CN111204969A - Optical glass, glass preform, optical element and optical instrument - Google Patents

Optical glass, glass preform, optical element and optical instrument Download PDF

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Publication number
CN111204969A
CN111204969A CN202010148865.8A CN202010148865A CN111204969A CN 111204969 A CN111204969 A CN 111204969A CN 202010148865 A CN202010148865 A CN 202010148865A CN 111204969 A CN111204969 A CN 111204969A
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Prior art keywords
bao
glass
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optical
optical glass
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孙伟
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides optical glass, which comprises the following components in percentage by weight: SiO 22：21～35％、B2O3：15～30％、BaO：31～50％、La2O3: 0 to 15% of (B)2O3+La2O3) The ratio of/BaO is 0.35 to 1.0. Through reasonable component design, the optical glass obtained by the invention has a lower thermal expansion coefficient and excellent intrinsic quality.

Description

Optical glass, glass preform, optical element and optical instrument
Technical Field
The invention relates to optical glass, in particular to optical glass with a refractive index of 1.58-1.65 and an Abbe number of 56-64, and a glass prefabricated member, an optical element and an optical instrument made of the optical glass.
Background
In recent years, with the rapid popularization and use of digital cameras, video cameras, and camera phones, optical materials have also been rapidly developed toward high precision and miniaturization. Optical elements and optical instruments are rapidly developed in terms of digitization, integration, and high refinement, and higher demands are made on the performance of optical glass used for optical elements of optical instruments and devices.
The optical glass with the refractive index of 1.58-1.65 and the Abbe number of 56-64 has important significance for simplifying an optical system and improving the imaging quality in the fields of optical design and optical communication. In the prior art, certain optical glass is easy to break in the processing process due to large thermal expansion coefficient, so that the yield of the glass is reduced; and the thermal shock resistance of the optical element is poor, and the service life of the optical element is shortened in the application process. The intrinsic quality of optical glass is critical to its application, and quality optical glass products require that they contain few or even no bubbles and inclusions.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an optical glass with a low thermal expansion coefficient and excellent intrinsic quality.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) the optical glass comprises the following components in percentage by weight: SiO 22：21～35％、B2O3：15～30％、BaO：31～50％、La2O3: 0 to 15% of (B)2O3+La2O3) The ratio of/BaO is 0.35 to 1.0.
(2) The optical glass according to (1), which comprises the following components in percentage by weight: gd (Gd)2O3：0～10％、Y2O3：0～10％、TiO2：0～5％、MgO：0～5％、CaO：0～5％、SrO：0～5％、Rn2O：0～8％、ZnO：0～5％、ZrO2：0～5％、Al2O3: 0-8% of a clarifying agent: 0 to 2%, the Rn2O is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2、SnO、CeO2One or more of (a).
(3) Optical glass, the composition of which is expressed in weight percentage by SiO2：21～35％、B2O3：15～30％、BaO：31～50％、La2O3：0～15％、Gd2O3：0～10％、Y2O3：0～10％、TiO2：0～5％、MgO：0～5％、CaO：0～5％、SrO：0～5％、Rn2O：0～8％、ZnO：0～5％、ZrO2：0～5％、Al2O3: 0-8% of a clarifying agent: 0 to 2% of a component (B) of2O3+La2O3) BaO is 0.35-1.0, and Rn is2O is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2、SnO、CeO2One or more of (a).
(4) The optical glass according to any one of (1) to (3), wherein the components are expressed by weight percentageThe method comprises the following steps: SiO 22: 23 to 33%, and/or B2O3: 17-26%, and/or BaO: 35 to 48% and/or La2O3: 1 to 12%, and/or Gd2O3: 0 to 5%, and/or Y2O3: 0 to 5%, and/or TiO2: 0-3%, and/or MgO: 0-3%, and/or CaO: 0-4%, and/or SrO: 0 to 3%, and/or Rn2O: 0-5%, and/or ZnO: 0 to 3%, and/or ZrO2: 0 to 3%, and/or Al2O3: 0.1-6%, and/or a clarifying agent: 0 to 1 percent.
