CN110342813A

CN110342813A - Optical glass, optical element and optical instrument

Info

Publication number: CN110342813A
Application number: CN201910660941.0A
Authority: CN
Inventors: 孙伟
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: CDGM Glass Co Ltd; Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2019-07-22
Filing date: 2019-07-22
Publication date: 2019-10-18
Anticipated expiration: 2039-07-22
Also published as: CN110342813B

Abstract

The present invention provides a kind of optical glass, and the component of the optical glass in terms of weight percentage, contains: SiO₂: 35~50%；TiO₂: 21~38%；Na₂O:5~22%；K₂O:1~12%；BaO:1~15%；Nb₂O₅: 0~10%, wherein TiO₂/(BaO+Nb₂O₅) it is 1.5~10.0.It designs and matches by reasonable component, optical glass of the present invention has excellent processing performance, preferably have good abrasion degree and thermal expansion coefficient, meet the needs of photoelectric field while meeting desired refractive index and Abbe number.

Description

Optical glass, optical element and optical instrument

Technical field

The present invention relates to a kind of optical glass, be 1.65~1.73 more particularly, to a kind of refractive index, Abbe number be 25~ 35 optical glass and optical element and optical instrument.

Background technique

With the development of photovoltaic industry, miniaturization, lightweight, the requirement of high performance are proposed to optical element, this is just So that the demand for the optical glass that refractive index is 1.65~1.73, Abbe number is 25~35 is increasing.

The superiority and inferiority of the processing performance of optical glass directly decides the yields of glass elements.Optical glass is swollen due to heat Swollen coefficient it is bigger than normal, be easy cause to rupture in process, reduce the yields of glass；Also result in the property of its heat shock resistance It can be also poor.Optical glass in process, the abrasion degree for not being suitable for due to it, it will usually lead to the difficulty of processing of glass Increase, is unfavorable for the machining of optical glass.

Summary of the invention

Based on the above reasons, technical problem to be solved by the invention is to provide a kind of refractions with excellent processability The optical glass that rate is 1.65~1.73, Abbe number is 25~35.

The technical proposal for solving the technical problem of the invention is: optical glass, component in terms of weight percentage, Contain: SiO₂: 35~50%；TiO₂: 21~38%；Na₂O:5~22%；K₂O:1~12%；BaO:1~15%；Nb₂O₅: 0~ 10%, wherein TiO₂/(BaO+Nb₂O₅) it is 1.5~10.0.

Further, above-mentioned optical glass, component in terms of weight percentage, also contain: B₂O₃: 0~10%；With/ Or SrO:0~10%；And/or CaO:0~10%；And/or MgO:0~10%；And/or Ln₂O₃: 0~5%；And/or ZrO₂: 0 ~5%；And/or Li₂O:0~8%；And/or Al₂O₃: 0~5%；And/or ZnO:0~5%；And/or Sb₂O₃: 0~1%, wherein The Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One of or it is a variety of.

Optical glass, component in terms of weight percentage, by SiO₂: 35~50%；TiO₂: 21~38%；Na₂O:5~ 22%；K₂O:1~12%；BaO:1~15%；Nb₂O₅: 0~10%；B₂O₃: 0~10%；SrO:0~10%；CaO:0~ 10%；MgO:0~10%；Ln₂O₃: 0~5%；ZrO₂: 0~5%；Li₂O:0~8%；Al₂O₃: 0~5%；ZnO:0~5%； Sb₂O₃: 0~1% forms, wherein TiO₂/(BaO+Nb₂O₅) it is 1.5~10.0, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃ One of or it is a variety of.

Further, above-mentioned optical glass, in terms of weight percentage, each component content meets 6 kinds following component One or more of situation:

1)TiO₂/SiO₂It is 0.45~1.0；

2)B₂O₃/SiO₂It is 0.2 or less；

3)(ZrO₂+K₂O)/Na₂O is 0.05~1.0；

4)(Nb₂O₅+K₂O)/SiO₂It is 0.02~0.45；

5)Nb₂O₅/TiO₂It is 0.3 or less；

6) (CaO+MgO+ZnO)/BaO is 0.6 or less.

