CN101016197A - Low reflective film and manufacturing method thereof - Google Patents
Low reflective film and manufacturing method thereof Download PDFInfo
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- CN101016197A CN101016197A CNA2007100075671A CN200710007567A CN101016197A CN 101016197 A CN101016197 A CN 101016197A CN A2007100075671 A CNA2007100075671 A CN A2007100075671A CN 200710007567 A CN200710007567 A CN 200710007567A CN 101016197 A CN101016197 A CN 101016197A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
Abstract
The invention relates to a low reflection film and its manufacturing method. Through forming coating for porous layer containing soluble matter, the soluble matter is solved and extracted by solvent to form gap to manufacture the porous layer. The refractive index can be adjusted by porosity, therefore the surface reflection is below 2%, with excellentanti-scuffing ability and low cost.
Description
Technical field
The present invention relates to low-reflection film and manufacture method thereof, especially relate to porous layer that a kind of formation comprises soluble substance with coating after, the use solvent dissolves soluble substance and extracts, thereby the space is set at above-mentioned porous layer on coating, forms the low-reflection film and the manufacture method thereof of porous layer.
Background technology
Current, technique of display develops rapidly, at LCD, on CRT, PDP or the OLED display unit such as (organic lcd indicating meters), usually in order to prevent that contrast gradient (Contrast) from reducing because of the reflection of extraneous light and the reflection of image, at the outermost surface configuration anti-reflective film of display unit.Have scribble on the anti-reflective film of this function antireflection (AR, Anti-Reflection) or low reflection (LR, Low-Reflection) material.
Existing anti-reflective film is laminated by the transparent layer that more than one metal oxide constitutes.The transparent layer that is made of metal oxide forms by methods such as CVD (chemical vapor deposition) method or PVD (physical vapor deposition) methods, wherein generally uses the PVD method.This metal oxide layer has excellent performance as anti-reflective film, but production cost is very high, so can't be applicable to mass production.
Afterwards, developed and to have contained inorganic particles and low refraction chemicals, be coated on the film, thereby made the method for anti-reflective film, substituted the evaporation operation such as the coating of fluoride compound.
Such as, stacked high refractive index layer on supporter is arranged, the stacked above it low-index layer that is made of inorganic particles produces the method for anti-reflective film, and uses two or more MgF
2Or SiO
2Deng particulate, change specific refractory power according to selected its blending ratio of thickness, thereby produce the method for anti-reflective film.
In addition, also have to form the low-index layer that uses hollow minute particle, produce the method for anti-reflective film.Specifically be to use the inorganic powder of hollow silicon oxide and the method that tackiness agent is made anti-reflective film.
But in the above-mentioned prior art, when using inorganic particles, the coating cost is too high, and when using fluoride compound, its surface hardness is low, easily scratches, and is used in display unit and occurs cut easily, also need overcome this type of problem at present.
Summary of the invention
The present invention is intended to address the above problem, it is a kind of by introducing hard coat that its purpose is to provide, form the porous layer coating that contains soluble substance above it, use solvent that soluble substance is dissolved then and extract,, produce porous layer to form the space, and according to its porosity adjusting specific refractory power, thereby make its surface reflection below 2%, have good scratch resistant performance, and low-reflection film cheap for manufacturing cost and manufacture method thereof.
To achieve these goals, the invention provides a kind of low-reflection film, described low-reflection film comprises: the porous layer that is formed on the hard coat above the transparent basement membrane and is formed on above-mentioned hard coat top.
In addition, above-mentioned low-reflection film is characterized in that, the porosity of above-mentioned porous layer is in 10～50% scopes.
In addition, above-mentioned low-reflection film is characterized in that, the specific refractory power of above-mentioned porous layer is less than hard coat, and its specific refractory power is within 1.25～1.45 scopes, and reflectivity is below 2%.
In addition, above-mentioned low-reflection film is characterized in that, the surface hardness of above-mentioned hard coat is more than the 2H.
In addition, above-mentioned low-reflection film is characterized in that, the pore size of above-mentioned porous layer is 10～70nm.
In addition, as another form of implementation of the present invention, the manufacture method of low-reflection film is characterized in that, comprising: coating contains the coating of soluble substance on the one side at least of transparent basement membrane, to form the step of porous layer with coating; And use solvent all or part of dissolving, thereby form the step of porous layer with above-mentioned soluble substance.
