CN101855303B - Coating composition for antireflection, antireflection film and method for preparing the same - Google Patents

Coating composition for antireflection, antireflection film and method for preparing the same Download PDF

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CN101855303B
CN101855303B CN2008801160072A CN200880116007A CN101855303B CN 101855303 B CN101855303 B CN 101855303B CN 2008801160072 A CN2008801160072 A CN 2008801160072A CN 200880116007 A CN200880116007 A CN 200880116007A CN 101855303 B CN101855303 B CN 101855303B
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coating
refraction
coating composition
low refractive
weight parts
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CN101855303A (en
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尹汉植
金惠珉
金芙敬
张影来
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LG Electronics Inc
LG Corp
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LG Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • C—CHEMISTRY; METALLURGY
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
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    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
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    • 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
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    • 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
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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Abstract

The present invention provides a coating composition for ant iref lection that includes a low refractive material having a refractive index of 1.2 to 1.45 and a high refractive resin having a refractive index of 1.46 to 2, in which the difference in the surface energy between two materials is 5 mN/m or more; an ant iref lection film manufactured using the coating composition for ant iref lection; and a method of manufacturing the ant iref lect ion film. According to the present invention, the ant iref lect ion film having excellent abrasion resistance and antiref lection characteristic can be manufactured using a single composition by one coating process, thereby reducing manufacturing cost.

Description

The method that is used for antireflecting coating composition, antireflective coating and this antireflective coating of preparation
Technical field
The present invention relates to a kind ofly to be used for antireflecting coating composition, adopt this antireflective coating that is used for antireflecting coating composition preparation and the method for preparing this antireflective coating.More specifically; The present invention relates to a kind of antireflecting coating composition that is used for; Although wherein use a kind of coating composition contain the resin that specific refractory power differs from one another to form single-layer coating through a step cladding process; But also occurred being separated at this single-layer coating, thereby antireflection characteristic and wear resistance are provided simultaneously; Adopt this to be used for the antireflective coating of antireflecting coating composition preparation; And the method for preparing this antireflective coating.
The korean patent application No.10-2007-0115348 that the application requires to submit on November 13rd, 2007 in Korea S Department of Intellectual Property and No.10-2007-0115329, the korean patent application No.10-2007-0115967 that submits on November 14th, 2007 and in the right of priority of submission on April 18th, 2008 korean patent application No.10-2008-0035891 are with the disclosure of above-mentioned application complete the application that incorporates into of mode with reference.
Background technology
On the surface of indicating meter, carrying out purpose of surface-treated is to send reflection of light with minimizing from external light source through the wear resistance that improves indicating meter to improve picture contrast.Reducing outside reflection of light can realize through two kinds of methods.A kind of method is through using the convex-concave shape to cause diffuse-reflectance from the teeth outwards, and another kind of method is through using multiple coating design (multi-coating design) to cause destructive interference.
At the widely-used Anti Glare Coatings (anti-glarecoating) that adopts the convex-concave shape from the teeth outwards of association area.Yet the problem of existence is because the sharpness deterioration that diffuse-reflectance makes the resolution deteriorates in the high resolution display and makes image.In order to solve the above problems, Japan patent applicant announce has disclosed optical diffusion film 11-138712 number, and wherein, light is spread in use has the film of organic filler preparation of the specific refractory power different with tackiness agent.Yet because it has the problem of brightness and contrast's deterioration, this optical diffusion film needs to improve.
In Japan patent applicant announce 02-234101 number and 06-18704 number, disclosed method through the catoptrical destructive interference of multiple coating design causing.According to this method, can obtain antireflection characteristic and do not make image distortion.In this case, the reflected light of each layer should have phase differential, thereby makes the reflected light destructive interference, thereby and catoptrical waveform should have amplitude and in the destructive interference process, make reflectivity can be the reflectivity of minimum.For example, when being 0 °, can obtain following expression formula with respect to the input angle that is arranged on the individual layer antireflection coatings on the substrate.
[mathematical expression 1]
n on s＝n 1 2
2n 1d 1＝(m+1/2)λ(m＝0、1、2、3...)
(n o: the specific refractory power of air; n s: the specific refractory power of substrate; n 1: the specific refractory power of film; d 1: the thickness of film; λ: the incident light wavelength)
Usually, if the specific refractory power of antireflection coatings less than the specific refractory power of substrate, then antireflective is effective.Yet, consider abrasion property, preferably, the antireflection coatings specific refractory power is 1.3 to 1.5 times of substrate specific refractory power.In this case, reflectivity is less than 3%.Yet, when antireflection coatings is formed on the plastic film, be the requirement that impossible meet the wear resistance of indicating meter.Based on this reason, need several microns hard coat be arranged on antireflection coatings below.That is to say that the antireflection coatings of using destructive interference comprises and is used to strengthen the hard coat of wear resistance and is formed on 1 to 4 layer of antireflection coatings on this hard coat.Therefore, said multiple coating method has obtained antireflection characteristic and has not made image distortion.Yet the problem that still exists is because multiple coating has improved preparation cost.
In recent years, the someone has proposed the method that makes the reflected light destructive interference through single layer coating design.In Japan patent applicant announce 07-168006 number, disclosed following method.According to this method, the ultramicro particle that is dispersed in the liquid is coated on the substrate, and the globular minuteness particle is exposed to make on the surface difference that between air (interface) and particle, produces specific refractory power gradually.Therefore, can obtain antireflection characteristic.Yet because shape and the granularity of said ultramicro particle should be even, and these particles should be evenly dispersed on the substrate, so be difficult to carry out this method through the coating method of using always.And, because in order on the surface of said film, to obtain the spheric shape, adhesive consumption should equate or be less than predetermined consumption with predetermined consumption, so the non-constant of the wear resistance that this method obtains.In addition since the thickness of coating also the diameter than minuteness particle is little, so be difficult to obtain wear resistance.
Summary of the invention
Technical problem
In order to address the above problem; The purpose of this invention is to provide a kind of antireflecting coating composition that is used for; Although wherein use a kind of coating composition to form coating through a step cladding process; But in this coating, occurred being separated so that antireflection characteristic and wear resistance to be provided simultaneously, thereby improved process efficiency and reduce production costs; Adopt this to be used for the antireflective coating of antireflecting coating composition preparation; And the method for preparing this antireflective coating.
Technical scheme
To achieve these goals; The invention provides a kind of antireflecting coating composition that is used for; It comprises specific refractory power is that 1.2 to 1.45 low refractive material and specific refractory power are 1.46 to 2 height refraction resin, and wherein the surface energy difference of two kinds of storerooms is more than the 5mN/m.
In addition, the invention provides a kind of method for preparing antireflective coating, it comprises the following steps:
A) preparation is used for antireflecting coating composition, and it is 1.2 to 1.45 low refractive material that said composition comprises specific refractory power and specific refractory power is that 1.46 to 2 height reflects resin, and wherein the surface energy difference of two kinds of storerooms is more than the 5mN/m;
B) said coating composition is coated on the substrate to form coating;
C) dry said coating so that said low refractive material and high-refraction material be separated; And
D) solidify the exsiccant coating.
Saidly be used for that antireflecting coating composition can further comprise fluorinated compound or nanoparticle dispersion liquid is beneficial to being separated of said low refractive material and high-refraction material.
