CN105579412A - Optical element and production method for same - Google Patents
Optical element and production method for same Download PDFInfo
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- CN105579412A CN105579412A CN201480053466.6A CN201480053466A CN105579412A CN 105579412 A CN105579412 A CN 105579412A CN 201480053466 A CN201480053466 A CN 201480053466A CN 105579412 A CN105579412 A CN 105579412A
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- glass
- film
- compression molding
- oxide
- optical element
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
- C03B11/06—Construction of plunger or mould
- C03B11/08—Construction of plunger or mould for making solid articles, e.g. lenses
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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Abstract
The invention provides a production method for an optical element, and the method can inhibit bubbles form being generated in the optical element after compression moulding. The invention relates to an optical element having an oxide glass, and a coating film coating at least a portion of the surface of the oxide glass. The coating film is a metal oxide film which is in a state of oxygen deficit with respect to the stoichiometric composition, and at a temperature at or above the glass transition temperature of the oxide glass, the speed at which the metal oxide film incorporates oxygen atoms contained in the oxide glass is faster than the speed at which metal atoms contained in the oxide glass diffuse into the oxide glass.
Description
Association request cross-referenced
The present invention advocates the right of priority of No. 2013-205497, the Japanese Patent Application that on September 30th, 2013 applies for, the institute of this application is on the books is all disclosed in this as quoting.
Technical field
The present invention relates to optical element and manufacture method thereof.
Background technology
As the method manufacturing the optical elements such as glass lens, there will be a known following method: by the relative upper die and lower die with molding surface, to shaping blank (hereinafter referred to as " compression molding glass blank " or " preformed parison ".) carry out compression molding.
When carrying out glass optical component shaping by compression molding, the molding surface of compression molding glass blank and forming mould is closely sealed at high operating temperatures, therefore produce chemical reaction in their interface, the reaction trace of hot sticky, fuzzy, scar shape etc. occurs sometimes thus causes the optical property of the optical element obtained by compression molding to decline.
In the past, as the means of the generation for preventing above-mentioned reaction trace, proposing to have film is set on the surface of compression molding glass blank to be suppressed to the reaction (such as reference patent documentation 1) of mould and glass.In addition, in patent documentation 2, propose have following proposal: in order to suppress the generation of wire trace, hydrogen capture membrane is set on the surface of compression molding glass blank.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-1259 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-250295 publication
Summary of the invention
The problem that invention will solve
But the result of study of the present inventor shows, in the manufacture of the glass optical component based on compression molding, after compression molding, small bubble can be produced in glass, thus the uniformity of optical element can be caused to decline.In order to provide the optical element with higher optical property, expect to suppress the foaming in glass.
Therefore, the present inventor, in order to find the means of the foaming suppressed in glass, conducts in-depth research the reason of bubbling.Its result is, has found following unexpected phenomenon: even if carry out compression molding at non-oxidizing atmosphere (oxygen containing ratio is a few ppm), and the bubble produced in the optical element after compression molding is also containing a large amount of oxygen.As the producing cause of oxygen in the compression molding of non-oxidizing atmosphere, because be only oxide glass, so think that the oxygen deriving from oxide glass is relevant with the generation of bubble.
A mode of the present invention provides a kind of manufacture method of optical element, and it can suppress to produce bubble in the optical element after compression molding.
For the means of dealing with problems
A mode of the present invention is a kind of optical element, it has the film at least partially on the surface of oxide glass and this oxide glass coating, above-mentioned film is the metal oxide film being in oxygen shortcoming state compared with stoichiometric composition, and, at temperature more than the glass transformation temperature of oxide glass, the speed that the speed of the Sauerstoffatom of metal oxide film collecting contained by oxide glass spreads to oxide glass than atoms metal contained in metal oxide film is fast.
Another mode of the present invention is a kind of manufacture method of optical element, it possesses following operation: the operation preparing compression molding glass blank, this compression molding glass blank has the film at least partially on the surface of oxide glass and this oxide glass coating, and above-mentioned film is the metal oxide film of oxygen shortcoming compared with stoichiometric composition; With compression molding is carried out to described compression molding glass blank thus forms the mold pressing procedure of compression molding body,
Above-mentioned compression molding body comprises the above-mentioned film after mold pressing procedure,
Further, the film after mold pressing procedure is the metal oxide film that oxygen containing ratio is higher than the film before mold pressing procedure.
In order to the foaming of the glass that the oxygen suppressing origin to come from oxide glass causes, the present inventor conducts in-depth research repeatedly, and its result is, obtains the scheme arranging above-mentioned film on the surface of compression molding glass blank.The metal oxide film being in the state of oxygen shortcoming compared with stoichiometric composition is the state of easily accommodating oxygen.Therefore, as long as be the metal oxide film of this state, then can remove from inside glass and draw vesicant oxygen when compression molding, suppress the generation of bubble.
But, when compression molding, between film and oxide glass, while Sauerstoffatom moves (entering) from oxide glass to film, also can there is the movement of atoms metal from film to oxide glass (diffusion).For the velocity of diffusion of this atoms metal to enter film fireballing metal oxide film than Sauerstoffatom, diffusion has precedence over and enters and carry out.Therefore, because compression molding can produce the remarkable minimizing of thickness or the disappearance of film, the foaming of inhibited oxidation thing inside glass is difficult to.On the other hand, for above-mentioned film, the diffusion that the entering of Sauerstoffatom has precedence over atoms metal and carrying out, therefore, it is possible to effectively make the Sauerstoffatom causing bubble to occur enter film from oxide glass, suppresses foaming.
There is the above-mentioned film through mold pressing procedure in the optical element so obtained.Film contained by this optical element accommodates oxygen when compression molding from oxide glass, therefore with containing compared with the state of compression molding glass blank, Sauerstoffatom is high relative to the containing ratio of atoms metal.But the film that optical element comprises still is in the state of oxygen shortcoming compared with stoichiometric composition, and this can be clear and definite by the result of study of the present inventor.
Invention effect
According to a mode of the present invention, can provide a kind of manufacture method of optical element, it can suppress to produce bubble at inside glass in compression molding.
Further, according to a mode of the present invention, can provide and not have bubble to occur and the optical element of homogeneous.
Accompanying drawing explanation
An example of compression molding device has been shown in Fig. 1.
The optical microscope photograph of the lens (core glass: the I-1 in table 1) made by embodiment 1 has been shown in Fig. 2.
Illustrate in Fig. 3 and a part for the lens made by comparative example 2 (core glass: the I-1 in table 1) has been expanded and the optical microscope photograph of taking pictures and obtaining.
The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (lens) after Fig. 4 shows the mold pressing about embodiment 1.
The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (non-mould) before Fig. 5 shows the mold pressing about embodiment 1.
Fig. 6 is to the ZrO in Fig. 4,5
2the result that the secondary ions strength ratio of/ZrO compares.
