CN104204864B - Antireflection film - Google Patents
Antireflection film Download PDFInfo
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- CN104204864B CN104204864B CN201380014317.4A CN201380014317A CN104204864B CN 104204864 B CN104204864 B CN 104204864B CN 201380014317 A CN201380014317 A CN 201380014317A CN 104204864 B CN104204864 B CN 104204864B
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- antireflection film
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- refractive index
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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
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- General Physics & Mathematics (AREA)
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- Surface Treatment Of Optical Elements (AREA)
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- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
The present invention provides a kind of antireflection film, in the antireflection film, not to the additional tone of reflected light from positive outdoor light, in addition, can also reduce the tone of the reflected light from the incident outdoor light of various angles.Specifically, such antireflection film is provided, it is characterized in that, for in the region as the wavelength 380nm to 780nm of the illuminant-C of CIE standard light source and incidence angle be 5 ° to 50 ° in the range of any incident light for, the form and aspect of the reflected light under the incidence angle conditioned reflex equal with angle of reflection are in CIE1976L*a*b*3≤a is met in color space*≦3、‑5≦b*≦5。
Description
Technical field
Content disclosed in this specification is related to prevent outdoor light to be reflected on the display screen of display device etc.
Antireflection film designed by purpose, the display device with the antireflection film, the Polarizer with the antireflection film and touch surface
Plate.This kind of antireflection panel suitably sets and used on a display screen of a display apparatus.
Background technology
Generally, no matter indoors or outdoor application, display can be all used under conditions of the reflection such as light out of doors.The family
The incident lights such as UV light are by regular reflection on display surface etc., and resulting reflected image is mixed with display image, from
And make screen display Quality Down.Therefore, it is necessary to assign display surface etc. anti-reflective function, and require to realize antireflection
Function high performance.
Usual anti-reflective function is obtained by forming the anti-reflection layer of sandwich construction on transparent support, wherein institute
It is to utilize the high refractive index layer and the repetitive structure of low-index layer being made up of transparent materials such as metal oxides to state sandwich construction
Formed.The anti-reflection layer that these sandwich constructions are constituted can utilize chemical vapor deposition method (CVD) or physical vapor deposition (PVD) so
Dry type membrane formation process formed.For in the case of using dry type membrane formation process formation anti-reflection layer, with can critically control
Advantage as low-index layer, the thickness of high refractive index layer, on the other hand, due to carrying out film forming in a vacuum, therefore is present
The problem of that productivity ratio is low, be unsuitable for largely producing such.In addition, as the forming method of antireflection film, using using masking liquid
Wet type membrane formation carry out the production of antireflection film and attract attention, this production can large area, continuous production and low
Cost.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-256346 publications
The content of the invention
Problems to be solved by the invention
Mobile terminal is popularized in recent years, and operates the situation of image display device in itself to increase in hand
Plus.In addition, for outdoor between daytime, due in the outdoor light more stronger than indoor service condition, therefore demand
A kind of antireflection film for the antiradar reflectivity that will not also damage visibility out of doors.
In addition, when being applied to be fixedly installed the image display device of type by antireflection film, it is come from admittedly with reducing mostly
Premised on the reflected light for determining light source.This means the invariable incident angle of outdoor light.On the other hand, in the situation of mobile terminal
In, use and operated in hand out of doors due to existing, therefore outdoor light is incident from various angles, spectator is various in addition
The situation of angle observation display also compares many.Thus, in mobile terminal application antireflection film, not only need research
From positive reflected light, in addition it is also necessary to study the tone of the reflected light, particularly reflected light to the light source of all incidence angles.Current shape
Under condition, most of antireflection films design to be corresponding with the image display device of type is fixedly installed, therefore do not contemplate outdoor light
Incidence angle and angle of reflection change film be designed to problem.
The content first purpose disclosed in this specification is there is provided antireflection film, the dress of the display with the antireflection film
Put, Polarizer and touch panel with the antireflection film, wherein the reflectance coating reduction the form and aspect from positive reflected light
While, also reduce the form and aspect of the reflected light from the incident outdoor light of various angles.
The method solved the problems, such as
By providing antireflection film described later, the image display device with the antireflection film or liquid crystal display device, tool
There is the Polarizer of the antireflection film to reach above-mentioned purpose.
I.e., in one embodiment, the antireflection film is characterised by, in the illuminant-C as CIE standard light source
Wavelength 380nm to 780nm region in and incidence angle be 5 ° to 50 ° in the range of any incident light for its incidence angle
The form and aspect of reflected light under the conditioned reflex equal with angle of reflection are in CIE1976L*a*b*- 3≤a is met in color space*≦
3、-5≦b*≦5。
There is provided a kind of antireflection film in the first embodiment, it is characterised in that the visual sense on the antireflection film surface
Average reflectance is more than 0.05% in less than 1.0% scope.
In other embodiment, it is possible to provide the display device with above-mentioned antireflection film.
In the case of this specification, used " display device " this term refers to be used for the person's of being used for sense of vision
The terminal installation of output, the display device (such as) mirrors image on its display screen (display screen).It is used as this
Class display device, can especially enumerate liquid crystal display (LCD), CRT monitor, display of organic electroluminescence (ELD), plasma
Display (PDP), surface field display (SED), Field Emission Display (FED) etc., but it is not limited to these display devices.