Further, above-mentioned optical glass, component is in terms of weight percentage, in which: SiO₂: 37~47%；With/ Or TiO₂: 25~35%；And/or Na₂O:8~18%；And/or BaO:2~10%；And/or Nb₂O₅: 0~7%；And/or K₂O:3 ~10%；And/or B₂O₃: 0~5%；And/or SrO:0~5%；And/or CaO:0~5%；And/or MgO:0~5%；And/or Ln₂O₃: 0~3%；And/or ZrO₂: 0~3%；And/or Li₂O:0~4%；And/or Al₂O₃: 0~3%；And/or ZnO:0~ 3%；And/or Sb₂O₃: 0~0.5%, wherein the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One of or it is a variety of.

Further, above-mentioned optical glass, in terms of weight percentage, each component content meets 7 kinds following component One or more of situation:

1)TiO₂/SiO₂It is 0.5~0.9；

2)B₂O₃/SiO₂It is 0.15 or less；

3)(ZrO₂+K₂O)/Na₂O is 0.1~0.8；

4)(Nb₂O₅+K₂O)/SiO₂It is 0.05~0.35；

5)Nb₂O₅/TiO₂It is 0.2 or less；

6) (CaO+MgO+ZnO)/BaO is 0.4 or less

7)TiO₂/(BaO+Nb₂O₅) it is 2.0~8.0.

Further, above-mentioned optical glass, component is in terms of weight percentage, in which: SiO₂: 40~45%；With/ Or TiO₂: 26~32%；And/or Na₂O:10~16%；And/or BaO:3~9%；And/or Nb₂O₅: 0~3%；And/or K₂O:4 ~9%；And/or B₂O₃: 0~3%；And/or SrO:0~3%；And/or CaO:0~3%；And/or MgO:0~3%；And/or Ln₂O₃: 0~1%；And/or ZrO₂: 0~2%；And/or Li₂O:0~3%；And/or Al₂O₃: 0~1%；And/or ZnO:0~ 1%, wherein the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One of or it is a variety of.

1)TiO₂/SiO₂It is 0.55~0.8；

2)B₂O₃/SiO₂It is 0.1 or less；

3)(ZrO₂+K₂O)/Na₂O is 0.2~0.6；

4)(Nb₂O₅+K₂O)/SiO₂It is 0.08~0.25；

5)Nb₂O₅/TiO₂It is 0.1 or less；

6) (CaO+MgO+ZnO)/BaO is 0.2 or less

7)TiO₂/(BaO+Nb₂O₅) it is 2.5~6.0.

Further, above-mentioned optical glass does not contain Li in component₂O；And/or ZrO is not contained₂；And/or it does not contain ZnO；And/or WO is not contained₃；And/or B is not contained₂O₃。

Further, the refractive index nd of above-mentioned optical glass is 1.65~1.73, preferably 1.66~1.72, more preferably It is 1.67~1.71；Abbe number ν_dIt is 25~35, preferably 28~33, more preferably 29~32.

Further, the acidproof effect stability D of above-mentioned optical glass_AMore than 2 classes, preferably 1 class；And/or it is resistance to Water acts on stability D_WMore than 2 classes, preferably 1 class；And/or density p is 3.2g/cm³Hereinafter, preferably 3.1g/cm³Hereinafter, More preferably 3.0g/cm³Below；And/or thermalexpansioncoefficientα_-30/70℃It is 98 × 10^-7/ K is hereinafter, preferably 96 × 10^-7/ K with Under, more preferably 93 × 10^-7/ K or less；And/or transition temperature T_gFor 600 DEG C hereinafter, preferably 590 DEG C hereinafter, more preferably 580 DEG C or less；And/or abrasion degree F_AIt is 150~200, preferably 160~190, more preferably 170~185.

Gas preform is made of above-mentioned optical glass.

Optical element is made of above-mentioned optical glass or above-mentioned gas preform.

Optical instrument is made of above-mentioned optical glass or above-mentioned optical element.

The beneficial effects of the present invention are: designing and matching by reasonable component, optical glass of the present invention is meeting expectation Refractive index and while Abbe number, there is excellent processing performance, preferably there is good abrasion degree and thermal expansion coefficient, it is full The demand of sufficient photoelectric field.

Specific embodiment

In the following, the embodiment of optical glass of the invention is described in detail, but the present invention is not limited to following realities Mode is applied, change appropriate can be carried out in the range of the object of the invention to be implemented.In addition, about repetitive specification, Although there is the case where omitting the description appropriate, but not therefore limit the purport invented.Sometimes this is sent out in the following contents Bright optical glass is referred to as glass.

