CN104743882A - Optical object and lens - Google Patents
Optical object and lens Download PDFInfo
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- CN104743882A CN104743882A CN201410820280.0A CN201410820280A CN104743882A CN 104743882 A CN104743882 A CN 104743882A CN 201410820280 A CN201410820280 A CN 201410820280A CN 104743882 A CN104743882 A CN 104743882A
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Abstract
[Problem] The present invention is to provide an optical article can be easily manufactured and is persistent in hydrophilicity. [Solution] Characteristics of the optical article that allows the light wavelength or being 1050 nm in being 587.6 nm in wavelength for more than 20%. Area from the surface of the optical article to less than 500 [mu]m toward the inside is a surface area as well as to areas beyond the surface area as an interior region. The inner region is formed of a glass phase, in accordance with an oxide basis in percentage by mass, the glass phases containing more than a total of 5% to 95% or less is selected from TiO2, P2O5, Nb2O5, SiO2 and WO3 in one or more of ingredients. A crystal, of which the composition is the same as with the glass phase, in the presence of at least a portion of the surface region.
Description
Technical field
The present invention relates to and there is excellent hydrophilic optical article.
Background technology
In the past, the vehicle-mounted camera for the blind area of eliminating the officer in car steering is popularized gradually.The optical articles such as the photographic lens used in such vehicle-mounted camera are always exposed to the external world, thus easily adhere to the dirts such as dust.In addition, if water droplet is attached on photographic lens, then due to this water droplet, light path distortion occurs, photographic element can not form normal images, and the visual field via vehicle-mounted camera becomes bad.
Except the photographic lens used in vehicle-mounted camera, in the optical article how used out of doors such as monitoring camera photographic lens, its cover glass etc. of cover cap, also there is same problem.
Therefore, propose following technology: by forming photocatalyst film on the surface of photographic lens, thus make surface hydrophilic, instantaneously the water droplet being attached to surface is spread into the whole surface of lens, prevent the surface contamination (patent documentation 1) caused because of dust etc.
But there is following such problem in this technology: is difficult to guarantee the adaptation of photographic lens and photocatalyst film and the weather resistance of photocatalyst film self.That is, for the optical article using these technology to produce, likely there is photocatalyst film and damage wetting ability from base material stripping or film deterioration.
In addition, in order to form photocatalyst film, need comparatively multiple operation, therefore, manufacturing cost uprises.
[patent documentation 1] Japanese Unexamined Patent Publication 2008-233547 publication
Summary of the invention
[inventing problem to be solved]
The object of the present invention is to provide a kind of optical article, this optical article can manufacture easily, maintains wetting ability constantly for a long time.
[for solving the means of problem]
The present inventor finds, by forming the interior region of optical article with the glassy phase with specific composition, makes the surface region of this optical article there is the crystallization of separating out from glassy phase, thus solves above-mentioned problem.Described in being constructed as follows specifically of the present invention.
(forming 1)
A kind of optical article, is characterized in that,
Its through more than 20% the light of wavelength 587.6nm or the light of wavelength 1050nm,
Be surface region from the surface of this optical article to the region inwardly within 500 μm, with the region beyond surface region for interior region time,
This interior region is formed by glassy phase, counts according to the quality % of oxide compound benchmark, and what described glassy phase contained total less than more than 5% 95% is selected from TiO
2, P
2o
5, Nb
2o
5, SiO
2and WO
3in the composition of more than a kind,
In this surface region at least partially, exist and form from the glassy phase of above-mentioned interior region the crystallization that identical glassy phase separates out.
(forming 2)
As formed the optical article as described in 1, wherein, above-mentioned crystallization is be selected from the crystallization of more than a kind in the crystallization comprising Ti, the crystallization comprising Nb, the crystallization comprising W, the crystallization comprising P, the crystallization comprising Si and their sosoloid.
(forming 3)
As formed the optical article as described in 1 or 2, wherein, at least there is the foursquare region that the length of side is 100 μm on the surface of above-mentioned optical article, is expose more than 1 crystallite in the foursquare region of 100 μm in the described length of side.
(forming 4)
As formed the optical article as described in 1 or 2, wherein, at least there is the foursquare region that the length of side is 100 μm on the surface of above-mentioned optical article, the described length of side is that the foursquare region of 100 μm is all covered by crystallization.
(forming 5)
As formed the optical article according to any one of 1 ~ 4, count according to the quality % of oxide compound benchmark, above-mentioned glassy phase contains:
TiO
2：0％～95％、
P
2O
5：0％～50％、
Nb
2O
5：0％～50％、
SiO
2：0％～95％、
WO
3：0％～95％、
Li
2O：0％～20％、
Na
2O：0％～20％、
K
2O：0％～30％、
Tl
2O：0％～70％、
BeO：0％～10％、
MgO：0％～20％、
CaO：0％～60％、
SrO：0％～10％、
BaO：0％～50％、
ZnO：0％～70％、
SnO：0％～10％、
CuO：0％～50％、
AgO：0％～10％、
Al
2O
3：0％～80％、
B
2O
3：0％～60％、
Ta
2O
5：0％～30％、
Bi
2O
3：0％～85％、
La
2O
3：0％～50％、
Fe
2O
3：0％～10％、
Gd
2O
3：0％～20％、
Sb
2O
3：0％～5％、
Lu
2O
3：0％～5％、
Y
2O
3：0％～20％、
GeO
2：0％～20％、
TeO
2：0％～85％、
ZrO
2：0％～50％、
V
2o
5: each composition of 0% ~ 60%.
(forming 6)
A kind of lens, it is formed by the optical article formed according to any one of 1 ~ 5.
[invention effect]
Optical article of the present invention not only has the perviousness of the visible or infrared light that can use as optical article, and has the high-hydrophilic of energy long term maintenance.In addition, optical article of the present invention is by easy method manufacture.
Accompanying drawing explanation
[Fig. 1] takes the surface of the optical article obtained in embodiment 1 and the figure of the image obtained for expression scanning electron microscope (SEM).
[Fig. 2] takes the surface of the optical article obtained in embodiment 7 and the figure of the image obtained for expression scanning electron microscope (SEM).
Embodiment
Optical article in the present invention refers to, with the article used through the object of light, such as, can enumerate lens, spectral filter, cover glass, prism etc.In addition, although the mirror forming silverskin on a glass and obtain uses for the purpose of reflected light, sheet glass is through light.Therefore, optical article of the present invention comprises the mirror in the region had through light.
Optical article of the present invention is formed based on the glass with specific composition, in the crystallization existed at least partially from glass precipitation of the surface region of this optical article.Therefore, the interior region of optical article is merely the region of the glassy phase that there is not crystallization, in surface region, there is crystallization in glassy phase.The crystallization being present in surface region is the crystallization of separating out by heat-treating glass.Therefore, the glassy phase of crystallization surface region has the composition identical with the glassy phase of interior region before heat treatment, and due to the precipitation of crystallization, the glassy phase of crystallization surface region forms from the glass of the glassy phase of interior region and become different slightly.But, for the glassy phase of surface region and crystallization phases generally speaking, there is the composition identical with the glassy phase of interior region.Optical article of the present invention presents wetting ability owing to being present in the crystallization of surface region.In other words, for the intermediate for making before the heat-treating of optical article, its entirety has identical glass composition, and the composition of intermediate is identical with the composition of the interior region of optical article of the present invention.