In other embodiment, it is possible to provide the Polarizer with above-mentioned antireflection film.
In other embodiment, it is possible to provide the touch panel with above-mentioned antireflection film.
Invention effect
By the way that antireflection film as described above is arranged at into image display device or liquid crystal display device, antireflection can be made
Visual sense average reflectance at film surface can be being reduced to from just more than 0.05% in less than 1.0% scope
While the reflected light in face additional tone, reduce to the additional tone of reflected light from the incident outdoor light of various angles.In addition,
By the way that the Polarizer using the antireflection film to be arranged to the surface of liquid crystal display device or by the way that the antireflection film is used
In touch panel, it is also possible to obtain same effect.
Brief Description Of Drawings
Fig. 1 is the constructed profile of the antireflection film of first embodiment.
Fig. 2 is the dependence of angle for the form and aspect for showing the reflected light in the antireflection film that is made in embodiment and comparative example
Figure.
Embodiment
Below, the exemplary antireflection film disclosed in this specification is described in detail.
Antireflection film disclosed in this specification, for the wavelength 380nm in the illuminant-C as CIE standard light source extremely
For in 780nm region and incidence angle is any incident light in the range of 5 ° to 50 °, incidence angle and angle of reflection are equal
Conditioned reflex under reflected light form and aspect in CIE1976L*a*b*- 3≤a is met in color space*≦3、-5≦b*≦5.Cause
This, even if in the case that the incident angle of light changes out of doors, the form and aspect of the reflected light of antireflection film are also neutral colour.
In addition, for the incident light that incidence angle is 5 °, angle of reflection exists for the form and aspect of the reflected light in the range of -5 ° to -80 °
CIE1976L*a*b*- 3≤a is met in color space*≦3、-5≦b*≤ 5, thus, only change the sight relative to antireflection film
The form and aspect of reflected light when examining angle turn into neutrality, therefore preferably meet this condition.
If in the region as the wavelength 380nm to 780nm of the illuminant-C of CIE standard light source and incidence angle
For arbitrary incident light in the range of 5 ° to 50 °, the color of the reflected light under the incidence angle conditioned reflex equal with angle of reflection
In CIE1976L*a*b*△ a are met in color space*≦3、△b*≤ 3 (wherein, △ a*=a*max-a*Min, △ b*=
b*max-b*Min, a*Max and a*Min represents a respectively*The maximum and minimum value of value, and b*Max and b*Min distinguishes
Represent b*The maximum and minimum value of value), then the change of form and aspect when incidence angle and the angle of angle of reflection change can diminish,
Therefore this condition is preferably met.The amplitude of form and aspect change is smaller more preferred, therefore more preferably △ a*≦1、△b*≦1。
In one embodiment, the visual sense average reflectance of antireflection film is less than 1.0% preferably more than 0.05%
In the range of.
(layer of antireflection film is constituted)
The layer that reference picture 1 describes antireflection film in detail is constituted.The antireflection film that this example is provided is taken in transparent support
Upper coating hard conating, stacks gradually the sandwich construction of high refractive index layer and low-index layer afterwards.Now, high index of refraction is not considered
The number of plies of layer and low-index layer.Wherein, in the case where considering cost and certified products productivity ratio etc., as shown in figure 1, this example
Antireflection film (10) if being coated with hard conating (12) on transparent support (11), and then be coated with thereon high refractive index layer
(13), and in stacking low-index layer (14) thereon, then it is suitable as antireflection film.
Now, by adjusting the thickness and refractive index of each layer, a of the form and aspect parameter as reflected light can be made*Value, b*Value
Meet desired value.For example, it is preferable that, the thickness of hard conating is adjusted to less than more than 3.0 μm 10 μm of scope, the folding of hard conating
The rate of penetrating is adjusted to less than more than 1.48 1.53 scope, and the thickness of high refractive index layer is adjusted to more than 230nm below 260nm model
Enclose, the adjustable refractive index of high refractive index layer is less than more than 1.58 1.64 scope, the thickness of low-index layer is adjusted to 115nm
Below above 135nm scope, the refractive index of low-index layer is to make visual sense average reflectance be less than more than 0.05% 1.0%
In the range of refractive index (such as refractive index 1.30).
As hard conating as described above and the coating method of high refractive index layer and low-index layer, spraying can be enumerated
Existing coating methods such as method, silk screen print method, scraping blade method, woodburytype, die coating method, spraying process etc., are not particularly limited.
In view of the optical characteristics such as the transparency and the refractive index of light, impact resistance, heat resistance, durability etc. are further contemplated in addition
Transparent support in all physical properties, the antireflection film of this example is prepared by various organic polymers.It is used as organic high score
Son, can enumerate but be not limited to：The polyolefins such as polyethylene, polypropylene, polyethylene terephthalate, poly- naphthalenedicarboxylic acid second two
The Polyesters such as alcohol ester, cellulose-based, 6- nylon, 6, the 6- nylon etc. such as tri acetyl cellulose, diacetyl cellulose, cellophane
It is polyamide-based, the acrylic acid series such as polymethyl methacrylate, polystyrene, polyvinyl chloride, polyimides, polyvinyl alcohol, poly- carbon
Acid esters, ethylene-vinyl alcohol etc..Preferably, the organic polymer is polyethylene terephthalate, TAC
Element, makrolon, polymethyl methacrylate.It is further preferred that the organic polymer is tri acetyl cellulose, this is due to
Its birefringence is small, transparent good, therefore is applicable to various displays.
