CN107207320B

CN107207320B - Glass, compression moulding glass material, optical element blank and optical element

Info

Publication number: CN107207320B
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: 2018-08-07
Anticipated expiration: 2036-01-13
Also published as: JP6291598B2; JP2021008397A; CN108715512B; JPWO2016114274A1; JP7514351B2; JP2018104283A; CN107207320A; JP7003198B2; JP2022050507A; TWI671270B; WO2016114274A1; TW201641456A; TWI641572B; JP2023085359A; JP7250106B2; JP6812382B2; TW201904900A; CN108715512A

Abstract

The present invention relates to a kind of glass, are oxide glass, are indicated with quality %, 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 5 mass % hereinafter, 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, ranging from the 1.800~1.850 of refractive index nd, and ranging from the 41.5~44 of Abbe number ν d.

Description

Glass, compression moulding glass material, optical element blank and optical element

Cross-reference to related applications

This application claims Japanese patent application filed in 13 days January in 2015 the 2015-004542nd and Japan Patent Shens 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, compression moulding glass material, optical element blank and optical elements.

Background technology

The glass (high-refractivity and low-dispersion glass) low as high refractive index, dispersion, such as remember in Patent Documents 1 to 18 Ranging from the 1.800~1.850 of refractive index nd and ranging from 41.5~44 glass of Abbe number ν d are carried.In this as public affairs It opens, the full content of special referenced patents document 1~18.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Invention content

Ranging from 41.5~44 glass of ranging from 1.800~1.850 and Abbe number ν d of refractive index nd is for color The useful material used for optical elements of the correction of aberration, the multifunction of optical system, densification.In addition, below as long as no spy Other record, refractive index refer to the refractive index nd of d lines (the wavelength 587.56nm of helium).In addition, recorded as long as no special, 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 as nF, nC, ν d are defined as ν d=(nd-1)/(nF-nC).

About the high-refractivity and low-dispersion glass of refractive index and Abbe number with above range, in order to further increase it Serviceability preferably satisfies the following.

It being capable of stable supplying.For this purpose, it is preferred that reducing as rare costly in recent years to the demand supplies in market deficiency Element Gd, Ta ratio shared in glass composition.In contrast, glass recorded in patent document 7 contains largely Ta.In addition, refractive index with above range recorded in glass and patent document 17 recorded in patent document 8~14 and The glass of Abbe number contains a large amount of Gd.

Ratio in glass composition shared by Yb is low.This is because caused by following reason.

Yb has near infrared region to be absorbed.Therefore, the glass containing a large amount of Yb is (such as recorded in patent document 16 Glass) it is unsuitable for the purposes for needing high-transmission rate in the range from visibility region near infrared region, such as monitor camera, red Outer video camera, vehicle-mounted vidicon lens etc. material used for optical elements.In addition, Yb belongs to heavy rare earth element, as glass Ingredient, atomic weight is big, and the proportion of glass is made to increase.When the proportion of glass increases, 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 larger, and the consumption of battery becomes serious.From above aspect, preferably Reduce the ratio shared by Yb in glass composition.

Excellent heat stability.The low glass of thermal stability glass during manufacturing glass can show tendency towards devitrification.So The thermal stability of glass and according to the research of the present inventor, such as recorded in patent document 6 is poor.

In view of above aspect, one embodiment of the present invention provides a kind of glass, refractive index nd ranging from 1.800~ 1.850, and ranging from the 41.5~44 of Abbe number ν d, reduce 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 1 or more in following aspect.

Inhibit the long wavelengthization at the light absorption end of the short wavelength side of glass.This is because caused by following reason.

For correcting chromatic aberration, it is known that there are as below methods：It is made using the glass for being respectively provided with different optical characteristics more A lens make the fitting of these lens make balsaming lens.During making balsaming lens, in order to make lens paste each other It closes, usually using ultraviolet hardening bonding agent.Concrete condition is as follows.The coated UV line on the surface for making lens be bonded each other Curing type bonding agent, makes lens be bonded.At this point, forming the very thin coating of ultraviolet hardening bonding agent usually between lens Layer.Then, ultraviolet light is irradiated to above-mentioned coating layer by lens, ultraviolet hardening bonding agent is made to cure.Therefore, when lens When transmission of ultraviolet rays is low, the ultraviolet light of not enough light quantities reaches above-mentioned coating layer by lens, and solidification is caused to become It obtains insufficient.Alternatively, solidification takes a long time.In addition, lens are bonded and are fixed using ultraviolet hardening bonding agent In the case ofs 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 which the glass of the transmission characteristics with the making for being suitable for optical system is made, glass is preferably improved The transmissivity of ultraviolet region in other words inhibit the long wavelengthization at the light absorption end of the short wavelength side of glass.

However, according to the research of the present inventor, such as in the glass recorded in patent document 5, the short wavelength side of glass Light absorption end carry out long wavelengthization, the decrease in transmission of ultraviolet region.In addition, in previous high-refractivity and low-dispersion glass In glass composition, when want to reduce the content of Gd, Ta, and at the same time maintaining high-refractivity and low-dispersion characteristic and when thermal stability, There are the tendencies that the light absorption end long wavelengthization of the short wavelength side of glass, transmission of ultraviolet rays are greatly reduced.

It is suitable for being machined.Concrete condition is as follows.As the method for obtaining optical element by glass, in addition to precision is suppressed Other than the method for forming (see, for example Patent Documents 1 to 4), also optical element blank is molded by glass, to optics member Part blank is ground the mechanical processing of processing, polishing etc. and the method that is processed into optical element.If in this machinery Glass is easy breakage in processing, then so that fabrication yield is reduced.In general, the glass transition of the glass of precision press molding method Temperature is low, but tendency of the glass with the easy breakage in mechanical processing that glass transition temperature is low.Therefore, suitable in order to be made Together in the glass of mechanical processing, preferably make glass transition temperature higher than the glass of precision press molding.

One embodiment 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 be 5 mass % hereinafter,

B₂O₃Content is relative to B₂O₃And SiO₂Total content mass ratio (B₂O₃/(B₂O₃+SiO₂)) be 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,

Ranging from the 1.800~1.850 of refractive index nd, and ranging from the 41.5~44 of Abbe number ν d.

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

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 be 3% hereinafter,

B³⁺Content is relative to B³⁺And Si⁴⁺Total content cation ratio (B³⁺/(B³⁺+Si⁴⁺)) it is 0.65 or more 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 the glass of refractive index nd and Abbe number the ν d with above range, including Gd₂O₃Various composition (i.e. La₂O₃、Y₂O₃、Gd₂O₃、Yb₂O₃) total content in the above range, meet Gd₂O₃Content as molecule, will be above-mentioned various Above-mentioned mass ratio of the total content of ingredient as denominator.Therefore, the ratio that Gd occupies in glass composition reduces.In turn, Ta₂O₅Content and Yb₂O₃Content difference is as described above, and the ratio that Ta and Yb occupy in glass composition also reduces.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 for measuring ratio, so as to realize high thermal stability (property for being not easy devitrification).In turn, short wavelength can also be inhibited The long wavelengthization at the light absorption end of side realizes that high glass-transition temperature (Tg) changes (high temperature of glass transition temperature).

Glass 2 is the glass of refractive index nd and Abbe number the ν d with above range, including Gd³⁺Various composition (i.e. La³ ⁺、Y³⁺、Gd³⁺、Yb³⁺) total content in the above range, meet Gd³⁺Content as molecule, by the conjunction of above-mentioned various composition Count above-mentioned cation ratio of the content as denominator.Therefore, the ratio that Gd occupies in glass composition reduces.In turn, Ta⁵⁺Content and Yb³⁺Content difference is as described above, and the ratio that Ta and Yb occupy in glass composition also reduces.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 thermal stability (property for being not easy devitrification).In turn, the light absorption of short wavelength side can also be inhibited The long wavelengthization at end realizes that high glass-transition temperature (Tg) changes (high temperature of glass transition temperature).

