CN111533446B

CN111533446B - Optical glass, glass preform, optical element and optical instrument

Info

Publication number: CN111533446B
Application number: CN202010454926.3A
Authority: CN
Inventors: 赖德光
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2020-05-26
Filing date: 2020-05-26
Publication date: 2022-04-15
Anticipated expiration: 2040-05-26
Also published as: CN111533446A

Abstract

The invention provides an optical glass, which comprises the following components in percentage by weight: p⁵⁺：10～20％；Ba²⁺：25～40％；Sr²⁺：0.5～8％；Zn²⁺：3～12％；Nb⁵⁺：0～6％；Gd³⁺：0～6％；Y³⁺：0～6％；Na⁺：1～10％；F^‑：2～12％；O^2‑: 18 to 32% of P, wherein⁵⁺/(Zn²⁺+Na⁺) 0.5 to 4.0 (Nb)⁵⁺+Sr²⁺)/Na⁺0.1 to 8.0. Through reasonable component design, the optical glass obtained by the invention has higher bubble degree grade while meeting the expected refractive index and Abbe number.

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 1.55-1.64 and an Abbe number of 56-63, and a glass prefabricated member, an optical element and an optical instrument made of the optical glass.

Background

The lens system of an optical instrument is usually designed by combining a plurality of glass lenses with different optical properties. 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 1.56-1.64 and the Abbe number of 56-64 has very important significance for simplifying an optical system and improving the imaging quality in the fields of optical design and optical communication, and can be applied to the fields of vehicles and the like.

The optical glass is generally applied to precise optical instruments, has extremely high requirements on the internal quality, and if the content of bubbles, inclusions and the like in the optical glass is high, the applicability of the optical glass is reduced, and even the optical glass is directly scrapped. Therefore, in the development of modern optical technology, further improvement of the optical glass in the degree of bubble and other related properties is required.

Disclosure of Invention

The invention aims to provide optical glass with higher bubble degree grade.

The technical scheme for solving the technical problem is as follows:

(1) the optical glass comprises the following components in percentage by weight: p⁵⁺：10～20％；Ba²⁺：25～40％；Sr² ⁺：0.5～8％；Zn²⁺：3～12％；Nb⁵⁺：0～6％；Gd³⁺：0～6％；Y³⁺：0～6％；Na⁺：1～10％；F^-：2～12％；O^2-: 18 to 32% of P, wherein⁵⁺/(Zn²⁺+Na⁺) 0.5 to 4.0 (Nb)⁵⁺+Sr²⁺)/Na⁺0.1 to 8.0.

(2) The optical glass according to (1), which comprises the following components in percentage by weight: al (Al)³⁺: 0 to 5 percent; and/or Mg²⁺: 0 to 3 percent; and/or Ca²⁺: 0 to 3 percent; and/or La³⁺: 0 to 5 percent; and/or Li⁺: 0 to 5 percent; and/or K⁺: 0 to 5 percent; and/or W⁶⁺: 0 to 5 percent; and/or Ti⁴⁺: 0 to 5 percent; and/or Zr⁴⁺: 0 to 5 percent; and/or Si⁴⁺: 0 to 5 percent; and/or B³⁺: 0 to 5 percent; and/or Sb³⁺: 0 to 1 percent; and/or Ce⁴⁺: 0 to 1 percent; and/or Sn⁴⁺: 0 to 1 percent; and/or Cl^-：0～1％。

(3) The optical glass comprises the following components in percentage by weight: p⁵⁺：10～20％；Sr²⁺：0.5～8％；Zn² ⁺：3～12％；Nb⁵⁺：0～6％；Na⁺：1～10％；F^-：2～12％；O^2-: 18 to 32% of P, wherein⁵⁺/(Zn²⁺+Na⁺) 0.5 to 4.0 (Nb)⁵⁺+Sr²⁺)/Na⁺The glass is 0.1 to 8.0, and the optical glass has a bubble degree of class A or higher.

(4) The optical glass according to (3), which further comprises, in terms of weight percent: ba²⁺：25～40％；Gd³⁺：0～6％；Y³⁺：0～6％；Al³⁺：0～5％；Mg²⁺：0～3％；Ca²⁺：0～3％；La³⁺：0～5％；Li⁺：0～5％；K⁺：0～5％；W⁶⁺：0～5％；Ti⁴⁺：0～5％；Zr⁴⁺：0～5％；Si⁴⁺：0～5％；B³⁺：0～5％；Sb³⁺：0～1％；Ce⁴⁺：0～1％；Sn⁴⁺：0～1％；Cl^-：0～1％。

(5) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: p⁵⁺/(Zn² ⁺+Na⁺) 0.8 to 3.0, preferably P⁵⁺/(Zn²⁺+Na⁺) Is 1.0 to 2.0.