Herein, surface region refers to, from the surface of optical article to the region inwardly within 500 μm.That is, suppose from the arbitrary point the surface of optical article inwardly distance 500 μm within region time, based on surface a little be surface region in the set in this region.Surface region also comprises surface.In addition, interior region refers to the region beyond surface region.
For optical article of the present invention, in surface region, comprise crystallization, because surface region also comprises surface, so crystallization is also exposed on the surface of optical article.Surface region is the region that there is crystallization.In order to the perviousness making optical article have the excellence relative to visible or infrared light, surface region is preferably not blocked up.Therefore, surface region is preferably less than 500 μm, is more preferably less than 100 μm, most preferably is less than 10 μm.On the other hand, if surface region is excessively thin, then become the hydrophilic long duration easily damaged relative to outer damage etc., therefore, surface region is preferably more than 0.00001 μm, is more preferably more than 0.0001 μm, most preferably is more than 0.001 μm.
The surface of optical article of the present invention has wetting ability.
More specifically, the contact angle having irradiated ultraviolet surface and water droplet is preferably less than 30 °.Thus, the water droplet be attached on the surface of optical article can be spread over the whole surface of optical article, therefore, can reduce that the surface caused because of water droplet hazes, light path distortion.In addition, by spreading over the water on the whole surface of optical article, the pollution on the whole surface caused because of dust etc. easily can be rinsed.
Especially, even if when not irradiation ultraviolet radiation, be also preferably less than 30 ° with the contact angle of water droplet.Thus, even without ultraviolet irradiation, the water droplet that also can make to be attached to surface spreads on the whole surface of optical article, therefore, can reduce the pollution of optical article in environment for use widely.
Herein, the surface of optical article and the contact angle of water droplet are preferably less than 30 °, are more preferably less than 25 °, most preferably are less than 20 °.
Optical article of the present invention has the light transmission relative to visible or infrared light.More specifically, optical article of the present invention through more than 20% the light of wavelength 587.6nm or the light of wavelength 1050nm, also comprise reflection loss.
Optical article through more than 20% only the referring to of this wavelength, in the use form of this optical article, in the light path that the plane of incidence of predetermined light is connected with exit facet, comprise reflection loss, comprise in the light path of the light path of the loss reduction of light, predetermined light, the outgoing intensity of light relative to the percentage of incident intensity of light be more than 20%.
Optical article of the present invention more preferably through more than 20% the light of wavelength 587.6nm or the light of wavelength 1050nm, most preferably through more than 30%.The upper limit of the transmittance of optical article of the present invention is 99.5%.
The measurement example of the transmittance of optical article is as by carrying out based on spectrophotometric determination of light transmittance.In the spectrophotometer of representative, be used as the deuterium discharge tube of the light source of the light of ultraviolet region, halogen lamp as the light source of the light of visibility region, according to point other use wavelength to switch.Also the spectrophotometer measuring the vacuum ultraviolet region of below 200nm, the near infrared region of more than 780nm is had.Ultimate principle is, utilizes diffraction grating by the light light splitting monochromatizing light being used for the wavelength measured from light source, incides in sample.Now, the incident intensity incided in sample is designated as I0.Sample is put in the container being called as cuvette (cell), is set in device, detect the light through the intensity I after sample with the detector such as photomultiplier, silicon photoelectric diode.To this, utilize formula 1 to calculate transmittance %T.
%T=(I/I0) × 100 ... (formula 1)
Such as, when employing the V-650 of Japan Spectroscopy Corporation, optical article of the present invention being clamped in FLH-741 type filter mount, being arranged in spectrophotometer, can transmittance be measured thus.For FLH-741 type filter mount, can measure and be of a size of, thick is 0.5 ~ 25mm, and size is the maximum 80mm of reaching × 100mm, minimumly reaches 5 × 5mm.For measure optical article for, in order to make light vertically through, preferred two sides is parallel plane, even but curved surface, also by thick light through measuring transmittance.Therefore, as long as is more than 20% by the light of thick through transmittance when measuring transmittance, just can estimate outgoing intensity in the light path of the light path of the loss reduction comprising light, light is more than 20% relative to the percentage of the incident intensity of light.
The crystallization existed in the surface region of optical article of the present invention is preferably selected from the crystallization of more than a kind in the crystallization comprising Ti, the crystallization comprising Nb, the crystallization comprising W, the crystallization comprising P, the crystallization comprising Si and their sosoloid.By there is these crystallizations, optical article of the present invention has wetting ability.As optical article of the present invention, there is hydrophilic reason, be presumed as follows: the photocatalytic activity original had because of above-mentioned crystallization and causing, the fine concaveconvex structure formed because of a part of exposing surface of the crystallite due to above-mentioned crystallization and causing.
As the crystallization of surface region being present in optical article of the present invention, the such as crystallization of NASICON type, TiO can be enumerated
2crystallization, WO
3crystallization, ZnO crystallization, SiO
2crystallization, phosphate crystal etc.
The crystallization of NASICON type can use general formula A
mm
2(XO
4)
3represent.This general formula A
mm
2(XO
4)
3the stability of compounds ground represented forms NASICON type structure, therefore, can obtain highlight catalytic active, therefore, can improve wetting ability.
Herein, what elements A was preferably selected from such as Li, Na, K, Cu, Ag, Mg, Ca, Sr, Ba and Zn is one kind or two or more.The ion of elements A is present in the position of the formation three-dimensional channel in crystallization, and thus these ions are easily mobile in crystallization inside, can reduce the probability be combined again in electronics and the hole produced because of the irradiation of light, improve the photocatalytic activity of NASICON type crystallization.
In addition, what element M was preferably selected from such as Zn, Al, Fe, Ti, Sn, Zr, Ge, Hf, V, Nb and Ta is one kind or two or more.Wherein, A and M is heterogeneity.The composition that they are crystalline texture in order to form stable NASICON type and need, and be participate in the formation of conduction band, form the composition of the band gap (band gap) in the scope of 2.5 ~ 4eV.Therefore, by containing the arbitrary element in above-mentioned, the photocatalytic activity of ultraviolet light response can not only be obtained, and the photocatalytic activity of visible light-responded property can be obtained.In addition, from the viewpoint of raising photocatalytic activity, as element M, more preferably comprise Ti, Zr, Fe etc., most preferably comprise Ti.
In addition, what element X was preferably selected from such as Si, P, S, Mo and W is one kind or two or more.These elements are the compositions needed to form stable NASICON type crystalline texture, and, there is the effect of the band gap size of adjustment NASICON type crystallization.As element X, from the viewpoint of easily forming the crystallization of NASICON type, more preferably comprising Si, P, S, W etc., most preferably comprising P.