According to one method of the present invention, it is capable of providing special with useful high-refractivity and low-dispersion in optical system Property, the glass for capableing of stable supplying and excellent heat stability.In turn, according to one method of the present invention, it is capable of providing by above-mentioned Compression moulding glass material, optical element blank and the optical element that glass is constituted.

Description of the drawings

Fig. 1 shows the spectral-transmission favtor curve of the thickness 10.0mm of aftermentioned glass A.

Fig. 2 shows the spectral-transmission favtor curves of the thickness 10.0mm of aftermentioned glass B.

Specific implementation mode

The glass composition of the present invention can be for example, by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) the methods of quantified.The assay value acquired 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%, does not include Or do not import and mean substantially not including this composition ingredient, refer to the content of this composition ingredient be impurity level degree with Under.

Hereinafter, about numberical range, (more) preferred lower limit is shown in (more) preferred upper limit described in table sometimes. In table, the numerical value for being recorded in lower section is the more preferred, and the numerical value for being recorded in bottom is most preferred.In addition, as long as no spy Other record, (more) preferred lower limit refer to the value (more) of the value recorded or more preferably, (more) preferred upper limit refers to recording It is preferred to be worth the following value (more).It can make the numerical value recorded in the row of (more) in table preferred lower limit and (more) the preferred upper limit Row recorded in numerical value arbitrarily combine and carry out specified value range.

[glass]

The glass 1 and glass 2 of one embodiment of the present invention are that there is above-mentioned glass to form, and refractive index nd is ranging from 1.800~1.850, and ranging from 41.5~44 oxide glass of Abbe number ν d.Hereinafter, to the details of glass 1 and glass 2 It illustrates.

In the present invention, the glass composition of glass 1 is indicated with oxide benchmark." the glass group of oxide benchmark herein At " refer to that glass raw material is all decomposed in melting, and is obtained as being carried out in glass as substance existing for oxide The glass composition arrived.In addition, recorded as long as no special, the glass composition of glass 1 be set as on the basis of quality (quality %, Mass ratio) it indicates.

B₂O₃、SiO₂It is the network forming component of glass.Work as B₂O₃And SiO₂Total content (B₂O₃+SiO₂) be 15% with When upper, the thermal stability of glass can be improved, inhibits the crystallization of the glass in manufacture.On the other hand, work as B₂O₃And SiO₂It is total When content is 35% or less, the reduction of refractive index nd can be inhibited, thus can make glass with above-mentioned optical characteristics, That is refractive index nd is present in 1.800~1.850 range and Abbe number ν d be present in 41.5~44 range glass.Cause This, the B in glass 1₂O₃And SiO₂The range of total content be set as 15~35%.B₂O₃And SiO₂Total content it is preferred Lower limit and the preferred upper limit are as shown in the table.

【Table 1】

The B of network forming component as glass₂O₃And SiO₂Each ingredient content thermostabilization of the ratio to glass Property, meltbility, mouldability, chemical durability, weatherability, machining property etc. impact.B₂O₃Compared to SiO₂Improve melting Property effect it is better, but melting when it is readily volatilized.In contrast, SiO₂With the chemical durability, weather-proof for improving glass Property, machining property, improve melting when glass viscosity effect.

In general, including B₂O₃And La₂O₃In the low dispersing glass of high refractive index of equal rare earth elements, glass when melting Viscosity is low.But glass upon melting viscosity it is low when, thermal stability reduce (becoming easy crystallization).About glass manufacture When crystallization, the state of crystallization is more more stable than amorphous state (amorphous state), be by constitute glass ion in glass It is moved in glass and is arranged and occurred in a manner of with crystal structure.Therefore, by B₂O₃And SiO₂Each ingredient The ratio of content is adjusted so that viscosity when melting increases, so as to make above-mentioned ion be not easy with crystal structure Mode is arranged, and the crystallization of glass is further suppressed, and improves the thermal stability 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 cured surface element be rolled into the glass for being still in molten condition inside and become striped, the optics of glass Homogenieity reduces.The excellent glass of mouldability, which will be equivalent in the high-refractivity and low-dispersion glass containing rare earth element, to be melted The higher glass of ratio of viscosities when the glass of state is poured into mold.

Work as B₂O₃Content is relative to B₂O₃And SiO₂Total content mass ratio (B₂O₃/(B₂O₃+SiO₂)) be 0.900 with When lower, viscosity when melting can be inhibited to reduce, thus, it is possible to improve the thermal stability of glass, inhibit volatilization when melting.It is molten The reason of variation that volatilization when melting becomes the variation, characteristic that make glass form becomes larger.Also, its result is difficult to optically equal The glass of matter is molded.Therefore, it from the viewpoint of the few glass of the deviation to composition, characteristic carries out volume production, is preferably able to By mass ratio (B₂O₃/(B₂O₃+SiO₂)) volatilization when being set as 0.900 or less and inhibiting melting.In turn, as mass ratio (B₂O₃/ (B₂O₃+SiO₂)) be 0.900 or less when, can also inhibit the reduction of the chemical durability, weatherability, machining property of glass. In contrast, in the glass composition recorded in the patent document 15 (Japanese Unexamined Patent Application 57-056344 bulletins), B₂O₃ Content is 28~30 mass %, SiO₂Content be 1~3 mass % (5 claims referring to patent document 1).By these Mass ratio (the B that the content of ingredient calculates₂O₃/(B₂O₃+SiO₂)) it is 0.903~0.968 this big value.

On the other hand, as mass ratio (B₂O₃/(B₂O₃+SiO₂)) be 0.4 or more when, can prevent melting when glass raw material Melting residue, therefore meltbility can be improved.

From above aspect, in glass 1, by mass ratio (B₂O₃/(B₂O₃+SiO₂)) range be set as 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 thermal stability, 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 to have the function of improving refractive index while inhibiting the reduction of Abbe number Ingredient.In addition, these ingredients also have the function of improving the chemical durability of glass, weatherability, improve glass transition temperature.

Work as La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content (La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃) be 45% or more when, energy Enough inhibit the reduction of refractive index, therefore the glass with above-mentioned optical characteristics can be made.Further, it is possible to inhibit glass The reduction of chemical durability, weatherability.In addition, when glass transition temperature reduces, glass is machined (cut-out, Cutting, grinding, polishing etc.) when glass become easy damaged (reduction of machining property), but work as La₂O₃、Y₂O₃、Gd₂O₃With Yb₂O₃Total content be 45% or more when, the reduction of glass transition temperature can be inhibited, thus can also improve machinery plus Work.On the other hand, work as La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content when being 65% or less, the heat that can improve glass is steady It is qualitative, thus also can inhibit manufacture glass when crystallization, reduce melten glass when raw material melting residue.Therefore, in glass In glass 1, La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃The range of total content be set as 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】

ZrO₂It is the ingredient improve with refractive index, by making it contain in right amount, also there is the heat for improving glass The effect of stability.In addition, ZrO₂Also have and improves glass transition temperature, makes glass not cracky when being machined Effect.In order to obtain these effects well, in glass 1, by ZrO₂Content be set as 3% or more.On the other hand, when ZrO₂Content when being 11% or less, crystallization, glass when can improve the thermal stability of glass, therefore can inhibit glass manufacture The generation of melting residue when glass melts.Therefore, the ZrO in glass 1₂The range of content be set as 3~11%.ZrO₂Content Preferred lower limit and the preferred upper limit are 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 ingredient of shared ratio in.In addition, Ta₂O₅It is the ingredient improve with refractive index, but is also the proportion for making glass The ingredient for increasing, meltbility being made to reduce.Therefore, the Ta in glass 1₂O₅Content is set as 5% or less.Ta₂O₅Content it is preferred Lower limit and the preferred upper limit are as shown in the table.