(6) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: (Nb)⁵⁺+Sr²⁺)/Na⁺0.5 to 5.0, preferably (Nb)⁵⁺+Sr²⁺)/Na⁺0.8 to 3.0.

(7) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: zn²⁺/(Nb⁵⁺+Y³⁺) 0.5 to 10.0, preferably Zn²⁺/(Nb⁵⁺+Y³⁺) 1.0 to 8.0, more preferably Zn²⁺/(Nb⁵⁺+Y³⁺) 1.5 to 5.0.

(8) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: sr²⁺/(Gd³⁺+Y³⁺) 0.1 to 10.0, preferably Sr²⁺/(Gd³⁺+Y³⁺) 0.3 to 6.0, more preferably Sr²⁺/(Gd³⁺+Y³⁺) 0.5 to 4.0.

(9) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: sr²⁺/Zn² ⁺0.1 to 2.0, preferably Sr²⁺/Zn²⁺0.15 to 1.0, more preferably Sr²⁺/Zn²⁺0.2 to 0.8.

(10) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: p⁵⁺/Ba² ⁺0.3 to 0.75, preferably P⁵⁺/Ba²⁺0.3 to 0.6, more preferably P⁵⁺/Ba²⁺0.35 to 0.55.

(11) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: 5 XNb⁵ ⁺/F^-0.2 to 10.0, preferably 5 XNb⁵⁺/F^-0.5 to 6.0, more preferably 5 XNb⁵⁺/F^-Is 1.0 to 4.0.

(12) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: na (Na)⁺/(Li⁺+Na⁺+K⁺) 0.7 to 1.0, preferably Na⁺/(Li⁺+Na⁺+K⁺) 0.8 to 1.0, more preferably Na⁺/(Li⁺+Na⁺+K⁺) 0.85 to 1.0.

(13) The optical glass according to any one of (1) to (4), which comprises, in terms of weight percent: p⁵⁺: 12-18%; and/or Ba²⁺: 30-36%; and/or Sr²⁺: 1-6%; and/or Zn²⁺: 5-10%; and/or Nb⁵⁺: 0.5-4%; and/or Gd³⁺: 0.5-4%; and/or Y³⁺: 0.5-4%; and/or Na⁺: 2-7%; and/or Al³⁺: 0.5-3%; and/or Mg² ⁺: 0-2%; and/or Ca²⁺: 0-2%; and/or La³⁺: 0-2%; and/or Li⁺: 0-2%; and/or K⁺: 0-2%; and/or W⁶⁺: 0-2%; and/or Ti⁴⁺: 0-2%; and/or Zr⁴⁺: 0-2%; and/or Si⁴⁺: 0-2%; and/or B³⁺: 0-2%; and/or Sb³⁺: 0 to 0.5 percent; and/or Ce⁴⁺: 0 to 0.5 percent; and/or Sn⁴⁺: 0 to 0.5 percent; and/or F^-: 3-9%; and/or O^2-: 22-30%; and/or Cl^-：0～0.5％。

(14) The optical glass according to any one of (1) to (4), wherein the optical glass has a refractive index of 1.55 to 1.64, preferably a refractive index of 1.57 to 1.62, more preferably a refractive index of 1.58 to 1.61, and an Abbe number of 56 to 63, preferably an Abbe number of 57 to 62, more preferably an Abbe number of 59 to 61.

(15) The optical glass according to any one of (1) to (4), wherein the optical glass has a bubble degree of class A or more, preferably class A₀More preferably A or more₀₀A stage; and/or a coefficient of thermal expansion of 150 x 10^-7Preferably 145X 10 or less,/K^-7A value of not more than 140X 10^-7and/K is less than or equal to.

(16) The optical glass according to any one of (1) to (4), wherein the glass has a transition temperature of 420 ℃ or lower, preferably 410 ℃ or lower, and more preferably 400 ℃ or lower; and/or a density of 4.2g/cm³Hereinafter, it is preferably 4.1g/cm³Hereinafter, more preferably 4.0g/cm³The following; and/or acid stability of 3 or more, preferably 2 or more, more preferably 1; and/or a moisture resistance stability of 3 or more, preferably 2 or more.

(17) A glass preform made of the optical glass according to any one of (1) to (16).

(18) An optical element produced from the optical glass according to any one of (1) to (16) or the glass preform according to (17).

