CN116893454A - Antiglare film - Google Patents

Antiglare film Download PDF

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Publication number
CN116893454A
CN116893454A CN202310052301.8A CN202310052301A CN116893454A CN 116893454 A CN116893454 A CN 116893454A CN 202310052301 A CN202310052301 A CN 202310052301A CN 116893454 A CN116893454 A CN 116893454A
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antiglare
layer
component
antiglare layer
film
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渡边旭平
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Lintec Corp
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Lintec Corp
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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
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C08J2301/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

The invention provides an antiglare film which has excellent antiglare property and little change in appearance with time, and is suitable for high-definition displays. An antiglare film, characterized in that: the antiglare film comprises a base layer and an antiglare layer, wherein the antiglare layer comprises a component (A): an active energy ray-curable resin (B) component: a filler containing an inorganic component and (C) a component: a layer formed from the composition for forming an antiglare layer of the dispersant, wherein the antiglare layer has an arithmetic average roughness (Ra) of 80nm or more, the antiglare film has a transmission clarity of 400 or more, and the antiglare film has a haze change rate of 5% or less on the surface of the antiglare layer after being left at 70 ℃ for 7 days.

Description

Antiglare film
Technical Field
The present invention relates to an antiglare film which has excellent antiglare properties and is less in change in appearance with time even when applied to a high-definition display, and which can effectively suppress occurrence of white unevenness or glare.
Background
Conventionally, in a display such as a cathode ray tube, a liquid crystal display, or a plasma display, an antiglare film having an antiglare layer has been used to prevent a display image from being easily recognized because incident light from the outside (hereinafter, sometimes referred to as "external light") is reflected on a screen.
As a method for forming an antiglare layer, a method using a composition for forming an antiglare layer containing a filler is known. Examples of the filler used include: an organic filler (resin fine particles) such as an acrylic filler, an inorganic filler such as a silica filler, and an organic-inorganic mixed filler such as an organosilicon filler.
For example, patent document 1 discloses a method for producing an antiglare hard coat film, which uses a composition containing both resin fine particles and silica fine particles.
Patent document 2 discloses a method for producing an antiglare film, which uses silica fine particles and silicone resin fine particles.
Patent document 3 discloses a method for producing an antiglare hard coat film, which uses particles formed by bonding inorganic oxide particles to an organic compound containing a polymerizable unsaturated group and silicone fine particles.
Patent document 4 discloses a method for producing an antiglare hard coat film, which uses silica fine particles or resin particles.
Patent document 5 discloses a method for producing an antiglare film, which uses spherical fine particles of an organic or inorganic system.
Patent document 6 discloses a method for producing an antiglare hard coat film, which uses 2 types of fine particles having different particle diameters.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6603652;
patent document 2: japanese patent application laid-open No. 2004-082613;
patent document 3: japanese patent application laid-open No. 2010-204479;
patent document 4: japanese patent application laid-open No. 2021-085014;
patent document 5: japanese patent application laid-open No. 2015-132744;
patent document 6: japanese patent application laid-open No. 2010-237585.
Disclosure of Invention
Problems to be solved by the invention
As described above, several methods for producing antiglare films using various fillers have been proposed so far.
However, the antiglare film obtained has problems such as change in appearance with time, or deterioration in antiglare property. In particular, in a high-definition display, such a change in appearance or a decrease in antiglare property is only slightly generated, and white unevenness or glare is likely to be generated, and image quality is likely to be reduced.
Therefore, an antiglare film which does not change in appearance with time and is also suitable for a high-definition display is desired.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide an antiglare film which has excellent antiglare properties and does not change in appearance with time.
Means for solving the problems
The present inventors have studied to solve the above problems, and as a result, have found that: an antiglare film which has excellent antiglare properties, does not change in appearance with time, and is effective in suppressing occurrence of white unevenness or glare, the antiglare film comprising a base layer and an antiglare layer, wherein the antiglare layer is a layer formed from a composition for antiglare layer formation comprising an active energy ray-curable resin, a silica filler and/or a silicone filler, and a dispersant, the antiglare layer has an arithmetic average roughness (Ra) of 80nm or more and a transmission clarity of 400 or more. Then, this knowledge was generalized, and the present invention was completed.
That is, according to the present invention, there is provided antiglare films of the following [1] to [6 ].
[1] An antiglare film, characterized in that: which is an antiglare film having a base material layer and an antiglare layer,
the antiglare layer comprises a composition (A): an active energy ray-curable resin (B) component: a filler containing an inorganic component and (C) a component: a layer formed from the composition for forming an antiglare layer of the dispersant,
the surface of the antiglare layer has an arithmetic average roughness (Ra) of 80nm or more,
the antiglare film has a transmission clarity of 400 or more,
The antiglare film has a haze change rate of 5% or less on the surface of the antiglare layer after being left at 70 ℃ for 7 days.
[2] The antiglare film according to [1], wherein the composition for forming an antiglare layer does not contain an organic filler, or the content of the organic filler is more than 0 parts by mass and less than 5 parts by mass relative to 100 parts by mass of the component (A).
[3] The antiglare film according to any one of [1] or [2], wherein the surface of the antiglare layer has a haze value of 3% or more and 30% or less.
[4] The antiglare film according to any one of [1] to [3], wherein the surface of the antiglare layer has a 60 ° gloss value of 20 or more.
[5] The antiglare film according to any one of [1] to [4], wherein the component (B) is a shaped filler containing an inorganic component.
[6] The antiglare film according to any one of [1] to [5], wherein the antiglare layer has an antireflection layer on a surface side opposite to the base material layer.
Effects of the invention
According to the present invention, an antiglare film is provided which has excellent antiglare properties and is free from temporal change in appearance, and which can effectively suppress occurrence of white unevenness or glare. The antiglare film of the present invention can be suitably used for a high-definition display.
Drawings
Fig. 1 is a schematic diagram for explaining the characteristics of the antiglare film of the present invention. Fig. 1 (a) is a schematic diagram illustrating the following case: the solvent absorbed by the acrylic filler is volatilized by the antiglare layer containing the acrylic filler as a filler with time, with the result that the appearance is changed. Fig. 1 (b) is a schematic view showing the change with time of the antiglare layer containing a silica filler as a filler.
Detailed Description
The antiglare film of the present invention is described in detail below.
The antiglare film of the present invention is characterized in that: the antiglare film comprises a base layer and an antiglare layer, wherein the antiglare layer comprises a component (A): an active energy ray-curable resin (B) component: a filler containing an inorganic component and (C) a component: a layer formed from the composition for forming an antiglare layer of the dispersant, wherein the antiglare layer has an arithmetic average roughness (Ra) of 80nm or more, the antiglare film has a transmission clarity of 400 or more, and the antiglare film has a haze change rate of 5% or less on the surface of the antiglare layer after being left at 70 ℃ for 7 days.
1. Substrate layer
The antiglare film of the present invention has a base material layer and an antiglare layer.
