CN103663961B - The manufacturing method of optical glass, optical element and glass forming body - Google Patents
The manufacturing method of optical glass, optical element and glass forming body Download PDFInfo
- Publication number
- CN103663961B CN103663961B CN201310389532.4A CN201310389532A CN103663961B CN 103663961 B CN103663961 B CN 103663961B CN 201310389532 A CN201310389532 A CN 201310389532A CN 103663961 B CN103663961 B CN 103663961B
- Authority
- CN
- China
- Prior art keywords
- glass
- ingredient
- upper limit
- optical glass
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Glass Compositions (AREA)
Abstract
The present invention provides the manufacturing method of the optical glass, optical element and glass forming body with desired high stability and high dispersion (low Abbe number).Amount of the optical glass relative to the total material of the glass formed to be converted with oxide contains 20% or more and 45% P below in terms of mole %2O5Ingredient, 15% or more and 60% Nb below2O5Ingredient, total amount are 5% or more and 50% or less ZnO component and MgO ingredient, and the refractive index of the optical glass is 1.75 or more, and Abbe number is 10 or more and 35 or less.The optical glass is 0.1% or more and 20% SiO below containing total amount preferably in terms of mole %2Ingredient and Al2O3One or both of ingredient ingredient.
Description
Technical field
The present invention relates to the manufacturing methods of optical glass, optical element and glass forming body.
Background technique
In recent years, rapidly developed using the digitlization of the instrument of optical system and high-definition, for digital camera
And the photographic instruments such as video camera be the high precision int of the optical elements such as lens, light weight used in the various optical instruments of representative and
The requirement of miniaturization is more strong.
In the optical glass of production optical element, the lightweight and miniaturization, tool of optical element can be especially realized
There is high refractive index (nd) and low Abbe number (νd) glass of high refractive index demand it is very high.As such glass of high refractive index,
For example, the optical glass recorded in patent document 1 has 21 Abbe number more than or lower than 31, the light recorded in patent document 2
Learning glass has 22 Abbe number more than or lower than 25.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 8-157231 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2001-58845 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2003-238197 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2003-321245 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2003-335549 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2005-154248 bulletin
Patent document 7: Japanese Unexamined Patent Publication 2009-143801 bulletin
Patent document 8: Japanese Unexamined Patent Publication 2010-83701 bulletin
Patent document 9: Japanese Unexamined Patent Publication 2011-57509 bulletin
Patent document 10: Chinese patent discloses No. 101134641 bulletins
Summary of the invention
Problems to be solved by the invention
However, for the optical glass documented by 1~patent document of patent document 10, it is steady although Abbe number is low
It is qualitative to be hard to call it height, it is possible to devitrification etc. occur.
Therefore, the present invention be complete in view of the above problems, it is intended that provide have desired high stability and
The manufacturing method of the optical glass of high dispersion (low Abbe number), optical element and glass forming body.
The solution to the problem
The present inventor has carried out deep experimental study to solve the above-mentioned problems, as a result, it has been found that, by with defined flat
Weighing apparatus is kept and the P containing specified amount2O5Ingredient, Nb2O5Ingredient, ZnO component and MgO ingredient can be improved stability, improve dispersion,
So as to complete the present invention.Specifically, the present invention provides technical solution below.
(1) a kind of optical glass, wherein the amount of the total material relative to the glass formed to be converted with oxide, to rub
Your % is counted, and contains 20% or more and 45% P below2O5Ingredient, 15% or more and 60% Nb below2O5Ingredient, total amount are 5% or more
And 50% ZnO component below and MgO ingredient, the refractive index of the optical glass is 1.75 or more, and Abbe number is 10 or more and 35
Below.
(2) optical glass according to (1), wherein the total material relative to the glass formed to be converted with oxide
Amount, in terms of mole %, containing total amount be 0.1% or more and 20% SiO below2Ingredient and Al2O3One or both of ingredient
Ingredient.
(3) optical glass according to (1) or (2), wherein relative to the total of the glass formed to be converted with oxide
The amount of substance contains 0% or more and 40% TiO below in terms of mole %2Ingredient.
(4) optical glass according to any one of (1)~(3), wherein formed relative to what is converted with oxide
Glass total material amount, in terms of mole %, contain 0% or more and 25% R below2O ingredient, R2It O/(ZnO+MgO) is 2.0
Below.
Wherein, R is selected from one or more of the group being made of Li, Na and K element.
(5) optical glass according to any one of (1)~(4), wherein formed relative to what is converted with oxide
Glass total material amount, in terms of mole %, contain 0% or more and 25% MO ingredient below, MO/(ZnO+MgO) be 0.5 with
Under.
Wherein, M is selected from one or more of the group being made of Ca, Sr and Ba element.
(6) a kind of optical element, the optical glass as described in any one of (1)~(5) are formed.
(7) a kind of manufacturing method of glass forming body uses optical glass described in any one of (1)~(6),
The aforementioned optical glass softened is pressed in mold.
The effect of invention
According to the present invention it is possible to provide the P by keeping with defined balance and containing specified amount2O5Ingredient, Nb2O5At
Point, ZnO component and MgO ingredient and optical glass, optical element and glass molding with desired high stability and high dispersion
The manufacturing method of body.
Detailed description of the invention
Fig. 1 is the curve graph for indicating the transmission characteristics of optical glass of embodiment 1.
Specific embodiment
The amount of optical glass of the invention relative to the total material of the glass formed to be converted with oxide, in terms of mole %
Contain 20% or more and 45% P below2O5Ingredient, 15% or more and 60% Nb below2O5Ingredient, total amount be 5% or more and 50% with
Under ZnO component and MgO ingredient, the refractive index of the optical glass be 1.75 or more, Abbe number is 10 or more and 35 or less.It is logical
Cross the P containing specified amount2O5Ingredient, Nb2O5Ingredient and TiO2The reduction of ingredient, the transmissivity to visible light of optical glass is pressed down
System, dispersion are improved.In addition, by reducing the Sb contained in optical glass2O3Ingredient, the influence to environment mitigate, in glass
The bumps and blushing on surface are reduced.It is, therefore, possible to provide there is desired high-transmission rate and high dispersion and surface can be reduced
The manufacturing method of concave-convex and blushing optical glass, optical element and glass forming body.