In addition, the manufacture method of low-reflection film is characterized in that, above-mentioned soluble substance is that selects in the organism of at least a solvent or the inorganics in being dissolved in water, alcohols, ketones solvent is at least a.
In addition, the manufacture method of low-reflection film is characterized in that, above-mentioned solvent is, at least a in water, alcohols and the ketones solvent.
In addition, the manufacture method of low-reflection film is characterized in that, the content of above-mentioned soluble substance is that the coating that comprises above-mentioned soluble substance with respect to 100 weight parts contains 10～50 weight parts.
The present invention's low-reflection film and manufacture method thereof form coating by adding soluble substance, and use solvent with its dissolution extraction, and make porous layer, have outstanding surface hardness thereby provide, and surface reflection are the antireflective property below 2%.In addition, can control specific refractory power, therefore be easy to control reflectivity, and use cheap material, reduce manufacturing cost according to the input amount of soluble substance.
Description of drawings
Fig. 1 is the sectional view of the low-reflection film of one of the present invention embodiment;
Fig. 2 is the manufacture method schema of the low-reflection film of another embodiment of the present invention.
The reference numeral explanation:
1: transparent basement membrane
2: hard coat
3: porous layer
Embodiment
Below, with reference to drawings and Examples, the present invention is described in detail.
Fig. 1 is the sectional view of the low-reflection film of one of the present invention embodiment.As shown in the figure, comprising: be formed on the hard coat 2 above the transparent basement membrane 1 and be formed on above the above-mentioned hard coat 2, and its specific refractory power is less than the porous layer 3 of the specific refractory power of above-mentioned hard coat.
As above-mentioned transparent basement membrane 1, so long as transparent film can use.For example, derivatived cellulose, specifically be, di-acetyl Mierocrystalline cellulose, triacetyl cellulose, propionyl Mierocrystalline cellulose, butyryl Mierocrystalline cellulose, acetyl-propionyl Mierocrystalline cellulose, and thermoplasticallies such as polyester, polymeric amide, polyimide, polyethersulfone, polysulfones, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylacetal, polyetherketone, polymethacrylate, polyethylene terephthalate, polycarbonate, urethane, Resins, epoxy polymericly extend, one or two extension films.Wherein, the preferred use has outstanding transparency and stable on heating polyester film through one or two extension, and has transparency and do not have optic anisotropic triacetylcellulose film.Though do not limit the thickness of transparent basement membrane, be generally about 8～1000 μ m, preferably use the scope of 40～100 μ m.
Be used in the material of above-mentioned hard coat 2,, be not particularly limited as long as have outstanding scratch resistant performance.Here said hard coat refers to, and in pencil hardness test, has the coating of the above hardness of H.The preferred use, the surface hardness that can make hard coat is more than the 2H, is preferably the above coating of 4H.Preferred use and reactive cured resin of solidified or reactive silicoorganic compound through ultraviolet ray or heat.
As an example, can use the ultraviolet curable resin of organic-inorganic compoiste (reactive oxidants silicon particle), it can be by with silicon oxide particle and have the water-disintegrable silane mixture of polymer unsaturated group, and passes through Chemical bond manufacturing.Be about 0.05～99 weight %, preferred 5～85 weight % with reactive oxidants silicon particle bonded, amount with water-disintegrable silane of polymer unsaturated group.Above-mentioned amount is as being lower than 0.05 weight %, and influence is through the transparency and the wear resistance of solidified resin, and as being higher than 99 weight %, the raising of its wear resistance is not obvious.Water-disintegrable silyl can use, halogenation silyl, amino or hydroxyl silyls such as alkoxysilyls such as carboxylicesters silyls such as acetoxy group silyl, methoxy or ethoxy silyl, chlorination silyl wherein preferably use alkoxysilyl.Above-mentioned polymolecularity unsaturated group can use, carboxyl, hydroxyl, acryl, iso-butylene acidic group, vinyl, propenyl, butadienyl, styryl, cinnamoyl, maleate, acrylamido etc.Wherein preferred unsaturated fatty acids carboxylic acid and the methylacrylic acid salt compound that contains hydroxyl that use.The median size of reactive oxidants silicon particle is preferably 0.0001～1 μ m, when being used in the solidified transparent film, is preferably 0.001～0.01 μ m.The specific surface area of silicon oxide particle is preferably 0.001～2m
2/ g, more preferably 0.001～0.1m
2/ g, most preferably 0.001～0.01m
2/ g.Silicon oxide particle can use dried powder, or is dispersed in the silica gel in the organic solvents such as silicon sol of methyl alcohol.Reactive oxidants silicon particle is made in 5 minutes to the 24 hours time ranges under 20～150 ℃ of temperature.