And then, by adding known additive into these organic polymers, such as ultra-violet absorber, infrared ray are inhaled
Agent, plasticizer, lubricant, colouring agent, antioxidant, fire retardant etc. are received, various functions can be assigned to transparent support.Separately
Outside, transparent support can be by a kind in above-mentioned organic polymer or mixture of more than two kinds or polymer system
It is standby or make the support of multiple layer stackups.
It should be noted that the thickness of transparent support in less than 200 μm of scope, more preferably exists preferably more than 20 μm
In less than more than 20 μm 80 μm of scope.
In one embodiment, as the hard conating in antireflection film, acrylic material can be used.As this third
Olefin(e) acid based material, can be used：The simple function of the acrylic or methacrylic acid esters of polyalcohol etc, 2 functions or 3 functions with
On (methyl) acrylate compounds, by diisocyanate and hydroxy ester etc. of polyalcohol and acrylic or methacrylic acid
Polyfunctional carbamate (methyl) acrylate compounds of synthesis.In addition, in addition to these compounds, being used as ionization
Radial type material, can also use the polyether resin with acrylic ester functional group, polyester resin, epoxy resin, alkyd
Resin, spiral shell acetal resin, polybutadiene, polymercaptan vistanex etc..
It should be noted that in this manual, used " (methyl) acrylate " this term represents " acrylic acid
Both ester " and " methacrylate ".For example, " carbamate (methyl) acrylate " expression " urethane acrylates
Both ester " and " urethane methacrylate ".
As (methyl) acrylate compounds of simple function, for example, it can enumerate：(methyl) acrylic acid 2- hydroxy methacrylates,
(methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) n-butyl acrylate, (methyl) acrylic acid
Isobutyl ester, (methyl) tert-butyl acrylate, (methyl) glycidyl acrylate, acryloyl morpholine, NVP,
Acrylic acid tetrahydro furfuryl ester, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) isobomyl acrylate
Base ester, (methyl) Isodecyl base ester, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl)
Aliphatic acrylate, (methyl) stearyl acrylate acyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- ethyoxyls
Ethyl ester, (methyl) acrylic acid 3- methoxybutyls, (methyl) acrylic acid ethyl carbitol ester, phosphoric acid (methyl) acrylate, ring
Oxidative ethane modified phosphate (methyl) acrylate, (methyl) acrylic acid phenoxy group ester, ethylene-oxide-modified (methyl) acrylic acid benzene
It is epoxide ester, epoxy pronane modification (methyl) acrylic acid phenoxy group ester, (methyl) nonylphenol acrylate phenol ester, ethylene-oxide-modified
(methyl) nonylphenol acrylate phenol ester, epoxy pronane modification (methyl) nonylphenol acrylate phenol ester, methoxyl group diethylene glycol (DEG) (methyl)
Acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, MPEG (methyl) acrylate, phthalic acid 2-
(methyl) acryloyl-oxyethyl -2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, 2- (methyl) propylene
Trimethylammonium hydrogen phthalic acid ester, 2- (methyl) acryloxypropyl hydrogen phthalic acid ester, 2- (methyl) acryloyl
Epoxide propyl group hexahydrophthalic acid ester, 2- (methyl) acryloxypropyl tetrahydrophthalic acid ester, (methyl) acrylic acid
Dimethylaminoethyl, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro propyl ester,
(methyl) acrylic acid octafluoro propyl ester, (methyl) acrylic acid octafluoro propyl ester, derived from 2- adamantane and adamantane glycol have one
Adamantane derivative list (methyl) acrylate such as the adamantyl acrylate of first single (methyl) acrylate etc., but be not limited to
This.
As (methyl) acrylate compounds of 2 function, for example, it can enumerate：Ethylene glycol two (methyl) acrylic acid
Ester, diethylene glycol (DEG) two (methyl) acrylate, butanediol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, nonyl two
Alcohol two (methyl) acrylate, ethoxylation hexylene glycol two (methyl) acrylate, propoxylation hexylene glycol two (methyl) propylene
Acid esters, diethylene glycol (DEG) two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylic acid
Ester, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl)
Two (the first such as acrylate, tripropylene glycol two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate
Base) acrylate etc., but not limited to this.
As (methyl) acrylate compounds more than 3 function, for example, it can enumerate：Trimethylolpropane tris (first
Base) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl)
Three (the first such as acrylate, three 2- hydroxyethyls isocyanuric acid ester three (methyl) acrylate, glycerine three (methyl) acrylate
Base) acrylate；Pentaerythrite three (methyl) acrylate, bipentaerythrite three (methyl) acrylate, double trihydroxy methyls third
(methyl) acrylate compounds of 3 functions such as alkane three (methyl) acrylate；And pentaerythrite four (methyl) acrylate,
Double trimethylolpropane four (methyl) acrylate, bipentaerythrite four (methyl) acrylate, bipentaerythrite five (methyl)
Acrylate, double trimethylolpropane five (methyl) acrylate, bipentaerythrite six (methyl) acrylate, double trihydroxy methyls
Multifunctional (methyl) acrylate compounds more than 3 functions such as propane six (methyl) acrylate, and by these (methyl)
Multifunctional (methyl) acrylate compounds after part alkyl or the 6-caprolactone substitution of acrylate etc., but be not limited to
This.
