
PET film: polyethylene terephthalate film, "O321", mitsubishi resin Co., ltd., thickness of 125 μm
PC film: polycarbonate film, "Lupilon FS-2000", manufactured by Mitsubishi gas chemical Co., ltd., thickness 400 μm.
[ thickness of antiglare layer ]
The average value was calculated by measuring 10 arbitrary sites using an optical film thickness measuring instrument.
[ haze ]
The antiglare layer surface was measured by setting the surface of the antiglare layer to the light receiver side using a haze meter (trade name "NDH-5000W" manufactured by japan electric color industry co., ltd.) based on JIS K7163.
[ Total light transmittance ]
The measurement was performed using a haze meter (trade name "NDH-5000W" manufactured by Nippon Denshoku Co., ltd.) based on JIS K7361.
[60 ° gloss ]
The gloss at an angle of 60℃was measured by using a gloss meter (TQC company, "polyglos KT-GL 0030") based on JIS Z8741.
[ arithmetical average roughness Ra, average length of roughness profile unit RSm, maximum section height of roughness profile Rt ]
The roughness of the antiglare layer surface was measured by a non-contact surface/layer cross-sectional shape measuring system [ VertScan2.0", made by rhombic systems, inc. ] based on JIS B0601, and the arithmetic average roughness Ra, the average length RSm of the roughness profile unit, and the maximum cross-sectional height Rt of the roughness profile were each obtained based on the obtained curves.
[ test for Steel Wool (SW) resistance ]
The maximum load without generating scratches was determined by visual observation after the load was changed at room temperature (20 to 25 ℃) using a steel wool durability tester for a bar having a diameter of 1cm covered with spare steel wool #0000 and rubbed back and forth 10 times at a speed of 50 mm/sec at a distance of 5cm on the surface of the antiglare layer.
[ antiglare property ]
The glare of the specular reflection light was confirmed by visual observation by mapping the illumination of a bare fluorescent lamp without a Louver (Louver) to an antiglare film, and evaluated according to the following criteria
And (3) the following materials: no glare is felt
O: slightly perceived glare
X: glare was perceived.
[ coefficient of kinetic friction ]
The friction force was measured with a dynamic friction coefficient measuring instrument (Trinity Lab "Handy Tribo Master TL Ts", co., ltd.) at a load of 0.2N, a speed of 50 mm/sec, and an effective measurement distance of 50 mm. As the surface contact, a contact in which an artificial skin (see Lux corporation "Bioskin") was stuck to a 5mm thick sponge sheet (cemed corporation "gap tape N-1") was used, and the surface of the antiglare layer was slid to determine the dynamic friction coefficient.
Preparation of coating liquid 1
The coating liquid 1 was prepared by dissolving 57.7 parts by mass of an acrylic resin having a polymerizable group, 7.1 parts by mass of cellulose acetate propionate, 105.7 parts by mass of urethane acrylate a, 1.4 parts by mass of a fluorine-containing ultraviolet-reactive surface modifier, and 2.8 parts by mass of a photoinitiator "IRGACURE 907" (manufactured by BASF corporation) in a mixed solvent of 250 parts by mass of Methyl Ethyl Ketone (MEK) and 39.2 parts by mass of 1-butanol.
Preparation of coating liquid 2
Coating liquid 2 was prepared in the same manner as coating liquid 1 except that urethane acrylate B was used instead of urethane acrylate a.
Preparation of coating liquid 3
Coating liquid 3 was prepared in the same manner as coating liquid 1 except that the ratio of the acrylic resin having a polymerizable group was changed to 59.2 parts by mass.
Preparation of coating liquid 4
Coating liquid 4 was prepared in the same manner as coating liquid 1 except that urethane acrylate C was used instead of urethane acrylate a.
Preparation of coating liquid 5
Coating liquid 5 was prepared in the same manner as coating liquid 1 except that urethane acrylate D was used instead of urethane acrylate a.
Preparation of coating liquid 6
Coating liquid 6 was prepared in the same manner as in preparation of coating liquid 1 except that the mixed solvent was changed to a mixed solvent of 18.61 parts by mass of MEK, 7.98 parts by mass of butyl acetate, and 3.92 parts by mass of 1-butanol.
Preparation of coating liquid 7
Coating liquid 7 was prepared in the same manner as in the preparation of coating liquid 4 except that the ratio of the acrylic resin having a polymerizable group was changed to 7.09 parts by mass, the ratio of the cellulose acetate propionate was changed to 0.57 parts by mass, and the ratio of the urethane acrylate C was changed to 10.78 parts by mass.