In addition; The present invention provides a kind of antireflective coating that comprises single-layer coating; It is that 1.2 to 1.45 low refractive material and specific refractory power are 1.46 to 2 height refraction resin that this single-layer coating comprises specific refractory power, and wherein the surface energy difference of two kinds of storerooms is that above and said low refractive material of 5mN/m and high-refraction material have concentration gradient on thickness direction.
In addition, the invention provides a kind of polaroid, it comprises a) light polarizing film, and b) be applied to said light polarizing film at least the one side according to antireflective coating of the present invention.
In addition, the invention provides a kind of display device, it comprises said antireflective coating or said polaroid.
Beneficial effect
Through using the above-mentioned method that is used for antireflecting coating composition and the said antireflective coating of preparation, the present invention can provide the antireflective coating that comprises the antireflection layer with excellent antireflection characteristic and wear resistance, and wherein, said antireflection layer is made up of single-layer coating.Because antireflective coating according to the present invention has excellent abrasive and low refracting characteristic and can therefore can improve working (machining) efficiency and reduce production cost through step cladding process preparation.
Description of drawings
Fig. 1 is the transmission electron microscope image of demonstration according to the viewgraph of cross-section of the antireflective coating of embodiment 1.
Embodiment
Hereinafter, will describe the present invention in detail.
Be used for antireflecting coating composition and be characterised in that according to of the present invention, it comprises specific refractory power is that 1.2 to 1.45 low refractive material and specific refractory power are 1.46 to 2 height refraction resin, and the surface energy difference of two kinds of storerooms is more than the 5mN/m.Surface energy difference between low refractive material and high-refraction material, occurs owing to be used for antireflecting coating composition, therefore in coating, drying and curing process, can occur being separated.Therefore, even use a kind of compsn to implement a step cladding process, excellent antireflection characteristic and wear resistance can be provided also.
In the present invention, surface measurements ability in the cured prod for preparing through solidify material.
After coating step was accomplished, because the surface energy difference between low refractive material and high-refraction material, said low refractive material was shifted to the top of coating gradually, and said high-refraction material is positioned at the bottom of coating.In order in dry and curing schedule, to make the also isolating position of stationary phase of maximization that is separated, preferably said low refractive material is at room temperature being softish and according to temperature solidified thermosetting material gradually.In addition, said low refractive material preferably has below the 25mN/m, and the more preferably surface energy of 5mN/m to 25mN/m.
In the present invention, preferably, based on total coating composition of 100 weight parts, the content of said low refractive material is 5 to 80 weight parts, and the content of said high-refraction material is 10 to 90 weight parts.
Said low refraction-thermosetting material is the thermosetting material of specific refractory power in 1.2 to 1.45 scopes.Organoalkoxysilane reactant, urethane reaction based compound, urea reactive group compound, reactant of esterification that for example, can cause sol gel reaction etc. can be used as said low refraction-thermosetting resin.
Said organoalkoxysilane reactant is a reacting oligomer, and this reacting oligomer is through carrying out organoalkoxysilane, fluorinated alkoxysilanes, preparing through sol gel reaction based on the hydrolysis and the condensation of the organic substituent of silane under water and catalyzer condition.Said sol gel reaction can adopt this area any method commonly used.The sol gel reaction 1 to 70 hour that under 0 to 150 ℃ temperature of reaction, comprises organoalkoxysilane, fluorinated alkoxysilanes, catalyzer, water and organic solvent.In this case, when using PS when measuring through GPC (GPC) with reference to material, the molecular-weight average of said reacting oligomer organoalkoxysilane is preferably 1,000 to 200,000.Under the temperature that is being equal to or higher than room temperature after the coating, carry out condensation reaction, so that the organoalkoxysilane reactant of preparation forms the net with crosslinking structure as stated.
Said organoalkoxysilane can be given the intensity of the level of outmost film needs.Particularly, said organoalkoxysilane can adopt tetraalkoxysilane or trialkoxy silane.Simultaneously; Said organoalkoxysilane is preferably and is selected from least a in tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, methyltrimethoxy silane, Union carbide A-162, glycidoxypropyltrime,hoxysilane and the glycidoxy propyl-triethoxysilicane, but is not limited thereto.
Based on the said organoalkoxysilane reactant of 100 weight parts, the content of basic monomer organoalkoxysilane is preferably 5 to 50 weight parts.If content less than 5 weight parts, then is difficult to obtain excellent abrasive.If content greater than 50 weight parts, then is difficult to realize the low refracting characteristic of organoalkoxysilane reactant and being separated from high-refraction material.
The surface tension that said fluorinated alkoxysilanes has reduced specific refractory power and coated film is beneficial to being separated from high-refraction material.Said fluorinated alkoxysilanes is preferably the low refractive material of the low surface tension with 1.3 to 1.4 low-refraction and 10 to 15mN/m.Said fluorinated alkoxysilanes is preferably and is selected from ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl Trimethoxy silanes and 17 fluorine decyls, the three isopropoxy silane one or more, but is not limited thereto.
In order to make the organoalkoxysilane reactant have 1.2 to 1.45 specific refractory power and to help from being separated of high-refraction material, based on the said organoalkoxysilane reactant of 100 weight parts, the content of said fluorinated alkoxysilanes is preferably 10 to 70 weight parts.If content less than 10 weight parts, then is difficult to realize low refracting characteristic and being separated from high-refraction material.If content greater than 70 weight parts, then is difficult to guarantee the stable and resistance to marring of solution.
Said organic substituent based on silane can with the organoalkoxysilane Chemical bond; Form two keys improving the consistency of low refractive material and high-refraction material with said high-refraction material, and in the adhesivity of back raising organoalkoxysilane and high-refraction material that is separated.Therefore, as long as it has above-mentioned functions, just can use any compound and not restriction.Said organic substituent based on silane is preferably and is selected from vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriethoxysilane, vinyl three positive propoxy silane, vinyl three n-pentyloxy silane, vinyl methyl dimethoxysilane, xenyl vinyl ethyl ether base silane, vinyl silane triisopropoxide, divinyl two ('beta '-methoxy oxyethyl group) silane, divinyl dimethoxy silane, divinyl diethoxy silane, divinyl two positive propoxy silane, divinyl two (isopropoxy) silane, divinyl two n-pentyloxy silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyldiethoxysilane, the γ-methacryloxypropyl methyldiethoxysilane one or more, but is not limited thereto.
In order to keep consistency and the stability of said organoalkoxysilane reactant in coating solution, based on the organoalkoxysilane reactant of 100 weight parts, the content of said organic substituent based on silane is preferably 0 to 50 weight part.If content greater than 50 weight parts, then is difficult to realize low refracting characteristic and being separated from high-refraction material.In addition, if not to the organic substituent that wherein adds based on silane, said low refractive material is not enough to the consistency of high-refraction material, so coating solution possibly not mix.
The catalyzer that in said sol gel reaction, uses is control required composition of sol gel reaction time.This catalyzer is preferably the acid like nitric acid, hydrochloric acid, sulfuric acid and acetate, and more preferably hydrochloride, nitrate salt, vitriol or the acetate of zirconium or indium, but is not limited thereto.Relevant therewith, based on the said organoalkoxysilane reactant of 100 weight parts, said catalyst consumption is preferably 0.1 to 10 weight part.