By the physics of formed hard conating can be obtained with the molecular weight of design, molecular structure and easily
The balance of property, therefore in acrylic material, preferably use polyfunctional carbamate acrylate.Carbamate
Acrylate can be obtained by reacting polyalcohol, multicomponent isocyanate and hydroxy acryl acid ester.Specifically, it can arrange
Lift：Chemical company of common prosperity society UA-306H, UA-306T, UA-306I etc.；Synthesis chemical company of Japan UV-1700B, UV-
6300B, UV-7600B, UV-7605B, UV-7640B, UV-7650B etc.；Chemical company of Xin Zhong villages U-4HA, U-6HA, UA-
100H, U-6LPA, U-15HA, UA-32P, U-324A etc.；Daicel UCB. S.A. (BE) Bruxelles Belgium Ebecryl-1290, Ebecryl-
1290K, Ebecryl-5129 etc.；Gen Shang industrial groups UN-3220HA, UN-3220HB, UN-3220HC, UN-3220HS etc.,
But not limited to this.
In addition, as ionizing radiation line section bar material, the polyether resin with acrylic ester functional group can be used, gathers
Ester resin, epoxy resin, alkyd resin, spiral shell acetal resin, polybutadiene, polymercaptan vistanex etc., and it is not special
The material is not limited.
Further, since ionizing radiation constrictive type material can be cured by ultraviolet, therefore in hard conating formation coating fluid
Middle addition Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, as long as the material of free radical, example are produced during ultraviolet irradiation
Acetophenones, benzoin class, benzophenone, phosphinoxides, ketal class, Anthraquinones, thioxanthene ketone class can such as be used.In addition,
Relative to 100 parts by weight ionizing radiation curing type materials, the addition of Photoepolymerizationinitiater initiater is the weight of 0.1 parts by weight~10
Part, the parts by weight of preferably 1 parts by weight~7, the parts by weight of more preferably 1 parts by weight~5.
In addition, as needed, solvent and various additives can be added in hard conating formation coating fluid.As solvent,
In view of coating appropriateness etc., can suitably it be selected from following solvent：The aromatic hydrocarbons such as toluene, dimethylbenzene, hexamethylene, cyclohexyl benzene
Class；The hydro carbons such as n-hexane；Butyl oxide, dimethoxymethane, dimethoxy-ethane, diethoxyethane, expoxy propane, bis- Evil
The ethers such as alkane, dioxolane, trioxanes, tetrahydrofuran, methyl phenyl ethers anisole and phenetole；And methyl iso-butyl ketone (MIBK), methyl butyl ketone,
Acetone, MEK, metacetone, dipropyl ketone, DIBK, cyclopentanone, cyclohexanone, methyl cyclohexanone and methyl cyclohexanone
Deng ketone；And Ethyl formate, propyl formate, formic acid n-pentyl ester, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate,
The esters such as n-amyl acetate and gamma-butyrolacton；Further, methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate etc.
Dioxane；The alcohols such as methanol, ethanol, isopropanol, butanol.Alternatively, it is also possible to add surface conditioner, refraction into coating fluid
Rate conditioning agent, adhesiveness modifier, curing agent etc. are used as additive.
Alternatively, it is also possible to hard conating formation with adding other additives in coating fluid.As this kind of additive, for example may be used
Enumerate defoamer, levelling agent, antioxidant, ultra-violet absorber, light stabilizer, polymerization inhibitor etc..
In one embodiment, as the high refractive index layer in antireflection film, it can use even by metal alkoxide, silane
Join that any one or more binding agent combined in agent, organic resin is constituted and be added with the binding agent
The material of metal particle or organic fine particles.According to the refractive index of required organic system coating, these compositions can be suitably selected, and
Refractive index is adjusted by the combination of material, mixing ratio etc..For example, as high-index material, can be used Ti, Ta, Zr, In,
The metal particle such as Zn etc. metal alkoxide or titanium oxide, zirconium oxide, zinc oxide, indium oxide.
Material as retarder thinner is not particularly limited.However, it is contemplated that the stability of composition, to hard conating
Wetability, volatility etc., as the retarder thinner utilized, can be enumerated：Methanol, ethanol, isopropanol, butanol, 2- methoxyl group second
The alcohols such as alcohol；The ketones such as acetone, MEK, methyl iso-butyl ketone (MIBK)；The esters such as methyl acetate, ethyl acetate, butyl acetate；Two is different
The ethers such as propyl ether；The glycols such as ethylene glycol, propane diols, hexylene glycol；Ethyl cellosolve, butyl cellosolve, ethyl carbitol, fourth
The glycol ethers such as base carbitol；The aliphatic hydrocarbons such as hexane, heptane, octane；Halogenated hydrocarbons；The aromatic hydrocarbons such as benzene,toluene,xylene；N-
Methyl pyrrolidone, dimethylformamide etc..In addition, solvent not only can be used a kind, mixture of more than two kinds can also be used as
Use.
As the binder matrix formation material for forming high refractive index layer, ionizing radiation curing type material is included.
