CN102557437B - Optical glass, optical element and preform - Google Patents

Abstract

It is an object of the invention to provide a kind of optical glass, optical element and preform, the anomalous dispersion of described optical glass is higher, thus the chromatic aberration of glass lens can be compensated accurately, and then possess high index of refraction, low dispersivity (high Abbe number), low in abrasion degree, be easily ground in terms of processing having with conventional optical glass on an equal basis more than performance.A kind of optical glass, wherein, contains P as cation constituent⁵⁺、Al³⁺、Ca²⁺、Ln³⁺(Ln³⁺It is to select free Y³⁺、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺At least one in the group of composition) and select free Mg²⁺、Sr²⁺And Ba²⁺At least one in the group of composition；Represent with cation %, Ln³⁺Total containing ratio for more than 1.1% and less than 10.0%, containing F as anion component^‑, its refractive index (nd) >=1.55, Abbe number (ν d) >=55.

Description

Optical glass, optical element and preform

Technical field

The present invention relates to optical glass, optical element and preform.

Background technology

The lens combination of optical instrument is typically to be combined by multiple glass lens with different optical property and design. In recent years, the characteristic required by lens system of optical instrument is the most diversified, in order to expand the degree of freedom of its design further, just The optical glass of optical characteristics being in the past not affected by attracting attention is possessed in exploitation.Wherein, anomalous dispersion (Δ θ g, F) is characterized Optical glass is attracted attention as the color correct of chromatic aberration is had the optical glass of remarkable result.

Such as proposing a kind of optical glass in patent documentation 1～3, it is except the most necessary high index of refraction and low color Dissipate beyond the character of property and excellent in workability, also there is higher anomalous dispersion；As this optical glass, such as cation Composition contains P⁵⁺、Al³⁺, alkaline-earth metal ions etc., anion component contains F^-And O^2-。

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2007-55883 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2008-137877 publication

Patent documentation 3: No. 2008/111439 pamphlet of International Publication

Summary of the invention

The problem that invention is to be solved

But, the conventional optical glass as patent documentation 1～3 is described, its anomalous dispersion degree is insufficient, Expect to develop the optical glass possessing higher anomalous dispersion.

Present invention aim to address such problem.

I.e. it is an object of the invention to, it is provided that a kind of optical glass, optical element and preform, described optical glass Anomalous dispersion is higher, thus can compensate the chromatic aberration of glass lens accurately, and then possesses high index of refraction, low dispersivity (high Abbe number), low in abrasion degree, be easily ground in terms of processing having with conventional optical glass on an equal basis more than performance.

For solving the scheme of problem

The present inventor etc. conduct in-depth research for solving above-mentioned problem, thus complete the present invention.

The present invention is following (1)～(11).

(1) a kind of optical glass, wherein, contains P as cation constituent⁵⁺、Al³⁺、Ca²⁺、Ln³⁺(Ln³⁺It is to select free Y^{3 +}、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺At least one in the group of composition) and select free Mg²⁺、Sr²⁺And Ba²⁺In the group of composition extremely Few one；

Represent with cation %, Ln³⁺Total containing ratio for more than 1.1% and less than 10.0%,

F is contained as anion component^-,

The refractive index (nd) >=1.55 of described optical glass, Abbe number (ν d) >=55.

(2) according to the optical glass described in above-mentioned (1), wherein, represent with cation %, contain as cation constituent:

P⁵⁺: 25～50%,

Al³⁺: 5～15%,

Ca²⁺: 1～8%,

R²⁺: 30～70% (R²⁺Refer to Ca²⁺+Mg²⁺+Sr²⁺+Ba²⁺),

Gd³⁺: more than 0% and less than 10.0%,

Represent with anion %, contain as anion component:

F^-: 15～40%.

(3) according to the optical glass described in above-mentioned (1) or (2), wherein, Y³⁺、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺Each sun from The containing ratio of subconstiuent meets Gd³⁺/(Y³⁺+La³⁺+Gd³⁺+Yb³⁺+Lu³⁺) relation of ＞ 0.74.

(4) according to the optical glass according to any one of above-mentioned (1)～(3), wherein, represent with cation %, R²⁺Total Containing ratio is 33～70%.

(5) according to the optical glass according to any one of above-mentioned (1)～(4), wherein, Sb is not contained.

(6) according to the optical glass according to any one of above-mentioned (1)～(5), wherein, Y is not contained.

(7) according to the optical glass according to any one of above-mentioned (1)～(6), its abrasion degree is less than 510.

(8) a kind of optical element, it is formed by the optical glass according to any one of above-mentioned (1)～(7).

(9) a kind of attrition process is used and/or the preform of precise press molding, and it is by arbitrary in above-mentioned (1)～(7) Optical glass described in Xiang is formed.

(10) a kind of optical element, it is for being ground forming by the preform described in above-mentioned (9).

(11) a kind of optical element, it forms for the preform precision described in above-mentioned (9) being suppressed.

The effect of invention

According to the present invention, it is possible to provide a kind of optical glass, optical element and preform, the unusual color of described optical glass Scattered property is higher, thus can compensate the chromatic aberration of glass lens accurately, and then possesses high index of refraction, low dispersivity (high Abbe Number), and, low in abrasion degree, be easily ground in terms of processing having with conventional optical glass on an equal basis more than performance.