Fig. 7 shows the depth direction analytical results of the secondary ions intensity based on TOF-SIMS of the lens made by comparative example 2.
Fig. 8 is for by result overlapping with the result of the comparative example 2 shown in Fig. 7 for the result of the embodiment 1 shown in Fig. 4.
The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (lens) after Fig. 9 shows the mold pressing about comparative example 1.
The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (non-mould) before Figure 10 shows the mold pressing about comparative example 1.
Embodiment
Below, the manufacture method of the optical element of a mode of the present invention is further elaborated.Hereinafter, with reference to accompanying drawing, embodiment is described, but the present invention is not limited to mode shown in the drawings.
In the manufacture method of above-mentioned optical element, compression molding glass blank has the metal oxide film of oxygen shortcoming compared with stoichiometric composition as the film at least partially on the surface of coating oxide glass, uses this compression molding glass blank to carry out compression molding.And, also containing with the form of metal oxide film at least partially of the surface of the compression molding body that above-mentioned film obtains carrying out compression molding to this compression molding glass blank, the film that the Sauerstoffatom of above-mentioned metal oxide film has higher than above-mentioned compression molding glass blank relative to the containing ratio of atoms metal.
As mentioned above, according to the new opinion that the present inventor finds by furtheing investigate, can infer that the bubble resulting from optical element after compression molding is the oxygen deriving from oxide glass.On the other hand, the metal oxide film of oxygen shortcoming is in the state of the easy collecting oxygen of the stoichiometric composition be tending towards as more stable state compared with stoichiometric composition.Therefore, utilize the metal oxide film of the state of oxygen shortcoming compared with stoichiometric composition, to oxide glass surface carry out at least partially coating after carry out compression molding, can make in mold pressing, draw vesicant oxygen and enter metal oxide film from oxide glass, therefore, it is possible to provide the high-quality optical element that the bubble after inhibit compression molding produces.And, the Sauerstoffatom entered from oxide glass is contained at the metal oxide film of the remained on surface of the compression molding body (optical element) so formed, therefore compared with the metal oxide film had with the compression molding glass before compression molding, containing more Sauerstoffatom.That is, compression molding body has metal oxide film at least partially on surface, the film that the Sauerstoffatom of this metal oxide film has higher than compression molding glass blank relative to the containing ratio of atoms metal.
In order to obtain the compression molding body of the metal oxide film that there is above-mentioned state after compression molding, as metal oxide film, following metal oxide film should be formed, at the temperature of this metal oxide film more than the glass transformation temperature of oxide glass, the speed (being recited as below " velocity of diffusion of atoms metal ") that the speed (being recited as below " admission velocity of Sauerstoffatom ") of the Sauerstoffatom of metal oxide film collecting contained by oxide glass spreads to oxide glass than atoms metal contained in metal oxide film is fast.
As mentioned above, during compression molding, between oxide glass and the film of this oxide glass coating, while Sauerstoffatom moves (entering) from oxide glass to film, also can produce the movement of atoms metal from film to oxide glass (diffusion).Under normal circumstances, the temperature of compression molding more than glass transformation temperature is carried out, therefore, when compression molding, the speed that the atoms metal in this metal oxide film of velocity ratio of the Sauerstoffatom in above-mentioned metal oxide film collecting oxide glass enters oxide glass is fast.If be the film with this character, then when compression molding, Sauerstoffatom has precedence over atoms metal carry out to entering of film to the diffusion of oxide glass.Therefore, after compression molding, can be present on compression molding body with the form of the metal oxide film of above-mentioned state.On the other hand, for atoms metal to enter film than fireballing metal oxide film from Sauerstoffatom to the velocity of diffusion of oxide glass, diffusion has precedence over and enters and carry out.Therefore, produce the remarkable minimizing of thickness or the disappearance of film because of compression molding, be difficult to the foaming of inhibited oxidation thing inside glass.It should be noted that, as long as the admission velocity of Sauerstoffatom just can play above-mentioned effect greatly than the velocity of diffusion of atoms metal, the difference therefore for the admission velocity of Sauerstoffatom and the velocity of diffusion of atoms metal is not particularly limited.
As mentioned above, the compression molding glass blank preferably used in the manufacture method of the optical element of an embodiment of the invention has oxide glass and metal oxide film, this metal oxide film is the film at least partially on the surface covering this oxide glass, it is in the state of oxygen shortcoming compared with stoichiometric composition, and the velocity of diffusion of the admission velocity of Sauerstoffatom and atoms metal meets above-mentioned relation.Via this compression molding glass blank being carried out to the operation of compression molding and the velocity of diffusion of the optical element the obtained admission velocity and atoms metal also with Sauerstoffatom meets the metal oxide film of above-mentioned relation.Wherein, be present in the metal oxide film on optical element, Sauerstoffatom relative to the containing ratio of atoms metal higher than the metal oxide film before compression molding.Its reason is, from oxide glass collecting Sauerstoffatom in compression molding.
Below further above-mentioned compression molding glass blank is described in detail.
film (metal oxide film)
As long as the film of coating oxide glass is formed by the membrane formation process of the metal oxide film that can form oxygen shortcoming state compared with stoichiometric composition.Such as, for the surface of the glass block be made up of oxide glass (hereinafter also referred to " core glass "), use metal as target (target), sputtering method, vacuum vapour deposition, CVD (ChemicalVaporDeposition is utilized in non-oxidizing atmosphere, chemical vapour deposition) etc. known membrane formation process carry out film forming, above-mentioned film can be formed.The lower limit of film-forming temperature (temperature of core glass) is preferably more than 150 DEG C and then preferably more than 200 DEG C.The upper limit is preferably less than the glass transformation temperature of core glass.Ceiling temperature is such as less than 450 DEG C.
As concrete mode, the core glass of more than 2 that are formed as regulation shape is arranged in pallet, is then configured in vacuum chamber, carry out vacuum exhaust in vacuum chamber, utilize well heater by core glass heats to about 300 DEG C simultaneously.Be exhausted until the vacuum tightness in vacuum chamber is 1 × 10
-5after till below Torr, import Ar gas, the atmosphere gas in vacuum chamber is replaced into Ar gas, afterwards high frequency is applied to target base material, make raw material plasma, carry out the film forming of film on the surface of core glass.For the thickness of film, can be controlled as desired thickness by the pressure (vacuum tightness) in adjustment vacuum chamber, power, film formation time.It should be noted that, if the surface of the coating core glass of film at least partially.Therefore, the core glass after film film forming can be the not coating state of a surface part, also can the whole face of effects on surface be coated to.In one embodiment, compression molding is carried out to compression molding glass blank thus shaping optics time, can at least be coated to the part of core glass in the optical function face forming optical element.Optical function face means the region in the effective diameter in such as optical lens.Wherein, as long as above-mentioned film is present in just from core glass collecting Sauerstoffatom, therefore can not limiting by above-mentioned embodiment at least partially of the arbitrary portion on compression molding glass blank surface.