Hereinafter, the embodiment of optical glass of the invention is described in detail, but the present invention is not by following implementation
Any restriction of mode can be suitably changed within the scope of the purpose of the present invention to implement.It should be noted that about explanation
Duplicate place, suitably omits the description sometimes, but and non-limiting invention purport.
Glass ingredient
The compositing range of each ingredient described below for constituting optical glass of the invention.In the present specification, in no spy
Not Xian Ding in the case where, the containing ratio of each ingredient is all with the amount of the total material relative to the glass formed to be converted with oxide
Mole % indicate.Herein, it " is formed " and is referred to using what oxide converted: it is assumed that as the original of glass constituent of the invention
In the case that oxide, complex salt and the metal fluoride etc. expected and used all decompose in melting and change to oxide,
Forming for each ingredient contained in glass is indicated as 100 moles of % using the amount of the total material of the generation oxide.
About essential component, any ingredient
Then, to as optical glass of the invention and it is preferable to use, the essential component of glass and any ingredient carry out
Explanation.
P2O5Ingredient is glass forming constituents, and is the essential component for reducing the melting temperature of glass.In particular, passing through
Make P2O5The containing ratio of ingredient is 20% or more, and devitrification resistance rises, and can be readily derived the high glass of stability.Another party
Face, by making P2O5The containing ratio of ingredient is 45% hereinafter, available high refractive index.Accordingly, with respect to what is converted with oxide
The amount of the total material of the glass of composition, P2O5The containing ratio of ingredient is preferably lower limit with 20%, with 22% is more preferably lower limit, optimal
Choosing with 24% is lower limit, is preferably the upper limit with 45%, with 35% is more preferably the upper limit, with 32% is most preferably the upper limit.P2O5Ingredient can be with
By using such as Al(PO3)3, Ca(PO3)2, Ba(PO3)2、BPO4、H3PO4It is contained in glass Deng as raw material.
Nb2O5Ingredient is the refractive index for improving glass and the essential component of dispersion.In particular, by making Nb2O5Ingredient contains
Having rate is 15% or more, available high refractive index, and available desired high dispersion.On the other hand, by making Nb2O5At
The containing ratio divided is 60% hereinafter, the stability of glass can be improved, devitrification resistance can be improved.Accordingly, with respect to oxide
The amount of the total material of the glass of the composition of conversion, Nb2O5Under the containing ratio of ingredient is preferably lower limit, is more preferably with 20% with 15%
Limit with 23% is most preferably lower limit, is preferably the upper limit with 60%, with 50% is more preferably the upper limit, with 40% is most preferably the upper limit.Nb2O5
Ingredient can be by using such as Nb2O5It is contained in glass Deng as raw material.
SiO2Ingredient is effective in the raising of the meltbility of glass, stability and chemical durability, therefore being can be with
The ingredient arbitrarily added.By making its content, particularly SiO2The containing ratio of ingredient is greater than 0%, and the devitrification of glass can be improved
Property.On the other hand, by making SiO2The containing ratio of ingredient is 15% hereinafter, by SiO2The reduction of stability caused by ingredient is pressed down
System can be readily derived high refractive index.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide,
SiO2The containing ratio of ingredient is preferably the upper limit with 15%, with 12% be more preferably the upper limit, with 10% be most preferably the upper limit.SiO2Ingredient can
By using such as SiO2、K2SiF6、Na2SiF6It is contained in glass Deng as raw material.
GeO2Ingredient has and above-mentioned SiO2Ingredient similarly acts on, therefore is the ingredient that can arbitrarily add.By making
GeO2The containing ratio of ingredient is 10% or less, it is possible to reduce material cost.Accordingly, with respect to the glass formed to be converted with oxide
The amount of the total material of glass, GeO2The containing ratio of ingredient is preferably the upper limit with 10%, with 5% be more preferably the upper limit, most preferably with 1% be
The upper limit.GeO2Ingredient can be by using such as GeO2It is contained in glass Deng as raw material.
Al2O3Ingredient is effective in the raising of the meltbility of glass, stability and chemical durability, therefore can be appointed
Meaning addition.In particular, by making Al2O3The containing ratio of ingredient is 15% hereinafter, the meltbility of glass can be improved and weaken glass
Tendency towards devitrification.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide, Al2O3The containing ratio of ingredient is excellent
Choosing is preferably the upper limit with 15%, with 10% is more preferably the upper limit, with 8% is most preferably the upper limit more than 0%.Al2O3Ingredient can pass through
Use such as Al2O3, Al(OH)3、AlF3It is contained in glass Deng as raw material.
Ga2O3Ingredient has and above-mentioned Al2O3The same effect of ingredient, therefore be the ingredient that can arbitrarily add.Pass through
Make Ga2O3The containing ratio of ingredient is 10% hereinafter, the devitrification resistance of glass can be improved and reduce material cost.Accordingly, with respect to
With the amount of the total material for the glass of oxide conversion formed, Ga2O3The containing ratio of ingredient is preferably the upper limit with 10%, more preferably with
8% it is the upper limit, with 5% is most preferably the upper limit.Ga2O3Ingredient can be by using such as Ga2O3、GaF3Glass is contained in Deng as raw material
In glass.
B2O3Ingredient is the ingredient for improving the meltbility and devitrification resistance of glass, is any ingredient in glass.In particular,
By making B2O3The containing ratio of ingredient is lower than 10%, can inhibit by B2O3The reduction of stability, glass caused by ingredient.Therefore, phase
For the amount of the total material of the glass formed to be converted with oxide, B2O3The containing ratio of ingredient is preferably set to lower than 10%, more excellent
Choosing with 5% is the upper limit, with 1% is most preferably the upper limit.B2O3Ingredient can be by using such as H3BO3、Na2B4O7、Na2B4O7·
10H2O、BPO4It is contained in glass Deng as raw material.
