CN107207320A

CN107207320A - Glass, compressing use glass material, optical element blank and optical element

Info

Publication number: CN107207320A
Application number: CN201680005396.6A
Authority: CN
Inventors: 根岸智明
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2015-01-13
Filing date: 2016-01-13
Publication date: 2017-09-26
Anticipated expiration: 2036-01-13
Also published as: JP6291598B2; JP2021008397A; CN108715512B; JPWO2016114274A1; JP7514351B2; JP2018104283A; JP7003198B2; JP2022050507A; TWI671270B; WO2016114274A1; TW201641456A; TWI641572B; CN107207320B; JP2023085359A; JP7250106B2; JP6812382B2; TW201904900A; CN108715512A

Abstract

It is oxide glass the present invention relates to a kind of glass, is represented with quality %, B₂O₃And SiO₂Total content be 15~35 mass %, La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content be 45~65 mass %, wherein, Yb₂O₃Content is below 3 mass %, ZrO₂Content is 3~11 mass %, Ta₂O₅Content is below 5 mass %, B₂O₃Content is relative to B₂O₃And SiO₂Total content mass ratio be 0.4~0.900, B₂O₃And SiO₂Total content relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio be 0.42~0.53, Y₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio be 0.05~0.45, Gd₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio be 0~0.05, Nb₂O₅Content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃The mass ratio of total content be 0.5~1, refractive index nd scope is 1.800~1.850, and Abbe number ν d scope is 41.5~44.

Description

Glass, compressing use glass material, optical element blank and optical element

Association request it is cross-referenced

This application claims Japanese patent application filed in 13 days January in 2015 the 2015-004542nd and Japan Patent Shen Priority that please be No. 2015-004544, in this as the open full content for especially quoting these patent applications.

Technical field

The present invention relates to glass, compressing use glass material, optical element blank and optical element.

Background technology

As the glass (high-refractivity and low-dispersion glass) that refractive index is high, dispersion is low, such as remember in patent document 1~18 The glass that the scope for having carried refractive index nd is 1.800~1.850 and Abbe number ν d scope is 41.5~44.In this as public affairs Open, the full content of special referenced patents document 1~18.

Patent document 1：Japanese Unexamined Patent Publication 2002-12443 publications；

Patent document 2：Japanese Unexamined Patent Publication 2003-267748 publications；

Patent document 3：Japanese Unexamined Patent Publication 2005-281124 publications；

Patent document 4：Japanese Unexamined Patent Publication 2005-298262 publications；

Patent document 5：Japanese Unexamined Patent Application 55-121925 publications；

Patent document 6：Japanese Unexamined Patent Publication 2009-203083 publications；

Patent document 7：Japanese Unexamined Patent Application 54-090218 publications；

Patent document 8：Japanese Unexamined Patent Application 56-160340 publications；

Patent document 9：Japanese Unexamined Patent Publication 2009-167080 publications；

Patent document 10：Japanese Unexamined Patent Publication 2009-167081 publications；

Patent document 11：Japanese Unexamined Patent Publication 2009-298646 publications；

Patent document 12：Japanese Unexamined Patent Publication 2010-111527 publications；

Patent document 13：Japanese Unexamined Patent Publication 2010-111528 publications；

Patent document 14：Japanese Unexamined Patent Publication 2010-111530 publications；

Patent document 15：Japanese Unexamined Patent Application 57-056344 publications；

Patent document 16：Japanese Unexamined Patent Application 61-163138 publications；

Patent document 17：Japanese Unexamined Patent Publication 2002-284542 publications；

Patent document 18：Japanese Unexamined Patent Publication 2007-269584 publications.

The content of the invention

The glass that refractive index nd scope is 1.800~1.850 and Abbe number ν d scope is 41.5~44 is for color The useful material used for optical elements of the correction of aberration, the multifunction of optical system, densification.In addition, following as long as no spy Other to record, refractive index refers to the refractive index nd of d lines (the wavelength 587.56nm of helium).In addition, as long as no special record, Ah Shellfish number refers to ν d.As known, distinguish by the refractive index of F lines (the wavelength 486.13nm of hydrogen), C lines (hydrogen 656.27nm) When being set to nF, nC, ν d are defined as ν d=(nd-1)/(nF-nC).

On the refractive index with above range and the high-refractivity and low-dispersion glass of Abbe number, in order to further improve it Serviceability, preferably meet it is following some.

Being capable of stable supplying.Therefore, it is preferred that reducing as rare costly not enough to the demand supplies in market in recent years Element Gd, Ta ratio shared in glass composition.On the other hand, glass described in patent document 7 contains largely Ta.In addition, refractive index with above range described in glass and patent document 17 described in patent document 8~14 and The glass of Abbe number contains substantial amounts of Gd.

Ratio in glass composition shared by Yb is low.The reasons why this is due to following is caused.

Yb has near infrared region to be absorbed.Therefore, the glass containing substantial amounts of Yb is (such as described in patent document 16 Glass) be unsuitable for needing the purposes of high-transmission rate in the scope from visibility region near infrared region, it is such as CCTV camera, red The material used for optical elements of outer video camera, the lens of vehicle-mounted vidicon etc..In addition, Yb belongs to heavy rare earth element, glass is used as Composition, atomic weight is big, increases the proportion of glass.When the proportion increase of glass, lens become weight.As a result, when will be this When mirror is installed to the camera lens of auto-focusing formula, power consumption becomes big, and the consumption of battery becomes serious.Aspect more than, preferably Reduce the ratio shared by Yb in glass composition.

Excellent heat stability.The low glass of heat endurance glass during glass is manufactured can show tendency towards devitrification.So And, according to the research of the present inventor, the heat endurance of such as glass described in patent document 6 is poor.

In view of the aspect of the above, a mode of the invention provides a kind of glass, refractive index nd scope for 1.800~ 1.850, and Abbe number ν d scope is 41.5~44, reduces the ratio shared by Gd, Ta and Yb in glass composition, and heat Excellent in stability.

In addition, in a mode, above-mentioned glass further preferably further meets more than 1 in following aspect.

Suppress the long wavelengthization at the light absorbs end of the short wavelength side of glass.The reasons why this is due to following is caused.

For correcting chromatic aberration, it is known that there are as below methods：Make many using the glass respectively with different optical characteristics Individual lens, make the laminating of these lens make balsaming lens.During balsaming lens is made, in order that lens are pasted each other Close, usually using ultraviolet hardening bonding agent.Concrete condition is as follows.The coated UV line on the surface for making lens fit each other Curing type bonding agent, makes lens fit.Now, the very thin coating of ultraviolet hardening bonding agent is formed generally between lens Layer.Then, by lens to above-mentioned coating layer irradiation ultraviolet radiation, solidify ultraviolet hardening bonding agent.Therefore, when lens When transmission of ultraviolet rays is low, the ultraviolet without enough light quantities reaches above-mentioned coating layer by lens, causes solidification to become Obtain insufficient.Or, solidification takes long enough.In addition, lens are bonded and fixed using ultraviolet hardening bonding agent In the case of lens barrel etc., similarly, when the ultraviolet transmittance of lens is low, solidification is insufficient, or solidification needs For a long time.

Therefore, in order to be made have be suitable for optical system making transmission characteristics glass, preferably improve glass Ultraviolet region transmissivity, in other words, suppress glass short wavelength side light absorbs end long wavelengthization.

However, according to the research of the present inventor, such as in the glass described in patent document 5, the short wavelength side of glass Light absorbs end carry out long wavelengthization, the decrease in transmission of ultraviolet region.In addition, in conventional high-refractivity and low-dispersion glass In glass composition, when wanting reduction Gd, Ta content, while maintaining high-refractivity and low-dispersion characteristic and during heat endurance, There is the light absorbs end long wavelengthization of the short wavelength side of glass, the tendency that transmission of ultraviolet rays is greatly reduced.

It is suitable for machining.Concrete condition is as follows.As the method that optical element is obtained by glass, except precision compacting Beyond the method for forming (see, for example patent document 1~4), also have and optical element blank is molded by glass, to optics member The method that part blank is ground the machining of processing, polishing etc. and is processed into optical element.If in this machinery Glass is easily damaged in processing, then reduces fabrication yield.Generally, the glass transition of the glass of precision press molding method Temperature is low, but the low glass of glass transition temperature has tendency easily damaged in machining.Therefore, it is suitable in order to be made Together in the glass of machining, preferably make glass transition temperature higher than the glass of precision press molding.

The mode of the present invention is related to a kind of glass (hereinafter referred to as " glass 1 "), is oxide glass, with quality % tables Show,

B₂O₃And SiO₂Total content be 15~35 mass %,

La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content be 45~65 mass %, wherein, Yb₂O₃Content is 3 mass % Hereinafter,

ZrO₂Content is 3~11 mass %,

Ta₂O₅Content is below 5 mass %,

B₂O₃Content is relative to B₂O₃And SiO₂Total content mass ratio (B₂O₃/(B₂O₃+SiO₂)) for 0.4~ 0.900,

B₂O₃And SiO₂Total content relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio ((B₂O₃ +SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) it is 0.42~0.53,

Y₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (Y₂O₃/(La₂O₃+Y₂O₃+ Gd₂O₃+Yb₂O₃)) it is 0.05~0.45,

Gd₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (Gd₂O₃/(La₂O₃+Y₂O₃ +Gd₂O₃+Yb₂O₃)) it is 0~0.05,

Nb₂O₅Content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+ Ta₂O₅+WO₃)) it is 0.5~1,

Refractive index nd scope is 1.800~1.850, and Abbe number ν d scope is 41.5~44.

In addition, the mode of the present invention is related to a kind of glass (hereinafter referred to as " glass 2 "), it is oxide glass, with sun Ion % represents,

B³⁺And Si⁴⁺Total content be 45~65%,

La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content be 25%~35%, still, Yb³⁺Content is less than 2%,

Zr⁴⁺Content is 2~8%,

Ta⁵⁺Content is less than 3%,

B³⁺Content is relative to B³⁺And Si⁴⁺Total content cation ratio (B³⁺/(B³⁺+Si⁴⁺)) it is more than 0.65 and small In 0.94,

B³⁺And Si⁴⁺Total content relative to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content cation ratio ((B³⁺+Si⁴ ⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) it is 1.65~2.60,

Y³⁺Content is relative to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content cation ratio (Y³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³ ⁺)) it is 0.05~0.45,

Gd³⁺Content is relative to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content cation ratio (Gd³⁺/(La³⁺+Y³⁺+Gd³⁺+ Yb³⁺)) it is 0~0.05,

Nb⁵⁺Content is relative to Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content cation ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+ W⁶⁺)) it is 0.4~1,

Glass 1 is refractive index nd with above range and Abbe number ν d glass, includes Gd₂O₃Various composition (i.e. La₂O₃、Y₂O₃、Gd₂O₃、Yb₂O₃) total content in the above range, meet Gd₂O₃Content as molecule, will be above-mentioned various Total content of composition as denominator above-mentioned mass ratio.Therefore, the ratio reduction that Gd occupies in glass composition.And then, Ta₂O₅Content and Yb₂O₃Respectively as described above, the ratio that Ta and Yb occupy in glass composition is also reduced content.Above-mentioned glass By carrying out meeting above-mentioned content, total content and matter in the composition for reducing the ratio that Gd, Ta and Yb occupy like this The composition adjustment of ratio is measured, so as to realize high heat endurance (property for being difficult devitrification).And then, short wavelength can also be suppressed The long wavelengthization at the light absorbs end of side, realizes that high glass-transition temperature (Tg) changes (high temperature of glass transition temperature).

