CN105319616A - Anti-dazzle film substrate and article - Google Patents
Anti-dazzle film substrate and article Download PDFInfo
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- CN105319616A CN105319616A CN201510395676.XA CN201510395676A CN105319616A CN 105319616 A CN105319616 A CN 105319616A CN 201510395676 A CN201510395676 A CN 201510395676A CN 105319616 A CN105319616 A CN 105319616A
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- antiglare film
- base material
- silicon dioxide
- antiglare
- coating fluid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention provides an anti-dazzle film substrate having an excellent anti-dazzle effect on incident light with a large incident angle, and an article using the substrate. The anti-dazzle film substrate (10) has a substrate (12) and an anti-dazzle film (14), the refractive index of the anti-dazzle film (14) is more than 1.2 and less than 1.4, the arithmetic mean roughness Ra of the surface is 0.112-0.700 [mu]m, and the 85 DEG relative specular glossiness is less than 70%, or the refractive index is more than 1.4 and less than 1.5, the arithmetic mean roughness Ra of the surface is 0.158-0.500 [mu]m, and the 85 DEG relative specular glossiness is less than 70%.
Description
Technical field
The present invention relates to band antiglare film base material and use the article of this base material.
Background technology
Be arranged in the image display device (liquid crystal display, OLED display, plasma display etc.) on various equipment (televisor, PC, smart mobile phone, mobile phone etc.), when the external light sources such as room lighting (fluorescent light etc.), sunshine map on the display face, due to reflected image, visuognosis degree declined.
Therefore, in order to suppress the mapping of external light source, the surface of the base material (glass plate etc.) of the display surface of composing images display device is implemented non-glare treated or low reflection process.
In recent years, in order to reduce sunshine reflection, improve generating efficiency and low reflection process implemented to the light entrance face of the cover glass of solar module, or the light pollution caused in order to the reflected light prevented due to reflection and surface enforcement non-glare treated to cover glass.
Non-glare treated be arrange from the teeth outwards concavo-convex, concavo-convexly make incident light generation scattering to make the feint process of reflected image by this.As non-glare treated, hitherto known have carry out roughened method by carrying out burn into sandblasting etc. to the surface of base material.In addition, the esters of silicon acis after by hydrolysis, alcohol, water and acid (hydrochloric acid/nitric acid etc.) and the treating fluid that obtain is coated with, burns till the method (patent documentation 1) forming light diffusion layer (antiglare film) is proposed.
Low reflection process is the process of the reflection suppressing incident light itself.As low reflection process, hitherto known have the method arranging low-reflection film.As low-reflection film, the multilayer film etc. that the known monofilm that is made up of low-index material and the layer be made up of low-index material and the layer be made up of high-index material combine.
Low-reflection film designs according to the optical path length based on vertical incidence angle, therefore there is the position according to the people of the incident angle of external light source or viewing picture and causes that optical path length off-design, reflectivity rise, the shortcoming of low reflecting effect loss.
Antiglare film then makes external light source scattered reflection, does not therefore rely on the position of the incident angle of external light source or the people of viewing picture and embodies antiglare effect, more favourable than low-reflection film in being shining into suppressing external light source.
The antiglare effect of antiglare film is evaluated with the glossiness of 60 ° of incident angles (60 ° of mirror surface lusters) usually.Therefore, antiglare film is typically designed to the film that 60 ° of mirror surface lusters are diminished.
But, even if in antiglare film, also there is incident angle and be greater than 60 °, especially close to the problem that can not give full play to antiglare effect when 90 °.
Time on roof solar module being arranged on inclination, sunshine is sometimes to inject cover glass close to the incident angle of 90 °.In this case, even if arrange antiglare film on the surface of cover glass, also have the reflected light reflected on the surface of cover glass inject near buildings in cause the sorrow of light pollution.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open No. Sho 60-109134 publication
Summary of the invention
Invent technical matters to be solved
The object of the invention is to, provide the band antiglare film base material of the antiglare effect excellence of the large incident light of incident angle and the article using this base material.
The technical scheme that technical solution problem adopts
The present invention includes following technology contents.
[1] a kind of band antiglare film base material, possesses base material and is formed in the antiglare film on above-mentioned base material,
The refractive index of above-mentioned antiglare film is more than 1.2 and lower than 1.4,
The arithmetic mean rugosity Ra on the surface of above-mentioned antiglare film is 0.112 ~ 0.700 μm,
85 ° of mirror surface lusters on the surface of above-mentioned antiglare film are less than 70%.
[2] a kind of band antiglare film base material, possesses base material and is formed in the antiglare film on above-mentioned base material,
The refractive index of above-mentioned antiglare film is more than 1.4 and below 1.5,
The arithmetic mean rugosity Ra on the surface of above-mentioned antiglare film is 0.158 ~ 0.500 μm,
85 ° of mirror surface lusters on the surface of above-mentioned antiglare film are less than 70%.
[3] the band antiglare film base material as described in [1] or [2], wherein, above-mentioned antiglare film contains either one or both of solid silicon dioxide granule and hollow silica particle.
[4] the band antiglare film base material according to any one of [1] ~ [3], wherein, above-mentioned antiglare film is formed by the coating fluid containing silica precursor and liquid medium.
[5] the band antiglare film base material according to any one of [1] ~ [4], wherein, above-mentioned base material is glass plate.
[6] the band antiglare film base material as described in [5], wherein, above-mentioned glass plate is strengthening glass sheets.
[7] the band antiglare film base material as described in [6], wherein, above-mentioned strengthening glass sheets is chemically reinforced glass plate, and thickness of slab is 0.4 ~ 1.1mm.
[8] article, possess [1] ~ [7] according to any one of band antiglare film base material.
[9] article as described in [8] wherein, are solar modules.
The effect of invention
By the present invention, then can provide the band antiglare film base material of the antiglare effect excellence of the large incident light of incident angle and the article using this base material.
Accompanying drawing explanation
Fig. 1 is the sectional view of the example schematically representing band antiglare film base material of the present invention.
Embodiment
The definition of following term is applicable to this instructions and claims.
" silica precursor " refers to the material of the matrix that can be formed using silicon dioxide as principal ingredient.
" using silicon dioxide as principal ingredient " refers to containing the above SiO of 90 quality %
2.
" using titanium dioxide as principal ingredient " refers to containing the above TiO of 90 quality %
2.
" solid " represents that inside does not have cavity.
" hollow " represents that inside has cavity.
" with the hydrolization group of silicon atom bonding " refers to can by being hydrolyzed, changing the group with the OH base of silicon atom bonding into.
" 85 ° of mirror surface lusters ", " 60 ° of mirror surface lusters " are the methods respectively by recording in JISZ8741:1997 (ISO2813:1994), to being that the band antiglare film base material that the face of opposition side is pasted with black belt measures with the side being formed with antiglare film.
" arithmetic mean rugosity Ra " is that the method by recording in JISB0601:2001 (ISO4287:1997) carries out measuring.
" mist degree " is that the method by recording in JISK7136:2000 (ISO14782:1999) carries out measuring.
(band antiglare film base material)
Fig. 1 is the sectional view of the example schematically representing band antiglare film base material of the present invention.
The band antiglare film base material 10 of this example possesses base material 12 and is formed at the antiglare film 14 on base material 12.
(base material)
As the form of base material 12, such as, plate, film etc. can be exemplified.
As the material of base material 12, such as, glass, resin etc. can be exemplified.
As glass, such as soda-lime glass, borosilicate glass, alumina silicate glass, alkali-free glass etc. can be exemplified.
As resin, such as polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethylmethacrylate etc. can be exemplified.
Base material 12 is preferably transparent.The transparent light average transmission more than 80% referred in the wavelength region may of 400 ~ 1100nm in base material 12.
As base material 12, preferred glass plate.
Glass plate can be the level and smooth glass plate be shaped by float glass process, fusion method etc., also can be the irregular ambetti of tool from the teeth outwards (Japanese: template ガ ラ ス) formed by roll-in method etc.In addition, can be not only smooth glass, can also be the glass with curve form.