General formula A
mm
2(XO
4)
3in m select according to the kind of M or X, be less than more than 05 scope in number.By making m within the scope of this, can keep NASICON type crystalline texture, thermostability and chemical stability uprise.In addition, the deterioration of the photocatalytic activity caused because of the change of environment reduces, and the reduction of the photocatalytic activity caused because of heating also becomes and not easily occurs.On the other hand, if m is greater than 5, then can not maintain NASICON type structure, photocatalytic activity reduces.
As the concrete example of NASICON type crystallization, RnTi can be enumerated
2(PO
4)
3, R
0.5ti
2(PO
4)
3, RnZr
2(PO
4)
3, R
0.5zr
2(PO
4)
3, RnGe
2(PO
4)
3, R
0.5ge
2(PO
4)
3, Rn
4alZn (PO
4)
3, Rn
3tiZn (PO
4)
3, Rn
3v
2(PO
4)
3, Al
0.3zr
2(PO
4)
3, Rn
3fe (PO
4)
3, RnNbAl (PO
4)
3, La
1/3zr
2(PO
4)
3, Fe
2(MoO
4)
3, Fe
2(SO
4)
3, Rn
4sn
2(SiO
4)
3, Rn
4zr
2(SiO
4)
3, Cu
4zr
2(SiO
4)
3, Ag
4zr
2(SiO
4)
3, R
2zr
2(SiO
4)
3, NbTi (PO
4)
3, RnZr
2(Si
2/3p
1/3o
4)
3, RTiCr (PO
4)
3, RTiFe (PO
4)
3, RTiIn (PO
4)
3, ZnTiFe (PO
4)
3(in formula, Rn is more than a kind of being selected from Li, Na, K, Rb and Cs, and R is more than a kind of being selected from Be, Mg, Ca, Sr and Ba).And then, in the crystallization of NASICON type, more preferably there is NaTi
2(PO
4)
3, LiTi
2(PO
4)
3, KTi
2(PO
4)
3deng alkali metal titanium phosphoric acid composite salt, Ca
0.5ti
2(PO
4)
3, Mg
0.5ti
2(PO
4)
3,sr
0.5ti
2(PO
4)
3, Ba
0.5ti
2(PO
4)
3deng the crystallization of alkaline-earth metal titanium phosphoric acid composite salt.By containing these NASICON type crystallizations, wetting ability is made to improve due to photocatalytic activity.
< TiO
2crystallization, WO
3crystallization, ZnO crystallization >
TiO
2crystallization preferably is contained in the TiO showing high light catalytic activity, especially anatase octahedrite (Anatase) type or rutile (Rutile) type in the ultra-violet region of below wavelength 400nm
2crystallization.WO
3crystallization until the visible ray of wavelength 480nm and display light catalytic activity, thus gives the photocatalytic activity of visible light-responded property owing to absorbing to photocatalyst member.The band gap of ZnO crystallization is about 3 ~ 4eV, with TiO
2crystallization similarly brings photocatalytic activity to photocatalyst member.
In order to present high-hydrophilic, at least there is the foursquare region that the length of side exposing more than 1 crystallite is 100 μm in preferred optical article of the present invention on its surface.In order to present high-hydrophilic, more preferably at least there is the foursquare region that the length of side exposing more than 1 crystallite is 100 μm, most preferably at least there is the foursquare region that the length of side exposing more than 2 crystallites is 100 μm.
For be present in optical article of the present invention surface region crystallization average crystallite particle diameter for, if excessive, then become and easily damage light transmission, if too small, then wetting ability becomes easy reduction.Therefore, the lower limit of the average crystallite particle diameter of this crystallization is preferably 0.00001 μm, is more preferably 0.0001 μm, most preferably is 0.001 μm.In addition, the upper limit of the average crystallite particle diameter of this crystallization is preferably 100 μm, is more preferably 1 μm, most preferably is 0.1 μm.
Herein, the average crystallite particle diameter being present in the crystallization of the surface region of optical article of the present invention refers to, for the image of the crystallite observed in the arbitrary region of 1000 μm × 1000 μm on the surface at optical article, using value time maximum for distance when pressing from both sides this crystallite with parallel 2 straight lines between 2 straight lines as crystallization particle diameter, get the median size of its mean value as crystallization.Optional 5 crystallites observed, remove crystallite that wherein crystallization particle diameter is maximum and the minimum crystallite of crystallization particle diameter, adopt the mean value of remaining 3.
In addition, also at least can there is the foursquare region that its surface by the length of side that crystallization covers is all 100 μm in optical article of the present invention.When surface is all covered by crystallization, compared with all not covering the situation of crystallization, the perviousness of light is slightly poor, but by the thickness of surface region, fully through the light of visible or infrared light, can become and easily present high-hydrophilic.
The compositing range of each composition of the interior region forming optical article of the present invention is below described.
Count according to the quality % of oxide compound benchmark, the interior region of optical article of the present invention is formed by following glassy phase, and what described glassy phase contained total less than more than 5% 95% is selected from TiO
2, P
2o
5, Nb
2o
3, SiO
2, and WO
3in the composition of more than a kind.In addition, the glass composition of interior region is also the composition of the glass forming the intermediate before implementing thermal treatment.By making the interior region of optical article have such composition, can high light transmittance be had, by thermal treatment, can separate out the contributive crystallization of wetting ability in surface region.In order to easily realize high light transmittance, easily being separated out in surface region by thermal treatment the contributive crystallization of wetting ability, for the glassy phase of interior region, being selected from TiO
2, P
2o
5, Nb
2o
3, SiO
2, and WO
3in the total amount of the composition of more than a kind be more preferably more than 10%, most preferably be more than 15%.In addition, similarly, for the glassy phase of interior region, TiO is selected from
2, P
2o
5, Nb
2o
3, SiO
2, and WO
3in the total amount of the composition of more than a kind be more preferably less than 93%, most preferably be less than 92%.
Below, the composition that can contain in the glass of the intermediate before illustrating the glassy phase forming interior region of the present invention and thermal treatment.
Herein, so-called oxide compound benchmark, refers to following methods: assuming that the oxide compound, nitrate etc. that use as the raw material of the constituent of glassy phase are all decomposed when melting and change into oxide compound, represent the composition of each composition contained in sintered glass ceramics.In this specification sheets, be 100 quality % with the summation of the quality of this generation oxide compound, represent the amount of each composition contained in glassy phase.For the content of each composition in this specification sheets, unless otherwise specified, all represent with the quality % of oxide compound benchmark.
TiO
2composition be by when having carried out thermal treatment to glass, Ti ion formed TiO
2crystallization or its sosoloid or the crystallization of NASICON type and separate out from glass thus can give to the surface of optical article the hydrophilic optional member produced by photocatalytic activity.Therefore, TiO
2the lower limit of the content of composition can be more preferably 0.1%, more preferably 1%, most preferably be 3%.
But, if TiO
2the content of composition is less than 5%, then separate out TiO
2crystallization, the crystallization of NASICON type and their solid solution crystal become difficulty, therefore, cannot obtain sufficient photocatalytic activity.Therefore, when especially wanting to make these crystallizations, TiO
2the lower limit of the content of composition is preferably 5%, is more preferably 8%, most preferably is 10%.