As ionizing radiation curing type material, it can use and contained in hard conating formation coating fluid solidify as ionizing radiation
Acrylic material shown in section bar material.As acrylic material, the acrylic acid or methyl-prop of such as polyalcohol can be used
Multifunctional or polyfunctional (methyl) acrylate compounds of olefin(e) acid ester etc, by diisocyanate and polyalcohol and propylene
Polyfunctional carbamate (methyl) acrylate compounds synthesized by hydroxy ester of acid or methacrylic acid etc..In addition,
In addition, as ionizing radiation line section bar material, the polyether resin with acrylic ester functional group, polyester tree be it is also possible to use
Fat, epoxy resin, alkyd resin, spiral shell acetal resin, polybutadiene, polymercaptan vistanex etc..
In one embodiment, as the low refractive particles in the low-index layer in antireflection film, can use by
LiF, MgF, 3NaFAlF or AlF (refractive index is 1.4) or Na3AlF6Low refractive materials such as (ice crystal, refractive indexes 1.33)
The low-refraction particle of composition.Further, it may be preferred that using the particle inside particle with space.There is space for particle inside
Particle for, due to gap can be set to the refractive index (≒ 1 of air), therefore can be made with low-down folding
Penetrate the low-refraction particle of rate.Specifically, the internal low refractive index silica particle with space can be used.
As low-refraction particle used in low-index layer, its particle diameter is preferably more than 1nm below 100nm.Work as grain
When footpath is more than 100nm, because Rayleigh scattering causes light by strong reflection, there is low-index layer and occur albefaction so as to antireflection film
The tendency that the transparency declines.On the other hand, when particle diameter is less than 1nm, it can produce because in low-index layer caused by particle aggregation
The problems such as particle is uneven.
As the binder matrix formation material for forming low-index layer, ionizing radiation curing type material is included.
As ionizing radiation curing type material, it can use and contained in hard conating formation coating fluid solidify as ionizing radiation
Acrylic material shown in section bar material.As acrylic material, the acrylic acid or methyl-prop of such as polyalcohol can be used
Multifunctional or polyfunctional (methyl) acrylate compounds of olefin(e) acid ester etc, by diisocyanate and polyalcohol and propylene
Polyfunctional carbamate (methyl) acrylate compounds synthesized by hydroxy ester of acid or methacrylic acid etc..In addition,
In addition, as ionizing radiation line section bar material, the polyether resin with acrylic ester functional group, polyester tree be it is also possible to use
Fat, epoxy resin, alkyd resin, spiral shell acetal resin, polybutadiene, polymercaptan vistanex etc..In addition, these resins
It is also possible by the material of appropriate fluorination.
Embodiment
Below, embodiment and comparative example are further illustrated, but the embodiment is for illustrative purposes, the present invention is not limited
In following embodiments.Preparation example 1 described later to the hard conating formation coating fluid, height that preparation example 3 is respectively used in embodiment 1 is rolled over
Penetrate rate layer formation coating fluid, the preparation example of low-index layer formation coating fluid.Using these preparation examples, according to formation example 1
To the order shown in 3, the antireflection film described in embodiment 1 is made.In addition, by changing manufacturing conditions described later come comparison
Example 1 to comparative example 7 film.
Embodiment 1
The ＞ of ＜ preparation examples 1
(hard conating formation coating fluid)
Use the mass parts of bipentaerythrite triacrylate 25, the mass parts of tetramethylol methane tetraacrylate 25, carbamic acid
The mass parts of ester acrylate 50, Irgacure184 (BASF AG's system (Photoepolymerizationinitiater initiater)) 5 mass parts, are dissolved them in
In the MEK of 118 mass parts coating fluid is formed so as to prepare hard conating.
The ＞ of ＜ preparation examples 2
(high refractive index layer formation coating fluid)
Use the mass parts of urethane acrylate 3, zirconia particles dispersion liquid (solids content 25%, solvent：Methyl
Isobutyl ketone) 18 mass parts, Irgacure184 (BASF AG's system (Photoepolymerizationinitiater initiater)) 0.1 mass parts, they are used into 79 weights
The methyl iso-butyl ketone (MIBK) dilution of amount part forms coating fluid so as to prepare high refractive index layer.
The ＞ of ＜ preparation examples 3
(low-index layer formation coating fluid)
By porous silica particle dispersion liquid (solids content 20%, solvent：Methyl iso-butyl ketone (MIBK)) 18 mass parts, EO change
Property double pentaerythritol methacrylate (trade name：DPEA-12, Japanese chemical drug system) 1.99 mass parts, (BASF is public for polymerization initiator
Department's system, trade name：Irgacure184) 0.07 mass parts, TSF4460 (trade name, Momentive Performance
Materials (Co., Ltd.) makes：Alkyl, polyether modified silicon oil) 0.20 mass parts are dilute with the parts by weight of solvent methylisobutyl ketone 80
Release to prepare low-index layer formation coating fluid.
[formation of the Rotating fields of antireflection film]
＜ formation examples 1 ＞
(formation of hard conating)
In tri acetyl cellulose film (Fuji's FILM systems：60 μm of thickness) one side on coating hard conating is formationed be coated with
Liquid, is dried 60 seconds at 80 DEG C with baking oven, after drying, uses ultraviolet lamp (FUSION UV SYSTEM JAPAN, light
Source H valves), by with dose of radiation 300mJ/m2Ultraviolet irradiation is carried out to form the transparent hard-coating layer that dry film thickness is 5 μm.