In order under ultraviolet ray, to solidify, can add photoinitiator (Photoinitiator) in the above-mentioned hard coat 2, can use photoinitiator well known in the art.Specifically be, can be used alone or as a mixture benzophenone, phenmethyl methyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-ketone, 4-hydroxyl ring benzophenone, dimethoxy-2-methyl phenyl ketone, anthraquinone, fluorenes, triphenylamine, carbazole, 3-methyl acetophenone, the 4-chloroacetophenone, 4 of 0.1～10 weight %, 4-dimethoxy-acetophenone, 4,4-diaminobenzene ketone.As be lower than 0.1 weight %, and curing speed reduces, and it is then uneconomical to be higher than 10 weight %.The light stimulus agent can be shared with photoinitiator, for example can use triethylamine, diethylamine, methyldiethanolamine, thanomin, 4-dimethylamino-phenylformic acid, isopentyl-4-dimethylaminobenzoic acid salt etc.Except above-mentioned substance, also can add antioxidant, UV light absorber, photostabilizer, hot high molecular inhibitor, levelling agent, tensio-active agent, lubricant etc.
Above-mentioned porous layer 3 is formed with the space on its surface and inside, and its porosity is not particularly limited, and is preferably 10～50%, more preferably 18～40%.When porosity less than 10% the time, the problem that low refraction effect and anti-surface reflection effect reduce might appear, and when porosity greater than 50% the time, then cause scratch resistant performance and transmittance reduction because of forming slight void.The pore size of above-mentioned porous layer is 10～70nm, is preferably 20～50nm.
The specific refractory power of above-mentioned porous layer 3 is preferably less than the specific refractory power of above-mentioned hard coat, and preferably within 1.25～1.45 scope, and reflectivity is preferably below 2%.The specific refractory power of above-mentioned porous layer can be regulated by the adjusting of above-mentioned porosity.
There is no particular restriction to the material of above-mentioned porous layer 3, the reactive cured resin of optional ultraviolet ray or thermofixation or reactive silicoorganic compound.In addition, also can use ultraviolet curable resin identical etc. to have the material of preferable surface strength with above-mentioned hard coat.
The formation method of above-mentioned porous layer can be used this area common method, preferably uses manufacture method described later to form.
Except above-mentioned formation, the present invention's low-reflection film, as required can be between above-mentioned layer and layer or outside the layer stacked again other layer, these changes all belong within the scope of the present invention.In addition, the present invention's low-reflection film can be made by low-reflection film manufacture method described later.
Fig. 2 is the schema of the low-reflection film manufacture method of another embodiment of the present invention.Go into shown in the figure, the manufacture method of the present invention's low-reflection film is characterized in that, comprises the steps: to form the step (S10) of hard coat on the one side at least of transparent basement membrane; The coating of above-mentioned hard coat top contains the coating of soluble substance, to form the step (S20) of porous layer with coating; And use all or part of above-mentioned soluble substance of dissolution with solvents, to form the step (S30) of porous layer.Except above-mentioned steps, can increase other step as required, and these changes belong to equally within the present invention's the scope.
At first, transparent basement membrane at least the one side on form hard coat (S10).Can comprise aforesaid cured resin and photoinitiator in the coating of above-mentioned hard coat, can comprise that also solvent is to satisfy the required viscosity of coating.The formation method of above-mentioned hard coat can be used this area method commonly used, such as. mouthful pattern coating (Die coating), casting (Casting), gravure formula coating (Gravure coating), rotary coating methods such as (Spin coating) are coated with.The thickness of coating is generally 0.1～400 μ m, preferred 1～200 μ m.The coating back was carried out preferred 5 seconds～2 hours volatile matter evaporation drying 1 second～24 hours under 10～100 ℃ temperature.Irradiation ultraviolet radiation makes its curing then.Ultraviolet irradiation amount is about 0.01～10J/cm
2, preferred 0.1～2J/cm
2The specific refractory power of formed hard coat cans be compared to the specific refractory power height of the porous layer that is laminated in this hard coat top most, more than the preferred 2H of its surface strength, more preferably more than the 4H.