On the other hand, if be greater than 95%, then vitrifying becomes very difficult.Therefore, TiO
2the upper limit of the content of composition is preferably 95%, be more preferably 90%, more preferably 85%, more preferably 75%, more preferably 55%, most preferably be 45%.
P
2o
5composition be form glass eyed structure, improve glass stability and pass through P
5+ion forms NASICON type crystalline texture thus can improve the hydrophilic optional member produced by photocatalytic activity.In addition, also have prevent separate out crystallization coarsening, improve optical article light transmission and it can be made to become good effect.Especially, by forming P
2o
5composition is the phosphate-based glass of the principal constituent of eyed structure, and by more TiO
2, WO
3, the composition such as ZnO is incorporated in glass.In addition, by containing P
2o
5composition, also can expect can separate out TiO under lower thermal treatment temp
2crystallization, the crystallization of NASICON type, WO
3the effect of crystallization, ZnO crystallization etc., can to reduce from the high Detitanium-ore-type TiO of photocatalytic activity
2crystallization is to the effect of the phase in version of the low rutile-type of photocatalytic activity.Therefore, when containing P
2o
5during composition, the amount contained is preferably greater than 0%, be more preferably more than 1%, more preferably more than 5%, most preferably be more than 13%.
But, if P
2o
5content be greater than 50%, then photocatalyst crystallization phases becomes and is difficult to separate out in surface region.Therefore, P
2o
5the upper limit of the content of composition is preferably 50%, be more preferably 45%, more preferably 40%, most preferably be 30%.
Nb
2o
5composition improves the meltbility of glass and the optional member of stability.In addition, the hydrophilic effect produced with cause photocatalytic activity by formation NASICON type crystallization itself is also had.But, if Nb
2o
5the content of composition is too much, then the stability of glass is obviously deteriorated.Therefore, Nb
2o
5the upper limit of the content of composition is preferably 70%, be more preferably 50%, more preferably 48%, most preferably be 45%.
SiO
2composition forms the eyed structure of glass, improves the composition of the stability of glass and the weather resistance of chemistry, and be pass through Si
4+ion is solid-solution in the crystallization of NASICON type thus contributes to the optional member of the hydrophilic raising produced by photocatalytic activity.In addition, also SiO is made
2the effect of crystallization.Therefore, SiO
2the lower limit of the content of composition can be more preferably 0.1%, more preferably 3%, most preferably be 8%.
But, if SiO
2the content of composition is greater than 95%, then the meltbility of glass is deteriorated, and desired photocatalyst crystallization phases becomes and is difficult to separate out.Therefore, SiO
2the upper limit of the content of composition is preferably 95%, be more preferably 80%, more preferably 70%, most preferably be 50%.
WO
3composition improves the meltbility of glass and stability and forms the crystallization of NASICON type or WO
3the optional member of crystallization, can give the wetting ability produced by photocatalytic activity.
Especially, WO
3composition has the effect improving specific refractory power, improve the devitrification resistance of glass.When obtaining this effect, WO
3the lower limit of composition is more preferably 2%, most preferably is 3%.
In addition, if WO
3the content of composition is less than 20%, be then difficult to separate out the WO with photocatalytic activity
3crystallization.Therefore, when going for because of WO
3crystallization and the photocatalytic activity caused time, WO
3the lower limit of the content of composition is more preferably 25%, most preferably is 30%.
On the other hand, if WO
3the content of composition is greater than 95%, then vitrifying becomes very difficult.Therefore, WO
3the upper limit of the content of composition is preferably 95%, is more preferably 90%, most preferably is 85%.Especially, when passing through WO
3when wetting ability is given in crystallization beyond crystallization, WO
3the upper limit of the content of composition can be less than 20%, can be less than 10%.
Li
2o composition, Na
2o composition and K
2o composition is the optional member improving the meltbility of glass and stability and form the crystallization of NASICON type.But, Li
2the content of O composition is greater than 20%, Na
2the content of O composition is greater than 20% or K
2when the content of O composition is greater than 30%, the stability of glass is deteriorated on the contrary, TiO
2crystallization, the crystallization of NASICON type, WO
3the precipitation of crystallization, ZnO crystallization etc. also easily becomes difficulty.
Therefore, Li
2the upper limit of the content of O composition is preferably 20%, is more preferably 18%, most preferably is 15%.Li
2the content of O composition can be preferably more than 0.5%, is more preferably more than 1%, most preferably is more than 2%.
In addition, Na
2the upper limit of the content of O composition is preferably 20%, is more preferably 18%, most preferably is 15%.Na
2the content of O composition can be preferably more than 0.5%, is more preferably more than 1%, most preferably is more than 2%.
In addition, K
2the upper limit of the content of O composition is preferably 30%, is more preferably 28%, most preferably is 25%.K
2the content of O composition can be preferably more than 0.5%, is more preferably more than 1%, most preferably is more than 2%.
For optical article of the present invention, therein in region, preferably make Rn
2the total amount of O composition (in formula, Rn is more than a kind of being selected from Li, Na, K) is less than 30%.Thus, the stability of glass improves, and desired crystallization phases becomes easy precipitation, therefore, can guarantee the wetting ability of optical article.Therefore, Rn
2the upper limit of the total amount of O composition is preferably 30%, is more preferably 28%, most preferably is 25%.In addition, Rn
2the content of O composition can be 0%, Rn
2the lower limit of the total amount of O composition can be preferably 0.5%, is more preferably 1%, most preferably is 2%.
Tl
2o composition is glass forming constituents, is optional member.The upper limit of content is preferably 70%, is more preferably 69%, most preferably is 67%.
BeO composition is glass forming constituents, is optional member.The upper limit of content is preferably 1%, is more preferably 0.5%, most preferably is 0.1%.But, because BeO composition is harmful to, so preferably do not contain environment, human body.
MgO composition, CaO composition, SrO composition and BaO composition are the optional members improving the meltbility of glass and stability and form the crystallization of NASICON type.But the content of MgO composition is greater than 20%, the content of CaO composition is greater than 60%, the content of SrO composition is greater than 10% or the content of BaO composition when being greater than 50%, the stability of glass is deteriorated on the contrary, TiO
2crystallization, the crystallization of NASICON type, WO
3the precipitation of crystallization, ZnO crystallization etc. also becomes difficulty.
Therefore, the upper limit of the content of MgO composition is preferably 20%, is more preferably 18%, most preferably is 15%.
In addition, the upper limit of the content of CaO composition is preferably 60%, is more preferably 55%, most preferably is 50%.The content of CaO composition can be preferably more than 1%, be more preferably more than 2%, more preferably more than 3%, most preferably be more than 5%.
In addition, the upper limit of the content of SrO composition is preferably 10%, is more preferably 9.5%, most preferably is 9%.The content of SrO composition can be preferably more than 1%, be more preferably more than 2%, more preferably more than 3%, most preferably be more than 4%.