ZnO component is any ingredient for the devitrification resistance for reducing the liquidus temperature of glass and improving glass, and is to make
It is any ingredient in glass to the ingredient that the transmissivity of visible light is difficult to decrease.In particular, by making containing for ZnO component
Rate is 50% hereinafter, high refractive index and high dispersion can be readily derived.Accordingly, with respect to the glass formed to be converted with oxide
The amount of the total material of glass, the containing ratio of ZnO component preferably with 50 be upper limit %, more preferably with 45% be the upper limit, most preferably with 40% be
The upper limit.ZnO component can be by using such as ZnO, ZnF2It is contained in glass Deng as raw material.
MgO ingredient is any ingredient for the devitrification resistance for reducing the liquidus temperature of glass and improving glass, and is to make
It is any ingredient in glass to the ingredient that the transmissivity of visible light is difficult to decrease.In particular, by making containing for MgO ingredient
Rate is 45% hereinafter, high refractive index and high dispersion can be readily derived.Accordingly, with respect to the glass formed to be converted with oxide
The amount of the total material of glass, the containing ratio of MgO ingredient is preferably the upper limit with 50%, with 45% be more preferably the upper limit, most preferably with 40% be
The upper limit.MgO ingredient can be by using such as MgCO3、MgF2It is contained in glass Deng as raw material.
CaO ingredient is any ingredient for the devitrification resistance for reducing the liquidus temperature of glass and improving glass, and is to make
It is any ingredient in glass to the ingredient that the transmissivity of visible light is difficult to decrease.In particular, by making containing for CaO ingredient
Rate is 25% hereinafter, high refractive index and high dispersion can be readily derived, and the devitrification resistance of glass and chemistry can be inhibited resistance to
The reduction of long property.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide, the containing ratio of CaO ingredient is excellent
Choosing with 25% is the upper limit, with 20% be more preferably the upper limit, with 15% be most preferably the upper limit.CaO ingredient can be by using for example
CaCO3、CaF2It is contained in glass Deng as raw material.
SrO ingredient is any ingredient of the devitrification resistance of the liquidus temperature for reducing glass, raising glass, is in glass
Any ingredient.In particular, by making the containing ratio 25% of SrO ingredient hereinafter, high refractive index and high color can be readily derived
It dissipates, and the devitrification resistance of glass and the reduction of chemical durability can be inhibited.It is formed accordingly, with respect to what is converted with oxide
Glass total material amount, the containing ratio of SrO ingredient is preferably the upper limit with 25%, with 20% be more preferably the upper limit, most preferably with
15% is the upper limit.SrO ingredient can be by using such as Sr(NO3)2、SrF2It is contained in glass Deng as raw material.
BaO ingredient is any ingredient for the devitrification resistance for improving the refractive index of glass and improving glass, and is to make to can
The ingredient that light-exposed transmissivity is difficult to decrease is any ingredient in glass.In particular, the containing ratio by making BaO ingredient
25% hereinafter, high refractive index and high dispersion can be readily derived, and can inhibit the drop of devitrification resistance and chemical durability
It is low.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide, the containing ratio of BaO ingredient is preferably with 25%
The upper limit, with 20% be more preferably the upper limit, with 15% be most preferably the upper limit.Herein, especially from the big (Abbe number of dispersion can be obtained
It is small) glass from the perspective of, the amount of the total material relative to the glass formed to be converted with oxide, BaO ingredient contains
Rate is preferably 12.0% or less.BaO ingredient can be by using such as BaCO3, Ba(NO3)2、BaF2Glass is contained in Deng as raw material
In glass.
Li2O ingredient is the stability and any ingredient that is transparent and reducing glass transition temperature (Tg) for improving glass,
It is any ingredient in glass.In particular, by making Li2The containing ratio of O ingredient is 25% hereinafter, high folding can be readily derived
Rate is penetrated, and the stability of glass can be improved, reduce the generation of devitrification etc..It is formed accordingly, with respect to what is converted with oxide
Glass total material amount, Li2The containing ratio of O ingredient is preferably the upper limit with 25%, with 20% be more preferably the upper limit, most preferably with
15% is the upper limit.Li2O ingredient can be by using such as Li2CO3、LiNO3, LiF etc. is contained in glass as raw material.
Na2O ingredient is the stability and any ingredient that is transparent and reducing glass transition temperature (Tg) for improving glass,
It is any ingredient in glass.In particular, by making Na2The containing ratio of O ingredient is lower than 25%, can be readily derived high refraction
Rate, and the stability of glass can be improved, reduce the generation of devitrification etc..Accordingly, with respect to forming of being converted with oxide
The amount of the total material of glass, Na2The containing ratio of O ingredient is preferably set to lower than 25%, be more preferably the upper limit with 20%, most preferably with
15% is the upper limit.Na2O ingredient can be by using such as Na2CO3、NaNO3、NaF、Na2SiF6Glass is contained in Deng as raw material
It is interior.
K2O ingredient is the stability and any ingredient that is transparent and reducing glass transition temperature (Tg) for improving glass,
It is any ingredient in glass.In particular, by making K2The containing ratio of O ingredient is 25% hereinafter, high refraction can be readily derived
Rate, and the stability of glass can be improved, reduce the generation of devitrification etc..Accordingly, with respect to forming of being converted with oxide
The amount of the total material of glass, K2The containing ratio of O ingredient is preferably the upper limit with 25%, with 20% is more preferably the upper limit, most preferably with 15%
For the upper limit.K2O ingredient can be by using such as K2CO3、KNO3、KF、KHF2、K2SiF6It is contained in glass Deng as raw material.
TiO2Ingredient be improve glass refractive index and dispersion and improve glass chemical durability any ingredient.Especially
It is, by making TiO2The containing ratio of ingredient is 0% or more, available high refractive index, and available desired high dispersion.
On the other hand, by making TiO2The containing ratio of ingredient is 40% hereinafter, the stability and the transparency of glass can be improved.Therefore, phase
For the amount of the total material of the glass formed to be converted with oxide, TiO2The containing ratio of ingredient is preferably lower limit with 0%, more excellent
Choosing with 1% is lower limit, with 3% is further preferably lower limit.On the other hand, relative to the total of the glass formed to be converted with oxide
The amount of substance, TiO2The containing ratio of ingredient is preferably the upper limit with 40%, with 35% be more preferably the upper limit, with 30% be most preferably the upper limit.