Secondly, be coated with the coating that contains soluble substance, form the porous layer coating on above-mentioned hard coat top.Coating method can use the coating method identical with above-mentioned hard coat, and this is not limited.Can use the coating of gravure formula, methods such as rotary coating.Though do not limit coating thickness, be generally 50～200nm, preferred 80～120nm.Coating under 10～100 ℃ of temperature, was carried out preferred 5 seconds～2 hours volatile matter evaporation drying with constituent 1 second～24 hours after implementing.Then, irradiation ultraviolet radiation is cured.The ultraviolet irradiation amount is about 0.01～10J/cm
2, preferred 0.1～2J/cm
2
In the above-mentioned steps, hard coat and porous layer can carry out respectively with the curing of coating, also can be cured once after forming each layer.
In the above-mentioned coating that contains soluble substance, can comprise above-mentioned tackiness agent and photoinitiator.Specifically be, the porous layer that is used to form above-mentioned porous layer is with comprising tackiness agent in the coating, it all can use so long as be not dissolved in the solvent of soluble substance dissolving usefulness, and above-mentioned porous layer material is preferably used through the reactive cured resin of ultraviolet ray or thermofixation or reactive silicoorganic compound.In addition, can use the ultraviolet curable resin that is same as above-mentioned hard coat with outstanding surface strength.
Above-mentioned soluble substance is used to form the space of porous layer, as long as can hold certainly in the organism or the inorganics of water, alcohols (methyl alcohol, ethanol, Virahol, butanols etc.), ketone (methyl ethyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), diethyl ketone, butyrone etc.) solvent, can select to use more than one.Such as, can use following monomer and polymeric materials thereof.Monomer has, the aromatic vinyl compounds of vinylbenzene, p-vinyl toluene, m-vinyl toluene, p-ethyl styrene, m-ethyl styrene, p-chloro-styrene, m-chloro-styrene, p-1-chloro-4-methyl-benzene, m-1-chloro-4-methyl-benzene, p-t-butyl phenyl ether ethene, m-t-butyl phenyl ether ethene, fluorostyrene, alpha-methyl styrene, vinyltoluene, chloro-styrene; Methacrylic ester, methyl methacrylate, the ethyl propylene acid esters, the ethylacrylic acid methyl esters, the butylacrylic acid ester, the butylacrylic acid methyl esters, the octyl group acrylate, the octyl group methyl acrylate, the stearyl acrylate, the stearyl methyl acrylate, the phenmethyl acrylate, the phenmethyl methyl acrylate, glycidyl acrylate, the glycidyl methyl acrylate, fluoro ethyl propylene acid esters, fluoro ethylacrylic acid methyl esters, hexafluoro-butylacrylic acid methyl esters, hexafluoro-isopropylacrylic acid methyl esters, the perfluoroalkyl acrylate, octafluoro is for propylene base class and fluoropropenes base class compounds such as phenylacrylic acid methyl esters; Unsaturated carboxylic acid compounds such as (methyl) vinylformic acid, toxilic acid, fumaric acid, Ba Dousuan, methylene-succinic acid, vinyl sulfonic acid; Unsaturated sulfonic acid compounds such as vinyl sulfonic acid, aryl sulfonic acid, p-styrene sulfonic acid; Acrylic ester compounds such as methyl acrylate, ethyl propenoate, butyl acrylate, Octyl acrylate, vinylformic acid methoxyl group ethyl ester, phenyl acrylate, cyclohexyl acrylate; Vinyl cyanide compounds such as (first) vinyl cyanide, methacrylonitrile; Aminated compoundss such as 2-(first) acrylamide-methyl-propyl sulfonic acid, (first) acrylamide, N-sec.-propyl (first) acrylamide, N-ethene ethanamide.In addition, mineral compound has, Zircosol ZN hydrate ([ZrO (NO
3)
2] H
2O), zirconium oxychloride hydrate (ZrOCl
2H
2O), lithium nitrate (LiNO
3), lithium oxalate (CH
3COOLi), tin protoxide hydrate (SnCl
4NH
2O), indium nitrate hydrate (In (NO
3)
3NH
2O), indium chloride hydrate (InCl
2NH
2O), 12-phospho-wolframic acid (H
3PW
12O
40), 12-silicotungstic acid (H
4SiW
12O
40) etc.Above-mentioned substance can be used alone or in combination.