As the metal forming film, as long as use the velocity of diffusion of the admission velocity and atoms metal that can form Sauerstoffatom to meet the metal of the metal oxide film of above-mentioned relation.As the concrete example of this metal, zirconium, titanium, niobium, tungsten, tantalum can be enumerated.Wherein, even if be herein and not illustrated metal, carry out suitable preliminary experiment thus be confirmed whether that the velocity of diffusion of the admission velocity and atoms metal that can form Sauerstoffatom meets the oxide film of above-mentioned relation, the metal that can form the metal oxide film meeting above-mentioned relation can be determined thus.As the target in above-mentioned membrane formation process, preferably use the simple substance of above-mentioned metal.In order to effectively make oxide glass enter film from oxide glass, the thickness of film is preferably more than 0.5nm, is more preferably more than 1.5nm.Fuzzy from the view point of preventing, the thickness of film is preferably below 15nm and then is preferably below 10nm.
As mentioned above, film described above is in the state of oxygen shortcoming compared with stoichiometric composition.Such as, if be Zirconium oxide, then stoichiometric composition is ZrO
2, when therefore film is Zirconium oxide film, it consists of ZrOx (x < 2).Herein, be not particularly limited as long as x is less than 2.Metal oxide film for other is also same.
oxide glass (core glass)
As surface at least partially by the core glass that above-mentioned film is coated to, the opticglass of normally used various composition in optical element makes can be enumerated.As the concrete mode of this opticglass, boric acid-rare earth metal system glass, phosphate glass, the silicate glasses such as boric acid lanthanide glass can be enumerated.
But, in opticglass, as the composition that the tendency producing foaming because of mold pressing is high, the Nb more giving composition containing promising high refractive index can be enumerated
2o
5, TiO
2, WO
3, Ta
2o
5oxide glass.In the manufacture method of the optical element of an embodiment of the invention, such as can using following oxide glass as core glass, arrange above-mentioned film at this core glass, carry out compression molding afterwards, above-mentioned oxide glass contains being selected from by Nb of more than one
2o
5, TiO
2, WO
3and Ta
2o
5high refractive index in the group of composition gives composition and the total content (Nb of high refractive index imparting composition
2o
5+ TiO
2+ WO
3+ Ta
2o
5) be more than 10 quality %.The bubble after mold pressing that can be inhibited thus occurs and the optical element of homogeneous.Total content (Nb
2o
5+ TiO
2+ WO
3+ Ta
2o
5) be more preferably more than 15 quality %.It should be noted that, the high temperature of the molding temperature caused from the view point of suppressing the remarkable rising of glass transformation temperature Tg and sag temperature Ts and vitrified easiness, total content (NbO
5+ TiO
2+ WO
3+ Ta
2o
5) be preferably below 50 quality %, be more preferably below 45 quality %.
The temperature of molding temperature usually more than the glass transformation temperature of core glass is carried out, therefore more for the glass of high glass transformation temperature then has the tendency that molding temperature improves all the more.On the other hand, the remarkable rising of molding temperature contributes to the generation of bubble sometimes.Therefore, as the preferred concrete mode of core glass, the appropriate glass ingredient with the effect reducing glass transformation temperature containing more than one can be enumerated.As the glass ingredient with the effect reducing glass transformation temperature, ZnO can be enumerated and be selected from by Li
2o, Na
2o and K
2alkalimetal oxide in the group of O composition.Total content (the ZnO+Li of ZnO and alkalimetal oxide
2o+Na
2o+K
2o) be preferably more than 5 quality %, be more preferably more than 10 quality %.On the other hand, from the view point of vitrified easiness, total content (ZnO+Li
2o+Na
2o+K
2o) be preferably below 25 quality %, be more preferably below 20 quality %.As core glass, from the view point of the availability of optical element, can exemplify that refractive index n d is 1.70 ~ 2.10, Abbénumber ν d is that the opticglass of 20 ~ 55 is as concrete mode.In addition, as other concrete mode, can exemplify and meet the glass of opticglass as compression molding, especially precise compression molding excellence that glass transformation temperature Tg is less than 630 DEG C, sag temperature Ts is arbitrary conditioned disjunction two conditions of less than 680 DEG C.But the manufacture method of the optical element of a mode of the present invention is not limited to above-mentioned concrete mode.
As the mode more specifically that can be the opticglass of core glass, such as following glass I, II, III can be enumerated.But, as long as core glass for oxide glass then its composition be not particularly limited.Glass I, II, III are all suitable as the opticglass for the manufacture of optical element.According to a mode of the present invention, compression molding is carried out to this opticglass thus the optical element not having alveolate high-quality can be provided in glass.
< glass I >
A kind of oxide glass, it is following oxide glass:
Represent with positively charged ion %,
Add up to the B containing 5 ~ 60%
3+and Si
4+(wherein, B
3+be 5 ~ 50%),
Add up to the Zn containing more than 5%
2+and Mg
2+,
Add up to the La containing 10 ~ 50%
3+, Gd
3+, Y
3+and Yb
3+,
Add up to the Ti containing 6 ~ 45%
4+, Nb
5+, Ta
5+, W
6+and Bi
3+(wherein, Ti
4+and Ta
5+total content more than 0% and W
6+content more than 5%),
Si
4+content relative to B
3+the cation ratio (Si of content
4+/ B
3+) be less than 0.70,
Ta
5+content relative to Ti
4+and Ta
5+the cation ratio (Ta of total content
5+/ (Ti
4++ Ta
5+)) be more than 0.23,
W
6+content relative to Nb
5+and W
6+the cation ratio (W of total content
6+/ (Nb
5++ W
6+)) be more than 0.30,
Ti
4+, Nb
5+, Ta
5+, W
6+and Bi
3+total content relative to B
3+and Si
4+the cation ratio ((Ti of total content
4++ Nb
5++ Ta
5++ W
6++ Bi
3+)/(B
3++ Si
4+)) for more than 0.37 and less than 3.00,
Zn
2+, Mg
2+and Li
+total content relative to La
3+, Gd
3+, Y
3+and Yb
3+the cation ratio ((Zn of total content
2++ Mg
2++ Li
+)/(La
3++ Gd
3++ Y
3++ Yb
3+)) be more than 0.40,
Refractive index n d is 1.90 ~ 2.00 and Abbénumber ν d meets following (1) formula,
25≤νd＜(3.91-nd)/0.06···(1)。
Although glass I is glass of high refractive index, lower glass transformation temperature can be demonstrated, therefore be suitable as the glass of precise compression molding.In the preferred mode of the opticglass of a mode of the present invention, glass transformation temperature is less than 650 DEG C.Glass transformation temperature is that the temperature of glass during precise compression molding can be maintained lower temperature range by the opticglass of less than 650 DEG C, and glass during suppression compression molding and the reaction being molded into profile, maintain good state by precise compression molding.From the above point of view, preferably make glass transformation temperature be less than 640 DEG C, be more preferably less than 630 DEG C and then be preferably less than 620 DEG C, more preferably less than 610 DEG C, further preferably less than 600 DEG C.