The water that in said sol gel reaction, uses is that hydrolysis and condensation are required, and based on the said organoalkoxysilane reactant of 100 weight parts, its consumption is 5 to 50 weight parts.
The organic solvent that in said sol gel reaction, uses is the composition of the molecular weight of control hydrolysis condenses.Organic solvent is preferably a kind of solvent or the mixed solvent that is selected from alcohol, cellosolve and the ketone.Relevant therewith, based on the said organoalkoxysilane reactant of 100 weight parts, the content of said organic solvent is preferably 0.1 to 50 weight part.
Simultaneously, said urethane reaction based compound can prepare through the reaction between pure and mild isocyanate compound, uses metal catalyst simultaneously.If the solution that will comprise metal catalyst, have the polyfunctional isocyanate of two above functional groups and have a polyfunctional alcohol of two above functional groups remains under the temperature that is equal to or higher than room temperature, just can form the reticulated structure that comprises the urethane reaction base.In this case, can with in fluorine-based introducing alcohol or the isocyanic ester to realize low refracting characteristic and to impel being separated from high-refraction material.
Said fluorine-containing polyfunctional alcohol's instance can comprise 1H, 1H, and 4H, 4H-perfluor-1, the 4-butyleneglycol,
1H, 1H, 5H, 5H-perfluor-1, the 5-pentanediol,
1H, 1H, 6H, 6H-perfluor-1, the 6-pinakon,
1H, 1H, 8H, 8H-perfluor-1, the 8-ethohexadiol,
1H, 1H, 9H, 9H-perfluor-1, the 9-nonanediol,
1H, 1H, 10H, 10H-perfluor-decamethylene-glycol,
1H, 1H, 12H, 12H-perfluor-1, is fluoridized triethylene glycol and is fluoridized TEG the 12-dodecanediol, but is not limited thereto.
Preferred aliphatic isocyanates, alicyclic ring isocyanic ester, aromatic isocyanate or the heterocycle isocyanic ester of using is as the isocyanate prepolymer composition that is used to prepare said urethane reaction based compound.Particularly, preferably use vulcabond, hexamethylene diisocyanate, 1,3 for example, 3-trimethylammonium hexamethylene diisocyanate, isophorone diisocyanate, Toluene-2,4-diisocyanate, 6-vulcabond and 4,4 '-the bicyclohexane vulcabond; The perhaps isocyanic ester of three above functional groups, for example by the DN950 of DIC company preparation and DN980 (trade(brand)name) as isocyanate prepolymer composition.
In the present invention, can use catalyzer to prepare said urethane reaction based compound.Lewis acid or Lewis base can be used as catalyzer.The specific examples of said catalyzer can comprise stannous octoate, oxalic acid two fourth tin, dibutyl tin dilaurate, mercaptan two fourth tin (dibutyltin mercaptide), toxilic acid hydrogen two fourth tin (dibutyltin dimaleate) and hydroxide methyl-tin and triethylamine, but is not limited to this.
Preferred settings is used to prepare the isocyanic ester of said urethane reaction based compound and polyfunctional alcohol's content, so that the mol ratio (NCO/OH) of the NCO of functional group group and OH group is preferably 0.5 to 2, and more preferably 0.75 to 1.1.If the mol ratio between the functional group is less than 0.5 or greater than 2, then unreacted functional group can increase.The problem that therefore, possibly exist said film strength to reduce.
Can prepare said urea reactive group compound through the reaction between amine and the isocyanic ester.Can use isocyanic ester to prepare said urea reactive group compound, this isocyanic ester is identical with the isocyanic ester that is used to prepare the urethane reaction based compound.Perfluamine with two above functional groups can be used as said amine.If necessary, can use catalyzer in the present invention.Lewis acid or Lewis base can be used as catalyzer.The concrete instance of said catalyzer comprises stannous octoate, oxalic acid two fourth tin, dibutyl tin dilaurate, mercaptan two fourth tin, toxilic acid hydrogen two fourth tin, hydroxide methyl-tin and triethylamine, but is not limited thereto.
Can obtain reactant of esterification through dehydration between acid and the alcohol and condensation reaction.If also reactant of esterification is mixed in the coating solution, then can form film with crosslinking structure.The fluoric-containing acid that preferably, will have two above functional groups is as said acid.Its concrete instance can comprise perfluor succsinic acid, perfluoroglutaric acid, perfluor hexanodioic acid, perfluor suberic acid, perfluor nonane diacid, perfluor sebacic acid and perfluor LAURIC ACID 99 MIN.Preferably, the polyfunctional alcohol is used as said alcohol.The specific examples of said institute functional alcohol comprises 1,4-butyleneglycol, 1, and 2-butyleneglycol, 1,5-pentanediol, 2,4-pentanediol, 1,4-cyclohexanediol, 1,6-pinakon, 2,5-pinakon, 2,4-heptanediol, tetramethylolmethane and TriMethylolPropane(TMP), but be not limited thereto.For example the vitriolic acid catalyst or for example the titan-alkoxide (alkoxytitan) of four titanium butoxide (tetrabutoxytitan) can be used for esterification.Yet the material that is used for esterification is not limited to above-mentioned materials.
Said high-refraction material is the resin with specific refractory power of 1.45 to 2, and this specific refractory power is relatively higher than the specific refractory power of said low refractive material, and the surface energy difference between the cured prod of said high-refraction material and low refractive material is more than the 5mN/m.Preferably, more than the high 5mN/m of surface energy of the surface energy of the cured prod of said high-refraction material than said low refractive material.
Said high-refraction material is preferably high refraction ultraviolet curable resin.The material that is used for high refraction ultraviolet curable resin can comprise acrylate resin, photoinitiator and solvent, if necessary, and also comprises surfactant.The instance of said acrylate resin can comprise acrylate monomer, urethane acrylate oligomer, epoxy acrylate oligomer and ester origoester acrylate.Ultraviolet curable resin can contain substituting group, for example sulphur, chlorine and metal, and perhaps aromatic material is to obtain high refractive index.1.62), two (4-methacryloxy thiophenyl) sulfide (specific refractory power: 1.689) with pair (4-vinyl benzene sulfenyl) sulfide (specific refractory power: 1.695) example can comprise dipentaerythritol acrylate, tetramethylolmethane three/tetraacrylate, trimethylene propane triacrylate, ethylene glycol diacrylate, 9, two (4-(the 2-acryloxy ethoxyl phenenyl) fluorine (specific refractory poweres: of 9-.Can use the mixture of above-mentioned a kind of compound or two or more compounds.
Based on the said high-refraction material of 100 weight parts, the content of said acrylate resin is preferably 10 to 80 weight parts.If content is less than 10 weight parts, the problem that resistance to marring that can occur filming and wear resistance descend, and the viscosity of coating solution obviously descends and can not transfer to and applies on machine and the substrate.If content is greater than 80 weight parts,, and there are the planeness of filming and the problem of coating property decline then owing to the HV of coating solution is difficult to realize from being separated of low refractive material.
Said photoinitiator is preferably the degradable compound through UV, and the example can comprise 1-hydroxy-cyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxyl dimethyl acetophenone, bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether and bitter almond oil camphor butyl ether.