(5) The optical glass according to any one of (1) to (3), which comprises the following components in percentage by weight: SiO 22: 25 to 32%, and/or B2O3: 20-25%, and/or BaO: 38-44% and/or La2O3: 3 to 10%, and/or Gd2O3: 0 to 2%, and/or Y2O3: 0 to 2%, and/or TiO2: 0-2%, and/or MgO: 0-2%, and/or CaO: 0-2%, and/or SrO: 0 to 2%, and/or Rn2O: 0-4%, and/or ZnO: 0 to 2%, and/or ZrO2: 0 to 2%, and/or Al2O3: 0.5 to 4%, and/or Sb2O3：0～1％。
(6) The optical glass according to any one of (1) to (3), wherein the content of each component satisfies one or more of the following 9 cases:
1)La2O3/SiO20.01 to 0.60;
2)La2O3/B2O30.01 to 0.80;
3)(B2O3+La2O3) The ratio of/BaO is 0.40-0.90;
4)B2O3/SiO20.45 to 1.20;
5)B2O3the ratio of/BaO is 0.35-0.80;
6)BaO/SiO21.0 to 2.0;
7)(TiO2+ZrO2)/BaO0.25 or less;
8)Rn2O/BaO is less than 0.20;
9)(ZnO+CaO+TiO2) The ratio of/BaO is 0.25 or less.
(7) The optical glass according to any one of (1) to (3), wherein the content of each component satisfies one or more of the following 9 cases:
1)La2O3/SiO20.10 to 0.45;
2)La2O3/B2O30.10 to 0.60;
3)(B2O3+La2O3) The ratio of/BaO is 0.55-0.75;
4)B2O3/SiO20.55 to 1.0;
5)B2O3the ratio of/BaO is 0.40-0.70;
6)BaO/SiO21.10 to 1.80;
7)(TiO2+ZrO2) The ratio of/BaO is less than 0.15;
8)Rn2O/BaO is less than 0.15;
9)(ZnO+CaO+TiO2) The ratio of/BaO is 0.20 or less.
(8) The optical glass according to any one of (1) to (3), wherein the content of each component satisfies one or more of the following 8 cases:
1)La2O3/SiO20.15 to 0.35;
2)La2O3/B2O30.16 to 0.40;
3)B2O3/SiO20.65 to 0.90;
4)B2O3the ratio of/BaO is 0.45-0.62;
5)BaO/SiO21.30 to 1.65;
6)(TiO2+ZrO2) The ratio of/BaO is less than 0.10;
7)Rn2O/BaO is less than 0.10;
8)(ZnO+CaO+TiO2) A BaO of0.10 or less.
(9) The optical glass according to any one of (1) to (3), which does not contain Rn2O, and/or does not contain ZnO, and/or does not contain Gd2O3And/or does not contain Y2O3And/or does not contain TiO2。
(10) The optical glass according to any one of (1) to (3), wherein the optical glass has a refractive index nd of 1.58 to 1.65, preferably a refractive index nd of 1.60 to 1.64, more preferably a refractive index nd of 1.61 to 1.63; abbe number vdThe Abbe number v is preferably 56-64d57 to 62, and more preferably Abbe number vdIs 58 to 61.
(11) The optical glass according to any one of (1) to (3), wherein the optical glass has a moisture resistance stability RC of 2 or more, preferably 1; and/or lambda80Less than or equal to 380nm, preferably lambda80Less than or equal to 370nm, more preferably lambda80Less than or equal to 365 nm; and/or lambda5Less than or equal to 330nm, preferably lambda5Less than or equal to 320nm, more preferably lambda5Less than or equal to 310 nm; and/or a density p of 3.70g/cm3Hereinafter, the density ρ is preferably 3.65g/cm3Hereinafter, the density ρ is more preferably 3.60g/cm3And/or coefficient of thermal expansion α-30/70℃Is 75X 10-7below/K, the thermal expansion coefficient is preferably α-30/70℃Is 70X 10-7A thermal expansion coefficient of α or less is more preferable-30/70℃Is 65X 10-7below/K; and/or Knoop hardness HKIs 550 multiplied by 107Pa or more, preferably Knoop hardness HKIs 560X 107Pa or more, more preferably Knoop hardness HKIs 570X 107Pa is above; and/or degree of wear FAThe abrasion degree is preferably 110 to 150, and F is the preferred abrasion degreeA120 to 145, more preferably a degree of abrasion FA125 to 140; and/or the degree of bubbling is class A or more, preferably the degree of bubbling is A0More preferably, the degree of bubbling is A00And (4) stages.