Add the soluble substance in the above-mentioned hard coating to, it with respect to the content that is coated with feed liquid 100 weight parts is 10～50 weight parts, preferred 18～40 weight parts.When the content of the soluble substance that adds is 10 weight parts when following, can not fully form the porous layer of millimicro (nano) level, the phenomenon that causes low refraction effect and anti-surface reflection effect to reduce.And its content is during greater than 50 weight parts, might cause soluble substance to remain in coatingsurface and because of forming the problem that slight void reduces scratch resistance and transmittance.The specific refractory power of above-mentioned porous layer is preferably less than the specific refractory power of above-mentioned hard coat, though indefinite, preferred 1.25～1.45 scopes, reflectivity is below 2%.The specific refractory power of above-mentioned porous layer can be regulated by the adjusting to above-mentioned porosity.
Secondly, use solvent to dissolve all or part of above-mentioned soluble substance, form the space at above-mentioned porous layer on coating, thereby form porous layer (S30).With the above-mentioned film that produces, though indefinite, under 25～80 ℃ of solvent temperatures, soaked 1～60 minute, preferred 5～15 minutes, with the dissolution extraction soluble substance, then under 60～150 ℃ of conditions, dry 1～10 minute, thus produce the low-reflection film of one of the present invention embodiment.
Above-mentioned solvent can be selected more than one in the group that water, alcohols (methyl alcohol, ethanol, Virahol, butanols etc.), ketone (methyl ethyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), diethyl ketone, butyrone etc.) equal solvent are formed.
Below, the present invention is described in detail by embodiment.Embodiments of the invention are concrete example, and it does not limit protection scope of the present invention.
＜embodiment 1 〉
(ProductName: DN-0080, manufacturing concern: DSM) be coated on the tri acetyl cellulose membrane (below, be called for short TAC film), heated drying is 1 minute under 70 ℃ of temperature, utilizes high-pressure mercury light irradiation 700mJ/cm then with hard coating
2Ultraviolet ray also makes its curing.As porous layer coating, with polyacrylic acid with 20 weight %, with hard coating (ProductName: DN-0080, manufacturing concern: DSM) mix.To be coated on the TAC film that is formed with hard coat with 110nm thickness with coating through the blended porous layer, and under 70 ℃ of temperature heated drying 1 minute, utilize high-pressure mercury light irradiation 700mJ/cm then
2Ultraviolet ray makes its curing.The film that produces is placed 10 minutes in the water as solvent of 50 ℃ of temperature, remove polyacrylic acid after, 80 ℃ of dryings 5 minutes, form porous layer, thereby produce low-reflection film.Formed pore size is about 50nm.
＜embodiment 2 〉
Except (ProductName: DN-0080, manufacturing concern: the porous layer when DSM) mixing changes to outside the 25 weight % with the polyacrylic acid content of coating, and all the other conditions are identical with the foregoing description 1 with hard coating.
＜embodiment 3 〉
Except (ProductName: DN-0080, manufacturing concern: the porous layer when DSM) mixing changes to outside the 30 weight % with the polyacrylic acid content of coating, and all the other conditions are identical with the foregoing description 1 with hard coating.
＜embodiment 4 〉
Except (ProductName: DN-0080, manufacturing concern: the porous layer when DSM) mixing changes to outside the 35 weight % with the polyacrylic acid content of coating, and all the other conditions are identical with the foregoing description 1 with hard coating.
＜embodiment 5 〉
(ProductName: DN-0080, manufacturing concern: DSM) be coated on the tri acetyl cellulose membrane (below, be called for short TAC film), heated drying is 1 minute under 70 ℃ of temperature, carries out ultraviolet curing then with hard coating.As porous layer coating, with the 12-phospho-wolframic acid of 20 weight %, with hard coating (ProductName: DN-0080, manufacturing concern: DSM) mix.To be coated on the TAC film that is formed with hard coat with 110nm thickness with coating through the blended porous layer, and under 70 ℃ of temperature heated drying 1 minute, carry out ultraviolet curing then.With the film that produces 50 ℃ of temperature as the ethanol of solvent in placed 10 minutes, remove the 12-phospho-wolframic acid after, 80 ℃ of dryings 5 minutes, form porous layer, thereby produce low-reflection film.Formed pore size is about 40nm.