Based on the said high-refraction material of 100 weight parts, preferably use the photoinitiator of the amount of 1 to 20 weight part.If content less than 1 weight part, suitable curing maybe not can occur.If content is greater than 20 weight parts, resistance to marring of filming and wear resistance may descend.
The instance of said solvent can comprise alcohol, acetic ester, ketone, aromatic solvent etc.The specific examples of this solvent can comprise methyl alcohol, ethanol, Virahol, butanols, 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2-isopropoxide ethanol, methyl acetate, ETHYLE ACETATE, butylacetate, methylethylketone, MIBK, hexanaphthene, pimelinketone, toluene, YLENE and benzene, but is not limited thereto.
Based on the said high-refraction material of 100 weight parts, the preferable amount of said solvent is 10 to 90 weight parts.If content is less than 10 weight parts, then owing to the HV of coating solution is difficult to realize from being separated of said low refractive material, and the problem that exists the planeness of filming to descend.Can not transfer to the problem that applies on machine and the substrate if, can there be the resistance to marring of filming greater than 90 weight parts in content and wear resistance possibly descend and the viscosity of coating solution possibly obviously descend.
Said high refraction ultraviolet curable resin can further comprise tensio-active agent.The instance of said tensio-active agent can comprise levelling agent or wetting agent, particularly is fluorine cpd or polysiloxane compound, but is not limited thereto.
Based on the said high-refraction material of 100 weight parts, the preferable amount of said tensio-active agent is 5 weight parts.If content greater than 5 weight parts, then is difficult to realize from being separated of said low refractive material, and has the problem that possibly descend to the adhesivity of substrate, the resistance to marring of filming and wear resistance.Based on the said high-refraction material of 100 weight parts, preferably add the said tensio-active agent of the amount of 0.05 above weight part, to obtain its enough effect.
After accomplishing dry and curing process, the refractive index difference of the cured prod of above-mentioned low refractive material and high-refraction material is preferably more than 0.01.In this case, said single-layer coating has functionally formed GRIN (graded index) structure that is made up of plural layer, thereby obtains the antireflective effect.Relevant therewith, when the low refractive material of solidified has the surface energy below the 25mN/m, and the surface energy difference between low refractive material and high-refraction material is 5mN/m when above, can occur effectively being separated.
What be used for according to the present invention that antireflecting coating composition can further comprise fluorinated compound and nanoparticle dispersion liquid at least aly is beneficial to being separated of low refractive material and high-refraction material.
Preferably the specific refractory power of fluorinated compound is below 1.5, and molecular weight is less than low refractive material, and surface energy is between the surface energy of high-refraction material and low refractive material.Based on total coating composition of 100 weight parts, the preferred content of said fluorinated compound is 0.05 to 72 weight part.
Said fluorinated compound is low refraction-thermosetting resin, like fluorinated alkoxysilanes, fluorinated alohol, fluoridize isocyanic ester, fluoride amine and the fluorine-containing acid with two above functional groups, and is preferably the fluorinated compound that is selected from example; Further contain C 1-C 6The straight or branched alkyl is as substituent one or more fluorinated acrylic esters (it is by 1 to 5 expression of following general formula); Like the multiple fluorinated additives of fluorine-containing levelling agent, dispersion agent, surface-modifying agent, wetting agent, skimmer and expanding material and one or more materials in the fluorated solvent.
[general formula 1]
Figure GPA00001137545200091
Wherein, R 1For-H or C 1-C 6Alkyl, a are 0 to 4 integer, and b is 1 to 3 integer.Said C 1-C 6Alkyl is preferably methyl (CH 3).
[general formula 2]
Wherein, c is 1 to 10 integer.
[general formula 3]
Figure GPA00001137545200101
Wherein, d is 1 to 9 integer.
[general formula 4]
Figure GPA00001137545200102
Wherein, e is 1 to 5 integer.
[general formula 5]
Figure GPA00001137545200103
Wherein, f is 4 to 10 integer.
Preferably use said fluorinated compound at the low refracting characteristic that keeps filming, the intensity of filming with in to the adhering scope of display base plate, particularly, based on the said low refractive material of 100 weight parts, its amount is 1 to 90 weight part.
Preferably, it is 1 that said nanoparticle dispersion liquid contains mean particle size, and below the 000nm, preferred 1 to 200nm, and more preferably 2 to 100nm nanoparticle, to obtain the transparent film of no visible light scattering or diffusion.Said nanoparticle dispersion liquid preferably has the specific refractory power below 1.45.Said nanoparticle dispersion liquid can further comprise enhancing dispersive sequestrant, fluorinated acrylic ester, solvent etc.Based on total coating composition of 100 weight parts, the preferred content of said nanoparticle dispersion liquid is 2 to 27 weight parts.
Said nanoparticle can be metal fluoride, other organic/inorganic hollow and porous granules.Particularly, metal fluoride is that mean particle size is 10 to 100nm particle, and comprises and be selected from NaF, LiF, AlF 3, Na 5Al 3F 14, Na 3AlF 6, MgF 2, NaMgF 3And YF 3In one or more.
Preferably use said nanoparticle at the low refracting characteristic that keeps filming, the intensity of filming with in to the adhering scope of display base plate.Based on the said nanoparticle dispersion liquid of 100 weight parts, the preferred content of said nanoparticle is 5 weight part to 70 weight parts.
Thereby said enhancing dispersive sequestrant is to be used to make between high-refraction material and low refractive material and nanoparticle have the liquid component that consistency makes the nanoparticle prevented from caking and prevents to film and haze.If desired, can add said enhancing dispersive sequestrant.Said enhancing dispersive sequestrant preferably adopts and is selected from Mg (CF 3COO) 2, Na (CF 3COO), K (CF 3COO), Ca (CF 3COO) 2, Mg (CF 2COCHCOCF 3) 2, Na (CF 2COCHCOCF 3), one or more materials among Zr (AcAc), Zn (AcAC), Ti (AcAc) and the Al (AcAc), wherein AcAc is an Acetyl Acetone.
In addition, said solvent can be preferably DAA, AcAc and cellosolve, but is not limited thereto.
Preferably keep the dispersiveness of nanoparticle, the intensity of filming and to the adhering scope of display base plate in use said enhancing dispersive sequestrant.Particularly, based on the said nanoparticle dispersion liquid of 100 weight parts, the preferable amount of said enhancing dispersive sequestrant is 10 to 80 weight parts.
Said fluorinated acrylic ester is used to make high-refraction material and low refractive material to have consistency and makes film have certain intensity through Chemical bond, its can be selected from by general formula 1 to 5 expression and further contain C 1-C 6Alkyl is as one or more materials in the substituent compound.Based on the said nanoparticle dispersion liquid of 100 weight parts, the preferable amount of said fluorinated acrylic ester is below 80 weight parts.
The instance that is used for the solvent of said nanoparticle dispersion liquid can comprise alcohol, acetic ester, ketone or aromatic solvent, particularly is methyl alcohol, ethanol, Virahol, butanols, 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2-isopropoxide ethanol, methyl acetate, ETHYLE ACETATE, butylacetate, methylethylketone, MIBK, hexanaphthene, pimelinketone, toluene, YLENE, benzene etc.Based on the said nanoparticle dispersion liquid of 100 weight parts, the preferable amount of said solvent is 10 to 90 weight parts.