In addition, the upper limit of the content of BaO composition is preferably 50%, is more preferably 45%, most preferably is 40%.The content of BaO composition can be preferably more than 1%, is more preferably more than 2%, most preferably is more than 3%.
The total amount of the RO composition (in formula, R is more than a kind of being selected from Be, Mg, Ca, Sr and Ba) that the interior region of optical article of the present invention contains is preferably less than 60%.Thus, the stability of glass improves, TiO
2crystallization, WO
3the crystallization phases of the crystallization phasess such as crystallization, ZnO crystallization and NASICON type becomes easy precipitation, and therefore, optical article can easily obtain the wetting ability produced by photocatalytic activity.Therefore, the upper limit of the total amount of RO composition be preferably 60%, be more preferably 55%, more preferably 50%, most preferably be 40%.
RO composition is optional member, but due to when containing RO composition, obtains good wetting ability, so the lower limit of the total amount of RO composition is preferably 1%, is more preferably 2%, most preferably is 3%.
ZnO component is the composition improving the meltbility of glass and stability and form the crystallization of NASICON type, can give the photocatalytic activity of responding to visible light, can give hydrophilic optional member thus when being and being separated out as crystallization phases from glass by thermal treatment.Therefore, from the viewpoint of the raising of the raising of stability, glass, photocatalyst effect, the ZnO component of more than 0.1% can be added, also can add the ZnO component of more than 3%.
Especially, when precipitation has the ZnO crystallization of photocatalytic activity, if the content of ZnO component is less than 20%, then separates out ZnO crystallization and become difficulty, sufficient photocatalytic activity cannot be obtained.
On the other hand, if the content of ZnO component is greater than 70%, then vitrifying becomes very difficult.Therefore, the upper limit of the content of ZnO component is preferably 70%, is more preferably 65%, most preferably is 60%.Its upper limit can be 30%, also can be 25%, also can be 10%.
SnO composition forms NASICON type crystallization and promotes the precipitation of NASICON type crystallization and be solid-solution in the crystallization of NASICON type, have the optional member of the effect improving photocatalyst characteristic.But if the content of these compositions is greater than 10%, then the bad stability of glass, photocatalyst characteristic also easily reduces.Therefore, the upper limit of the content of SnO composition is preferably 10%, is more preferably 8%, most preferably is 5%.
CuO composition is the optional member of the effect of the minimizing with the transmittance suppressed under wavelength 400nm.And be contribute to TiO
2the composition of the raising of the photocatalytic activity of crystallization etc.Therefore, the upper limit of the content of CuO composition is preferably 50%, is more preferably 45%, most preferably is 40%.
AgO composition contributes to TiO
2the optional member of the raising of the photocatalytic activity of crystallization etc.Therefore, the upper limit of the content of AgO composition is preferably 10%, is more preferably 9%, most preferably is 8%.
Al
2o
3composition improves the stability of glass and the weather resistance of chemistry and Al
3+ion is solid-solution in TiO
2crystallization, NASICON type crystallization phases and contribute to the raising of photocatalytic activity thus hydrophilic optional member can be given.Therefore, Al
2o
3the lower limit of the content of composition can be more preferably 0.1%, more preferably 1%, most preferably be 2%.
But if its content is greater than 80%, then the melting temperature (Tm) of raw material during glass manufacture significantly rises, vitrifying becomes difficult.Therefore, Al
2o
3the upper limit of the content of composition is preferably 80%, be more preferably 75%, more preferably 70%, more preferably 50%, more preferably 20%, most preferably be 10%.
B
2o
3composition is eyed structure by forming glass thus improves the optional member of stability of glass.Therefore, B
2o
3the lower limit of the content of composition can be more preferably 1%, most preferably be 3%.
But if its content is greater than 60%, then the chemical durability of glass reduces, when carrying out heating during crystallization, the tendency that desired photocatalyst crystallization is difficult to separate out strengthens, and thus, wetting ability becomes easy reduction.Therefore, B
2o
3the upper limit of the content of composition is preferably 60%, be more preferably 55%, more preferably 50%, most preferably be 30%.
Ta
2o
5composition is the optional member of the stability improving glass.In addition, have by self forming NASICON type crystallization thus bringing the effect of photocatalytic activity.But, if Ta
2o
5the content of composition is greater than 30%, then the stability of glass is obviously deteriorated.Therefore, Ta
2o
5the upper limit of the content of composition is such as 30%, is preferably 20%, is more preferably 15%, most preferably is 10%.
Bi
2o
3composition improves the meltbility of glass and the composition of stability, and then, be the optional member improving photocatalytic activity by being solid-solution in photocatalyst crystallization.But, if Bi
2o
3the content of composition is greater than 85%, then the stability of glass is obviously deteriorated.Therefore, Bi
2o
3the upper limit of the content of composition is preferably 85%, be more preferably 80%, more preferably 75%, more preferably 50%, more preferably 25%, most preferably be 10%.
La
2o
3composition is the optional member that can obtain the effect realizing high refractive index and low dispersion.Therefore, La
2o
3the upper limit of the content of composition is preferably 50%, be more preferably 49%, more preferably 48%, more preferably 40%, most preferably be 30%.
Fe
2o
3composition be improve the stability of glass and the chemistry of optical article weather resistance, promote the optional member that the crystallization of NASICON type is separated out from glass.In addition, be also form NASICON type crystallization by self thus bring the composition of photocatalytic activity.But if its content is greater than 10%, then vitrifying becomes difficult.Therefore, Fe
2o
3the upper limit of the content of composition is preferably 10%, is more preferably 5%, most preferably is 3%.
Gd
2o
3composition be improve glass specific refractory power and the optional member of Abbe number can be improved.On the other hand, by the Gd by costliness in rare earth element
2o
3composition is reduced to less than 20%, can reduce the material cost of glass.Therefore, Gd
2o
3the upper limit of the content of composition is preferably 20.0%, is more preferably 15%, most preferably is 10%.
As
2o
3composition and Sb
2o
3composition is the optional member making glass clarifying, deaeration.But if these compositions content is separately greater than 5%, then the bad stability of glass, photocatalytic activity also becomes easy reduction.Therefore, As
2o
3composition or Sb
2o
3the upper limit of the composition content of composition is separately preferably 5%, is more preferably 3%, most preferably is 1%.In addition, when adding these compositions, the lower limit of the content of each composition can be preferably 0.001%, is more preferably 0.002%, most preferably is 0.005%.
But, As
2o
3composition is harmful to environment, human body, does not therefore preferably contain.In addition, Sb
2o
3although composition and As
2o
3composition is compared more unharmful, but also remains and cause dysgenic composition to environment, human body, therefore, if even if not containing this composition, also can make glass clarifying, just preferably do not contained.
Lu
2o
3composition is the optional member that can obtain the effect realizing high refractive index and low dispersion.But, owing to being rare mineral wealth, so excessively containing being undesirable.Lower limit is preferably 5%, is more preferably 3%, does not most preferably contain completely.
Y
2o
3composition is the optional member that can obtain the effect regulating specific refractory power and dispersion.The upper limit of content is preferably 20%, be more preferably 18%, more preferably 15%, most preferably be 10%.