The base material layer according to the present invention can be suitably selected from known resin films used as optical films, and is preferably used.
As the resin material constituting the resin film, there may be mentioned: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane (cellophane), cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, polyamide, acrylic resin, norbornene resin, cycloolefin resin, and the like.
Among these, polyethylene terephthalate and cellulose triacetate are preferable from the viewpoints of excellent transparency, excellent substrate adhesion, excellent heat resistance, and easy satisfaction of optical properties described below.
The base material layer may be a layer formed of a single layer or a resin film having 2 or more layers as long as it satisfies optical properties described later. In addition, physical treatments such as corona discharge treatment and oxidation treatment may be applied to the surface of the base material layer in order to improve adhesion, such as formation of an antiglare layer thereon.
The thickness of the base material layer is preferably 15 to 300 μm in view of the handleability as the antiglare film to be obtained, and is more preferably 20 to 200 μm, even more preferably 40 to 160 μm, particularly preferably 50 to 120 μm, and most preferably 60 to 90 μm from the viewpoint of easily satisfying optical properties such as a haze change rate described later.
2. Antiglare layer
The antiglare layer according to the present invention comprises a composition (A): an active energy ray-curable resin (B) component: a filler containing an inorganic component and (C) a component: and a layer formed from the composition for forming an antiglare layer of the dispersant.
(A) The components are as follows: active energy ray-curable resin
The composition for forming an antiglare layer according to the present invention contains an active energy ray-curable resin (in this specification, may be referred to as "(component a)") as the component (a). The component (A) is a polymerizable compound which is crosslinked and cured by irradiation with active energy rays such as ultraviolet rays, electron rays, and X-rays.
The component (a) is not particularly limited, and may be selected from conventionally known components, and active energy ray-curable monomers, oligomers, resins, or mixtures thereof may be used.
Among them, the polyfunctional (meth) acrylic monomer, (meth) acrylic prepolymer and the like are preferably used as the component (a) from the viewpoints of kneading with the component (B) and the component (C) and easy adjustment of the optical properties such as the haze change rate to a desired range.
Here, in the present specification, (meth) acrylic monomer means acrylic monomer or methacrylic monomer, and (meth) acrylate prepolymer means acrylate prepolymer or methacrylate prepolymer.
Examples of the polyfunctional (meth) acrylic monomer include: polyfunctional (meth) acrylates such as 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxy tertiary valerate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tri (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.
These monomers may be used singly or in combination of 1 or more than 2.
The (meth) acrylate prepolymer includes: polyester acrylate prepolymers, epoxy acrylate prepolymers, urethane acrylate prepolymers, polyol acrylate prepolymers, and the like.
The polyester acrylate prepolymer can be obtained by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, which is obtained by the condensation of a polycarboxylic acid and a polyhydric alcohol, with (meth) acrylic acid, or esterifying the hydroxyl groups at the ends of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth) acrylic acid.
The epoxy acrylate prepolymer can be obtained by esterifying (meth) acrylic acid with an oxirane ring of a bisphenol type epoxy resin or a novolac type epoxy resin having a relatively low molecular weight.
Urethane acrylate prepolymers are obtainable by esterifying urethane oligomers obtained by reacting polyether polyols or polyester polyols with polyisocyanates with (meth) acrylic acid.
The polyol acrylate prepolymer can be obtained by esterifying the hydroxyl groups of a polyether polyol with (meth) acrylic acid.
These prepolymers may be used singly or in combination of 2 or more. In addition, the above-mentioned polyfunctional (meth) acrylic monomer may be used in combination.
In addition, from the viewpoint of easily obtaining an antiglare film having excellent hardness or scratch resistance, and from the viewpoint of easily adjusting the haze change rate, optical properties, and the like described later to desired ranges, it is also preferable to use an active energy ray-curable resin containing a silica sol as the component (a).
The active energy ray-curable resin containing a silica sol includes: the above-mentioned polyfunctional (meth) acrylic monomer containing a silica sol, the above-mentioned (meth) acrylic prepolymer containing a silica sol, and the like.
(B) The components are as follows: filler containing inorganic component
The composition for forming an antiglare layer according to the present invention contains a filler containing an inorganic component (in this specification, sometimes referred to as "(component B)") as the component (B). The component (B) is a filler which remains an inorganic residue when the filler itself is fired. The component (B) contains a so-called inorganic filler and an organic-inorganic mixed filler.
The antiglare layer of the present invention contains the component (B), so that it is easy to satisfy optical properties such as a haze change rate, and it is easy to obtain surface roughness suitable for a high-definition display in addition to desired hardness and scratch resistance.
In addition, the component (B) has a characteristic of being less likely to absorb a solvent than the organic filler. Therefore, when the antiglare layer forming composition for forming an antiglare layer contains a solvent, the composition for forming an antiglare layer is inhibited from changing in particle diameter due to the absorption and swelling of the component (B) by the solvent. Thus, after the antiglare layer is formed, the solvent volatilizes from the component (B) in the antiglare layer with time, and the occurrence of defects such as a change in the optical properties (haze or the like) of the antiglare layer can be prevented.
Examples of the inorganic filler include: oxide particles of at least one metal selected from the group consisting of silicon, zirconium, titanium, indium, zinc, tin, antimony, tungsten; calcium carbonate microparticles; barium sulfate particles; talc particles; kaolin particles; calcium sulfate fine particles, and the like. Among them, from the viewpoint of easy improvement of kneading property of the component (a) and the component (C) and easy adjustment of optical properties such as haze change rate to a desired range, oxide particles of at least one metal selected from silicon, zirconium, titanium, indium, zinc, tin, antimony, and tungsten are preferably used, and from the viewpoint of easy formation of surface roughness suitable for a high-definition display in cooperation with the component (a) and the component (C), silicon oxide particles are particularly preferably used.
Examples of the organic-inorganic mixed filler include: and silicone-based fillers.
Among these, from the viewpoint of easy improvement of kneading with component (a) and component (C) and easy adjustment of optical properties such as haze change rate to a desired range, it is preferable to use oxide particles of at least one metal selected from silicon, zirconium, titanium, indium, zinc, tin, antimony, and tungsten, and silicone-based fillers, and from the viewpoint of easy obtaining of surface roughness suitable for high-definition displays in antiglare layers, it is more preferable to use silicon oxide particles (in this specification, sometimes referred to as "silica-based fillers"), and silicone-based fillers, and from the viewpoint of easy achievement of haze change rate to a desired range, it is particularly preferable to use silica-based fillers.
Examples of the silica-based filler include: dry silica particles, wet silica particles, silica gel particles, calcium ion-exchanged silica particles, colloidal silica particles, silica particles having a surface functional group, and the like.