(19) An optical device produced using the optical glass according to any one of (1) to (16), or the optical element according to (18).

The invention has the beneficial effects that: through reasonable component design, the optical glass obtained by the invention has higher bubble degree grade while meeting the expected refractive index and Abbe number.

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 (components) constituting the optical glass of the present invention are explained below. In the present specification, the content, the total content, of each ionic component is expressed as a weight percentage of the ionic component to the total weight of all anionic and cationic ionic components, if not specifically stated.

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.

The ion valence of each component described below is a representative value used for convenience, and is not different from other ion valence. The ion valence of each component in the optical glass may be out of the representative value. For example, P is typically present in the glass in a state where the ionic valence is +5, and thus is referred to as "P" in this disclosure⁵⁺"as a representative value, but there is a possibility that the ion valence state may exist in other ion valence states, which is also within the scope of the present disclosure.

< essential Components and optional Components >

P⁵⁺Is a main component forming the glass, and can increase the viscosity of the glass. When P is present⁵⁺When the content is too small, the viscosity of the glass decreases, the glass becomes unstable, and the devitrification resistance is deteriorated, so that P⁵⁺The lower limit of the content of (B) is 10%, and the preferable lower limit is 12%. When P is present⁵⁺When the content is too large, the abrasion of the glass is deteriorated and the refractive index and chemical stability are lowered, so that P⁵⁺The upper limit of the content of (B) is 20%, preferably 18%.

Al³⁺The chemical stability of the glass can be improved, but when the content is more than 5%, the melting difficulty of the glass is increased, the transmittance of the glass is reduced, and the lowering of the transition temperature of the glass is not favorable. Therefore, Al in the present invention³⁺The content of (b) is 5% or less, preferably 0.5 to 3%.

Ba²⁺Is an essential component for improving the transmittance of the glass, improving the chemical stability and the refractive index of the glass, and more than 25 percent of Ba is introduced into the invention²⁺In order to obtain the above effects, it is preferable to introduce 30% or more of Ba²⁺. When Ba is present²⁺Is more than 40%, the transition temperature and density of the glass are increased, and thus, Ba²⁺The content of (b) is 40% or less, preferably 36% or less.

In some embodiments of the invention, if P⁵⁺/Ba²⁺Higher than 0.75, glassThe coefficient of thermal expansion of the glass is increased if P⁵⁺/Ba²⁺Below 0.3, the chemical and thermal stability of the glass is reduced. Therefore, P is preferred⁵⁺/Ba²⁺The range of (A) is 0.3 to 0.75, more preferably 0.3 to 0.6, and still more preferably 0.35 to 0.55.

In the invention, more than 0.5 percent of Sr is introduced²⁺So as to improve the weather resistance and the refractive index of the glass and optimize the abrasion degree and the density of the glass; when Sr is²⁺When the content exceeds 8%, the chemical stability of the glass is lowered and the cost of the glass is rapidly increased. Therefore, Sr in the present invention²⁺The content of (b) is 0.5 to 8%, preferably 1 to 6%.

In some embodiments of the invention, the Sr is replaced by²⁺/Zn²⁺The value of (A) is in the range of 0.1 to 2.0, the chemical stability of the glass can be improved, preferably Sr²⁺/Zn²⁺The value of (A) is in the range of 0.15 to 1.0, and the abrasion degree of the glass can be further optimized, more preferably Sr²⁺/Zn²⁺The value of (b) is 0.2 to 0.8.

Ca²⁺Contribute to the adjustment of the optical constants of the glass and improve the processability of the glass, but Ca²⁺When the amount of the additive is too large, the optical constants of the glass do not satisfy the design requirements, and the devitrification resistance is deteriorated. Thus, Ca²⁺The content is limited to 0 to 3%, preferably 0 to 2%, and more preferably no Ca is contained²⁺。

Mg²⁺The melting temperature of the glass can be lowered, but when the amount of MgO added is too large, the devitrification resistance and stability of the glass are lowered, and the cost of the glass is increased. Thus, Mg²⁺The content is limited to 0 to 3%, preferably 0 to 2%, and more preferably no Mg is contained²⁺。

Nb⁵⁺The optical constant of the glass can be adjusted by adding the glass into the glass, the stability and the anti-crystallization performance of the glass are improved, when the content of the glass is excessive, the optical constant of the glass is difficult to meet the design requirement, the optical transmittance of the glass is poor, and the secondary compression crystallization of the glass is easy to cause. Therefore, Nb in the present invention⁵⁺The content of (b) is 0 to 6%, preferably 0.5 to 4%.