Glass 2 is refractive index nd with above range and Abbe number ν d glass, includes Gd³⁺Various composition (i.e. La³ ⁺、Y³⁺、Gd³⁺、Yb³⁺) total content in the above range, meet Gd³⁺Content is as molecule, by the conjunction of above-mentioned various composition Content is counted as the above-mentioned cation ratio of denominator.Therefore, the ratio reduction that Gd occupies in glass composition.And then, Ta⁵⁺Content and Yb³⁺Respectively as described above, the ratio that Ta and Yb occupy in glass composition is also reduced content.Above-mentioned glass passes through like this Reduce the composition for carrying out meeting above-mentioned content, total content and cation ratio in the composition for the ratio that Gd, Ta and Yb occupy Adjustment, so as to realize high heat endurance (property for being difficult devitrification).And then, the light absorbs of short wavelength side can also be suppressed The long wavelengthization at end, realizes that high glass-transition temperature (Tg) changes (high temperature of glass transition temperature).

According to the mode of the present invention, using the teaching of the invention it is possible to provide special with useful high-refractivity and low-dispersion in optical system Property, the glass for being capable of stable supplying and excellent heat stability.And then, according to the mode of the present invention, using the teaching of the invention it is possible to provide by above-mentioned Compressing use glass material, optical element blank and optical element that glass is constituted.

Brief description of the drawings

Fig. 1 shows glass A described later thickness 10.0mm spectral-transmission favtor curve.

Fig. 2 shows glass B described later thickness 10.0mm spectral-transmission favtor curve.

Embodiment

The glass composition of the present invention can be for example, by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) etc. method quantified.The assay value tried to achieve by ICP-AES is sometimes for example comprising analysis ± 5% or so evaluated error of value.In addition, in this specification and the present invention, the content of constituent is 0%, not included Or do not import and mean substantially not including this composition composition, refer to the content of this composition composition for impurity level degree with Under.

Hereinafter, on number range, (more) preferred lower limit and (more) preferred upper limit are shown in described in table sometimes. In table, the numerical value for being recorded in lower section is more preferred, and the numerical value for being recorded in bottom is most preferred.In addition, as long as no spy It is other record, (more) preferred lower limit refer to record value more than value (more) preferably, (more) preferred upper limit refer to record The following value (more) of value is preferably.The numerical value and (more) preferred upper limit described in the row of (more) in table preferred lower limit can be made Row described in numerical value arbitrarily combine and carry out specified value scope.

[glass]

The glass 1 and glass 2 of the mode of the present invention are that, with above-mentioned glass composition, refractive index nd scope is 1.800~1.850, and Abbe number ν d scope is 41.5~44 oxide glass.Hereinafter, to the details of glass 1 and glass 2 Illustrate.

In the present invention, the glass composition of glass 1 is represented with oxide benchmark." the glass group of oxide benchmark herein Into " refer to that frit is all decomposed in melting, and carry out and obtain as the material existed in glass as oxide The glass composition arrived.In addition, as long as no special record, the glass composition of glass 1 be set on the basis of quality (quality %, Mass ratio) represent.

B₂O₃、SiO₂It is the network forming component of glass.Work as B₂O₃And SiO₂Total content (B₂O₃+SiO₂) for 15% with When upper, it is possible to increase the heat endurance of glass, suppressed the crystallization of the glass in manufacture.On the other hand, B is worked as₂O₃And SiO₂It is total When content is less than 35%, refractive index nd reduction can be suppressed, thus can make the glass with above-mentioned optical characteristics, That is refractive index nd is present in 1.800~1.850 scope and Abbe number ν d be present in 41.5~44 scope glass.Cause This, the B in glass 1₂O₃And SiO₂The scope of total content be set to 15~35%.B₂O₃And SiO₂Total content it is preferred Lower limit and the preferred upper limit are as shown in the table.

【Table 1】

It is used as the B of the network forming component of glass₂O₃And SiO₂Each composition content ratio to the thermally-stabilised of glass Property, meltbility, mouldability, chemical durability, weatherability, machining property etc. are impacted.B₂O₃Compared to SiO₂Improve melting Property effect it is more excellent, but melting when it is readily volatilized.On the other hand, SiO₂With improving the chemical durability, weather-proof of glass Property, machining property, improve melting when glass sticky effect.

Generally, B is being included₂O₃And La₂O₃In the low dispersing glass of high index of refraction Deng rare earth element, glass during melting Viscosity is low.But, glass upon melting it is sticky low when, heat endurance reduction (becoming easy crystallization).On glass manufacture When crystallization, the state of crystallization is more more stable than amorphous state (amorphous state), and it is by constituting the ion of glass in glass Moved in glass and arranged and occurred in the way of with crystal structure.Therefore, by B₂O₃And SiO₂Each composition The ratio of content is adjusted so that viscosity when melting increases, so as to make above-mentioned ion be difficult with crystal structure Mode is arranged, and further suppresses the crystallization of glass, improves the heat endurance of glass.

Melten glass is poured into be molded in mold when, when the viscosity of melten glass is low, be poured into mold Glass solidification surface element be rolled into the inside for the glass for being still in molten condition and as striped, the optics of glass Homogenieity is reduced.The excellent glass of mouldability will melted equivalent in the high-refractivity and low-dispersion glass containing rare earth element The glass of state is poured into the higher glass of ratio of viscosities when in mold.

Work as B₂O₃Content is relative to B₂O₃And SiO₂Total content mass ratio (B₂O₃/(B₂O₃+SiO₂)) for 0.900 with When lower, viscosity reduction during melting can be suppressed, the heat endurance thus, it is possible to improve glass suppresses volatilization during melting.It is molten Volatilization when melting turns into the reason for variation for constituting glass, the variation of characteristic become big.Also, its result is difficult to optically equal The glass of matter is molded.Therefore, from the viewpoint of the few glass of the deviation to composition, characteristic carries out volume production, it is preferably able to By mass ratio (B₂O₃/(B₂O₃+SiO₂)) volatilization when being set to less than 0.900 and suppressing melting.And then, as mass ratio (B₂O₃/ (B₂O₃+SiO₂)) when being less than 0.900, it can also suppress the chemical durability of glass, weatherability, the reduction of machining property. On the other hand, in the glass composition described in described patent document 15 (Japanese Unexamined Patent Application 57-056344 publications), B₂O₃ Content is 28~30 mass %, SiO₂Content for 1~3 mass % (with reference to patent document 15 claims).By these Mass ratio (the B that the content of composition is calculated₂O₃/(B₂O₃+SiO₂)) it is 0.903~0.968 this big value.

On the other hand, as mass ratio (B₂O₃/(B₂O₃+SiO₂)) be more than 0.4 when, can prevent melting when frit Melting residual, therefore, it is possible to improve meltbility.

Aspect more than, in glass 1, by mass ratio (B₂O₃/(B₂O₃+SiO₂)) scope be set to 0.4~ 0.900.Mass ratio (B in glass 1₂O₃/(B₂O₃+SiO₂)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 2】

From the sight of heat endurance, meltbility, mouldability, chemical durability, weatherability, the machining property for improving glass etc. Point sets out, for B₂O₃Content, SiO₂Content, respective preferred lower limit and the preferred upper limit are as shown in the table.

【Table 3】

【Table 4】

La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃It is with the effect that refractive index is improved while the reduction of Abbe number is suppressed Composition.In addition, these compositions also have the chemical durability for improving glass, weatherability, the effect for improving glass transition temperature.

Work as La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content (La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃) be more than 45% when, energy Enough suppress the reduction of refractive index, therefore, it is possible to make the glass with above-mentioned optical characteristics.Further, it is possible to suppress glass The reduction of chemical durability, weatherability.In addition, when glass transition temperature is reduced, glass is machined (cut-out, Cutting, grinding, polishing etc.) when glass become easily damaged (reduction of machining property), but work as La₂O₃、Y₂O₃、Gd₂O₃With Yb₂O₃Total content be more than 45% when, the reduction of glass transition temperature can be suppressed, thus can also improve machinery plus Work.On the other hand, La is worked as₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content when being less than 65%, it is possible to increase the heat of glass is steady It is qualitative, thus also can suppress manufacture glass when crystallization, reduction melten glass when raw material melting residual.Therefore, in glass In glass 1, La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃The scope of total content be set to 45~65%.La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃ Total content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 5】

ZrO₂Be with improve refractive index effect composition, by making it contain in right amount, also with improve glass heat The effect of stability.In addition, ZrO₂Also have and improve glass transition temperature, make glass not cracky when being machined Effect.In order to obtain these effects well, in glass 1, by ZrO₂Content be set to more than 3%.On the other hand, when ZrO₂Content when being less than 11%, the heat endurance of glass can be improved, therefore, it is possible to suppress crystallization during glass manufacture, glass The generation of melting residual when glass is melted.Therefore, the ZrO in glass 1₂The scope of content be set to 3~11%.ZrO₂Content It is preferred that lower limit and the preferred upper limit it is as shown in the table.

【Table 6】

As above-mentioned record, from the viewpoint of the stable supplying of glass, Ta₂O₅It is preferably to reduce it in glass group The composition of shared ratio in.In addition, Ta₂O₅It is the composition with the effect for improving refractive index, but is also to make the proportion of glass The composition for increasing, reducing meltbility.Therefore, the Ta in glass 1₂O₅Content is set to less than 5%.Ta₂O₅Content it is preferred Lower limit and the preferred upper limit are as shown in the table.

【Table 7】

In order to realize above-mentioned optical characteristics while improving the heat endurance of glass, suppressing the increase of proportion, in glass In glass 1, by B₂O₃And SiO₂Total content relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio ((B₂O₃ +SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) scope be set to 0.42~0.53.As mass ratio ((B₂O₃+SiO₂)/(La₂O₃+ Y₂O₃+Gd₂O₃+Yb₂O₃)) be more than 0.42 when, the heat endurance of glass can be improved, therefore, it is possible to suppress the devitrification of glass.This Outside, the increase of the proportion of glass can also be suppressed.When the proportion increase of glass, the optical element made using the glass is become Weight.As a result it is mounted with that the optical system of the optical element becomes weight.The optical element of weight is arranged on auto-focusing formula for example, working as When in camera, power consumption increase during driving auto-focusing, battery can be consumed quickly.From the optical element made using the glass From the viewpoint of the light-weighted reduction for the optical system for being mounted with the optical element, it is preferably able to suppress the proportion of glass Increase.On the other hand, as mass ratio ((B₂O₃+SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) be less than 0.53 when, can realize Above-mentioned optical characteristics.In addition, the viewpoint that the improvement, high glass-transition temperature (Tg) from the chemical durability of glass are changed goes out Hair, it is also preferred that mass ratio ((B₂O₃+SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) it is less than 0.53.Mass ratio ((B₂O₃+ SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 8】

In La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃In, according to the reasons why above-mentioned record, Y₂O₃It is preferably to reduce it in glass group The composition of shared ratio in.Therefore in glass 1, by Y₂O₃Content is set to less than 3%.Y₂O₃The preferred lower limit of content It is as shown in the table with the preferred upper limit.

【Table 9】

Y₂O₃It is the work for being greatly reduced the light transmittance of near infrared region and playing the heat endurance for improving glass Composition.Further, since atomic weight is small, so Y₂O₃It is preferred composition in terms of the increase of the proportion of glass is suppressed.But It is to work as Y₂O₃Content it is excessive when, the heat endurance of glass is significantly reduced, easy crystallization.In addition, meltbility is reduced.From being produced on The light transmittance of near infrared region is not set to be greatly reduced and suppress the increase of proportion, with upper while improving heat endurance From the viewpoint of the glass for the optical characteristics stated, in glass 1, by Y₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃'s Mass ratio (the Y of total content₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) scope be set to 0.05~0.45.Mass ratio (Y₂O₃/ (La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 10】

According to the reasons why above-mentioned record, Gd₂O₃It is preferably to reduce the composition of its shared ratio in glass composition.In addition, Gd belongs to heavy rare earth element in the same manner as Yb, as the composition of glass, and Gd atomic weight is big, increases the proportion of glass.From the party Face is set out, it is also preferred that the reduction ratio that Gd occupies in glass composition.