The thickness of glass plate is not particularly limited.Such as can use the glass plate of below thickness 10mm.Then more the absorption of light can be suppressed in low-level, therefore for being preferred by the purposes improved for the purpose of transmissivity because thickness is thinner.
When glass is soda-lime glass, preferably there is following composition.
Represent with the mass percent of oxide benchmark, contain:
SiO
2：65～75％，
Al
2O
3：0～10％，
CaO：5～15％，
MgO：0～15％，
Na
2O：10～20％，
K
2O：0～3％，
Li
2O：0～5％，
Fe
2O
3：0～3％，
TiO
2：0～5％，
CeO
2：0～3％，
BaO：0～5％，
SrO：0～5％，
B
2O
3：0～15％，
ZnO：0～5％，
ZrO
2：0～5％，
SnO
2：0～3％，
SO
3：0～0.5％。
When glass is alumina silicate glass, preferably there is following composition.
Represent with the molar percentage of oxide benchmark, contain
SiO
2：62～68％，
Al
2O
3：6～20％，
MgO：7～13％，
Na
2O：9～17％，
K
2O：0～7％，
ZrO
2：0～8％。
The preferred strengthening glass sheets of glass plate.Strengthening glass sheets is the glass plate implementing intensive treatment.By intensive treatment, the intensity of glass improves, and such as can cut down thickness of slab while maintenance intensity.
But in the present invention, the glass plate beyond strengthening glass sheets can also be used, suitably can set according to the purposes etc. of band antiglare film base material 10.
As intensive treatment, the known process forming compressive stress layers in glass pane surface usually.The compressive stress layers of glass pane surface improves glass plate to the intensity damaged or impact.As the method forming compressive stress layers in glass pane surface, with air-cooled reinforcement (physical strengthening method), chemical enhanced method for representative.
In air-cooled reinforcement, the glass pane surface of (such as 600 ~ 700 DEG C) near the softening point temperature being heated to glass is carried out quenching by air-cooled etc.By this, between the surface and inside of glass plate, produce temperature difference, glass plate top layer generates compression stress.
In chemical enhanced method, at the temperature below the DEFORMATION POINTS temperature of glass, be immersed in by glass plate in fuse salt, the ion (such as sodion) on glass plate top layer exchanges with the ion (such as potassium ion) of more heavy ion radius.By this, glass plate top layer produces compression stress.In addition, the DEFORMATION POINTS of glass is lower than softening point.
If the lower thickness of glass plate (such as lower than 2mm), then in air-cooled reinforcement, be difficult to produce temperature difference between inside of glass plate and top layer thus can not abundant strengthening glass sheets, therefore preferably uses chemical enhanced method.
As long as have the composition that can carry out chemical intensification treatment, then be not particularly limited having the glass plate can implementing chemical enhanced composition, the glass plate of various composition can be used, such as soda-lime glass, sillico aluminate glass, borate glass, lithium alumina silicate glass, borosilicate glass, alkali-free glass, other various glass can be exemplified.Chemical enhanced from the viewpoint of easily carrying out, as glass composition, represent with the molar percentage of oxide benchmark, preferably containing SiO
256 ~ 75%, Al
2o
31 ~ 20%, Na
2o8 ~ 22%, K
2o0 ~ 10%, MgO0 ~ 14%, ZrO
20 ~ 5%, CaO0 ~ 10%.Wherein preferred alumina silicate glass.
Implement the thickness of slab preferably 0.4 ~ 1.1mm of the glass plate of chemical intensification treatment, particularly preferably 0.5 ~ 1.0mm.If the thickness of slab of chemically reinforced glass plate is below the higher limit of above-mentioned scope, be then with antiglare film base material 10 deal light, if more than the lower limit of above-mentioned scope, be then with antiglare film base material 10 excellent strength.
In addition, chemical enhanced front and back thickness of slab does not change.That is, the thickness of slab implementing the glass plate of chemical intensification treatment is exactly the thickness of slab of chemically reinforced glass plate (implementing the glass plate after chemical intensification treatment).
(antiglare film)
Antiglare film 14 is following (α) or (β).
(α) refractive index more than 1.2 and lower than 1.4, the arithmetic mean rugosity Ra on surface is 0.112 ~ 0.700 μm, the antiglare film of 85 ° of mirror surface lusters below 70% on surface.
(β) refractive index more than 1.4 and below 1.5, surface arithmetic mean rugosity Ra be 0.158 ~ 0.500 μm, surface the antiglare film of 85 ° of mirror surface lusters below 70%.
Here, the surface of antiglare film 14 refers to that with base material 12 side be the face of opposition side, is namely with the surface of antiglare film 14 side of antiglare film base material 10.
Arithmetic mean rugosity Ra is the index of the average height of the concavo-convex fluctuating (Japanese: mountain valley) of presentation surface.
When the refractive index of antiglare film 14 is identical, the arithmetic mean rugosity Ra on surface is larger, and 85 ° of mirror surface lusters just become less, have the tendency of antiglare effect excellence incident angle being greater than to the incident light (hereinafter referred to as oblique incident ray) of 60 °.In addition, when the arithmetic mean rugosity Ra on the surface of antiglare film 14 is identical, refractive index is less, and 85 ° of mirror surface lusters become less, has the tendency of the antiglare effect excellence to oblique incident ray.
If the refractive index of antiglare film 14 is below 1.5, especially lower than 1.4, then the reflectivity step-down on the surface of antiglare film 14, even if Ra is below 0.700 μm, further below 0.500 μm, also can obtain enough antiglare effect.
If the refractive index of antiglare film 14 is more than 1.2, especially more than 1.4, then the compactness of antiglare film 14 is enough high, with the excellent adhesion of the base materials 12 such as glass plate.In addition, if the arithmetic mean rugosity Ra on surface becomes large, then have the tendency of the physical strength step-downs such as the abrasion resistance of antiglare film 14, but due to the compactness of antiglare film 14 high, even if then arithmetic mean rugosity Ra becomes large, the physical strength of antiglare film 14 is also enough excellent.
(α) refractive index of antiglare film preferably more than 1.25 and lower than 1.4.
(α) the arithmetic mean rugosity Ra of antiglare film preferably 0.113 ~ 0.650 μm.If the arithmetic mean rugosity Ra on the surface of antiglare film (α) is more than the lower limit of above-mentioned scope, then antiglare effect can be given full play to.If the arithmetic mean rugosity Ra on the surface of antiglare film (α) is below the higher limit of above-mentioned scope, then the mechanical strength of antiglare film 14, in addition, the mist degree of antiglare film base material 10 is with also to become enough little.
(α) 85 ° of mirror surface lusters of antiglare film preferably less than 65%, more preferably less than 60%.From the viewpoint of the antiglare effect to oblique incident ray, the lower limit of these 85 ° of mirror surface lusters to be not particularly limited, but from the viewpoint of the physical strength of antiglare film 14, preferably more than 15%, more preferably more than 20%.
(α) 60 ° of mirror surface lusters on the surface of antiglare film preferably less than 60%, more preferably less than 50%.If 60 ° of mirror surface lusters are below 60%, then also can play excellent antiglare effect to the incident light (incident angle is the incident light of 0 ~ 60 °) beyond oblique incident ray.
(β) refractive index of antiglare film preferably more than 1.40 and below 1.46.
(β) the arithmetic mean rugosity Ra of antiglare film preferably 0.200 ~ 0.500 μm.If the arithmetic mean rugosity Ra on the surface of antiglare film (β) is more than the lower limit of above-mentioned scope, then antiglare effect can be given full play to.If the arithmetic mean rugosity Ra on the surface of antiglare film (β) is below the higher limit of above-mentioned scope, then the mechanical strength of antiglare film 14, in addition, the mist degree of antiglare film base material 10 is with also to become enough little.
(β) preferable range of 85 ° of mirror surface lusters of antiglare film, the preferable range of 60 ° of mirror surface lusters are identical with the antiglare film of (α) respectively.