(12) A glass preform made of the optical glass according to any one of (1) to (11).
(13) An optical element produced from the optical glass according to any one of (1) to (11) or the glass preform according to (12).
(14) An optical device produced using the optical glass of any one of (1) to (11) or the optical element of (13).
The invention has the beneficial effects that: through reasonable component design, the optical glass obtained by the invention has a lower thermal expansion coefficient and excellent intrinsic quality.
Detailed Description
The optical glass of the present invention is obtained by the following steps, which are not limited to the above-described embodiments, and can be appropriately modified within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the gist of the present invention is not limited thereto, and the optical glass of the present invention may be simply referred to as glass in the following description.
[ optical glass ]
The ranges of the respective components of the optical glass of the present invention are explained below. In the present specification, unless otherwise specified, the contents and total contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter converted into the composition of oxides. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.
Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
< essential Components and optional Components >
SiO2Is a skeleton of optical glass, and can be used as a glass network forming body for maintaining the chemical stability of glassQualitative, improving the devitrification resistance of the glass when in SiO2The content is less than 21%, the above effects are not significant, and therefore SiO2The lower limit of the content of (B) is 21%, preferably 23%, more preferably 25%. When SiO is present2The content of (3) is more than 35%, the glass melting property is lowered, the transition temperature is raised, and it is difficult to obtain the refractive index desired in the present invention, therefore, SiO2The upper limit of the content of (B) is 35%, preferably 33%, more preferably 32%.
B2O3The glass is a component for forming a glass network structure, and the glass can obtain the effects of low dispersion and low-temperature softening property and optimize the abrasion degree of the glass by adding the glass. In the invention, more than 15 percent of B is introduced2O3To achieve the above effects, it is preferable to introduce 17% or more of B2O3More preferably, more than 20% of B is introduced2O3. When B is present2O3Above 30%, the chemical stability and resistance to devitrification of the glass are reduced. Thus, B2O3The upper limit of the content of (B) is 30%, preferably 26%, more preferably 25%.
In some embodiments of the invention, if B2O3With SiO2Ratio B of contents of2O3/SiO2When the value of (A) is less than 0.45, the glass has a high transition temperature and poor melting property, and is not favorable for discharging bubbles in the glass, and stones are likely to be generated in the glass; if B is2O3/SiO2The value of (A) exceeds 1.20, the chemical stability and devitrification resistance of the glass are lowered. On the other hand, by controlling B2O3/SiO2In the range of 0.45-1.20, the proper abrasion degree of the glass is favorably obtained. Therefore, in the present invention, B is preferred2O3/SiO20.45 to 1.20, and more preferably B2O3/SiO20.55 to 1.0, and preferably B2O3/SiO20.65 to 0.90.
Proper amount of TiO is introduced2Can make the glass more stable, reduce the viscosity of the glass and improve the water resistance of the glass, but introduces TiO in a large amount2After which the glass will be colored and devitrifiedTo increase, the refractive index is difficult to meet design requirements. Thus, TiO in the present invention2The upper limit of the content of (3) is 5%, preferably 3%, more preferably 2%, and further preferably TiO is not contained2。
Suitable amount of La2O3The refractive index and the chemical stability, especially the water resistance, of the glass can be improved by adding the glass into the glass; when the content is high, it is disadvantageous in lowering the thermal expansion coefficient of the glass. Therefore, La is defined in the present invention2O3The content of (b) is 15% or less, preferably 1 to 12%, more preferably 3 to 10%.
In some embodiments of the invention, the La is prepared by subjecting La2O3/SiO2The value of (A) is in the range of 0.01 to 0.60, the optical glass can easily obtain expected optical constants, has excellent anti-crystallization performance and chemical stability, and inhibits the increase of the temperature coefficient of the refractive index. Therefore, La is preferable2O3/SiO2The value of (A) is 0.01 to 0.60, more preferably La2O3/SiO2The value of (A) is 0.10 to 0.45, and La is more preferable2O3/SiO2The value of (A) is 0.15 to 0.35.
