CN109052930A

CN109052930A - Environmental protection optical glass

Info

Publication number: CN109052930A
Application number: CN201810931088.7A
Authority: CN
Inventors: 钟义刚
Original assignee: Salience Science & Technology Industrial Co Ltd
Current assignee: Salience Science & Technology Industrial Co Ltd
Priority date: 2018-08-16
Filing date: 2018-08-16
Publication date: 2018-12-21

Abstract

The present invention relates to a kind of optical glass more particularly to a kind of environmental protection optical glass with high refraction, low dispersion.Its refractive index (nd) is between 1.87-1.91, and Abbe number (ν d) is between 38.5-42；It includes following component by weight percentage: the SiO of 1-10%₂, the B of 10-40%₂O₃, total amount is the La of 30wt%-45wt%₂O₃、Gd₂O₃And Y₂O₃, the TiO of the ZnO of 0.5wt%-20wt%, 1wt%-20wt%₂, the ZrO of 1wt%-4wt%₂, total amount is the Li of 1-5wt%₂O、Na₂O and K₂The Ta of the SrO of O, 0-5wt%, 0-5wt%₂O₅, the TeO of 0-5wt%₂, the Bi of 0-10wt%₂O₃, the Sb of 0-1wt%₂O₃。

Description

Environmental protection optical glass

Technical field

The present invention relates to a kind of optical glass more particularly to a kind of environmental protection optical glass with high refraction, low dispersion.

Background technique

In recent years, in order to meet the requirement of high-grade digital product high pixel, small portable, there is high refraction, low dispersion etc. The demand of the optical glass of advantage is increasing.Such as: two one group of lens formed by high refractive index, low dispersing glass, energy It enough corrects color difference and minimizes optical system.Therefore, the low dispersed optical glass of high refractive index is in optical system or projector Occupy very important position in equal projection optics systems.

La in order to make glass that there is the above performance, in glass₂O₃、TiO₂、Nb₂O₅Component content is also being gradually increased, but These ingredients excessively will lead to that glass viscosity is small, molding difficulty is big, be not easy to obtain better quality striped and crystallization is serious etc. and lack It falls into.In addition, in order to obtain the glass that refractive index nd is 1.85 or more being both needed to that a large amount of Ta is added₂O₅.This is because in refractive index In the high-refractive-index regions that nd is 1.85 or more, as it ensure that importing a large amount of Ta the reason of the aspect of stability, glass₂O₅It is It is required.In this way, the Ta in the low dispersing glass of high refractive index₂O₅Become main ingredient.

It however, tantalum (Ta) is the high element of scarcity value, and is originally very expensive substance.Moreover, nearest full generation The rapid rise of price of the rare metal on boundary, the supply of tantalum are also insufficient.It is also tantalum insufficient raw material in glass manufacturing area, such as If situation as fruit continues, then can not probably it stablize for essential high refractive index for reply optical device industrial circle Low dispersing glass.Similarly for commonly used Gd in the low dispersing glass of high refractive index₂O₃, Y2O3 or Nb₂O₅It all has expensive With the disadvantage of raw material rareness.

Therefore for dispersed optical glass low for high refractive index, rare earth element usage amount how is reduced as this field One compared with hang-up.

Summary of the invention

The present invention provides a kind of environmental protection optical glass of the low dispersion of high refractive index, and refractive index (nd) is in 1.87-1.91 Between, Abbe number (ν d) is between 38.5-42；It includes following component by weight percentage: the SiO of 1-10%₂, 10-40% B₂O₃, total amount is the La of 30wt%-45wt%₂O₃、Gd₂O₃And Y₂O₃, the ZnO of 0.5wt%-20wt%, 1wt%-20wt% TiO₂, the ZrO of 1wt%-4wt%₂, total amount is the Li of 1-5wt%₂O、Na₂O and K₂The SrO of O, 0-5wt%, 0-5wt%'s Ta₂O₅, the TeO of 0-5wt%₂, the Bi of 0-10wt%₂O₃, the Sb of 0-1wt%₂O₃。

In some embodiments, SiO₂Content be 5-10%, B₂O₃Content be 15-25%.

In other embodiments, La₂O₃、Gd₂O₃And Y₂O₃Total content be 35-40%.Wherein, La₂O₃Content For 30-40%, Gd₂O₃Content is 0-5%, Y₂O₃Content be 0-5%.

In other embodiment, Ta₂O₅Content be 1-2%；TeO₂Content be 2-4%；Bi₂O₃Content be 4- 6%.

In further carrying out scheme, TeO₂/(Ta₂O₅+Bi₂O₃) weight ratio between 0.3-0.6.

The present invention also provides gas preforms made of the environmental protection optical glass.

The present invention also provides optical elements made of the environmental protection optical glass.

The present invention also provides optical instruments made of the environmental protection optical glass.