It should be noted that, if excessively reduce glass transformation temperature, then demonstrate the tendency that stability declines or specific refractory power declines of glass, therefore preferably make glass transformation temperature be more than 500 DEG C, be more preferably more than 520 DEG C and then preferably more than 540 DEG C, more preferably more than 560 DEG C, further preferably more than 570 DEG C.
< glass II >
A kind of oxide glass, it is following oxide glass:
Containing B
2o
3, La
2o
3and ZnO, % by mole to represent, containing B
2o
320 ~ 60%, SiO
20 ~ 20%, ZnO22 ~ 42%, La
2o
35 ~ 24%, Gd
2o
30 ~ 20% (wherein, La
2o
3and Gd
2o
3total amount be 10 ~ 24%), ZrO
20 ~ 10%, Ta
2o
50 ~ 10%, WO
30 ~ 10%, Nb
2o
50 ~ 10%, TiO
20 ~ 10%, Bi
2o
30 ~ 10%, GeO
20 ~ 10%, Ga
2o
30 ~ 10%, Al
2o
30 ~ 10%, BaO0 ~ 10%, Y
2o
30 ~ 10% and Yb
2o
30 ~ 10%, and Abbénumber (ν d) is more than 40, and essence is not containing lithium.
About glass II, essence does not mean, by Li containing lithium
2the import volume of O suppresses the content for can not there is to produce the use as optical element the grade (level) of the fuzzy or weathering of obstacle at glass surface.Specifically, mean and be scaled Li
2the content for being less than 0.5 % by mole is suppressed during the amount of O.The amount more reducing lithium then more can reduce risk that is fuzzy, weathering generation, therefore with Li
2it is less than 0.4 % by mole that the gauge of O preferably suppresses, more preferably suppress to be less than 0.1 % by mole and then preferably not import.
Glass II is suitable for precise compression molding and uses, from the view point of the damage of the mold release film preventing the consumption of compression molding die or formed at mould surface, preferred transition temperature (Tg) is low, preferably make transition temperature (Tg) be less than 630 DEG C, be more preferably less than 620 DEG C.On the other hand, from the view point of preventing the fuzzy of glass surface or weathering, as above the lithium amount in glass is limited, when therefore wanting excessively to reduce transition temperature (Tg), degradation problem under the stability of the reduction of easy generation specific refractory power or glass.Therefore, and then preferably make transition temperature (Tg) be more than 530 DEG C, further be preferably more than 540 DEG C.
About the detailed content of glass II, can with reference to 0013rd ~ 0039 section, Japanese Unexamined Patent Publication 2006-137662 publication.
< glass III >
A kind of oxide glass, it is following oxide glass:
% by mole to represent, containing SiO
20 ~ 20%,
B
2O
35～40％、
SiO
2+B
2O
3＝15～50％、
Li
2O0～10％、
ZnO12～36％、
Wherein, 3 × Li
2o+ZnO>=18%,
La
2O
35～30％、
Gd
2O
30～20％、
Y
2O
30～10％、
La
2O
3+Gd
2O
3＝10～30％、
La
2O
3/ΣRE
2O
3＝0.67～0.95％、
(wherein, Σ RE
2o
3=La
2o
3+ Gd
2o
3+ Y
2o
3+ Yb
2o
3+ Sc
2o
3+ Lu
2o
3)
ZrO
20.5～10％、
Ta
2O
51～15％、
WO
31～20％、
Ta
2o
5/ WO
3≤ 2.5 (mol ratios),
Nb
2O
50～8％、
TiO
20 ~ 8%, refractive index n d is more than 1.87,
Abbénumber ν d is more than 35 and is less than 40.
Glass III demonstrates the softening temperature that glass transformation temperature is less than 650 DEG C.The preferred scope of the glass transformation temperature that glass III has is less than 640 DEG C and then is preferably less than 630 DEG C, more preferably less than 620 DEG C, further preferably 610 DEG C.On the other hand, if excessively reduce glass transformation temperature, then demonstrate further high refractive index, low decentralized become difficulty, and/or the tendency that the stability of glass or chemical durability decline, therefore expects to make glass transformation temperature be more than 510 DEG C, is preferably more than 540 DEG C, is more preferably more than 560 DEG C and then preferably more than 580 DEG C.
Further, the preferred scope of sag temperature (Ts) that glass III has is less than 700 DEG C, be more preferably less than 690 DEG C and then be preferably less than 680 DEG C, more preferably less than 670 DEG C, further preferably less than 660 DEG C.If excessively reduce sag temperature (Ts), then demonstrate further high refractive index, lowly decentralizedly become difficulty, and/or the tendency that the stability of glass or chemical durability decline.Therefore, preferably make sag temperature (Ts) be more than 550 DEG C, be more preferably more than 580 DEG C and then preferably more than 600 DEG C, more preferably more than 620 DEG C.
About the detailed content of glass III, can with reference to 0016th ~ 0065 section, Japanese Unexamined Patent Publication 2008-201661 publication.
core glass shaping
For core glass, the preformed parison using oxide glass as optical element forming, utilizes the method for forming as preformed parison and known method is shaped to known shape.For shape and the forming method of core glass, such as can with reference to the record of the record of 0087th ~ 0106 section, Japanese Unexamined Patent Publication 2011-1259 publication and embodiment, 0040th ~ 0044 section, Japanese Unexamined Patent Publication 2004-250295 publication and embodiment.
arbitrary tunicle
For the compression molding glass blank used in the manufacture method of the optical element of a mode of the present invention, can obtain by carrying out being coated to the film forming process of above-mentioned metal oxide film at core glass discussed above.The compression molding glass blank so obtained is the formation that above-mentioned metal oxide film is directly contacted with the surface of core glass.The tunicle of more than one deck at random can be formed further on the compression molding glass blank of this formation.The release property etc. that this tunicle is detached into mould for raising glass in compression molding is effective.
As a mode of above-mentioned arbitrary tunicle, can enumerate containing carbon film.Containing carbon film can before stamping and glass blank is supplied to forming mould time bring the sufficient smoothness with forming mould, glass blank can be made smoothly to move to the prescribed position (central position) of forming mould, and make utilizing mold pressing that glass blank is softening, distortion time, the surface that can contribute to glass blank is followed the extension of glass deformation, glass blank in the extension of molding die surface.Further, after molding and formed body is cooled to specified temperature time, it is useful for glass being easily separated with molding die surface, peeling off, contributing to these aspects of the demoulding.In addition, it is also effective in compression molding, for suppression, crackle occurring containing carbon film in above-mentioned metal oxide film lamination.