As the silica fine particles having a surface functional group, there can be mentioned: silica particles having a group containing a polymerizable unsaturated group as a surface functional group (in this specification, sometimes referred to as "reactive silica particles"). Such reactive silica fine particles can be obtained, for example, by reacting an organic compound containing a polymerizable unsaturated group having a functional group reactive with a silanol group on the surface of the silica fine particles with the silanol group.
Examples of the polymerizable unsaturated group include: free radically polymerizable (meth) acryl, and the like.
As the organic compound having a polymerizable unsaturated group having a functional group reactive with a silanol group, it is preferable to use: acrylic acid, acrylic acid chloride, 2-isocyanatoethyl acrylate, glycidyl acrylate, 2, 3-iminopropyl acrylate, 2-hydroxyethyl acrylate, acryloxypropyl trimethoxysilane, and the like; and methacrylic acid derivatives corresponding to these acrylic acid derivatives.
These acrylic acid derivatives or methacrylic acid derivatives may be used singly or in combination of 1 or more than 2.
Examples of the silicone-based filler include: silicone resin fillers such as silicon compound particles having a polyorganosiloxane skeleton; epoxy modified silicone resin filler, aryl modified silicone resin filler, terminal alkenyl modified silicone resin filler, acrylic modified silicone resin filler, and the like.
The relationship between the component (B) used in the present invention and the solvent described below is as follows: the solvent absorption amount when 10mg of the filler is immersed in 10ml of the solvent for 24 hours is preferably 1mg or less, more preferably 0.1mg or less, particularly preferably 0.01mg or less. By setting the solvent absorption amount to such a range, the optical properties such as the haze value change rate can be adjusted to a desired range, and the surface roughness suitable for a high-definition display can be easily formed. The lower limit of the amount of the solvent absorbed is usually 0mg.
(B) The shape of the composition may be either a fixed shape or an amorphous shape. Here, shaping means that the filler has a substantially certain shape, and amorphous means that the filler does not have a particularly defined shape. The shape of the component (B) is preferably a shape, more preferably a sphere, and particularly preferably a sphere, from the viewpoint of uniformly dispersing the component (a) in the component (a) and homogenizing the scattering state of light to stabilize the antiglare property when mixed with the component (a). Here, spherical means a polyhedral shape which can be approximated as a sphere, including a rotational ellipsoid, an oval shape, a golden sugar shape, a cocoon shape, and the like, in addition to a spherical shape.
When the component (B) is spherical in shape, the volume average particle diameter is not particularly limited, but is usually 0.1 to 10. Mu.m, preferably 0.5 to 6. Mu.m, more preferably 1.0 to 3. Mu.m, still more preferably 1.2 to 2.0. Mu.m, particularly preferably 1.3 to 1.8. Mu.m. Thus, the optical properties such as the rate of change of haze value can be adjusted to a desired range, and the surface roughness suitable for a high-definition display can be easily formed.
The volume average particle diameter of the component (B) can be measured by using a laser diffraction scattering particle size distribution measuring apparatus.
(B) The refractive index of the component (A) is preferably 1.2 to 1.6, more preferably 1.3 to 1.55, still more preferably 1.4 to 1.5, particularly preferably 1.42 to 1.45. This makes it easy to satisfy optical properties such as a change rate of haze value.
The blending amount of the component (B) is not particularly limited, but is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, still more preferably 1 to 30 parts by mass, particularly preferably 2 to 20 parts by mass, and most preferably 3 to 12 parts by mass, based on 100 parts by mass of the component (A). Thus, the optical properties such as the rate of change of haze value can be adjusted to a desired range, and the surface roughness suitable for a high-definition display can be easily formed.
When the blending amount of the component (B) is 0.1 part by mass or more, the filler is offset in an appropriate range on the surface of the antiglare layer, and fine irregularities are formed, whereby the desired antiglare property can be easily obtained.
Further, when the blending amount of the component (B) is 100 parts by mass or less, deterioration in visibility of a display image of a display due to an excessive haze value is prevented, and scratch resistance and excellent hardness can be easily obtained without lowering the blending ratio of the active energy ray-curable resin.
The composition for forming an antiglare layer according to the present invention does not contain an organic filler (a filler that does not leave an inorganic residue when the filler itself is fired), or the content of the organic filler is preferably more than 0 parts by mass and less than 5 parts by mass, particularly preferably no organic filler, relative to 100 parts by mass of the component (a).
The organic filler has a characteristic of easily absorbing a solvent as compared with the filler containing an inorganic component. Therefore, in the antiglare layer formed from the composition for forming an antiglare layer containing the organic filler and the solvent, the organic filler absorbs the solvent and is easily swelled during the formation thereof, and is easily left in the antiglare layer in a swelled state (state in which the solvent is absorbed). Further, the solvent remaining in the organic filler may volatilize with time after film formation, and thus there is a possibility that the optical properties such as haze value may be changed. Therefore, it is preferable not to use an organic filler.
(C) The components are as follows: dispersing agent
The composition for forming an antiglare layer according to the present invention contains a dispersant (in this specification, sometimes referred to as "(component C)") as component (C).
By containing the component (C), the optical properties such as the rate of change of haze value can be adjusted to a desired range, and the surface roughness suitable for a high-definition display can be provided. It is presumed as follows.
Since the inorganic component-containing filler as the component (B) has a higher specific gravity and is more likely to be precipitated (precipitated) than the organic filler, it is difficult to control the precipitation, and it is difficult to segregate the inorganic component-containing filler on the antiglare layer surface and stably obtain surface roughness, antiglare properties and optical properties suitable for high-definition displays. Therefore, it is considered that the use of the component (B) is not suitable for producing a high-definition antiglare film. However, by using the component (C) in combination, the sedimentation of the component (B) in the coating film of the antiglare layer-forming composition can be suppressed even though the component (B) which is liable to sediment is used. Thus, the component (B) is properly biased on the surface of the antiglare layer, and fine irregularities are stably formed, thereby producing excellent antiglare properties. Accordingly, it is considered that the antiglare layer according to the present invention can have surface roughness suitable for a high-definition display while adjusting optical properties such as a change rate of haze value to a desired range by containing the component (C).
In order to achieve the above object, the component (C) is preferably a compound having at least 1 polar group in the molecule. Here, the polar group means a functional group (or an atomic group) having polarity, and examples thereof include: carboxyl, hydroxyl, sulfo, primary amino, secondary amino, tertiary amino, amide, quaternary ammonium, pyridinium, sulfonium, phosphonium, and the like.
By using the component (C) having these polar groups, the sedimentation of the filler containing an inorganic component in the coating film of the composition for forming an antiglare layer can be more effectively controlled.
The mechanism of this component (C) has not been clarified, but is presumed to be as follows: the polar groups in the dispersant coordinate to the surface of the inorganic component-containing filler, and as a result, the polarity of the surface of the inorganic component-containing filler changes, and the probability that the inorganic component-containing filler exists near the surface of the coating film increases.