TiO2Ingredient can be by using such as TiO2It is contained in glass Deng as raw material.
ZrO2Ingredient is the coloring for reducing glass, improves the transmissivity to the visible light of short wavelength and promote stable glass
Any ingredient for forming, improving the devitrification resistance of glass, is any ingredient in glass.In particular, by making ZrO2Ingredient
Containing ratio is 10% hereinafter, due to by ZrO2The reduction of refractive index caused by ingredient is suppressed, therefore can be readily derived expectation
High refractive index.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide, ZrO2The containing ratio of ingredient is excellent
Choosing with 10% is the upper limit, with 8% be more preferably the upper limit, with 5% be most preferably the upper limit.ZrO2Ingredient can be by using such as ZrO2、
ZrF4It is contained in glass Deng as raw material.
Ta2O5Ingredient is the ingredient for improving the refractive index of glass, is any ingredient in glass.In particular, by making
Ta2O5The containing ratio of ingredient is 10% hereinafter, glass can be made to be difficult to devitrification.Accordingly, with respect to forming of being converted with oxide
The amount of the total material of glass, Ta2O5The containing ratio of ingredient is preferably the upper limit with 10%, with 8% is more preferably the upper limit, most preferably with 5%
For the upper limit.Ta2O5Ingredient can be by using such as Ta2O5It is contained in glass Deng as raw material.
WO3Ingredient be improve glass refractive index, improve glass dispersion any ingredient, be in glass it is any at
Point.In particular, by making WO3The containing ratio of ingredient is 10% hereinafter, the devitrification resistance of glass can be improved and inhibit to short wavelength
Visible light glass transmissivity reduction.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide,
WO3The containing ratio of ingredient is preferably the upper limit with 10%, with 5% be more preferably the upper limit, with 1% be most preferably the upper limit.WO3Ingredient can lead to
It crosses and uses such as WO3It is contained in glass Deng as raw material.
Y2O3Ingredient is the refractive index for improving glass, the ingredient to the adjustment of dispersion with huge effect, is light of the invention
Learn any ingredient in glass.In particular, by making Y2O3The containing ratio of ingredient is 10% hereinafter, can inhibit the devitrification of glass
The reduction of property and the rising for inhibiting glass transition point (Tg).Accordingly, with respect to the total of the glass formed to be converted with oxide
The amount of substance, Y2O3The containing ratio of ingredient is preferably the upper limit with 10%, with 8% be more preferably the upper limit, with 5% be most preferably the upper limit.
Y2O3Ingredient can be by using such as Y2O3、YF3It is contained in glass Deng as raw material.
La2O3Ingredient is the ingredient for improving the refractive index of glass and having huge effect to the adjustment of dispersion, is glass
Any ingredient in glass.In particular, by making La2O3The containing ratio of ingredient is 10% hereinafter, can increase the dispersion of glass, and
The devitrification resistance of glass can be improved.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide, La2O3At
Point containing ratio be preferably the upper limit with 10%, with 8% be more preferably the upper limit, with 5% be most preferably the upper limit.La2O3Ingredient can pass through
Use such as La2O3、La(NO3)3·XH2O(X is arbitrary integer) etc. be contained in glass as raw material.
Gd2O3Ingredient is the ingredient for improving the refractive index of glass and having huge effect to the adjustment of dispersion, is glass
Any ingredient in glass.In particular, by making Gd2O3The containing ratio of ingredient be 10% hereinafter, can increase the dispersion of glass and
The devitrification resistance of glass can be improved.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide, Gd2O3At
Point containing ratio be preferably the upper limit with 10%, with 8% be more preferably the upper limit, with 5% be most preferably the upper limit.Gd2O3Ingredient can pass through
Use such as Gd2O3、GdF3It is contained in glass Deng as raw material.
Bi2O3Ingredient be improve glass refractive index and dispersion ingredient, be in optical glass of the invention it is any at
Point.In particular, by making Bi2O3The containing ratio of ingredient is 10% hereinafter, the stability of glass is improved, therefore can be inhibited resistance to
The reduction of increased devitrification resistance, and the reduction of the transmissivity of glass can be inhibited.Accordingly, with respect to the glass formed to be converted with oxide
The amount of the total material of glass, Bi2O3The containing ratio of ingredient is preferably the upper limit with 10%, with 5% be more preferably the upper limit, be most preferably set as low
In 1%.
TeO2Ingredient be glass forming constituents, be improve glass refractive index and dispersion and improve transmissivity it is any at
Point.In particular, by making TeO2The containing ratio of ingredient is more than 0%, and the dispersion of glass and refractive index are improved, therefore can be obtained
To desired Abbe number (νd) and refractive index.On the other hand, by making TeO2The containing ratio of ingredient is 30.0% hereinafter, can reduce
The liquidus temperature of glass, devitrification resistance when improving glass formation.In addition, if a large amount of contain and abrasion resistence can be made to deteriorate.Cause
This, the amount of the total material relative to the glass formed to be converted with oxide, TeO2The containing ratio of ingredient is preferably lower limit with 0%,
It is more preferably lower limit with 0.5%, with 1% is most preferably lower limit.In addition, the TeO2The containing ratio of ingredient is preferably the upper limit, more with 30%
It is preferred that being the upper limit with 20%, most preferably to be the upper limit lower than 5%.TeO2Ingredient can be by using such as TeO2Deng as raw material
Contained in glass.
SnO2Ingredient is to reduce the oxidation of melten glass and clarify melten glass and make the saturating of the light irradiation to glass
The rate of penetrating is difficult to the ingredient deteriorated, is any ingredient in optical glass of the invention.In particular, by making SnO2The content of ingredient
For 6% hereinafter, the coloring of the glass as caused by the reduction of melten glass can be made, the devitrification of glass is difficult to generate.Further, since
SnO2The alloying of ingredient and melting equipment (noble metals such as especially Pt) is reduced, therefore the long-life of melting equipment may be implemented
Change.Accordingly, with respect to the amount of the total material of the glass formed to be converted with oxide, SnO2The content of ingredient is preferably upper with 6%
Limit, with 5% be more preferably the upper limit, with 4% be most preferably the upper limit.SnO2Ingredient can be by using such as SnO, SnO2、SnF2、
SnF4It is contained in glass Deng as raw material.