In glass 1, Gd₂O₃Content according to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content and total relative to this The Gd of content₂O₃Content is determined.In glass 1, there is the high-refractivity and low-dispersion glass of above-mentioned optical characteristics from stable supplying From the viewpoint of glass, and then from the viewpoint of the small glass of proportion is made as high-refractivity and low-dispersion glass, by Gd₂O₃Contain Amount is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (Gd₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) Scope is set to 0~0.05.Mass ratio (Gd₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) preferred lower limit and the preferred upper limit such as Shown in following table.

【Table 11】

Never it is greatly reduced the light transmittance of near infrared region, proportion is suppressed while heat endurance is improved From the aspect of increase is there is provided high-refractivity and low-dispersion glass, La₂O₃It is useful composition.Therefore in glass 1, preferably will La₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (La₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+ Yb₂O₃)) scope be set to 0.55~0.95.Mass ratio (La₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) preferred lower limit It is as shown in the table with the preferred upper limit.

【Table 12】

La₂O₃、Y₂O₃、Gd₂O₃Each composition content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 13】

【Table 14】

【Table 15】

Nb₂O₅、TiO₂、Ta₂O₅And WO₃It is the composition with the effect for improving refractive index, by making it contain in right amount, also has There is the heat endurance for improving glass.From the optical characteristics stated in realization while further improve the thermally-stabilised of glass From the aspect of property, preferably Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content (Nb₂O₅+TiO₂+Ta₂O₅+WO₃) scope for 3~ 15%.Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 16】

ZnO has the effect of the melting for the raw material for promoting glass in melten glass, improves the effect of meltbility.This Outside, it may have adjustment refractive index, Abbe number, the effect for reducing glass transition temperature.From the aspect of meltbility is improved, It is preferred that ZnO content divided by B₂O₃And SiO₂The obtained value, i.e. mass ratio (ZnO/ (B of total content₂O₃+SiO₂)) for 0.04 with On.On the other hand, from the aspect of suppressing the reduction (high dispersion) of Abbe number, realizing above-mentioned optical characteristics, preferred matter Amount is than (ZnO/ (B₂O₃+SiO₂)) it is less than 0.4.In addition, from improve glass heat endurance and high glass-transition temperature (Tg) From the aspect of changing, it is also preferred that mass ratio (ZnO/ (B₂O₃+SiO₂)) it is less than 0.4.It is therefore preferable that by ZnO content be set to Mass ratio meter B₂O₃And SiO₂0.04~0.4 times of total content, i.e. by mass ratio (ZnO/ (B₂O₃+SiO₂)) it is set to 0.04 ~0.4.Mass ratio (ZnO/ (B₂O₃+SiO₂)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 17】

From meltbility, heat endurance, mouldability, machining property for improving glass etc., above-mentioned optical characteristics is realized Viewpoint is set out, and the preferred lower limit of ZnO content and the preferred upper limit are as shown in the table.

【Table 18】

From the optical characteristics stated in realization while suppress degree of staining λ 5 described later increase and improve the ultraviolet of glass From the aspect of line transmissivity, preferably B₂O₃And SiO₂Total content relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content Mass ratio ((B₂O₃+SiO₂)/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) scope be set to 2.65~10.In addition, from improving glass From the aspect of heat endurance, it is also preferred that by mass ratio ((B₂O₃+SiO₂)/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) be set to 2.65 with On.Mass ratio ((B₂O₃+SiO₂)/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) preferred lower limit and the preferred upper limit such as following table It is shown.

【Table 19】

On Nb₂O₅、TiO₂、Ta₂O₅And WO₃, by making it contain in right amount, play the work for the heat endurance for improving glass With.

As TiO in these compositions₂Content increase when, there is the decrease in transmission of the viewing area of glass, glass The tendency of color increase.

Ta₂O₅Function as described above.

For WO₃, when its content increase, there is the decrease in transmission of the viewing area of glass, the coloring increase of glass Tendency, exist in addition proportion increase tendency.

On the other hand, Nb₂O₅With being difficult the proportion of glass, coloring, manufacturing cost to increase, improve refractive index, improve glass The effect of the heat endurance of glass.Therefore, in glass 1, in order to effectively utilize Nb₂O₅Excellent effect, effect, by Nb₂O₅'s Content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) Scope is set to 0.5~1.From degree of staining λ 5 is reduced, promote to irradiate consolidating for caused ultraviolet hardening bonding agent by ultraviolet From the viewpoint of change, preferably increase mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)).Mass ratio (Nb₂O₅/(Nb₂O₅+ TiO₂+Ta₂O₅+WO₃)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 20】

On Ta₂O₅, according to the reasons why above-mentioned record, glass is not preferably imported energetically.Therefore, to Nb₂O₅Content phase For in Nb₂O₅、TiO₂、Ta₂O₅And WO₃Middle exclusion Ta₂O₅Nb afterwards₂O₅、TiO₂And WO₃Total content mass ratio (Nb₂O₅/ (Nb₂O₅+TiO₂+WO₃)) preferred scope illustrate.In order to make with the few glass of excellent heat endurance, coloring, Preferred mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+WO₃)) scope be 0.50~1.Mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+WO₃)) Preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 21】

From the viewpoint of meltbility is improved, preferably ZnO content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content Mass ratio (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) it is set to more than 0.1.In addition, for the low glass of meltbility, when in order to The melting for not having frit remains and improved the melting temperature of glass, and during the extension melting time, the coloring that there is glass increases Big tendency.It can be speculated as because in the melting crucible of the noble metal such as platinum during melten glass, being melted when raising Temperature, during the extension melting time, constitutes the precious metal melting into melten glass of crucible, produces the light as caused by precious metal ion Absorb, the coloring of glass, particularly λ 5 value increase.On the other hand, when the desired content by adjusting other glass ingredients To improve during meltbility, there is heat endurance reduction, it is difficult to obtain the glass of the homogeneous with above-mentioned optical characteristics. Therefore, in order to improve the meltbility of glass, from the aspect of the coloring for suppressing glass, it is also preferred that by mass ratio (ZnO/ (Nb₂O₅ +TiO₂+Ta₂O₅+WO₃)) it is set to more than 0.1.In addition, improving the heat endurance of glass from further, suppress glass transition temperature From the viewpoint of the reduction (the thus improvement of caused machining property) of degree, improvement chemical durability, preferably by mass ratio (ZnO/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) it is set to less than 3.Mass ratio (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) more preferably Lower limit and the preferred upper limit it is as shown in the table.

【Table 22】

For Nb₂O₅Content, TiO₂Content, WO₃The respective preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 23】

【Table 24】

【Table 25】

From the reduction of the further heat endurance for improving glass, suppression glass transition temperature, (thus caused machinery adds The improvement of work), improve chemical durability, from the viewpoint of weatherability, preferably Li₂O content is set to less than 1%.Li₂O content It is preferred that lower limit and the preferred upper limit it is as shown in the table.

【Table 26】

Na₂O、K₂O、Rb₂O、Cs₂O is respectively provided with the effect for the meltbility for improving glass, but when these content increase, shows Go out heat endurance, chemical durability, weatherability, the tendency of machining property reduction of glass.It is therefore preferable that Na₂O、K₂O、 Rb₂O、Cs₂The lower and upper limit difference of O each content is as shown in the table.

【Table 27】

【Table 28】

【Table 29】

【Table 30】

Rb₂O、Cs₂O is expensive composition, with Li₂O、Na₂O、K₂O is compared, and is the composition for being unsuitable for general glass.Cause This, the meltbility of glass is improved from while the heat endurance of maintenance glass, chemical durability, weatherability, machining property From the viewpoint of, preferably Li₂O、Na₂O and K₂O total content (Li₂O+Na₂O+K₂O lower and upper limit) are set to as follows Shown in table.

【Table 31】

MgO, CaO, SrO, BaO are the compositions with the effect for improving the meltbility of glass.But, when these compositions Content increase when, glass heat endurance reduction, tendency towards devitrification is shown.Therefore, each content of these compositions is preferably set respectively For more than the lower limit shown in following table, below the upper limit.

【Table 32】

【Table 33】

【Table 34】

【Table 35】

In addition, from the viewpoint of the further heat endurance for improving glass, MgO, CaO, SrO and BaO total content (MgO+CaO+SrO+BaO) it is preferably set to more than the lower limit shown in following table, below the upper limit.

【Table 36】

Al₂O₃It is chemical durability, the composition of the effect of weatherability with improvement glass.But, work as Al₂O₃Content During increase, the tendency, the tendency of the heat endurance of glass reduction, the tendency of meltbility reduction of refractive index reduction are shown sometimes.Examine Consider the aspect of the above, Al₂O₃Content is preferably set to more than the lower limit shown in following table, below the upper limit.

【Table 37】

Ga₂O₃、In₂O₃、Sc₂O₃、HfO₂It is respectively provided with the effect for improving refractive index nd.But, these compositions are expensive, no The required composition from the aspect of glass 1 is obtained.Therefore, Ga₂O₃、In₂O₃、Sc₂O₃、HfO₂Each content be preferably set to down More than the lower limit shown in table, below the upper limit.

【Table 38】

【Table 39】

【Table 40】

【Table 41】

Lu₂O₃With the effect for improving refractive index nd, but it is also that can make the increased composition of proportion of glass.In addition, being also high Expensive composition.Aspect more than, Lu₂O₃Content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 42】

GeO₂With improving refractive index nd effect, but in usually used glass ingredient be it is extremely expensive into Point.From the viewpoint of the manufacturing cost of reduction glass, GeO₂The preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 43】

Bi₂O₃It is the composition for improving refractive index nd and reducing Abbe number.In addition, being also easily to increase the coloring of glass Big composition.From the viewpoint of making has the few glass of above-mentioned optical characteristics, coloring, Bi₂O₃The preferred lower limit of content It is as shown in the table with the preferred upper limit.

【Table 44】

From the aspect of various effects described above, effect is obtained well, each glass ingredient that the above is recorded Total (the total content) of content is preferably greater than 95%, more preferably greater than 98%, further preferably greater than 99%, further excellent Choosing is more than 99.5%.

In glass ingredient beyond the glass ingredient recorded more than, P₂O₅It is the composition for reducing refractive index, is also to make glass The composition of the heat endurance reduction of glass, but if importing very small amount, then improve sometimes the heat endurance of glass.In order to make Glass with above-mentioned optical characteristics and excellent heat stability, P₂O₅The preferred lower limit of content and the preferred upper limit are as follows Shown in table.

【Table 45】

TeO₂It is the composition for improving refractive index, but is also the virose composition of tool, therefore preferably reduces TeO₂Content. TeO₂The preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 46】

In addition, recording (more) preferred lower limit or 0% composition in above-mentioned each table it is also preferred that content is 0%.For Total content of Multiple components is also same.

Pb, As, Cd, Tl, Be, Se each have toxicity.It is therefore preferable that not containing these elements, i.e. not by these elements Imported as glass ingredient in glass.

U, Th, Ra are radioactive elements.It is therefore preferable that not containing these elements, i.e. do not regard these elements as glass Composition is imported in glass.

V, Cr, Mn, Fe, Co, Ni, Cu, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Ce increase the coloring of glass Greatly, or the occurring source as fluorescence, not preferably as the element for containing glass used for optical elements.It is therefore preferable that not containing These elements, i.e. do not imported these elements as glass ingredient in glass.

Sb, Sn are the elements that can arbitrarily add as fining agent function.

Sb addition is being scaled Sb₂O₃, by Sb in the glass composition of oxide benchmark₂O₃Glass ingredient in addition Total content when being set to 100 mass %, the scope that Sb addition is preferred is 0~0.11 mass %, and preferred scope is 0.01~0.08 mass %, further preferred range is 0.02~0.05 mass %.Herein, " the glass group of oxide benchmark Into " refer to that frit is all decomposed in melting, converted as the material existed in glass as oxide and Obtained glass composition.The Sb in glass composition shown in table described later₂O₃Content is also by containing that above-mentioned method is calculated Amount.