The refractive index of hard conating is 1.52.
＜ formation examples 2 ＞
(formation of high refractive index layer)
High refractive index layer formation coating fluid is coated with the hard conating formed by the above method so that dried film
Thickness is 250nm.Ultraviolet lamp (FUSION UV SYSTEM JAPAN, light source H valve) is used for dose of radiation
192mJ/m2Carrying out ultraviolet irradiation makes its solidification form high refractive index layer.The refractive index of high refractive index layer is 1.60.
＜ formation examples 3 ＞
(formation of low-index layer)
Low-index layer formation coating fluid is coated with the high refractive index layer formed by the above method to cause after drying
Thickness be 120nm.Ultraviolet lamp (FUSION UV SYSTEM JAPAN, light source H valve) is used for radiation agent
Measure 192mJ/m2Carrying out ultraviolet irradiation makes its solidification so as to form low-index layer, thus makes antireflection film.Low-refraction
The refractive index of layer is 1.30.
[on comparative example]
With the mass parts of urethane acrylate 3 of preparation example 2, zirconia particles dispersion liquid (solids content 20%, it is molten
Agent：Methyl iso-butyl ketone (MIBK)) 18 mass parts, Irgacure184 (BASF AG's system (Photoepolymerizationinitiater initiater)) 0.1 mass parts, methyl
On the basis of the parts by weight of isobutyl ketone 79, the main amount for changing methyl iso-butyl ketone (MIBK) carrys out comparison example 2 to the antireflection of comparative example 3
Film, in addition, mainly the amount of change urethane acrylate and zirconia particles dispersion liquid carrys out comparison example 4 to comparative example
5 antireflection film.
With porous silica particle dispersion liquid (solids content 20%, solvent of preparation example 3：Methyl iso-butyl ketone (MIBK)) 18 matter
Measure part, EO and be modified double pentaerythritol methacrylate (trade name：DPEA-12, Japanese chemical drug system) 1.99 mass parts, polymerization trigger
Agent (BASF AG's system, trade name：Irgacure184) 0.07 mass parts, TSF4460 (trade name, Momentive
Performance Materials (Co., Ltd.) make：Alkyl, polyether modified silicon oil) 0.20 mass parts, methyl iso-butyl ketone (MIBK) 80
On the basis of parts by weight, the main amount for changing methyl iso-butyl ketone (MIBK) carrys out comparison example 6 to the antireflection film of comparative example 7.
Illustrate the more specifically content of comparative example 1 to 7 below.
The ＞ of ＜ comparative examples 1
It is not coated with forming the high refractive index layer shown in example 2 on hard conating in this example, but is coated with hard conating low
Index layer.
The ＞ of ＜ comparative examples 2
It is coated in this example so that the dried thickness of the high refractive index layer for forming example 2 is 290nm.Herein, it will make
High refractive index layer formation coating fluid is prepared by 74 parts by weight for the methyl iso-butyl ketone (MIBK) of solvent.
The ＞ of ＜ comparative examples 3
Being coated in this example must make the dried thickness of high refractive index layer to form example 2 be 190nm.Herein, it will make
High refractive index layer formation coating fluid is prepared by 84 parts by weight for the methyl iso-butyl ketone (MIBK) of solvent.
The ＞ of ＜ comparative examples 4
The urethane acrylate for the high refractive index layer that will form example 2 in this example is set to 1.5 parts by weight, will aoxidized
Particulate zirconia dispersion liquid is set to 24 parts by weight, and is coated so that the dried refractive index for forming film is 1.66.
The ＞ of ＜ comparative examples 5
The urethane acrylate for the high refractive index layer that will form example 2 in this example is set to 6 parts by weight, by zirconium oxide
Particle dispersion liquid is set to 6 parts by weight, and is coated so that the dried refractive index for forming film is 1.56.
The ＞ of ＜ comparative examples 6
It is coated in this example so that the dried thickness of the low-index layer for forming example 3 is 140nm.Herein, it will make
Low-index layer formation coating fluid is prepared by 75 parts by weight for the methyl iso-butyl ketone (MIBK) of solvent.
The ＞ of ＜ comparative examples 7
It is coated in this example so that the dried thickness of the low-index layer for forming example 3 is 110nm.Herein, it will make
Low-index layer formation coating fluid is prepared by 85 parts by weight for the methyl iso-butyl ketone (MIBK) of solvent.
For the content being not particularly illustrated, the preparation method in above-mentioned comparative example is using the operation in embodiment 1 as standard.
[evaluation of antireflection film]
For the antireflection film obtained by embodiment 1 and comparative example 1 are into comparative example 7, commented using the following method
Valency.
(visual sense average reflectance)
For the low-refraction layer surface of resulting antireflection film, using automatic spectrophotometer (Hitachi's system,
U-4100), spectral reflectance during 5 ° of incidence angle is determined.In addition, according to JlSR3106 from resulting spectral reflectance curve
Obtain visual sense average reflectance.It should be noted that as in the tri acetyl cellulose film of transparent support when determining, not
Formed in the one side of low-index layer and be coated with delustring blacking to carry out antireflection process.