[optical glass]

The each component range of optical glass of the present invention is illustrated below.In the present specification, if without special theory Bright, the content of each component is all using the weight percent table of the glass substance total amount relative to the composition for being converted into oxide Show.Herein, described " composition for being converted into oxide " refers to, as optical glass constituent of the invention raw material and make In the case that oxide, complex salt and hydroxide etc. decompose when melting and are changed into oxide, by the object of the oxide Matter total amount is as 100%.

Unless in particular situations it is further noted that numberical range listed herein includes upper and lower bound value, " more than " " following " includes endpoint value, and including all integers and score in the range, and is not limited to limited range when institute The occurrence of column.Herein referred "and/or" is inclusive, such as " A and/or B ", refers to only A, or only B, Huo Zhetong When have A and B.

SiO₂It is the skeleton of optical glass, generates body as glass network, has and maintain chemical durability of glass, improve glass The effect of glass devitrification resistance.Work as SiO₂When content is lower than 35%, it is difficult to reach said effect, therefore SiO₂The lower limit of content be 35%, preferred lower limit 37%, more preferable lower limit is 40%；Work as SiO₂Content be higher than 50% when, then glass melting reduce, Transition temperature rises, therefore, SiO₂Upper content limit be 50%, preferred upper limit 47%, the more preferable upper limit be 45%.

TiO₂Have the function of improving glass refraction and dispersion, and glass network can be participated in and formed, appropriate introduce can Keep glass more stable and reduce the viscosity of glass, passes through the TiO of 21% or more introducing in the present invention₂It is excellent to obtain said effect Select TiO₂Content lower limit be 25%, more preferable lower limit be 26%；But largely introduce TiO₂It can make glass visible light region afterwards The tendency towards devitrification of the decrease in transmission of shortwave part, glass increases, therefore, TiO in the present invention₂Upper content limit be 38%, it is excellent It chooses and is limited to 35%, the more preferable upper limit is 32%.

In certain embodiments of the present invention, work as TiO₂/SiO₂Lower than 0.45, the meltbility of glass is reduced, and striped degree becomes Difference works as TiO₂/SiO₂More than 1.0, the chemical stability and optical transmittance of glass decline, and density rises, therefore in the present invention TiO₂/SiO₂It is 0.45~1.0, preferably TiO₂/SiO₂It is 0.5~0.9, more preferable TiO₂/SiO₂It is 0.55~0.8.

Na₂O has the function of improving glass melting have apparent effect for improving melted effect, while may be used also The transition temperature of glass is reduced, the Na of 5% or more introducing is led in the present invention₂O is to obtain said effect, preferably Na₂Under the content of O It is limited to 8%, more preferable lower limit is 10%；Work as Na₂O content is more than 22%, and the chemical stability and weatherability of glass reduce, therefore Na₂The upper content limit of O is 22%, preferred upper limit 18%, and the more preferable upper limit is 16%.

K₂O has the function of improvement thermal stability and meltbility, passes through the K of 1% or more introducing in the present invention₂O is to obtain Obtain said effect, preferably K₂The content lower limit of O is 3%, more preferable K₂The content lower limit of O is 4%；But work as K₂The content of O is more than 12%, the devitrification resistance decline of glass, therefore K₂The upper content limit of O is 12%, preferred upper limit 10%, and the more preferable upper limit is 9%.

Li₂O can reduce the transition temperature of glass, but its content height to the acid-resistant stability and thermal expansion coefficient of glass not Benefit, and there is corrosion, therefore, Li for container (such as platinum crucible) is melted₂The content of O is preferably 8% hereinafter, more preferably 4% hereinafter, further preferably 3% or less.In some embodiments, even if a small amount of contains Li₂O also results in glass Thermal expansion coefficient exceed design requirement, devitrification resistance can reduce, therefore not contain Li still more preferably₂O。

MgO can reduce the refractive index and glass melting temperature of glass, but the refractive index of glass is not achieved when MgO is added excessive The devitrification resistance of design requirement, glass can decline with stability, while the cost of glass can rise.Therefore, content of MgO is limited to 0~10%, preferably 0~5%, more preferably 0~3%.

CaO helps to adjust the optical constant of glass, improves the processing performance of glass, but when CaO addition is excessive, can make The optical data for obtaining glass does not reach requirement, and devitrification resistance can deteriorate.Therefore, CaO content be limited to 0~10%, preferably 0~ 5%, more preferably 0~3%, CaO is not introduced further preferably.