Preparation of coating liquid 8
Coating liquid 8 was prepared in the same manner as in preparation of coating liquid 1 except that the ratio of the acrylic resin having a polymerizable group was changed to 6.71 parts by mass, the ratio of cellulose acetate propionate was changed to 0.52 parts by mass, the ratio of urethane acrylate a was changed to 11.91 parts by mass, and the mixed solvent was changed to a mixed solvent of 16.6 parts by mass of MEK, 3.92 parts by mass of 1-butanol and 10.74 parts by mass of butyl acetate.
Preparation of coating liquid 9
Coating liquid 9 was prepared in the same manner as in the preparation of coating liquid 4 except that the proportion of cellulose acetate propionate was changed to 0.76 parts by mass.
Preparation of coating liquid 10
Coating liquid 4 and the silica-containing acrylic coating liquid were mixed so that the solid content mass ratio was the former/the latter=40/60, to prepare coating liquid 10.
Examples 1 to 6 and comparative examples 1 to 3
Each coating liquid was coated on a PET film using a wire bar, and dried in an oven at 80 ℃ for 1 minute, thereby forming a coating film having a thickness of 6 μm. Then, the coating film was irradiated with ultraviolet light from a high-pressure mercury lamp (Eye graphics) for about 10 seconds, and the coating film was cured to form an antiglare layer, thereby obtaining an antiglare film.
Example 7
Anti-glare films were obtained in the same manner as in examples 1 to 6 and comparative examples 1 to 3 except that a PC film was used instead of the PET film and the coating liquid 10 was applied.
The evaluation results of the antiglare films obtained in examples and comparative examples are shown in table 1.
TABLE 1
Figure BDA0002644023680000221
As is clear from the results in table 1, the antiglare film of the examples has a low coefficient of dynamic friction, is excellent in slidability with fingers, and can also improve scratch resistance and antiglare properties. In contrast, the antiglare film of the comparative example has low scratch resistance.
Industrial applicability
The antiglare film of the present invention can be used as an antiglare film used in various display devices such as LCD, cathode-ray tube display device, organic or inorganic EL display, field Emission Display (FED), surface electric field display (SED), rear projection television display, etc., and is particularly suitable for display devices with touch panels such as automobile navigation display, game machine, smart phone, personal Computer (PC) (tablet PC, notebook or portable PC, desktop PC, etc.), television, etc., in view of excellent slidability with fingers and scratch resistance.

Claims (7)

1. An antiglare film comprising an antiglare layer on the surface,
wherein the haze of the anti-dazzle film is 1 to 60 percent, the 60-degree glossiness of the surface of the anti-dazzle layer is 0.1 to 70 percent,
When the steel wool # 0000 is reciprocated 10 times on the surface of the antiglare layer at a speed of 50 mm/sec at a distance of 5cm, the maximum load without generating flaws is 100g load or more,
and the uneven shape of the antiglare layer surface satisfies all of the following characteristics (1) to (3):
(1) The arithmetic average roughness Ra is 0.05-0.14 mu m;
(2) The average length RSm of the roughness profile unit is 5-25 mu m;
(3) The maximum section height Rt of the roughness profile is 0.1-1 μm,
the antiglare layer is a cured product of a curable composition containing one or more polymer components and one or more curable resin precursor components, and the curable resin precursor components contain a urethane (meth) acrylate having 8 to 10 (meth) acryloyl groups in one molecule and a fluorine compound having a polymerizable group.
2. The antiglare film according to claim 1, wherein,
the dynamic friction coefficient of the antiglare layer surface measured under conditions of a load of 0.2N, a moving speed of 50 mm/sec and an effective measurement distance of 50mm was 3 or less by using a surface contact to which an artificial skin was adhered.
3. The antiglare film according to claim 1 or 2, wherein,
the polymer component comprises cellulose esters and/or (meth) acrylic polymers optionally having polymerizable groups.
4. The antiglare film according to claim 1 or 2, wherein,
the curable composition further comprises a filler.
5. A method for producing the antiglare film according to any one of claims 1 to 4, comprising:
an antiglare layer forming step of forming a concave-convex shape by phase separation by wet spinodal decomposition.
6. A display device comprising the antiglare film according to any one of claims 1 to 4.
7. The display device according to claim 6, which is a liquid crystal display device with a touch panel or an organic EL display.
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