Accompanying drawing explanation

Fig. 1 be take partial dispersion ratio (θ g, F) as the longitudinal axis, with the Abbe number (ν d) rectangular coordinate as transverse axis in represent The figure of datum line.

Detailed description of the invention

The present invention will be described.

The optical glass of the present invention, contains P as cation constituent⁵⁺、Al³⁺、Ca²⁺、Ln³⁺(Ln³⁺It is to select free Y³⁺、La^{3 +}、Gd³⁺、Yb³⁺And Lu³⁺At least one in the group of composition) and Mg²⁺、Sr²⁺And Ba²⁺At least one in the group of composition, with Cation % represents, Ln³⁺Total containing ratio for more than 1.1% and less than 10.0%；F is contained as anion component^-；Described light Learn the refractive index (nd) >=1.55 of glass, Abbe number (ν d) >=55.

Hereinafter also this optical glass is referred to as " optical glass of the present invention ".

<glass ingredient>

Each composition of the optical glass constituting the present invention is illustrated.

In this specification, as long as no special declaration, the containing ratio of each composition is all with cation % based on mol ratio Or anion % represents.Herein, " cation % " refers to " anion % " constitute into the glass of the optical glass of the present invention It is separated into cation constituent and anion component and each as 100 moles of % representing, glass contains using toatl proportion The composition of each composition.

It addition, for convenience, the ioni valence of each composition uses representative value, and the ioni valence with other does not makes a distinction.Light Present in glass, the ioni valence of each composition, is not likely to be representative value.Such as P is generally present in the state that ioni valence is 5 In glass, thus in this manual with " P⁵⁺" represent, it is also possible to exist with the state of other ioni valences.Like this, strictly Ground is said, each composition also exists with the state of other ioni valences, but in this manual, each composition is considered as the ion with representative value Valency is present in optical glass.

About cation constituent

<P⁵⁺>

The optical glass of the present invention contains P⁵⁺。P⁵⁺It is glass forming constituents, there is the devitrification of suppression glass, improve refraction The character that rate, suppression Abbe number reduce.

Owing to such character strengthens, so P⁵⁺Containing ratio be preferably 25.0～50.0%.It addition, more preferably More than 26.0%, more preferably more than 28.0%.It addition, more preferably less than 48.0%, further preferred less than 47.0%.

Can be by using such as Al (PO₃)₃、Ca(PO₃)₂、Ba(PO₃)₂、Zn(PO₃)₂、BPO₄、H₃PO₄Deng as raw material Make P⁵⁺It is included in glass.

<Al³⁺>

The optical glass of the present invention contains Al³⁺。Al³⁺Have make the devitrification resistance of glass, refractive index and Abbe number improve, Reduce abrasion degree and then improve the character of processability.

Owing to such character strengthens, so Al³⁺Containing ratio be preferably 5.0～15.0%.It addition, more preferably More than 6.0%, more preferably more than 7.0%.It addition, more preferably less than 13.0%, more preferably 12.0% with Under.

Can be by using such as Al (PO₃)₃、AlF₃、Al₂O₃Al is made Deng as raw material³⁺It is included in glass.

<alkaline-earth metal>

In the present invention, alkaline-earth metal means Ca²⁺、Mg²⁺、Sr²⁺And Ba²⁺, sometimes with R²⁺Represent.It addition, R²⁺Always contain Rate refers to total containing ratio (Ca of these 4 kinds of ions²⁺+Mg²⁺+Sr²⁺+Ba²⁺)。

The optical glass of the present invention necessarily contains as R²⁺The Ca of one of (alkaline-earth metal)²⁺, additionally contain the free Mg of choosing^{2 +}、Sr²⁺And Ba²⁺At least one in the group of composition.

It addition, R²⁺Total containing ratio be preferably 30.0～70.0%, more preferably 33.0～70.0%.This is because, contain There is rate when such scope, available more stable glass.

R²⁺Total containing ratio be more preferably more than 35.0%, more preferably more than 38.0%.It addition, more preferably Less than 65.0%, more preferably less than 60.0%.

<Ca²⁺>

The optical glass of the present invention necessarily contains Ca²⁺。Ca²⁺There is raising devitrification resistance, the suppression reduction of refractive index, fall The character of the abrasion degree of low glass.

Owing to such character strengthens, so Ca²⁺Containing ratio be preferably 1.0%～8.0%.It addition, more preferably More than 2.0%, more preferably more than 3.0%.It addition, more preferably less than 7.0%, more preferably less than 6.0%.

If it addition, Ca²⁺With other alkaline-earth metal, the i.e. free Mg of choosing²⁺、Sr²⁺And Ba²⁺At least one in the group of composition Be concurrently present in glass, then it improves the character increasing of the devitrification resistance of glass, the reduction of suppression refractive index, reduction abrasion degree By force, particularly its improve glass devitrification resistance character strengthen.The optical glass of the present invention is with Ca²⁺As essential component, this Outward possibly together with selecting free Mg²⁺、Sr²⁺And Ba²⁺At least one in the group of composition.Owing to such character strengthens, so Ca²⁺'s Containing ratio is preferably 1.0%～8.0%, and, R²⁺Total containing ratio be preferably 30.0～70.0%, more preferably 33.0～ 70.0%.