Sb2O3Ingredient is the ingredient for improving the transmissivity of the glass to the visible light of short wavelength, and is in melten glass
Ingredient with deaeration effect is any ingredient in optical glass of the invention.Herein, by making Sb2O3The content of ingredient is
1.0% hereinafter, excessive foaming when glass melting is difficult to generate, therefore can make Sb2O3Ingredient is difficult to melting equipment (especially
It is the noble metals such as Pt) alloying occurs.Therefore, Sb2O3The content of ingredient is preferably the upper limit with 1.0%, more preferably with 0.9% be on
Limit with 0.8% is further preferably the upper limit.In particular, even containing Sb on a small quantity2O3In the case where ingredient, Sb2O3Ingredient
It can volatilize from melten glass and be attached to mold in the form of impurity, therefore can be recessed as being generated on the surface of glass forming body
The reason of convex and blushing.So by making Sb2O3The content of ingredient is for 0.7% hereinafter, the Sb ingredient of the main component as impurity
It is removed from glass, the impurity for thereby adhering to mold is reduced, therefore can be reduced in the recessed of the surface of glass forming body formation
Convex and blushing.Therefore, Sb2O3The content of ingredient is preferably the upper limit with 0.7%, with 0.6% be more preferably the upper limit, further preferably with
0.5% is the upper limit.It for the purpose of the present invention, is most preferred especially with the glass for being substantially free of Sb ingredient.It is suppressed improving
When forming temperature, the formation of the impurity on mold becomes significantly, therefore is substantially free of effect brought by Sb ingredient and becomes
Significantly.
In optical glass of the invention, preferably comprising total amount is 5% or more and 50% ZnO component below and MgO ingredient.
Rise significantly with the meltbility of glass, stability and the transparency as a result, and to be easy to get desired optics normal
Several effects.Therefore, ZnO component and MgO ingredient preferably with 5% are in the total amount lower limit, with 7% are more preferably lower limit, most preferably
It is lower limit with 9%, preferably with 50% be the upper limit, with 45% be more preferably the upper limit, with 40% is most preferably the upper limit.
In optical glass of the invention, preferably comprising total amount is 0.1% or more and 20% SiO below2Ingredient and Al2O3
One or both of ingredient ingredient.
Have the effect of that the meltbility, stability and chemical durability of glass greatly improve as a result,.Therefore, SiO2Ingredient
And Al2O3One or both of ingredient ingredient preferably with 0.5% is in the total amount lower limit, with 1% is more preferably lower limit, most preferably
It is lower limit with 3%, is preferably the upper limit with 20%, with 15% is more preferably the upper limit, with 10% is most preferably the upper limit.
In optical glass of the invention, 0% or more and 30% R below is preferably comprised2O ingredient.Herein, R be selected from by
One or more of the group of Li, Na and K composition element.
The meltbility with glass, stability and the transparency rise and are easy to get the glass with lower Tg as a result,
Effect.Therefore, R2O ingredient preferably with 30% is in the total amount the upper limit, with 25% be more preferably the upper limit, most preferably with 20% be on
Limit.
In optical glass of the invention, R2It O/(ZnO+MgO) is preferably 2.0 or less.Herein, R be selected from by Li, Na,
And one or more of group of K composition element.
Thus, it is possible to manufacture the higher optical glass of stability.Therefore, R2O/(ZnO+MgO) preferably with 2.0% to be upper
Limit, with 1.5% be more preferably the upper limit, with 0.8% be most preferably the upper limit.
In optical glass of the invention, 0% or more and 30% MO ingredient below is preferably comprised.Herein, M be selected from by
One or more of the group of Ca, Sr and Ba composition element.
Thus, it is possible to manufacture the higher optical glass of stability.Therefore, MO ingredient be preferably the upper limit with 30%, more preferably with
20% it is the upper limit, with 15% is most preferably the upper limit.
In optical glass of the invention, MO/(ZnO+MgO) it is preferably 0.5 or less.Herein, M be selected from by Ca, Sr,
And one or more of group of Ba composition element.
Thus, it is possible to manufacture the higher optical glass of stability.Therefore, MO/(ZnO+MgO) be preferably the upper limit with 0.5%,
It is more preferably the upper limit with 0.45%, with 0.4% is most preferably the upper limit.
In optical glass of the invention, it is preferred that (1) contain 20% or more and 45% P below2O5Ingredient, 15% with
Upper and 60% Nb below2O5Ingredient, total amount be 5% or more and 50% ZnO component below and MgO ingredient, the optical glass
Refractive index is 1.75 or more, Abbe number is 10 or more and 35 hereinafter, (2) are relative to the total of the glass formed to be converted with oxide
The amount of substance, in terms of mole %, SiO2Ingredient and Al2O3The total amount of the ingredient of one or both of ingredient be 0.1% or more and
20% or less.
Thus, it is possible to manufacture stability and transparent high optical glass.
About the ingredient that should not contain
Then, the ingredient that should not contain in optical glass of the invention and the ingredient not preferably comprised are illustrated.
It, can be in the range of not damaging the characteristic of glass of the present application according to need in optical glass of the invention
Add other ingredients.
But for each transiting metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if individually
Or in the case that compound ground contains on a small quantity, it may have make glass coloration, generate absorption at the specific wavelength of visible region
Property, therefore especially preferably contained substantially no in the optical glass using the wavelength of visible light region.
In turn, the lead compounds such as PbO and As2O3Each ingredient of equal arsenic compounds and Th, Cd, Tl, Os, Be and Se are in recent years
Have the tendency that controlling and use as harmful chemical substance, not only in the manufacturing process of glass, in manufacturing procedure or even
Handling in environmental cure is required in processing after commercialization.Therefore, in the case where paying attention to influence environmentally, in addition to not
It is evitable to be mixed into outside, preferably contain substantially no these ingredients.Pollution environment is contained substantially no in optical glass as a result,
Substance.Therefore, the optical glass can also be manufactured, processed and is given up even if not seeking handling in special environmental cure
It abandons.