(form and aspect of reflected light)
For the low-refraction layer surface of resulting antireflection film, using automatic spectrophotometer (Hitachi's system,
U-4100), spectral reflectance during 5 ° of incidence angle is determined, the color of reflected light is obtained according to resulting spectral reflectance curve
Phase.It should be noted that being formed without low-index layer as in the tri acetyl cellulose film of transparent support when determining
Face on coating delustring blacking so as to carrying out antireflection process.
(dependence of angle of the form and aspect of reflected light)
On the low-refraction layer surface of resulting antireflection film, using automatic spectrophotometer (Hitachi's system,
U-4100), in incidence angle and angle of reflection under the same conditions, determine incidence angle be 5 ° to 50 ° (5 °, 10 °, 20 °, 30 °, 40 ° and
50 °) when spectral reflectance, the form and aspect of reflected light are obtained according to resulting spectral reflectance curve.It should be noted that surveying
Timing is coated with delustring black as in the tri acetyl cellulose film of transparent support on the face for be formed without low-index layer
Coating is so as to carry out antireflection process.
(evaluation result)
Evaluation result is shown in table 1, Fig. 2.It should be noted that in fig. 2, the end points of arrow is to be corresponding to incidence angle
The form and aspect result of 5 ° to 50 ° scopes, i.e. the starting point of arrow is the result of 5 ° of incidence angle, the terminal of arrow is the knot of 50 ° of incidence angle
Really.
[table 1]
According to the result of table 1, embodiment 1 shows good performance.In addition, according to Fig. 2 result, on reflected light
The dependence of angle of form and aspect, embodiment 1 also shows good performance.It should be noted that in fig. 2, shown in symbol 21
Tone range of the Range Representation to the neutral colour of the not additional tone of reflected light of antireflection film.Further, since comparative example 4 is not formed
Uniform film, therefore can not determine.In the above-described embodiment, antireflection film can make the visual sense average reflection on antireflection film surface
Rate reduces the form and aspect from positive reflected light more than 0.05% in less than 1.0% scope, comes while can reduce
From the form and aspect of the reflected light of the incident outdoor light of various angles.
Symbol description
10 ... antireflection films
11 ... transparent supports
12 ... hard conatings
13 ... high refractive index layers
14 ... low-index layers
21 ... to the hue range of the neutral colour of the not additional tone of reflected light of antireflection film
Claims (10)
1. a kind of antireflection film, it is characterised in that for the wavelength 380nm to 780nm in the illuminant-C as CIE standard light source
Region in and incidence angle be 5 ° to 50 ° in the range of any incident light for, the reflection equal with angle of reflection of its incidence angle
Under the conditions of reflected light form and aspect in CIE1976L*a*b*0.19≤a is met in color space*≦2.28、-0.65≦b*≦
4.66,
The antireflection film is the multilayer that hard conating, high refractive index layer and low-index layer are sequentially laminated with transparent support
Structure,
The thickness of the high refractive index layer more than 230nm below 260nm scope,
The thickness of the hard conating less than 10 μm of scope more than 3.0 μm, and the hard conating refractive index 1.48 with
Upper less than 1.53 scope.
2. a kind of antireflection film, it is characterised in that for the wavelength 380nm to 780nm in the illuminant-C as CIE standard light source
Region in and incidence angle be 5 ° to 50 ° in the range of any incident light for, the reflection equal with angle of reflection of its incidence angle
Under the conditions of reflected light form and aspect in CIE1976L*a*b*0.19≤a is met in color space*≦2.28、-0.65≦b*≦
4.66,
The antireflection film is the multilayer that hard conating, high refractive index layer and low-index layer are sequentially laminated with transparent support
Structure,
The refractive index of the high refractive index layer more than 1.58 less than 1.64 scope,
The thickness of the hard conating less than 10 μm of scope more than 3.0 μm, and the hard conating refractive index 1.48 with
Upper less than 1.53 scope.
3. antireflection film according to claim 1 or 2, it is characterised in that the visual sense on the antireflection film surface is averaged
Reflectivity is more than 0.05% in less than 1.0% scope.
4. antireflection film according to claim 1 or 2, it is characterised in that the thickness of the low-index layer 115nm with
Upper below 135nm scope.
5. antireflection film according to claim 1 or 2, it is characterised in that the refractive index of the low-index layer is to make to regard
It is the refractive index in less than more than 0.05% 1.0% scope to feel average reflectance.
6. antireflection film according to claim 1 or 2, it is characterised in that for the incident light that incidence angle is 5 °, angle of reflection
For the reflected light in the range of -5 ° to -80 ° form and aspect in CIE1976L*a*b*- 3≤a is met in color space*≦3、-5≦
b*≦5。
7. antireflection film according to claim 1 or 2, it is characterised in that in the illuminant-C as CIE standard light source
Wavelength 380nm to 780nm region in and incidence angle is incidence angle in the range of 5 ° to 50 ° for arbitrary incident light
The form and aspect of reflected light under the conditioned reflex equal with angle of reflection are in CIE1976L*a*b*Δ a is met in color space*≦3、Δ
b*≤ 3,
Wherein, Δ a*=a*max-a*Min, Δ b*=b*max-b*Min, a*Max and a*Min represents a respectively*The maximum of value
Value and minimum value, and b*Max and b*Min represents b respectively*The maximum and minimum value of value.
8. a kind of display device, with the antireflection film described in any one in claim 1~7.
9. a kind of Polarizer, with the antireflection film described in any one in claim 1~7.