Can be by using such as Ca (PO₃)₂、CaCO₃、CaF₂Ca is made Deng as raw material²⁺It is included in glass.

It addition, the devitrification resistance of the optical glass in order to improve the present invention especially, Ca²⁺Containing ratio and whole alkaline-earth metal The ratio (Ca of total amount (total containing ratio)²⁺/R²⁺) lower limit be preferably 0.001, more preferably 0.005, most preferably 0.01.Separately Outward, its upper limit is preferably 0.90, and more preferably 0.70, most preferably 0.50.

<Mg²⁺>

The optical glass of the present invention has containing as R²⁺The Mg of one of (alkaline-earth metal)²⁺Situation.Mg²⁺There is raising The devitrification resistance of glass, the character of reduction abrasion degree.

Owing to such character strengthens, Mg²⁺Containing ratio be preferably 1.0～20.0%.It addition, more preferably more than 3.0%, More preferably more than 5.0%.It addition, more preferably less than 17.0%, more preferably less than 15.0%.

Can be by using such as MgO, MgF₂Mg is made Deng as raw material²⁺It is included in glass.

<Sr²⁺>

The optical glass of the present invention has containing as R²⁺The Sr of one of (alkaline-earth metal)²⁺Situation.Sr²⁺There is raising The character that the devitrification resistance of glass, suppression refractive index reduce.

Owing to such character strengthens, so Sr²⁺Containing ratio be preferably 0%～20.0%.It addition, more preferably Less than 10.0%, more preferably less than 5.0%.

Can be by using such as Sr (NO₃)₂、SrF₂Sr is made Deng as raw material²⁺It is included in glass.

<Ba²⁺>

The optical glass of the present invention has containing as R²⁺The Ba of one of (alkaline-earth metal)²⁺Situation.Ba²⁺Containing rule There is time quantitatively the character of the devitrification resistance improving glass.It addition, have the character maintaining low dispersivity, improving refractive index.

Owing to such character strengthens, so Ba²⁺Containing ratio be preferably 15.0%～40.0%.It addition, more preferably More than 16.0%, more preferably more than 17.0%.It addition, more preferably less than 38.0%, more preferably 37.0% Below.

Can be by using such as Ba (PO₃)₂、BaCO₃、Ba(NO₃)₂、BaF₂Ba is made Deng as raw material²⁺It is included in glass In.

<Ln³⁺>

Ln in the present invention³⁺Refer to select free Y³⁺、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺At least one in the group of composition.It addition, Ln³⁺Total containing ratio refer to total containing ratio (Y of these 5 kinds of ions³⁺+La³⁺+Gd³⁺+Yb³⁺+Lu³⁺)。

The optical glass of the present invention, contains Ln with the total containing ratio more than 1.1% and less than 10.0%³⁺.That is, the present invention Optical glass contains the free Y of choosing³⁺、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺At least one in the group of composition, and Y³⁺、La³⁺、Gd³⁺、Yb³⁺ And Lu³⁺The summation of containing ratio of each composition for more than 1.1% and less than 10.0%.Owing to the optical glass of the present invention contains spy Quantitative Ln³⁺, therefore the character of the more high and low dispersion of refractive index is notable.

Owing to such character strengthens, so Ln³⁺Total containing ratio be preferably more than 1.5%, more preferably 2.0% with On.Additionally, it is preferred that be less than 9.0%, more preferably less than 8.0%, more preferably less than 7.0%.

It addition, relative to Ln³⁺The Gd of total containing ratio³⁺Containing ratio be preferably greater than 0.74.That is, Y³⁺、La³⁺、Gd³⁺、Yb³⁺ And Lu³⁺The containing ratio of each cation constituent preferably meet Gd³⁺/(Y³⁺+La³⁺+Gd³⁺+Yb³⁺+Lu³⁺) relation of ＞ 0.74.This Outward, the Gd on the left side³⁺/(Y³⁺+La³⁺+Gd³⁺+Yb³⁺+Lu³⁺) more preferably more than 0.80, more preferably more than 0.90, further preferably It is 1.00.If this is because, meet such relation, then there is the tendency that devitrification resistance uprises, refractive index uprises of glass.

<Y³⁺>

The optical glass of the present invention has containing Y³⁺Situation.Y³⁺Have and not only improve the refractive index of glass but also make glass The anomalous dispersion of glass is difficult to reduce, suppress the character of the devitrification resistance of the rising of glass transition point (Tg) and raising glass. But, if if excess contains, then stability easily deteriorates, the most more preferably less than 9.0%, more preferably less than 8.0%, enter One step is preferably less than 7.0%.Even if further, since without Y³⁺It also is able to obtain the glass of the present invention, the most from this point of view, Y can also not contained³⁺。

Can be by using such as Y₂O₃、YF₃Y is made Deng as raw material³⁺It is included in glass.