Sn addition is being scaled SnO₂, by SnO in the glass composition of oxide benchmark₂Glass ingredient in addition When total content is set to 100 mass %, the preferred scope of Sn addition is 0~1.0 mass %, preferred scope is 0~ 0.5 mass %, further preferred range is 0~0.2 mass %, is still more preferably 0 mass %.

In the present invention, the glass for glass 2 being represented with cation % for cation constituent is constituted.As it is known that Sample, cation % refers to that the total content for the whole cation constituents that will be included in glass is set to 100% percentage.

On cation constituent, such as B³⁺、Si⁴⁺、La³⁺So represent, and the valence mumber of cation constituent is (for example, B³⁺'s Valence mumber is+3, Si⁴⁺Valence mumber for+4, La³⁺Valence mumber be+3) be according to the conventional value determined, with by B, Si, La with oxide Benchmark is expressed as B₂O₃、SiO₂、La₂O₃It is the same.For being expressed as A with oxide benchmark_mO_n(A represents cation, and O is represented Oxygen, m and n are the integers determined with stechiometry.) composition, cation A is expressed as A^s+, herein, s=2n/m.Therefore, example Such as, being analyzed glass composition, it is quantitative when, can also without analyzing the valence mumber of cation constituent, below, as long as no Especially record, the content of cation constituent, total (the total content) of the content of a variety of cation constituents are used into cation % tables Show.And then, in cation % is represented, the content between cation constituent (is also contained comprising the total of a variety of cation constituents Amount) ratio be referred to as cation ratio.

B³⁺、Si⁴⁺It is the network forming component of glass.Work as B³⁺And Si⁴⁺Total content (B³⁺+Si⁴⁺) be more than 45% when, The heat endurance of glass can be improved, suppresses the crystallization of the glass in manufacture.On the other hand, B is worked as³⁺And Si⁴⁺Total content be When less than 65%, the reduction of refractive index can be suppressed, therefore the glass with above-mentioned optical characteristics, i.e. refractive index can be made Nd is in 1.800~1.850 scope and glass of the Abbe number ν d in 41.5~44 scope.Therefore, in glass 2 B³⁺And Si⁴⁺The scope of total content be set to 45~65%.B³⁺And Si⁴⁺The preferred lower limit of total content and preferred upper Limit is as shown in the table.

【Table 47】

It is used as the B of the network forming component of glass³⁺And Si⁴⁺Each composition content ratio to the heat endurance of glass, Meltbility, mouldability, chemical durability, weatherability, machining property etc. are impacted.B³⁺Improvement meltbility effect ratio Si⁴⁺It is more excellent but readily volatilized during melting.On the other hand, Si⁴⁺Chemical durability, weatherability, machinery with improvement glass The sticky effect of glass when processability, raising melting.

Generally, B is being included³⁺And La³⁺Deng rare earth element high-refractivity and low-dispersion glass in, glass during melting Viscosity is low.But, glass upon melting it is sticky low when, heat endurance reduction (becoming easy crystallization).On glass manufacture When crystallization, the state of crystallization is more more stable than amorphous state (amorphous state), and it is by constituting the ion of glass in glass Moved in glass and arranged and occurred in the way of with crystal structure.Therefore, by B³⁺And Si⁴⁺Each composition The ratio of content is adjusted so that viscosity when melting increases, so as to make above-mentioned ion be difficult with crystal structure Mode is arranged, and is further suppressed the crystallization of glass, is further improved the heat endurance of glass.

If B³⁺Content relative to B³⁺And Si⁴⁺Total content cation ratio (B³⁺/(B³⁺+Si⁴⁺)) it is less than 0.94, Viscosity reduction during melting can then be suppressed, the heat endurance thus, it is possible to improve glass suppresses volatilization during melting.During melting Volatilization turn into make glass constitute variation, characteristic variation become it is big the reason for.Also, its result is difficult to optically homogeneous Glass is molded.Therefore, from the viewpoint of the few glass of the deviation to composition, characteristic carries out volume production, it is preferably able to sun Ion ratio (B³⁺/(B³⁺+Si⁴⁺)) it is set to volatilization when suppression is melted less than 0.94.And then, as cation ratio (B³⁺/(B³⁺+Si⁴ ⁺)) when being less than 0.94, it can also suppress the chemical durability of glass, weatherability, the reduction of machining property.On the other hand, exist In glass composition described in described patent document 15 (Japanese Unexamined Patent Application 57-056344 publications), B₂O₃Content is 28~30 Quality %, SiO₂Content for 1~3 mass % (with reference to patent document 15 claims).Calculated by the content of these compositions Cation ratio (the B gone out³⁺/(B³⁺+Si⁴⁺)) it is 0.942~0.981 this big value.

On the other hand, as cation ratio (B³⁺/(B³⁺+Si⁴⁺)) when being more than 0.65, glass during melting can be prevented former The melting residual of material, therefore, it is possible to improve meltbility.

Aspect more than, in glass 2, by cation ratio (B³⁺/(B³⁺+Si⁴⁺)) be set to 0.65 less than 0.94.Cation ratio (B in glass 2³⁺/(B³⁺+Si⁴⁺)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 48】

From the viewpoint of heat endurance, meltbility, mouldability, chemical durability, weatherability, the machining for improving glass etc. Set out, for B³⁺Content, Si⁴⁺The respective preferred lower limit of content and the preferred upper limit it is as shown in the table.

【Table 49】

【Table 50】

La³⁺、Y³⁺、Gd³⁺And Yb³⁺It is the composition with the effect that refractive index is improved while the reduction of Abbe number is suppressed. In addition, these compositions also have the chemical durability for improving glass, weatherability, the effect for improving glass transition temperature.

Work as La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content (La³⁺+Y³⁺+Gd³⁺+Yb³⁺) be more than 25% when, can suppress folding The reduction of rate is penetrated, therefore, it is possible to make the glass with above-mentioned optical characteristics.Further, it is possible to suppress the chemical durable of glass Property, the reduction of weatherability.In addition, when glass transition temperature is reduced, being machined to glass and (cutting off, cut, grinding Mill, polishing etc.) when glass become easily damaged (reduction of machining property), but work as La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total contain Measure for more than 25% when, the reduction of glass transition temperature can be suppressed, therefore can also improve machining property.The opposing party Face, works as La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content when being less than 35%, it is possible to increase the heat endurance of glass, therefore also can Suppress manufacture glass when crystallization, reduction melten glass when raw material melting residual.Therefore, in glass 2, La³⁺、Y³⁺、Gd³ ⁺And Yb³⁺The scope of total content be set to 25~35%.La³⁺、Y³⁺、Gd³⁺And Yb³⁺The preferred lower limit of total content and excellent The upper limit of choosing is as shown in the table.

【Table 51】

Zr⁴⁺It is the composition with the effect for improving refractive index, it is also steady with the heat for improving glass by making it contain in right amount Qualitatively act on.In addition, Zr⁴⁺Also have and improve glass transition temperature, make when being machined glass not cracky Effect.In order to obtain these effects well, in glass 2, by Zr⁴⁺Content be set to more than 2%.On the other hand, Zr is worked as⁴⁺ Content when being less than 8%, the heat endurance of glass can be improved, melted therefore, it is possible to suppress crystallization during glass manufacture, glass The generation of melting residual when melting.Therefore, the Zr in glass 2⁴⁺The scope of content be set to 2~8%.Zr⁴⁺Content it is preferred Lower limit and the preferred upper limit are as shown in the table.

【Table 52】

As above-mentioned record, from the viewpoint of the stable supplying of glass, Ta⁵⁺It is preferably to reduce it to constitute in glass In shared ratio composition.In addition, Ta⁵⁺It is the composition with the effect for improving refractive index, but is also that the proportion for making glass increases Greatly, the composition for reducing meltbility.Therefore, the Ta in glass 2⁵⁺Content is set to less than 3%.Ta⁵⁺Content preferred lower limit It is as shown in the table with the preferred upper limit.

【Table 53】

In order to realize above-mentioned optical characteristics while improving the heat endurance of glass, suppressing the increase of proportion, in glass In glass 2, by B³⁺And Si⁴⁺Total content relative to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content cation ratio ((B³⁺+Si⁴ ⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) scope be set to 1.65~2.60.As cation ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+ Yb³⁺)) be more than 1.65 when, the heat endurance of glass can be improved, therefore, it is possible to suppress the devitrification of glass.It is further possible to press down The increase of the proportion of glass processed.When the proportion increase of glass, the optical element made using the glass becomes weight.As a result it is mounted with The optical system of the optical element becomes weight.For example, when the optical element of weight is arranged in the camera of auto-focusing formula, driving Power consumption increase during dynamic auto-focusing, battery can be consumed quickly.From the optical element that is made using the glass and it is mounted with the light From the viewpoint of the light-weighted reduction for the optical system for learning element, it is preferably able to suppress the increase of the proportion of glass.The opposing party Face, as cation ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) when being less than 2.60, it can realize that above-mentioned optics is special Property.In addition, from the viewpoint of the chemical durability, high glass-transition temperature (Tg) from improvement glass are changed, preferred cationic ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) it is less than 2.60.Cation ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) Preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 54】

According to the reasons why above-mentioned record, in La³⁺、Y³⁺、Gd³⁺And Yb³⁺In, Yb³⁺It is preferably to reduce it in glass composition The composition of shared ratio.Therefore in glass 2, by Yb³⁺Content is set to be less than 2%.Yb³⁺The preferred lower limit of content and excellent The upper limit of choosing is as shown in the table.

【Table 55】

Y³⁺It is the work for being greatly reduced the light transmittance of near infrared region and playing the heat endurance for improving glass Composition.Further, since atomic weight is small, so Y³⁺It is preferred composition in terms of the increase of the proportion of glass is suppressed.But It is to work as Y³⁺Content it is excessive when, the heat endurance of glass is significantly reduced, easy crystallization.In addition, meltbility is reduced.From being produced on The light transmittance of near infrared region is not set to be greatly reduced and suppress the increase of proportion, with upper while improving heat endurance From the viewpoint of the glass for the optical characteristics stated, preferably by Y in glass 2³⁺Content relative to La³⁺、Y³⁺、Gd³⁺And Yb³⁺'s Cation ratio (the Y of total content³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) scope be set to 0.05~0.45.Cation ratio (Y³⁺/ (La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 56】

According to the reasons why above-mentioned record, Gd³⁺It is preferably to reduce the composition of its shared ratio in glass composition.In addition, Gd belongs to heavy rare earth element in the same manner as Yb, as the composition of glass, and Gd atomic weight is big, increases the proportion of glass.From the party Face is set out, it is also preferred that the reduction ratio that Gd occupies in glass composition.

In glass 2, Gd³⁺Content according to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content and relative to total content Gd³⁺Content is determined.Have from stable supplying from the viewpoint of the high-refractivity and low-dispersion glass of above-mentioned optical characteristics, enter And from the viewpoint of the small glass of proportion is made as high-refractivity and low-dispersion glass, by Gd³⁺Content is relative to La³⁺、Y³⁺、 Gd³⁺And Yb³⁺Total content cation ratio (Gd³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) scope be set to 0~0.05.Cation Than (Gd³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 57】

Never it is greatly reduced the light transmittance of near infrared region, proportion is suppressed while heat endurance is improved From the aspect of increase is there is provided high-refractivity and low-dispersion glass, La³⁺It is useful composition.Therefore in glass 2, preferably by La³ ⁺Content is relative to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content cation ratio (La³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) scope It is set to 0.55~0.95.Cation ratio (La³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) preferred lower limit and the preferred upper limit such as Shown in following table.