Li⁺Can reduce the transition temperature of the glassWhen the content is too large, the thermal expansion coefficient of the glass is deteriorated and the refractive index is lowered. Thus, Li⁺The content of (A) is 5% or less, preferably 2% or less, more preferably no introduction of Li⁺。

In the invention, more than 1 percent of Na is introduced⁺In order to lower the liquidus temperature of the glass, improve the devitrification resistance of the glass, and optimize the meltability and the bubble degree of the glass, it is preferable to introduce 2% or more of Na⁺. When Na is present⁺More than 10%, the chemical stability, especially the moisture resistance, of the glass is lowered, the elastic modulus is deteriorated, and therefore Na is contained⁺The content of (b) is 10% or less, preferably 7% or less.

In the present invention, (Nb) is⁵⁺+Sr²⁺)/Na⁺Below 0.1, the coefficient of thermal expansion of the glass increases, if (Nb)⁵⁺+Sr²⁺)/Na⁺Above 8.0, the glass transition temperature increases and the density increases. Therefore, the temperature of the molten metal is controlled,

(Nb⁵⁺+Sr²⁺)/Na⁺0.1 to 8.0, preferably (Nb)⁵⁺+Sr²⁺)/Na⁺0.5 to 5.0, more preferably (Nb)⁵⁺+Sr²⁺)/Na⁺0.8 to 3.0.

K⁺The glass is improved in devitrification resistance and the transition temperature is lowered, but if the content is too large, the glass is deteriorated in weather resistance. Thus, K⁺The content of (b) is 5% or less, preferably 2% or less.

In some embodiments of the invention, the compound is prepared by reacting Na⁺/(Li⁺+Na⁺+K⁺) In the range of 0.7 to 1.0, the devitrification resistance of the glass can be improved, especially Na is added⁺/(Li⁺+Na⁺+K⁺) In the range of 0.8-1.0, the bubble degree of the glass can be further improved, the abrasion degree of the glass is optimized, and Na is more preferable⁺/(Li⁺+Na⁺+K⁺) 0.85 to 1.0.

Zn²⁺Can improve the weather resistance and the mould pressing performance of the optical glass and reduce the liquid phase temperature of the glass, when the content of the Zn is less than 3 percent, the effect is not obvious, and Zn with more than 5 percent is preferably introduced²⁺. When Zn²⁺When the content of (A) is excessiveThe chemical stability of the glass is easily deteriorated, the thermal stability is lowered, and the thermal expansion coefficient and the temperature coefficient of refractive index of the glass are increased. Therefore, the upper limit of the content is 12%, preferably 10%.

The inventor finds that if P is P through a large amount of experimental researches⁵⁺/(Zn²⁺+Na⁺) Below 0.5, the coefficient of thermal expansion of the glass increases, if P is⁵⁺/(Zn²⁺+Na⁺) Above 4.0, the bubble size of the glass decreases. Thus, P in the present invention⁵⁺/(Zn²⁺+Na⁺) 0.5 to 4.0, preferably P⁵⁺/(Zn²⁺+Na⁺) 0.8 to 3.0, more preferably P⁵⁺/(Zn²⁺+Na⁺) Is 1.0 to 2.0.

La³⁺The refractive index and weather resistance of the glass can be improved, and it is an optional component in the present invention, and when the content is too large, the transition temperature and the temperature coefficient of refractive index of the glass are increased. Therefore, La in the present invention³⁺The content of (b) is in the range of 0 to 5%, preferably 0 to 2%.

Y³⁺The glass has the effects of improving the refractive index of the glass and optimizing the hardness and abrasion degree of the glass, and when the content of the glass exceeds 6 percent, the refractive index of the glass exceeds the design requirement, and the thermal stability is reduced. Thus, Y in the present invention³⁺The content of (b) is in the range of 0 to 6%, preferably 0.5 to 4%.

In some embodiments of the invention, Zn is controlled²⁺Content and Nb⁵⁺And Y³⁺Of the total content of (A) Zn²⁺/(Nb⁵⁺+Y³⁺) In the range of 0.5 to 10.0, excellent chemical stability of the glass can be obtained, and Zn is particularly preferable²⁺/(Nb⁵⁺+Y³⁺) In the range of 1.0 to 8.0, the bubble degree of the glass can be further improved, and Zn is more preferable²⁺/(Nb⁵⁺+Y³⁺) 1.5 to 5.0.