<La³⁺>

The optical glass of the present invention has containing La³⁺Situation.La³⁺Have and not only improve the refractive index of glass but also make Anomalous dispersion is difficult to the character reduced.

Owing to such character strengthens, so La³⁺Containing ratio be more preferably more than 1.5%, more preferably 2.0% Above.It addition, more preferably less than 9.0%, more preferably less than 8.0%, more preferably less than 7.0%.

Can be by using such as La₂O₃、LaF₃La is made Deng as raw material³⁺It is included in glass.

<Gd³⁺>

The optical glass of the present invention preferably comprises Gd³⁺, more preferably contain with the containing ratio more than 0% and less than 10.0% Gd³⁺。Gd³⁺Have and not only improve the refractive index of glass but also make anomalous dispersion be difficult to reduce and then improve devitrification resistance Character.Though there is other compositions (such as Y³⁺、La³⁺、Yb³⁺And Lu³⁺) situation about also having the quality that, but Crinis Carbonisatus of the present invention Existing Gd³⁺Compared with other compositions, have the quality that higher tendency.

Owing to such character strengthens, so Gd³⁺Containing ratio be more preferably more than 1.5%, more preferably 2.0% Above.It addition, more preferably less than 9.0%, more preferably less than 8.0%, more preferably less than 7.0%.

Can be by using such as Gd₂O₃、GdF₃Gd is made Deng as raw material³⁺It is included in glass.

<Yb³⁺>

The optical glass of the present invention has containing Yb³⁺Situation.Yb³⁺Have and not only improve the refractive index of glass but also make Anomalous dispersion is difficult to reduce and then improve the character of devitrification resistance.

Owing to such character strengthens, so Yb³⁺Containing ratio be more preferably more than 1.5%, more preferably 2.0% Above.It addition, more preferably less than 9.0%, more preferably less than 8.0%, more preferably less than 7.0%.

Can be by using such as Yb₂O₃Yb is made Deng as raw material³⁺It is included in glass.

<Lu³⁺>

The optical glass of the present invention has containing Lu³⁺Situation.Lu³⁺Have and not only improve the refractive index of glass but also make Anomalous dispersion is difficult to reduce and then improve the character of devitrification resistance.

Owing to such character strengthens, so Lu³⁺Containing ratio be more preferably more than 1.5%, more preferably 2.0% Above.It addition, more preferably less than 9.0%, more preferably less than 8.0%, more preferably less than 7.0%.

Can be by using such as Lu₂O₃Lu is made Deng as raw material³⁺It is included in glass.

<Zn²⁺>

The optical glass of the present invention can also be containing the Zn as any composition²⁺。Zn²⁺There is suppression abrasion degree, improve folding Penetrate the character of rate.But, if if excess contains, then the stability of glass easily deteriorates, the most preferably less than 6.5%, and more excellent Elect less than 6.0% as, more preferably less than 5.5%.Even if further, since without Zn²⁺It also is able to obtain the glass of the present invention Glass, the most from this point of view, it is also possible to without Zn²⁺。

Can be by using such as Zn (PO₃)₂、ZnO、ZnF₂Zn is made Deng as raw material²⁺It is included in glass.

<Si⁴⁺>

The optical glass of the present invention can also be containing the Si as any composition⁴⁺。Si⁴⁺Have when containing ormal weight and carry The devitrification resistance of high glass, improve refractive index and reduce abrasion degree and improve the character of processability.

Owing to such character strengthens, so Si⁴⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, enter One step preferably less than 5.0%.

Can be by using such as SiO₂、K₂SiF₆、Na₂SiF₆Si is made Deng as raw material⁴⁺It is included in glass.

<B³⁺>

The optical glass of the present invention can also be containing the B as any composition³⁺。B³⁺When containing ormal weight, there is raising The devitrification resistance of glass, improve refractive index and reduce abrasion degree and improve processability and then make chemical durability be difficult to dislike Change, reduce the character of the formation of glass cord.

Owing to such character strengthens, so B³⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, enter One step preferably less than 5.0%.

Can be by using such as H₃BO₃、Na₂B₄O₇、BPO₄B is made Deng as raw material³⁺It is included in glass.

<Li⁺>

The optical glass of the present invention can also be containing the Li as any composition⁺。Li⁺Have maintain glass formed time resistance to Increased devitrification resistance, and reduce the character of glass transition point (Tg).

Owing to such character strengthens, so Li⁺Containing ratio be preferably less than 20.0%, more preferably 15.0% with Under, more preferably less than 10.0%.

Can be by using such as Li₂CO₃、LiNO₃, LiF etc. make Li as raw material⁺It is included in glass.

<Na⁺>

The optical glass of the present invention can also be containing the Na as any composition⁺。Na⁺Have maintain glass formed time resistance to Increased devitrification resistance and reduce the character of glass transition point (Tg).

Owing to such character strengthens, so Na⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, More preferably less than 5.0%.

Can be by using such as Na₂CO₃、NaNO₃、NaF、Na₂SiF₆Na is made Deng as raw material⁺It is included in glass.