SrO is added to the refractive index and Abbe number of adjustable glass in glass, if but additive amount it is excessive, the chemistry of glass Stability can decline, while the cost of glass also can rapid increase.Therefore, SrO content be limited to 0~10%, preferably 0~ 5%, more preferably 0~3%.

BaO is in the present invention the necessary component for adjusting glass refraction, improving glass transmitance and intensity, when its content Act on unobvious when lower than 1%, the content lower limit of preferably BaO is 2%, and the content lower limit of more preferable BaO is 3%；But when it contains Amount can then enable the devitrification resistance of glass and chemical stability be deteriorated more than 15%.Therefore, BaO upper content limit is 15%, preferably The upper limit is 10%, and the more preferable upper limit is 9%.

Nb₂O₅It is high-refraction high-dispersion component, is the optional components in the present invention, passes through control Nb in the present invention₂O₅Contain Amount is 10% hereinafter, can inhibit the reduction of glass devitrification resistance and thermal stability.Therefore, Nb in optical glass of the present invention₂O₅'s Content is for 10% hereinafter, preferably 7% hereinafter, more preferably 3% or less.

In the present invention, if TiO₂/(BaO+Nb₂O₅) be lower than 1.5, the abrasion degree of glass does not reach requirement, thermal stability and Devitrification resistance reduces, if TiO₂/(BaO+Nb₂O₅) more than 10.0, the thermal expansion coefficient of glass increases, and optical transmittance reduces.Cause This, TiO₂/(BaO+Nb₂O₅) range be 1.5~10.0, preferably TiO₂/(BaO+Nb₂O₅) range be 2.0~8.0, it is more excellent Select TiO₂/(BaO+Nb₂O₅) range be 2.5~6.0.

In certain embodiments of the present invention, by by Nb₂O₅/TiO₂Control is 0.3 hereinafter, the light of glass can be improved It learns transmitance and at glass stability, optimizes the chemical stability of glass, preferably Nb₂O₅/TiO₂For 0.2 hereinafter, glass is easier to obtain Suitable abrasion degree, more preferable Nb₂O₅/TiO₂It is 0.1 or less.

In certain embodiments of the present invention, if (Nb₂O₅+K₂O)/SiO₂Lower than 0.02, glass melting degradation, Transition temperature rises, if (Nb₂O₅+K₂O)/SiO₂More than 0.45, the thermal expansion coefficient of glass increases, chemical stability decline.Cause This, (Nb₂O₅+K₂O)/SiO₂Range be 0.02~0.45, preferably (Nb₂O₅+K₂O)/SiO₂Range be 0.05~0.35, more It is preferred that (Nb₂O₅+K₂O)/SiO₂Range be 0.08~0.25.

Al₂O₃The chemical stability of glass can be improved to a certain extent, but its content is excessive, the devitrification resistance of glass and Meltbility reduces, therefore its content is 5% hereinafter, preferably 3% hereinafter, more preferably 1% or less.

B₂O₃Have the function of improving glass melting, but when its content is higher than 10%, the chemical stability of glass and resistance to Increased devitrification resistance decline.Therefore, B in the present invention₂O₃Upper content limit be 10%, preferred upper limit 5%, the more preferable upper limit be 3%.? In some embodiments, by not introducing B₂O₃, can get desired chemical stability.

In certain embodiments of the present invention, if B₂O₃/SiO₂More than 0.2, the chemical stability and devitrification resistance of glass It reduces, optical transmittance is deteriorated, therefore B₂O₃/SiO₂For 0.2 hereinafter, preferably 0.15 hereinafter, more preferably 0.1 or less.

Ln₂O₃It is to improve glass refraction, and improve the component of chemical durability of glass, is in optical glass of the present invention Optional components, wherein Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One of or it is a variety of.By by Ln₂O₃Content control be 5% or less can be improved the devitrification resistance property of glass, and obtain desired refractive index and Abbe number.Therefore, in light of the invention It learns in glass, Ln₂O₃The upper limit value of content range is 5%, preferred upper limit 3%, and the more preferable upper limit is 1%.

ZnO is added in system glass of the present invention, and the refractive index and dispersion of adjustable glass reduce the transformation temperature of glass Degree, but when its content is more than 5%, the devitrification resistance of glass can decline, while high temperature viscosity is smaller, difficulty is brought to molding, and Increase the thermal expansion coefficient and thermal refractive index coefficient of glass.Therefore, the present invention in ZnO content be 0~5%, preferably 0~ 3%, more preferably 0~1%, it does not contain further preferably.