The invention provides a kind of the employing and above-mentionedly be used for the antireflective coating that antireflecting coating composition prepares, and the method for preparing this antireflective coating.
The preparation method for preparing antireflective coating according to the present invention comprises the following steps:
A) prepare the above-mentioned antireflecting coating composition that is used for;
B) said coating composition is coated on the substrate to form coating;
C) dry said coating so that low refractive material and high-refraction material be separated; And
D) solidify the exsiccant coating.
In step b), said substrate can be glass, plastic sheet and film, and the not restriction of its thickness.The instance of plastic film can comprise three cellulose acetate membrane, norbornene cycloolefin polymer film, polyester film, Rohm tech inc film and polycarbonate membrane, but is not limited thereto.
In step b); The method that applies said coating composition can adopt the several different methods that is coated with method, two rollers or the reverse cladding process of three rollers, intaglio plate cladding process, mold pressing cladding process (die coating), nick version cladding process and continuous cladding process (comma coating) like rod, can select coating method to have no restriction according to the liquid phase or the rheological property of substrate and coating solution.
Be not specially limited the thickness of coating, but be preferably 0.5 to 30 μ m, and behind coating processes, be used for the drying process of dry solvent.Behind drying process, if the thickness of coating less than 0.5 μ m, then can not fully improve wear resistance.If the thickness of coating greater than 30 μ m, then is difficult to realize being separated of low refractive material and high-refraction material, thereby can not obtains required refracting characteristic.
In step c), from coating composition, removed the organic solvent and the low refractive material on solidified coating top gradually in 0.1 to 30 minute thereby can under 40 to 150 ℃ temperature, carry out drying process.If temperature is lower than 40 ℃, then can not remove organic solvent fully and state of cure when UV is solidified descends.If temperature is higher than 150 ℃, may, low refractive material just solidify before being positioned at coating top.
In step d), can be cured technology through UV or heating according to the type of used resin.When using thermoset and UV cured resin simultaneously, at first carry out the UV curing process, then carry out heat curing process.
Can be 0.01 to 2J/cm 2The UV irradiation dose under carry out UV curing process 1 to 600 second so that coating has enough wear resistancies.If the UV irradiation dose not in above-mentioned scope, has then kept uncured resin on the coating, so the surface becomes sticky and can not guarantee wear resistance.If the UV irradiation dose surpasses above-mentioned scope, then the quantity of UV cured resin increases too much, therefore possibly in thermal cure step, hinder the curing of thermosetting resin.
Can under 20 to 200 ℃, carry out thermofixation 1 to 72 hour.If temperature is less than 20 ℃, then curing degree is too low and can not reduce set time.If temperature is greater than 200 ℃, then the stability of coated substrate can have problems.Curing process preferably carried out 1 to 72 hour, and in order to make the resistance to marring maximization of coating, thermosetting resin should be by abundant curing.
Use the above-mentioned antireflective coating according to the present invention that is used for antireflecting coating composition preparation to comprise single-layer coating; It is that 1.2 to 1.45 low refraction resin and specific refractory power are 1.46 to 2 high-refraction material that this single-layer coating comprises specific refractory power; Preferred further comprise at least a in fluorinated compound and the nanoparticle dispersion liquid; Wherein the surface energy difference of two kinds of storerooms is more than the 5mN/m, and low refractive material and high-refraction material have had concentration gradient on thickness direction.Said antireflective coating can further comprise the substrate that is applied on face of coating.
In antireflective coating, based on the gross weight of low refractive material, be included in that the low refractive material in thickness direction is equivalent to 50% zone is preferably more than 70% to the surface of air from coat side, more preferably more than 85%, and most preferably more than 95%.Reflectivity according to antireflective coating of the present invention is less than 3%, thereby shows excellent antireflective effect.
In addition, the invention provides a kind of polaroid that comprises according to above-mentioned antireflective coating of the present invention.Particularly, polaroid according to the present invention comprises a) light polarizing film, and b) be applied to said light polarizing film at least the one side on according to antireflective coating of the present invention.Between light polarizing film and antireflective coating, protective membrane can be set.In addition, in fact can be with the substrate that in the process of preparation antireflective coating, is used to form single-layer coating as protective membrane.Light polarizing film and antireflective coating can be bonded to each other through tackiness agent.Can use light polarizing film known in the art.
The invention provides a kind of display device, it comprises antireflective coating or polaroid.Said display device can be liquid-crystal display or plasma display.Except being provided with, can have structure known in the art according to display device of the present invention according to this situation of antireflective coating of the present invention.For example, in display device according to the present invention, can antireflective coating be arranged on display panel towards on spectators' the outmost surface or be arranged on it on the outmost surface of backlight.In addition, can comprise display panel, be arranged on the light polarizing film at least one face of this panel and be arranged on the antireflective coating of light polarizing film according to display device of the present invention towards the opposite side of panel one side.
Preferred forms
Hereinafter, the invention provides preferred embodiment for better understanding.Yet these embodiment have been merely the purpose of example, but not are intended to limit the present invention through these embodiment.
Embodiment
Preparation embodiment
The preparation of low refraction-thermosetting material (materials A)
Mix the DN 980 (producing) (wherein isocyanate functional group's mean number is 3) of 15.3 weight parts, the fluorine-containing difunctional alcohol 1H of 14 weight parts equably by DIC company; 1H; 12H; 12H-perfluor-1, prepares with methylethylketone (MEK) as the dibutyl tin dilaurate of 0.7 weight part of metal catalyst and as the Pyranton (DAA) of each 35 weight part of solvent and to hang down refraction-thermoset solution the 12-dodecanediol.
The preparation of low refraction-thermosetting material (material B)
The mixture of the 2-butanols of the ethanol of the hydrochloric acid of the water of the methacryloyl Trimethoxy silane of 17 fluorine decyl Trimethoxy silanes of the tetraethoxysilane of 10 weight parts, 30 weight parts, 20 weight parts, 10 weight parts, 0.5 weight part, 40 weight parts and 40 weight parts is at room temperature carried out sol gel reaction prepared low refraction-thermoset solution in 12 hours.
The preparation of low refraction-thermosetting material (material C)
The mixture of the 2-butanols of the methyl alcohol of the nitric acid of the water of the 3-methacryloxypropyl trimethoxy silane of the tetraethoxysilane of the fluoro-alkyl methoxy silane of 25 weight parts, 20 weight parts, 7 weight parts, 7.5 weight parts, 0.5 weight part, 20 weight parts and 20 weight parts is at room temperature carried out sol gel reaction prepared low refraction-thermoset solution in 24 hours.
The preparation of low refraction-thermosetting material (material D)
The mixture of the 2-butanols of the methyl alcohol of the nitric acid of the water of the 3-methacryloxy Trimethoxy silane of the tetraethoxysilane of the fluoro-alkyl methoxy silane of 15 weight parts, 25 weight parts, 12 weight parts, 7.5 weight parts, 0.5 weight part, 20 weight parts and 20 weight parts is at room temperature carried out sol gel reaction prepared low refraction-thermoset solution in 24 hours.