＜comparative example 1 〉
(ProductName: DN-0080, manufacturing concern: DSM) be coated on the TAC film, heated drying is 1 minute under 70 ℃ of temperature, carries out ultraviolet curing then, does not form porous layer with hard coating.
＜comparative example 2 〉
Except as porous layer coating, with the polyacrylic acid and the hard coating of 7 weight % content (ProductName: DN-0080, manufacturing concern: DSM) mix outside, all the other are identical with the foregoing description 1
＜experimental example 〉
To the low-reflection film of making in the foregoing description and the comparative example, test its characteristic under the following conditions, its result is as shown in table 1.
(1) specific refractory power and porosity
Use Ellipso spectrophotometer (Elli-SE Korea S Ellipso Technology company), at input angle 60 degree,, photon energy 1.20～4.80eV area test reflected light, to measure the specific refractory power and the porosity of the porous layer of making in the foregoing description and the comparative example.
(2) transmittance and Haze
Use spectrophotometer (HZ-1, Japanese SUGA company), measure the total transmittance (Total Transmittance) and the Haze of the low-reflection film of making in the foregoing description and the comparative example.
Total transmittance (%)
More than the 5:95%
More than the 4:93%
More than the 3:90%
More than the 2:85%
More than the 1:80%
(3) reflectivity
Use UV spectrophotometer (UV-Spectrophotometer, Japanese SHIMADZU company) that the reflectivity of the low-reflection film of manufacturing in the foregoing description and the comparative example is measured.The wavelength region may of being measured is the visible region of 380～780nm.In the reflectance spectrum that obtains, drawn the minimum reflectivity (%) of low-reflection film.
(4) pencil hardness
Use pencil hardness test instrument (PHT, Korea S SukBo Science company) to apply under the condition of 500g loading, measured the pencil hardness (pencil hardness) of the low-reflection film of manufacturing in the foregoing description and the comparative example.
Employed pencil is the Mitsubishi product, and each pencil hardness is carried out 5 tests.
Scratch be 2 when above except.
Scratch: OK in the time of 0
Scratch: OK in the time of 1
Scratch: 2 NG when above
(5) scratch resistance
Use to scratch (Steel wool Steel Wool) tester (WT-LCM100, Korea S PROTECH company), (under the condition of 2cm * 2cm), carry out 10 to-and-fro movements, measure the scratch resistance of the low-reflection film of manufacturing in the foregoing description and the comparative example at 1Kg/.
Steel Wool uses #0000.
A: scratch (Scratche) number is 0
A ': the scratch number is 1～10
B: the scratch number is 11～20
C: the scratch number is 21～30
D: the scratch number is more than 31
(6) cementability
The low-reflection film surface of manufacturing in the foregoing description and comparative example, with 1 centimeter at interval along laterally and vertically draw 11 straight lines respectively, 100 squares that draw use adhesive tape (CT-24, Japanese NICHIBAN) to carry out 3 stripping tests then.100 foursquare mensuration are carried out 3 times and are obtained its mean value.
Cementability is calculated as follows:
Cementability=n/100
N: the square number of not being stripped from all squares
100: all square numbers
Therefore, when a square is all unstripped, count 100/100.
(7) size in space
Use FE-SEM (S4300, HIT) to measure void size.
Table 1
| Embodiment 1 | |
Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | |
| Soluble substance content (weight %) | 20 | 25 | 30 | 35 | 20 | - | 7 |
| The specific refractory power of low-index layer (%) | 1.41 | 1.38 | 1.36 | 1.32 | 1.40 | - | 1.48 |
| The voidage of low-index layer (%) | 19 | 23 | 29 | 37 | 18 | - | 4 |
| Total transmittance (%) | 4 | 4 | 4 | 5 | 4 | 3 | 3 |
| Haze(％) | 0.4 | 0.3 | 0.4 | 0.4 | 0.3 | 0.3 | 0.4 |
| Reflectivity (%) | 1.9 | 1.6 | 1.1 | 0.6 | 1.9 | 4.1 | 3.9 |
| Pencil hardness | 5H | 4H | 4H | 4H | 5H | 5H | 5H |
| Scratch resistance | A | A | A | A | A | A | A |
| Cementability | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 |
| Low-refraction void size (nm) | 30～50 | 30～50 | 30～50 | 30～50 | 30～50 | - | 30～50 |
Claims (9)
1, a kind of low-reflection film is characterized in that, comprising:
Be formed on the hard coat on transparent basement membrane top, and the porous layer that is formed on above-mentioned hard coat top.