【Table 58】

La³⁺、Y³⁺、Gd³⁺Each composition content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 59】

【Table 60】

【Table 61】

Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺It is the composition with the effect for improving refractive index, by making it contain in right amount, also has Improve the effect of the heat endurance of glass.From the optical characteristics stated in realization while further improve the heat endurance of glass From the aspect of, preferably Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content (Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺) scope be 2~10%.Nb⁵ ⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 62】

Zn²⁺Effect, the effect of improvement meltbility of melting with the raw material for promoting glass in melten glass.This Outside, it may have adjustment refractive index, Abbe number, the effect for reducing glass transition temperature.From the aspect of meltbility is improved, It is preferred that Zn²⁺Content divided by B³⁺And Si⁴⁺The obtained value, i.e. cation ratio (Zn of total content²⁺/(B³⁺+Si⁴⁺)) for 0.01 with On.On the other hand, it is preferably positive from the aspect of suppressing the reduction (high dispersion) of Abbe number, realizing above-mentioned optical characteristics Ion ratio (Zn²⁺/(B³⁺+Si⁴⁺)) it is less than 0.22.In addition, from improve glass heat endurance and high glass-transition temperature (Tg) from the aspect of changing, it is also preferred that cation ratio (Zn²⁺/(B³⁺+Si⁴⁺)) it is less than 0.22.It is therefore preferable that by Zn²⁺Content It is set to B in cation ratio³⁺And Si⁴⁺0.01~0.22 times of total content, i.e. by cation ratio (Zn²⁺/(B³⁺+Si⁴⁺)) set For 0.01~0.22.Cation ratio (Zn²⁺/(B³⁺+Si⁴⁺)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 63】

From meltbility, heat endurance, mouldability, machining property for improving glass etc., above-mentioned optical characteristics is realized Viewpoint is set out, Zn²⁺The preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 64】

From the optical characteristics stated in realization while suppress degree of staining λ 5 described later increase and improve the ultraviolet of glass From the aspect of line transmissivity, preferably B³⁺And Si⁴⁺Total content relative to Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content sun Ion ratio ((B³⁺+Si⁴⁺)/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) scope be set to 9.0~32.In addition, from improve glass it is thermally-stabilised From the aspect of property, it is also preferred that by cation ratio ((B³⁺+Si⁴⁺)/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set to more than 9.0.Cation Than ((B³⁺+Si⁴⁺)/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 65】

On Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺, by making it contain in right amount, play the effect for the heat endurance for improving glass.

As Ti in these compositions⁴⁺Content increase when, there is the decrease in transmission of the viewing area of glass, the coloring of glass The tendency of increase.

Ta⁵⁺Function as described above.

For W⁶⁺, when its content increase, there is the decrease in transmission of the viewing area of glass, the coloring increase of glass Tendency, the tendency that there is proportion increase in addition.

On the other hand, Nb⁵⁺With being difficult the proportion of glass, coloring, manufacturing cost to increase, improve refractive index, improve glass The effect of the heat endurance of glass.Therefore, in glass 2, in order to effectively utilize Nb⁵⁺Excellent effect, effect, by Nb⁵⁺Contain Amount is relative to Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content cation ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) scope set For 0.4~1.From degree of staining λ 5 is reduced, promote to irradiate the sight of the solidification of caused ultraviolet hardening bonding agent by ultraviolet Point sets out, and preferably increases cation ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)).Cation ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶ ⁺)) preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 66】

On Ta⁵⁺, according to the reasons why above-mentioned record, glass is not preferably imported energetically.Therefore, to Nb⁵⁺Content it is relative In in Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Middle exclusion Ta⁵⁺Nb afterwards⁵⁺、Ti⁴⁺And W⁶⁺Total content cation ratio (Nb⁵⁺/(Nb⁵⁺+ Ti⁴⁺+W⁶⁺)) preferred scope illustrate.It is preferably positive in order to make with the few glass of excellent heat endurance, coloring Ion ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+W⁶⁺)) scope be 0.4~1.Cation ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+W⁶⁺)) more preferably Lower limit and the preferred upper limit it is as shown in the table.

【Table 67】

From the viewpoint of meltbility is improved, preferably Zn²⁺Content is relative to Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content Cation ratio (Zn²⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set to more than 0.1.In addition, for the low glass of meltbility, when in order to not The melting for having frit remains and improved the melting temperature of glass, during the extension melting time, there is the coloring increase of glass Tendency.It can be speculated as because in the melting crucible of the noble metal such as platinum during melten glass, temperature is melted when raising Degree, during the extension melting time, constitutes the precious metal melting into melten glass of crucible, produces the light as caused by precious metal ion and inhales Receive, the coloring of glass, particularly λ 5 value increase.On the other hand, when want by adjust the content of other glass ingredients come When improving meltbility, there is heat endurance reduction, it is difficult to obtain the glass of the homogeneous with above-mentioned optical characteristics.Cause This, in order to improve the meltbility of glass, from the aspect of the coloring for suppressing glass, it is also preferred that by cation ratio (Zn²⁺/(Nb⁵⁺ +Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set to more than 0.1.In addition, improving the heat endurance of glass from further, suppress glass transition temperature Reduction (the thus improvement of caused machining property), improve chemical durability from the viewpoint of, preferably by cation ratio (Zn²⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set to less than 5.Cation ratio (Zn²⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is preferred under Limit and the preferred upper limit are as shown in the table.

【Table 68】

For Nb⁵⁺Content, Ti⁴⁺Content, W⁶⁺The respective preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 69】

【Table 70】

【Table 71】

Improve the heat endurance of glass from further, (thus caused machinery adds for the reduction of suppression glass transition temperature The improvement of work), improve chemical durability, from the viewpoint of weatherability, preferably Li⁺Content is set to less than 3%.Li⁺Content it is excellent The lower limit of choosing and the preferred upper limit are as shown in the table.

【Table 72】

Na⁺、K⁺、Rb⁺、Cs⁺The effect for the meltbility for improving glass is respectively provided with, but when these content increase, glass is shown Heat endurance, chemical durability, weatherability, the tendency of machining property reduction of glass.It is therefore preferable that Na⁺、K⁺、Rb⁺、Cs⁺'s The lower and upper limit difference of each content is as shown in the table.

【Table 73】

【Table 74】

【Table 75】

【Table 76】

Rb⁺、Cs⁺It is expensive composition, with Li⁺、Na⁺、K⁺Compare, be the composition for being unsuitable for general glass.Therefore, from The viewpoint for improving the meltbility of glass while the heat endurance of glass, chemical durability, weatherability, machining property is maintained to go out Hair, preferably Li⁺、Na⁺、K⁺Total content (Li⁺+Na⁺+K⁺) lower and upper limit be set to it is as shown in the table.

【Table 77】

Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺It is the composition with the effect for improving the meltbility of glass.But, when these into During the content increase divided, the heat endurance reduction of glass shows tendency towards devitrification.Therefore, each content difference of these compositions is preferred It is set to more than the lower limit shown in following table, below the upper limit.

【Table 78】

【Table 79】

【Table 80】

【Table 81】

In addition, from the viewpoint of the further heat endurance for improving glass, Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total content (Mg²⁺+Ca²⁺+Sr²⁺+Ba²⁺) be preferably set to more than the lower limit shown in following table, below the upper limit.

【Table 82】

Al³⁺It is chemical durability, the composition of the effect of weatherability with improvement glass.But, work as Al³⁺Content increase Added-time, the tendency, the tendency of the heat endurance of glass reduction, the tendency of meltbility reduction of refractive index reduction are shown sometimes.Consider Aspect above, Al³⁺Content is preferably set to more than the lower limit shown in following table, below the upper limit.

【Table 83】

Ga³⁺、In³⁺、Sc³⁺、Hf⁴⁺It is respectively provided with the effect for improving refractive index.But, these compositions are expensive, be not from Required composition from the aspect of to glass 2.Therefore, Ga³⁺、In³⁺、Sc³⁺、Hf⁴⁺Each content be preferably set to shown in following table under More than limit, below the upper limit.

【Table 84】

【Table 85】

【Table 86】

【Table 87】

Lu³⁺With the effect for improving refractive index, but it is also that can make the increased composition of proportion of glass.In addition, being also expensive Composition.Aspect more than, Lu³⁺Content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 88】

Ge⁴⁺With the effect for improving refractive index, but it is extremely expensive composition in usually used glass ingredient.From From the viewpoint of the manufacturing cost for reducing glass, Ge⁴⁺The preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 89】

Bi³⁺It is the composition for improving refractive index and reducing Abbe number.In addition, being also easily to make the coloring increase of glass Composition.From the viewpoint of making has the few glass of above-mentioned optical characteristics, coloring, Bi³⁺The preferred lower limit of content and excellent The upper limit of choosing is as shown in the table.

【Table 90】

From the aspect of various effects described above, effect is obtained well, the cation constituent that the above is recorded Total (the total content) of each content is preferably greater than 95%, more preferably greater than 98%, further preferably greater than 99%, further Preferably greater than 99.5%.

In cation constituent beyond the cation constituent recorded more than, P⁵⁺It is the composition for reducing refractive index, is also The composition for reducing the heat endurance of glass, but if importing very small amount, then improve sometimes the heat endurance of glass.In order to Make the glass with above-mentioned optical characteristics and excellent heat stability, P⁵⁺The preferred lower limit of content and the preferred upper limit are such as Shown in following table.

【Table 91】

Te⁴⁺It is the composition for improving refractive index, but is also the virose composition of tool, therefore preferably reduces Te⁴⁺Content. Te⁴⁺The preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 92】

Sb, Sn are the elements that can arbitrarily add as fining agent function.

Sb addition is being scaled Sb₂O₃, by Sb in the glass composition of oxide benchmark₂O₃Glass ingredient in addition Total content when being set to 100 mass %, the scope that Sb addition is preferred is 0~0.11 mass %, and preferred scope is 0.01~0.08 mass %, further preferred range is 0.02~0.05 mass %.Herein, " the glass group of oxide benchmark Into " refer to that frit is all decomposed in melting, converted as the material existed in glass as oxide and Obtained glass composition.The Sb of glass composition shown in table described later₂O₃Content is also the content calculated by above-mentioned method.

More than, cation constituent is illustrated.Then, anion component is illustrated.

Glass 2 is oxide glass, therefore includes O as anion component^2-。O^2-The preferred scope of content for 98~ 100 anion %, preferred scope is 99~100 anion %, further preferred range be 99.5~100 it is cloudy from Sub- %, is still more preferably 100 anion %.

It is used as O^2-Anion component in addition, can illustrate F^-、Cl^-、Br^-、I^-.But, F^-、Cl^-、Br^-、I^-In glass It is readily volatilized in melting.Due to the volatilization of these compositions, there is characteristic variation, homogenieity reduction, the melting of glass of glass The consumption of equipment becomes significant tendency.It is therefore preferable that by F^-、Cl^-、Br^-And I^-Total content suppress from 100 it is cloudy from Sub- % subtracts O^2-Content amount.

As known, anion % refers to that the total content for the whole anion components that will be included in glass is set to 100% percentage.

Then, glass 1 and the common glass performance of glass 2 are illustrated.Described glass refers to the He of glass 1 below Glass 2.

(optical characteristics of glass)

The refractive index nd of above-mentioned glass scope is 1.800~1.850, and Abbe number ν d are 41.5~44.

Refractive index is more than 1.800 glass, is suitable as the material of the optical element of the big lens of refractive power etc..It is another , when refractive index is higher than 1.850, there is the tendency that Abbe number is reduced, the heat endurance of glass is reduced, there is coloring in addition in aspect The tendency of increase.The preferred lower limit of refractive index and the preferred upper limit are as shown in the table.

【Table 93】

The glass that Abbe number is more than 41.5 is effective in terms of correcting chromatic aberration as the material of optical element.It is another , when Abbe number is bigger than 44, there is refractive index reduction, the tendency of the heat endurance reduction of glass in aspect.Abbe number it is preferred Lower limit and the preferred upper limit are as shown in the table.

【Table 94】

(partial dispersion characteristic)

From the viewpoint of correcting chromatic aberration, the above-mentioned glass preferably relative partial dispersion when Abbe number is fixed is small Glass.

Here, relative partial dispersion Pg, F using g lines (the wavelength 435.84nm of mercury), F lines, each refractive index ng of C lines, NF, nC are expressed as (ng-nF)/(nF-nC).