Among the polar groups mentioned above, carboxyl groups, sulfo groups, primary amino groups, secondary amino groups, tertiary amino groups are also particularly preferred. This is due to: dispersants having these polar groups can coordinate more effectively to the surface of the filler containing inorganic components.
The polar groups may be randomly arranged in the resin molecule, but it is preferable that the polar groups are arranged at the terminal portions in the molecule by a block structure or a graft structure. This improves the adsorption performance on the filler.
The polar group of 1 component (C) may be incorporated into the molecule, or a plurality of polar groups may be incorporated. In the case of having a plurality of polar groups in a molecule, a basic skeleton in which organic compounds having respective polar groups are bonded to each other is required, and as such a basic skeleton, a skeleton composed of an ester chain, a vinyl chain, an acrylic chain, an ether chain, a urethane chain, or the like is preferable. Moreover, a part of hydrogen atoms in these molecules may be substituted with halogen atoms.
Among these, the component (C) is preferably an acrylic resin, a urethane resin, a polyester resin or an alkyd resin, and particularly preferably an acrylic resin, a urethane resin or a polyester resin from the viewpoint of being able to adjust the optical properties such as the haze value change rate to a desired range and having a surface roughness suitable for a high-definition display.
The molecular weight of the component (C) is not particularly limited, and may be selected from a wide range of molecular weights of 100 to 90 ten thousand.
(C) The components may be used singly or in combination of 1 or more than 2.
The blending amount of the component (C) is preferably more than 0 part by mass and 2 parts by mass or less, more preferably 0.1 to 1.5 parts by mass, still more preferably 0.2 to 1 part by mass, and particularly preferably 0.3 to 0.6 part by mass, per 100 parts by mass of the component (A). By setting the blending amount of the component (C) to such a range, the optical properties such as the haze value change rate can be adjusted to a desired range, and the high-definition display has a more suitable surface roughness.
If the component (C) is not blended, it is difficult to deviate the component (B) in an appropriate range on the surface of the antiglare layer, and it may be difficult to obtain desired antiglare properties. On the other hand, if the blending amount of the component (C) exceeds 2 parts by mass, the scratch resistance or hardness of the antiglare layer may be lowered.
(D) The components are as follows: other ingredients
The antiglare layer-forming composition for forming an antiglare layer according to the present invention may contain other components in addition to the above components (a) to (C).
As other components, there may be preferably mentioned: leveling agents, photopolymerization initiators, and the like.
By using the leveling agent, the film thickness of the antiglare layer to be formed becomes uniform, and the antiglare layer is free from streak defects, unevenness, and the like, and has an excellent appearance, and can exhibit desired optical properties.
As the leveling agent, there may be mentioned: silicone leveling agents, fluorine leveling agents, acrylic leveling agents, vinyl leveling agents, and the like. Among them, silicone leveling agents and fluorine leveling agents are preferable in terms of high leveling property, good compatibility with other components, and the like.
Examples of the silicone leveling agent include: polydimethylsiloxane or modified polydimethylsiloxane, and the like.
Examples of the fluorine-based leveling agent include: compounds having a perfluoroalkyl group or a fluorinated alkenyl group in the main chain or side chain, and the like.
The leveling agent may be used alone or in combination of 1 or more than 2.
When the leveling agent is used, the blending ratio is usually 0.0005 to 10 parts by mass, preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass, still more preferably 0.05 to 0.6 part by mass, and particularly preferably 0.1 to 0.3 part by mass, per 100 parts by mass of the component (a). When the blending ratio of the leveling agent is in such a range, the leveling effect can be sufficiently obtained, and the obtained antiglare layer exhibits desired optical properties and has a surface roughness suitable for a high-definition display.
In addition, by using a photopolymerization initiator, polymerization curing time and light irradiation amount can be reduced when forming the antiglare layer. In particular, when active light such as ultraviolet rays is irradiated as active energy rays to crosslink the active energy rays, a photopolymerization initiator is preferably present.
The photopolymerization initiator is not particularly limited, and conventionally known ones can be used. For example, there may be mentioned: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, dimethylaminoacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, p-phenylbenzophenone, 2-methylanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, benzyl dimethyl ketal, p-dimethylaminobenzoate, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, and the like.
The photopolymerization initiator may be used alone or in combination of 1 or more than 2.
When the photopolymerization initiator is used, the blending ratio is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the component (a). When the blending amount of the photopolymerization initiator is less than 0.1 part by mass, the blending effect cannot be obtained. On the other hand, if the blending amount of the photopolymerization initiator exceeds 20 parts by mass, the scratch resistance and hardness of the antiglare layer may be lowered.
(E) Preparation of antiglare layer-forming composition
The antiglare layer-forming composition used in the present invention can be prepared by adding the above-described components (a) to (C) as essential components and, if necessary, (D) to an appropriate solvent, and dissolving or dispersing the components.
In this case, in addition to the components (a) to (D), for example, other components such as an antioxidant, an ultraviolet absorber, a silane coupling agent, a light stabilizer, an antifoaming agent, an infrared absorber, a colorant, an antistatic agent, and the like may be appropriately blended within a range that does not affect the effect of the present invention.
The solvents used include: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; alcohols such as methanol, ethanol, propanol, butanol, etc.; ketones such as acetone, butanone, 2-pentanone, diisobutanone, cyclohexanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolve such as ethyl cellosolve, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, and propylene glycol monomethyl ether; glycol ethers such as 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutylacetate, diethylene glycol monobutyl ether, and 1-ethoxy-2-propanol.
Among these, in the present invention, the solvent is preferably 20 to 80% by mass, preferably 30 to 70% by mass, more preferably 40 to 60% by mass of the total solvent, and the evaporation rate is 0.5 (mg/cm) 2 /min) the following solvents. That is, it is preferable to use a catalyst containing a catalyst having an evaporation rate of 0.5 (mg/cm 2 Per minute) below and evaporation rates exceeding 0.5 (mg/cm) 2 /min).
By using such a solvent, the component (B) can be easily biased in an appropriate range on the surface of the antiglare layer, and an antiglare layer having a surface roughness suitable for a high-definition display while exhibiting desired optical properties can be obtained. Further, for example, the change in haze with time can be further suppressed, and further the change in appearance of the antiglare film with time can be suppressed.
As an evaporation rate, 0.5 (mg/cm) 2 The following solvents are mentioned: 1-butanol (0.47), diisobutanone (0.2), cyclohexanone (0.32), isophorone (0.026), ethylcellosolve (0.38), ethylene glycol mono-n-butyl ether (0.08), ethylene glycol mono-tert-butyl ether (0.19), 3-methoxy-3-methylbutanol (0.07), 3-methoxy-3-methylbutyl acetate (0.10), diethylene glycol mono-butyl ether (0.004), 1-ethoxy-2-propanol (0.34) and the like (the evaporation rate (mg/cm) is expressed in brackets 2 /min)).
The amount of the solvent to be used may be appropriately determined depending on the situation so that the antiglare layer-forming composition is in a state (concentration, viscosity) suitable for forming a coating film.