In some embodiments of the invention, the La is prepared by subjecting La2O3/B2O3The value of (A) is within the range of 0.01-0.80, so that the optical glass has low transition temperature and high hardness while easily obtaining proper abrasion degree. Therefore, La is preferable2O3/B2O3The value of (A) is 0.01 to 0.80, more preferably La2O3/B2O3The value of (A) is 0.10 to 0.60, and La is more preferable2O3/B2O3The value of (A) is 0.16 to 0.40.
Gd2O3The refractive index of the glass can be improved, but if the content is higher than 10%, the temperature coefficient of the refractive index of the glass is increased, the cost is rapidly increased, and the devitrification resistance of the glass is reduced. Thus, Gd2O3The content of (b) is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably no Gd is contained2O3。
Y2O3If the content is too large, devitrification resistance of the glass is likely to deteriorate, the temperature coefficient of refractive index of the glass increases, and the cost of the glass increases. Thus, Y in the present invention2O3The content of (B) is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably no introduction of Y2O3。
BaO has the effect of adjusting the refractive index of the glass, improving the transmittance of the glass, and resistance to devitrification, and can reduce the refractive index temperature coefficient and the thermal expansion coefficient of the glass in the present invention, and in the present invention, the above effect is obtained by introducing 31% or more of BaO, preferably 35% or more of BaO, and more preferably 38% or more of BaO. On the other hand, by setting the content of BaO to 50% or less, it is possible to reduce the decrease in chemical stability of the glass caused by an excessively high content of BaO, and the optical constant is out of the design range, and the content of BaO is preferably 48% or less, and more preferably 44% or less.
Through a large amount of experimental researches, the invention discovers that B2O3And La2O3The ratio (B) of the total content of (A) to the content of BaO2O3+La2O3) the/BaO exceeding 0.35 is advantageous in increasing the bubble degree of the glass, but when it exceeds 1.0, the thermal expansion coefficient of the glass increases. Therefore, in the present invention (B)2O3+La2O3) The ratio of/BaO is 0.35 to 1.0, preferably (B)2O3+La2O3) The ratio of/BaO is 0.40 to 0.90, and (B) is more preferable2O3+La2O3) The ratio of/BaO is 0.55-0.75.
In some embodiments of the invention, if B2O3the/BaO is lower than 0.35, the optical constant of the glass is difficult to meet the design requirement, and the density is increased; if B is2O3When the/BaO content exceeds 0.80, the hardness of the glass tends to be low and the chemical stability tends to be low. Therefore, in the present invention, B is preferred2O3A ratio of/BaO is 0.35 to 0.80, and B is more preferably2O3A ratio of/BaO is 0.40 to 0.70, and B is more preferably2O3The ratio of/BaO is 0.45-0.62.
In some embodiments of the invention, BaO is mixed with SiO2Ratio between contents of BaO/SiO2Has an important influence on the thermal stability and thermal expansion coefficient of the glass. In particular, if BaO/SiO2When the temperature coefficient of the glass is lower than 1.0, the thermal expansion coefficient and the temperature coefficient of the refractive index of the glass are increased, and the abrasion degree is deteriorated; if BaO/SiO2Above 2.0, the thermal and chemical stability of the glass is reduced. Therefore, BaO/SiO is preferred in the present invention21.0 to 2.0, more preferably BaO/SiO21.10 to 1.80, and further preferably BaO/SiO2Is 1.30 to 1.65.
MgO can reduce the melting temperature of the glass, but when the MgO is added excessively, the refractive index of the glass cannot meet the design requirement, the devitrification resistance and the stability of the glass are reduced, and the cost of the glass is increased. Therefore, the MgO content is limited to 0 to 5%, preferably 0 to 3%, and more preferably 0 to 2%.
CaO is useful for adjusting the optical constants of the glass and improving the processability of the glass, but when added in an excessive amount, the optical constants of the glass fail to meet the requirements and the devitrification resistance deteriorates. Therefore, the CaO content is limited to 0 to 5%, preferably 0 to 4%, and more preferably 0 to 2%.
The addition of SrO to glass makes it possible to adjust the refractive index and abbe number of the glass, but if the addition amount is too large, the chemical stability of the glass decreases and the cost of the glass rapidly increases. Therefore, the SrO content is limited to 0 to 5%, preferably 0 to 3%, and more preferably 0 to 2%.