It is suitable for from providing from the viewpoint of the glass of the chromatic aberration correction of high-order, the relative partial dispersion of above-mentioned glass Pg, F preferred lower limit and the preferred upper limit are as shown in the table.

【Table 95】

(glass transition temperature)

From the viewpoint of machining property is improved, the glass transition temperature of preferably above-mentioned glass is more than 640 DEG C.It is logical Cross and glass transition temperature is set to more than 640 DEG C, so as to being cut off to glass, the machining such as cut, grind, polish When, glass not cracky can be made.

On the other hand, when setting glass transition temperature too high, it is necessary to glass is annealed at high temperature, annealing Stove is significantly consumed.In addition, when being molded to glass, it is necessary to be molded with high temperature, mould disappears used in shaping Consumption becomes notable.

From the viewpoint of improving machining property, mitigating to annealing furnace, the burden of shaping mould, glass transition temperature It is preferred that lower limit and the preferred upper limit it is as shown in the table.

【Table 96】

(the light transmittance of glass)

The light transmittance of glass specifically suppresses the long wavelengthization at the light absorbs end of short wavelength side, can pass through Colourity λ 5 is evaluated.Degree of staining λ 5 refers to the spectral-transmission favtor (bag of the glass for 10mm from ultraviolet region to viewing area thickness Reflection loss containing surface) turn into 5% wavelength.λ 5 shown in embodiment described later is in 250~700nm wavelength region The value of measure.More specifically spectral-transmission favtor for example refers to there is that into 10.0 ± 0.1mm thickness using optical polish The glass specimen of this parallel plane, for the above-mentioned face through optical polish from spectral transmission obtained from vertical direction incident light Rate, i.e. the intensity of the light by above-mentioned glass specimen is injected into is set to Iin, the intensity for the light that will transmit above-mentioned glass specimen is set Strength ratio Iout/Iin during for Iout.

According to degree of staining λ 5, the absorption edge of the short wavelength side of spectral-transmission favtor can be quantitatively evaluated.As described above, for Making balsaming lens and utilize ultraviolet hardening bonding agent by lens it is glued each other when etc., by optical element to bonding agent Irradiation ultraviolet radiation and solidify bonding agent.It is excellent from the aspect of the solidification for efficiently carrying out ultraviolet hardening bonding agent The absorption edge of the short wavelength side of spectral-transmission favtor is selected to be in short wavelength region.It is used as the absorption for quantitatively evaluating the short wavelength side The index at end, can use degree of staining λ 5.Above-mentioned glass can show which preferably 335nm by composition adjustment noted before Below, it is more preferably below 332nm, more preferably below 330nm, is still more preferably below 328nm, further Preferably below 326nm λ 5.As an example, 315nm can be set to target by λ 5 lower limit, but more low more preferred, not have It is particularly limited to.

On the other hand, as glass degree of staining index, degree of staining λ 70 can be enumerated.λ 70 is with described in λ 5 Method determine spectral-transmission favtor be 70% wavelength.From the viewpoint of being made and colouring few glass, λ 70 preferred model Enclose for below 420nm, preferred scope is below 400nm, and further preferred range is below 390nm, further excellent The scope of choosing is below 380nm.The target of λ 70 lower limit is 340nm, but more low more preferred, is not particularly limited.

In addition, the index of the degree of staining as glass, can also enumerate degree of staining λ 80.λ 80 is with described in λ 5 The spectral-transmission favtor that method is determined is 80% wavelength.From the viewpoint of being made and colouring few glass, λ 80 preferred scope For below 480nm, preferred scope is below 460nm, and further preferred range is below 440nm, still more preferably Scope be below 420nm.The target of λ 80 lower limit is 350nm, but more low more preferred, is not particularly limited.

(proportion of glass)

In the optical element (lens) for constituting optical system, according to the refractive index and the light of lens of the glass for constituting lens The curvature of functional surfaces (face of incidence, the outgoing of the light to be controlled) is learned to determine refractive power.When the song in optical function face to be made When rate increases, the thickness of lens also increases.As a result lens become weight.On the other hand, if using the high glass of refractive index, even if Do not increase the curvature in optical function face, can obtain big refractive power yet.

Thus, as long as refractive index can be improved while the increase of proportion of glass is suppressed, it becomes possible to make to have and fix Refractive power optical element lightweight.

On effects of the refractive index nd for refractive power, by taking the proportion d of glass relative to the refractive index nd from glass In subtract refractive index 1 in vacuum value (nd-1) ratio, so as to be used as the index during lightweight for seeking optical element. That is, using d/ (nd-1) as seeking index during optical element lightweight, by reducing the value, so as to seek lens Lightweight.

Above-mentioned glass causes proportion increased Gd, Ta, Yb ratio occupied few, therefore is both high-refractivity and low-dispersion glass Glass, again being capable of low-gravity.Therefore, the d/ (nd-1) of above-mentioned glass can be such as less than 5.70.But, when making d/ (nd-1) When excessively reducing, the heat endurance of glass shows the tendency of reduction.It is therefore preferable that d/ (nd-1) is set into more than 5.00.d/ (nd-1) preferred lower limit and the preferred upper limit is as shown in the table.

【Table 97】

And then, the proportion d of above-mentioned glass preferred lower limit and the preferred upper limit are as shown in the table.Formed from by the glass Optical element lightweight from the viewpoint of, preferably proportion d is set to below the upper limit shown in following table.In addition, from further From the aspect of the heat endurance for improving glass, preferably by than more than the lower limit that is reset to shown in following table.

【Table 98】

(liquidus temperature)

Liquidus temperature is one of index of heat endurance of glass.From crystallization when suppressing glass manufacture, the side of devitrification Face consider, preferred liquid phase line temperature LT be less than 1300 DEG C, more preferably less than 1250 DEG C, more preferably 1200 DEG C with Under, it is still more preferably less than 1150 DEG C.Liquidus temperature LT lower limit is more than 1100 DEG C as an example, but preferably Low temperature, there is no particular limitation.

The glass (glass 1 and glass 2) of one mode of present invention mentioned above is high-refractivity and low-dispersion glass, its It is useful as glass material used for optical elements.And then, the composition above recorded by progress is adjusted, so as to can also make Glass homogenizes and coloured reduction.In addition, above-mentioned glass is easily molded, also easily it is machined.Therefore, above-mentioned glass is fitted Cooperate as optical glass.

Above-mentioned glass can be obtained in the following way：Weighed in the way of it can obtain the glass of target and constitute, allocate work For the oxide of raw material, carbonate, sulfate, nitrate, hydroxide etc., it is sufficiently mixed and batch mixture is made, holds in melting Heated, melted in device, carrying out deaeration, stirring, made homogeneous and the melten glass without foam, be molded.It is specific and Speech, can use known fusion method to be made.Above-mentioned glass is the high-refractivity and low-dispersion with above-mentioned optical characteristics Glass and excellent heat stability, therefore, it is possible to stably be manufactured using known fusion method, the method for forming.

[compressing use glass material, optical element blank and their manufacture method]

Another mode of the present invention is related to：

Compressing glass material is used by what above-mentioned glass 1 or glass 2 were formed；

The optical element blank formed by above-mentioned glass 1 or glass 2；

According to another mode of the present invention, it is possible to provide：

Glass is used with above-mentioned glass 1 or glass 2 are shaped into compressing the compressing of the process with glass material The manufacture method of glass material；

With by compressing being pressed with glass material by above-mentioned and making light using being pressed into pattern Learn the manufacture method of the optical element blank of the process of member blanks；

The manufacture of optical element blank with the process that above-mentioned glass 1 or glass 2 are shaped to optical element blank Method.

Due to it is compressing with glass material, optical element blank made of above-mentioned glass 1 or glass 2, therefore It is clear that compressing also correspond to above-mentioned glass with glass material, optical element blank.

Optical element blank is, in shape adding in optical element approximate with being set to the shape of the optical element of target Polish surplus (superficial layer removed by polishing), add the grind (surface removed by grinding as needed Layer) optical element mother metal.By the way that the surface of optical element blank is polished, or by grinding and polishing, so as to make Into optical element., can be by above-mentioned glass be carried out into melten glass pressure obtained from melting in right amount in a mode The method (being referred to as straight pressing) of type is made, so as to make optical element blank.In another mode, it can also pass through To by above-mentioned glass, melten glass obtained from melting is solidified and is processed further in right amount, so as to make optical element base Part.

In addition, in another mode, can be by making compressing use glass material, by the compressing use of making Glass material is pressed and makes optical element blank.

It is compressing to use glass by by heating in the compressing of soft state with the compressing of glass material Glass material is carried out with the known method that pattern suppressed is pressed into.Heating, compressing it can carry out in an atmosphere.Energy It is enough to reduce the stress of inside glass by being annealed after compressing, so as to obtain the optical element blank of homogeneous.

It is compressing with glass material except with the state of former state be supplied to for optical element blank make being pressed into Type is referred to as the compressing with beyond glass material of compressing use glass gob, also comprising applying cut-out, grinding, polishing Compressing compressing glass material is used Deng machining, by compressing be supplied to glass gob.As cutting Disconnected method, has in the part of the desired cut-out on the surface of glass plate using the method formation groove for being referred to as delineation, from the groove of formation The back side in face local pressure is applied to the part of groove, in the method for the partial cut glass plate of groove；Glass is cut off with cutting edge Method of plate etc..In addition, processing method known to tumbling etc. can be enumerated as grinding and polishing method.

It is compressing to be molded into glass plate for example, by melten glass is cast in mold with glass material, will The glass plate cuts into multiple sheet glass to make, or these multiple sheet glass are carried out tumbling to make.Or, Appropriate melten glass can be molded and be made and compressing use glass gob.Can also be by using glass by compressing Glass gob reheats, softens and be pressed to make optical element blank.Glass is reheated, soften, pressed The method that type is made and optical element blank is made is referred to as reheating pressing relative to straight pressing.

[optical element and its manufacture method]

Another mode of the present invention is related to

The optical element formed by above-mentioned glass 1 or glass 2.

Above-mentioned optical element is made using above-mentioned glass 1 or glass 2., can also be in glass in above-mentioned optical element The coated film that more than one layer of glass surface formation multilayer film such as antireflection film etc..

Because optical element is made by above-mentioned glass 1 or glass 2, it is therefore evident that, optical element is suitable In above-mentioned glass.In addition, in the case where the glass surface of optical element is formed with coated film, the glass in addition to coated film The part of glass is equivalent to above-mentioned glass.

In addition, according to the mode of the present invention,

Also provide with the process by being at least polished by above-mentioned optical element blank and making optical element The manufacture method of optical element.

In the manufacture method of above-mentioned optical element, as long as grinding, the known method of polishing application, can by Optical element surface is fully cleaned after processing, its drying etc. is obtained inside quality and the high optical element of surface quality. Like this, the optical element formed by above-mentioned glass can be obtained.As optical element, spherical lens can be illustrated, aspherical The various lens such as lens, lenticule, prism etc..

In addition, the optical element formed by above-mentioned glass 1 or glass 2 is also suitable as the lens of glued optical element are constituted Close.As glued optical element, it can illustrate and lens be carried out to the glued optical element (balsaming lens) of gluing each other, by thoroughly Mirror and prism carry out glued glued optical element etc..For example, glued optical element can make in the following manner：By gluing The cemented surfaces of 2 optical elements critically processed that (for example spherical polishing adds in the way of shape turns into reversion shape Work), in above-mentioned cemented surface coated UV line curing type bonding agent, make after cemented surface fits each other, by optical element to glue The bonding agent irradiation ultraviolet radiation in conjunction face, solidifies bonding agent.In order to so make glued optical element, preferably above-mentioned glass.It is logical Cross and make multiple optical elements of gluing respectively using the different a variety of glass of Abbe number, they are subjected to gluing, so as to The element for the correction for being suitable for chromatic aberation is enough made.