GeO
2composition has and above-mentioned SiO
2the optional member of similar effect.Especially, by making GeO
2the content of composition is less than 20%, can suppress expensive GeO
2the use of composition, therefore, can reduce the material cost of optical article.Therefore, GeO
2the upper limit of the content of composition is preferably 20%, is more preferably 15%, most preferably is 10%.
TeO
2composition is the optical transparency that has relative to the wavelength of the region of ultra-red near visible region to 5.5 μm and shows the optional member of the effect of high refractive index.In addition, be the composition of effect of the clarification that can obtain when promoting glass melting.In addition, be also improve the meltbility of glass and the composition of stability, and then, be also the composition being solid-solution in photocatalyst crystallization, improving photocatalytic activity.
But, if TeO
2the content of composition is too much, then the stability of glass is obviously deteriorated.Therefore, TeO
2the upper limit of the content of composition is preferably 85%, is more preferably 80%, more preferably 75%.Herein, TeO
2the upper limit of the content of composition can be preferably 20%, is more preferably 15%, most preferably is 10%.
ZrO
2composition being the crystallization of formation NASICON type, improving the chemical durability of optical article, bringing photocatalytic activity by forming NASICON type crystallization, can giving hydrophilic optional member thus.But, if ZrO
2the content of composition is greater than 50%, then vitrifying becomes difficult.Therefore, ZrO
2the upper limit of the content of composition is preferably 50%, be more preferably 45%, more preferably 40%, more preferably 20%, most preferably be 10%.In addition, as interpolation ZrO
2during composition, lower limit can be more preferably 0.5%, most preferably be 1%.
V
2o
5composition is by formation NASICON type crystallization thus brings the optional member of photocatalytic activity.In addition, have by self forming NASICON type crystallization thus bringing the effect of photocatalytic activity.In addition, by by V
2o
5as principal constituent, there is the ultrared effect through 1 ~ 5 μm.But, if V
2o
5the content of composition is greater than 60%, then vitrifying becomes difficult.Therefore, V
2o
5the upper limit of the content of composition is preferably 60%, is more preferably 55%, most preferably is 50%.
HfO
2composition is by formation NASICON type crystallization thus brings the optional member of photocatalytic activity.But, if HfO
2the content of composition is greater than 40%, then vitrifying becomes difficult.Therefore, HfO
2the upper limit of the content of composition is such as 40%, is preferably 10%, is more preferably 5%, most preferably is 3%.
MoO
3composition improves the meltbility of glass and the optional member of stability.In addition, have by self forming NASICON type crystallization thus bringing the effect of photocatalytic activity.But, if MoO
3the content of composition is greater than 30%, then the stability of glass is obviously deteriorated.Therefore, MoO
3the upper limit of the content of composition is preferably 30%, is more preferably 20%, most preferably is 10%.
Ga
2o
3composition improves the stability of glass and Ga
3+ion is solid-solution in TiO
2crystallization, NASICON type crystallization phases and contribute to the optional member of the raising of photocatalytic activity.But if its content is greater than 30%, then melting temperature (Tm) obviously raises, vitrifying becomes difficult.Therefore, Ga
2o
3the upper limit of the content of composition is preferably 30%, is more preferably 15%, most preferably is 10%.
In
2o
3composition has and above-mentioned Al
2o
3and Ga
2o
3the optional member of similar effect.In
2o
3composition is expensive, and therefore, the upper limit of its content is preferably 10%, is more preferably 8%, most preferably is 5%.
Ln
2o
3composition is (in formula, Ln is more than a kind of being selected from Sc, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb) be the composition of chemical durability improving optical article, and be crystallization phases by being solid-solution in photocatalyst or exist in its vicinity thus improve the optional member of photocatalytic activity.But, if Ln
2o
3the total content of composition is greater than 30%, then the stability of glass is obviously deteriorated.Therefore, Ln
2o
3the upper limit of the total amount of composition is preferably 30%, is more preferably 10%, most preferably is 5%.
M
xo
y(in formula, M is more than a kind of being selected from Cr, Mn, Co, Ni to composition, x and y is respectively the minimum natural number of the valence mumber meeting x:y=2:M.Herein, the valence mumber of the valence mumber of Cr to be the valence mumber of 3, Mn be 1, Co is the valence mumber of 2, Ni is 2.) be crystallization phases by being solid-solution in photocatalyst or exist in its vicinity thus contribute to the optional member of the raising of photocatalytic activity.When comprising M
xo
yduring composition, by making M
xo
ythe total amount of composition is less than 10%, can improve the stability of glass-ceramic.Therefore, M
xo
ythe upper limit of the total amount of composition is preferably 10%, is more preferably 5%, most preferably is 3%.But, owing to absorbing the visible ray of the wavelength of a part, so when using optical article in visible region, preferably not containing this composition.
Also can containing the non-metallic element composition of more than a kind that is selected from F composition, Cl composition, Br composition, S composition, N composition and C composition in the interior region of optical article of the present invention.These compositions are crystallization phasess by being solid-solution in photocatalyst or exist in its vicinity thus improve the optional member of photocatalytic activity.
But if the content of these composition adds up to be greater than 20%, then the stability of glass is obviously deteriorated, and photocatalytic activity becomes easy reduction.Therefore, in order to ensure good characteristic, the content of non-metallic element composition is preferably 20% relative to the upper limit of the total of the outer ratio mass ratio of the total mass of interior region, is more preferably 10%, most preferably is 5%.
It should be noted that, the content of the outer ratio of the non-metallic element composition in this specification sheets is, relative to the percentage of the total quality of the oxide compound benchmark of the composition of the formation interior region except this non-metallic element composition, the quality of this composition.
Raw material for non-metallic element composition is not particularly limited, such as, by using ZrF
4, AlF
3, NaF, CaF
2deng the raw material as F composition, NaCl, AgCl etc. as the raw material of Cl composition, NaBr etc. as the raw material of Br composition, NaS, Fe
2s
3, CaS
2deng the raw material as S composition, AlN
3, SiN
4deng the raw material as N composition, TiC, SiC or ZrC etc. as C composition raw material and import.It should be noted that, these raw materials can combine and add two or more, also can add separately.
In the interior region of optical article of the present invention, also can comprise the metallic element composition of at least a kind be selected from Cu composition, Ag composition, Au composition, Pd composition, Ru composition, Rh composition, Re composition and Pt composition.These metallic element compositions, by existing near photocatalyst crystallization phases thus the composition of raising photocatalytic activity, are the compositions that can optionally add.Wherein, especially, Cu composition and Ag composition form NASICON type crystallization and have the effect bringing photocatalytic activity in the same manner as above-mentioned alkalies and alkaline earth compositions.But if ratio meter is greater than 50% beyond the total content of these metallic element compositions, then the stability of glass is obviously deteriorated, and photocatalytic activity becomes easy reduction on the contrary.Therefore, beyond the upper limit of the total of these compositions, ratio meter is preferably 50%, is more preferably 40%, most preferably is 30%.These metallic element compositions can use such as CuO, Cu
2o, Ag
2o, AuCl
3, PtCl
2, PtCl
4, H
2ptCl
6, RuO
2, RhCl
3, ReCl
3, PdCl
2import Deng as raw material.In addition, when adding these compositions, ratio meter in addition, lower limit is more preferably 0.001%, most preferably is 0.005%.