Gd³⁺The chemical stability of the glass can be improved, the optical constant of the glass is adjusted, the glass forming stability of the glass is optimized, when the content of the glass exceeds 6%, the optical constant of the glass exceeds the design requirement, and meanwhile, the devitrification resistance of the glass is poor. Thus, Gd is present in the invention³⁺In the content range of0 to 6%, preferably 0.5 to 4%.

In some embodiments of the invention, the Sr is replaced by²⁺/(Gd³⁺+Y³⁺) In the range of 0.1 to 10.0, the chemical stability of the glass can be improved, and Sr is particularly preferable²⁺/(Gd³⁺+Y³⁺) In the range of 0.3 to 6.0, the optical transmittance of the glass can be optimized, and Sr is more preferable²⁺/(Gd³⁺+Y³⁺) 0.5 to 4.0.

W⁶⁺The refractive index and dispersion of the glass can be improved, the devitrification resistance of the glass is optimized, and when the content of the devitrification resistance is excessive, the light transmittance of the glass is reduced. Therefore, W in the present invention⁶⁺The upper limit of the content of (B) is 5%, preferably 2%, more preferably W is not contained⁶⁺。

Proper amount of Ti is introduced⁴⁺Can reduce the viscosity of the glass and improve the water resistance of the glass, but introduces a large amount of Ti⁴⁺The glass has increased coloring and devitrification tendency, and the refractive index is difficult to meet the design requirement. Thus, Ti in the present invention⁴⁺The upper limit of the content of (B) is 5%, preferably 2%, more preferably Ti is not contained⁴⁺。

Zr⁴⁺The 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, Zr⁴⁺The content is 0 to 5%, preferably 0 to 2%.

Si⁴⁺Can be used to adjust the optical constants of the glass, but it is difficult to obtain the low transition temperature desired in the present invention when the content is too large. Thus, Si⁴⁺The content of (B) is limited to 0 to 5%, preferably 0 to 2%, and more preferably Si is not contained⁴⁺。

B³⁺Is an optional component in the present invention, and is useful for improving the meltability of the glass, and when the content is too large, the weatherability and chemical stability of the glass are deteriorated. Thus, B³⁺The content of (B) is limited to 0 to 5%, preferably 0 to 2%, more preferably B is not contained³⁺。

O^2-Is to maintain the inventionThe necessary components for the thermal stability of the glass are obtained by introducing more than 18% of O^2-The devitrification of the glass can be suppressed and the abrasion can be reduced. However, when the amount of incorporation is more than 32%, the viscosity of the glass increases and the melting temperature increases, which tends to deteriorate the transmittance. Thus, O in the present invention^2-The content of (b) is 18 to 32%, preferably 22 to 30%.

F^-Can reduce the dispersion and transition temperature of the glass, and the invention introduces more than 2 percent of F^-To obtain the above effects, it is preferable to introduce F in an amount of 3% or more^-. On the other hand, in the present invention, by controlling F^-The content of (A) is 12% or less, and the glass can be suitably abraded, the processability of the glass can be improved, and the dispersion of the glass can be prevented from exceeding the design range, preferably F^-The content of (A) is less than 9%.

The inventors have found through extensive experimental studies that, in some embodiments of the present invention, the above-mentioned method is performed by using 5 × Nb⁵⁺/F^-Within the range of 0.2-10.0, the optical constant of the glass can be adjusted, the volatilization of F in the glass can be inhibited, the degree of striae of the glass is optimized, and 5 multiplied by Nb is preferred⁵⁺/F^-0.5 to 6.0, more preferably 5 XNb⁵⁺/F^-Is 1.0 to 4.0.

In the invention, 0-1% of Sb is added³⁺、Ce⁴⁺、Sn⁴⁺、Cl^-One or more of the components can be used as a clarifying agent to improve the clarifying effect of the glass. But when Sb is³⁺At contents exceeding 1%, 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 invention³⁺The amount of (B) is 0 to 1%, preferably 0 to 0.5%. Sn (tin)⁴⁺It may be added as a fining agent, but when the content exceeds 1%, the glass is colored, or when the glass is heated, softened, press-molded or the like and then re-molded, Sn is added⁴⁺The content of the compound is preferably 0 to 1%, more preferably 0 to 0.5%, and the compound tends to be devitrified when it becomes a starting point of crystal nucleus formation. Ce⁴⁺Action and addition amount ratio of (2) to Sn⁴⁺In agreement, the content thereof is preferably0 to 1%, more preferably 0 to 0.5%. In the invention, 0-1% of Cl can be introduced^-As a clarifying agent, the defoaming effect of the glass is improved, and the preferable range is 0-0.5%. Since the glass of the present invention has an excellent degree of foaming even without adding a fining agent, it is further preferable not to contain Sb³⁺、Ce⁴ ⁺、Sn⁴⁺、Cl^-And (4) and the like.