85 ° of mirror surface lusters and 60 ° of mirror surface lusters on the surface of antiglare film 14 can adjust according to the arithmetic mean rugosity Ra etc. on the surface of the refractive index of antiglare film 14, antiglare film 14.
The refractive index of antiglare film 14 by the host material of antiglare film 14, antiglare film 14 voidage, in matrix, add the material etc. with arbitrary refractive index adjust.Such as, the voidage by improving antiglare film 14 reduces refractive index.The refractive index of antiglare film 14 is also reduced by adding the low material of refractive index (solid silicon dioxide granule, hollow silica particle etc.) in matrix.
The method of adjustment of the arithmetic mean rugosity Ra on the surface of antiglare film 14 as described later in detail.
As antiglare film 14, from considerations such as easy adjustment refractive index or arithmetic surface roughness Ra, chemical stability are excellent, either party or both sides (hereinafter also referred to silicon dioxide granule (I)) preferably containing solid silicon dioxide granule and hollow silica particle.
The matrix of film containing silicon dioxide granule (I) typically also containing the space of filling between silicon dioxide granule (I).Matrix also can cover the upside (opposition side of base material 12 side) of silicon dioxide granule (I) in the mode not making silicon dioxide granule (I) expose.
As antiglare film 14, that be made up of matrix, not containing silicon dioxide granule (I) film also can be used.
Antiglare film 14 can also contain other particles beyond silicon dioxide granule (I).
Antiglare film 14 can also contain terpene compound.
Antiglare film 14 can also contain other compositions (hereinafter also referred to " other any compositions ") beyond silicon dioxide granule (I), matrix, other particles and terpene compound further.
Matrix:
As the matrix of antiglare film 14, can exemplified by silica class matrix, titanium oxide based matrix etc.
" silica-based matrix " refers to silicon dioxide to be the matrix of principal ingredient.
" titanium oxide based matrix " refers to titanium dioxide to be the matrix of principal ingredient.
As the matrix of antiglare film 14, preferred silica-based matrix.If matrix is silica-based matrix, then easily reduce the refractive index (reflectivity) of antiglare film 14.In addition, chemical stability, abrasion resistance etc. are also good.When base material 12 is glass, adaptation is good especially.
Silica-based matrix can on a small quantity containing the composition beyond silicon dioxide.As this composition, one or more ions of being selected from Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi and lanthanum element and or the compound such as oxide can be exemplified.
As silica-based matrix, be preferably made up of silicon dioxide in fact.Be made up of silicon dioxide in fact and refer to and to be only made up of silicon dioxide except inevitable impurity.
As silica-based matrix, such as, can exemplify the matrix formed by the coating fluid containing silica precursor and liquid medium.Silica precursor as described later in detail.
Silicon dioxide granule (I):
Silicon dioxide granule (I) is either party or both sides of solid silicon dioxide granule and hollow silica particle.
As the shape of solid silicon dioxide granule, spherical, ellipticity, needle-like, tabular, bar-shaped, coniform, cylindric, cubic, rectangular-shaped, diamond shaped, starlike, irregularly shaped etc. can be exemplified.Solid silicon dioxide granule both with the independently state existence of each particle, also can connect to chain by each particle, can also each particles aggregate.
As solid silicon dioxide granule, from the viewpoint of easy low-refraction, the solid silicon dioxide granule of preferred chain.
The solid silicon dioxide granule of chain is the solid silicon dioxide granule with chain shape.Such as can exemplify and multiplely there is solid silicon dioxide granule that is spherical, the shape such as ellipticity, needle-like connect the solid silicon dioxide granule of catenulate shape.The shape of the solid silicon dioxide granule of chain confirms by electron microscope.
The solid silicon dioxide granule of chain can be used as commercially available product and easily obtains.In addition, the particle manufactured by known manufacture method can also be used.As commercially available product, the SNOWTEXST-OUP etc. that such as Nissan Chemical Ind Ltd's (Nissan Chemical Industries (strain)) makes can be exemplified.
The average aggegation particle diameter preferably 5 ~ 300nm of solid silicon dioxide granule, more preferably 5 ~ 200nm.If the average aggegation particle diameter of solid silicon dioxide granule is in above-mentioned scope, then the arithmetic mean rugosity Ra on the surface of antiglare film 14 is easily in above-mentioned scope.
Average aggegation particle diameter can use dynamic light scattering method particle-size analyzer (Nikkiso Company Limited (Machine fills society) to make, MICROTRACUPA) measure.
Hollow silica particle is owing to having cavity in inside, therefore low with solid silicon dioxide granule phase specific refractivity.Therefore, there is the advantage of the reduction effect that can obtain refractive index with the amount fewer than solid silicon dioxide granule.
As hollow silica particle, can exemplify and possess silicon dioxide (SiO
2) shell, be in the enclosure shaped with cavity particle.
The average primary particle diameter preferably 40 ~ 150nm of hollow silica particle, more preferably 50 ~ 100nm.If the average primary particle diameter of hollow silica particle is in above-mentioned scope, then the arithmetic mean rugosity Ra on the surface of antiglare film 14 is easily in above-mentioned scope.
The average primary particle diameter of hollow silica particle is obtained as follows.
Hollow silica particle is observed with scanning electron microscope (being denoted as SEM below) or transmission electron microscope (being denoted as TEM below), select 100 hollow silica particles at random, measure the particle diameter of each hollow silica particle, ask the mean value of the particle diameter of 100 hollow silica particles.
Other particles:
As other particles, metal oxide particle, metallics, pigment class particle, resin particle etc. can be exemplified.Other particles can be hollow structures also can be solid construction.
As the material of metal oxide particle, Al can be exemplified
2o
3, SiO
2, SnO
2, TiO
2, ZrO
2, ZnO, CeO
2, containing the SnO of Sb
x(ATO), containing the In of Sn
2o
3(ITO), RuO
2deng.
As the material of metallics, metal (Ag, Ru etc.), alloy (AgPd, RuAu etc.) etc. can be exemplified.
As pigment class particle, inorganic pigment (titanium black, carbon black etc.), organic pigment can be exemplified.
As the material of resin particle, polystyrene, melamine resin etc. can be exemplified.
As the shape of other particles, flakey, spherical, ellipticity, needle-like, tabular, bar-shaped, coniform, cylindric, cubic, rectangular-shaped, diamond shaped, starlike, irregularly shaped etc. can be exemplified.Other particles both with the independently state existence of each particle, also can connect to chain by each particle, can also each particles aggregate.
Other particle can be used alone a kind, also can two or more also use.
As other particles, peel off from the viewpoint of the crackle or film that can suppress antiglare film 14, You Xuan Scales platy particle.“ Scales platy particle " refer to the particle with flat pattern.The shape of particle can use TEM to confirm.
Zuo Wei Scales platy particle, can Li Ju Scales flaky silicon dioxide particle, Scales tabular alumina particle, Scales lamellar titanium oxide, Scales flaky zirconia etc., rises, reduces reflectivity, You Xuan Scales flaky silicon dioxide particle from the viewpoint of suppressing the refractive index of film.
Zuo is Scales flaky silicon dioxide particle, preferably by the particle that the manufacture method recorded in Japanese Patent Laid-Open 2014-94845 publication manufactures.
Terpene compound:
Terpene compound as described later in detail.
Other any compositions:
Other any compositions as described later in detail.
In antiglare film 14, the total content of matrix and silicon dioxide granule (I) relative to the gross mass of antiglare film 14, preferably 10 ~ 100 quality %, more preferably 20 ~ 100 quality %, particularly preferably 30 ~ 100 quality %.If the total content of matrix and silicon dioxide granule (I) is more than the lower limit of above-mentioned scope, then abrasion resistance is excellent.
The content of the silicon dioxide granule (I) in antiglare film 14 can consider that the kind etc. of the refractive index of antiglare film 14, arithmetic surface roughness Ra, silicon dioxide granule (I) suitably sets.