Specific embodiment

Also the present invention further can be understood by embodiment, wherein the embodiment illustrates some preparations or user Method.It is to be appreciated, however, that these embodiments do not limit the present invention.The change of the invention of currently known or further exploitation Change is considered within the scope of the invention described herein and claimed below.

The component that can include to optical glass of the invention is described.Unless otherwise indicated, the group of every kind of component At than all being indicated with weight %.

SiO₂It is indispensable component, it is resistance to for improving glass viscosity, the devitrification resistance ability for improving glass and chemistry Long property is highly effective.But if the amount of the component is insufficient, these effects are unable to fully realize；However, if the component Measure excessive, then glass transition temperature raising, the melting property deterioration of glass.So the lower limit of the group component should be preferably big In 5%, the upper limit of the amount of the component should be 10%.SiO₂It can be by using such as SiO₂Glass is integrated to as raw material In.

B₂O₃It is also the component of network former.For La as the present invention₂O₃The higher optical glass of content comes It says, is indispensable.But if the amount of the component is insufficient, devitrification resistance scarce capacity；However, if the component Measure excessive, then refractive index drops to the degree for deviateing objective optics constant, and chemical durability also deteriorates.So the component The lower limit of amount should be preferably 15%, the upper limit of the component is preferably smaller than 25%.B₂O₃Can by using such as H3BO3 or Person B2O3 is integrated in glass as raw material.

La₂O₃It is indispensable component, it effectively improves refractive index and reduces dispersion.But if component Amount it is insufficient, then be difficult to for optical constant being maintained within above-mentioned value；However, if the amount of the component is excessive, devitrification resistance energy Power deteriorates.So the lower limit of the amount of the component should be preferably 25%, more preferable 30%, the upper limit of the amount of the component should be excellent Choosing is 40%.La₂O₃It can be by using such as La₂O₃, lanthanum nitrate or its hydrate be integrated in glass as raw material.

Gd₂O₃Effectively increase refractive index and reduces dispersion.But if the amount of the component is excessive, devitrification resistance ability and Chemical durability is deteriorated.In addition costly in view of its price, so the upper limit of the amount of the component should be preferably 5%. Gd₂O₃It can be by using such as Gd₂O₃It is integrated in glass as raw material.

Y₂O₃Effectively increase refractive index and reduces dispersion.But if the amount of the component is excessive, devitrification resistance ability and Chemical durability is deteriorated.In addition costly in view of its price, so the upper limit of the amount of the component should be preferably 5%, more Preferably smaller than 2%.Y₂O₃It can be by using such as Y₂O₃It is integrated in glass as raw material.

TeO₂It can effectively improve refractive index, it is used to replace the rare metal oxidation that this field is often used in the present invention Object, when frit melts in platinum alloy crucible, TeO₂In tellurium and platinum occur alloying, the heat resistance qualitative change of alloying part Difference causes to form hole in the alloying part, and melten glass is leaked from the hole.So TeO₂The upper limit of amount should Preferably 4%.TeO₂It can be by using such as TeO₂It is integrated in glass as raw material.

Bi₂O₃Refraction coefficient can be effectively improved.If the amount of the component is excessive, devitrification resistance ability often declines.Institute With the upper limit of the amount of the component should be preferably smaller than 10%, more preferable 6%.

Ta₂O₅Refraction coefficient can be effectively increased and improve chemical durability and devitrification resistance ability.But if component Amount it is excessive, then become difficult to keep above-mentioned optical constant, devitrification of glass degradation.So the upper limit of the amount of the component is answered 2% should be preferably smaller than.

It is a discovery of the invention that Bi₂O₃And Ta₂O₅Tellurium platinum alloy in glass melting process, therefore TeO can effectively be inhibited₂/ (Ta₂O₅+Bi₂O₃) weight ratio preferably between 0.3-0.6.If ratio is too low, desired value, glass is not achieved in optical constant Glass is easy devitrification；If ratio is excessively high, it is easy to damage platinum crucible in melting process, chemical durability of glass can also become Difference.

ZnO is indispensable component, it significantly reduces glass transition temperature (Tg) and improves glass system Devitrification resistance property.But if the amount of the component is insufficient, it cannot sufficiently realize this effect；However, if the component Measure excessive, then devitrification is less able.So the lower limit of the amount of the component should be preferably 10%, the upper limit of the amount of the component 20% should be preferably smaller than.

TiO₂Optical constant can effectively be adjusted and improve devitrification resistance ability.In glass system of the invention, such as The amount of the fruit component is excessive, then devitrification resistance does not increase not only and declines instead, but also the transmissivity in the shortwave area in luminous ray area Deteriorate.So the upper limit of the amount of the component should be preferably smaller than 20%, more preferable 15%, more preferably less than 10%.

Li₂O、Na₂O and K₂O can be effectively reduced glass transition temperature and improve the melting behaviour of glass.But such as The amount of the fruit component is excessive, then devitrification resistance ability often declines.So the upper limit of the amount of the component should be preferably 5%.