As containing carbon film, preferably using carbon as main component, but it also can be the film that hydrocarbon film etc. contains the composition beyond carbon.As the film containing carbon film, the known film such as vacuum evaporation, sputtering, ion plating (ionplating), plasma CVD (ChemicalVaporDeposition) that make use of carbon raw material can be used.In addition, the film forming containing carbon film is carried out in the thermolysis that also can contain thing by carbon such as hydrocarbon.
In addition, as arbitrary tunicle, such as, also can form the tunicle being recited as the 1st upper layer and the 2nd upper layer in Japanese Unexamined Patent Publication 2011-1259 publication.About their detailed content, can refer to Japanese Unexamined Patent Publication 2011-1259 publication.
the manufacture of optical element
Prepare compression molding glass blank discussed above, then obtain compression molding body by compression molding, thus the optical element of a mode of the present invention can be obtained with the form of this compression molding body itself; Or above-mentioned compression molding body is implemented to the subsequent handlings such as tunicle formation, thus the optical element of a mode of the present invention can be obtained.
Compression molding can utilize the forming method as optical element and known compression molding method and carrying out.Below, concrete mode is described, but the present invention is not limited to following manner.
As the forming mould used in compression molding, can use the forming mould that there is sufficient thermotolerance, rigidity and the material of densification carry out precision sizing.Such as, silicon carbide, silicon nitride, wolfram varbide, aluminum oxide or the metal such as titanium carbide, stainless steel can be enumerated; Or at their the surface-coated material of the films such as carbon, heating resisting metal, precious metal alloys, carbide, nitride, boride.Never be attended by hot sticky, fuzzy, scar etc. and the viewpoint that compression molding glass blank is shaped to glass optical component is set out, as the film of coating molding surface, be preferably the film containing carbon.For containing carbon film, can with reference to the 0116th section, Japanese Unexamined Patent Publication 2011-1259 publication.As forming mould, be used in the forming mould that molding surface has carbon containing mold release film, thus the smoothness that there is molding surface and glass blank is improved, formability further improves such advantage.
An example of compression molding device has been shown in Fig. 1.When compression molding, as shown in Figure 1, in the forming mould 6 comprising patrix 3, counterdie 4 and body mould 5, supply core glass 1 by the coating compression molding glass blank PF of above-mentioned film 2, be warming up to moldable temperature province.
Such as, Heating temperature can according to form core glass 1 oxide glass kind and suitably set, but the viscosity being preferably in glass blank PF at glass blank PF and forming mould 6 is 10
5~ 10
10compression molding is carried out during the temperature province of dPas.For molding temperature, such as so that be preferably form core glass 1 oxide glass for being equivalent to 10
7.2before and after dPas 10
6~ 10
8the temperature of dPas, be more preferably equivalent to 10 according to core glass 1
7.2the mode of dPas carrys out design temperature.Usually, molding temperature is set as the temperature of more than the glass transformation temperature of core glass.At these temperatures, utilize be in compared with stoichiometric composition oxygen shortcoming state and the metal oxide film that the velocity of diffusion of the admission velocity of Sauerstoffatom and atoms metal meets above-mentioned relation core glass is coated to, compression molding is carried out to this compression molding glass blank, thus make the Sauerstoffatom of the occurrence cause as bubble enter metal oxide film, bubbling in the compression molding body obtained by compression molding can be prevented thus.It should be noted that, molding temperature and the Heating temperature relevant with mold pressing refer to, carry out the temperature of the atmosphere of compression molding.Compression molding can decline by making pressure head 7 thus the load applying to specify carries out.
Glass blank PF is supplied to forming mould 6, glass blank PF and forming mould 6 is all warming up to the scope of regulation; Or glass blank PF and forming mould 6 can be warming up to respectively the temperature range of regulation, then glass blank PF be configured in forming mould 6.Further, following method can be adopted: be warming up to by glass blank PF and be equivalent to viscosity 10
5~ 10
9the temperature of dPas, forming mould 6 is warming up to is equivalent to glass viscosity 10
9~ 10
12the temperature of dPas, is configured at forming mould 6 by glass blank PF, then carries out compression molding at once.Now, can relatively be lowered into mould temperature, therefore there is following effect: the deterioration that the heating/cooling loop cycle and can suppressing that can shorten shaped device causes because of the heat of forming mould 6.No matter in any situation, begin to cool down when compression molding starts or after starting, be suitable for suitable load applying progress chart (schedule), be maintained in the closely sealed of profile and glass, while lower the temperature simultaneously.Afterwards, carry out the demoulding, formed body is taken out.Calcining temperature is preferably to be equivalent to 10
12.5~ 10
13.5the form of dPas is carried out.
There is the high metal oxide film of film that oxygen containing ratio has than the compression molding glass blank before compression molding relative to the containing ratio of atoms metal than film high before compression molding, i.e. Sauerstoffatom in glass forming body after demoulding, its reason is, is arranged at the metal oxide film of compression molding glass blank from core glass collecting Sauerstoffatom.Known by the research of the present inventor, this metal oxide film is in the state of oxygen shortcoming compared with stoichiometric composition.
The formed body obtained can directly as the finished product, i.e. optical element shipment; Or also can implement to obtain the finished product after the following process such as the film forming process of the optically functional films such as antireflection film are processed or formed on surface in centering.Such as, on the glass forming body with above-mentioned upper layer, with the form of individual layer or lamination suitably to Al
2o
3, ZrO
2-TiO
2, MgF
2carry out film forming Deng material, thus desired antireflection film can be formed.The film of antireflection film can utilize the known methods such as vapour deposition method, ion assisted deposition method, ion plating, sputtering method to carry out.Such as, when utilizing vapour deposition method, use evaporation coating device, 10
-4in the vacuum atmosphere of about Torr, utilize electron beam, direct-electrifying or electric arc to heat deposition material, by the delivery of steam of the material from material evaporation and distillation generation to base material, carry out condensing/precipitation, thus can antireflection film be formed.About base material heating temperature can be set to room temperature ~ 400 DEG C.But when the glass transformation temperature (Tg) of base material is below 450 DEG C, the ceiling temperature of base material heating is preferably Tg-50 DEG C.
The optical element of a mode of the present invention can be the little quality lens that diameter is little, wall is thin, such as, be the object lens, collimating lens etc. of the small-sized image pickup system lens of the lift-launchs such as field camera, communication lens, light pickup.Being not particularly limited for lens shape, can be the different shapes such as male bend moon-shaped lens, recessed meniscus shaped lens, biconvex lens, biconcave lens.
Embodiment
Based on embodiment, the present invention will be described further below.But the present invention is not limited to the mode shown in embodiment.
The glass transformation temperature of the following stated and sag temperature utilize the thermo-mechanical analysis device of Rigaku Denki Co., Ltd heat-up rate to be set as 4 DEG C/min and measure the value that obtains.