2, low-reflection film as claimed in claim 1 is characterized in that:
The porosity of above-mentioned porous layer is within 10～50% scopes.
3, low-reflection film as claimed in claim 1 is characterized in that:
The specific refractory power of above-mentioned porous layer is less than the specific refractory power of above-mentioned hard coat, and its specific refractory power is within 1.25～1.45 scopes, and reflectivity is below 2%.
4, low-reflection film as claimed in claim 1 is characterized in that:
The surface hardness of above-mentioned hard coat is more than the 2H.
5, low-reflection film as claimed in claim 1 is characterized in that:
The space of above-mentioned porous layer is of a size of within 10～70nm scope.
6, a kind of manufacture method of low-reflection film is characterized in that, comprises the steps:
On the one side at least of transparent basement membrane, form the step of coating;
Contain the coating of soluble substance in the coating of above-mentioned hard coat top, thereby form the step of porous layer with coating;
Use solvent with all or part of above-mentioned soluble substance dissolving, thereby form the step of porous layer.
7, as the manufacture method of low-reflection film as described in the claim 6, it is characterized in that:
Above-mentioned soluble substance is that selects in the organism of at least a solvent or the inorganics in being dissolved in water, alcohols, ketones solvent is at least a.
8, as the manufacture method of low-reflection film as described in the claim 7, it is characterized in that:
According to the content of above-mentioned soluble substance, regulate optical characteristics.
9, as the manufacture method of low-reflection film as described in the claim 6, it is characterized in that:
The content of above-mentioned soluble substance is that the coating that comprises above-mentioned soluble substance with respect to 100 weight parts contains 10～50 weight parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2006-0012066 | 2006-02-08 | ||
| KR20060012066 | 2006-02-08 | ||
| KR1020060012066 | 2006-02-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016197A true CN101016197A (en) | 2007-08-15 |
| CN101016197B CN101016197B (en) | 2010-12-22 |
Family
ID=38491489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100075671A Expired - Fee Related CN101016197B (en) | 2006-02-08 | 2007-02-08 | Low reflective film and manufacturing method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4762165B2 (en) |
| KR (1) | KR101312064B1 (en) |
| CN (1) | CN101016197B (en) |
| TW (1) | TW200730866A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102588752A (en) * | 2011-01-07 | 2012-07-18 | 晶元光电股份有限公司 | Light emitting device |
| CN101858994B (en) * | 2009-04-10 | 2013-09-11 | 东丽先端素材株式会社 | Low reflection film |
| CN107118607A (en) * | 2017-07-06 | 2017-09-01 | 四川粒界科技有限公司 | A kind of preparation method of high transmittance antireflective organic coating |
| CN110621493A (en) * | 2017-05-19 | 2019-12-27 | 东友精细化工有限公司 | Hard coat film and image display device including the same |
Families Citing this family (5)
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| WO2010108156A2 (en) * | 2009-03-20 | 2010-09-23 | Eric William Hearn Teather | Diffusively light reflective paint composition, method for making paint composition, and diffusively light reflective articles |
| US8361611B2 (en) | 2009-03-20 | 2013-01-29 | Whiteoptics Llc | Diffusively light reflective paint composition, method for making paint composition, and diffusively light reflective articles |
| JP5237506B1 (en) * | 2012-02-28 | 2013-07-17 | 三菱樹脂株式会社 | Scratch-resistant resin laminate, display front cover material, and image display device |
| KR20140118692A (en) * | 2012-02-28 | 2014-10-08 | 미쓰비시 쥬시 가부시끼가이샤 | Abrasion-resistant resin laminate, material for front cover of display and image display device |