【Table 7】

In order in the thermal stability of improvement glass, inhibit to realize above-mentioned optical characteristics while 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)) range be set as 0.42~0.53.As mass ratio ((B₂O₃+SiO₂)/(La₂O₃+ Y₂O₃+Gd₂O₃+Yb₂O₃)) be 0.42 or more when, the thermal stability of glass can be improved, therefore the devitrification of glass can be inhibited.This Outside, the increase of the proportion of glass can also be inhibited.When the proportion of glass increases, become using the optical element that the glass makes Weight.As a result it is mounted with that the optical system of the optical element becomes weight.For example, when optical element that will be is mounted on auto-focusing formula again When in camera, power consumption when auto-focusing is driven to increase, battery can be consumed quickly.From the optical element for using the glass to make From the perspective of light-weighted reduction with the optical system for being mounted with the optical element, it is preferably able to inhibit the proportion of glass Increase.On the other hand, as mass ratio ((B₂O₃+SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) be 0.53 or less when, can realize Above-mentioned optical characteristics.In addition, the viewpoint changed from the improvement of the chemical durability of glass, high glass-transition temperature (Tg) goes out Hair, it is also preferred that mass ratio ((B₂O₃+SiO₂)/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃)) it is 0.53 or less.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 above records the reasons why, Y₂O₃It is preferably to reduce it in glass group The ingredient of shared ratio in.Therefore in glass 1, by Y₂O₃Content is set as 3% or less.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 not making the light transmittance of near infrared region be greatly reduced and playing the thermal stability for improving glass Ingredient.Further, since atomic weight is small, so Y₂O₃It is the preferred ingredient in terms of inhibiting the increase of proportion of glass.But It is to work as Y₂O₃Content it is excessive when, the thermal stability of glass significantly reduces, and is easy crystallization.In addition, meltbility reduces.From being produced on It is greatly reduced the light transmittance of near infrared region while improving thermal stability and inhibits the increase of proportion, with upper From the perspective 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)) range be set as 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 above records the reasons why, Gd₂O₃It is the ingredient for preferably reducing its shared ratio in glass composition.In addition, Belong to heavy rare earth element in the same manner as Gd and Yb, as the ingredient of glass, Gd atomic weight is big, and the proportion of glass is made to increase.From the party Face is set out, it is also preferred that reducing the 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 determines.In glass 1, there is the high-refractivity and low-dispersion glass of above-mentioned optical characteristics from stable supplying From the perspective of glass, and then from the viewpoint of making the small glass of proportion 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)) Range is set as 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】

It is never greatly reduced the light transmittance of near infrared region, inhibits proportion while improving thermal stability Increase, from the aspect of high-refractivity and low-dispersion glass is provided, La₂O₃It is useful ingredient.Therefore in glass 1, preferably will La₂O₃Content is relative to La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content mass ratio (La₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+ Yb₂O₃)) range be set as 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 ingredient 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 to have the function of that the ingredient for improving refractive index also has by making it contain in right amount Play the role of improving the thermal stability of glass.From the optical characteristics stated in realization while further improve the thermostabilization of glass From the aspect of property, preferably Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content (Nb₂O₅+TiO₂+Ta₂O₅+WO₃) ranging from 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 function of the melting for promoting the raw material of glass in melten glass, the effect for improving meltbility.This Outside, it may have adjustment refractive index, Abbe number, the effect for making glass transition temperature reduce.From the aspect of improving meltbility, It is preferred that ZnO content divided by B₂O₃And SiO₂The obtained value, i.e. mass ratio (ZnO/ (B of total content₂O₃+SiO₂)) be 0.04 with On.On the other hand, from the reduction (high dispersion) for inhibiting Abbe number, from the aspect of realizing above-mentioned optical characteristics, preferred matter Amount is than (ZnO/ (B₂O₃+SiO₂)) it is 0.4 or less.In addition, from the thermal stability and high glass-transition temperature (Tg) that improve glass From the aspect of change, it is also preferred that mass ratio (ZnO/ (B₂O₃+SiO₂)) it is 0.4 or less.It is therefore preferable that by the content of ZnO be set as with Mass ratio meter B₂O₃And SiO₂0.04~0.4 times of total content, that is, by mass ratio (ZnO/ (B₂O₃+SiO₂)) it is set as 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, thermal stability, mouldability, the machining property etc. for improving glass, 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 inhibit the increase of aftermentioned degree of staining λ 5 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)) range be set as 2.65~10.In addition, from glass is improved From the aspect of thermal stability, it is also preferred that by mass ratio ((B₂O₃+SiO₂)/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) be set as 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】

About Nb₂O₅、TiO₂、Ta₂O₅And WO₃, by making it contain in right amount, play the work for the thermal stability for improving glass With.

As TiO in these ingredients₂Content when increasing, there are the decrease in transmission of the visible area of glass, glass The increased tendency of color.

Ta₂O₅Function as described above.

For WO₃, when its content increases, there are the decrease in transmission of the visible area of glass, the coloring of glass increases Tendency, there is the increased tendency of proportion in addition.

In contrast, Nb₂O₅With making the proportion of glass, coloring, manufacturing cost be not easy to increase, improve refractive index, improve glass The effect of the thermal stability of glass.Therefore, in glass 1, in order to efficiently use Nb₂O₅Excellent effect, effect, by Nb₂O₅'s Content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) Range is set as 0.5~1.From the reductions of degree of staining λ 5 are made, promote consolidating for ultraviolet hardening bonding agent caused by being irradiated by ultraviolet light From the perspective 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】

About Ta₂O₅, according to the above records the reasons why, preferably do not import glass energetically.Therefore, to Nb₂O₅Content phase For in Nb₂O₅、TiO₂、Ta₂O₅And WO₃Middle exclusion Ta₂O₅Nb afterwards₂O₅、TiO₂And WO₃Total content mass ratio (Nb₂O₅/ (Nb₂O₅+TiO₂+WO₃)) preferred range illustrate.In order to make with the few glass of excellent thermal stability, coloring, Preferred mass ratio (Nb₂O₅/(Nb₂O₅+TiO₂+WO₃)) ranging from 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 improving meltbility, preferably ZnO content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content Mass ratio (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) it is set as 0.1 or more.In addition, for the low glass of meltbility, when in order to The melting residue of glass raw material is not had and improves the melting temperature of glass, and when extending the melting time, there are the coloring of glass increasings Big tendency.It can be speculated as, this is because in the melting crucible of the noble metals such as such as platinum when melten glass, melting when increasing Temperature when extending the melting time, constitutes the precious metal melting in melten glass of crucible, generates the light caused by precious metal ion It absorbs, the coloring of glass, particularly the value of λ 5 increase.On the other hand, when the desired content by adjusting other glass ingredients Come when improving meltbility, there are thermal stability reductions, it is difficult to the case where obtaining 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 inhibiting glass, it is also preferred that by mass ratio (ZnO/ (Nb₂O₅ +TiO₂+Ta₂O₅+WO₃)) it is set as 0.1 or more.In addition, from the further thermal stability for improving glass, inhibit glass transition temperature The reduction (improvement of machining property caused by thus) of degree, from the perspective of improving chemical durability, preferably by mass ratio (ZnO/(Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) it is set as 3 or less.Mass ratio (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) it is more preferable 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 for the thermal stability, inhibition glass transition temperature for further improving glass, (machinery caused by thus adds The improvement of work), improve chemical durability, from the perspective of weatherability, preferably Li₂O content is set as 1% or less.Li₂O content Preferred lower limit and the preferred upper limit are as shown in the table.

【Table 26】

Na₂O、K₂O、Rb₂O、Cs₂O all has the effect for the meltbility for improving glass, but when these content increases, shows Go out the tendency that the thermal stability of glass, chemical durability, weatherability, machining property reduce.It is therefore preferable that Na₂O、K₂O、 Rb₂O、Cs₂The lower and upper limit difference of each content of O is as shown in the table.