For specific refractory power (nd) and Abbénumber (ν d), to slow cooling cooling rate being set as-30 DEG C/h and the opticglass obtained measures.
[embodiment 1]
(1) making of compression molding glass blank
For as the opticglass of compression molding with the core glass 1 of glass blank PF, belonging to the opticglass I-1 of glass I, belong to the opticglass II-1 of glass II described in use table 1, following operation is utilized to carry out the film forming of Zirconium oxide film on its surface.
First, the opticglass as core glass 1 is dropped to collecting mould with molten state, cools, be pre-formed as one-sided for convex surface, opposition side be the glass block of the shape of concave surface.For this preformed glass block, by metal zirconium (Zr) for target, in the atmosphere of Ar100%, sputtering method is utilized to carry out the film forming of film (thickness: about 5nm) with the film-forming temperature of 300 DEG C.Thickness is adjusted by sputtering condition.The physical dimension of the compression molding glass blank so obtained is 10mm ~ 11mm, and central part wall thickness is 7mm ~ 11mm.
[table 1]
(unit: quality %)
| Glass I-1 | Glass II-1 | |
| SiO 2 | 1.17 | 2.6 |
| B 2O 3 | 11.04 | 16.2 |
| ZnO | 14.3 | 15.6 |
| La 2O 3 | 29.0 | 32.4 |
| Gd 2O 3 | 0.86 | 10.0 |
| ZrO 2 | 2.72 | 3.7 |
| Ta 2O 5 | 10.8 | 14.1 |
| WO 3 | 18.81 | 5.5 |
| TiO 2 | 1.5 | |
| Nb 2O 5 | 9.8 | |
| Sb 2O 3 | 0.05 | |
| Glass transformation temperature | 590℃ | 612℃ |
| Sag temperature | 635℃ | 652℃ |
| Refractive index n d | 1.9515 | 1.85135 |
| Abbénumber ν d | 29.8 | 40.10 |
(2) based on the making of the compression molding body of precise compression molding
Then, in a nitrogen atmosphere, mould compression molding device is utilized to carry out compression molding to the compression molding glass blank PF that above-mentioned (1) makes.That is, the forming mould be made up of upper and lower mould and the body mould of SiC that molding surface defines the carbon containing mold release film based on sputtering method is used in, with non-oxidizing N
2the chamber internal ambience of shaped device is full of by gas, and the viscosity being then heated to core glass is 10
7.2the temperature of dPas, is supplied to and is heated to be equivalent to 10 with the viscometer of core glass
8.5the forming mould of the temperature of dPas.And, soon between upper/lower die, carry out the mold pressing (molding temperature 675 DEG C) of glass blank after supply, temperature below the slow cooling temperature being cooled to core glass when maintaining glass and upper/lower die closely sealed, takes out molding (optical lens) in forming mould.The outside dimension of formed body is 20.0mm, center wall thickness is 0.70mm.Then, for the peripheral part of compression molding body, utilize ground finish to feel relieved, obtain the aspherical glass lens of the recessed crescent moon of φ 18mm.
[embodiment 2]
In the making (1) of compression molding glass blank, metal titanium (Ti) is used to replace metal zirconium, form at core glass I-1, II-1 the film that thickness is about 5nm respectively, in addition, obtain the aspherical glass lens of recessed crescent moon similarly to Example 1.
[embodiment 3]
In the making (1) of compression molding glass blank, metal tantalum (Ta) is used to replace metal zirconium, form at core glass I-1, II-1 the film that thickness is about 5nm respectively, in addition, obtain the aspherical glass lens of recessed crescent moon similarly to Example 1.
[embodiment 4]
In the making (1) of compression molding glass blank, tungsten (W) is used to replace metal zirconium, form at core glass II-1 the film that thickness is about 5nm, in addition, obtain the aspherical glass lens of recessed crescent moon similarly to Example 1.
[embodiment 5]
In the making (1) of compression molding glass blank, metal niobium (Nb) is used to replace metal zirconium, form at core glass II-1 the film that thickness is about 5nm, in addition, obtain the aspherical glass lens of recessed crescent moon similarly to Example 1.
[comparative example 1]
In the making (1) of compression molding glass blank, metallic yttrium (Y) is used to replace metal zirconium, form at core glass I-1 the film that thickness is about 5nm, in addition, obtain the aspherical glass lens of recessed crescent moon similarly to Example 1.
[comparative example 2]
The ZrO as upper layer in the embodiment 1 ~ 6 of Japanese Unexamined Patent Publication 2011-1259 publication is formed successively on the surface of core glass I-1
2film and SiO
2film, in addition, obtains the aspherical glass lens of recessed crescent moon similarly to Example 1.ZrO
2film and SiO
2the thickness of film is respectively about 5nm.
< bubble evaluates > with presence or absence of occurring
Utilize opticmicroscope to observe each lens made in embodiment, comparative example with the multiplying power of 50 times, confirm there is bubble-free in lens, result is, in the lens made by embodiment 1 ~ 4, does not observe bubble completely.As representative examples, the optical microscope photograph of the lens (core glass: the I-1 in table 1) made by embodiment 1 has been shown in Fig. 2.Can confirm: obtain and there is no bubble and the lens with the homogeneous of high transparent.
On the other hand, in the lens made by comparative example 1,2, the bubble of a large amount of diameter more than 50 μm is confirmed.Illustrate in Fig. 3 and a part for the lens made by comparative example 2 (core glass: the I-1 in table 1) has been expanded and the optical microscope photograph of taking pictures and obtaining.Can confirm: create a large amount of bubble.
In comparative example 2, the film of coating core glass is ZrO
2the film of the stoichiometric compositions such as film.This metal oxide film can make when compression molding the oxygen that dissociates out from oxide glass through, cannot enter in film.Oxygen through film is closed in compression molding die and cannot externally releases.Its result is, again gets back to glass through film, causes foaming in glass.
The confirmation > of the gas composition in < bubble
Utilize mass analysis (MassSpectrometry) to analyze the gas composition in the bubble in the lens made by comparative example 2 (core glass: glass I-1), result is N
2: 89%, O
2: 11%, even if carry out compression molding in a nitrogen atmosphere, also detected the oxygen more than 10%.This result can prove, as mentioned above, the oxygen deriving from oxide glass is the reason that bubble occurs.
State confirmation (embodiment 1, the comparative example 2) > of the film before and after < compression molding
For the lens using glass I-1 to be made by embodiment 1, comparative example 2 as core glass and with the compression molding glass made under the condition that the compression molding glass blank of this shaping middle use is identical, utilize following methods to carry out the compositional analysis of depth direction from surface by TOF-SIMS (Time-of-flightsecondaryionmassspectrometer: time of flight secondary ion massspectrometry analytical method).
based on the depth direction analysis of TOF-SIMS
Use the TOF-SIMS300 that ION-TOF society manufactures, implement depth direction and measure.TOF-SIMS be radiation pulses primary ions and to the gimmick that detects of secondary ions occurred.In the depth direction of TOF-SIMS is analyzed, repeatedly carry out following (i) ~ (iii): (i) irradiates primary ions, (ii) calculates occurred secondary ions, (iii) irradiates plasma sputter, thus obtain data.