In certain embodiments of the present invention, by making (CaO+MgO+ZnO)/BaO 0.6 hereinafter, glass can be made to obtain The abrasion degree and hardness that must be suitable for, improve the water-fast effect stability of glass, preferably (CaO+MgO+ZnO)/BaO be 0.4 hereinafter, More preferably (CaO+MgO+ZnO)/BaO is 0.2 or less.

ZrO₂It is with the component for improving refractive index effect, when its content is more, the devitrification resistance of glass declines, the present invention Middle ZrO₂Content be 5% hereinafter, preferably 3% hereinafter, more preferably 2% hereinafter, not introducing further preferably.

In certain embodiments of the present invention, (ZrO is controlled₂+K₂O)/Na₂O can adjust glass in 0.05~1.0 range The melting behaviour and viscosity of glass, improve the processability of glass, reduce the molding striped of glass, improve the devitrification resistance of glass Can, preferably (ZrO₂+K₂O)/Na₂O is 0.1~0.8, more preferable (ZrO₂+K₂O)/Na₂O is 0.2~0.6.

By the Sb for being added 0~1%₂O₃、SnO₂, SnO and CeO₂One of or various ingredients as clarifying agent, can be with The clarifying effect for improving glass, is preferably added to 0~0.5% clarifying agent.But work as Sb₂O₃When content is more than 1%, glass has clarification The tendency of reduced performance, simultaneously because its strong oxidation promotes the deterioration of molding die, therefore Sb of the present invention₂O₃Addition Amount is for 1% hereinafter, preferably 0.5% or less.SnO₂, SnO can also be used as clarifying agent to add, but when its content is more than 1% When, glass can colour, or when heat, soften glass and carry out die forming etc. shape again when, Sn can become nucleus and generate Starting point, generate the tendency of devitrification, therefore SnO of the invention₂With the difference content of SnO be 1% hereinafter, preferably 0.5% with Under, it does not contain further preferably.CeO₂Effect and additive amount ratio and SnO₂Unanimously, content is 1% hereinafter, preferably 0.5% hereinafter, do not contain further preferably.

To make glass of the present invention while obtaining desired refractive index and Abbe number, the chemical stability and abrasion of glass Spend excellent, transition temperature and thermal expansion coefficient are low, preferably TiO₂、SiO₂、Na₂O、K₂Total content of O and BaO is 96% or more, More preferable TiO₂、SiO₂、Na₂O、K₂Total content of O and BaO is 97% or more, further preferred TiO₂、SiO₂、Na₂O、K₂O and Total content of BaO is 98% or more.

In the range of not damaging glass performance of the invention, above-mentioned other groups not referred to can be added as needed Point, such as P₂O₅、GeO₂、TeO₂、Bi₂O₃、Ta₂O₅And Ga₂O₃Etc. components, but individually or mixing the content containing the above component on Limit preferably 5%, the more preferable upper limit is 3%, and the further preferred upper limit is 1%, is not contained still more preferably.Of the invention In some embodiments, WO₃Introducing will lead to glass devitrification resistance can and degree of staining deteriorate, therefore preferably do not contain WO₃。

In glass of the present invention, the oxide of the transition metal 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, glass is also subject to coloration, the specific wavelength in visible light region generates absorption, thus The property for weakening raising visible light transmittance effect of the invention, therefore it is desirable, especially for the transmitance of visible light region wavelength The optical glass required, does not preferably contain actually.

The oxide of Th, Cd, Tl, Os, Be and Se have what control used to incline as harmful chemical substance in recent years To being to the measure of environmental protection in the manufacturing process of glass, the disposition after manufacturing procedure and commercialization not only must It needs.Therefore, it in the case where paying attention to the influence to environment, other than being inevitably mixed into, does not preferably contain actually They.Optical glass becomes the substance for not including pollution environment actually as a result,.Therefore, even if not taking special environment pair Measure in plan, optical glass of the invention are also able to carry out manufacture, processing and discard.

Environmental-friendly in order to realize, optical glass of the invention does not contain As₂O₃And PbO.Although As₂O₃With elimination gas Bubble and the effect for preferably preventing glass coloration, but As₂O₃Addition can increase glass smelting furnace is especially to the platinum of platinum smelting furnace Gold corrodes, and causes more platinum ions to enter glass, adversely affects to the service life of platinum smelting furnace.