10. a kind of touch panel, with the antireflection film described in any one in claim 1~7.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2012-067468 | 2012-03-23 | ||
| JP2012067468 | 2012-03-23 | ||
| PCT/JP2013/001937 WO2013140811A1 (en) | 2012-03-23 | 2013-03-21 | Anti-reflection film |
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| CN104204864B true CN104204864B (en) | 2017-09-05 |
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| KR (1) | KR102014569B1 (en) |
| CN (1) | CN104204864B (en) |
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| JP6561519B2 (en) * | 2015-03-20 | 2019-08-21 | 大日本印刷株式会社 | Antireflection film, display device using the antireflection film, and method for selecting antireflection film |
| JP6561520B2 (en) * | 2015-03-20 | 2019-08-21 | 大日本印刷株式会社 | Antireflection film, display device using the antireflection film, and method for selecting antireflection film |
| KR101956830B1 (en) | 2015-08-18 | 2019-03-12 | 주식회사 엘지화학 | Low refractive layer and anti-reflective film comprising the same |
| KR101807208B1 (en) | 2015-08-18 | 2017-12-08 | 주식회사 엘지화학 | Low refractive layer and anti-reflective film comprising the same |
| JP2018072807A (en) * | 2016-10-20 | 2018-05-10 | 日油株式会社 | Antiglare antireflection film and image display device having the same |
| CN106441126A (en) * | 2016-10-26 | 2017-02-22 | 电子科技大学 | Method and system for measuring optical film thicknesses based on reflectivity spectra |
| JP2018197829A (en) * | 2017-05-25 | 2018-12-13 | 日油株式会社 | Anti-glare anti-reflection film and image display device including the same |
| JP7100225B2 (en) * | 2017-08-02 | 2022-07-13 | 日東電工株式会社 | Anti-reflective film |
| JP7349235B2 (en) | 2017-10-10 | 2023-09-22 | 株式会社ダイセル | anti-reflection film |
| JP2019091023A (en) * | 2017-11-10 | 2019-06-13 | 住友化学株式会社 | Circularly polarizing plate |
| CN116299791A (en) * | 2018-03-02 | 2023-06-23 | 康宁公司 | Antireflective coatings and articles and methods of forming antireflective coatings and articles |
| WO2020218374A1 (en) * | 2019-04-23 | 2020-10-29 | パナソニックＩｐマネジメント株式会社 | Optical film laminate |
| JP7433779B2 (en) * | 2019-05-21 | 2024-02-20 | 日本ペイント・オートモーティブコーティングス株式会社 | Coated member and method for manufacturing coated member |
| JP6956909B2 (en) * | 2020-03-23 | 2021-11-02 | デクセリアルズ株式会社 | Optical laminates and articles |
| KR20240169130A (en) * | 2021-05-14 | 2024-12-02 | 가부시키가이샤 도판 도모에가와 옵티컬 필름 | In-vehicle reflection control film |
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| JP2012032661A (en) * | 2010-07-30 | 2012-02-16 | Fujifilm Corp | Laminate and optical film, production method for the same, polarizer plate, image display device, three dimensional image display system |
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| JP2004138662A (en) * | 2002-10-15 | 2004-05-13 | Fuji Photo Film Co Ltd | Anti-reflection coating, anti-reflection film, and image display device |
| JP2005043749A (en) * | 2003-07-24 | 2005-02-17 | Fuji Photo Film Co Ltd | Antireflection coating, antireflection film, polarizing plate, image display device and hard-coated article |
| JP2006072315A (en) * | 2004-05-20 | 2006-03-16 | Fuji Photo Film Co Ltd | Polarization plate with antireflection function, process for producing the same and image display unit utilizing the same |
| JP2006126799A (en) * | 2004-09-28 | 2006-05-18 | Fuji Photo Film Co Ltd | Manufacturing method of antireflection film, antireflection film, polarizing plate using same, and image display device using them |
| JP2006235336A (en) * | 2005-02-25 | 2006-09-07 | Fuji Photo Film Co Ltd | Antireflection film, polarizing plate and image display device using the same |
| JP2007256346A (en) * | 2006-03-20 | 2007-10-04 | Fujifilm Corp | Anti-reflection film, polarizing plate and image display device, liquid crystal display device |
| JP5352644B2 (en) * | 2006-03-30 | 2013-11-27 | 富士フイルム株式会社 | Manufacturing method of optical film |
| JP2008116597A (en) * | 2006-11-02 | 2008-05-22 | Riken Technos Corp | Antireflection film |
| WO2009081596A1 (en) * | 2007-12-20 | 2009-07-02 | Toppan Printing Co., Ltd. | Antireflection film |
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| JP5750231B2 (en) * | 2010-03-30 | 2015-07-15 | 富士フイルム株式会社 | Coating composition, optical film, polarizing plate, and image display device |
| JP2012058415A (en) * | 2010-09-07 | 2012-03-22 | Toppan Printing Co Ltd | Antireflection film and method for producing the same |
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| WO2013140811A1 (en) | 2013-09-26 |
| CN104204864A (en) | 2014-12-10 |
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| JPWO2013140811A1 (en) | 2015-08-03 |
| TW201339628A (en) | 2013-10-01 |
| KR20140138262A (en) | 2014-12-03 |
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| JP6233298B2 (en) | 2017-11-22 |
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