The amount of the solvent to be used is preferably 50 to 500 parts by mass, more preferably 70 to 300 parts by mass, still more preferably 90 to 200 parts by mass, particularly preferably 100 to 150 parts by mass, per 100 parts by mass of the component (A). By setting the amount of the solvent to the above range, the filler containing an inorganic component can be easily biased in an appropriate range on the surface of the antiglare layer, and an antiglare layer having a surface roughness suitable for a high-definition display while exhibiting desired optical properties can be easily obtained. Further, for example, the change in haze with time can be further suppressed, and further the change in appearance of the antiglare film with time can be further suppressed.
(F) Formation of antiglare layer
The method for forming the antiglare layer is not particularly limited.
For example, the antiglare layer-forming composition is applied directly or via another layer to the base film as a base layer by a conventionally known coating method to form a coating film. Examples of the coating method include: bar coating, blade coating, roll coating, blade coating, die coating, gravure coating, and the like.
Then, the obtained coating film is dried, and then, an active energy ray is irradiated to cure the coating film, whereby an antiglare layer can be formed.
Examples of the active energy ray used for curing the coating film include: ultraviolet rays; an electron beam; laser such as semiconductor laser, argon laser, he-Cd laser, etc.; and ionizing radiation such as α rays, β rays, γ rays, neutron rays, X rays, and accelerated electron rays.
Among these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable, from the viewpoint of being able to use relatively simple devices for generating active energy rays.
In the case of using ultraviolet rays as active energy rays, an ultra-high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, or the like can be used as the ultraviolet source.
The amount of ultraviolet light is not particularly limited, but is usually 100 to 1,000mJ/cm 2 The illuminance is usually 100-1000 mW/cm 2 . The irradiation time is usually 1 second to 1 hour, and the irradiation temperature is usually 20 to 100 ℃.
The thickness of the antiglare layer according to the present invention is not particularly limited, but is usually 0.5 to 20. Mu.m, preferably 0.8 to 15. Mu.m, more preferably 1 to 10. Mu.m, still more preferably 1.5 to 6. Mu.m, particularly preferably 2 to 5. Mu.m.
By setting the film thickness of the antiglare layer to such a range, an antiglare film suitable for a high-definition display while exhibiting desired optical properties can be more easily obtained.
If the film thickness of the antiglare layer is less than 0.5 μm, it may be difficult to obtain a pencil hardness that is required for practical use.
On the other hand, if the film thickness of the antiglare layer exceeds 20 μm, it may be difficult to suppress curling accompanied by curing shrinkage of the active energy ray-curable resin or cracks in the antiglare layer that occur when the antiglare film is bent.
As the other layers, there may be mentioned: and (3) an undercoating layer. The primer layer has affinity with the surfaces of both the base material layer and the antiglare layer, and is made of a material having strong adhesion. The primer layer can be formed by, for example, applying 0.5 to 2g/m of the primer layer to the surface of the base material layer 2 Is formed from a reactive coating liquid composed of a polyester polyol or polyether polyol and a polyisocyanate.
(G) Anti-reflection layer
The antiglare film of the present invention may have an antireflection layer on the surface side of the antiglare layer opposite to the substrate layer side.
By providing the antireflection layer, reflection of a screen due to reflection of sunlight, a fluorescent lamp, or the like is eliminated, and by suppressing the reflectance of the surface, the total light transmittance is improved, and the transparency is improved. The antistatic property can be improved depending on the type of the antireflection layer.
In the present invention, even when the step of forming the antireflection layer is increased and more time is required for forming the antiglare film, the appearance of the antiglare layer does not change with time, and the antiglare layer is easy to manage.
The antireflection layer can be formed, for example, by applying a coating liquid containing an antireflection layer-forming composition such as an acrylic resin, hollow silica particles, and a photopolymerization initiator directly or via another layer to the antiglare layer, and drying the coating liquid.
The thickness of the antireflection layer is usually 5 to 200nm, preferably 50 to 150nm.
In the case where the antiglare film of the present invention has an antireflection layer, the reflectance thereof is preferably 3.0% or less. The reflectance is usually 0% or more.
Since the reflectance is in such a range, an optical product having excellent visibility, in particular, an optical product suitable for a high-definition display, can be provided in which reflection of external light is suppressed.
The reflectivity may be measured using an ultraviolet visible near infrared (UV-VIS-NIR) spectrophotometer.
(H) Constitution of antiglare film, etc
The antiglare film of the present invention is suitable for use as a display body, in particular, for a high-definition display. Here, in this specification, a high-definition display means a display having a resolution of 100ppi (pixels/inch) or more. The resolution of the high-definition display is preferably 140ppi or more, more preferably 180ppi or more, still more preferably 220ppi or more, particularly preferably 260ppi or more.
In a high-definition display having such a resolution, the antiglare film of the present invention is suitable for use because the antiglare film is likely to cause a decrease in antiglare property or a problem such as glare, and the antiglare film suppresses the problem even when it is laminated on the surface of the high-definition display having such a resolution.
The layer structure of the antiglare film of the present invention includes: the following layers.
Substrate layer/antiglare layer, substrate layer/primer layer/antiglare layer, substrate layer/antiglare layer/antireflection layer, substrate layer/primer layer/antiglare layer/antireflection layer.
The antiglare film may have a surface protective sheet on one or both sides in order to protect the surface of the antiglare layer before use. The surface protective sheet is peeled off and removed at the time of use.
As the surface protective sheet, a conventionally known resin film is used. Specifically, there may be mentioned: polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polyethylene naphthalate films, polybutylene terephthalate films, polyurethane films, ethylene vinyl acetate films, ionomer resin films, ethylene/(meth) acrylic acid copolymer films, ethylene/(meth) acrylic acid ester copolymer films, polystyrene films, polycarbonate films, polyimide films, fluororesin films, and the like; their crosslinked films; laminated films thereof, and the like.
The antiglare film of the present invention may be bonded to a polarizer (polarizer) to form a polarizing plate.
3. Characteristics of antiglare film
The antiglare film of the present invention has an arithmetic average roughness (Ra) of 80nm or more and a transmission clarity of 400 or more on the surface of the antiglare layer, and has a haze change rate of 5% or less on the surface of the antiglare layer after the antiglare film is left at 70 ℃ for 7 days.
Thus, the anti-glare film has excellent anti-glare properties, does not change in appearance with time, and can effectively suppress generation of white unevenness or glare, and is particularly suitable for high-definition displays. (1) Surface roughness [ arithmetic average roughness (Ra), root mean square roughness (Rq), maximum protrusion height (Rp) ]
In the antiglare film of the present invention, the arithmetic average roughness (Ra) of the antiglare layer surface (surface on the side opposite to the base layer side) is preferably 80nm or more, more preferably 90nm or more, still more preferably 100nm or more, particularly preferably 120nm or more.