【Table 27】

【Table 28】

【Table 29】

【Table 30】

Rb₂O、Cs₂O is the ingredient of costliness, with Li₂O、Na₂O、K₂O is compared, and is the ingredient for being unsuitable for general glass.Cause This, from the meltbility for improving glass while the thermal stability of maintenance glass, chemical durability, weatherability, machining property From the perspective of, preferably Li₂O、Na₂O and K₂Total content (Li of O₂O+Na₂O+K₂O lower and upper limit) are set to as follows Shown in table.

【Table 31】

MgO, CaO, SrO, BaO are the ingredients for having the function of that the meltbility of glass is made to improve.But when these ingredients Content when increasing, the thermal stability of glass reduces, and shows tendency towards devitrification.Therefore, each content of these ingredients is preferably set respectively For more than 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 thermal stability for further improving glass, total content of MgO, CaO, SrO and BaO (MgO+CaO+SrO+BaO) it is preferably set to lower limit shown in following table or more, below the upper limit.

【Table 36】

Al₂O₃It is the chemical durability with improvement glass, the ingredient of weatherability.But work as Al₂O₃Content When increase, the tendency that the tendency of refractive index reduction, tendency, the meltbility of the thermal stability reduction of glass reduce is shown sometimes.It examines Aspect more than worry, Al₂O₃Content is preferably set to lower limit shown in following table or more, below the upper limit.

【Table 37】

Ga₂O₃、In₂O₃、Sc₂O₃、HfO₂All have the effect for improving refractive index nd.But these ingredients are expensive, no It is the required ingredient from the aspect of obtaining glass 1.Therefore, Ga₂O₃、In₂O₃、Sc₂O₃、HfO₂Each content be preferably set to down More than lower limit shown in table, below the upper limit.

【Table 38】

【Table 39】

【Table 40】

【Table 41】

Lu₂O₃Have the function of improving refractive index nd, but is also that can make the increased ingredient of the proportion of glass.In addition, and high Expensive ingredient.From above aspect, Lu₂O₃Content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 42】

GeO₂Have the function of improving refractive index nd, but in usually used glass ingredient be it is extremely expensive at Point.From the viewpoint of the manufacturing cost for reducing glass, GeO₂The preferred lower limit of content and the preferred upper limit are as shown in the table.

【Table 43】

Bi₂O₃It is the ingredient for improving refractive index nd and Abbe number being made to reduce.In addition, and being easy to make the coloring of glass to increase Big ingredient.From the viewpoint made from 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 obtaining various effects described above well, from the aspect of effect, each glass ingredient of the above record 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 the glass ingredient other than the glass ingredient recorded above, P₂O₅It is the ingredient for making refractive index reduce, and makes glass The ingredient that the thermal stability of glass reduces, but if importing minute quantity, sometimes improve the thermal stability 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 ingredient of raising refractive index, but is also the virose ingredient 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 the ingredient of (more) preferred lower limit or 0% 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 respectively have toxicity.It is therefore preferable that not containing these elements, that is, not by these elements It is imported in glass as glass ingredient.

U, Th, Ra are radioactive elements.It is therefore preferable that not containing these elements, that is, not using these elements as glass Ingredient imports in glass.

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

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

The additive amount of Sb is being scaled Sb₂O₃, Sb during the glass of oxide benchmark is formed₂O₃Glass ingredient in addition Total content when being set as 100 mass %, preferred ranging from 0~0.11 mass % of the additive amount of Sb, more preferably ranging from 0.01~0.08 mass %, further preferred range are 0.02~0.05 mass %.Herein, " the glass group of oxide benchmark At " to refer to glass raw material in melting be all decomposed, as being converted in glass as substance existing for oxide Obtained glass composition.Sb in glass composition shown in aftermentioned table₂O₃Content is also to be contained by what above-mentioned method calculated Amount.

The additive amount of Sn is being scaled SnO₂, SnO during the glass of oxide benchmark is formed₂Glass ingredient in addition When total content is set as 100 mass %, the additive amount of Sn preferred ranging from 0~1.0 mass %, more preferably ranging from 0~ 0.5 mass %, further preferred range are 0~0.2 mass %, are still more preferably 0 mass %.

In the present invention, the glass of glass 2, which forms, to be indicated with cation % for cation constituent.As it is well known that Sample, cationic % refer to the percentage that the total content for the whole cation constituents for including is set as to 100% in glass.

About cation constituent, such as B³⁺、Si⁴⁺、La³⁺It indicates in this way, and the valence mumber of cation constituent is (for example, B³⁺'s Valence mumber is+3, Si⁴⁺Valence mumber be+4, La³⁺Valence mumber be+3) be according to routinely determining value, 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 indicates that cation, O indicate Oxygen, m and n are the integers determined with stechiometry.) ingredient, cation A is expressed as A^s+, herein, s=2n/m.Therefore, example Such as, when glass composition is analyzed, quantified, the valence mumber for analyzing cation constituent can not also be used, hereinafter, as long as no It especially records, the content of cation constituent, total (the total content) of the content of a variety of cation constituents is used into cation % tables Show.In turn, in cationic % expressions, the content between cation constituent (is also contained comprising the total of a variety of cation constituents Amount) ratio be known as cation ratio.

B³⁺、Si⁴⁺It is the network forming component of glass.Work as B³⁺And Si⁴⁺Total content (B³⁺+Si⁴⁺) be 45% or more when, The thermal stability of glass can be improved, the crystallization of the glass in manufacture is inhibited.On the other hand, work as B³⁺And Si⁴⁺Total content be When 65% or less, the reduction of refractive index can be inhibited, therefore glass, the i.e. refractive index with above-mentioned optical characteristics can be made Nd is in 1.800~1.850 range and glass of the Abbe number ν d in 41.5~44 range.Therefore, in glass 2 B³⁺And Si⁴⁺The range of total content be set as 45~65%.B³⁺And Si⁴⁺Total content preferred lower limit and it is preferred on Limit is as shown in the table.

【Table 47】

The B of network forming component as glass³⁺And Si⁴⁺Each ingredient content ratio to the thermal stability of glass, Meltbility, mouldability, chemical durability, weatherability, machining property etc. impact.B³⁺Improvement meltbility effect ratio Si⁴⁺It is better but readily volatilized when melting.In contrast, Si⁴⁺With chemical durability, weatherability, the machinery for improving glass The effect of the viscosity of glass when processability, raising melting.

In general, including B³⁺And La³⁺Deng rare earth element high-refractivity and low-dispersion glass in, glass when melting Viscosity is low.But glass upon melting viscosity it is low when, thermal stability reduce (becoming easy crystallization).About glass manufacture When crystallization, the state of crystallization is more more stable than amorphous state (amorphous state), be by constitute glass ion in glass It is moved in glass and is arranged and occurred in a manner of with crystal structure.Therefore, by B³⁺And Si⁴⁺Each ingredient The ratio of content is adjusted so that viscosity when melting increases, so as to make above-mentioned ion be not easy with crystal structure Mode is arranged, and the crystallization of glass is further suppressed, and further improves the thermal stability of glass.

If B³⁺Content relative to B³⁺And Si⁴⁺Total content cation ratio (B³⁺/(B³⁺+Si⁴⁺)) it is less than 0.94, It can then inhibit viscosity when melting to reduce, thus, it is possible to improve the thermal stability of glass, inhibit volatilization when melting.When melting Volatilization become variation the reason of becoming larger of the variation, characteristic that make glass form.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, being preferably able to will be positive Ion ratio (B³⁺/(B³⁺+Si⁴⁺)) it is set as the volatilization less than 0.94 and when inhibiting to melt.In turn, as cation ratio (B³⁺/(B³⁺+Si⁴ ⁺)) be less than 0.94 when, can also inhibit the reduction of the chemical durability, weatherability, machining property of glass.In contrast, exist In glass composition recorded in the patent document 15 (Japanese Unexamined Patent Application 57-056344 bulletins), B₂O₃Content is 28~30 Quality %, SiO₂Content be 1~3 mass % (5 claims referring to patent document 1).It is calculated by the content of these ingredients 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 0.65 or more, glass when melting can be prevented former The melting residue of material, therefore meltbility can be improved.