Preferably exemplify as the interior region of optical article of the present invention and the composition of intermediate composed as follows shown in.
1st exemplifies, with P
2o
5composition is 15 ~ 35%, TiO
2composition is 10 ~ 35%, Nb
2o
5composition is 30 ~ 45%, Na
2o composition is 0% ~ 15%, K
2o composition is 0% ~ 12%, BaO composition is 0% ~ 7% and Sb
2o
3composition is 0% ~ 1%, WO
3composition be 0 ~ 15% scope contain the composition of each composition.
2nd exemplifies, with SiO
2composition is 30% ~ 55%, TiO
2composition is 0% ~ 15%, B
2o
3composition is 0% ~ 10%, Na
2o composition is 1% ~ 20%, K
2o composition is 5% ~ 25%, BaO composition is 10% ~ 30%, Al
2o
3composition is 0% ~ 10% and Sb
2o
3composition be 0% ~ 1% scope contain the composition of each composition.
3rd exemplifies, with SiO
2composition is 15% ~ 35%, TiO
2composition is 10% ~ 35%, Na
2o composition is 1% ~ 20%, ZrO
2composition is 0% ~ 10%, BaO composition is 10% ~ 30%, Nb
2o
5composition is 5% ~ 30% and Sb
2o
3composition be 0% ~ 1% scope contain the composition of each composition.
4th exemplifies, with SiO
2composition is 20% ~ 50%, TiO
2composition is 10% ~ 35%, Na
2o composition is 1% ~ 20%, Li
2o composition is 0% ~ 10%, BaO composition is 0% ~ 20%, K
2o composition is 5% ~ 20% and Sb
2o
3composition be 0% ~ 1% scope contain the composition of each composition.
5th exemplifies, with SiO
2composition is 60% ~ 70%, Na
2o composition is 5% ~ 25%, CaO composition is 3% ~ 25%, Al
2o
3composition be 0% ~ 20% scope contain the composition of each composition.
The manufacture method of optical article of the present invention is described.First, the amount of desired composition is become with optical article of the present invention, mix known frit, the mixture be made into is put in quartz crucible or alumina crucible, carry out thick melting, then put in platinum crucible, platinum alloy crucibles or iridium crucible, melting 2 ~ 10 hours in the temperature range of 700 ~ 1300 DEG C, stirring homogenizes, carry out de-bubble etc., then be reduced to the temperature of less than 1250 DEG C, then carry out meticulous stirring, removing brush line, be injected in mould, Slow cooling, thus, makes glass blank.
Then, the glass blank be made into is processed into the shape that lens shape etc. is desired, as required, effects on surface carries out mirror ultrafinish, makes intermediate thus.Intermediate, as optical article, becomes the state had the desired basic optical property such as light optically focused.
Then, heat-treat the intermediate be made into, thus, crystallization in surface region, can manufacture optical article of the present invention thus.In this thermal treatment, if the precipitation of crystallization is too much, then light transmission reduces, if the precipitation of crystallization is very few, then becomes the wetting ability be difficult to desired by acquisition.Therefore, preferably make the conditions such as heat treated temperature, time in certain scope.
In order to make light transmission and hydrophilic harmony well, this heat treated temperature, preferably in the scope of 100 DEG C ~ 450 DEG C, more preferably in the scope of 110 DEG C ~ 350 DEG C, most preferably is the scope of 120 DEG C ~ 300 DEG C.
In order to make light transmission and hydrophilic harmony good, the treatment time of the operation of heat-treating is preferably in the scope of 0.1 hour ~ 120 hours, preferably in the scope of 0.1 hour ~ 72 hours, more preferably in the scope of 0.5 hour ~ 70 hours, most preferably in the scope of 1 hour ~ 65 hours.
In the operation of heat-treating, in order to make light transmission and hydrophilic harmony good, be applied to pressure on intermediate preferably between 0.09MPa ~ 22MPa, more preferably between 0.09MPa ~ 10MPa, most preferably between 0.09MPa ~ 5MPa.
In the operation of heat-treating, as around the atmosphere of intermediate or environment, be preferably air, oxygen, nitrogen, hydrogen, carbonic acid gas, halogen, rare gas, water, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution, ammoniacal liquor, aqueous sodium carbonate, sodium bicarbonate aqueous solution, hydrogen fluoride aqueous acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid, alcohol etc. or the such gas of their mixture or liquid.
[embodiment]
Then, embodiments of the invention are described.
The composition of the glass blank used in embodiment (glass A ~ glass I) is shown in table 1 ~ table 3.
These glass blanks are made all in such a way: select as the raw material of each composition oxide compound suitable respectively, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide, the common highly purified raw materials that can use in opticglass such as metaphosphoric acid compound, weighing is carried out and Homogeneous phase mixing according to the ratio becoming the composition shown in table 1 ~ table 3, then put in platinum crucible, according to the melting difficulty of glass composition, carry out dissolving for 2 ~ 10 hours in electric furnace in the temperature range of 700 ~ 1300 DEG C, carry out stirring to homogenize, carry out de-bubble etc., then temperature is reduced to less than 1250 DEG C, be injected into after stirring homogenizes in mould, Slow cooling, be made into glass blank.
[table 1]
[table 2]
[table 3]
The glass blank obtained is processed into the tabular of 10mm × 10mm × 5mm, heat-treats under the heat-treat condition recorded in table 4 ~ table 7, be made into optical article.For thermal treatment, when atmosphere is " air ", by directly intermediate to be rested in electric furnace and to carry out heating to carry out.In addition, when atmosphere is " H
2o " time, in the autoclave of 100ml capacity, put into 15ml pure water, and put into intermediate, airtight, then this autoclave to be rested in electric furnace and to heat, carrying out thus.It should be noted that, comparative example 1,2 and 4 is not heat-treated.
For the optical article carrying out heat treated tabular, with UV intensity for 1mW/cm
2irradiate the UV-light of irradiating from black light (black light) (Toshiba Lighting & TechnologyCorporation model: FL10BLB), utilize θ/2 method, determine the contact angle of the water droplet on the surface being added drop-wise to optical article.Because the contact angle of water droplet changes along with the passing of the irradiation time of UV-light, therefore, in table, record the contact angle of irradiation time and the water under this irradiation time.