In the antiglare film that antiglare film 14 is above-mentioned (α), when silicon dioxide granule (I) is for solid silicon dioxide granule, the content of the solid silicon dioxide granule in antiglare film 14 relative to the gross mass of antiglare film 14 preferably greater than 0 quality % and at below 70 quality %, more preferably above 0 quality % and at below 60 quality %, particularly preferably more than 0 quality % and at below 50 quality %.If the content of solid silicon dioxide granule is in above-mentioned scope, then have that the content of solid silicon dioxide granule is more, the refractive index of antiglare film 14 just becomes lower, arithmetic surface roughness Ra just becomes larger tendency.If the content of solid silicon dioxide granule is below the higher limit of above-mentioned scope, then easily makes the refractive index of antiglare film 14 more than the lower limit of above-mentioned scope, make arithmetic surface roughness Ra below the higher limit of above-mentioned scope.
Based on identical reason, when antiglare film 14 be the antiglare film of above-mentioned (β), silicon dioxide granule (I) for solid silicon dioxide granule, the content of the solid silicon dioxide granule in antiglare film 14 is relative to gross mass preferably 60 ~ 80 quality % of antiglare film 14, more preferably 70 ~ 80 quality %.
When antiglare film 14 be the antiglare film of above-mentioned (α), silicon dioxide granule (I) for hollow silica particle, the content of the hollow silica particle in antiglare film 14 relative to the gross mass of antiglare film 14 preferably greater than 0 quality % and at below 20 quality %, more preferably above 0 quality % and at below 15 quality %, particularly preferably more than 0 quality % and at below 20 quality %.If the content of hollow silica particle is in above-mentioned scope, then have that the content of hollow silica particle is more, the refractive index of antiglare film 14 just becomes lower, arithmetic surface roughness Ra just becomes larger tendency.If the content of hollow silica particle is below the higher limit of above-mentioned scope, then easily makes the refractive index of antiglare film 14 more than the lower limit of above-mentioned scope, make arithmetic surface roughness Ra below the higher limit of above-mentioned scope.
Based on identical reason, when antiglare film 14 be the antiglare film of above-mentioned (β), silicon dioxide granule (I) for hollow silica particle, the content of the hollow silica particle in antiglare film 14 is relative to gross mass preferably 21 ~ 80 quality % of antiglare film 14, more preferably 30 ~ 70 quality %.
(mist degree)
Mist degree with antiglare film base material 10 preferably 5 ~ 20%, more preferably 5 ~ 15%.If mist degree is below the higher limit of above-mentioned scope, then the contrast of the image when band antiglare film base material 10 being used for display device, generating efficiency when maybe band antiglare film base material 10 being used for solar module are good.If mist degree more than the lower limit of above-mentioned scope, then easily plays antiglare effect.
< is with the manufacture method > of antiglare film base material
As the manufacture method of band antiglare film base material 10, such as,
Coating on the base substrate 12 can be exemplified and contain the coating fluid (hereinafter also referred to antiglare film coating fluid) of silica precursor and liquid medium, be formed the method for antiglare film 14 by drying.
Antiglare film coating fluid can contain silicon dioxide granule (I), other particles, terpene compound, other any compositions etc. as required.Antiglare film with coating fluid as described later in detail.
When forming antiglare film 14, the coating of antiglare film coating fluid and drying are carried out under making the arithmetic mean rugosity Ra on the surface of antiglare film 14 condition within the limits prescribed.
(coating)
As the coating process of antiglare film coating fluid, known wet coating method (spraying process, spin-coating method, dip coating, mould are coated with method, curtain coating method, serigraphy rubbing method, ink-jet method, flow coat method, gravure coat method, stick coating method, soft version rubbing method, slot coated method, rolling method) etc. can be exemplified.
As coating process, enough concavo-convex from the viewpoint of easily being formed, preferred spraying process.
As the nozzle that spraying process uses, second fluid nozzle, fluid nozzle etc. can be exemplified.
The size droplet diameter of the coating fluid spued from nozzle is generally 0.1 ~ 100 μm, preferably 1 ~ 50 μm.If size droplet diameter is more than 1 μm, then can be formed at short notice and can give full play to the concavo-convex of antiglare effect.If size droplet diameter is below 50 μm, is then easily formed and can give full play to the concavo-convex of antiglare effect.
Size droplet diameter suitably adjusts by the kind, spray pressure, liquid measure etc. of nozzle.Such as, in second fluid nozzle, the higher then drop of spray pressure is less, and in addition, liquid measure more at most drop is larger.
The particle diameter of drop carries out with laser detector Suo Te (Sauter) mean grain size that measures.
The arithmetic mean rugosity Ra on the surface of antiglare film can adjust according to the application conditions (spraying pressure, liquid measure, base material temperature, application frequency etc. during applied coating solution) etc. of the composition of antiglare film coating fluid (kinds, size, content etc. of solid component concentration, silicon dioxide granule (I) or other particles), antiglare film coating fluid.
Such as, the condition except the solid component concentration except antiglare film coating fluid is identical, there is higher, that then arithmetic mean rugosity Ra the is larger tendency of solid component concentration.
When antiglare film coating fluid contain silicon dioxide granule (I), condition except the mean grain size (average primary particle diameter, average aggegation particle diameter etc.) of silicon dioxide granule (I) identical, the mean grain size that there is silicon dioxide granule (I) is larger, then the tendency that arithmetic mean rugosity Ra is larger.
When antiglare film coating fluid contain silicon dioxide granule (I), condition except the content of silicon dioxide granule (I) identical, the content that there is silicon dioxide granule (I) is more, then the tendency that arithmetic mean rugosity Ra is larger.
When the condition except spraying pressure during coating antiglare film coating fluid is identical, there is spraying pressure lower, then the tendency that arithmetic mean rugosity Ra is larger.
When the condition except liquid measure during coating antiglare film coating fluid is identical, there is liquid measure more, then the tendency that arithmetic mean rugosity Ra is larger.
When the condition except base material temperature during coating antiglare film coating fluid is identical, there is base material temperature higher, then the tendency that arithmetic mean rugosity Ra is larger.
When the condition except application frequency during coating antiglare film coating fluid is identical, there is application frequency, namely use the coated face number (repeatedly application frequency) of spraying process more, then the tendency that arithmetic mean rugosity Ra is larger.
And if there is arithmetic mean rugosity Ra to become large, then 85 ° of mirror surface lusters diminish, and to the tendency that the antiglare effect of oblique incident ray uprises, and mist degree becomes large tendency.
During with spraying process coating antiglare film coating fluid, base material 12 is preferably heated to 30 ~ 90 DEG C in advance.If the temperature of base material 12 more than 30 DEG C, then easily forms enough convex-concaves because liquid medium evaporates rapidly.The temperature of base material 12 is below 90 DEG C, then the adaptation of base material 12 and antiglare film 14 is good.When base material 12 is the glass plate of below thickness 5mm, the warming plate that can be redefined for the temperature of more than the temperature of base material 12 in base material 12 times configurations declines to suppress the temperature of base material 12.
(drying)
Film coating by antiglare film coating fluid being formed to antiglare film coating fluid on the base substrate 12 carries out drying.By this, remove the liquid medium in film, also carrying out silica precursor remaining in film to the conversion of silica-based matrix (is such as when having the silane compound with the hydrolization group of silicon atom bonding at silica precursor, hydrolization group decomposes substantially, be hydrolyzed the condensation of thing), make film densification simultaneously, form antiglare film 14.
Dry undertaken by heating, the mode that also can not heat (natural drying, air-dry etc.) is carried out.
The heating of film can by antiglare film coating solution on the base substrate 12 time carried out by heated substrate 12 and coating simultaneously, also antiglare film coating solution can carried out by heating film on the base substrate 12 afterwards.
Baking temperature preferably more than 30 DEG C, suitably can determine according to the material of the material of base material 12, antiglare film coating fluid etc.