ZrO2The optical constants can be adjusted to improve devitrification resistance and chemical stability, and when the content exceeds 5%, the glass melting property is lowered, the melting temperature is raised, inclusions in the glass are likely to appear, the transmittance is lowered, and it is difficult to maintain a low transition temperature. Thus, ZrO2The content is 0 to 5%, preferably 0 to 3%, more preferably 0 to 2%.
In some embodiments of the invention, if TiO2And ZrO2Ratio of the total content of (A) to BaO (TiO)2+ZrO2) If the amount of/BaO exceeds 0.25, the coloring degree and striae of the glass are deteriorated, and the meltability of the glass is lowered. Therefore, the temperature of the molten metal is controlled,preferred in the present invention is (TiO)2+ZrO2) A value of/BaO of 0.25 or less, more preferably (TiO)2+ZrO2) A BaO of 0.15 or less, more preferably (TiO)2+ZrO2) The ratio of/BaO is 0.10 or less.
The addition of an appropriate amount of ZnO to the glass can increase the refractive index of the glass and increase the acid resistance of the glass, and if the content thereof is more than 5%, the devitrification resistance of the glass is lowered while the high temperature viscosity is small and the thermal expansion coefficient and the refractive index temperature coefficient of the glass are increased. Therefore, in the present invention, the ZnO content is 0 to 5%, preferably 0 to 3%, more preferably 0 to 2%, and further preferably no ZnO is contained.
In some embodiments of the invention, the (ZnO + CaO + TiO) is controlled by2) The value of/BaO is less than 0.25, which can improve the bubble degree of the glass, improve the crystallization resistance of the glass and reduce the thermal expansion coefficient of the glass. Therefore, (ZnO + CaO + TiO) is preferable2) The content of/BaO is 0.25 or less, and (ZnO + CaO + TiO) is more preferable2) The content of/BaO is 0.20 or less, and (ZnO + CaO + TiO) is more preferable2) The value of/BaO is 0.10 or less.
Rn2O is an alkali metal oxide, Rn2O is Li2O、Na2O、K2O may improve the melting property of the glass, lower the glass transition temperature, and when the content exceeds 8%, the devitrification resistance and the thermal stability of the glass are deteriorated, so that Rn of the present invention2The O content is 0 to 8%, preferably 0 to 5%, more preferably 0 to 4%, and further preferably no introduction.
In some embodiments of the invention, the Rn is generated by reacting Rn2The O/BaO is less than 0.20, which is beneficial to obtaining lower density and transition temperature of the glass and improving the devitrification resistance of the glass. Therefore, Rn is preferred in the present invention2O/BaO is 0.20 or less, and Rn is more preferable2O/BaO is 0.15 or less, and Rn is more preferable2The ratio of O/BaO is 0.10 or less.
The invention introduces proper amount of Al2O3The stability and the devitrification resistance of the formed glass can be improved, and the strength of the glass is improved; when the content exceeds 8%, the chemical stability and meltability of the glass are deteriorated. Accordingly, the present inventionMiddle Al2O3The content of (b) is 0 to 8%, preferably 0.1 to 6%, more preferably 0.5 to 4%.
In the invention, 0-2% of Sb is added2O3、SnO、SnO2、CeO2One or more of the components can be used as a clarifying agent to improve the clarifying effect of the glass. But when Sb is2O3At contents exceeding 2%, the glass tends to have a reduced fining ability, and since the strong oxidizing action promotes the corrosion of the platinum or platinum alloy vessel from which the glass is melted and the deterioration of the forming mold, Sb is preferred in the present invention2O3The amount of (B) is 0 to 2%, preferably 0 to 1%, and more preferably 0 to 0.5%. SnO and SnO2However, when the content exceeds 2%, the glass is colored, or when the glass is heated, softened, press-molded or the like and then re-molded, Sn becomes a starting point of crystal nucleus generation, and thus, devitrification tends to occur. Thus the SnO of the invention2The content of (b) is preferably 0 to 2%, more preferably 0 to 1%, further preferably 0 to 0.5%, further preferably not contained; the SnO content is preferably 0 to 2%, more preferably 0 to 1%, even more preferably 0 to 0.5%, and even more preferably not contained. CeO (CeO)2Action and addition amount ratio of (B) and SnO2The content is preferably 0 to 2%, more preferably 0 to 1%, further preferably 0 to 0.5%, and further preferably not contained.