From above aspect, in glass 2, by cation ratio (B³⁺/(B³⁺+Si⁴⁺)) be set as 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 thermal stability, meltbility, mouldability, chemical durability, weatherability, the mechanical processing for improving glass etc. It sets 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 ingredient improve while inhibiting the reduction of Abbe number with refractive index. In addition, these ingredients also have the function of improving the chemical durability of glass, weatherability, improve glass transition temperature.

Work as La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content (La³⁺+Y³⁺+Gd³⁺+Yb³⁺) be 25% or more when, can inhibit to roll over The reduction of rate is penetrated, therefore the glass with above-mentioned optical characteristics can be made.Further, it is possible to inhibit the chemistry of glass durable The reduction of property, weatherability.In addition, when glass transition temperature reduces, glass is machined and (cuts off, cut, grinding Mill, polishing etc.) when glass become easy damaged (reduction of machining property), but work as La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total contain When amount is 25% or more, the reduction of glass transition temperature can be inhibited, therefore can also improve machining property.Another party La is worked as in face³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content be 35% or less when, the thermal stability of glass can be improved, therefore also can Inhibit manufacture glass when crystallization, reduce melten glass when raw material melting residue.Therefore, in glass 2, La³⁺、Y³⁺、Gd³ ⁺And Yb³⁺The range of total content be set as 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 ingredient improve with refractive index, by making it contain in right amount, also has the heat for improving glass steady Qualitatively effect.In addition, Zr⁴⁺Also have and improve glass transition temperature, makes when being machined glass not cracky Effect.In order to obtain these effects well, in glass 2, by Zr⁴⁺Content be set as 2% or more.On the other hand, work as Zr⁴⁺ Content when being 8% or less, the crystallization, glass when can improve the thermal stability of glass, therefore can inhibit glass manufacture are molten The generation of melting residue when melting.Therefore, the Zr in glass 2⁴⁺The range of content be set as 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 form in glass In shared ratio ingredient.In addition, Ta⁵⁺It is the ingredient improve with refractive index, but is also that the proportion of glass is made to increase Greatly, the ingredient for reducing meltbility.Therefore, the Ta in glass 2⁵⁺Content is set as 3% or less.Ta⁵⁺Content preferred lower limit It is as shown in the table with the preferred upper limit.

【Table 53】

In order in the thermal stability of improvement glass, inhibit to realize above-mentioned optical characteristics while 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⁺)) range be set as 1.65~2.60.As cation ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+ Yb³⁺)) be 1.65 or more when, the thermal stability of glass can be improved, therefore the devitrification of glass can be inhibited.It is further possible to press down The increase of the proportion of glass processed.When the proportion of glass increases, become weight using the optical element that the glass makes.As a result it is mounted with The optical system of the optical element becomes weight.For example, when optical element that will be is mounted in the camera of auto-focusing formula again, drive Power consumption when dynamic auto-focusing increases, and battery can be consumed quickly.From the optical element for using the glass to make and it is mounted with the light From the perspective of the light-weighted reduction for learning the optical system of element, it is preferably able to inhibit the increase of the proportion of glass.Another party Face, as cation ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) when being 2.60 or less, it can realize that above-mentioned optics is special Property.In addition, from the viewpoint of improving the chemical durability of glass, high glass-transition temperature (Tg) is changed, preferred cationic ratio ((B³⁺+Si⁴⁺)/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) it is 2.60 or less.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 above records the reasons why, in La³⁺、Y³⁺、Gd³⁺And Yb³⁺In, Yb³⁺It is preferably to reduce it in glass composition The ingredient of shared ratio.Therefore in glass 2, by Yb³⁺Content is set as being 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 not making the light transmittance of near infrared region be greatly reduced and playing the thermal stability for improving glass Ingredient.Further, since atomic weight is small, so Y³⁺It is the preferred ingredient of increased aspect in the proportion for inhibiting glass.But It is to work as Y³⁺Content it is excessive when, the thermal stability of glass significantly reduces, and is easy crystallization.In addition, meltbility reduces.From being produced on It is greatly reduced the light transmittance of near infrared region while improving thermal stability and inhibits the increase of proportion, with upper From the perspective 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⁺)) range be set as 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 above records the reasons why, Gd³⁺It is the ingredient for preferably reducing its shared ratio in glass composition.In addition, Belong to heavy rare earth element in the same manner as Gd and Yb, as the ingredient of glass, Gd atomic weight is big, and the proportion of glass is made to increase.From the party Face is set out, it is also preferred that reducing the ratio that Gd occupies in glass composition.

In glass 2, Gd³⁺Content according to La³⁺、Y³⁺、Gd³⁺And Yb³⁺Total content and add up to content relative to this Gd³⁺Content determines.From the viewpoint of stable supplying has the high-refractivity and low-dispersion glass of above-mentioned optical characteristics, into And from the viewpoint of making the small glass of proportion 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⁺)) range be set as 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】

It is never greatly reduced the light transmittance of near infrared region, inhibits proportion while improving thermal stability Increase, from the aspect of high-refractivity and low-dispersion glass is provided, La³⁺It is useful ingredient.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⁺)) range It is set as 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 ingredient 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 to have the function of that the ingredient for improving refractive index also has by making it contain in right amount Improve the effect of the thermal stability of glass.From the optical characteristics stated in realization while further improve the thermal stability of glass From the aspect of, preferably Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content (Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺) ranging from 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⁺Have the function of the melting for promoting the raw material of glass in melten glass, the effect for improving meltbility.This Outside, it may have adjustment refractive index, Abbe number, the effect for making glass transition temperature reduce.From the aspect of improving meltbility, It is preferred that Zn²⁺Content divided by B³⁺And Si⁴⁺The obtained value, i.e. cation ratio (Zn of total content²⁺/(B³⁺+Si⁴⁺)) be 0.01 with On.On the other hand, preferably positive from the aspect of realizing above-mentioned optical characteristics from the reduction (high dispersion) for inhibiting Abbe number Ion ratio (Zn²⁺/(B³⁺+Si⁴⁺)) it is 0.22 or less.In addition, from the thermal stability and high glass-transition temperature that improve glass (Tg) from the aspect of changing, it is also preferred that cation ratio (Zn²⁺/(B³⁺+Si⁴⁺)) it is 0.22 or less.It is therefore preferable that by Zn²⁺Content It is set as B in cation ratio³⁺And Si⁴⁺0.01~0.22 times of total content, that is, by cation ratio (Zn²⁺/(B³⁺+Si⁴⁺)) set It is 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, thermal stability, mouldability, the machining property etc. for improving glass, 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 inhibit the increase of aftermentioned degree of staining λ 5 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⁺)) range be set as 9.0~32.In addition, from the thermostabilization for improving glass From the aspect of property, it is also preferred that by cation ratio ((B³⁺+Si⁴⁺)/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set as 9.0 or more.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】

About Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺, by making it contain in right amount, play the effect for the thermal stability for improving glass.

As Ti in these ingredients⁴⁺Content increase when, there are the decrease in transmission of the visible area of glass, the colorings of glass Increased tendency.

Ta⁵⁺Function as described above.

For W⁶⁺, when its content increases, there are the decrease in transmission of the visible area of glass, the coloring of glass is increased , there is the increased tendency of proportion in addition in tendency.