Primary ion source uses Bi
3 ++, put on Bi
3 ++the voltage of the post (column) of primary ion source is 25kV.Be that 0.2pA measures by the current settings of primary ion source.The irradiated area of primary ion source (=mensuration region that secondary ions is detected) be 100 μm square, secondary ions is detected as negative ion.
Sputtering source uses Cs.The acceleration of sputtering source adjusts under being the condition of 75.4nA at 1kV, current value.The area of sputtering source is sputter under 400 μm of square conditions.
The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (lens) after Fig. 4 shows the mold pressing about embodiment 1.The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (non-mould) before Fig. 5 shows the mold pressing about embodiment 1.In figure, the unit of secondary ions intensity is arbitrary unit.Also be same in accompanying drawing described later.
In embodiment 1, the thickness of the Zirconium oxide formed as film at core glass is about 5nm.In figure, as the secondary ions deriving from Zirconium oxide in each test portion, be recited as ZrO and ZrO
2.In addition, although omit from figure, in each test portion, all detected Zr simple substance.Zr do not detected
2, therefore the Zr of simple substance not derives from metallic Z r, but derives from Zirconium oxide.Thus, the film before and after mold pressing is Zirconium oxide.It should be noted that, ZrO, ZrO before the mold pressing shown in Fig. 5
2analytical results in, confirm 2 peaks respectively near surface.The present inventor infers, first peak of near surface is natural oxide film, and second peak is produce because of the reaction with glass when film forming.By the SiO that the depth direction analyzing and testing of the secondary ions intensity based on TOF-SIMS goes out
2derive from the SiO contained by glass
2.In each test portion, as SiO
2the reason that intensity rises near surface is because surface exists a little tramp material (such as siloxanes etc.).
Fig. 6 is to the ZrO in Fig. 4,5
2the secondary ions strength ratio of/ZrO (is recited as " ZrO below
2/ ZrO strength ratio ") result that compares.ZrO
2/ ZrO strength ratio is the index of the degree of the oxidation represented in Zirconium oxide film.But, in the scope for about 2nm from the surface of Zirconium oxide, cannot as the object of commenting because of the impact of natural oxide film.In the result shown in Fig. 6, for from the ZrO of about degree of depth 2nm to the region of about 5nm
2/ ZrO strength ratio, compared with before mold pressing, increases after mold pressing to some extent.Can be confirmed by this result: the oxidation of Zirconium oxide is promoted because of mold pressing.
It should be noted that, when the above-mentioned film before compression molding is Zirconium oxide film, following Zirconium oxide film can be obtained, in this Zirconium oxide film, before described ZrO
2/ ZrO strength ratio mold pressing precedent as 0.5 ~ 1.9 scope, this film such as demonstrates the ZrO of the scope of 2.0 ~ 2.3 after molding
2/ ZrO strength ratio.This means, ZrO
2/ ZrO higher then more oxidized, containing more oxygen.It should be noted that, carry out ZrO
2during the film forming of film, the ZrO of this film
2/ ZrO strength ratio can get the value of about 2.4 ~ 3.2 usually.
The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of the lens made by comparative example 2 has been shown in Fig. 7.Fig. 8 is for by result overlapping with the result of the comparative example 2 shown in Fig. 7 for the result of the embodiment 1 shown in Fig. 4.Comparative example 2 is SiO
2/ ZrO
2the structure of/glass, confirms SiO in advance
2and ZrO
2it is stoichiometric composition before and after mold pressing.It should be noted that, in the figure 7, in the statement of the degree of depth of comparative example 2, by SiO
2and ZrO
2interface be designated as 0, SiO
2part represents with negative (minus).
If be directed to the region (degree of depth 0 ~ 5nm) of the expression ZrOx of Fig. 8, then the ZrO after the mold pressing of embodiment 1
2/ ZrO strength ratio is less than comparative example 2.From this result, the degree of the oxidation produced because of mold pressing of embodiment 1 is lower than comparative example 2.That is, can confirm: with the ZrO of the stoichiometric composition of comparative example 2
2compare, the oxygen shortcoming of the Zirconium oxide after the mold pressing of embodiment 1.It should be noted that, comparative example 2 defines SiO in the most surface of compression molding glass blank
2film, therefore without the need to considering the impact of natural oxide film, but for embodiment 1, from surface, the region of about 2nm is subject to the impact of natural oxide film, therefore cannot as the object of commenting.
That is, can be confirmed by the result being shown in Fig. 4 ~ Fig. 8: for embodiment 1, before and after mold pressing, Zirconium oxide film all has and stoichiometric composition ZrO
2compare the composition of oxygen shortcoming, wherein, the oxygen containing ratio of the Zirconium oxide film after mold pressing is higher than before mold pressing.
State confirmation (comparative example 1) > of the film before and after < compression molding
For the lens using glass I-1 to be made by comparative example 1 as core glass and with the compression molding glass made under the condition that the compression molding glass blank of this shaping middle use is identical, utilize aforesaid method to carry out the depth direction analysis of secondary ions intensity by TOF-SIMS.
The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (lens) after Fig. 9 shows the mold pressing about comparative example 1.The depth direction analytical results of the secondary ions intensity based on TOF-SIMS of (non-mould) before Figure 10 shows the mold pressing about comparative example 1.Can be confirmed by the result being shown in Fig. 9, Figure 10: after molding, yttrium oxide film disappears.This is the result that following shown phenomenon produces: in comparative example 1, in the yttrium oxide film of film forming on core glass, when compression molding, compared with the speed of accommodating the Sauerstoffatom contained by core glass with yttrium oxide film, the speed that the atoms metal (Y) contained by yttrium oxide film spreads to core glass is fast.
For each metal oxide film be made on core glass in embodiment 2 ~ 5, also profit uses the same method and confirms: the state being all in compared with stoichiometric composition oxygen shortcoming before and after mold pressing, but the oxygen containing ratio of metal oxide film after mold pressing is higher than before mold pressing.
For the glass III-1 shown in the following table 2 being equivalent to oxide glass III, carry out compression molding similarly to Example 1, confirm and obtain bubble-free and the lens of homogeneous.