< component which should not be contained >

In the glass of the present invention, even when a small amount of a transition metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained alone 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, components such as Th, Cd, Tl, Os, Be, and Se tend to Be used under control as harmful chemical substances, 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 As³⁺And Pb²⁺. Although As³⁺Has the effects of eliminating bubbles and better preventing the glass from coloring, but As³⁺The 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 "no incorporation", "no inclusion", "0%" described herein means that the component and the like are not intentionally added as raw materials 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 glass_d) The test was carried out according to the method specified in GB/T7962.1-2010.

The optical glass of the present invention has a lower limit of refractive index (nd) of 1.55, preferably 1.57, more preferably 1.58, and an upper limit of refractive index (nd) of 1.64, preferably 1.62, more preferably 1.61; abbe number (v)_d) Has a lower limit of 56, preferably 57, more preferably 59, and an Abbe number (. nu._d) The upper limit of (3) is 63, preferably 62, and more preferably 61.

< 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 4.2g/cm³Hereinafter, it is preferably 4.1g/cm³Hereinafter, more preferably 4.0g/cm³The following.

< coefficient of thermal expansion >

Coefficient of thermal expansion (alpha) of optical glass_20/120℃) And testing data at 20-120 ℃ according to a method specified in GB/T7962.16-2010.

The coefficient of thermal expansion (. alpha.) of the optical glass of the present invention_20/120℃) Is 150X 10^-7Preferably 145X 10 or less,/K^-7A value of not more than 140X 10^-7and/K is less than or equal to.

< transition temperature >

Transition temperature (T) of optical glass_g) The test was carried out according to the method specified in GB/T7962.16-2010.

Transition temperature (T) of the optical glass of the present invention_g) Is 420 ℃ or lower, preferably 410 ℃ or lower, and more preferably 400 ℃ or lower.

< stability against acid >

The acid resistance RA (surface method) of the optical glass was tested according to the test method specified in GB/T7962.14-2010.

The acid resistance stability (RA) of the optical glass of the present invention is 3 or more, preferably 2 or more, and more preferably 1.

< 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 3 or more, preferably 2 or more.

< degree of bubbling >

The bubble degree of the optical glass was measured according to the test 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.

[ production method ]

The method for manufacturing the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and a conventional process, carbonate, nitrate, sulfate, hydroxide, oxide, fluoride, phosphate, metaphosphate 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) with the temperature of 850-1000 ℃ for smelting 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 mould 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

TABLE 2

< 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 optically designed to form an optical component or an optical assembly by using one or more optical elements, and can be used, for example, for imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automotive field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for camera devices and apparatuses in the field of vehicle-mounted, surveillance and security.

Claims

1. Optical glass, characterized in that its components, expressed in weight percent, contain: p⁵⁺：10～20％；Ba²⁺：25～40％；Sr²⁺：0.5～8％；Zn²⁺：3～12％；Nb⁵⁺：0.5～6％；Gd³⁺：0.5～6％；Y³⁺：0～6％；Na⁺：1～10％；F^-：2～12％；O^2-: 18 to 32% of P, wherein⁵⁺/(Zn²⁺+Na⁺) 0.5 to 4.0 (Nb)⁵⁺+Sr²⁺)/Na⁺0.1 to 8.0, Zn²⁺/(Nb⁵⁺+Y³⁺) 2.37 to 5.0, P⁵⁺/Ba²⁺0.3 to 0.75.

2. An optical glass according to claim 1, characterised in that it further comprises, in percentages by weight: al (Al)³ ⁺: 0 to 5 percent; and/or Mg²⁺: 0 to 3 percent; and/or Ca²⁺: 0 to 3 percent; and/or La³⁺: 0 to 5 percent; and/or Li⁺: 0 to 5 percent; and/or K⁺: 0 to 5 percent; and/or W⁶⁺: 0 to 5 percent; and/or Ti⁴⁺: 0 to 5 percent; and/or Zr⁴⁺: 0 to 5 percent; and/or Si⁴⁺: 0 to 5 percent; and/or B³⁺: 0 to 5 percent; and/or Sb³⁺: 0 to 1 percent; and/or Ce⁴⁺: 0 to 1 percent; and/or Sn⁴⁺: 0 to 1 percent; and/or Cl^-：0～1％。

3. Optical glass, characterized in that its components, expressed in weight percent, contain: p⁵⁺：10～20％；Sr²⁺：0.5～8％；Zn²⁺：3～12％；Nb⁵⁺：0～6％；Na⁺：1～10％；Ba²⁺：25～40％；F^-：2～12％；O^2-: 18 to 32% of P, wherein⁵⁺/(Zn²⁺+Na⁺) 0.5 to 4.0 (Nb)⁵⁺+Sr²⁺)/Na⁺0.1 to 8.0, and the optical glass has a bubble degree of A₀More than grade Sr²⁺/Zn²⁺0.28 to 1.0, Zn²⁺/(Nb⁵⁺+Y³⁺) 2.37 to 5.0.