In contrast, Nb⁵⁺With making the proportion of glass, coloring, manufacturing cost be not easy to increase, improve refractive index, improve glass The effect of the thermal stability of glass.Therefore, in glass 2, in order to efficiently use 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⁺)) range set It is 0.4~1.From the reductions of degree of staining λ 5 are made, promote the cured sight of ultraviolet hardening bonding agent caused by being irradiated by ultraviolet light 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】

About Ta⁵⁺, according to the above records the reasons why, preferably do not import glass energetically.Therefore, to Nb⁵⁺Content it is opposite In in Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Middle exclusion Ta⁵⁺Nb afterwards⁵⁺、Ti⁴⁺And W⁶⁺Total content cation ratio (Nb⁵⁺/(Nb⁵⁺+ Ti⁴⁺+W⁶⁺)) preferred range illustrate.It is preferably positive in order to make with the few glass of excellent thermal stability, coloring Ion ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+W⁶⁺)) ranging from 0.4~1.Cation ratio (Nb⁵⁺/(Nb⁵⁺+Ti⁴⁺+W⁶⁺)) it is more preferable Lower limit and the preferred upper limit it is as shown in the table.

【Table 67】

From the viewpoint of improving meltbility, preferably Zn²⁺Content is relative to Nb⁵⁺、Ti⁴⁺、Ta⁵⁺And W⁶⁺Total content Cation ratio (Zn²⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set as 0.1 or more.In addition, for the low glass of meltbility, when in order not to It has the melting residue of glass raw material and improves the melting temperature of glass, when extending the melting time, there are the coloring of glass increases Tendency.It can be speculated as, this is because in the melting crucible of the noble metals such as such as platinum when melten glass, temperature being melted when increasing Degree when extending the melting time, constitutes the precious metal melting of crucible and inhales in melten glass, generating the light caused by precious metal ion It receives, the coloring of glass, particularly the value of λ 5 increase.On the other hand, next by adjusting the content of other glass ingredients when wanting When improving meltbility, there are thermal stability reductions, it is difficult to the case where obtaining 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 inhibiting glass, it is also preferred that by cation ratio (Zn²⁺/(Nb⁵⁺ +Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set as 0.1 or more.In addition, from the further thermal stability for improving glass, inhibit glass transition temperature The reduction improvement of machining property (thus caused by), from the perspective of improving chemical durability, preferably by cation ratio (Zn²⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) it is set as 5 or less.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】

From the further thermal stability for improving glass, inhibit the reduction of glass transition temperature (mechanical caused by thus to add The improvement of work), from the perspective of improving chemical durability, weatherability, preferably Li⁺Content is set as 3% or less.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 all had, but when these content increases, glass is shown The tendency that the thermal stability of glass, chemical durability, weatherability, machining property reduce.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 the ingredient of costliness, with Li⁺、Na⁺、K⁺It compares, is the ingredient for being unsuitable for general glass.Therefore, from The viewpoint for improving the meltbility of glass while the thermal stability 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 as shown in the table.

【Table 77】

Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺It is the ingredient for having the function of that the meltbility of glass is made to improve.But when these at When the content divided increases, the thermal stability of glass reduces, and shows tendency towards devitrification.Therefore, each content difference of these ingredients is preferred It is set as lower limit shown in following table or more, below the upper limit.

【Table 78】

【Table 79】

【Table 80】

【Table 81】

In addition, from the viewpoint of the thermal stability for further improving glass, Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total content (Mg²⁺+Ca²⁺+Sr²⁺+Ba²⁺) it is preferably set to lower limit shown in following table or more, below the upper limit.

【Table 82】

Al³⁺It is the chemical durability with improvement glass, the ingredient of weatherability.But work as Al³⁺Content increase Added-time shows the tendency that the tendency of refractive index reduction, tendency, the meltbility of the thermal stability reduction of glass reduce sometimes.Consider Above aspect, Al³⁺Content is preferably set to lower limit shown in following table or more, below the upper limit.

【Table 83】

Ga³⁺、In³⁺、Sc³⁺、Hf⁴⁺All have the effect for improving refractive index.But these ingredients are expensive, be not from Required ingredient 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⁺Have the function of improving refractive index, but is also that can make the increased ingredient of the proportion of glass.In addition, and expensive Ingredient.From above aspect, Lu³⁺Content preferred lower limit and the preferred upper limit it is as shown in the table.

【Table 88】

Ge⁴⁺Have the function of improving refractive index, but in usually used glass ingredient is extremely expensive ingredient.From From the perspective 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 ingredient for improving refractive index and Abbe number being made to reduce.In addition, and being easy to make the coloring of glass increased Ingredient.From the viewpoint made from 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 obtaining various effects described above well, from the aspect of effect, the cation constituent of the above record 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 the cation constituent other than the cation constituent recorded above, P⁵⁺It is the ingredient for making refractive index reduce, and The ingredient for making the thermal stability of glass reduce, but if importing minute quantity, sometimes improve the thermal stability 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 ingredient of raising refractive index, but is also the virose ingredient 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 functioned as fining agent.

The additive amount of Sb is being scaled Sb₂O₃, Sb during the glass of oxide benchmark is formed₂O₃Glass ingredient in addition Total content when being set as 100 mass %, preferred ranging from 0~0.11 mass % of the additive amount of Sb, more preferably ranging from 0.01~0.08 mass %, further preferred range are 0.02~0.05 mass %.Herein, " the glass group of oxide benchmark At " to refer to glass raw material in melting be all decomposed, as being converted in glass as substance existing for oxide Obtained glass composition.The Sb that glass shown in aftermentioned table forms₂O₃Content 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-Content preferably ranging from 98~ 100 anion %, more preferably ranging from 99~100 anion %, further preferred range be 99.5~100 it is cloudy from Sub- % is still more preferably 100 anion %.

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 ingredients, there are the characteristics of glass to change, the homogenieity of glass reduces, melting The consumption of equipment becomes significantly to be inclined to.It is therefore preferable that by F^-、Cl^-、Br^-And I^-Total content inhibit from 100 it is cloudy from Sub- % subtracts O^2-Content amount.

As known, anion % refers to being set as the total content for the whole anion components for including in glass 100% percentage.

Then, the glass performance common to glass 1 and glass 2 illustrates.Recorded glass refers to 1 He of glass below Glass 2.

(optical characteristics of glass)

Ranging from the 1.800~1.850 of the refractive index nd of above-mentioned glass, and Abbe number ν d are 41.5~44.

The glass that refractive index is 1.800 or more, is suitable as the material of the optical element of big lens of refractive power etc..It is another Aspect, when refractive index is higher than 1.850, there is coloring in the tendency that there are Abbe numbers to reduce, the thermal stability of glass reduces in addition Increased tendency.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 41.5 or more is effective in terms of correcting chromatic aberration as the material of optical element.It is another Aspect, when Abbe number is bigger than 44, there are refractive index to reduce, the tendency of the thermal stability reduction of glass.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 fixing Abbe number is small Glass.

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

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

【Table 95】

(glass transition temperature)

From the viewpoint of improving machining property, the glass transition temperature of preferably above-mentioned glass is 640 DEG C or more.It is logical It crosses and glass transition temperature is set as 640 DEG C or more, to the mechanical processings such as cut off, cut, ground, polished to glass When, glass not cracky can be made.

On the other hand, when setting glass transition temperature excessively high, it is necessary to anneal, anneal to glass at high temperature Stove significantly consumes.In addition, when being molded to glass, it is necessary to be molded with high temperature, be molded disappearing for used mold Consumption becomes notable.

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

【Table 96】

(the light transmittance of glass)

The light transmittance of glass specifically inhibits the long wavelengthization at the light absorption end of short wavelength side, can by Coloration λ 5 is evaluated.Degree of staining λ 5 refers to the spectral-transmission favtor (packet of the glass for 10mm from ultraviolet region to visible area thickness Containing surface reflection lose) become 5% wavelength.λ 5 shown in aftermentioned embodiment is in the wavelength region of 250~700nm The value of measurement.More specifically spectral-transmission favtor for example refers to that optical polish is used to have that at the thickness of 10.0 ± 0.1mm 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, that is, the intensity for being injected into the light of above-mentioned glass specimen is being set as Iin, is setting the intensity for the light for transmiting above-mentioned glass specimen For Iout when intensity ratio Iout/Iin.