<K⁺>

The optical glass of the present invention can also be containing the K as any composition⁺。K⁺There is resistance to mistake when maintaining glass to be formed Thoroughly property and also reduce the character of glass transition point (Tg).

Owing to such character strengthens, so K⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, Further preferred less than 5.0%.

Can be by using such as K₂CO₃、KNO₃、KF、KHF₂、K₂SiF₆K is made Deng as raw material⁺It is included in glass.

<Rn⁺>

In the optical glass of the present invention, Rn⁺(Rn⁺It is to select free Li⁺、Na⁺And K⁺Composition group at least one) total Containing ratio is preferably less than 20.0%, and more preferably less than 15.0%, more preferably less than 10.0%.

<Nb⁵⁺>

The optical glass of the present invention can also be containing the Nb as any composition⁵⁺。Nb⁵⁺Have improve glass refractive index, Improve chemical durability and then suppression Abbe number reduces, the character of suppression melt temperature rising.

Owing to such character strengthens, so Nb⁵⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, More preferably less than 5.0%.

Can be by using such as Nb₂O₅Nb is made Deng as raw material⁵⁺It is included in glass.

<Ti⁴⁺>

The optical glass of the present invention can also be containing the Ti as any composition⁴⁺。Ti⁴⁺Have improve glass refractive index, Reduce the character of coloring.

Owing to such character strengthens, so Ti⁴⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, enter One step preferably less than 5.0%.

Can be by using such as TiO₂Ti is made Deng as raw material⁴⁺It is included in glass.

<Zr⁴⁺>

The optical glass of the present invention can also be containing the Zr as any composition⁴⁺。Zr⁴⁺Have improve glass refractive index, Improve the character of the mechanical strength of glass.

Owing to such character strengthens, so Zr⁴⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, More preferably less than 5.0%.

Can be by using such as ZrO₂、ZrF₄Zr is made Deng as raw material⁴⁺It is included in glass.

<Ta⁵⁺>

The optical glass of the present invention can also be containing the Ta as any composition⁵⁺。Ta⁵⁺There is the refractive index improving glass Character.

Owing to such character strengthens, so Ta⁵⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, More preferably less than 5.0%.

Can be by using such as Ta₂O₅Ta is made Deng as raw material⁵⁺It is included in glass.

<W⁶⁺>

The optical glass of the present invention can also be containing the W as any composition⁶⁺。W⁶⁺There is the refractive index of raising glass, enter And suppress the character of the reduction of Abbe number.

Owing to such character strengthens, so W⁶⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, More preferably less than 5.0%.

Can be by using such as WO₃W is made Deng as raw material⁶⁺It is included in glass.

<Ge⁴⁺>

The optical glass of the present invention can also be containing the Ge as any composition⁴⁺。Ge⁴⁺Have improve glass refractive index, Improve the character of the devitrification resistance of glass.

Owing to such character becomes obvious, so Ge⁴⁺Containing ratio be preferably less than 10.0%, more preferably 8.0% Hereinafter, more preferably less than 5.0%.

Can be by using such as GeO₂Ge is made Deng as raw material⁴⁺It is included in glass.

<Bi³⁺>

The optical glass of the present invention can also be containing the Bi as any composition³⁺。Bi³⁺Have improve glass refractive index, Reduce the character of glass transition point.

Owing to such character strengthens, so Bi³⁺Containing ratio be preferably less than 10.0%, more preferably less than 8.0%, enter One step is preferably less than 5.0%.

Can be by using such as Bi₂O₃Bi is made Deng as raw material³⁺It is included in glass.

<Te⁴⁺>

The optical glass of the present invention can also be containing the Te as any composition⁴⁺。Te⁴⁺There is the folding that can improve glass Penetrate rate, be difficult to devitrification, the character of suppression coloring.

Owing to such character strengthens, so Te⁴⁺Containing ratio be preferably less than 15.0%, more preferably 10.0% with Under, more preferably less than 8.0%, more preferably less than 5.0%.

Can be by using such as TeO₂Te is made Deng as raw material⁴⁺It is included in glass.

About anion component

<F^->

The optical glass of the present invention contains F^-。F^-Have and improve the anomalous dispersion of glass and Abbe number and then make glass difficult Character with devitrification.

Owing to such character strengthens, so, represent with anion %, F^-Containing ratio be preferably 15.0～40.0%. It addition, more preferably more than 18.0%, more preferably more than 20.0%.It addition, more preferably less than 35.0%, further It is preferably less than 33.0%.

Can be by using such as AlF₃、MgF₂、BaF₂F is made as raw material etc. the fluoride of various cation constituents^-Comprise In glass.

<O^2->

The optical glass of the present invention contains O^2-。O^2-It is for having character and the shape that the abrasion degree of suppression glass rises Reticulate composition necessary to structure.

Represent with anion %, O^2-Containing ratio and F^-The summation of containing ratio be preferably more than 98.0%, more preferably More than 99.0%, more preferably 100%.This is owing to so can obtain stable glass.

Can be by using such as Al₂O₃, the oxide of the various cation constituent such as MgO, BaO, Al (PO)₃、Mg(PO)₂、 Ba(PO)₂O is made as raw material etc. the phosphate etc. of various cation constituents^2-It is included in glass.