[table 2]
(unit: quality %)
As mentioned above, according to a mode of the present invention, the bubble after mold pressing can be suppressed to occur.Preferably, use opticmicroscope when carrying out observing with the multiplying power of 10 times ~ 50 times, can be using diameter the bubble of more than 50 μm be less than 1 or diameter be the bubble of more than 25 μm be less than 2 or diameter be the bubble of more than 10 μm be less than 5 and the total of the diameter of the bubble situation that is no more than 50 μm as the index of the optical element of the generation and homogeneous that inhibit bubble.More preferably, use opticmicroscope when carrying out observing with the multiplying power of 10 times ~ 50 times, can be using diameter the bubble of more than 25 μm be less than 1 or diameter be the bubble of more than 10 μm be less than 3 and the total of the diameter of bubble be no more than 25 μm situation as bubble-free and the index of the optical element of homogeneous.The lens made by above-described embodiment all meet preferred index and preferred index.Herein, the total of bubble diameter refers to, such as diameter be the bubble of 50 μm exist 2 then bubble diameter add up to 100 μm.In addition, diameter herein when referring to diameter for when circular bubble, in the distance for referring to long axis direction when oval bubble, when for referring to the longest distance that can measure when amorphous bubble.
In an embodiment, metal oxide film is utilized to cover almost whole of core glass surface, even if but a part is not for be coated to, as long as be in the state of compared with stoichiometric composition oxygen shortcoming and the metal oxide film that the velocity of diffusion of the admission velocity of Sauerstoffatom and atoms metal meets above-mentioned relation is present in core glass surface, then can obtain same effect, this is from need not.
Finally above-mentioned each mode is summarized.
According to a mode, a kind of manufacture method of optical element can be provided, it possesses following operation: the operation preparing compression molding glass blank, this compression molding glass blank has the film at least partially on the surface of oxide glass and this oxide glass coating, and above-mentioned film is the metal oxide film of oxygen shortcoming compared with stoichiometric composition; With compression molding is carried out to compression molding glass blank thus forms the mold pressing procedure of compression molding body,
Above-mentioned compression molding body comprises the above-mentioned film after described mold pressing procedure, and,
Film after mold pressing procedure is the metal oxide film that oxygen containing ratio is higher than the film before mold pressing procedure.
According to the manufacture method of above-mentioned optical element, being inhibited and the optical element of homogeneous of bubble can be provided.In addition, according to the manufacture method of above-mentioned optical element, a kind of optical element can be provided, it has the film at least partially on the surface of oxide glass and this oxide glass coating, above-mentioned film is the metal oxide film being in oxygen shortcoming state compared with stoichiometric composition, and, at temperature more than the glass transformation temperature of oxide glass, the speed that the speed of the Sauerstoffatom of metal oxide film collecting contained by oxide glass spreads to oxide glass than atoms metal contained in metal oxide film is fast.
In a mode, above-mentioned metal oxide is the oxide compound of the metal in the group of selected among zirconium, titanium, niobium, tungsten and tantalum composition.
In a mode, the metal oxide film that the compression molding body obtained by compression molding has is in the state of oxygen shortcoming compared with stoichiometric composition.
In a mode, above-mentioned oxide glass contains being selected from by Nb of more than one
2o
5, TiO
2, WO
3and Ta
2o
5high refractive index in the group of composition gives composition.This high refractive index gives the total content (Nb of composition
2o
5+ TiO
2+ WO
3+ Ta
2o
5) be preferably more than 10 quality % and below 50 quality %.
In a mode, above-mentioned oxide glass contains ZnO and is selected from alkalimetal oxide Li
2o, Na
2o, K
2o) more than one in the group formed.Preferably, the total content (ZnO+Li of ZnO and alkalimetal oxide
2o+Na
2o+K
2o) be more than 5 quality % and below 25 quality %.
In a mode, the Heating temperature more than 650 DEG C carries out heating during compression molding.According to the manufacture method of above-mentioned optical element, the bubble in mold pressing at these high temperatures can be suppressed to occur.
In a mode, a kind of compression molding glass blank also can be provided, it has the film at least partially on the surface of oxide glass and this oxide glass coating, above-mentioned film is the metal oxide film being in oxygen shortcoming state compared with stoichiometric composition, and, at temperature more than the glass transformation temperature of oxide glass, the speed that the speed of the Sauerstoffatom of metal oxide film collecting contained by oxide glass spreads to oxide glass than atoms metal contained in metal oxide film is fast.This compression molding glass blank is applicable to the manufacture method of the optical element of an above-mentioned mode.
Should think, the embodiment disclosed in this is example in all respects, not restriction.Scope of the present invention is not above-mentioned explanation but shown by claims, this means to comprise the meaning equal with claims and all changes in scope.
The present invention is useful in the manufacture field of the optical elements such as glass lens.
Claims (5)
1. an optical element, it has the film at least partially on the surface of oxide glass and coating described oxide glass, described film is the metal oxide film being in oxygen shortcoming state compared with stoichiometric composition, and, at temperature more than the glass transformation temperature of described oxide glass, the speed that the speed that described metal oxide film accommodates the Sauerstoffatom contained by described oxide glass spreads to described oxide glass than atoms metal contained in described metal oxide film is fast.
2. compression molding glass blank as claimed in claim 1, wherein, described metal oxide is the oxide compound of the metal in the group of selected among zirconium, titanium, niobium, tungsten and tantalum composition.
3. a manufacture method for optical element, it possesses following operation:
Prepare the operation of compression molding glass blank, this compression molding glass blank has the film at least partially on the surface of oxide glass and coating described oxide glass, and described film is the metal oxide film of oxygen shortcoming compared with stoichiometric composition; With
Compression molding is carried out to described compression molding glass blank thus the mold pressing procedure of formation compression molding body,
Described compression molding body comprises the described film after described mold pressing procedure,
Further, the film after described mold pressing procedure is the metal oxide film that oxygen containing ratio is higher than the described film before mold pressing procedure.
4. the manufacture method of optical element as claimed in claim 3, wherein, described metal oxide is the oxide compound of the metal in the group of selected among zirconium, titanium, niobium, tungsten and tantalum composition.
5. the manufacture method of the optical element as described in claim 3 or 4, wherein, the metal oxide film that described compression molding body has is in the state of oxygen shortcoming compared with stoichiometric composition.
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| JP2013205497A JP6218536B2 (en) | 2013-09-30 | 2013-09-30 | Optical element and manufacturing method thereof |
| PCT/JP2014/075887 WO2015046509A1 (en) | 2013-09-30 | 2014-09-29 | Optical element and production method for same |
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| JP2004250295A (en) * | 2003-02-21 | 2004-09-09 | Hoya Corp | Glass base material for optical element molding, manufacturing method of optical element, and optical element |
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| WO2015046509A1 (en) | 2015-04-02 |
| KR20160065080A (en) | 2016-06-08 |
| JP2015067525A (en) | 2015-04-13 |
| TWI621594B (en) | 2018-04-21 |
| JP6218536B2 (en) | 2017-10-25 |
| CN105579412B (en) | 2018-09-14 |
| TW201527229A (en) | 2015-07-16 |
| KR102219149B1 (en) | 2021-02-22 |
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