< component which should not be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.
In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As2O3And PbO. Although As2O3Has the effects of eliminating bubbles and better preventing the glass from coloring, but As2O3The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace.
The term "not introduced", "not containing" or "0%" as used herein means that the compound, molecule or element is not intentionally added as a raw material to the optical glass of the present invention; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.
The performance of the optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (nd) and Abbe number (. nu.) of optical glassd) The test was carried out according to the method specified in GB/T7962.1-2010.
The refractive index (nd) of the optical glass is 1.58-1.65, preferably 1.60-1.64, and more preferably 1.61-1.63; abbe number (v)d) 56 to 64, preferably 57 to 62, and more preferably 58 to 61.
< degree of bubbling >
The bubble degree of the optical glass is tested according to the method specified in GB/T7962.8-2010.
The optical glass of the present invention has a bubble degree of class A or more, preferably class A0More preferably A or more00And (4) stages.
< Density >
The density (. rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.
The optical glass of the present invention has a density (. rho.) of 3.70g/cm3Hereinafter, it is preferably 3.65g/cm3Hereinafter, more preferably 3.60g/cm3The following.
< coefficient of thermal expansion >
Coefficient of thermal expansion of optical glass (α)-30/70℃) And testing data at-30-70 ℃ according to a method specified in GB/T7962.16-2010.
The thermal expansion coefficient (α) of the optical glass of the present invention-30/70℃) Is 75X 10-7Preferably 70X 10 or less,/K-7A value of less than or equal to K, more preferably 65X 10-7and/K is less than or equal to.
< degree of abrasion >
Degree of abrasion (F) of optical glassA) The abrasion loss of the sample is multiplied by 100 under the same conditions, and the value is expressed by the following formula:
FA＝V/V0×100＝(W/ρ)/(W0/ρ0)×100
in the formula: v is the volume abrasion amount of the sample to be measured;
V0-the amount of wear of the standard sample volume;
w is the abrasion loss of the quality of the sample to be measured;
W0-abrasion loss of standard sample mass;
rho is the density of the sample to be measured;
ρ0-standard sample density.
Degree of abrasion (F) of optical glass of the present inventionA) Is 110 to 150, preferably 120 to 145, and more preferably 125 to 140.
< degree of coloration >
Coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention80And λ5) And (4) showing. Lambda [ alpha ]80It refers to the wavelength corresponding to the glass transmittance of 80%. Lambda [ alpha ]80Is a using toolA glass having a thickness of 10 + -0.1 mm with two opposing planes parallel to each other and optically polished, was measured for spectral transmittance in a wavelength region from 280nm to 700nm and exhibited a wavelength of transmittance of 80%. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glassinLight transmitted through the glass and having an intensity I emitted from a planeoutIn the case of light of (1) through (I)out/IinThe quantity expressed and also the transmission of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glasses, λ80A small value of (a) means that the glass itself is colored very little.
Lambda of the optical glass of the present invention80Less than or equal to 380nm, preferably lambda80Is less than or equal to 370nm, more preferably lambda80Less than or equal to 365 nm; lambda [ alpha ]5Less than or equal to 330nm, preferably lambda5Is less than or equal to 320nm, more preferably lambda5Is less than or equal to 310 nm.
< Knoop hardness >
Knoop hardness (H) of optical glassK) The test was carried out according to the test method specified in GB/T7962.18-2010.
Knoop hardness (H) of the optical glass of the present inventionK) Is 550 multiplied by 107Pa or more, preferably 560X 107Pa or more, more preferably 570X 107Pa or above.
< moisture resistance stability >
The moisture resistance stability RC (surface method) of the optical glass was measured according to the test method specified in GB/T7962.15-2010.
The moisture resistance stability (RC) of the optical glass of the present invention is 2 or more, preferably 1.