In the optical glass of the present invention, can add as required in the range of the characteristic of glass not damaging the present application Add other compositions.

About the composition that should not contain

Below the composition that should not contain in the optical glass of the present invention and the composition that do not preferably comprises are illustrated.

Even if individually or compoundlyly containing a small amount of V in addition to Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu, Cr, During the cation of the transition metal such as Mn, Fe, Co, Ni, Cu, Ag and Mo, owing to having glass coloration, ripple specific to visibility region The long character producing absorption, so particularly the most actually do not contain this in using the optical glass of wavelength of visibility region A little compositions.

Control as harmful chemical to use it addition, the cation of Pb, Th, Cd, Tl, Os, Be and Se has in recent years Tendency, not only in glass manufacture operation, so that process after manufacturing procedure and commercialization needs to take in environmental cure Measure.Therefore, pay attention to environmentally when affecting, in addition to being inevitably mixed into, the most actually do not contain these become Point.Thus so that optical glass does not contains the material polluting environment.Therefore, even if not taking in special environmental cure Measure, it is also possible to manufacture, process and this optical glass discarded.

It addition, although Sb is useful as deaeration agent, but, S b brings disadvantageous composition as to environment in recent years And have and make its tendency being not included in optical glass, from this point of view, preferably do not contain Sb.

Sum up the above, it is shown that the optimal way of the optical glass of the present invention.

The optical glass of the present invention is preferably following optical glass: represent with cation %, contains as cation constituent Have:

P⁵⁺: 25～50%,

Al³⁺: 5～15%,

Ca²⁺: 1～8%,

R²⁺: 30～70%,

Gd³⁺: more than 0% and less than 10.0%,

Ln³⁺: more than 1.1% and less than 10.0%；

Represent with anion %, contain as anion component:

F^-: 15～40%,

The refractive index (nd) >=1.55 of described optical glass, Abbe number (ν d) >=55.

It addition, and then more preferably Y³⁺、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺The containing ratio of each cation constituent meet Gd³⁺/(Y³⁺ +La³⁺+Gd³⁺+Yb³⁺+Lu³⁺) optical glass of relation of ＞ 0.74.

Manufacture method

The manufacture method of the optical glass of the present invention is not particularly limited.Such as can manufacture as follows: above-mentioned raw materials is pressed Uniformly mix in the range of the containing ratio of regulation according to each composition, the mixture of preparation is put into silica crucible or oxidation After aluminum crucible or platinum crucible slightly melt, put in platinum crucible, platinum alloy crucibles or iridium crucible, at 900～1200 DEG C Temperature range under melted 2～10 hours, stirring, after carrying out froth breaking etc., be reduced to the temperature of less than 850 DEG C, then Carry out post-treatment stirring and remove striped, be poured into Slow cooling in mould thus manufacture.

Physical property

The optical glass of the present invention is characterized with partial dispersion ratio (θ g, F).Therefore, it is readily obtained and can compensate accurately The optical glass of chromatic aberration.

Partial dispersion ratio (θ g, F) is preferably more than 0.535, more preferably more than 0.538, more preferably more than 0.540, More preferably more than 0.542.

It addition, partial dispersion ratio (θ g, F) refers to measure according to Japanese Optical nitre industry meeting standard JOGIS01-2003 The value obtained.

It addition, the partial dispersion described in the present invention is than the partial dispersion ratio referred in short wavelength region.

The anomalous dispersion (Δ θ g, F) of the optical glass of the present invention is high.Therefore, being readily obtained can complementary color accurately The lens of aberration.

Anomalous dispersion (Δ θ g, F) be preferably more than 0.006, more preferably more than 0.008, more preferably 0.010 with On, more preferably more than 0.011, more preferably more than 0.012, more preferably more than 0.013.

Here, partial dispersion ratio (θ g, F) and anomalous dispersion (Δ θ g, F) are illustrated, then, the light to the present invention The feature learned in the physical property of glass illustrates in greater detail.

First, partial dispersion ratio (θ g, F) is illustrated.

Partial dispersion ratio (θ g, F) is for representing the refractive index difference of certain 2 wavelength region in the wavelength dependency of refractive index Ratio, in order to following formula (1) represent.

θ g, F=(n_g-n_F)/(n_F-n_C) ... formula (1)

Here, n_gIt is the refractive index of g ray (435.83nm), n_FIt is the refractive index of F ray (486.13nm), n_CIt it is C ray (656.27nm) refractive index.

Further, if tying up to the pass of this partial dispersion ratio (θ g, F) Yu Abbe number (ν d) map on XY chart, the most common The situation of optical glass is substantially to fall on the straight line being referred to as datum line.Datum line refers to: use partial dispersion ratio (θ g, F) be the longitudinal axis, Abbe number (ν d) be on the XY chart of transverse axis (on rectangular coordinate), connect by partial dispersion than and Abbe number map Obtained by NSL7 Yu PBM2 these 2 and slope be positive straight line (with reference to Fig. 1).As the normal glass of the benchmark of datum line, though The most different according to the difference of each optical glass manufacturer, but each company is all to carry out determining with almost equal slope and intercept Justice (NSL7 Yu PBM2 be Kabushiki Kaisya Ohara manufacture optical glass, the Abbe number (ν d) of NSL 7 is 60.5, partial dispersion Being 0.5436 than (θ g, F), the Abbe number (ν d) of PBM2 is 36.3, and partial dispersion ratio (θ g, F) is 0.5828).