SrO can effectively adjust optical constant.But if the amount of the component is excessive, devitrification resistance ability is toward down Drop.So the upper limit of the amount of the component should be preferably 5%.

ZrO₂Optical constant can be effectively adjusted, devitrification resistance ability is improved and improves chemical durability.But it if should The amount of component is excessive, then devitrification resistance ability deteriorates, it becomes difficult to which glass transition temperature is remained to required low temperature.So The upper limit of the amount of the component should be preferably 4%, and lower limit is preferably 1%.

Sb₂O₃It can be optionally added into, for being defoamed in glass melting process.If the amount of the component is excessive, can Transmissivity decline in the shortwave area in light-exposed line area.So the upper limit of the amount of the component should be preferably 1%, more preferably 0.5%, most preferably 0.1%.

In the optical glass of this field, Nb can be generally added₂O₅And WO₃To improve the refractive index and devitrification resistance of glass Energy.But in glass system of the invention, preferably do not add Nb₂O₅And WO₃, this is primarily due to present invention discover that in this hair Nb is added in bright glass system₂O₅And WO₃Afterwards, the optical constant of glass can exceed desired value, and devitrification resistance property deteriorates, In addition the price of the two is more expensive, and the production cost of optical glass can be saved by not adding above two oxide.

Embodiment

Production method of the invention is: by Optical Glass Materials such as oxide, carbonate, nitrate according to the pre- of each composition Certainty ratio weighs, and melts, clarifies at 1200-1400 DEG C after mixing, stirring 2-4 hours, pouring after being reduced to proper temperature Enter in the metal pattern of preheating and slowly cool down, so that it may optical glass of the invention be made；Specifically it see the table below

Optical glass performance test

1) transmitted spectrum characteristic: optical glass transmitted spectrum characteristic is indicated with degree of staining (80/ λ 5 of λ), and glass is fabricated to The sample of 10mm ± 0.1mm thickness, it is λ 80 that test glass transmitance, which reaches 80% corresponding wavelength, and it is corresponding that transmitance reaches 5% Wavelength be λ 5.

2) chemical stability: using powder method according to GB/T17129 standard, gained optical glass is tested, by institute The chemical stability data obtained: acid resistance and water resistance.

3) it thermal expansion coefficient: is measured using the thermal dilatometer of Nai Chi company, the data that the coefficient of expansion uses is 20-100 DEG C Linear expansion coefficient α.

Concrete outcome is as follows:

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
						80/ λ 5 of degree of staining λ	37/28	37/29	38/29	37/28	38/28
Acid resistance	1 grade	1 grade	1 grade	1 grade	1 grade
						Water resistance	1 grade	1 grade	1 grade	1 grade	1 grade
α(×10⁷)	59.3	61.4	58.9	60.4	62.7

The content of present invention merely illustrates claimed some specific embodiments, one of them or more skill Documented technical characteristic can be combined with arbitrary one or more technical solutions in art scheme, these are combined and obtain Technical solution also in the application protection scope, the technical solution just as obtained from these are combined is disclosed in the present invention It is specifically recorded in content the same.

Claims

1. a kind of environmental protection optical glass of the low dispersion of high refractive index, refractive index (nd) is between 1.87-1.91, Abbe number (ν d) Between 38.5-42；It includes following component by weight percentage: the SiO of 1-10%₂, the B of 10-40%₂O₃, total amount is The La of 30wt%-45wt%₂O₃、Gd₂O₃And Y₂O₃, the TiO of the ZnO of 0.5wt%-20wt%, 1wt%-20wt%₂, 1wt%- The ZrO of 4wt%₂, total amount is the Li of 1-5wt%₂O、Na₂O and K₂The Ta of the SrO of O, 0-5wt%, 0-5wt%₂O₅, 0-5wt% TeO₂, the Bi of 0-10wt%₂O₃, the Sb of 0-1wt%₂O₃。

2. environmental protection optical glass according to claim 1, which is characterized in that SiO₂Content be 5-10%, B₂O₃Content For 15-25%.

3. environmental protection optical glass according to claim 1, which is characterized in that La₂O₃、Gd₂O₃And Y₂O₃Total content be 35-40%.Wherein, La₂O₃Content be 30-40%, Gd₂O₃Content is 0-5%, Y₂O₃Content be 0-5%.

4. environmental protection optical glass according to claim 1, which is characterized in that Ta₂O₅Content be 1-2%.

5. environmental protection optical glass according to claim 1, which is characterized in that TeO₂Content be 2-4%.

6. environmental protection optical glass according to claim 1, which is characterized in that Bi₂O₃Content be 4-6%.

7. environmental protection optical glass according to claim 1, which is characterized in that TeO₂/(Ta₂O₅+Bi₂O₃) weight ratio be Between 0.3-0.6.