The antiglare film of the present invention has an antiglare layer surface having an arithmetic average roughness (Ra) of 80nm or more, and therefore exhibits excellent antiglare properties, and is particularly suitable for high-definition displays.
The arithmetic average roughness (Ra) of the antiglare layer surface is preferably 400nm or less, more preferably 300nm or less, further preferably 250nm or less from the viewpoint of easily satisfying desired optical properties, and particularly preferably 200nm or less from the viewpoint of easily satisfying the haze change rate.
The root mean square roughness (Rq) of the antiglare layer surface is preferably 80 to 500nm, more preferably 110 to 400nm, still more preferably 120 to 300nm, and particularly preferably 180 to 300nm from the viewpoint of easily satisfying the haze change rate.
The maximum protrusion height (Rp) of the antiglare layer surface is preferably 1 μm or more, more preferably 2 μm or more. The maximum protrusion height (Rp) is preferably 15 μm or less.
The antiglare film of the present invention has such values of surface roughness (Ra, rq, rp) of the antiglare layer that the filler segregates on the surface of the antiglare layer, has high definition and dense irregularities, and has high antiglare properties, and is less likely to cause white unevenness or glare even when applied to a high definition display.
The surface roughness [ arithmetic average roughness (Ra), root mean square roughness (Rq), maximum protrusion height (Rp) ] can be measured using a surface roughness measuring device according to JIS B601-2001.
In the case where the antireflection layer is provided on the antiglare layer, the "surface of the antiglare layer" refers to the "surface of the antireflection layer on the antiglare layer". The following is the same.
(2) Transmission clarity
The antiglare film of the present invention preferably has a transmission clarity of 400 or more, more preferably 400 to 480.
The transmission clarity becomes an index of visibility, and if the value is low, sufficiently good display image quality (visibility) cannot be obtained. The antiglare film of the present invention satisfies the above range in transmission clarity and is excellent in clear feel, and is therefore particularly suitable for high-definition displays.
The transmission clarity can be determined as follows: the transmission clarity was obtained by irradiating light from the antiglare layer side in a transmission mode using a mapping test apparatus in accordance with JIS K7374, and calculating a total mapping value (comb width: 0.125mm, 0.25mm, 0.5mm, 1.0mm, 2.0 mm) of 5 combs.
(3) Haze value and haze change rate
In the antiglare film of the present invention, the haze value of the surface of the antiglare layer is preferably 3 to 30%, more preferably 4 to 25%, further preferably 5 to 18%, particularly preferably 7 to 15%. Since the haze value is in such a range, the antiglare film exhibits excellent antiglare properties, and is particularly suitable for a high-definition display.
If the haze value is less than 3%, it may be difficult to obtain excellent antiglare properties.
On the other hand, if the haze value exceeds 30%, the visibility of the display image of the display may be reduced.
The haze value may be in accordance with JIS K7136: 2000, measured using a haze meter.
In the antiglare film of the present invention, the change rate of haze of the antiglare layer surface after leaving the antiglare film at 70 ℃ for 7 days is 5% or less, preferably 3% or less, more preferably 1.5% or less, further preferably 1.0% or less, particularly preferably 0.6% or less, and most preferably 0.1% or less.
Here, the haze change rate is represented by the formula: the values calculated by [ (initial haze value) - (haze value after leaving at 70 ℃ for 7 days) ]/(initial haze value) ×100 (%).
Fig. 1 shows a schematic diagram showing the change with time of the surface of the antiglare layer.
Fig. 1 (a) shows a case of using an acrylic filler as an organic filler, and fig. 1 (b) shows a case of using a silica filler as a filler containing an inorganic component.
In the case of using an acrylic filler as an organic filler, the acrylic filler absorbs solvent molecules to swell as shown in the left diagram of fig. 1 (a). Then, the solvent molecules volatilize from the acrylic filler with time, and thus the state of the surface of the antiglare layer changes, resulting in a change in the haze of the antiglare layer.
On the other hand, in the case of using a silica filler as a filler containing an inorganic component, as shown in the left diagram of fig. 1 (b), the silica filler does not absorb solvent molecules like an acrylic filler. Therefore, the solvent molecules do not volatilize with time, and as a result, the haze of the antiglare layer does not decrease.
In the antiglare film of the present invention, an organic filler that readily absorbs a solvent (the content of the organic filler is usually less than 5 parts by mass per 100 parts by mass of the component (a)) is substantially not used in the antiglare layer, and a filler containing an inorganic component is used. Therefore, the absorbed solvent does not volatilize from the filler on the surface of the antiglare layer, resulting in a decrease in haze with time. Therefore, even in the case where the antiglare film of the present invention is applied to a high-definition display, white unevenness or glare can be suppressed.
(4) Residual solvent concentration
In the antiglare film of the present invention, the residual solvent concentration of the antiglare layer is preferably 30 (ppm) or less, more preferably 20 (ppm) or less, further preferably 10 (ppm) or less, particularly preferably less than 10 (ppm). The lower limit of the residual solvent concentration is usually 0 (ppm).
Since the antiglare layer of the antiglare film of the present invention contains substantially no organic filler that readily absorbs a solvent, by setting the residual solvent concentration to the above range, there is no possibility that the solvent volatilizes over time to cause a change in haze, and the antiglare film is suitable for use in high-definition displays in particular.
The residual solvent concentration can be measured by the method shown in the test example described later.
(5) 60 degree gloss
The antiglare film of the present invention has a 60 ° gloss (gloss) of the antiglare layer surface of preferably 20 or more, more preferably 30 or more, and further preferably 40 or more, particularly preferably 50 or more, and most preferably 55 or more, from the viewpoint of satisfying the change rate of haze. The 60 ° gloss is preferably 150 or less, more preferably 120 or less, and particularly preferably 100 or less.
Since the 60 ° glossiness is in the above range, even in the case where the antiglare film of the present invention is applied to a high-definition display, white unevenness or glare can be more effectively suppressed.
If the 60 ° glossiness exceeds 150, the surface glossiness becomes excessively high (the reflection of light becomes excessively high), and the antiglare property may be adversely affected.
The 60 ° gloss can be measured according to JIS Z8741: 1997, using a gloss meter.
(7) Total light transmittance
The antiglare film of the present invention preferably has a total light transmittance of 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 91% or more. The upper limit value of the total light transmittance is usually 100%.
The antiglare film of the present invention has high total light transmittance, and therefore, the display image of the display is excellent in visibility, and is particularly suitable for use in a high-definition display.
The total light transmittance can be measured according to JIS K7361-1 using a haze meter.
(8) Hardness of
The antiglare layer of the antiglare film of the present invention preferably has a pencil hardness of H or more, and more preferably 2H or more. The pencil hardness is usually 9H or less, preferably 7H or less, more preferably 5H or less, further preferably 4H or less, and particularly preferably 3H or less. The antiglare film of the present invention has such hardness and therefore is excellent in scratch resistance, and exhibits excellent surface protection properties when used on the surface of a display body such as a high-definition display. In particular, the surface is not easily damaged, and thus the appearance of the display body can be maintained well.