Relative to such partial dispersion ratio (θ g, F), anomalous dispersion (Δ θ g, F) is to represent partial dispersion ratio (θ g, F) Which kind of degree the figure made with Abbe number (ν d) is offset to from benchmark alignment y direction.Big by anomalous dispersion (Δ θ g, F) The optical element that glass is constituted can compensate by colour produced by other lens in having the wave-length coverage near blueness The character of difference.

It addition, low dispersion area (Abbe number is the region of more than about 55) in, had in the past Abbe number (ν d) the biggest, The tendency that anomalous dispersion (Δ θ g, F) is the biggest.And then, in distress so that abrasion degree be 510 as follows time make anomalous dispersion maintain In high-order tendency.

The present inventor furthers investigate, and successfully have developed compared with conventional optical glass relative to Abbe number (ν The higher optical glass of value of anomalous dispersion (Δ θ g, F) d).

Such as, if the optical glass of the optimal way shown in Examples hereinafter, then can obtain Abbe number (ν d) is 66 ～when about 68, the optics that partial dispersion ratio (θ g, F) is more than 0.545 and anomalous dispersion (Δ θ g, F) is more than 0.013 Glass.The value of such partial dispersion ratio (θ g, F) and anomalous dispersion (Δ θ g, F) and the Abbe number (ν d) with same degree Conventional optical glass is compared, for obvious high level.

The optical glass of the present invention not only has high refractive index (nd), and has low dispersivity (high Abbe number).

Refractive index (nd) is more than 1.55, preferably more than 1.56, more preferably more than 1.57.

Abbe number (ν d) is more than 55, preferably more than 58, more preferably more than 60, more preferably more than 66.

The optical glass of the present invention owing to possessing such refractive index (nd) and Abbe number (ν d), so optical design from Expanded by degree, even and if then seeking the slimming of element and can also obtain big light refraction amount.

It addition, refractive index (nd) and Abbe number (ν d) refer to according to Japanese Optical nitre industry meeting standard JOGIS01-2003 And measure the value obtained.

The optical glass abrasion degree of the present invention is low.Therefore, the unnecessary abrasion of optical glass or damage can be reduced, make optics Process in the attrition process of glass becomes easy, it is easy to be ground processing.

Abrasion degree is preferably less than 510, and more preferably less than 500, more preferably less than 490, more preferably less than 480, More preferably less than 470, more preferably less than 460, more preferably less than 450, more preferably less than 440, more preferably 430 with Under, more preferably less than 420.

On the other hand, if abrasion degree too low have on the contrary attrition process become difficulty tendency.Therefore, abrasion degree be preferably 80 with On, more preferably more than 100, more preferably more than 120.

It addition, abrasion degree refers to measure based on " assay method of the abrasion degree of JOGIS10-1994 optical glass " obtain Value.

" preform and optical element "

The optical glass of the present invention is useful on various optical elements and optical design, wherein, particularly preferably by this The optical glass of invention forms preform, and this preform uses the method such as attrition process or precise press molding, system Make the optical elements such as lens, prism, mirror.Thus, for photographing unit, projector or the like make visible light-transmissive optics unit During the optical instrument of part, fine and high-precision imaging characteristic can be realized, and the optics in these optical instruments can be sought The miniaturization of system.Here, the method manufacturing preform material is not particularly limited, and can use such as by Japanese Unexamined Patent Publication 8- The manufacture method of the optical glass described in the manufacturing process of the glass gob described in 319124 or Japanese Unexamined Patent Publication 8-73229 With manufacture the method directly being manufactured preform material as device by melten glass, alternatively, it is also possible to use by optics glass The strip that glass is formed carries out the method that the cold working such as grinding grinding manufacture.

Embodiment

The glass composition of embodiment 1～5 of optical glass, refractive index (nd), Abbe number (ν d), part as the present invention Dispersion ratio (θ g, F), anomalous dispersion (Δ θ g, F), abrasion degree and proportion (g/cm³) be shown in Table 1.

The optical glass of embodiments of the invention 1～5, all selects respective oxide, carbonate, nitrate, fluorine The high-purity raw that the common fluorphosphate glasses such as compound, Metaphosphoric acid compound are used as the raw material of each composition, according to The ratio of the composition of each embodiment shown in table 1 weighs, and uniformly after mixing, puts in platinum crucible, forms according to glass Melted difficulty electric furnace melt 2～10 hours within the temperature range of 900～1200 DEG C, stir, carry out froth breaking etc. After, drop temperature to less than 850 DEG C and be poured into again in mould, after Slow cooling, make glass.