4. An optical glass according to claim 3, characterised in that it further comprises, in percentages by weight: gd (Gd)³ ⁺：0～6％；Y³⁺：0～6％；Al³⁺：0～5％；Mg²⁺：0～3％；Ca²⁺：0～3％；La³⁺：0～5％；Li⁺：0～5％；K⁺：0～5％；W⁶⁺：0～5％；Ti⁴⁺：0～5％；Zr⁴⁺：0～5％；Si⁴⁺：0～5％；B³⁺：0～5％；Sb³⁺：0～1％；Ce⁴ ⁺：0～1％；Sn⁴⁺：0～1％；Cl^-：0～1％。

5. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: p⁵⁺/(Zn²⁺+Na⁺) 0.8 to 3.0.

6. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: p⁵⁺/(Zn²⁺+Na⁺) Is 1.0 to 2.0.

7. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: p⁵⁺/(Zn²⁺+Na⁺) Is 1.0 to 1.51.

8. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: (Nb)⁵⁺+Sr²⁺)/Na⁺0.5 to 5.0.

9. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: (Nb)⁵⁺+Sr²⁺)/Na⁺0.8 to 3.0.

10. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: (Nb)⁵⁺+Sr²⁺)/Na⁺0.8 to 2.14.

11. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: zn²⁺/(Nb⁵⁺+Y³⁺) 2.38 to 5.0.

12. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: zn²⁺/(Nb⁵⁺+Y³⁺) Is 2.38 to 4.23.

13. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: zn²⁺/(Nb⁵⁺+Y³⁺) Is 2.61 to 5.0.

14. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: zn²⁺/(Nb⁵⁺+Y³⁺) Is 2.61 to 4.23.

15. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: zn²⁺/(Nb⁵⁺+Y³⁺) Is 3.03 to 5.0.

16. An optical glass according to any of claims 1 to 4, characterised in that its components are in weight percentThe ratio is represented, wherein: zn²⁺/(Nb⁵⁺+Y³⁺) Is 3.03 to 4.23.

17. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: sr²⁺/(Gd³⁺+Y³⁺) 0.1 to 10.0.

18. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: sr²⁺/(Gd³⁺+Y³⁺) 0.3 to 6.0.

19. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: sr²⁺/(Gd³⁺+Y³⁺) 0.5 to 4.0.

20. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: sr²⁺/(Gd³⁺+Y³⁺) 0.72 to 3.20.

21. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: sr²⁺/(Gd³⁺+Y³⁺) 0.80 to 2.83.

22. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: sr²⁺/(Gd³⁺+Y³⁺) Is 0.93 to 1.98.

23. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentages, wherein: sr²⁺/Zn²⁺0.1 to 2.0.

24. According to claimThe optical glass according to claim 1 or 2, characterized in that its components are expressed in weight percentage, wherein: sr²⁺/Zn²⁺0.15 to 1.0.

25. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentages, wherein: sr²⁺/Zn²⁺0.2 to 0.8.

26. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentages, wherein: sr²⁺/Zn²⁺0.2 to 0.66.

27. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentages, wherein: sr²⁺/Zn²⁺0.27 to 0.55.

28. An optical glass according to claim 3 or 4, characterised in that its components are expressed in weight percentages, in which: sr²⁺/Zn²⁺0.28 to 0.8.

29. An optical glass according to claim 3 or 4, characterised in that its components are expressed in weight percentages, in which: sr²⁺/Zn²⁺0.28 to 0.66.

30. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: sr²⁺/Zn²⁺0.28 to 0.55.

31. An optical glass according to claim 3 or 4, characterised in that its components are expressed in weight percentages, in which: p⁵⁺/Ba²⁺0.3 to 0.75.

32. An optical glass according to any of claims 1 to 4, characterised in that it consists ofIn percent by weight, wherein: p⁵⁺/Ba²⁺0.3 to 0.6.

33. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: p⁵⁺/Ba²⁺0.35 to 0.55.

34. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: p⁵⁺/Ba²⁺0.41 to 0.50.

35. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: 5 XNb⁵⁺/F^-0.2 to 10.0.

36. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: 5 XNb⁵⁺/F^-0.5 to 6.0.

37. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: 5 XNb⁵⁺/F^-Is 1.0 to 4.0.

38. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: 5 XNb⁵⁺/F^-1.0 to 3.13.

39. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: 5 XNb⁵⁺/F^-Is 1.0 to 2.25.

40. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: n is a radical ofa⁺/(Li⁺+Na⁺+K⁺) 0.7 to 1.0.

41. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: na (Na)⁺/(Li⁺+Na⁺+K⁺) 0.8 to 1.0.

42. An optical glass according to any one of claims 1 to 4, characterised in that its components, expressed in weight percentage, are: na (Na)⁺/(Li⁺+Na⁺+K⁺) 0.85 to 1.0.

43. An optical glass according to any one of claims 1 to 4, comprising, in weight percent: p⁵⁺: 12-18%; and/or Ba²⁺: 30-36%; and/or Sr²⁺: 1-6%; and/or Zn²⁺: 5-10%; and/or Nb⁵ ⁺: 0.5-4%; and/or Gd³⁺: 0.5-4%; and/or Y³⁺: 0.5-4%; and/or Na⁺: 2-7%; and/or Al³⁺: 0.5-3%; and/or Mg²⁺: 0-2%; and/or Ca²⁺: 0-2%; and/or La³⁺: 0-2%; and/or Li⁺: 0-2%; and/or K⁺: 0-2%; and/or W⁶⁺: 0-2%; and/or Ti⁴⁺: 0-2%; and/or Zr⁴⁺: 0-2%; and/or Si⁴⁺: 0-2%; and/or B³ ⁺: 0-2%; and/or Sb³⁺: 0 to 0.5 percent; and/or Ce⁴⁺: 0 to 0.5 percent; and/or Sn⁴⁺: 0 to 0.5 percent; and/or F^-: 3-9%; and/or O^2-: 22-30%; and/or Cl^-：0～0.5％。

44. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.55 to 1.64 and an Abbe number of 56 to 63.

45. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.55 to 1.64 and an Abbe number of 57 to 62.

46. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.55 to 1.64 and an Abbe number of 59 to 61.

47. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.57 to 1.62 and an Abbe number of 56 to 63.

48. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.57 to 1.62 and an Abbe number of 57 to 62.

49. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.57 to 1.62 and an Abbe number of 59 to 61.

50. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.58 to 1.61 and an Abbe number of 56 to 63.

51. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.58 to 1.61 and an Abbe number of 57 to 62.

52. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index of 1.58 to 1.61 and an Abbe number of 59 to 61.

53. The optical glass according to claim 1 or 2, wherein the optical glass has a bubble degree of class a or more; and/or a coefficient of thermal expansion of 150 x 10^-7and/K is less than or equal to.

54. An optical glass according to claim 3 or 4, wherein the optical glass has a coefficient of thermal expansion of 150 x 10^-7and/K is less than or equal to.

55. The optical glass according to claim 1 or 2, wherein the optical glass has a bubble degree of A₀More than grade; and/or a coefficient of thermal expansion of 145 x 10^-7and/K is less than or equal to.

56. An optical glass according to claim 3 or 4, wherein the optical glass has a coefficient of thermal expansion of 145 x 10^-7and/K is less than or equal to.

57. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a bubble degree A₀₀A stage; and/or a coefficient of thermal expansion of 140 x 10^-7and/K is less than or equal to.

58. The optical glass according to any one of claims 1 to 4, wherein the transition temperature of the optical glass is 420 ℃ or lower; and/or a density of 4.2g/cm³The following; and/or acid stability is more than 3 types; and/or a moisture resistance stability of 3 or more.

59. The optical glass according to any one of claims 1 to 4, wherein the transition temperature of the optical glass is 410 ℃ or lower; and/or a density of 4.1g/cm³The following; and/or the acid stability is more than 2 types; and/or a moisture resistance stability of class 2 or more.

60. The optical glass according to any one of claims 1 to 4, wherein the transition temperature of the optical glass is 400 ℃ or lower; and/or a density of 4.0g/cm³The following; and/or acid stability is class 1.

61. A glass preform made of the optical glass according to any one of claims 1 to 60.

62. An optical element produced from the optical glass according to any one of claims 1 to 60 or the glass preform according to claim 61.

63. An optical device comprising the optical glass according to any one of claims 1 to 60 or the optical element according to claim 62.