| KR102226138B1 (en) * | 2019-01-09 | 2021-03-11 | 율촌화학 주식회사 | Cpi film for flexible displays comprising low-reflection coating layer |
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| JP2913715B2 (en) * | 1989-12-28 | 1999-06-28 | 日本板硝子株式会社 | Antireflection film and method of forming the same |
| JPH04121701A (en) * | 1990-09-12 | 1992-04-22 | Canon Inc | Antireflection film |
| JPH07140303A (en) * | 1993-11-22 | 1995-06-02 | Sekisui Chem Co Ltd | Production of antireflection coating film |
| JP2000052492A (en) * | 1998-08-12 | 2000-02-22 | Toppan Printing Co Ltd | Anti-reflective laminate, optically functional laminate, and display device |
| JP2000147750A (en) * | 1998-11-18 | 2000-05-26 | Mitsui Chemicals Inc | Pellicle |
| JP2001164117A (en) * | 1999-12-07 | 2001-06-19 | Toppan Printing Co Ltd | High-refractive-index composition and antireflection laminate |
| JP4801263B2 (en) * | 2000-02-04 | 2011-10-26 | 東レ株式会社 | Plastic laminate and image display protection film |
| JP4046921B2 (en) * | 2000-02-24 | 2008-02-13 | 触媒化成工業株式会社 | Silica-based fine particles, method for producing the fine particle dispersion, and coated substrate |
| JP2003131001A (en) * | 2001-05-25 | 2003-05-08 | Shipley Co Llc | Porous optical materials |
| KR20040070225A (en) * | 2001-12-14 | 2004-08-06 | 아사히 가세이 가부시키가이샤 | Coating composition for forming low-refractive index thin layers |
| JP4013557B2 (en) * | 2002-01-18 | 2007-11-28 | 日本製紙株式会社 | Surface protection film |
| JP4299513B2 (en) * | 2002-08-13 | 2009-07-22 | 三菱レイヨン株式会社 | Coating composition and article |
| JP2004169028A (en) * | 2002-11-08 | 2004-06-17 | Mitsubishi Chemicals Corp | Radiation-curable resin composition and cured product thereof |
| JP2004212791A (en) * | 2003-01-07 | 2004-07-29 | Dainippon Printing Co Ltd | Optical member and its manufacturing method |
| JP4404336B2 (en) * | 2003-02-20 | 2010-01-27 | 大日本印刷株式会社 | Anti-reflection laminate |
| TWI238894B (en) * | 2003-02-21 | 2005-09-01 | Asahi Kasei Corp | Laminate containing silica and application composition for forming porous silica layer |
| JP2005274696A (en) * | 2004-03-23 | 2005-10-06 | Konica Minolta Opto Inc | Antireflective film, polarizing plate, and display device |
| JP4948805B2 (en) * | 2004-09-13 | 2012-06-06 | 日東電工株式会社 | Method for manufacturing porous body for antireflection sheet, porous body for antireflection sheet, antireflection film, method for manufacturing antireflection sheet, and antireflection sheet |
-
2007
- 2007-01-26 KR KR1020070008325A patent/KR101312064B1/en not_active IP Right Cessation
- 2007-02-06 TW TW096104316A patent/TW200730866A/en not_active IP Right Cessation
- 2007-02-08 CN CN2007100075671A patent/CN101016197B/en not_active Expired - Fee Related
- 2007-02-08 JP JP2007029776A patent/JP4762165B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101858994B (en) * | 2009-04-10 | 2013-09-11 | 东丽先端素材株式会社 | Low reflection film |
| CN102588752A (en) * | 2011-01-07 | 2012-07-18 | 晶元光电股份有限公司 | Light emitting device |
| CN110621493A (en) * | 2017-05-19 | 2019-12-27 | 东友精细化工有限公司 | Hard coat film and image display device including the same |
| US11364712B2 (en) | 2017-05-19 | 2022-06-21 | Dongwoo Fine-Chem Co., Ltd | Hard coating film and image display apparatus comprising same |
| CN107118607A (en) * | 2017-07-06 | 2017-09-01 | 四川粒界科技有限公司 | A kind of preparation method of high transmittance antireflective organic coating |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI346792B (en) | 2011-08-11 |
| JP4762165B2 (en) | 2011-08-31 |
| JP2007213079A (en) | 2007-08-23 |
| KR20070080820A (en) | 2007-08-13 |
| CN101016197B (en) | 2010-12-22 |
| TW200730866A (en) | 2007-08-16 |
| KR101312064B1 (en) | 2013-09-25 |
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