For glass constitute quantitative analysis result, sometimes glass ingredient represented with oxide benchmark, glass ingredient Content is represented with quality %.The composition so represented with oxide benchmark with quality % can convert according to example method described as follows Into the composition represented with cation %, anion %.

For example, the oxide formed by cation A and oxygen is expressed as A_mO_n.M and n are determined with stechiometry respectively Integer.For example, in B³⁺In the case of B is expressed as based on oxide benchmark₂O₃, m=2, n=3；In Si⁴⁺In the case of be expressed as SiO₂, m=1, n=2.

First, A quality % represented_mO_nContent divided by A_mO_nMolecular weight, and then be multiplied by m.The value is set to P.Connect , added up to P for whole cation constituents.When total P value is set into Σ P, turn into 100% side with Σ P Value after formula is standardized to the P of each cation constituent value turns into the A that cation % is represented^s+Content.Herein, s is 2n/ m。

In addition, for micro additive, such as Sb²O³Such fining agent, can also be not included in ∑ P.At this In the case of, Sb content is set to be converted into Sb as described above₂O₃Additional content (quality %).That is, it will remove Sb₂O₃The total of content of glass ingredient of content be set to 100 mass %, by Sb₂O₃Content be expressed as relative to 100 matter Measure % value.

As long as in addition, above-mentioned molecular weight using the 4th after decimal point is rounded up as represented after decimal point The value of the 3rd is calculated.In addition, for example, oxide A_mO_nMolecular weight for elements A atomic weight m times of value and oxygen Atomic weight n times of value it is total.The molecular weight represented for some glass ingredients, additive using oxide benchmark is as follows Shown in table.

【Table 99】

Oxide	Molecular weight	Oxide	Molecular weight
				B₂O₃	69.621	Cs₂O	281.810
SiO₂	60.084	ZnO	81.389
				La₂O₃	325.809	MgO	40.304
Y₂O₃	225.810	CaO	56.077
				Gd₂O₃	362.498	SrO	81.389
Yb₂O₃	394.084	BaO	153.326
				Nb₂O₅	265.810	Al₂O₃	101.961
TiO₂	79.882	Ga₂O₃	187.444
				WO₃	231.839	In₂O₃	277.634
Ta₂O₅	441.893	Sc₂O₃	137.910
				Bi₂O₃	465.959	HfO₂	210.489
ZrO₂	123.223	Lu₂O₃	397.932
				Li₂O	29.882	GeO₂	104.629
Na₂O	61.979	P₂O₅	141.945
				K₂O	94.196	TeO₂	159.599
Rb₂O	186.935	Sb₂O₃	291.518

Embodiment

Hereinafter, the present invention is further described based on embodiment.But, the present invention is not limited to shown in embodiment Mode.

(embodiment 1)

In the way of it can obtain the glass with the composition shown in following table, weigh and change as oxide, boric acid of raw material etc. Compound, is sufficiently mixed, and makes batch materials.

The batch materials are put into platinum crucible, 1350~1450 DEG C are heated to together with crucible, after 2~3 hours, By glass melting, clarification.After melten glass is stirred and is homogenized, melten glass is cast to the shaping by preheating Glass, after placement is cooled to glass transition temperature nearby, is put into annealing furnace by mould together with shaping mould at once.Then, The annealing of about 1 hour is carried out near glass transition temperature.After being annealed, placed in annealing furnace and be cooled to room temperature.

The glass made like this is observed, does not as a result find that precipitation, bubble, striped, the melting of raw material of crystal are remained. Thereby, it is possible to make the glass that homogenieity is high.

During No.1~33 in table 100 (table 100-1~100-7) are glass 1, table 101 (table 101-1~101-6) No.1~33 are glass 2.

The glass performance of glass to obtaining is measured with method as shown below.Measurement result is as shown in the table.

(1) refractive index nd, nF, nC, ng, Abbe number ν d

Glass obtained from cooling for the cooling rate with -30 DEG C/h, according to the industrial meeting of Japanese Optical Glass The refractometry of standard, refractive index nd, nF, nC, ng are measured.Calculated using refractive index nd, nF, nC each measured value Go out Abbe number ν d.

(2) glass transition temperature Tg

Using Differential Scanning Calorimetry analytical equipment (DSC), it is measured with 10 DEG C/min of programming rate.

(3) proportion

It is measured using Archimedes method.

(4) degree of staining λ 5, λ 70, λ 80

Using the glass specimen that the thickness with 2 planes through optical polish relative to each other is 10 ± 0.1mm, pass through Spectrophotometer injects intensity I in light, the intensity of the light to having transmitted glass specimen to polished face from vertical direction Iout is measured, and calculates spectral-transmission favtor Iout/Iin, spectral-transmission favtor is set into λ 5 for 5% wavelength, by spectral transmission Rate is set to λ 70 for 70% wavelength, and spectral-transmission favtor is set into λ 80 for 80% wavelength.

(5) relative partial dispersion Pg, F

Calculated according to nF, nC, ng for being determined by above-mentioned (1) value.

(6) liquidus temperature

Glass is put into the stove for being heated to set point of temperature, kept for 2 hours, after cooling, with 100 times of light microscope Inside sight glass, liquidus temperature is determined according to the presence or absence of crystal.

[table 100-1]

[table 100-2]

[table 100-3]

[table 100-4]

[table 100-5]

[table 100-6]

[table 100-7]

[table 101-1]

[table 101-2]

[table 101-3]

[table 101-4]

[table 101-5]

[table 101-6]

(embodiment 2)

The various glass obtained using embodiment 1, make compressing use glass blocks (glass gob).The glass blocks is existed Heat, soften, be pressed with being pressed into pattern in air, make lens blank (optical element blank).By making Lens blank takes out from pattern is pressed into, and is annealed, and include the machining of polishing, makes what is made by embodiment 1 The spherical lens of various glass formation.

(embodiment 3)

The desired amount of melten glass made in embodiment 1 is obtained, is used during the glass of acquisition is in soft state It is pressed into pattern to be pressed, and is cooled down, makes lens blank (optical element blank).By the lens blank of making Take out, annealed from pattern is pressed into, include the machining of polishing, make the various glass made by embodiment 1 The spherical lens of formation.

(embodiment 4)

The glass blocks (optical element blank) that the melten glass made in embodiment 1 is solidified and is made is carried out Annealing, include the machining of polishing, makes the spherical lens that the various glass made by embodiment 1 are formed.

(embodiment 5)

The spherical lens made in embodiment 2~4 is fitted with the spherical lens formed by the glass of other species, made Make balsaming lens.The cemented surface of the spherical lens made in embodiment 2~4 is the sphere of convex, by the optics of other species The cemented surface of the spherical lens of glass formation is concave sphere.2 above-mentioned cemented surfaces with the absolute value of radius of curvature each other Equal mode makes.In the glued ultraviolet hardening bonding agent of cemented surface coated optical element, by 2 lens gluings Fit each other in face.Hereafter, purple is irradiated to the bonding agent for being coated on cemented surface by the spherical lens made in embodiment 2~4 Outside line, solidifies bonding agent.

Balsaming lens is made as described above.The bonding strength of balsaming lens is sufficiently high, and optical property is also enough degree.

(research of influences of the Yb to the transmissivity of near infrared region)

(" glass A " is recited as below to the glass with the composition shown in following tables 102.), with following tables 103 The glass of shown composition (is recited as " glass B " below.) melted, be molded respectively, it is processed into tabular.These glass plates have There are 2 relative planes.2 planes are parallel to each other, by optical polish.2 planes at intervals of 10.0mm.

Using this glass plate, spectral-transmission favtor is determined.To above-mentioned relative 2 plane vertically incident light, on one side Scanning wavelength, while calculating the intensity for the incident light for being injected into glass plate and having transmitted the ratio of the intensity of the transmitted light of glass plate (intensity of intensity/incident light of transmitted light), obtains the spectral-transmission favtor of glass plate.By the thickness 10.0mm's of this 2 kinds of glass Spectral-transmission favtor curve is shown respectively in Fig. 1, Fig. 2 (Fig. 1：Glass A, Fig. 2：Glass B).

【Table 102】

	Quality %	Cation %
			B₂O₃	26.16	57.85
SiO₂	3.62	4.64
			La₂O₃	45.53	21.5
Y₂O₃	12.9	8.79
			Yb₂O₃	0.1	0.04
ZrO₂	7.9	4.94
			TiO₂	0.1	0.1
Nb₂O₅	3.69	2.14
			It is total	100	100
Sb₂O₃	0.02	0.02 mass %

【Table 103】

	Quality %	Cation %
			B₂O₃	10.97	33.75
SiO₂	1.17	2.09
			La₂O₃	25.78	16.94
Gd₂O₃	0.85	0.50
			Yb₂O₃	3.68	2.00
ZrO₂	2.7	2.35
			ZnO	14.2	18.69
TiO₂	1.49	2.00
			Nb₂O₅	9.74	7.85
Ta₂O₅	10.73	5.2
			WO₃	18.69	8.63
It is total	100	100

Glass B in the glass composition that quality % is represented due to not containing Y₂O₃, therefore it is mass ratio (Y₂O₃/(La₂O₃+ Y₂O₃+Gd₂O₃+Yb₂O₃)) glass outside above-mentioned scope.In addition, glass B is due in the glass composition that cation % is represented Y is not contained³⁺, therefore it is cation ratio (Y³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) glass outside above-mentioned scope.Therefore, glass Glass B not equivalent to the glass 1 and glass 2 of the of the invention mode above recorded, but the absorption of near infrared region according to The size of Yb contents and situation about increasing and decreasing is not rely on whether there is Y₂O₃And Y³⁺.Therefore, can by contrasting glass A and glass B Confirm the influence that Yb is caused to the transmissivity of near infrared region.

As shown in figure 1, in glass that quality % is represented composition the Yb containing 0.1 mass %₂O₃, represent in cation % Glass composition in the Yb containing 0.04 cation %³⁺Glass A, due to the Yb centered near wavelength 950nm light inhale Receive, cause the decrease in transmission near this.

In addition, as shown in Fig. 2 in glass that quality % is represented composition the Yb containing 3.68 mass %₂O₃, sun from Yb containing 2.00 cation % in the glass composition that sub- % is represented³⁺Glass B, due to centered near wavelength 960nm Yb light absorbs, cause the transmissivity near this to be greatly reduced.

So, the increase of adjoint Yb content, the transmissivity of the near infrared region of glass is greatly reduced, therefore is used as use In the glass of the purposes in the area requirement high-transmission rate from viewing area near infrared region, the glass containing many Yb is not Suitable.

(comparative example 1)

Attempt to reproduce the glass of the embodiment 4 of patent document 6 (Japanese Unexamined Patent Publication 2009-203083 publications), but The crystallization during glass making.This is due to glass mass ratio (B in the glass composition that quality % is represented₂O₃/(B₂O₃+ SiO₂)) it is 1, the glass composition cationic ratio (B represented in cation %³⁺/(B³⁺+Si⁴⁺)) for 1 thus heat endurance reduction Caused.

(comparative example 2)

(" glass below, is recited as to the glass of the embodiment 28 of patent document 5 (Japanese Unexamined Patent Application 55-121925 publications) Glass C ") reproduced, it is 348nm to determine the results of λ 5 using the above method.

Spherical lens is made using glass C.Then, by the sphere of the convex of the spherical lens and the optics by other species The concave sphere of the spherical lens of glass formation is as cemented surface, the glued ultraviolet hardening bonding of coated optical element Agent, attempts to make balsaming lens similarly to Example 5.But, by by glass C-shaped into lens to the purple that is coated with cemented surface Outside line curing type bonding agent irradiation ultraviolet radiation, because glass C ultraviolet transmittance is low, therefore can not cure sufficiently bonding agent.