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 when utilizing ultraviolet hardening bonding agent that lens are glued each other etc., by optical element to bonding agent It irradiates ultraviolet light and bonding agent is made to cure.From efficiently carry out ultraviolet hardening bonding agent it is cured from the aspect of, it is excellent The absorption edge of the short wavelength side of spectral-transmission favtor is selected to be in short wavelength region.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 332nm or less, further preferably 330nm or less, is still more preferably 328nm or less, further Preferably 326nm λ 5 below.As an example, 315nm can be set as target by the lower limit of λ 5, but more low the more preferred, not had It is particularly limited to.

On the other hand, the index as the degree of staining of glass can enumerate degree of staining λ 70.λ 70 is with about recorded in λ 5 Method measure spectral-transmission favtor be 70% wavelength.From the viewpoint of being made and colouring few glass, the preferred model of λ 70 It encloses for 420nm hereinafter, preferred ranging from 400nm is hereinafter, further preferred range is 390nm hereinafter, further excellent The ranging from 380nm or less of choosing.The target of the lower limit of λ 70 is 340nm, but more low the 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 about recorded in λ 5 The wavelength that the spectral-transmission favtor that method measures is 80%.From the viewpoint of being made and colouring few glass, the preferred range of λ 80 For 480nm hereinafter, preferred ranging from 460nm is hereinafter, further preferred range is 440nm hereinafter, still more preferably Ranging from 420nm or less.The target of the lower limit of λ 80 is 350nm, but more low the more preferred, is not particularly limited.

(proportion of glass)

In the optical element (lens) for constituting optical system, according to the light of the refractive index and 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.In contrast, if using high refractive index glass, even if Do not increase the curvature in optical function face, can obtain big refractive power yet.

As long as a result, refractive index can be improved while inhibiting the increase of proportion of glass, it will be able to make to have and fix Refractive power optical element lightweight.

The refractive index nd of effect about to(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, index when so as to as the lightweight for seeking optical element. That is, by d/ (nd-1) as index when seeking optical element lightweight, by reducing the value, so as to seek lens Lightweight.

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

【Table 97】

In turn, the preferred lower limit of the proportion d of above-mentioned glass and the preferred upper limit are as shown in the table.It is formed from by the glass Optical element lightweight from the perspective of, proportion d is preferably set as the upper limit shown in following table or less.In addition, from further It, preferably will be than being reset to lower limit shown in following table or more from the aspect of the thermal stability for improving glass.

【Table 98】

(liquidus temperature)

Liquidus temperature is one of index of thermal stability of glass.From the side of crystallization, devitrification when inhibiting glass manufacture Face consider, preferred liquid phase line temperature LT be 1300 DEG C hereinafter, more preferably 1250 DEG C hereinafter, further preferably 1200 DEG C with Under, it is still more preferably 1150 DEG C or less.The lower limit of liquidus temperature LT is 1100 DEG C or more 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, It is useful as glass material used for optical elements.In turn, it is adjusted by carrying out the composition of front record, to make Glass homogenizes and colours reduction.In addition, above-mentioned glass is easy molding, also it is easy to be machined.Therefore, above-mentioned glass is suitable Cooperation is optical glass.

Above-mentioned glass can obtain in the following way：Glass target can be obtained weighs in the way of forming, allocates work It for the oxide of raw material, carbonate, sulfate, nitrate, hydroxide etc., is sufficiently mixed and batch mixture is made, hold in melting It heated, melted in device, carry out deaeration, stirring, made homogeneous and the melten glass without foam, be molded.It is specific and Speech, can be made using well known fusion method.Above-mentioned glass is the high-refractivity and low-dispersion for having above-mentioned optical characteristics Glass and excellent heat stability, therefore well known fusion method, the method for forming can be used steadily to manufacture.

[compression moulding glass material, optical element blank and their manufacturing method]

Another mode of the present invention is related to：

The compression moulding glass material formed by above-mentioned glass 1 or glass 2；

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

Another mode according to the present invention, it is possible to provide：

Compression moulding glass with the process that above-mentioned glass 1 or glass 2 are shaped to compression moulding glass material The manufacturing method of glass material；

With making light by the way that above-mentioned compression moulding glass material use to be pressed by pattern is pressed Learn the manufacturing 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.

Since compression moulding glass material, optical element blank are made of above-mentioned glass 1 or glass 2, It is clear that compression moulding glass material, optical element blank also correspond to above-mentioned glass.

Optical element blank is, in shape increasing in optical element approximate with the shape for the optical element for being set as target Polishing surplus (passing through the superficial layer that polishing removes) increases grind (by the surface that grinding removes as needed Layer) optical element base material.By polishing the surface of optical element blank, or by grinding and polishing, to make At optical element.It, can be as to above-mentioned glass be carried out melten glass pressure obtained from melting in right amount in a mode Molding method (being referred to as straight pressing) is made, to make optical element blank.In another mode, can also it pass through To being cured and being further processed melten glass obtained from above-mentioned glass in right amount melting, to make optical element base Part.

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

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

Compression moulding is pressed into addition to being supplied to the state of original sample for what optical element blank made with glass material Type is referred to as other than the compression moulding glass material of compression moulding glass gob, also includes to apply cut-out, grinding, polishing The compression moulding glass material of compression moulding is supplied to Deng mechanical processing, by compression moulding glass gob.As cutting Disconnected method has and forms slot using the method for being referred to as delineation in the part of the desired cut-out on the surface of glass plate, from the slot of formation The back side in face local pressure is applied to the part of slot, in the method for the partial cut glass plate of slot；Glass is cut off with cutting edge The method etc. of plate.In addition, processing method well known to tumbling etc. can be enumerated as grinding and polishing method.

Compression moulding can be molded into glass plate, incited somebody to action with glass material for example, by melten glass to be cast in mold The glass plate cuts into multiple sheet glass to make, or carries out tumbling to these multiple sheet glass to make.Alternatively, Suitable melten glass can be molded and make compression moulding glass gob.It can also be by by compression moulding glass Glass gob reheats, softens and be pressed to make optical element blank.Glass is reheated, soften, is pressed The method that type is made and makes optical element blank is referred to as reheating pressing relative to straight pressing.

[optical element and its manufacturing 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.It, can also be in glass in above-mentioned optical element Glass surface forms the coated film of one layer or more of multilayer film such as antireflection film etc..

Due to optical element be 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 other than coated film The part of glass is equivalent to above-mentioned glass.

In addition, according to one method of the present invention,

Also providing has the process that optical element is made by being at least polished above-mentioned optical element blank The manufacturing method of optical element.

In the manufacturing method of above-mentioned optical element, as long as grinding, polishing using well known method, can by Optical element surface is fully cleaned after processing, is made it dry etc. to obtain 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, aspherical can be illustrated 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 It closes.As glued optical element, it can illustrate and lens are carried out to glued glued optical element (balsaming lens) each other, will be saturating Mirror and prism carry out glued glued optical element etc..For example, glued optical element can make in the following manner：It will be glued The cemented surfaces of 2 optical elements critically processed that (such as spherical polishing adds in such a way that shape becomes reversion shape Work), in above-mentioned cemented surface coated UV line curing type bonding agent, after so that cemented surface is bonded each other, by optical element to glue The bonding agent in conjunction face irradiates ultraviolet light, and bonding agent is made to cure.In order to make glued optical element in this way, preferably above-mentioned glass.It is logical It crosses and makes glued multiple optical elements 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 composition quantitative analysis as a result, sometimes glass ingredient indicated with oxide benchmark, glass ingredient Content is indicated with quality %.It is formed and can be converted according to example method described as follows with what quality % was indicated with oxide benchmark in this way It is formed at what is indicated with cationic %, anion %.