When silica precursor be have with the silane compound of the hydrolization group of silicon atom bonding (silane compound described later (A)), baking temperature preferably more than 80 DEG C, more preferably more than 100 DEG C.If baking temperature is more than 80 DEG C, then can makes film densification and improve the permanance such as the physical strength of antiglare film 14.
When the material of base material 12 is resin, baking temperature is below the heat resisting temperature of resin.When the material of base material 12 is glass, baking temperature is preferably below the softening point temperature of glass.
When base material 12 is chemically reinforced glass plate, baking temperature preferably 80 ~ 450 DEG C.
When base material 12 is without chemical enhanced glass plate, drying process during band formation antiglare film 14 of can also holding concurrently and physical strengthening (air-cooled strengthening) operation of glass plate.In physical strengthening operation, glass is heated near the softening temperature of glass.In this case, baking temperature is typically set in about about 600 ~ 700 DEG C.
Even polymerization to a certain degree also can occur in natural drying, if so to the time without any restriction, then also baking temperature can be set as the temperature of near room temperature in theory.
(antiglare film coating fluid)
Antiglare film coating fluid comprises silica precursor and liquid medium.
Antiglare film coating fluid can as required further containing silicon dioxide granule (I), other particles, terpene compound, other any compositions etc.
Silica precursor:
As silica precursor, the hydrolytic condensate (sol-gel silica), silazane etc. that have with the silane compound of the hydrolization group of silicon atom bonding (hereinafter also referred to silane compound (A)), silane compound (A) can be exemplified, from the viewpoint of each characteristic of antiglare film 14, either party or both sides, the more preferably hydrolytic condensate of silane compound (A) of preferred silane compound (A) and hydrolytic condensate thereof.
As silane compound (A), the silane compound (A1), alkoxy silane (except silane compound (A1)) etc. that have with the alkyl of silicon atom bonding and hydrolization group can be exemplified.
In silane compound (A1), can be the 1 valency alkyl with 1 silicon atom bonding with the alkyl of silicon atom bonding, also can be the divalent alkyl with 2 silicon atom bondings.As 1 valency alkyl, can exemplified by alkyl groups, alkenyl, aryl etc.As divalent alkyl, alkylidene, alkylene group, arlydene etc. can be exemplified.
Alkyl can have between carbon atom be selected from-O-,-S-,-CO-and-NR '-the group combined of more than 1 or 2 of (wherein R ' is hydrogen atom or 1 valency alkyl).
As the hydrolization group with silicon atom bonding, alkoxy, acyloxy, ketoxime base, alkenyloxy, amino, amino oxygen base, amide group, isocyanate group, halogen atom etc. can be exemplified.In these groups, balance from the viewpoint of between the stability and the difficulty of hydrolysis of silane compound (A1), preferred alkoxy, isocyanate group and halogen atom (especially chlorine atom).
As alkoxy, the alkoxy of preferred carbon number 1 ~ 3, more preferably methoxy or ethoxy.
When there is multiple hydrolization group in silane compound (A1), hydrolization group can be identical group, also can be different groups, from the viewpoint of obtaining difficulty, and preferred identical group.
As silane compound (A1), the compound that formula described later (I) represents can be exemplified, there is the alkoxy silane (methyltrimethoxy silane of alkyl, ethyl triethoxysilane etc.), there is the alkoxy silane (vinyltrimethoxy silane of vinyl, vinyltriethoxysilane etc.), there is the alkoxy silane (2-(3 of epoxy radicals, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxysilane etc.), there is the alkoxy silane (3-acryloxypropyl trimethoxy silane etc.) etc. of acryloxy.
As silane compound (A1), from the viewpoint of the physical strength of antiglare film 14, the compound that preferred following formula (I) represents.
R
3-pL
pSi-Q-SiL
pR
3-p…(I)
In formula (I), Q is divalent alkyl (can have between carbon atom and be selected from-O-,-S-,-CO-and-NR '-the group combined of more than 1 or 2 of (wherein, R ' is hydrogen atom or 1 valency alkyl)).As divalent alkene, above-mentioned divalent alkene can be exemplified.
As Q, consider from viewpoints such as the physical strength of antiglare film 14, the difficulties that obtains, the alkylidene of preferred carbon number 2 ~ 8, further the alkylidene of preferred carbon number 2 ~ 6.
In formula (I), L is hydrolization group.As hydrolization group, can exemplify said hydrolyzed group, preferred configuration is also identical.
R is hydrogen atom or 1 valency alkyl.As 1 valency alkene, above-mentioned 1 valency alkene can be exemplified.
P is the integer of 1 ~ 3.Viewpoint that p never makes reaction velocity excessively slow is considered, preferably 2 or 3, particularly preferably 3.
As alkoxy silane (except above-mentioned silane compound (A1)), the alkoxy silane (perfluoro-ethyl triethoxysilane etc.) etc. that can exemplify tetraalkoxysilane (tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc.), there is the alkoxy silane of perfluor polyether base (perfluor polyether triethoxysilane etc.), there is perfluoroalkyl.
Hydrolysis and the condensation of silane compound (A) are undertaken by known method.
Such as when silane compound (A) is for tetraalkoxysilane, use the water of more than 4 times moles of tetraalkoxysilane and carry out as the acid of catalyzer or alkali.
As acid, mineral acid (HNO can be exemplified
3, H
2sO
4, HCl etc.), organic acid (formic acid, oxalic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid etc.).As alkali, ammonia, NaOH, potassium hydroxide etc. can be exemplified.As catalyzer, from the viewpoint of the long-term preservability of the hydrolytic condensate of silane compound (A), preferred acid.
As the catalyzer of the hydrolysis for silane compound (A), preferably do not hinder the catalyzer of the dispersion of the particles such as silicon dioxide granule (I).
As silica precursor, can be used alone a kind, but also two or more combinationally uses.
Silica precursor is peeled off from the viewpoint of preventing the crackle of antiglare film 14 or film, preferably contains either party or both sides of silane compound (A1) and hydrolytic condensate thereof.
Silica precursor from the viewpoint of the resistance to abrasion intensity of antiglare film 14, either party or both sides preferably containing tetraalkoxysilane and hydrolytic condensate thereof.
Either party or both sides of any one party of silica precursor particularly preferably containing silane compound (A1) and hydrolytic condensate thereof or both sides and tetraalkoxysilane and hydrolytic condensate thereof.
Silane compound (A1) in silica precursor and the ratio of hydrolytic condensate thereof are scaled SiO relative to silica precursor
2solid constituent (100 quality %), preferably 5 ~ 30 quality %.
Liquid medium:
Liquid medium is the liquid of dissolving or dispersed silicon dioxide precursor.When antiglare film coating fluid contains the particle such as silicon dioxide granule, other particles, liquid medium can possess the function of the dispersion medium as this particle of dispersion.
As liquid medium, such as, can exemplify water, alcohols, ketone, ethers, cellosolve class, ester class, glycol ethers, nitrogen-containing compound, sulfocompound etc.
As alcohols, methyl alcohol, ethanol, isopropyl alcohol, butanols, diacetone alcohol etc. can be exemplified.
As ketone, acetone, MEK, methylisobutylketone etc. can be exemplified.
As ethers, tetrahydrofuran, Isosorbide-5-Nitrae-two can be exemplified
alkane etc.
As cellosolve class, can exemplified by methyl cellosolve, ethyl cellosolve etc.
As ester class, methyl acetate, ethyl acetate etc. can be exemplified.
As glycol ethers, ethylene glycol monoalkyl ether etc. can be exemplified.
As nitrogen-containing compound, DMA, DMF, 1-METHYLPYRROLIDONE etc. can be exemplified.
As sulfocompound, dimethyl sulfoxide etc. can be exemplified.
Liquid medium can be used alone a kind, but also two or more combinationally uses.
Because the hydrolysis of the alkoxy silane in silica precursor etc. needs water, when therefore not carrying out the displacement of liquid medium after hydrolyzing, at least containing water in liquid medium.