The preparation of high refraction-UV solidify material (material E)
Mix equably 28 weight parts dipentaerythritol acrylate (DPHA) (as the polyfunctional acrylic ester that is used to improve coating strength), 2 weight parts prepare height refraction-UV curing solution as the Darocur 1173 of UV initiator and the Pyranton as solvent (DAA) of each 35 weight part with methylethylketone (MEK).
The preparation of high refraction-UV solidify material (material F)
Ethanol, the propyl carbinol of 29 weight parts and the methyl ethyl diketone as solvent (AcAc) of 20 weight parts as Darocur 1173,20 weight parts of UV initiator that mix dipentaerythritol acrylate (DPHA) (as the polyfunctional acrylic ester that is used to improve the intensity of filming), 1 weight part of 30 weight parts equably prepare high refraction-UV curing solution.
The preparation of low refraction-thermosetting material (material G)
The methanol mixture of the nitric acid of the water of the vinyltrimethoxy silane of the tetramethoxy-silicane of the fluoro-alkyl Ethoxysilane of 5 weight parts, 37 weight parts, 10 weight parts, 7.5 weight parts, 0.5 weight part and 40 weight parts is at room temperature carried out sol gel reaction prepared low refraction-thermoset solution in 24 hours.
The preparation of high refraction-UV solidify material (material H)
Mix equably trimethylene propane triacrylate, 1 weight part of tetramethylolmethane three/tetraacrylate (as the polyfunctional acrylic ester that is used to improve coating strength), 10 weight parts of 20 weight parts the Darocur 1173 as the UV initiator, prepare high refraction-UV curing solution as the BYK371 of the BYK 333 of 5 weight parts of tensio-active agent and 4 weight parts and as ethanol, the propyl carbinol of 20 weight parts and the methylethylketone (MEK) of 20 weight parts of 20 weight parts of solvent.
Embodiment 1
Height refraction-UV solidify material the E that mixes low refraction-thermosetting material A and 70 weight parts of 30 weight parts equably prepares and is used for antireflecting coating composition.
Use line rod (wire bar) (No.5) compsn that makes to be coated on the three cellulose acetate membrane that thickness is 80 μ m.This film of 60 ℃ of baking oven inner dryings 2 minutes, and through irradiation 1J/cm 2The UV of dosage solidifies, then thermofixation 1 day in 120 ℃ of baking ovens.Final coat-thickness is 1 μ m, and under transmission electron microscope, observes xsect, and it is presented among Fig. 1.
With reference to Fig. 1, find on substrate, to have formed high-refraction material layer and low refractive material layer respectively with layer structure.Compare with single layer structure,, can obtain more effective reflectivity when when having the material form layers structure of different refractivity.
Embodiment 2
Except with material B substitute material A as the low refraction-thermosetting material, with embodiment 1 in identical method prepare film.
Embodiment 3
Mix the low refraction-thermosetting material C of 25 weight parts and the height refraction-UV solidify material F of 75 weight parts equably and prepare compatible mixing solutions, generate coating composition.
Use line rod (No.5) that the coating composition that makes is coated on the three cellulose acetate membrane that thickness is 80 μ m.This film of 120 ℃ of baking oven inner dryings 2 minutes, and through irradiation 200mJ/cm 2The UV of dosage solidifies, then thermofixation 1 day in 120 ℃ of baking ovens.Final coat-thickness is 1 μ m.
Embodiment 4
Mix the low refraction-thermosetting material A of 30 weight parts and the height refraction-UV solidify material F of 70 weight parts equably and prepare compatible coating composition.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 5
Mix the low refraction-thermosetting material C of 20 weight parts, the height refraction-UV solidify material F of 75 weight parts and the vinylformic acid trifluoro ethyl ester as fluorinated compound of 5 weight parts equably and prepare the compatible antireflecting coating composition that is used for.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 6
Mix the low refraction-thermosetting material A of 25 weight parts, the height refraction-UV solidify material F of 70 weight parts and the vinylformic acid trifluoro ethyl ester as fluorinated compound of 5 weight parts equably and prepare the compatible antireflecting coating composition that is used for.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 7
Mix the low refraction-thermosetting material D of 25 weight parts, the height refraction-UV solidify material F of 70 weight parts and the vinylformic acid trifluoro ethyl ester as fluorinated compound of 5 weight parts equably and prepare the compatible antireflecting coating composition that is used for.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 8
Mix the low refraction-thermosetting material C of 22 weight parts, the height refraction-UV solidify material F of 70 weight parts and the ten trifluoro octyltri-ethoxysilane as fluorinated compound of 8 weight parts equably and prepare the compatible antireflecting coating composition that is used for.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 9
Mix the low refraction-thermosetting material C of 26 weight parts, the height refraction-UV solidify material F of 70 weight parts and the Fluorad FC4430 (3M) as fluorinated compound of 4 weight parts equably and prepare the compatible antireflecting coating composition that is used for.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 10
The 10%MgF that mixes 50 weight parts equably 2The methylethylketone (MEK) of the trifluoroacetic acid magnesium of-dispersion liquid, 30 weight parts and 20 weight parts prepares metal fluoride-dispersion liquid.
Mix the low refraction-thermosetting material C of 8 weight parts, the height refraction UV solidify material F of 75 weight parts and the said metal fluoride-dispersion liquid of 17 weight parts equably and prepare the compatible antireflecting coating composition that is used for.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 11
Except with materials A substitute material C as the low refraction-thermosetting material, with embodiment 10 in identical method prepare coating solution and film.
Embodiment 12
Mix the low refraction-thermosetting material D of 25 weight parts, the height refraction-UV solidify material F of 70 weight parts and the metal fluoride-dispersion liquid that in embodiment 10, prepares of 5 weight parts equably and prepare the compatible antireflecting coating composition that is used for.Use said composition with embodiment 3 in identical mode prepare and film.
Embodiment 13
The mean particle size of mixing 10 weight parts equably is 30 to 40nm NaMgF 3Prepare metal fluoride-dispersion liquid with the Virahol (IPA) of 90 weight parts.Except using this metal fluoride-dispersion liquid, with embodiment 10 in identical mode prepare coating solution with film.
Embodiment 14
The mean particle size of mixing 10 weight parts equably is that 20nm and voidage are that 20% the mesoporous silica and the methyl alcohol of 90 weight parts prepare nanoparticle dispersion liquid.Except using this nanoparticle dispersion liquid, with embodiment 10 in identical mode prepare coating solution with film.
The comparative example 1
Only use high refraction-UV solidify material E as the material that is used to form coating, and use line rod (No.5) that it is coated on the three cellulose acetate membrane that thickness is 80 μ m.This film of 60 ℃ of baking oven inner dryings 2 minutes, and through irradiation 1J/cm 2The UV of dosage solidifies to prepare and films.The thickness of filming is about 1 μ m.
The comparative example 2
Only use low refraction-thermosetting material A as the material that is used to form coating, and use line rod (No.5) that it is coated on the three cellulose acetate membrane that thickness is 80 μ m.This film of thermofixation prepares over 1 day and films in 120 ℃ of baking ovens.The thickness of filming is about 1 μ m.
The comparative example 3
Only use low refraction-thermosetting material B as the material that is used to form coating, and use line rod (No.5) that it is coated on the three cellulose acetate membrane that thickness is 80 μ m.This film of thermofixation prepares over 1 day and films in 120 ℃ of baking ovens.The thickness of filming is about 1 μ m.