(comparative example 3)

Mass ratio (the Gd of the glass of the embodiment 7 of patent document 17 (Japanese Unexamined Patent Publication 2002-284542 publications)₂O₃/ (La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) it is 0.09, mass ratio (B₂O₃/(B₂O₃+SiO₂)) it is 0.92.For the glass, by La₂O₃、 Y₂O₃、Gd₂O₃The content of composition in addition is set to fixed, to by Gd₂O₃Part or all be replaced into La₂O₃And Y₂O₃When The change of the heat endurance of glass is verified.

First, constituted as the glass of oxide benchmark, by the Gd containing 5.15 mass %₂O₃0% is set to, by Gd₂O₃Contain The mass % of decrement 5.15 of amount is according to La₂O₃Content and Y₂O₃Content be respectively allocated to La₂O₃And Y₂O₃.Specifically, will It is used as 5.15 mass % × (La₂O₃Content/(La₂O₃Content and Y₂O₃Content total content)) 4.09 matter that calculate % is measured from Gd₂O₃It is replaced into La₂O₃, 5.15 mass % × (Y will be used as₂O₃Content/(La₂O₃Content and Y₂O₃Content Total content)) the 1.06 mass % that calculate are from Gd₂O₃It is replaced into Y₂O₃.Hereinafter, the composition is recited as " composition a ".

Then, by the Gd containing 5.15 mass %₂O₃3 mass % are reduced to, by Gd₂O₃The matter of decrement 2.15 of content % is measured according to La₂O₃Content and Y₂O₃Content be respectively allocated to La₂O₃And Y₂O₃.Specifically, will as 2.15 mass % × (La₂O₃Content/(La₂O₃Content and Y₂O₃Content total content)) the 1.71 mass % that calculate are from Gd₂O₃It is replaced into La₂O₃, 5.15 mass % × (Y will be used as₂O₃Content/(La₂O₃Content and Y₂O₃Content total content)) calculate 0.44 mass % is from Gd₂O₃It is replaced into Y₂O₃.Hereinafter, the composition is recited as " composition b ".

The composition of the embodiment 7 of patent document 17, " composition a " and " composition b " as shown in table 104.

【Table 104】

(unit：Quality %, mass ratio)

Using the glass 150g with composition a, b, glass is made according to the method described in the embodiment of patent document 17, Periphery in the glass that melten glass is poured into mold and is molded, i.e. due to causing what is quickly cooled down with mold contact There is no the precipitation for finding crystal in part, but central portion, i.e. cooling velocity in the glass part smaller than periphery has been separated out greatly The crystal of amount.In addition, when making the glass for the embodiment above recorded by identical method, being not limited to the periphery of glass Portion, does not have the precipitation for finding crystal in entire scope.

Result above is regarded as representing in mass ratio (B₂O₃/(B₂O₃+SiO₂)) beyond the glass for the scope above recorded Make Gd in glass composition₂O₃The result of heat endurance reduction when content is reduced.

(comparative example 4)

Cation ratio (the Gd of the glass of the embodiment 7 of patent document 17 (Japanese Unexamined Patent Publication 2002-284542 publications)³⁺/ (La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) it is 0.08, cation ratio (B³⁺/(B³⁺+Si⁴⁺)) it is 0.95.For the glass, by La³⁺、Y³⁺、 Gd³⁺The content of composition in addition is set to fixed, to by Gd³⁺Part or all be replaced into La³⁺And Y³⁺When glass heat it is steady Qualitatively change is verified.

First, by the Gd containing 2.31 cation %³⁺0% is set to, by Gd³⁺The cation % roots of decrement 2.31 of content According to La³⁺Content and Y³⁺Content be respectively allocated to La³⁺And Y³⁺.Specifically, 2.31 cation % × ((La will be used as³⁺'s Content/(La³⁺Content and Y³⁺Content total content)) the 1.68 cation % that calculate are from Gd³⁺It is replaced into La³⁺, using as 2.31 cation % × ((Y³⁺Content/(La³⁺Content and Y³⁺Content total content)) the 0.63 cation % that calculates From Gd³⁺It is replaced into Y³⁺.Hereinafter, the composition is recited as " composition c ".

Then, by the Gd containing 2.31 cation %³⁺1.5 cation % are reduced to, by Gd³⁺The decrement 0.81 of content Cation % is according to La³⁺Content and Y³⁺Content be respectively allocated to La³⁺And Y³⁺.Specifically, 0.81 cation % will be used as ×((La³⁺Content/(La³⁺Content and Y³⁺Content total content)) the 0.59 cation % that calculates is replaced into La³⁺, will It is used as 0.81 cation % × ((Y³⁺Content/(La³⁺Content and Y³⁺Content total content)) calculate 0.22 sun from Sub- % is replaced into Y³⁺.Hereinafter, the composition is recited as " composition d ".

The composition of the embodiment 7 of patent document 17, " composition c " and " composition d " as shown in table 105.

【Table 105】

(unit：Cation %, cation ratio)

Using the glass 150g with composition c, d, glass is made according to the method described in the embodiment of patent document 17, Periphery in the glass that melten glass is poured into mold and is molded, i.e. due to causing what is quickly cooled down with mold contact There is no the precipitation for finding crystal in part, but central portion, i.e. cooling velocity in the glass part smaller than periphery has been separated out greatly The crystal of amount.In addition, when making the glass for the embodiment above recorded by identical method, being not limited to the periphery of glass Portion, does not have the precipitation for finding crystal in entire scope.

Result above is regarded as representing in cation ratio (B³⁺/(B³⁺+Si⁴⁺)) beyond the glass for the scope above recorded Make Gd in glass composition³⁺The result of heat endurance reduction when content is reduced.

Finally, above-mentioned each mode is summarized.

According to a mode, using the teaching of the invention it is possible to provide a kind of glass (glass 1), it is oxide glass, is represented with quality %, B₂O₃With SiO₂Total content be 15~35 mass %, La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content be 45~65 mass %, but It is, Yb₂O₃Content is below 3 mass %, ZrO₂Content is 3~11 mass %, Ta₂O₅Content is below 5 mass %, B₂O₃Content Relative to B₂O₃And SiO₂Total content mass ratio (B₂O₃/(B₂O₃+SiO₂)) it is 0.4~0.900, B₂O₃And SiO₂It is total Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio ((B₂O₃+SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+ Yb₂O₃)) it is 0.42~0.53, Y₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (Y₂O₃/ (La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) it is 0.05~0.45, Gd₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃It is total Mass ratio (the Gd of content₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) it is 0~0.05, Nb₂O₅Content is relative to Nb₂O₅、TiO₂、 Ta₂O₅And WO₃Total content mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) it is 0.5~1, refractive index nd scope For 1.800~1.850, and Abbe number ν d scope is 41.5~44.

According to a mode, using the teaching of the invention it is possible to provide a kind of glass (glass 2), it is oxide glass, is represented with cation %, B³⁺With Si⁴⁺Total content be 45~65%, La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content be 25%~35%, still, Yb³⁺Content Less than 2%, Zr⁴⁺Content is 2~8%, Ta⁵⁺Content is less than 3%, B³⁺Content is relative to B³⁺And Si⁴⁺Total content sun Ion ratio (B³⁺/(B³⁺+Si⁴⁺)) for 0.65 less than 0.94, B³⁺And Si⁴⁺Total content relative to La³⁺、Y³⁺、Gd³⁺ And Yb³⁺Total content cation ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) it is 1.65~2.60, Y³⁺Content phase For La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content cation ratio (Y³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) it is 0.05~0.45, Gd³⁺Content is relative to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content cation ratio (Gd³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) it is 0 ~0.05, Nb⁵⁺Content is relative to Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content cation ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+ W⁶⁺)) it is 0.4~1, refractive index nd scope is 1.800~1.850, and Abbe number ν d scope is 41.5~44.

Glass 1 and glass 2 are refractive index nd and Abbe number ν d with above range, as the optics for constituting optical system The useful Spectralite with high refractivity and low dispersion of the material of element.Above-mentioned glass is the reduction of Gd, Ta and Yb content and can shown Go out the glass of high heat endurance.

In a mode, for glass 1, from raising meltbility, further improve the heat endurance of glass, suppress glass From the viewpoint of changing the reduction (the thus improvement of caused machining property) of transition temperature, improving chemical durability, preferred matter Amount is than (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) scope be less than 0.1~3.

In a mode, for glass 2, from raising meltbility, further improve the heat endurance of glass, suppress glass It is preferably positive from the viewpoint of changing the reduction (the thus improvement of caused machining property) of transition temperature, improving chemical durability Ion ratio (Zn²⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) scope be less than 0.1~5.

In a mode, for glass 1 and glass 2, preferably suppress the long wave at the light absorbs end of the short wavelength side of glass Lengthization is so that degree of staining λ 5 is below 335nm.

In a mode, for glass 1 and glass 2, from the optical element light weight that can make there is fixed refractive power From the viewpoint of change, proportion d and refractive index nd preferably meet above-mentioned (A) formula.

In a mode, for glass 1 and glass 2, from the viewpoint of machining property is improved, preferably vitrifying turns Temperature is more than 640 DEG C.

By glass 1 described above or glass 2, can make compressing use glass material, optical element blank and Optical element.That is, according to other modes, there is provided the compressing use glass material formed by glass 1 or glass 2, optics member Part blank and optical element.

In addition, according to another mode, it may also provide with being shaped to glass 1 or glass 2 compressing to use glass material The manufacture method of the compressing use glass material of the process of material.

And then, according to another mode, it may also provide with by the way that above-mentioned compressing used with glass material is pressed The manufacture method that pattern is pressed and makes the optical element blank of the process of optical element blank is made.

And then, according to another mode, it may also provide with the work that glass 1 or glass 2 are shaped to optical element blank The manufacture method of the optical element blank of sequence.

And then, according to another mode, it may also provide with by being at least polished above-mentioned optical element blank Make the manufacture method of the optical element of the process of optical element.

It is believed that the mode of implementation of disclosure is illustrated without restricted in all aspects.This hair Bright scope is not by above-mentioned explanation but represented by the scope of claim, it is intended to encompass the model with claim Enclose whole changes in the meaning and scope of equalization.

For example, the composition illustrated by the glass composition to above-mentioned illustration described in book is adjusted, this can be obtained The glass of one mode of invention.

In addition, more than 2 of the item for illustrating or being recorded as preferred scope in specification can be made to be appointed certainly The combination of meaning ground.

In addition, there is also the situation that certain glass meets glass 1 and the both sides of glass 2.

The present invention is useful in the manufacture field of various optical elements.

Claims

1. a kind of glass, is oxide glass,

Represented with quality %,

B₂O₃And SiO₂Total content be 15~35 mass %,

La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content be 45~65 mass %, wherein, Yb₂O₃Content is below 3 mass %,

ZrO₂Content is 3~11 mass %,

Ta₂O₅Content is below 5 mass %,

B₂O₃Content is relative to B₂O₃And SiO₂Total content mass ratio (B₂O₃/(B₂O₃+SiO₂)) it is 0.4~0.900,

B₂O₃And SiO₂Total content relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio ((B₂O₃+ SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) it is 0.42~0.53,

Y₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (Y₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+ Yb₂O₃)) it is 0.05~0.45,

Gd₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (Gd₂O₃/(La₂O₃+Y₂O₃+ Gd₂O₃+Yb₂O₃)) it is 0~0.05,

Nb₂O₅Content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅ +WO₃)) it is 0.5~1,

2. glass according to claim 1, wherein,

ZnO content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content mass ratio (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+ WO₃)) scope be 0.1~3.

3. glass according to claim 1 or 2, wherein,

Degree of staining λ 5 is below 335nm.

4. according to glass according to any one of claims 1 to 3, wherein,

Proportion d and refractive index nd meet following (A) formulas：

d/(nd-1)≤5.70 …(A)。

5. according to glass according to any one of claims 1 to 4, wherein,

Glass transition temperature is more than 640 DEG C.

6. a kind of compressing use glass material, is formed by glass according to any one of claims 1 to 5.

7. a kind of optical element blank, is formed by glass according to any one of claims 1 to 5.

8. a kind of optical element, is formed by glass according to any one of claims 1 to 5.