Herein, the optical glass of embodiment 1～5 is determined based on Japanese Optical nitre industry meeting standard JOGIS01-2003 Refractive index (nd), Abbe number (ν d) and partial dispersion ratio (θ g, F).It addition, as in this mensuration use glass, use with Annealing conditions is set to that the Slow cooling stove that Slow cooling cooling rate is-25 DEG C/hr carries out the glass processed.And, by surveying The value of in the Abbe number (ν d) obtained, the to be positioned at Fig. 1 partial dispersion ratio (θ g, F) on datum line and the partial dispersion ratio recorded The difference of the value of (θ g, F), obtains anomalous dispersion (Δ θ g, F).

It addition, abrasion degree is measured based on " assay method of the abrasion degree of JOGIS10-1994 optical glass ".That is, will The square glass plate sample of 30 × 30 × 10mm size is placed horizontally in the cast iron plane ware (250mm φ) of rotation per minute 60 times The fixed position away from center 80mm, limit vertically applies the loading of 9.8N (1kgf), while similarly supply within the time of 5 minutes The lapping liquid that with the addition of 10g#800 (mean diameter 20 μm) grinding-material (aluminum oxide A abrasive particle) in water 20mL rubs, Measure the sample mass before and after grinding, obtain abrasion quality.Same operation, obtains the standard that Japanese Optical nitre industry can be specified The abrasion quality of sample,

Abrasion degree is calculated by following formula: abrasion degree=(the abrasion quality/proportion of sample)/(the abrasion quality of standard specimen/ Proportion) } × 100.

It addition, proportion represents the value of the pure water relative to+4 DEG C, Archimedes method try to achieve.

Table 1

As shown in table 1, the optical glass of embodiments of the invention, its refractive index (nd) is more than 1.55, Abbe number (ν D) it is more than 55.

It addition, specifically, in all of the embodiments illustrated, refractive index (nd) is also more than 1.59, and Abbe number (ν D) it is more than 66.It addition, partial dispersion ratio (θ g, F) is more than 0.545, anomalous dispersion (Δ θ g, F) is more than 0.013.

Such partial dispersion ratio (θ g, F) and the value of anomalous dispersion (Δ θ g, F) and the Abbe number (ν with same degree D) conventional optical glass is compared, and is the highest value.

And then, the abrasion degree of all embodiments is less than 510.

It addition, proportion is less than 4.22.

And then, use the optical glass of embodiments of the invention, formed after attrition process preform, carry out grinding and Grind, be processed into the shape of lens and prism.It addition, use the optical glass of the embodiment of the present invention, form precise press molding With preform, and precise press molding preform is carried out precise press molding processing and it is processed into lens and prism Shape.In either case, the shape of various lens or prism can be processed into.

Claims (10)

1. an optical glass, wherein, contains P as cation constituent⁵⁺、Al³⁺、Ca²⁺、Ln³⁺And select free Mg²⁺、Sr²⁺With Ba²⁺At least one in the group of composition, wherein, Ln³⁺It is to select free Y³⁺、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺In the group of composition at least A kind of；

Represent with cation %, containing 31.65～the Ba of 40.0%²⁺,

Represent with cation %, Ln³⁺Total containing ratio for more than 1.1% and less than 10.0%,

Y³⁺、La³⁺、Gd³⁺、Yb³⁺And Lu³⁺The containing ratio of each cation constituent meet Gd³⁺/(Y³⁺+La³⁺+Gd³⁺+Yb³⁺+Lu³⁺) The relation of ＞ 0.74,

Wherein, cation % refer to be separated into the glass constituent of optical glass cation constituent and anion component and The composition of each composition contained in glass is represented using the toatl proportion of cation as 100 moles of %,

F is contained as anion component^-,

Refractive index nd >=1.55 of described optical glass, Abbe number ν d >=55.

Optical glass the most according to claim 1, wherein, represents with cation %, contains as cation constituent:

P⁵⁺: 25～50%,

Al³⁺: 5～15%,

Ca²⁺: 1～8%,

R²⁺: 30～70%, wherein, R²⁺Refer to Ca²⁺+Mg²⁺+Sr²⁺+Ba²⁺,

Gd³⁺: more than 0% and less than 10.0%；

Represent with anion %, contain as anion component:

F^-: 15～40%,

Wherein, anion % refer to be separated into the glass constituent of optical glass cation constituent and anion component and The composition of each composition contained in glass is represented using the toatl proportion of anion as 100 moles of %.

Optical glass the most according to claim 1 and 2, wherein, represents with cation %, R²⁺Total containing ratio be 33～ 70%,

Wherein, R²⁺Total containing ratio refer to the Ca that represents with cation %²⁺、Mg²⁺、Sr²⁺、Ba²⁺Total containing ratio of these 4 kinds of ions.

Optical glass the most according to claim 1 and 2, wherein, does not contains Sb.

Optical glass the most according to claim 1 and 2, wherein, does not contains Y.

Optical glass the most according to claim 1 and 2, its abrasion degree is less than 510.

7. an optical element, it is formed by the optical glass according to any one of claim 1～6.

8. attrition process is used and/or a preform for precise press molding, and it is by institute any one of claim 1～6 The optical glass stated is formed.

9. an optical element, it is for being ground forming by the preform described in claim 8.

10. an optical element, it forms for the preform precision described in claim 8 being suppressed.