The physical property of optical glass
Optical glass of the invention has high refractive index (nd) and there is defined dispersion.In particular, light of the invention
Learn the refractive index (n of glassd) be preferably lower limit with 1.75, with 1.80 be more preferably lower limit, with 1.84 be most preferably lower limit, preferably
It is the upper limit with 2.20, with 2.10 be more preferably the upper limit, with 2.02 is most preferably the upper limit.In addition, optical glass of the invention Ah
Shellfish number (νd) be preferably lower limit with 10, with 13 be more preferably lower limit, with 17 be most preferably lower limit, preferably with 35 be the upper limit, more excellent
Choosing with 30 is the upper limit, with 24 is most preferably the upper limit.Even if expanding the freedom degree of optical design as a result, further seeking element
It is thinned, also the amount of refraction of available big light.
Although glass of the invention is deposited and is sent out at the time of molding due to composition in addition, needing to colour less when being optical glass
The case where raw coloring.However, thereafter by near glass transition point at a temperature of carry out 4 hours or more being heat-treated, be somebody's turn to do
Color can disappear, the available transparent glass for meeting application.In particular, for optical glass of the invention, with glass
Transmissivity when indicating, the wavelength (λ of spectral transmission 70% is shown with the sample of thickness 10mm70) it is 500nm or less, more preferable
For 480nm or less, most preferably 450nm or less.Thus, it can be seen that the transparency of the glass in light area is improved, therefore can be with
Using the optical glass as the materials'use of the optical elements such as lens.It should be noted that in the present invention, although by glass material
Glass obtained from being heat-treated after material melting, Slow cooling has above-mentioned transmissivity, but never needs to carry out
It is heat-treated from the perspective of the coloring to inhibit glass, the transmissivity of the glass before being heat-treated has above-mentioned transmissivity
It is preferred.
The manufacturing method of glass forming body
Optical glass of the invention for example makes in the following way.That is, with each ingredient defined containing ratio range
Interior mode equably mixes above-mentioned raw materials, and the mixture of production is put into silica crucible or alumina crucible, is carried out slightly
After melting, put into golden crucible, platinum crucible, platinum alloy crucibles or iridium crucible, it is molten in 1250~1500 DEG C of temperature ranges
Melt, stirring homogenizing defoams etc., is then reduced to temperature appropriate, is then poured into mold, carries out Slow cooling, thus
Production.
The means of optical element are made about the optical glass by making in this way, can be used after carrying out reheating compacting
The method for being ground and being ground, or the method that preform is made, is molded.
In particular, when being molded, by the preform that will be formed by optical glass of the invention for example by wrapping
It includes upper die and lower die, heated in the mold that the mold component of cover die is constituted, to make its softening, be pressed.This
The material for the protective film that place, the quality of parent material about mold and the forming surface in mold are formed, as long as not in the pre- of softening
It is just not particularly limited at the material melted in parison, well known material can be used.Wherein, the material of the base material of mold is preferably
Mold materials well known to tungsten carbide (WC), silicon carbide (SiC) or stainless steel alloy etc., the preferred most surface layer of the material of protective film
Comprising selected from by Pt, Au, Ir, Ni, Cr, Mo, Rh, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Re and C group
At the above element of at least one of element group material.By making the base material of mold, the mother of mold by such material
Material becomes difficult to deform, therefore the long lifetime of mold may be implemented.It wherein, can be in mold from the easiness of processing
Base material in use the metals such as stainless steel alloy.In addition, by using selected from by Pt, Au, Ir, Ni, Cr, Mo, Rh, Ce, Pr,
Element production more than at least one of element group of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Re and C composition
The glass of the most surface layer of protective film, softening is suppressed with reacting for protective film, therefore can be further reduced impurity to protective film
Attachment.In addition, the softening of preform be not limited to by the heating in mold carry out in the way of.
Compression moulding is for example carried out according to following step.The forming surface for the lower die being inserted into the through hole of cover die
After center configuration preform, upper mold is inserted into the through hole of cover die.At this point, the forming surface of lower die and the forming surface of upper mold
It is arranged in an opposing fashion.Then, by heating preform and mold together, the Glass Transition of preform is constituted, is tied
Fruit is suppressed by being pressurizeed with upper die and lower die to preform.As a result, preform by molding upper mold, under
The inside for the die cavity that mould and cover die surround is extruded extension, therefore can be by the inside of glass filled to die cavity.I.e., it is possible to by mould
In the shape transfer to glass of the inner surface of chamber.
Herein, mold be deliberately formed in such a way that die cavity becomes defined shape upper die and lower die in molding state and
The relative position of each forming surface of cover die and the normal institute angle degree of forming surface.In addition, to the compacting carried out using mold
Until completion, by being oriented in a manner of mutually opposite and the central axis of upper mold and lower die is consistent accurately for upper mold and lower die
It maintains.Optical function face and position can be made as a result, determines what datum level positional relationship mutually with high precision and angle were formed
Glass forming body.
The production of optical element
Optical glass of the invention is all useful in various optical elements and optical design, wherein particularly preferably right
Optical glass of the invention is pressed to make the optical elements such as lens, prism and mirror.As a result, by obtained light
When learning element for making the optical instrument of visible light-transmissive as camera and projector etc., high-resolution and height may be implemented
The imaging characteristic of precision, and the miniaturization of the optical system in these optical instruments may be implemented.
Embodiment
Composition (mole %), the refractive index (n of the embodiment of the present invention (No.1~No.32) are shown in 1~table of table 3d),
Abbe number (νd), glass transition temperature (DEG C), deformation point (At, DEG C) and linear expansion coefficient (10-7/ K) measurement result.It needs
It is noted that embodiment below is only used for illustrating, the present invention is not limited to these embodiments.