" not introducing " " not containing " " 0% " described herein refers to not deliberately by the compound, molecule or element etc. It is added in optical glass of the present invention as raw material；But as the raw material and/or equipment of production optical glass, can exist certain It is not the impurity deliberately added or component, a small amount of or trace can contains in final optical glass, such situation is also in this hair In the protection scope of bright patent.

In the following, being illustrated to the performance of optical glass of the invention.

The refractive index (nd) and Abbe number (ν of optical glass_d) tested according to method as defined in GB/T 7962.1-2010.

The refractive index (nd) of optical glass of the present invention is 1.65~1.73, preferably 1.66~1.72, more preferably 1.67 ~1.71；Abbe number (ν_d) it is 25~35, preferably 28~33, more preferably 29~32.

The acidproof effect stability (D of optical glass_A) (powder method) according to method as defined in GB/T 17129 test.

The acidproof effect stability (D of optical glass of the present invention_A) it is 2 classes or more, preferably 1 class.

<water-fast effect stability>

The water-fast effect stability (D of optical glass_W) (powder method) according to method as defined in GB/T 17129 test.

The water-fast effect stability (D of optical glass of the present invention_W) it is 2 classes or more, preferably 1 class.

The density (ρ) of optical glass is tested by method as defined in GB/T7962.20-2010.

The density (ρ) of optical glass of the present invention is 3.2g/cm³Hereinafter, preferably 3.1g/cm³Hereinafter, more preferably 3.0g/ cm³Below.

Thermal expansion coefficient (the α of optical glass_-30/70℃) carry out testing -30 according to method as defined in GB/T7962.16-2010 ~70 DEG C of data.

Thermal expansion coefficient (the α of optical glass of the invention_-30/70℃) it is 98 × 10^-7/ K is hereinafter, preferably 96 × 10^-7/K Hereinafter, more preferably 93 × 10^-7/ K or less.

Transition temperature (the T of optical glass_g) tested by method as defined in GB/T7962.16-2010.

Transition temperature (the T of optical glass of the present invention_g) be 600 DEG C hereinafter, preferably 590 DEG C hereinafter, more preferably 580 DEG C Below.

Abrasion degree (the F of optical glass_A) refer under conditions of identical, the abrasion loss and standard sample (K9 of sample Glass) abrasion loss (volume) ratio multiplied by resulting numerical value after 100, be formulated as follows:

F_A=V/V₀× 100=(W/ ρ)/(W₀/ρ₀)×100

In formula: V-sample volume worn amount；

V₀- standard sample volume worn amount；

W-sample quality abrasion loss；

W₀- standard sample quality abrasion loss；

ρ-sample density；

ρ₀- standard sample density.

Abrasion degree (the F of optical glass of the present invention_A) it is 150~200, preferably 160~190, more preferably 170~185.

The bubble degree of optical glass is by the test of method as defined in GB/T7962.8-2010.

The bubble degree of optical glass of the present invention is B grades or more, preferably A grades or more, more preferably A₀Grade or more.

[manufacturing method]

The manufacturing method of optical glass of the present invention is as follows: glass of the invention is produced using conventional raw material and common process, It the use of carbonate, nitrate, sulfate, hydroxide, oxide etc. is raw material, according to a conventional method after ingredient, the furnace that will prepare Material is put into 1100~1350 DEG C of smelting furnace and is melted, and after clarified, stirring and homogenizing, obtains no bubble and be free of The homogeneous melt glass of undissolved substance casting mold and anneals this melten glass in mold.Those skilled in the art's energy Enough according to actual needs, raw material, process and technological parameter are properly selected.

[gas preform and optical element]

Molded such as the means of attrition process or reheating, compression molding precise punch forming means can be used, Gas preform is made by made optical glass.I.e., it is possible to mechanical by being ground and being ground to optical glass etc. Processing makes gas preform, or by the preform for making compression molding by optical glass, to the preform Carry out carrying out attrition process again after reheating is molded to make gas preform, or and to attrition process is carried out it is manufactured pre- Precise punch forming is carried out at parison to make gas preform.

It should be noted that the means for preparing gas preform are not limited to above-mentioned means.As described above, optics of the invention Glass is useful for various optical elements and optical design, wherein particularly preferably by optical glass of the invention formed it is pre- at Parison carries out molded, precise punch forming of reheating etc., the optical elements such as production lens, prism using the preform.