For the optical article of embodiment 1 ~ embodiment 11, its cross section is observed with transmission electron microscope (TEM), as a result, crystallization in from the surface of optical article to the region inwardly within 100 μm, does not find the precipitation of crystallization at interior region.In addition, the image (multiplying power 20000 times) that utilization scanning electron microscope (SEM) is taken its surface and obtained is observed, result,, there is the foursquare region that the length of side exposing more than 1 crystallite is 100 μm in the optical article of the embodiment 1 ~ embodiment 11 except embodiment 7.For the optical article of embodiment 1, measure the average crystallite particle diameter being present in the crystallization of its surface region, result is 2000nm.In addition, for the optical article of embodiment 7, the image (multiplying power 20000 times) that utilization scanning electron microscope (SEM) is taken its surface and obtained is observed, as a result, there is the foursquare region that its surface by the length of side that the crystallization of squamous covers is all 100 μm.
In addition, utilize visual observation, the optical article of embodiment 1 ~ 6 and 8 ~ 11 is water white transparency.For the optical article of embodiment 1 ~ 11, make the light of wavelength 587.6nm and the light transmission in a thickness direction of wavelength 1050nm, measure whether emergent light has more than 20% intensity relative to incident light, result, all has the intensity of more than 20%.Be determined as follows and carry out: optical article of the present invention is clipped on FLH-741 type filter mount, be arranged at spectrophotometer (Japan Spectroscopy Corporation V-650), determine transmittance thus.In addition, the optical article of embodiment 1 is parallel flat, because this has been the mensuration of degree of staining.Except sample thickness is this point of 8mm, understand according to the industry of Japanese Optical nitre the degree of staining that standard JOGIS 02-2003 determines the optical article of embodiment 1, result, the spectrophotometric light transmittance comprising reflection loss be 70% wavelength be 430nm.
[table 4]
[table 5]
[table 6]
[table 7]
For the optical article recorded in embodiment, by ultraviolet irradiation, the contact angle of water droplet becomes less than 30 °, confirms to have wetting ability.Especially, for the optical article described in embodiment 3 ~ 6,7,9 and 10, although non-irradiation ultraviolet radiation, the contact angle of water droplet also becomes less than 30 °, confirms to have wetting ability.
(embodiment 12)
Carry out the endurance test of the optical article made in embodiment 2.The optical article be made in cutting embodiment 2, makes its 1 face become about 0.5cm
2, be made into test film.On the brass abrasive sheet of the thick polyester cloth of the 0.16mm sprawling Dongli Ltd. (TORAYSEE (registered trademark) MC CLOTH), laminating has been cut into about the thick polyurethane foam sponge of 10mm.Sponge places test film, applies the load of 158g from top.Then, the Northeast loam specified by JIS Z 8901 mixes with pure water, makes the muddy water of 10 quality %, is added dropwise on sponge, is infiltrated up to wherein, with the speed of 10Hz, abrasive sheet is rotated, 5 minutes, the surface of rub(bing)test sheet.
With 1mW/cm
2uV intensity irradiated the UV-light of irradiating from black light (Toshiba Lighting & Technology Corporation model: FL10BLB) to surface by the test film after rubbing, utilize θ/2 method, determine the contact angle of the water droplet be added drop-wise on test film surface.
Measure as a result, unchanged compared with not carrying out the situation of endurance test relative to the value of the contact angle of the irradiation time of UV-light, even if confirm, after having carried out this test, also to keep same wetting ability.
(embodiment 13)
Use the glass A recorded in table 1, make lens, the diameter of these lens is 60mm, 1st for radius-of-curvature be the convex form of 77.5mm, 2nd for radius-of-curvature be the convex form of 291.5mm, the 1st of central part is 6mm with the distance of the 2nd, heat-treats under the same conditions as example 1, has made the optical article as lens.These lens of visual observation are water white transparency, determine the transmittance by the light in the light path of the central shaft of these lens, and confirming result is more than 20%.
In addition, utilize the cross section of these lens of tem observation, results verification, in the surface region on 100 μm, distance surface, there is crystallization, interior region is formed by the glassy phase that there is not crystallization.
Claims (6)
1. an optical article, is characterized in that,
Its through more than 20% the light of wavelength 587.6nm or the light of wavelength 1050nm,
Be surface region from the surface of described optical article to the region inwardly within 500 μm, with the region beyond surface region for interior region time,
Described interior region is formed by glassy phase, counts according to the quality % of oxide compound benchmark, and what described glassy phase contained total less than more than 5% 95% is selected from TiO
2, P
2o
5, Nb
2o
5, SiO
2and WO
3in the composition of more than a kind,
In described surface region at least partially, exist and form from the glassy phase of described interior region the crystallization that identical glassy phase separates out.
2. optical article as claimed in claim 1, wherein, described crystallization is be selected from the crystallization of more than a kind in the crystallization comprising Ti, the crystallization comprising Nb, the crystallization comprising W, the crystallization comprising P, the crystallization comprising Si and their sosoloid.
3. optical article as claimed in claim 1 or 2, wherein, at least there is the foursquare region that the length of side is 100 μm on the surface of described optical article, is expose more than 1 crystallite in the foursquare region of 100 μm in the described length of side.
4. optical article as claimed in claim 1 or 2, wherein, at least there is the foursquare region that the length of side is 100 μm on the surface of described optical article, the described length of side is that the foursquare region of 100 μm is all covered by crystallization.
5. the optical article according to any one of Claims 1 to 4, count according to the quality % of oxide compound benchmark, described glassy phase contains each composition of following content:
TiO
2：0％～95％、
P
2O
5：0％～50％、
Nb
2O
5：0％～50％、
SiO
2：0％～95％、
WO
3：0％～95％、
Li
2O：0％～20％、
Na
2O：0％～20％、
K
2O：0％～30％、
Tl
2O：0％～70％、
BeO：0％～10％、
MgO：0％～20％、
CaO：0％～60％、
SrO：0％～10％、
BaO：0％～50％、
ZnO：0％～70％、
SnO：0％～10％、
CuO：0％～50％、
AgO：0％～10％、
Al
2O
3：0％～80％、
B
2O
3：0％～60％、
Ta
2O
5：0％～30％、
Bi
2O
3：0％～85％、
La
2O
3：0％～50％、
Fe
2O
3：0％～10％、
Gd
2O
3：0％～20％、
Sb
2O
3：0％～5％、
Lu
2O
3：0％～5％、
Y
2O
3：0％～20％、
GeO
2：0％～20％、
TeO
2：0％～85％、
ZrO
2：0％～50％、
V
2O
5：0％～60％。
6. lens, its optical article according to any one of Claims 1 to 5 is formed.
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| JP2014247355A JP2015143833A (en) | 2013-12-27 | 2014-12-05 | Optical article and lens |
| JP2014-247355 | 2014-12-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084763A (en) * | 2015-07-31 | 2015-11-25 | 安徽和润特种玻璃有限公司 | Method for preparing high-tenacity high-hardness anti-dazzle glass |
| CN107902891A (en) * | 2017-11-08 | 2018-04-13 | 柳州市奥康眼镜有限公司 | A kind of optical glass and optical element |
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| CN105084763A (en) * | 2015-07-31 | 2015-11-25 | 安徽和润特种玻璃有限公司 | Method for preparing high-tenacity high-hardness anti-dazzle glass |
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| CN112876066B (en) * | 2020-06-30 | 2022-04-15 | 成都光明光电股份有限公司 | Environment-friendly glass material |
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