The pencil hardness can be measured according to JIS K5600 using a pencil scratch hardness tester.
(9) Scratch resistance
The antiglare layer of the antiglare film of the present invention preferably has no change in appearance in the evaluation of scratch resistance using steel wool. In particular, for preventingThe surface of the glare layer was treated with #0000 steel wool at 250g/cm in accordance with JIS K5600-5-10 2 It is preferable that the surface is not damaged after 10 times of back and forth rubbing at 10 cm. Thus, when the display is used on the surface of a display body such as a high-definition display, excellent surface protection can be exhibited, and the appearance of the display body can be maintained satisfactorily.
The scratch resistance can be evaluated by the method described in the test example described below.
As described above, the antiglare film of the present invention has moderate surface roughness and transmission clarity, has a small rate of change in haze with time, has excellent antiglare properties, and is suitable for use in high-definition displays.
In the present specification, when the term "X to Y" (X, Y is an arbitrary number), unless otherwise specified, the term "X or more and Y or less" is included, and the term "preferably greater than X" or "preferably less than Y" is included. Note that, unless otherwise specified, the meaning of "preferably greater than X" is included in the case of "X or more" (X is an arbitrary number), and the meaning of "preferably less than Y" is included in the case of "Y or less" (Y is an arbitrary number) unless otherwise specified.
Examples
The present invention will be described in further detail with reference to examples. The present invention is not limited to the following examples.
Examples 1 to 3, 5 and 6 and comparative examples 1 to 3
(1) Preparation of antiglare layer-forming composition
As shown in table 1 and below, an active energy ray-curable resin as component (a), an inorganic component-containing filler as component (B), a dispersant as component (C), and a leveling agent as component (D) were mixed in a solvent to prepare a composition for forming an antiglare layer.
The blending amount of the component (a) and the component (B) in table 1 and the following represents the value obtained by converting the solid content.
(A) Composition of the components
Urethane acrylate containing silica sol (OPSTAR 7530, concentration: 73 mass%, manufactured by kawa chemical corporation): 100 parts by mass;
(B) Composition of the components
B1: high purity silica spherical fine particle powder (average particle diameter 1.5 μm, seahostar KE-S150, manufactured by Japanese catalyst Co., ltd., refractive index 1.43);
b2: silicone resin particles (average particle diameter 2 μm, spherical, tospearl 120, manufactured by Momentive company, refractive index 1.43);
b3: crosslinked acrylic beads (average particle size 1.2 μm, spherical, ART PEARL J-3PY, manufactured by Gen-Wipe Co., ltd., refractive index 1.50): it does not belong to the component (B) of the present invention per se, but is referred to as component B3 for convenience.
(C) Composition of the components
Carboxyl group-containing polymer modified material (fefin G-700 (concentration 100 mass%), manufactured by co-processing chemical company);
(D) Composition of the components
Leveling agent (polydimethylsiloxane: SH28 (concentration 100% by mass), manufactured by Dow Toray Co.).
< solvent >
100ml of the following solvents were used.
S1: propylene glycol monomethyl ether (PGM)/cyclohexanone mixed solvent (mass ratio: 1:1);
S2：PGM。
(2) Coating process
The obtained antiglare layer-forming composition was coated on a cellulose triacetate film (product name "Konica TAC KC8UAW", thickness 80 μm, manufactured by Konica Minolta corporation) as a base layer using a bar #14 so that the film thickness after curing was 5 μm, to form a coating layer.
(3) Drying process
The resulting coating layer was dried at 70℃for 1 minute using a hot air drying apparatus.
(4) Curing step
Then, using an ultraviolet irradiation device (light source: high-pressure mercury lamp, manufactured by GS Yuasa Corporation), the irradiation intensity was set to: 200mW/cm 2 Light amount: 200mJ/cm 2 The dried coating layer was irradiated with ultraviolet rays and the coating layer was cured to form an antiglare layer, whereby antiglare films of examples 1 to 3, 5, and 6 and comparative examples 1 to 3 were obtained.
Example 4
10 parts by mass of an acrylic resin (product name "NK ester A-DPH", solid content 100% by mass, manufactured by Xinzhou chemical Co., ltd.), 30 parts by mass of hollow silica particles (product name "so 4320", solid content 20.5% by mass, manufactured by Nivocatalyst Co., ltd.), 0.3 parts by mass of a photopolymerization initiator (product name "OMNIRAD 907", solid content 100% by mass, manufactured by BASF Co., ltd.), and 0.2 parts by mass of a fluorine-based antifouling agent (product name "Mega Fuck RS-90", solid content 10% by mass, manufactured by DIC Co., ltd.) were mixed in a mixed solvent (mass ratio: 1:1), to obtain a coating liquid of the composition for forming an antireflection layer having a solid content of 1.0 to 2.0% by mass.
Then, the surface of the antiglare layer of the antiglare film obtained in example 3 opposite to the base layer was coated with the coating liquid so that the thickness after drying was 100nm. The obtained coating film was dried at 70℃for 1 minute using a hot air drying apparatus, and then irradiated with ultraviolet light (light source: high-pressure mercury lamp, manufactured by GS Yuasa Corporation), at illuminance: 200mW/cm 2 Light amount: 200mJ/cm 2 Ultraviolet rays are irradiated under the condition of (2) to form an antireflection layer.
Thus, an antiglare film with an antireflection layer of example 4 composed of a layer including a base material layer, an antiglare layer, and an antireflection layer was obtained.
The antiglare films obtained in examples 1 to 6 and comparative examples 1 to 3 were evaluated as follows.
(1) Surface roughness
The surface roughness [ arithmetic average roughness Ra (nm), root mean square roughness Rq (nm), and maximum protrusion height Rp (μm) ] of the antiglare layer surface of the obtained antiglare film was measured using a surface roughness measuring device (manufactured by Sanfeng Co., ltd.) according to JIS B601-2001.
The results are shown in Table 1.
(2) Transmission clarity
The obtained antiglare film was irradiated with light from the antiglare layer side in a transmission mode using an imaging property test apparatus (manufactured by ICM-1T, suga tester Co.) in accordance with JIS K7374, and an imaging property total value (comb width: 0.125mm, 0.25mm, 0.5mm, 1.0mm, 2.0 mm) of 5 comb was calculated.
The results are shown in Table 1.
(3) Haze value and haze change rate
According to JIS K7136: 2000, a haze value (%) of the antiglare layer surface of the obtained antiglare film was measured by irradiating light from the antiglare layer side after correction with a blank using a haze meter (NDH 5000, manufactured by japan electric color industry).
The haze value (%) of the antiglare film after being left at 70℃for 7 days was also measured. Then, by the formula: the haze change rate (%) was calculated as [ (initial haze value) - (haze value after leaving at 70 ℃ for 7 days) ]/(initial haze value) ×100 (%).