Gas preform and optical element of the invention is formed by the optical glass of aforementioned present invention.Glass of the invention Prefabricated component has excellent characteristics possessed by optical glass；Optical element of the invention has excellent spy possessed by optical glass Property, it is capable of providing the optical elements such as the costly various lens of optics, prism.

As the example of lens, can enumerate lens face be spherical surface or aspherical recessed meniscus shaped lens, male bend moon-shaped lens, The various lens such as biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.

[optical instrument]

Optical glass of the present invention is formed by optical element and can make such as camera installation, picture pick-up device, display equipment and prison Control the optical instruments such as equipment.

Embodiment

In order to further clearly illustrate and illustrate technical solution of the present invention, non-limiting embodiment below is provided.

The present embodiment obtains the optics glass with composition shown in 1~table of table 2 using the manufacturing method of above-mentioned optical glass Glass.In addition, the test method measures the characteristic of each glass through the invention, and measurement result is indicated in 1~table of table 2 In.

Table 1

Table 2

The means of the obtained glass of optical glass Examples 1 to 20 use such as attrition process or reheating are molded, The means of the compression moldings such as precise punch forming, it is saturating to make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, concave-concave The prefabricated component of the various lens such as mirror, plano-convex lens, plano-concave lens, prism etc..

By obtained these prefabricated components annealing of above-mentioned gas preform embodiment, the same of the deformation of inside glass is being reduced When be finely adjusted so that the optical characteristics such as refractive index reach desirable value.

Then, each prefabricated component is ground, ground, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The various lens such as biconcave lens, plano-convex lens, plano-concave lens, prism.It can also Tu Bufang on the surface of obtained optical element Reflectance coating.

By optical element made from above-mentioned optical element embodiment by optical design, by using one or more optics Element forms optical component or optical module, can be used for such as imaging device, sensor, microscope, medical science, number and throws Shadow, communication, optical communication technique/information transmission, optics/illumination in automotive field, photoetching technique, excimer laser, crystalline substance Piece, computer chip and integrated circuit and electronic device including such circuit and chip, or taking the photograph for automotive field As equipment and device.

Claims

1. optical glass, which is characterized in that its component in terms of weight percentage, contains: SiO₂: 35~50%；TiO₂: 21~ 38%；Na₂O:5~22%；K₂O:1~12%；BaO:1~15%；Nb₂O₅: 0~10%, wherein TiO₂/(BaO+Nb₂O₅) be 1.5~10.0.

2. optical glass as described in claim 1, which is characterized in that its component in terms of weight percentage, also contains: B₂O₃: 0~10%；And/or SrO:0~10%；And/or CaO:0~10%；And/or MgO:0~10%；And/or Ln₂O₃: 0~5%； And/or ZrO₂: 0~5%；And/or Li₂O:0~8%；And/or Al₂O₃: 0~5%；And/or ZnO:0~5%；And/or Sb₂O₃: 0~1%, wherein the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One of or it is a variety of.

3. optical glass, which is characterized in that its component in terms of weight percentage, by SiO₂: 35~50%；TiO₂: 21~ 38%；Na₂O:5~22%；K₂O:1~12%；BaO:1~15%；Nb₂O₅: 0~10%；B₂O₃: 0~10%；SrO:0~ 10%；CaO:0~10%；MgO:0~10%；Ln₂O₃: 0~5%；ZrO₂: 0~5%；Li₂O:0~8%；Al₂O₃: 0~5%； ZnO:0~5%；Sb₂O₃: 0~1% forms, wherein TiO₂/(BaO+Nb₂O₅) it is 1.5~10.0, the Ln₂O₃For La₂O₃、 Gd₂O₃、Y₂O₃、Yb₂O₃One of or it is a variety of.

4. the optical glass as described in claims 1 to 3 any claim, which is characterized in that its component is with weight percent It indicates, each component content meets one or more of following 6 kinds of situations:

1)TiO₂/SiO₂It is 0.45~1.0；

2)B₂O₃/SiO₂It is 0.2 or less；

3)(ZrO₂+K₂O)/Na₂O is 0.05~1.0；

4)(Nb₂O₅+K₂O)/SiO₂It is 0.02~0.45；

5)Nb₂O₅/TiO₂It is 0.3 or less；

6) (CaO+MgO+ZnO)/BaO is 0.6 or less.