The optical glass of the embodiment of the present invention (No.1~No.32) has chosen respectively corresponding as the raw material of each ingredient
The common optical glass such as oxide, hydroxide, carbonate, nitrate, fluoride, hydroxide, metaphosphoric acid compound
Used high-purity raw carries out weighing according to the ratio of the composition of each embodiment shown in 1~table of table 3 and equably mixes
It after conjunction, puts into silica crucible or platinum crucible, according to the melting difficulty electric furnace of glass composition in 1300~1450 DEG C
Temperature range melted, stirring homogenizing after is poured into mold, make test film.
About the optical glass of comparative example, which employs relative to the embodiment of the present invention (No.1~No.32) by ZnO at
Point and MgO at the composition for being divided into 0%, but non-vitrifying.
Herein, the refractive index (n of the glass of embodiment (No.1~No.32)d) and Abbe number (νd) it is according to Japanese Optical nitre
Sub- industry meeting standard JOGIS01-2003 measurement.It should be noted that having used and having moved back as the glass used in this measurement
Fiery condition be Slow cooling cooling rate is set as -25 DEG C/h and handled in Slow cooling furnace and obtain
Glass.
In addition, glass transition temperature (DEG C), deformation point (At, DEG C) are found out using thermal dilatometry, the heat is swollen
Swollen curve is can standard JOGIS08-2003 " measuring method of the thermal expansion of optical glass ", survey according to the industry of Japanese Optical nitre
Obtained from the elongation of fixed above-mentioned temperature and sample.
About linear expansion coefficient (10-7/ K), it can standard JOGIS08-2003 " optical glass according to Japanese Optical nitre industry
Thermal expansion measuring method " found out average linear expansion coefficient at 100~300 DEG C.Table 1
Table 2
Table 3
As shown in Table 1 to Table 3, the Abbe number (ν of the optical glass of the embodiment of the present inventiond) it is 10 or more, in more detail
For be 17 or more, and the Abbe number (νd) be 35 or less, be more specifically 24 or less.On the other hand, comparative example
The non-vitrifying of glass.
In addition, refractive index (the n of the optical glass of the embodiment of the present inventiond) be 1.75 or more, be more specifically
1.84 or more, and the refractive index (nd) be 2.20 or less, be more specifically 2.02 hereinafter, in desired range.
On the other hand, the non-vitrifying of the glass of comparative example.
Furthermore devitrification etc. does not occur for the optical glass of the embodiment of the present invention.On the other hand, the optical glass of comparative example
Non- vitrifying.Hence it is evident that as can be seen that optical glass of the invention has high devitrification resistance.
In addition, not generated using the optical element that the glass for the composition recorded in Examples 1 to 31 makes on surface recessed
Convex and blushing.Hence it is evident that as can be seen that optical glass of the invention reduces the bumps and mist on the surface of glass forming body
It is turbid and can steadily compression moulding be various optical elements, i.e. lens and prism shape.
Fig. 1 is the curve graph for indicating the transmission characteristics of optical glass of embodiment 1.Optical glass used in measuring
With a thickness of 10mm.As shown in Figure 1, transmissivity is more than 70% since about 430nm, 80% or more high-transmission rate is realized.
Herein, the transmissivity of glass is according to Japanese Optical nitre industry meeting standard JOGIS02 measurement.
Hence it is evident that as can be seen that the optical glass of the embodiment of the present invention have desired high stability and high dispersion,
And the bumps and blushing on surface can be reduced.
More than, invention is explained in detail for illustrative purposes, however the present embodiment is only used for example eventually
Show, it should be understood that those skilled in the art are variously changed in which can not depart from thought and range of the invention.
Claims (11)
1. a kind of precision press molding optical glass, wherein the total material relative to the glass formed to be converted with oxide
Amount, in terms of mole %, contain 20% or more and 45% P below2O5Ingredient, 15% or more and 60% Nb below2O5At
Point, total amount be 7% or more and 50% ZnO component below and MgO ingredient, the refractive index of the optical glass is 1.75 or more,
Abbe number is 10 or more and 35 or less, wherein R2O/ (ZnO+MgO) is 0 or more and 1.5 hereinafter, R is selected from by Li, Na and K group
At one or more of group element.
2. precision press molding optical glass according to claim 1, wherein formed relative to what is converted with oxide
Glass total material amount, in terms of mole %, containing total amount be 0.1% or more and 20% SiO below2Ingredient and Al2O3At
Point one or both of ingredient.
3. according to claim 1 or precision press molding optical glass as claimed in claim 2, wherein relative to oxidation
The amount of the total material of the glass of the composition of object conversion contains 0% or more and 40% TiO below in terms of mole %2Ingredient.
4. according to claim 1 or precision press molding optical glass as claimed in claim 2, wherein relative to oxidation
The amount of the total material of the glass of the composition of object conversion contains 0% or more and 25% R below in terms of mole %2O ingredient.
5. precision press molding optical glass according to claim 3, wherein formed relative to what is converted with oxide
Glass total material amount, in terms of mole %, contain 0% or more and 25% R below2O ingredient.
6. according to claim 1 or precision press molding optical glass as claimed in claim 2, wherein relative to oxidation
The amount of the total material of the glass of the composition of object conversion contains 0% or more and 25% MO ingredient below, MO/ in terms of mole %
(ZnO+MgO) be 0.5 hereinafter,
Wherein, M is selected from one or more of the group being made of Ca, Sr and Ba element.
7. precision press molding optical glass according to claim 3, wherein formed relative to what is converted with oxide
Glass total material amount, in terms of mole %, contain 0% or more and 25% MO ingredient below, MO/ (ZnO+MgO) be 0.5
Hereinafter,
Wherein, M is selected from one or more of the group being made of Ca, Sr and Ba element.
8. precision press molding optical glass according to claim 4, wherein formed relative to what is converted with oxide
Glass total material amount, in terms of mole %, contain 0% or more and 25% MO ingredient below, MO/ (ZnO+MgO) be 0.5
Hereinafter,
Wherein, M is selected from one or more of the group being made of Ca, Sr and Ba element.