The comparative example 4
Only use high refraction-UV solidify material F as the material that is used to form coating, and use line rod (No.5) that it is coated on the three cellulose acetate membrane that thickness is 80 μ m.This film of 120 ℃ of baking oven inner dryings 2 minutes, through irradiation 200mJ/cm 2The UV of dosage solidifies, and places 120 ℃ of baking ovens interior 1 day.The thickness of filming is about 1 μ m.
The comparative example 5
Mix the low refraction-thermosetting material G of 25 weight parts, the height refraction-UV solidify material H of 70 weight parts and the vinylformic acid trifluoro ethyl ester as fluorinated compound of 5 weight parts equably and prepare the compatible antireflecting coating composition that is used for.With with embodiment 3 in identical mode use said composition to prepare to film.
The comparative example 6
Mix the low refraction-thermosetting material G of 25 weight parts, the height refraction-UV solidify material H of 70 weight parts and the metal fluoride-dispersion liquid that in embodiment 10, prepares of 5 weight parts equably and prepare the compatible antireflecting coating composition that is used for.With with embodiment 3 in identical mode use said composition to prepare to film.
Test example
The low refractive material and the high-refraction material that will in preparation embodiment, prepare are used to prepare cured prod, and measure its specific refractory power and surface energy, and it is presented in the table 1.The method for preparing cured prod with various materials is described below.Use line rod (No.5) will hang down refraction-thermosetting material and be coated on the three cellulose acetate membrane that thickness is 80 μ m, and placed 120 ℃ of baking ovens interior 1 day.Except with it 60 ℃ of baking oven inner dryings 2 minutes and pass through 200mJ/cm 2Dosage irradiation UV solidify outside, apply high refraction-UV solidify material with the mode identical with low refractive material.Adopt prism coupler (Sairon Technology) to come refractive Index Measurement, and adopt a DSA100 (KRUSS) of conformal analysis system (Drop shape analysis system) to come the surface measurements ability, and with water and methylene iodide (CH 2I 2) as standard specimen.
[table 1]
Figure GPA00001137545200181
The thickness of filming by the preparation of embodiment and comparative example's method is 1 μ m.Be described below the wear resistance of the antireflective coating that evaluation and test prepares and the optical characteristics that comprises reflectivity, transparency and mist degree in embodiment and comparative example:
1) evaluation and test of resistance to marring
With Steel Wool (#0000) various filming 10 times under the load of 1kg, the scratch of evaluation and test appearance then.
2) evaluation and test of reflectivity
Handle the dorsal part of filming with black, use Solid Spec.3700 spectrophotometer (Shimadzu) measurement of reflectivity to depend on the reflection preventing ability of minimum reflectance with mensuration then.
3) evaluation and test of transparency and mist degree
Use HR-100 (Murakami, Japan) to evaluate and test the transparency and the mist degree of filming.
The evaluation result of reflectivity, transparency and mist degree is presented in following table 2 and 3.
[table 2]
[table 3]
Figure GPA00001137545200192
Shown in table 2 and 3, thereby filming of preparation shown good resistance to marring and had excellent abrasive in embodiment 1 to 14, and shows excellent optical (comprising reflectivity, transparency and mist degree).Simultaneously, film with those of embodiment and to compare, filming of preparation shown relatively poor optical characteristics (comprising transparency and mist degree) in comparative example 1 and 4 to 6.Because filming of preparation manifests the resistance to marring except relatively poor in comparative example 2 and 3, so need other hard coating processes.Therefore, the problem that working (machining) efficiency reduces appears.
According to embodiment and comparative example, can prepare through a step cladding process according to antireflective coating of the present invention, thereby improve working (machining) efficiency and reduced production cost, and realize excellent antireflection characteristic and wear resistance.
With reference to preferred embodiment having described the present invention, although adopted concrete term in this application, scope of the present invention is not limited to these concrete embodiments, and should on the basis of claim of enclosing, understand this scope.

Claims (21)

1. one kind is used for antireflecting coating composition; It comprises specific refractory power is that 1.2 to 1.45 low refractive material and specific refractory power are 1.46 to 2 height refraction resin; Wherein, The surface energy difference of two kinds of storerooms is more than the 5mN/m, and wherein, said low refractive material is a thermosetting resin and said high-refraction material is the UV cured resin.
2. according to claim 1ly be used for antireflecting coating composition, wherein, the surface energy of said low refractive material is below the 25mN/m.
3. according to claim 1ly be used for antireflecting coating composition; Wherein, said low refractive material comprises and is selected from organoalkoxysilane reactant, urethane reaction based compound, urea reactive group compound and the reactant of esterification that causes sol gel reaction one or more.
4. according to claim 1ly be used for antireflecting coating composition, wherein, said high-refraction material comprises acrylate resin, photoinitiator and solvent.
5. according to claim 1ly be used for antireflecting coating composition, wherein, based on total said coating composition of 100 weight parts, the content of said high-refraction material is 10 to 90 weight parts and the content of said low refractive material is 5 to 80 weight parts.
6. according to claim 1ly be used for antireflecting coating composition, wherein, the difference of the specific refractory power of the cured prod of said low refractive material and high-refraction material is more than 0.01.
7. according to claim 1ly be used for antireflecting coating composition, wherein, saidly be used for antireflecting coating composition and further comprise at least a of fluorinated compound and nanoparticle dispersion liquid.
8. according to claim 7ly be used for antireflecting coating composition; Wherein, The specific refractory power of said fluorinated compound is below 1.5, and the molecular weight of the said low refractive material of its molecular weight ratio is little, and surface energy is between the surface energy of high-refraction material and low refractive material.
9. according to claim 7ly be used for antireflecting coating composition, wherein, it is 1 that said nanoparticle dispersion liquid comprises mean particle size, the nanoparticle below the 000nm.
10. according to claim 7ly be used for antireflecting coating composition, wherein, the specific refractory power of said nanoparticle dispersion liquid is below 1.45.
11. according to claim 9ly be used for antireflecting coating composition, wherein, said nanoparticle dispersion liquid further comprises and strengthens dispersive sequestrant, fluorinated acrylic ester and solvent.
12. according to claim 9ly be used for antireflecting coating composition, wherein, said nanoparticle is metal fluoride or is organic/inorganic hollow or porous particle.
13. a method for preparing antireflective coating, it comprises following step:
A) preparation is according to each describedly is used for antireflecting coating composition in the claim 1 to 12;
B) said coating composition is coated on the substrate to form coating;
C) dry said coating so that low refractive material and high-refraction material be separated; And
D) solidify the exsiccant coating.
14. the method for preparing antireflective coating according to claim 13, wherein, in step b), the thickness of exsiccant coating is 1 to 30 μ m.
15. the method for preparing antireflective coating according to claim 13, wherein, step d) may further comprise the steps: d1) with 0.1 to 2J/cm 2Dosage solidified said high refraction-UV cured resin in 1 to 600 second through irradiation UV; And d2) under 20 to 200 ℃ temperature, solidified said low refraction-thermosetting resin 1 to 72 hour.
16. antireflective coating; It adopts according to each describedly is used for antireflecting coating composition and prepares in the claim 1 to 12; Wherein, said antireflective coating comprises single-layer coating, on thickness direction, has concentration gradient at low refractive material and high-refraction material described in this single-layer coating.