[ production method ]
The method for manufacturing the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the prepared furnace burden is put into a smelting furnace (such as a platinum crucible, a quartz crucible and the like) at 1200-1350 ℃ to be smelted after being mixed according to a conventional method, and homogeneous molten glass without bubbles and undissolved substances is obtained after clarification, stirring and homogenization, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
Glass preform and optical element
The glass preform can be produced from the optical glass produced by, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass preform may be produced by machining the optical glass by grinding, polishing, or the like, or by producing a preform for press molding from the optical glass, subjecting the preform to reheat press molding, and then polishing, or by precision press molding the preform obtained by polishing.
It should be noted that the means for producing the glass preform is not limited to the above means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
The glass preform of the present invention and the optical element are each formed of the above-described optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide optical elements such as various lenses and prisms having high optical values.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instruments ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, display equipment, monitoring equipment and the like.
Examples
< example of optical glass >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 1 to 2 were obtained by the above-mentioned method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2.
TABLE 1
Figure BDA0002401731110000131
Figure BDA0002401731110000141
TABLE 2
Figure BDA0002401731110000142
Figure BDA0002401731110000151
< glass preform example >
Various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens and a plano-concave lens, and preforms such as prisms were produced from the glasses obtained in examples 1 to 20 of optical glass by means of polishing or press molding such as reheat press molding and precision press molding.
< optical element example >
The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to desired values.
Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be coated with an antireflection film.
< optical Instrument example >
The optical element obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.

Claims (14)

1. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 22：21～35％、B2O3：15～30％、BaO：31～50％、La2O3: 0 to 15% of (B)2O3+La2O3) The ratio of/BaO is 0.35 to 1.0.
2. An optical glass according to claim 1, characterised in that it further comprises, in percentages by weight: gd (Gd)2O3：0～10％、Y2O3：0～10％、TiO2：0～5％、MgO：0～5％、CaO：0～5％、SrO：0～5％、Rn2O：0～8％、ZnO：0～5％、ZrO2：0～5％、Al2O3: 0-8% of a clarifying agent: 0 to 2%, the Rn2O is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2、SnO、CeO2One or more of (a).
3. Optical glass, characterized in that its composition, expressed in weight percentage, is represented by SiO2：21～35％、B2O3：15～30％、BaO：31～50％、La2O3：0～15％、Gd2O3：0～10％、Y2O3：0～10％、TiO2：0～5％、MgO：0～5％、CaO：0～5％、SrO：0～5％、Rn2O：0～8％、ZnO：0～5％、ZrO2：0～5％、Al2O3: 0-8% of a clarifying agent: 0 to 2% of a component (B) of2O3+La2O3) BaO is 0.35-1.0, and Rn is2O is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2、SnO、CeO2One or more of (a).
4. An optical glass according to any one of claims 1 to 3, characterised in that its components are expressed in weight percentage, in which: SiO 22: 23 to 33%, and/or B2O3: 17-26%, and/or BaO: 35 to 48% and/or La2O3: 1 to 12%, and/or Gd2O3: 0 to 5%, and/or Y2O3: 0 to 5%, and/or TiO2: 0-3%, and/or MgO: 0-3%, and/or CaO: 0-4%, and/or SrO: 0 to 3%, and/or Rn2O: 0-5%, and/or ZnO: 0 to 3%, and/or ZrO2: 0 to 3%, and/or Al2O3: 0.1-6%, and/or a clarifying agent: 0 to 1 percent.
5. An optical glass according to any one of claims 1 to 3, characterised in that its components are expressed in weight percentage, in which: SiO 22: 25 to 32%, and/or B2O3: 20-25%, and/or BaO: 38-44% and/or La2O3: 3 to 10%, and/or Gd2O3: 0 to 2%, and/or Y2O3: 0 to 2%, and/or TiO2: 0-2%, and/or MgO: 0-2%, and/or CaO: 0-2%, and/or SrO: 0 to 2%, and/or Rn2O: 0-4%, and-Or ZnO: 0 to 2%, and/or ZrO2: 0 to 2%, and/or Al2O3: 0.5 to 4%, and/or Sb2O3：0～1％。
6. An optical glass according to any one of claims 1 to 3, wherein the components are present in an amount, expressed as a percentage by weight, that satisfies one or more of the following 9 conditions:
1)La2O3/SiO20.01 to 0.60;
2)La2O3/B2O30.01 to 0.80;
3)(B2O3+La2O3) The ratio of/BaO is 0.40-0.90;
4)B2O3/SiO20.45 to 1.20;
5)B2O3the ratio of/BaO is 0.35-0.80;
6)BaO/SiO21.0 to 2.0;
7)(TiO2+ZrO2) The ratio of/BaO is less than 0.25;
8)Rn2O/BaO is less than 0.20;
9)(ZnO+CaO+TiO2) The ratio of/BaO is 0.25 or less.