The results are shown in Table 1.
(4) Residual solvent concentration
The residual solvent concentration of the antiglare layer of the antiglare film obtained was measured.
Specifically, the residual solvent concentration in the antiglare layer was measured by heating at 120℃for 20 minutes using a gas chromatograph (device name "GC-2010", manufactured by Shimadzu corporation) using nitrogen as a carrier gas and a column oven (column oven).
The results are shown in Table 1.
(5) 60 degree gloss (glossiness)
The obtained antiglare film was measured for 60 ° gloss of the surface of the antiglare layer by using a gloss meter (VG 7000, manufactured by japan electrochromic co.) in accordance with JIS Z8741.
The results are shown in Table 1.
(6) Total light transmittance
The obtained antiglare film was subjected to blank correction by a haze meter (NDH 5000, manufactured by japan electric color industry corporation) according to JIS K7361-1, and then irradiated with light from the antiglare layer side, and the total light transmittance (%) was measured.
The results are shown in Table 1.
(7) Hardness of
The pencil hardness of the antiglare layer surface in the antiglare film obtained was measured according to JIS K5600 using a pencil scratch hardness tester (product name "No.553-M", manufactured by An Tian Sema-ku-ji).
The results are shown in Table 1.
(8) Scratch resistance
Scratch resistance of the antiglare layer surface in the antiglare film obtained was evaluated.
That is, according to JIS K5600-5-10, a steel wool of #0000 was used at 250g/cm 2 Is rubbed back and forth against the antiglare layer surface 10 times with a sliding distance of 10 cm. Then, whether or not the surface of the antiglare layer was damaged was visually confirmed under a 3-wavelength fluorescent lamp, and evaluation was performed according to the following criteria.
O: no change in the appearance of the antiglare layer was confirmed (the number of confirmed damaged bars was 0);
x: the change in the appearance of the antiglare layer was confirmed (the number of lesions confirmed was 1 or more).
The results are shown in Table 1.
(9) Reflectivity of
The anti-glare film of example 4 provided with an anti-reflection layer was measured for reflectance using a UV-VIS-NIR meter (UV-3600, manufactured by Shimadzu corporation).
The reflectance was 2.4%.
(10) Antiglare property
The surfaces of the antiglare films obtained in examples and comparative examples on the substrate layer side were bonded to a blackboard using an adhesive, and samples for measurement were obtained. For this measurement sample, a 3-wavelength fluorescent lamp was turned on above the surface on the antiglare layer side (the surface opposite to the substrate layer side), and the light was reflected by this surface.
The reflected light was visually observed, and the antiglare property was evaluated according to the following criteria.
The results are shown in Table 1.
And (3) the following materials: the identified outline of the fluorescent lamp is blurred.
And (2) the following steps: the outline of the identified fluorescent lamp is slightly blurred.
X: the outline of the identified fluorescent lamp is completely obscured.
(11) Glare light
The surfaces of the antiglare films obtained in examples and comparative examples on the substrate layer side were laminated in contact with the display surface of a tablet terminal (product name "NEW iPad (registered trademark)", resolution: 264ppi, manufactured by apple corporation). Then, in a state where the flat panel terminal was displayed in a full-face green state (RGB values (R, G, B) =0, 255, 0), the presence or absence of glare was visually confirmed. Based on the results, glare was evaluated according to the following criteria.
The results are shown in Table 1.
And (3) the following materials: no glare was confirmed at all.
And (2) the following steps: glare was slightly confirmed.
X: glare was confirmed over the entire surface.
TABLE 1
As can be seen from table 1: the antiglare films of the present invention of examples 1 to 6 are excellent in optical characteristics, hardness, scratch resistance and antiglare properties, and have a low rate of change in haze with time and less glare.
On the other hand, the antiglare film of comparative example 1 has a surface roughness of less than 80nm, and thus has low antiglare properties.
The antiglare film of comparative example 2 uses an acrylic filler as the filler, and therefore has a high residual solvent concentration and a large change in haze.
The antiglare film of comparative example 3 in which the dispersing agent was not used was less likely to segregate the filler, had a smaller surface roughness, and had a lower antiglare property than the antiglare film of example 3 in which the dispersing agent was used.
Industrial applicability
As described in detail above, the antiglare film of the present invention is expected to contribute significantly to the improvement of visibility of a high-definition display, while maintaining excellent antiglare properties and effectively suppressing occurrence of white unevenness or glare.

Claims (6)

1. An antiglare film, characterized in that: which is an antiglare film having a base material layer and an antiglare layer,
the antiglare layer comprises a composition (A): an active energy ray-curable resin (B) component: a filler containing an inorganic component and (C) a component: a layer formed from the composition for forming an antiglare layer of the dispersant,
The surface of the antiglare layer has an arithmetic average roughness (Ra) of 80nm or more,
the antiglare film has a transmission clarity of 400 or more,
the antiglare film has a haze change rate of 5% or less on the surface of the antiglare layer after being left at 70 ℃ for 7 days.
2. The antiglare film according to claim 1, wherein the composition for forming an antiglare layer does not contain an organic filler, or the content of the organic filler is more than 0 parts by mass and less than 5 parts by mass relative to 100 parts by mass of the component (a).
3. The antiglare film according to any one of claims 1 or 2, wherein the antiglare layer has a surface haze value of 3% or more and 30% or less.
4. The antiglare film according to any one of claims 1 to 3, wherein the antiglare layer has a 60 ° gloss value of 20 or more.
5. The antiglare film according to any one of claims 1 to 4, wherein the component (B) is a shaped filler containing an inorganic component.
6. The antiglare film according to any one of claims 1 to 5, wherein the antiglare layer has an antireflection layer on a side opposite to the base layer.
CN202310052301.8A 2022-03-29 2023-02-02 Antiglare film Pending CN116893454A (en)

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JPH033652A (en) 1989-05-31 1991-01-09 Tokyo Electric Co Ltd Stepping motor
JP4082965B2 (en) 2002-08-28 2008-04-30 リンテック株式会社 Anti-glare hard coat film
JP2006227353A (en) * 2005-02-18 2006-08-31 Fuji Photo Film Co Ltd Coating film, optical film, antireflection film, polarizing plate, and display device using them
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JP2010204479A (en) 2009-03-04 2010-09-16 Nitto Denko Corp Glare-proof hard coat film and polarizing plate using the same, and image display device
JP5308215B2 (en) 2009-03-31 2013-10-09 日本製紙株式会社 Anti-glare hard coat film
JP5412390B2 (en) * 2009-09-11 2014-02-12 株式会社日本触媒 Method for producing scandia-stabilized zirconia sheet for solid oxide fuel cell and scandia-stabilized zirconia sheet for solid oxide fuel cell
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JP2015132744A (en) 2014-01-15 2015-07-23 株式会社きもと Antiglare film
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