17. antireflective coating according to claim 16; Wherein, The method preparation of said antireflective coating through comprising the following steps: a) preparation is used for antireflecting coating composition, and it contains specific refractory power is that 1.2 to 1.45 low refraction resin and specific refractory power are 1.46 to 2 high-refraction material, and the surface energy difference of two kinds of storerooms is more than the 5mN/m; Wherein, said low refractive material is a thermosetting resin and said high-refraction material is the UV cured resin;
B) said coating composition is coated on the substrate to form coating;
C) dry said coating so that said low refractive material and high-refraction material be separated; And
D) solidify the exsiccant coating.
18. antireflective coating according to claim 16, wherein, based on the gross weight of said low refractive material, the low refractive material that in thickness direction is equivalent to 50% zone, comprises on the surface from said single-layer coating towards air is more than 70%.
19. antireflective coating according to claim 16, wherein, reflectivity is lower than 3%.
20. a polaroid, it comprises: a) light polarizing film; And b) antireflective coating of claim 16.
21. a display device, it comprises antireflective coating according to claim 16.
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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101144932B1 (en) * 2009-09-04 2012-05-11 위더스케미칼 주식회사 Composition for hard coating and method of preparing the same and hard coating film produced by using the same
DE102010012841A1 (en) * 2010-03-25 2011-09-29 Schott Ag Method for applying an antireflection coating and glass with an antireflection coating
KR101092573B1 (en) * 2010-04-06 2011-12-13 주식회사 엘지화학 Anti-reflective coating composition, anti-reflection film and method for manufacturing the same
WO2012005542A2 (en) * 2010-07-08 2012-01-12 주식회사 엘지화학 Antireflection film and method for manufacturing same
EP2594614B1 (en) * 2010-07-14 2015-07-08 LG Chem, Ltd. Antireflective and antiglare coating composition, antireflective and antiglare film, and method for producing same
JP5810504B2 (en) * 2010-10-18 2015-11-11 Jnc株式会社 Laminated body and method for producing the same
CN102061111B (en) * 2010-10-27 2013-12-25 中山市旌旗纳米材料科技有限公司 Preparation method of self-cleaning ceramic nanometer glass antireflective coating material and preparation method of reflection deducting coating
JP2014529762A (en) * 2011-08-26 2014-11-13 エルジー・ケム・リミテッド Anti-reflection coating composition and anti-reflection film manufactured using the same
KR101226229B1 (en) * 2011-08-26 2013-01-28 주식회사 엘지화학 Anti-reflective coating film
CN104066799B (en) * 2011-11-25 2016-06-01 Lg化学株式会社 Resin blend
KR101470468B1 (en) * 2013-03-15 2014-12-08 주식회사 엘지화학 Plastic film
KR102118368B1 (en) * 2015-07-29 2020-06-03 주식회사 엘지화학 The compositions using conductive film
KR102118369B1 (en) * 2015-07-29 2020-06-03 주식회사 엘지화학 The compositions using conductive film
KR101813707B1 (en) 2015-11-04 2017-12-29 주식회사 엘지화학 Anti-reflective film and preparation method of the same
TWI663063B (en) 2016-03-09 2019-06-21 Ｌｇ化學股份有限公司 Anti-reflective film
WO2017155358A1 (en) * 2016-03-11 2017-09-14 주식회사 엘지화학 Anti-reflective film and method for producing same
KR101973195B1 (en) 2016-03-11 2019-04-26 주식회사 엘지화학 Anti-reflective film and preparation method of the same
WO2017160027A1 (en) * 2016-03-14 2017-09-21 주식회사 엘지화학 Antireflection film
KR102040301B1 (en) * 2017-06-08 2019-11-04 삼성에스디아이 주식회사 Antireflection film, polarizing plate comprising the same and optical display apparatus comprising the same
CN107652718B (en) * 2017-09-27 2020-03-31 广东星星光电科技有限公司 Antireflection coating liquid and preparation method thereof
CN109502987B (en) * 2018-12-17 2021-09-28 常州大学 Method for preparing high-hardness anti-reflection film based on hollow silicon oxide
KR20220059812A (en) * 2020-11-03 2022-05-10 주식회사 엘지화학 Optical laminate
WO2022249730A1 (en) * 2021-05-26 2022-12-01 ステラケミファ株式会社 Liquid dispersion of fluoride particles, composition for forming optical film, and optical film
CN114895386B (en) * 2022-04-12 2024-03-29 深圳纳弘熠岦光学科技有限公司 Anti-glare film, manufacturing method and mold manufacturing method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1297535A (en) * 1999-03-31 2001-05-30 大赛璐化学工业株式会社 Light scattering sheet, light scattering composite sheet, and liquid crystal display
CN1368650A (en) * 2001-02-07 2002-09-11 三星Sdi株式会社 Functional film improved optical property and electrical property
TW200404846A (en) * 2002-09-19 2004-04-01 Optimax Tech Corp Antiglare and antireflection coatings of surface active nanoparticles
EP1418448A1 (en) * 2002-11-06 2004-05-12 Koninklijke DSM N.V. Preparation of a mechanically durable single layer coating with anti-reflective properties

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2162451A1 (en) * 1994-12-22 1996-06-23 John P. Murphy Anti-reflective clarifier film for eyeglasses
WO2003027189A1 (en) * 2001-09-04 2003-04-03 Dai Nippon Printing Co., Ltd. Coating composition, coating formed therefrom, anti-reflection coating, anti-reflection film, and image display device
JP2004143202A (en) * 2002-10-22 2004-05-20 Toyo Ink Mfg Co Ltd Active energy ray curing composition, method for forming cured film using the same and cured product thereof and antireflection body
JP4393232B2 (en) * 2004-03-09 2010-01-06 富士フイルム株式会社 Method for producing antireflection film
US20060147614A1 (en) * 2004-12-30 2006-07-06 3M Innovative Properties Company Transferable antireflection material for use on optical display
US7323514B2 (en) * 2004-12-30 2008-01-29 3M Innovative Properties Company Low refractive index fluoropolymer coating compositions for use in antireflective polymer films
US7264872B2 (en) * 2004-12-30 2007-09-04 3M Innovative Properties Company Durable high index nanocomposites for AR coatings
JP5075333B2 (en) * 2005-11-11 2012-11-21 富士フイルム株式会社 Optical film, polarizing plate, and image display device
KR20070075937A (en) 2006-01-17 2007-07-24 도레이새한 주식회사 Anti reflective film
JP5049628B2 (en) * 2006-03-30 2012-10-17 富士フイルム株式会社 Coating composition, optical film, polarizing plate, image display device, and method for producing optical film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1297535A (en) * 1999-03-31 2001-05-30 大赛璐化学工业株式会社 Light scattering sheet, light scattering composite sheet, and liquid crystal display
CN1368650A (en) * 2001-02-07 2002-09-11 三星Sdi株式会社 Functional film improved optical property and electrical property
TW200404846A (en) * 2002-09-19 2004-04-01 Optimax Tech Corp Antiglare and antireflection coatings of surface active nanoparticles
EP1418448A1 (en) * 2002-11-06 2004-05-12 Koninklijke DSM N.V. Preparation of a mechanically durable single layer coating with anti-reflective properties

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