7. An optical glass according to any one of claims 1 to 3, wherein the components are present in an amount, expressed as a percentage by weight, that satisfies one or more of the following 9 conditions:
1)La2O3/SiO20.10 to 0.45;
2)La2O3/B2O30.10 to 0.60;
3)(B2O3+La2O3) The ratio of/BaO is 0.55-0.75;
4)B2O3/SiO20.55 to 1.0;
5)B2O3the ratio of/BaO is 0.40-0.70;
6)BaO/SiO2is 1.10 to 1.80；
7)(TiO2+ZrO2) The ratio of/BaO is less than 0.15;
8)Rn2O/BaO is less than 0.15;
9)(ZnO+CaO+TiO2) The ratio of/BaO is 0.20 or less.
8. An optical glass according to any one of claims 1 to 3, wherein the components are present in an amount, expressed as a percentage by weight, that satisfies one or more of the following 8 conditions:
1)La2O3/SiO20.15 to 0.35;
2)La2O3/B2O30.16 to 0.40;
3)B2O3/SiO20.65 to 0.90;
4)B2O3the ratio of/BaO is 0.45-0.62;
5)BaO/SiO21.30 to 1.65;
6)(TiO2+ZrO2) The ratio of/BaO is less than 0.10;
7)Rn2O/BaO is less than 0.10;
8)(ZnO+CaO+TiO2) The ratio of/BaO is 0.10 or less.
9. An optical glass according to any one of claims 1 to 3, characterised in that Rn is absent2O, and/or does not contain ZnO, and/or does not contain Gd2O3And/or does not contain Y2O3And/or does not contain TiO2。
10. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a refractive index nd of 1.58 to 1.65, preferably a refractive index nd of 1.60 to 1.64, more preferably a refractive index nd of 1.61 to 1.63; abbe number vdThe Abbe number v is preferably 56-64d57 to 62, and more preferably Abbe number vdIs 58 to 61.
11. The optical glass according to any one of claims 1 to 3, wherein the optical glass has a moisture resistance stability RC of 2 or more, preferably a moisture resistance stability RC of 1; and/or lambda80Less than or equal to 380nm, preferably lambda80Less than or equal to 370nm, more preferably lambda80Less than or equal to 365 nm; and/or lambda5Less than or equal to 330nm, preferably lambda5Less than or equal to 320nm, more preferably lambda5Less than or equal to 310 nm; and/or a density p of 3.70g/cm3Hereinafter, the density ρ is preferably 3.65g/cm3Hereinafter, the density ρ is more preferably 3.60g/cm3And/or coefficient of thermal expansion α-30/70℃Is 75X 10-7below/K, the thermal expansion coefficient is preferably α-30/70℃Is 70X 10-7A thermal expansion coefficient of α or less is more preferable-30/70℃Is 65X 10-7below/K; and/or Knoop hardness HKIs 550 multiplied by 107Pa or more, preferably Knoop hardness HKIs 560X 107Pa or more, more preferably Knoop hardness HKIs 570X 107Pa is above; and/or degree of wear FAThe abrasion degree is preferably 110 to 150, and F is the preferred abrasion degreeA120 to 145, more preferably a degree of abrasion FA125 to 140; and/or the degree of bubbling is class A or more, preferably the degree of bubbling is A0More preferably, the degree of bubbling is A00And (4) stages.
12. A glass preform made of the optical glass according to any one of claims 1 to 11.
13. An optical element produced from the optical glass according to any one of claims 1 to 11 or the glass preform according to claim 12.
14. An optical device comprising the optical glass according to any one of claims 1 to 11 or the optical element according to claim 13.
CN202010148865.8A 2020-03-06 2020-03-06 Optical glass, glass preform, optical element and optical instrument Withdrawn CN111204969A (en)

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