5. the optical glass as described in claims 1 to 3 any claim, which is characterized in that its component is with weight percent It indicates, in which: SiO₂: 37~47%；And/or TiO₂: 25~35%；And/or Na₂O:8~18%；And/or BaO:2~10%； And/or Nb₂O₅: 0~7%；And/or K₂O:3~10%；And/or B₂O₃: 0~5%；And/or SrO:0~5%；And/or CaO:0 ~5%；And/or MgO:0~5%；And/or Ln₂O₃: 0~3%；And/or ZrO₂: 0~3%；And/or Li₂O:0~4%；With/ Or Al₂O₃: 0~3%；And/or ZnO:0~3%；And/or Sb₂O₃: 0~0.5%, wherein the Ln₂O₃For La₂O₃、Gd₂O₃、 Y₂O₃、Yb₂O₃One of or it is a variety of.

6. the optical glass as described in claims 1 to 3 any claim, which is characterized in that its component is with weight percent It indicates, each component content meets one or more of following 7 kinds of situations:

1)TiO₂/SiO₂It is 0.5~0.9；

2)B₂O₃/SiO₂It is 0.15 or less；

3)(ZrO₂+K₂O)/Na₂O is 0.1~0.8；

4)(Nb₂O₅+K₂O)/SiO₂It is 0.05~0.35；

5)Nb₂O₅/TiO₂It is 0.2 or less；

6) (CaO+MgO+ZnO)/BaO is 0.4 or less

7)TiO₂/(BaO+Nb₂O₅) it is 2.0~8.0.

7. the optical glass as described in claims 1 to 3 any claim, which is characterized in that its component is with weight percent It indicates, in which: SiO₂: 40~45%；And/or TiO₂: 26~32%；And/or Na₂O:10~16%；And/or BaO:3~9%； And/or Nb₂O₅: 0~3%；And/or K₂O:4~9%；And/or B₂O₃: 0~3%；And/or SrO:0~3%；And/or CaO:0~ 3%；And/or MgO:0~3%；And/or Ln₂O₃: 0~1%；And/or ZrO₂: 0~2%；And/or Li₂O:0~3%；And/or Al₂O₃: 0~1%；And/or ZnO:0~1%, wherein the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One of or it is more Kind.

8. the optical glass as described in claims 1 to 3 any claim, which is characterized in that its component is with weight percent It indicates, each component content meets one or more of following 7 kinds of situations:

1)TiO₂/SiO₂It is 0.55~0.8；

2)B₂O₃/SiO₂It is 0.1 or less；

3)(ZrO₂+K₂O)/Na₂O is 0.2~0.6；

4)(Nb₂O₅+K₂O)/SiO₂It is 0.08~0.25；

5)Nb₂O₅/TiO₂It is 0.1 or less；

6) (CaO+MgO+ZnO)/BaO is 0.2 or less

7)TiO₂/(BaO+Nb₂O₅) it is 2.5~6.0.

9. the optical glass as described in claims 1 to 3 any claim, which is characterized in that do not contain Li in its component₂O； And/or ZrO is not contained₂；And/or ZnO is not contained；And/or WO is not contained₃；And/or B is not contained₂O₃。

10. the optical glass as described in claims 1 to 3 any claim, which is characterized in that the refraction of the optical glass Rate nd is 1.65~1.73, preferably 1.66~1.72, more preferably 1.67~1.71；Abbe number ν_dIt is 25~35, preferably 28~33, more preferably 29~32.

11. the optical glass as described in claims 1 to 3 any claim, which is characterized in that the optical glass it is acidproof Act on stability D_AMore than 2 classes, preferably 1 class；And/or water-fast effect stability D_WMore than 2 classes, preferably 1 class；And/or Density p is 3.2g/cm³Hereinafter, preferably 3.1g/cm³Hereinafter, more preferably 3.0g/cm³Below；And/or thermal expansion coefficient α_-30/70℃It is 98 × 10^-7/ K is hereinafter, preferably 96 × 10^-7/ K is hereinafter, more preferably 93 × 10^-7/ K or less；And/or transformation temperature Spend T_gFor 600 DEG C hereinafter, preferably 590 DEG C hereinafter, more preferably 580 DEG C or less；And/or abrasion degree F_AIt is 150~200, preferably It is 160~190, more preferably 170~185.

12. gas preform is made of optical glass described in claim 1~11 any claim.

13. optical element, using described in optical glass described in claim 1~11 any claim or claim 12 Gas preform is made.

14. optical instrument, using described in optical glass described in claim 1~11 any claim or claim 13 Optical element is made.