9. precision press molding optical glass according to claim 5, wherein formed relative to what is converted with oxide
Glass total material amount, in terms of mole %, contain 0% or more and 25% MO ingredient below, MO/ (ZnO+MgO) be 0.5
Hereinafter,
Wherein, M is selected from one or more of the group being made of Ca, Sr and Ba element.
10. a kind of optical element, the precision press molding as described in any one of 1~claim 9 of claim is used up
Glass is learned to be formed.
11. a kind of manufacturing method of glass forming body uses essence described in any one of 1~claim 9 of claim
Close compression moulding optical glass is pressed the optical glass of softening in mold.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012190501A JP6037501B2 (en) | 2012-08-30 | 2012-08-30 | Optical glass, optical element, and method for producing glass molded body |
| JP2012-190501 | 2012-08-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103663961A CN103663961A (en) | 2014-03-26 |
| CN103663961B true CN103663961B (en) | 2018-12-07 |
Family
ID=50302864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310389532.4A Active CN103663961B (en) | 2012-08-30 | 2013-08-30 | The manufacturing method of optical glass, optical element and glass forming body |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6037501B2 (en) |
| CN (1) | CN103663961B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015163564A (en) * | 2014-02-28 | 2015-09-10 | 株式会社オハラ | optical glass, lens preform and optical element |
| JP6692570B2 (en) * | 2014-10-07 | 2020-05-13 | 株式会社オハラ | Optical glass, lens preform and optical element |
| CN105481244A (en) * | 2014-10-07 | 2016-04-13 | 株式会社小原 | Optical glass, lens preforming and optical element |
| JP6635667B2 (en) * | 2015-03-24 | 2020-01-29 | 株式会社オハラ | Optical glass, lens preform and optical element |
| CN106915901A (en) * | 2015-12-25 | 2017-07-04 | 株式会社小原 | A kind of optical glass, prefabricated component and optical element |
| CN110234613B (en) * | 2017-01-25 | 2022-06-28 | 康宁股份有限公司 | High refractive index titanium-niobium phosphate glass |
| JP7116095B2 (en) * | 2018-02-01 | 2022-08-09 | Hoya株式会社 | Colored glass and its manufacturing method |
| JP2022510686A (en) | 2018-12-07 | 2022-01-27 | コーニング インコーポレイテッド | High refractive index phosphate glass |
| WO2020203673A1 (en) * | 2019-04-05 | 2020-10-08 | 日本電気硝子株式会社 | Decorative glass article |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05116988A (en) * | 1991-04-16 | 1993-05-14 | Nippon Soda Co Ltd | Multiple oxide thin film for half mirror |
| JP3260046B2 (en) * | 1994-09-30 | 2002-02-25 | ホーヤ株式会社 | Optical glass |
| JPH09188540A (en) * | 1995-12-29 | 1997-07-22 | Ohara Inc | Optical glass free from solarization |
| US5792716A (en) * | 1997-02-19 | 1998-08-11 | Ferro Corporation | Thick film having acid resistance |
| JP3798268B2 (en) * | 2000-06-30 | 2006-07-19 | Ｈｏｙａ株式会社 | Optical glass and optical product using the same |
| DE102007008300B4 (en) * | 2006-08-12 | 2011-08-25 | Schott Ag, 55122 | Lead-free optical glass of heavy flint and Lanthanschwerflintlage and its production and use |
| JP2008133148A (en) * | 2006-11-28 | 2008-06-12 | Nihon Yamamura Glass Co Ltd | Optical glass |
| JP2010083701A (en) * | 2008-09-30 | 2010-04-15 | Hoya Corp | Optical glass, glass gob for press forming and optical element |
| WO2010084925A1 (en) * | 2009-01-26 | 2010-07-29 | 旭硝子株式会社 | Glass composition and member having the same on substrate |
| JP2011140434A (en) * | 2009-12-11 | 2011-07-21 | Ohara Inc | Optical glass, optical element and preform |
| CN102206043B (en) * | 2010-03-18 | 2016-08-17 | 株式会社小原 | Optical glass, optical element and preformed articles |
-
2012
- 2012-08-30 JP JP2012190501A patent/JP6037501B2/en active Active
-
2013
- 2013-08-30 CN CN201310389532.4A patent/CN103663961B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014047095A (en) | 2014-03-17 |
| CN103663961A (en) | 2014-03-26 |
| JP6037501B2 (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103663961B (en) | The manufacturing method of optical glass, optical element and glass forming body | |
| JP5727689B2 (en) | Optical glass, optical element and optical instrument | |
| TWI594966B (en) | Optical glass, preform and optical element | |
| JP6341836B2 (en) | Optical glass and optical element | |
| CN104010982A (en) | Optical glass and optical element | |
| CN104341102A (en) | Optical glass and optical element | |
| WO2013018586A1 (en) | Optical glass | |
| CN106587599A (en) | Optical glass and method for suppressing the deterioration of spectral transmittance | |
| JP5727691B2 (en) | Optical glass, optical element and optical instrument | |
| JP2009286680A (en) | Optical glass, optical element and optical instrument | |
| CN102241478A (en) | Optical glass and method of suppressing deterioration of spectral transmittance | |
| CN107721160A (en) | Optical glass, preforming material and optical element | |
| CN104341101A (en) | Optical glass, preform material and optical element | |
| CN105565658A (en) | Optical glass, preformed body and optical element | |
| CN104445922A (en) | Optical glass and optical element | |
| JP2014034472A (en) | Optical glass, optical element, and method of producing glass molding | |
| CN105565659A (en) | Optical glass, preformed body, and optical element | |
| JP2009269770A (en) | Optical glass, preform for precision press molding and optical element | |
| TW201731785A (en) | Optical glass, preform material and optical element | |
| TWI666187B (en) | Optical glass, optical element, and method for manufacturing glass mold material | |
| CN109279772A (en) | Optical glass, preform and optical element | |
| JP5988427B2 (en) | Optical glass, optical element, and method for producing glass molded body | |
| JP2013151402A (en) | Optical glass, preform and optical element | |
| CN104926101A (en) | Optical glass, lens performing body and optical element | |
| JP6086941B2 (en) | Optical glass and method for suppressing deterioration of spectral transmittance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |