CN110228945A

CN110228945A - A kind of optical glass and its gas preform, element and instrument

Info

Publication number: CN110228945A
Application number: CN201910575912.4A
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: 2019-06-28
Filing date: 2019-06-28
Publication date: 2019-09-13

Abstract

The invention discloses a kind of optical glass and its prefabricated components, element and instrument；It is counted according to wt%, comprising: SiO₂40~60%；B₂O₃1~15%；Rn₂O 0~20%；RO 5~35%；ZnO 0~8%；Rn₂O is selected from Na₂O、K₂O、Li₂One of O or a variety of, RO are selected from one of CaO, BaO, SrO, MgO or a variety of；Wherein, ZnO/ (B₂O₃+SiO₂) value be 0.17 hereinafter, B₂O₃/SiO₂Value be 0.14 or less.The present invention is cooperated by the mutual optimization for forming and matching between chemical element, in SiO₂Content be increased to 50wt% or more after, still can be by reducing the content of ZnO, while the mode for optimizing the proportion of other elements obtains high-weatherability, high transmittance, high rigidity, high chemical stability and more light-weighted effect.

Description

A kind of optical glass and its gas preform, element and instrument

Technical field

The present invention relates to glass arts, and in particular to a kind of optical glass and its prefabricated component, element and instrument.

Background technique

From the point of view of optical property, the glass that refractive index 1.54-1.62, Abbe number are 50-65 generally falls into traditional crown Glass, this kind of glass is usually by SiO₂-B₂O₃-RO-Rn₂O component system is constituted, wherein RO refers to alkaline earth oxide, Rn₂O Refer to alkali metal oxide.

A kind of optical glass based on silicic acid base, SiO are disclosed in documents CN1450010A (2002)₂'s Content is 36-66 moles of %, by the conversion of the documents embodiment: SiO in this document₂Content be 39.41- 48.32wt%, such glass have excellent resistance to environmental test capability, high transmittance, the higher coefficient of expansion and Young mould Amount, but the transition temperature (Tg) of such glass is also relatively high.

Since temperature when molding can be reduced by using the low glass of transition temperature (Tg), die surface oxygen is reduced Change, extends die life, to reduce manufacturing cost.

Thus, it is disclosed in patent CN101445322A (2008) a kind of without P₂O₅, avoid corruption of the element to mold Erosion, and there is low transition temperature (Tg), it is adapted for the dense-crown optical glass of precision press formation.The glass is mainly with 20 The SiO of~50wt%₂For main component, pass through B₂O₃、ZnO、Li₂O、Na₂O and K₂The content of O is adjusted, and then reaches reduction The effect of transition temperature (Tg).

It records in this document: SiO₂It is the neccessary composition to form glass network, when its content is lower than 20wt%, glass The chemical stability of glass is deteriorated, and optical constant is difficult to reach requirement, and when its content is more than 50wt%, the meltbility of glass becomes Difference, it is difficult to keep low softening temperature.

And it is 1.54-1.62, Abbe number that a kind of refractive index is disclosed in 108975687 A of documents CN (2015) For the high-weatherability of 50-65, high transmittance and the optical glass for being suitable for accurate die pressing.Wherein, SiO is recorded₂Content change It is counted as weight percent timing, range is in 51.74~59.98wt%.That is, by increasing SiO in 108975687 A of CN₂'s Content achievees the effect that improve weatherability in turn, but is improving SiO₂While content achievees the effect that improve weatherability, The problem of bringing meltbility and refractive index decline.Therefore, in 108975687 A of documents CN, inventor passes through increase Na₂O, the content of ZnO, CaO reduces Li₂O, the content of BaO improves meltbility and refractive index.

But in 108975687 A of CN, i.e. SiO₂In the increased system of content, before guaranteeing refractive index and dispersion It puts, although the weatherability and chemical stability of optical glass have certain promotion, but the effect promoted is not obvious, also, existing There is the hardness of the optical crown in technology unsatisfactory.

Summary of the invention

It is an object of that present invention to provide the optical glass that one kind newly matches, and pass through what is formed and match between chemical element Mutually optimization cooperation, in SiO₂Content be increased to 50wt% or more after, still can be while excellent by reducing the content of ZnO The mode for changing the proportion of other elements obtains high-weatherability, high transmittance, high rigidity, high chemical stability and more light-weighted crown Glass.

The present invention is achieved through the following technical solutions:

A kind of optical glass, is counted according to wt%, comprising:

Rn₂O is selected from Na₂O、K₂O、Li₂One of O or a variety of, RO are selected from one of CaO, BaO, SrO, MgO or more Kind；

Wherein, ZnO/ (B₂O₃+SiO₂) value be 0.17 hereinafter, B₂O₃/SiO₂Value be 0.14 or less.

Further, described

Further, Rn₂The Na that O is 0~10%₂The K of O and/or 0~10%₂O, it is preferred that Rn₂The Na that O is 1~10%₂O And/or 1~10% K₂O, it is furthermore preferred that Rn₂The Na that O is 2~8%₂The K of O and/or 2~8%₂O；And/or

The BaO for the CaO and/or 5~20% that RO is 0~15%, it is preferred that the CaO and/or 5~15% that RO is 5~15% BaO, it is furthermore preferred that RO be 5~12% CaO and/or 8~15% BaO.

Further,

B₂O₃/SiO₂Value be 0.05~0.14, it is preferred that B₂O₃/SiO₂Value be 0.05~0.10；And/or

ZnO/(B₂O₃+SiO₂) value be 0.01~0.17, it is preferred that ZnO/ (B₂O₃+SiO₂) value be 0.03~0.10； And/or

RO/(B₂O₃+SiO₂) value be 0.19~0.48, it is preferred that RO/ (B₂O₃+SiO₂) value be 0.29~0.33；

Rn₂O/(B₂O₃+SiO₂) value be set as 0.03~0.30, it is preferred that Rn₂O/(B₂O₃+SiO₂) value 0.06~ 0.28。

Further, the invention also includes:

TiO₂0~10%；And/or

Sb₂O₃0~2%；And/or

Al₂O₃0~10%.

Further, described

TiO₂1~8%, preferably 1~5%；And/or

Sb₂O₃0~1%, be preferably free of；And/or

Al₂O₃0~5%, preferably 0~2%.

Further, the refractive index nd of glass be 1.50~1.60, preferably 1.53~1.60, further preferably 1.55~ 1.58；Abbe number ν_dIt is 50~60, preferably 52~60, further preferably 55~58.

Further, the moisture resistant atmospheric action stability RC of glass is 2 classes or more, more than preferably 1 class；Antiacid effect is steady Qualitative RA is 2 classes or more, more than preferably 1 class；Acidproof effect stability D_AMore than 2 classes, more than preferably 1 class；Water-fast work With stability D_WMore than 2 classes, more than preferably 1 class.

Further, the λ of glass₈₀For 380nm hereinafter, preferably 370nm or less；The λ of glass₅For 350nm hereinafter, preferably 340nm or less.

Further, the transition temperature of glass is 620 DEG C hereinafter, preferably 600 DEG C or less；The density of glass is 3.50g/ cm³Hereinafter, preferably 3.0g/cm³Below.

The invention also discloses a kind of gas preform, optical element and optical instruments, and wherein gas preform uses Above-mentioned optical glass is made.Optical element is made of above-mentioned optical glass, or is made of above-mentioned gas preform.Light Instrument is learned, is made of above-mentioned optical element.

Compared with prior art, the present invention having the following advantages and benefits:

1, the present invention is cooperated by the mutual optimization for forming and matching between chemical element, in SiO₂Content be increased to , still can be by the content of reduction ZnO after 50wt% or more, while the mode for optimizing the proportion of other elements obtains high durable Property, high transmittance, high rigidity and more light-weighted crown glass；

2, weatherability of the invention is very significant, and transition temperature Tg and Knoop hardness is significantly better than the prior art Effect, the present invention have hardness higher, and glass machinery intensity is higher, and anti-press capacity is higher in use process, and specific gravity is lower easily In the lightweight the advantages that.

Specific embodiment

To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, the present invention is made Further to be described in detail, exemplary embodiment of the invention and its explanation for explaining only the invention, are not intended as to this The restriction of invention.In the present specification, if without specified otherwise, the content of each component (ingredient) is all using relative to conversion It is indicated at the weight percent of the glass substance total amount of the composition of oxide.Herein, described " composition for being converted into oxide " Refer to, in the case that the raw material as optical glass constituent of the invention decomposes when melting and is changed into oxide, by this The substance total amount of oxide 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, all integers and score in the range, and is not limited to listed specific when limited range Value.Herein referred "and/or" is inclusive, such as " A and/or B ", refers to only A, perhaps only B or have simultaneously A and B。

[necessary component and optional components]

In the present invention, SiO₂It is the Network former of glass, is the bulk composition for constituting glass, in glass system of the present invention In, when its content is higher than 60%, the fusing point of glass can be increased, and glass melting becomes difficult, and high temperature viscosity rises, the refraction of glass Rate decline；When its content is lower than 40%, the chemical stability of glass can be deteriorated, and weatherability can reduce.Therefore, of the invention SiO₂Content be limited between 40~60%, preferably 50~60%, be more preferably 53~60%.

B₂O₃It is also one of the composition for constituting glass skeleton, can be improved glass refraction, reduce dispersion, improves glass light Pool, meanwhile, the B₂O₃It is good cosolvent, it is appropriate that the solubility property that can significantly improve glass raw material is added, so that raw material melts It is more easier, stability, glass is more preferable.And B₂O₃Different content under will form different structures, the weatherability of glass is generated Large effect.Under system of the invention, in order to obtain preferable weatherability and lower high temperature viscosity, B simultaneously₂O₃ Content be limited between 1~15%, preferably 1~10%, be more preferably 3~8%.

In system of the present invention, work as B₂O₃/SiO₂Value it is too high or too low, can reduce the meltbility, weatherability, change of glass It learns stability, the high temperature viscosity of glass is made to become larger, be unfavorable for glass molding.The present invention passes through SiO₂The increase of content, and limit B₂O₃/SiO₂Ratio, can improving weatherability and in the case where chemical stability, to obtain lower high temperature viscosity, and Reach refractive index and dispersion demand provides premise, in the present invention system, B₂O₃/SiO₂Ratio be limited to 0.14 hereinafter, it is preferred that It is 0.05~0.14, is more preferably 0.05~0.10.

Rn₂O is alkali metal oxide, including Na₂O、K₂O、Li₂O etc., it is appropriate that the transition temperature that can reduce glass is added, change The fusible property and weatherability of kind glass reduce high temperature viscosity and crystallization tendency；Wherein Na₂O content is too low, high temperature viscosity of glass Design object is not achieved；If excessively high, glass weatherability will be remarkably decreased.K₂O is larger to the destruction of glass weatherability, therefore its content Cannot be excessively high, it is excessively high to will affect weatherability.Li₂The ability that O destroys glass network is most strong, reduces the ability of high temperature viscosity of glass most To be significant, if content is too low, the effect for reducing high temperature viscosity is not significant；If too high levels, the devitrification resistance energy of glass can be reduced. Therefore, Rn in the present invention₂The content of O is limited to 0~20%, preferably 2~20%, is more preferably 5~13%.Some In embodiment, Rn₂O is selected from Na₂O、K₂O、Li₂One of O or a variety of；Preferably, Rn₂The Na that O is 0~10%₂O and 0~ 10% K₂O；More preferably, Rn₂The Na that O is 1~10%₂The K of O and 1~10%₂O；It is highly preferred, Rn₂O is 2~8% Na₂The K of O and 2~8%₂O。

In order to obtain preferable glass transformation temperature, the high temperature viscosity of glass is reduced, while improving glass weatherability and change Learn stability, Rn₂O/(B₂O₃+SiO₂) value be 0.03~0.30, it is preferred that Rn₂O/(B₂O₃+SiO₂) value be set as 0.06 ~0.28.In system of the invention, in the range when, glass have lower transition temperature, can when heating glass Form glass with lower temperature, and can reduce precision glass mold molding when and mold the extent of reaction, extend mould The service life of tool, and can guarantee that glass has preferable weatherability simultaneously.

RO is alkaline earth oxide, and including CaO, BaO, MgO etc., adjustable glass refraction in glass is added in RO in right amount Rate and dispersion, while glass ingredient can be balanced, so that glass is tended towards stability, it is steady to improve glass weatherability, devitrification resistance and chemistry It is qualitative.In the present invention system, the content of RO is limited between 5~35%, preferably 10~30%, more preferably for 15~ 25%.Wherein, RO is selected from one of CaO, BaO, SrO, MgO or a variety of；Preferably, the CaO and 5 that RO is 0~15%~ 20% BaO；More preferably, the BaO for the CaO and 5~15% that RO is 5~15%；Highly preferred, RO is 5~12% The BaO of CaO and 8~15%.

In some embodiments, by controlling RO/ (B₂O₃+SiO₂) value can be further improved the fusible of glass Property, obtain suitable high temperature viscosity, easy to form and processing, in the present invention system, preferred RO/ in some embodiments (B₂O₃+SiO₂) value between 0.19~0.48, it is preferred that RO/ (B₂O₃+SiO₂) value be 0.29~0.33, more can be into one Step reduces the transition temperature (Tg) of optical glass.

In the appropriate addition glass of ZnO, the transition temperature of glass can be significantly reduced, improve the devitrification resistance energy of glass. But if ZnO additional amount is excessive, the devitrification resistance of glass can decline, and cannot meet other performances simultaneously, if very few, Preferable transition temperature cannot then be obtained.In glass system of the invention, ZnO content is limited between 0~8%, preferably 1~ 8%, it is more preferably 2~6%.

In system of the invention, pass through ZnO and B₂O₃+SiO₂Ratio optimize, can effectively meet refractive index and While the demand of dispersion, the weatherability of glass, chemical stability are further increased, and reduce high temperature viscosity, present system Middle ZnO/ (B₂O₃+SiO₂) value be set as 0.17 hereinafter, preferably 0.01~0.17, more preferably, ZnO/ (B₂O₃+SiO₂) Value be 0.03~0.10, specific gravity of glass can be further decreased and guarantee higher hardness, lower glass transformation temperature.

TiO₂Belong to high refraction oxide, the refractive index and dispersion of glass can be significantly improved by being added into glass, simultaneously The weatherability of glass can be improved.But if TiO2 is excessively added in glass, glass coloration is easily caused, enter₈₀With enter₅It reaches Fall short value.TiO₂Additional amount be limited to 0~10%, preferably 1~8%, be more preferably 1~5%.

Al₂O₃Introducing can reduce the devitrification behavior of glass, improve thermal stability and chemical stability, but its additive amount Conference is crossed to glass tape to melt difficulty, the risk of crystallization property decline, and specific gravity of glass increase can be made to be unfavorable for product Lightweight, therefore, in this glass system, Al₂O₃Additional amount be limited to 0~10%, preferably 0~5%, more preferably It is 0~2%.

Sb₂O₃After being added in glass, can make bubble elimination become to be more easier, preferably improve glass refractive index and Dispersion.Sb₂O₃Additional amount is limited to 0~2%, preferably 0~1%, is more preferably free of.

Refer to it should be noted that " not including " " not containing " " not introducing " " 0% " documented by the present invention without intentional The compound, molecule or element etc. are added in glass of the invention as raw material；But as production glass raw material and/ Or equipment, can exist certain is not the impurity deliberately added or component, a small amount of or trace can be contained in final glass, such Situation is also in the scope of protection of the patent of the present invention.

In the following, the performance and test method to fluorphosphate glass of the invention are illustrated.

1, degree of staining (λ₈₀/λ₅)

The shortwave transmitted spectrum characteristic degree of staining (λ of glass of the present invention₈₀/λ₅) indicate.λ₈₀Refer to that glass transmittance reaches Corresponding wavelength, λ when 80%₅Refer to that glass transmittance reaches corresponding wavelength when 5%, wherein λ₈₀Measurement be using having The glass with a thickness of 10 ± 0.1mm of two parallel to each other and optical polish opposite planes, measures from 280nm to 700nm Spectral transmission in wavelength domain and the wavelength for showing transmissivity 80%.So-called spectral transmission or transmissivity are to glass Above-mentioned surface vertically incident intensity I_inLight, project intensity I through glass and from plane_outLight in the case where lead to Cross I_out/I_inThe amount of expression, and also contain the transmissivity of the surface reflection loss on the above-mentioned surface of glass.The folding of glass It is higher to penetrate rate, surface reflection loss is bigger.

Use the glass sample with a thickness of 10 ± 0.1mm with two optical polish planes relative to each other, measurement point Light transmission is calculated according to its result.

In optical glass of the invention, λ₈₀The small coloring for meaning glass itself of value it is few.Optical glass of the invention is saturating Corresponding wavelength (λ when penetrating than reaching 80%₈₀) it is no more than 380nm, preferably not greater than 370nm；Its glass transmittance reaches Corresponding wavelength (λ when 5%₅) it is not more than 350nm, preferably not greater than 340nm.

2, transition temperature T_g

Transition temperature T_gRefer to glass specimen from room temperature to the temperature T that hangs down that speeds_s, low-temperature region and high-temperature area straight line Temperature corresponding to the intersection point of part extended line intersection.Transition temperature T_gIt is surveyed by method as defined in GB/T7962.16-2010 Amount.

The transition temperature of glass is 620 DEG C hereinafter, preferably 600 DEG C or less；The density of glass is 3.50g/cm³Hereinafter, Preferably 3.0g/cm³Below.

3, refractive index and Abbe number

Refractive index and Abbe number are tested according to method as defined in GB/T7962.1-2010.

The refractive index nd of glass of the present invention be 1.50~1.60, preferably 1.53~1.60, further preferably 1.55~ 1.58；Abbe number ν_dIt is 50~60, preferably 52~60, further preferably 55~58.

4, chemical stability (D_W、D_A、RA、RC)

For optical glass device during manufacture and use, polished surface resists the various etching medium effects such as water, acid Ability be known as the chemical stability of optical glass, depend primarily on the chemical constituent of glass.By the test of GB/T 17129 Method tests water-fast effect stability D_w, acidproof effect stability D_A；It is anti-by the test method test of GB/T 7962.14-2010 Acid effect stability RA；Moisture resistant atmospheric action stability RC is tested by the test method of GB/T 7962.15-2010.

The moisture resistant atmospheric action stability RC of glass of the present invention is 2 classes or more, more than preferably 1 class；Antiacid effect is steady Qualitative RA is 2 classes or more, more than preferably 1 class；Acidproof effect stability D_AMore than 2 classes, more than preferably 1 class；Water-fast work With stability D_wMore than 2 classes, more than preferably 1 class.

5, weatherability

By sample be placed on relative humidity be 90% saturated steam environment test box in, 40 DEG C~50 DEG C every 1h alternate cycles recycle 15 periods.Weatherability classification is divided according to the turbidity variable quantity of sample placement front and back, wherein turbidity Refer to colouless optical glass by after atmospheric corrosion, surface generates " hickie " or " blushing " iso-metamorphism layer.The erosion of glass surface Degree corrodes forward and backward turbidity difference by measurement sample to determine.Turbidimetry use mist degree relative error of indicating value ± 5% with Interior turbidimeter with integrating sphere carries out.The following table 1 is weatherability classification situation:

Table 1

Glass weatherability of the invention is not less than 2 grades, preferably not less than 1 grade.

6, Knoop hardness Hk

Knoop hardness Hk is tested according to method as defined in GB/T7962.18-2010.

Knoop hardness Hk of the invention is 550 × 10⁷Pa or more, preferably 565 × 10⁷Pa or more.

Embodiment

A kind of optical glass, is counted according to wt%, and composition and performance is as shown in 2~table of table 4.

Table 2

Table 3

Table 4

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.By using the above-mentioned optical element with excellent properties on the optical instrument, this can be improved The customer experience of optical instrument.It should be noted that above-mentioned be equally applicable to for feature and advantage described in optical element The optical instrument, details are not described herein again.

Claims

1. a kind of optical glass, which is characterized in that counted according to wt%, comprising:

Rn₂O is selected from Na₂O、K₂O、Li₂One of O or a variety of, RO are selected from one of CaO, BaO, SrO, MgO or a variety of；

2. a kind of optical glass according to claim 1, which is characterized in that it is counted according to wt%, it is described

3. a kind of optical glass according to claim 1, which is characterized in that it is counted according to wt%, it is described

4. a kind of optical glass according to claim 1, which is characterized in that

Rn₂The Na that O is 0~10%₂The K of O and/or 0~10%₂O, it is preferred that Rn₂The Na that O is 1~10%₂O and/or 1~10% K₂O, it is furthermore preferred that Rn₂The Na that O is 2~8%₂The K of O and/or 2~8%₂O；And/or

The BaO for the CaO and/or 5~20% that RO is 0~15%, it is preferred that the CaO's and/or 5~15% that RO is 5~15% BaO, it is furthermore preferred that the BaO for the CaO and/or 8~15% that RO is 5~12%.

5. a kind of optical glass according to claim 1, which is characterized in that

ZnO/(B₂O₃+SiO₂) value be 0.01~0.17, it is preferred that ZnO/ (B₂O₃+SiO₂) value be 0.03~0.10；With/ Or

Rn₂O/(B₂O₃+SiO₂) value be set as 0.03~0.30, it is preferred that Rn₂O/(B₂O₃+SiO₂) value 0.06~0.28.

6. a kind of optical glass according to claim 1, which is characterized in that counted according to wt%, further includes:

TiO₂0~10%；And/or

Sb₂O₃0~2%；And/or

Al₂O₃0~10%.

7. a kind of optical glass according to claim 6, which is characterized in that it is counted according to wt%, it is described

TiO₂1~8%, preferably 1~5%；And/or

Sb₂O₃0~1%, be preferably free of；And/or

Al₂O₃0~5%, preferably 0~2%.

8. any a kind of optical glass according to claim 1~7, which is characterized in that the refractive index nd of glass is 1.50 ~1.60, preferably 1.53~1.60, further preferably 1.55~1.58；Abbe number ν_dIt is 50~60, preferably 52~60, Further preferably 55~58.

9. any a kind of optical glass according to claim 1~7, which is characterized in that the moisture resistant atmospheric action of glass Stability RC is 2 classes or more, more than preferably 1 class；Antiacid effect stability RA is 2 classes or more, more than preferably 1 class；It is acidproof Act on stability D_AMore than 2 classes, more than preferably 1 class；Water-fast effect stability D_WMore than 2 classes, more than preferably 1 class.

10. any a kind of optical glass according to claim 1~7, which is characterized in that the λ of glass₈₀For 380nm hereinafter, Preferably 370nm or less；The λ of glass₅For 350nm hereinafter, preferably 340nm or less.

11. any a kind of optical glass according to claim 1~7, which is characterized in that the transition temperature of glass is 620 DEG C hereinafter, preferably 600 DEG C or less；The density of glass is 3.50g/cm³Hereinafter, preferably 3.0g/cm³Below；Hardness Hk is 550×10⁷Pa or more, preferably 565 × 10⁷Pa or more.

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

13. optical element is made of any optical glass of claim 1~11, or uses claim 12 institute The gas preform stated is made.

14. optical instrument is made of the optical element described in claim 12.