In this case, liquid medium can be only water, also can be the mixed liquor of water and other liquid.As other liquid, such as alcohols, ketone, ethers, cellosolve class, ester class, glycol ethers, nitrogen-containing compound, sulfocompound etc. can be exemplified.In other liquid, as the solvent of silica precursor, preferred alcohols, particularly preferably methyl alcohol, ethanol, isopropyl alcohol, butanols.
In liquid medium, also can containing acid or alkali.Acid or alkali when preparing the solution of silica precursor as the hydrolysis of raw material (alkoxy silane etc.), the catalyzer of condensation and adding, also can add after preparing the solution of silica precursor.
Silicon dioxide granule (I):
Same as described above to the explanation of silicon dioxide granule (I).
Other particulates:
Same as described above to the explanation of other particulates.
Terpene compound:
If antiglare film coating fluid, when also containing terpene compound, then formation space around particle further containing when the particles such as silicon dioxide granule (I), compared with the situation not containing terpene compound, has the tendency of refractive index step-down.
Terpenes refers to isoprene (C
5h
8) consist of (C for structural unit
5h
8)
nthe hydrocarbon of (herein, n is the integer of more than 1).Terpene compound refers to the terpenes with the functional group derived by terpenes.Terpene compound also comprises the different terpene compound of degree of unsaturation.
In addition, although also there is the material of the effect played as liquid medium in terpene compound, " with isoprene be structural unit consist of (C
5h
8)
nhydrocarbon " be equivalent to terpene derivatives, be not equivalent to liquid medium.
As terpene compound, the terpene derivatives etc. recorded in No. 2010/018852nd, International Publication can be used.
Other any compositions:
As other any compositions, can exemplify such as improve homogenization surfactant, for improving the metallic compound, ultraviolet light absorber, infrared reflection/infrared absorbent, antireflection agent etc. of the permanance of antiglare film 14.
As surfactant, silicone oil, acrylic compounds etc. can be exemplified.
As metallic compound, be better zirconium chelate, titanium chelate, aluminium chelate compound etc.As zirconium chelate, four acetyl acetone zirconiums can be exemplified, three butoxy stearic acid close zirconium etc.
Composition:
Content (the SiO of the silica precursor in antiglare film coating fluid
2convert) relative to the solid constituent (100 quality %) in antiglare film coating fluid, (wherein, silica precursor is SiO
2convert), preferably more than 20 quality %, more preferably more than 25 quality %.If the content of silica-based matrix precursor is more than above-mentioned lower limit, then antiglare film 14 mechanical strength.In addition, enough dhering strengths can be obtained between base material 12 and antiglare film 14.
To the content (SiO of silica precursor relative to solid constituent
2convert) the upper limit be not particularly limited, can be 100 quality %.Can according to the needs of antiglare film coating fluid, the content of other compositions of suitably setting institute fusion.
Such as when antiglare film coating fluid contains silicon dioxide granule (I), silica precursor relative to solid constituent content (SiO
2convert) relative to the solid constituent (100 quality %) in antiglare film coating fluid, preferably below 50 quality %, more preferably below 45 quality %.
The content of the liquid medium in coating fluid sets according to the solid component concentration of coating fluid.
Solid component concentration preferably 2 ~ 7 quality % of antiglare film coating fluid, more preferably 3 ~ 5 quality %.If solid component concentration is in above-mentioned scope, then easily obtain the antiglare film 14 of arithmetic mean rugosity Ra in above-mentioned scope on surface.
The solid constituent of antiglare film coating fluid is that the content of the whole compositions in antiglare film coating fluid except liquid medium amounts to.Wherein the content of silica precursor is SiO
2convert.
The content of the silicon dioxide granule (I) in antiglare film coating fluid as previously mentioned, can consider that the content of the silicon dioxide granule (I) in antiglare film 14 suitably sets.
(wherein, silica precursor is SiO relative to the solid constituent (100 quality %) in antiglare film coating fluid for the content of the silicon dioxide granule (I) in antiglare film 14 and silicon dioxide granule (I)
2convert) content substantially identical.
When antiglare film coating fluid contains terpene compound, relative to the solid constituent (100 quality %) in antiglare film coating fluid, (wherein, silica precursor is SiO to the content of the terpene compound in antiglare film coating fluid
2convert), preferably 0.05 ~ 0.25 quality %, more preferably 0.1 ~ 0.15 quality %.If the content of terpene compound is more than the lower limit of above-mentioned scope, then easily obtain the effect because producing containing terpene compound.If the content of terpene compound is below the higher limit of above-mentioned scope, then mechanical strength.
The mixing of the dispersion liquid, terpene compound, other any compositions etc. of the dispersion liquid of the liquid medium added as required, silicon dioxide granule (I), other particles, by such as preparing solution silane precursor be dissolved in liquid medium, is prepared by antiglare film coating fluid.
(action effect)
With antiglare film base material 10 because antiglare film 14 is above-mentioned (α) or (β), therefore compared with the past, excellent to the antiglare effect of the oblique incident ray close to level.
In addition, in band antiglare film base material 10, also good to the antiglare effect close to the light beyond the oblique incident ray of level.
In addition, as the surface roughness characteristic of film, except arithmetic mean rugosity Ra, also there will be a known the various key element such as the average length RSm of roughness curve key element, maximum height rugosity Rz, kurtosis (Japanese: the Network Le ト シ ス) Rku of roughness curve, the degree of bias (Japanese: the ス キ ュ ー ネ ス) Rsk of roughness curve.The present inventor confirms that the correlativity of 85 ° of mirror surface lusters on the surface of arithmetic mean rugosity Ra and antiglare film 14 is high, and the correlativity of 85 ° of mirror surface lusters on the surface of other surface roughness characteristics and antiglare film 14 low (with reference to [embodiment] described later).
(purposes)
To being with the purposes of antiglare film base material 10, there is no particular limitation.As concrete example, automotive clear parts (head lamp case can be exemplified, sidepiece rearview mirror, transparent front substrate, sidepiece transparency carrier, rear portion transparency carrier etc.), automotive clear parts (instrument panel surface etc.), measurer, building window, show window, display (notebook computer, monitor, LCD, PDP, ELD, CRT, PDA etc.), LCD color filter, touch-screen substrate, pick-up lens, optical lens, eyeglass, camera component, video camera parts, CCD covered substrate, fiber end face, projector components, copier part, transparency carrier used for solar batteries (cover glass etc.), mobile phone window, back light unit parts (light guide plate, cold-cathode tube etc.), the brightness of back light unit parts liquid crystal improves film (prism, semi-permeable diaphragm etc.), liquid crystal brightness improves film, organic EL luminous element parts, inorganic EL light-emitting component parts, fluorescent light-emitting element parts, optical filter, the end face of optics, illuminating lamp, the cover of ligthing paraphernalia, amplifying laser light source, antireflection film, polarizing coating, film for agricultural use etc.
With antiglare film base material 10 from the viewpoint of the antiglare effect excellence to oblique incident ray, preferably transparency carrier used for solar batteries.
In solar module, before solar cell, wait configuration transparency carrier (cover glass etc.) in order to protecting solar cell.According to setting place, light pollution can be produced due to the reflected light that the surface of transparency carrier is reflected.If especially arrange solar module on the first-class dip plane, roof tilted, then light is with close to the incident angles of 90 °, likely produces strong reflected light.By using band antiglare film base material 10 as transparency carrier used for solar batteries, the generation of the light pollution caused due to reflected light as above can be suppressed.
Above, illustrate that an example of band antiglare film base material of the present invention is described, but the present invention not limit by above-mentioned example.Each structure in above-mentioned embodiment and combination etc. thereof are an example, in the scope not departing from technological thought of the present invention, can carry out forming additional, omit, displacement and other change.
Such as, the functional layers such as AFP (removal finger print layer) can be had on the upside of antiglare film 14 (side contrary with base material 12 side).Also the functional layers such as Alkali-barrier layer, reflectivity waveform adjustment layer, infrared ray shielding layer can be had between base material 12 and antiglare film 14.Functional layer is formed by known methods such as rubbing methods.
The form of base material 12 is not limited to the sheet such as plate, film.Also can be the such as form such as rectangle or curved surface.
Manufacture method with antiglare film base material is not limited by base material, is coated with above-mentioned antiglare film coating fluid, carry out drying and form the method for antiglare film 14.
(article)
Article of the present invention possess the band antiglare film base material of the invention described above.
Article of the present invention can be made up of band antiglare film base material of the present invention, also can also possess other materials beyond band antiglare film base material of the present invention.
As the example of article of the present invention, the above-mentioned purposes as band antiglare film base material 10 can be exemplified and the article exemplified, the device etc. of wantonly more than a kind that possesses these article.
As device, such as, can exemplify solar module, display device, lighting device etc.
As solar module, preferably possess solar cell and be configured at respectively for the protection of solar cell transparency carrier (cover glass etc.) before solar cell and on the back side, use band antiglare film base material of the present invention as the solar module of at least one party's transparency carrier transparency carrier of front face side (preferably at least) of above-mentioned transparency carrier.
As the example of display device, mobile phone, smart mobile phone, panel computer, Vehicular navigation system etc. can be exemplified.
As the example of lighting device, organic EL (electroluminescence) lighting device, LED (light emitting diode) lighting device etc. can be exemplified.
Embodiment
Below, embodiment is shown, and the present invention is described in detail.But the present invention is not subject to the restriction of following record.
In example 1 ~ 16 described later, example 1 ~ 4,10 ~ 15 is embodiment, and example 5 ~ 9,16 is comparative example.
The mensuration that each example uses, evaluation method and material (obtaining source or compound method) are as follows.
< measures, evaluation method >
(glossiness)
As the glossiness on the surface of antiglare film, measure 60 ° of mirror surface lusters and 85 ° of mirror surface lusters.Each mirror surface luster uses Grossmeters (Konica Minolta Opto Inc. (コ ニ カ ミ ノ Le タ society) makes, GM-268plus) according to the method specified in JISZ8741:1997, measuring close to central portion in antiglare film.In addition, each mirror surface luster is pasted black tape by the back side (with the face of antiglare film opposite side) on a glass, is measured under the state not by the impact of the backside reflection of glass plate.Glossiness is less, then represent that anti-glare is more excellent.
(surface roughness)
The surface roughness (the average length RSm of arithmetic mean rugosity Ra, roughness curve key element, maximum height rugosity Rz, the kurtosis Rku of roughness curve, the degree of bias Rsk of roughness curve) of antiglare film uses surface roughness meter (the accurate society in Tokyo Precision Co., Ltd (East capital) system, SURFCOM (registered trademark) 1500DX) measure according to the method recorded in JISB0601:2001.The datum length lr (boundary value λ c) of roughness curve is set to 0.08mm.
(refractive index of antiglare film)
The refractive index n of antiglare film is measured by following method.
The surface of glass plate is formed with spin-coating method the single flat synovial membrane of the layer for asking its refractive index, black pvc adhesive tape is pasted not contain alveolate condition in this monofilm in this glass plate and the surface of opposition side.Afterwards, by spectrophotometer (Otsuka Electronics Co., Ltd. (great mound Electricity society) system, moment Multi spot metering system MCPD-3000), be determined at the reflectivity of above-mentioned monofilm within the scope of wavelength 300 ~ 780nm.When measuring reflectivity, the incident angle of light is set to 2 °.According to minimum reflectivity (the minimum reflectivity R within the scope of wavelength 300 ~ 780nm
min) and the refractive index n of above-mentioned glass plate
s, utilize following formula (1) to calculate refractive index n.
R
min＝(n-n
s)
2/(n+n
s)
2…(1)
< uses material >
(preparation of silica precursor solution (a-1))
To 69.0g denatured ethanol (Japanese alcohols peddle Co., Ltd. (Japanese ア ル コ ー Le Trafficking Sales society) system, trade name " SOLMIXAP-11 ", take ethanol as the mixed solvent of host, identical below) carry out stirring while, add the mixed liquor of the 61 quality % nitric acid of 11.9g ion exchange water and 0.1g, stir 5 minutes.Add 19.0g tetraethoxysilane (SiO wherein
2conversion solid component concentration: 29 quality %), stirred at ambient temperature 30 minutes, makes SiO
2conversion solid component concentration is the silica precursor solution (a-1) of 5.5 quality %.
In addition, SiO here
2conversion solid component concentration is that whole Si of tetraethoxysilane are changed into SiO
2time solid component concentration.
(preparation of silica precursor solution (a-2))
While 80.3g denatured ethanol is stirred, add the mixed liquor of the 61 quality % nitric acid of 7.9g ion exchange water and 0.2g, stir 5 minutes.Then, 1,6-two (trimethoxysilyl) hexane (organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI (シ リ コ ー Application society of SHIN-ETSU HANTOTAI) system, trade name " KBM3066 ", the SiO of 11.6g is added
2conversion solid component concentration: 37 quality %), 60 DEG C of stirred in water bath 15 minutes, preparation SiO
2conversion solid component concentration is the silica precursor solution (a-2) of 4.3 quality %.
In addition, SiO here
2conversion solid component concentration is that whole Si of two for 1,6-(trimethoxysilyl) hexane are changed into SiO
2time solid component concentration.
(preparation of silica precursor solution (a))
While the silica precursor solution (a-1) stirring 81.8g, add the silica precursor solution (a-2) of 11.7g, stir 30 minutes.Then, add the denatured ethanol of 6.5g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is silica precursor solution (a) of 5.0 quality %.
(preparation of silica precursor solution (b))
While 91.1g denatured ethanol is stirred, add the mixed liquor of the 36 quality % hydrochloric acid of 1.2g ion exchange water and 0.4g, stir 5 minutes.Add 7.3g ethyl silicate 40 (Tama Chemicals Co., Ltd. (Duo Mo chemical industry society), poly-tetraethoxysilane, SiO wherein
2conversion solid component concentration: 40 quality %), stirred at ambient temperature 30 minutes, makes SiO
2conversion solid component concentration is silica precursor solution (b) of 3.0 quality %.
(solid silicon dioxide granule dispersion liquid (c))
The chain SiO of Nissan Chemical Ind Ltd (Nissan Chemical Industries society)
2particle dispersion liquid, trade name: " SNOWTEXOUP ", SiO
2conversion solid component concentration: 15.5 quality %, average primary particle diameter: 10 ~ 20nm, average aggegation particle diameter: 40 ~ 100nm.
(hollow silica particle dispersion (d))
The hollow SiO that Hui Catalysts & Chem Ind Co (day Play catalyst changes into industry) makes
2particle dispersion liquid, trade name: ス ル ー リ ア 4110, SiO
2conversion solid component concentration: 20.5 quality %, average primary particle diameter: 60nm.
(preparation of coating fluid (A))
Then, while silica precursor solution (a) stirring 60.0g, add the denatured ethanol of 40.0g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (A) of 3.0 quality %.
(preparation of coating fluid (B))
Direct use silica precursor solution (a), obtains SiO
2conversion solid component concentration is the coating fluid (B) of 5.0 quality %.
(preparation of coating fluid (C))
While silica precursor solution (a) stirring 80.0g, add the denatured ethanol of 20.0g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (C) of 4.0 quality %.
(preparation of coating fluid (D))
While the denatured ethanol stirring 47.4g, add silica precursor solution (a) of 30.0g, then, add solid silicon dioxide granule dispersion liquid (c) of 22.6g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (D) of 5.0 quality %.
(preparation of coating fluid (E))
While the denatured ethanol stirring 7.4g, add the isobutyl alcohol of 24.0g, the diacetone alcohol of 15.0g, the α terpilenol of 1.00g, silica precursor solution (a) of 30.0g wherein, then, add solid silicon dioxide granule dispersion liquid (c) of 22.6g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (E) of 5.0 quality %.
(preparation of coating fluid (F))
While the denatured ethanol stirring 37.8g, add silica precursor solution (a) of 50.0g, then, add hollow silica particle dispersion (d) of 12.2g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (D) of 5.0 quality %.
(preparation of coating fluid (G))
While the denatured ethanol stirring 76.3g, add silica precursor solution (a) of 12.0g, then, add hollow silica particle dispersion (d) of 11.7g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (G) of 3.0 quality %.
(preparation of coating fluid (H))
While the denatured ethanol stirring 71.8g, add silica precursor solution (a) of 18.0g, then, add hollow silica particle dispersion (d) of 10.2g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (H) of 3.0 quality %.
(preparation of coating fluid (I))
While the denatured ethanol stirring 22.8g, add silica precursor solution (a) of 70.0g, then, add hollow silica particle dispersion (d) of 7.3g, at room temperature stir 30 minutes, obtain SiO
2conversion solid component concentration is the coating fluid (I) of 5.0 quality %.
(preparation of coating fluid (J))
Direct use silica precursor solution (b), obtains SiO
2conversion solid component concentration is the coating fluid (J) of 3.0 quality %.
< example 1>
(cleaning of glass plate)
As glass plate, prepare through chemical enhanced alumina silicate glass plate (Asahi Glass Co., Ltd (Asahi Glass society) system, trade name " Leoflex ".Size: 300mm × 300mm, thickness 0.85mm).Clean the surface of this glass plate with sodium bicarbonate water after, rinse with ion exchange water, then carry out drying.
(making of band antiglare film glass plate)
Above-mentioned glass plate preheating furnace (Isuzu Motors Co., Ltd. (ISUZU society) makes, VTR-115) carries out preheating.Then, the surface temperature of glass plate is being incubated under the state of 90 DEG C, by spraying process on above-mentioned glass plate, according to following application conditions applied coating solution (A) with make the arithmetic mean rugosity Ra on surface of antiglare film of coating formation for the value shown in table 2.That is, the spray pressure air of the nozzle (spue pressure) is set as 0.2MPa, repeatedly carrying out following coating process, is 0.247 μm to make the arithmetic mean rugosity Ra on the surface of formed antiglare film.
Coating process: repeatedly carry out following operation: namely, nozzle is moved in the transverse direction with the speed of 750mm/ minute on a glass, then forwards 22mm is moved, since then on a glass with the operation of the speed of 750mm/ minute movement in the transverse direction, until whole applied coating solution (A) of glass plate.(application conditions)
The liquid measure of coating fluid: 40cm
3/ minute,
Spray pressure: 0.2MPa,
Nozzle translational speed: 750mm/ minute,
Spraying spacing: 22mm.
Afterwards, in an atmosphere, carry out at 200 DEG C 3 minutes heat aging, obtain band antiglare film glass plate.
In the coating utilizing spraying process, use 6 axle application robots (Kawasaki Robotics Co., Ltd. (Kawasaki ロ ボ テ ィ ッ Network ス society) system, JF-5).In addition, as nozzle, VAU nozzle (spraying system Amada Co., Ltd. (ス プ レ ー イ Application グ シ ス テ system ジ ャ パ Application society) system) is used.
< example 2 ~ 16>
Except the kind of coating fluid, the liquid measure of coating fluid and spray pressure are as shown in table 1, arithmetic mean rugosity Ra is as shown in table 2 change beyond, obtain band antiglare film glass plate in mode same as Example 1.
The band antiglare film glass plate obtained each example is measured the refractive index in antiglare film, glossiness (60 ° of mirror surface lusters, 85 ° of mirror surface lusters) under incident angle 60 ° or 85 °, antiglare film the result of surface roughness (the average length RSm of arithmetic mean rugosity Ra, roughness curve key element, maximum height rugosity Rz, the kurtosis Rku of roughness curve, the degree of bias Rsk of roughness curve) on surface be shown in table 1 ~ 2.
[table 1]
[table 2]
As shown in the result of table 1, the refractive index of antiglare film more than 1.4 and below 1.5, the arithmetic mean rugosity Ra on surface be the glossiness of antiglare film under incident angle 85 ° of the example 1 ~ 4 of 0.158 ~ 0.500 μm is less than 70%, has excellent antiglare effect to oblique incident ray.
On the other hand, arithmetic mean rugosity Ra lower than glossiness under incident angle 85 ° of the antiglare film of the example 5 ~ 9 of 0.158 μm more than 70%, compared with the antiglare film of example 1 ~ 4, poor to the antiglare effect of oblique incident ray.Especially the antiglare film of example 7,9, although the glossiness ratio 1 under incident angle 60 ° is lower, the glossiness ratio 1 under incident angle 85 ° is higher.
As shown in the result of table 2, the refractive index of antiglare film more than 1.2 and lower than 1.4, the arithmetic mean rugosity Ra on surface be the glossiness of antiglare film under incident angle 85 ° of the example 10 ~ 15 of 0.112 ~ 0.700 μm is less than 70%, has excellent antiglare effect to oblique incident ray.
On the other hand, arithmetic mean rugosity Ra lower than glossiness under incident angle 85 ° of the antiglare film of the example 16 of 0.112 μm more than 70%, compared with example 10 ~ 15, poor to the antiglare effect of oblique incident ray.
In addition, in the surface roughness characteristic on the surface of antiglare film, high correlation is had as seen between arithmetic mean rugosity Ra and the glossiness under incident angle 85 °, and in other characteristics (the average length RSm of roughness curve key element, maximum height rugosity Rz, the kurtosis Rku of roughness curve, the degree of bias Rsk of roughness curve), do not find there is correlativity between the glossiness under incident angle 85 °.Thus, can confirm that arithmetic mean rugosity Ra is useful as the index of the antiglare effect to oblique incident ray.
Symbol description
10 band antiglare film base materials
12 base materials
14 antiglare film
Claims (9)
1. be with an antiglare film base material, it is characterized in that,
The antiglare film possessing base material and formed on the substrate,
The refractive index of described antiglare film is more than 1.2 and lower than 1.4,
The arithmetic mean rugosity Ra on the surface of described antiglare film is 0.112 ~ 0.700 μm,
85 ° of mirror surface lusters on the surface of described antiglare film are less than 70%.
2. be with an antiglare film base material, it is characterized in that,
The antiglare film possessing base material and formed on the substrate,
The refractive index of described antiglare film is more than 1.4 and below 1.5,
The arithmetic mean rugosity Ra on the surface of described antiglare film is 0.158 ~ 0.500 μm,
85 ° of mirror surface lusters on the surface of described antiglare film are less than 70%.
3. as described in claim 1 or 2 band antiglare film base material, is characterized in that, described antiglare film contains either one or both of solid silicon dioxide granule and hollow silica particle.
4. the band antiglare film base material according to any one of claims 1 to 3, it is characterized in that, described antiglare film is formed by the coating fluid containing silica precursor and liquid medium.
5. the band antiglare film base material according to any one of Claims 1 to 4, is characterized in that, described base material is glass plate.
6. band antiglare film base material as claimed in claim 5, it is characterized in that, described glass plate is strengthening glass sheets.
7. band antiglare film base material as claimed in claim 6, it is characterized in that, described strengthening glass sheets is chemically reinforced glass plate, and thickness of slab is 0.4 ~ 1.1mm.
8. article, is characterized in that, possess the band antiglare film base material according to any one of claim 1 ~ 7.
9. article as claimed in claim 8, it is characterized in that, be solar module.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014140380A JP2016018068A (en) | 2014-07-08 | 2014-07-08 | Substrate with anti-glare film, and articles having the same |
| JP2014-140380 | 2014-07-08 |
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| Publication Number | Publication Date |
|---|---|
| CN105319616A true CN105319616A (en) | 2016-02-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510395676.XA Pending CN105319616A (en) | 2014-07-08 | 2015-07-07 | Anti-dazzle film substrate and article |
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| Country | Link |
|---|---|
| JP (1) | JP2016018068A (en) |
| CN (1) | CN105319616A (en) |
| TW (1) | TW201606357A (en) |
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| JP2016018068A (en) | 2016-02-01 |
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