For example, the oxide formed by cation A and oxygen is expressed as A_mO_n.M and n is 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 % indicated_mO_nContent divided by A_mO_nMolecular weight, and then be multiplied by m.The value is set as P.It connects It, adds up to P for whole cation constituents.When the value of the P added up to is set as Σ P, become 100% side with Σ P Value after formula is standardized the value of the P of each cation constituent becomes the A that cation % is indicated^s+Content.Herein, s 2n/ m。

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

As long as in addition, above-mentioned molecular weight as using the 4th after decimal point is rounded up and after indicating decimal point 3rd value is calculated.In addition, for example, oxide A_mO_nMolecular weight be elements A atomic weight m times of value and oxygen Atomic weight n times of value it is total.The molecular weight indicated using oxide benchmark for some glass ingredients, additive 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, based on embodiment, invention is further explained.But the present invention is not limited to shown in embodiment Mode.

(embodiment 1)

In the way of it can obtain that there is the glass formed shown in following table, the changes such as oxide, the boric acid as raw material are weighed Object is closed, is sufficiently mixed, batch materials are made.

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 molding by preheating Glass is put into togerther together with shaping mould in annealing furnace by mould at once after placement is cooled to glass transition temperature nearby.Then, Annealing in about 1 hour is carried out near glass transition temperature.After being annealed, places and be cooled to room temperature in annealing furnace.

The glass made like this is observed, as a result without finding the precipitation of crystal, the melting residue of bubble, striped, raw material. Thereby, it is possible to make the high glass of homogenieity.

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

Glass performance method shown in following of glass to obtaining is measured.Measurement result is as shown in the table.

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

Glass obtained from cooling down for the cooling rate with -30 DEG C/h, according to Japanese Optical Glass industry meeting The refractometry of standard, refractive index nd, nF, nC, ng are measured.It is calculated using each measured value of refractive index nd, nF, nC 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 heating 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 polished face from vertical direction the light of intensity Iin, the intensity of the light to having transmitted glass specimen Iout is measured, and calculates spectral-transmission favtor Iout/Iin, the wavelength that spectral-transmission favtor is 5% is set as λ 5, by spectral transmission The wavelength that rate is 70% is set as λ 70, and the wavelength that spectral-transmission favtor is 80% is set as λ 80.

(5) relative partial dispersion Pg, F

It is calculated according to the value of nF, nC, the ng measured by above-mentioned (1).

(6) liquidus temperature

Glass is put into the stove for being heated to set point of temperature, is kept for 2 hours, after cooling, with 100 times of light microscope Inside glass is observed, 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 compression moulding with glass blocks (glass gob).The glass blocks is existed It heats in air, soften, be pressed with being pressed into pattern, make lens blank (optical element blank).By making Lens blank takes out from pattern is pressed into, and anneals, and carries out the mechanical processing for including polishing, what making was made by embodiment 1 The spherical lens that various glass are formed.

(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, make lens blank (optical element blank).By the lens blank of making It takes out, anneals from pattern is pressed into, carry out the mechanical processing for including polishing, make the various glass made by embodiment 1 The spherical lens of formation.

(embodiment 4)

To the melten glass made in embodiment 1 being cured and manufactured glass blocks (optical element blank) progress Annealing carries out the mechanical processing for including polishing, makes the spherical lens formed by the various glass that embodiment 1 makes.

(embodiment 5)

The spherical lens made in embodiment 2~4 is bonded with the spherical lens that the glass by other types is formed, is made Make balsaming lens.The cemented surface of the spherical lens made in embodiment 2~4 is the spherical surface of convex, by the optics of other types The cemented surface for the spherical lens that glass is formed is concave spherical surface.2 above-mentioned cemented surfaces with the absolute value of radius of curvature each other Equal mode makes.It is in the ultraviolet hardening bonding agent of cemented surface coated optical element gluing, 2 lens are glued Face is bonded each other.Hereafter, the bonding agent for being coated on cemented surface is irradiated by the spherical lens made in embodiment 2~4 purple Outside line makes bonding agent cure.

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

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

To (being recorded as below " glass A " with the glass formed shown in following tables 102.), with following tables 103 Shown in the glass that forms (be recorded as below " glass B ".) melted, be molded respectively, it is processed into plate.These glass plates have There are 2 opposite planes.2 planes are parallel to each other, by optical polish.It is divided into 10.0mm between 2 planes.

Using this glass plate, spectral-transmission favtor is measured.To above-mentioned 2 opposite planes vertically incident light, on one side Scanning wavelength calculates the intensity for the incident light for being injected into glass plate and has transmitted the ratio of the intensity of the transmitted light of glass plate on one side (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 %	Cationic %
			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 %	Cationic %
			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 indicated due to not containing Y₂O₃, therefore it is mass ratio (Y₂O₃/(La₂O₃+ Y₂O₃+Gd₂O₃+Yb₂O₃)) glass outside above-mentioned range.In addition, glass B is due in the glass composition that cationic % is indicated Without containing Y³⁺, therefore it is cation ratio (Y³⁺/(La³⁺+Y³⁺+Gd³⁺+Yb³⁺)) glass outside above-mentioned range.Therefore, glass Glass B is not equivalent to the glass 1 and glass 2 for the one embodiment of the present invention that front is recorded, but the absorption of near infrared region according to The size of Yb contents and the case where increasing and decreasing, are not rely on that whether there is or not Y₂O₃And Y³⁺.It therefore, can by comparing glass A and glass B Confirm that Yb is influenced caused by the transmissivity of near infrared region.

As shown in Figure 1, the Yb containing 0.1 mass % in the glass composition that quality % is indicated₂O₃, cationic % indicate Glass composition in the Yb containing 0.04 cation %³⁺Glass A, due to the Yb centered near wavelength 950nm light inhale It receives, leads to the decrease in transmission near this.

In addition, as shown in Fig. 2, in the glass composition that quality % is indicated the Yb containing 3.68 mass %₂O₃, sun from Yb containing 2.00 cation % in the glass composition that sub- % is indicated³⁺Glass B, due to centered near wavelength 960nm The light absorption of Yb causes the transmissivity near this to be greatly reduced.

In this way, the increase of the content with Yb, the transmissivity of the near infrared region of glass are greatly reduced, therefore as use In the glass of the purposes in the area requirement high-transmission rate from visible area near infrared region, containing being not there are many glass of Yb Suitable.

(comparative example 1)

Trial reproduces the glass of the embodiment 4 of patent document 6 (Japanese Unexamined Patent Publication 2009-203083 bulletins), but Crystallization during glass makes.This is because glass mass ratio (B in the glass composition that quality % is indicated₂O₃/(B₂O₃+ SiO₂)) it is 1, the cation ratio (B in the glass composition that cationic % is indicated³⁺/(B³⁺+Si⁴⁺)) be 1 thus thermal stability reduce Caused.

(comparative example 2)

To the glass of the embodiment 28 of patent document 5 (Japanese Unexamined Patent Application 55-121925 bulletins) (hereinafter, being recorded as " glass Glass C ") it is reproduced, it is 348nm to measure 5 results of λ using the above method.

Spherical lens is made using glass C.Then, by the spherical surface of the convex of the spherical lens and by the optics of other types The concave spherical surface for the spherical lens that glass is formed is bonded as cemented surface, the ultraviolet hardening of coated optical element gluing Agent is attempted to make balsaming lens similarly to Example 5.But lens by being formed by glass C in cemented surface to being coated with Ultraviolet hardening bonding agent irradiation ultraviolet light cannot cure sufficiently bonding since the ultraviolet transmittance of glass C is low 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 bulletins)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 ingredient in addition is set as fixed, to by Gd₂O₃Part or all be replaced into La₂O₃And Y₂O₃When The variation of the thermal stability of glass is verified.

First, it is formed as the glass of oxide benchmark, by the Gd containing 5.15 mass %₂O₃It is set as 0%, by Gd₂O₃Contain The 5.15 mass % of decrement of amount is according to La₂O₃Content and Y₂O₃Content be respectively allocated to La₂O₃And Y₂O₃.Specifically, will As 5.15 mass % × (La₂O₃Content/(La₂O₃Content and Y₂O₃Content total content)) calculate 4.09 matter % 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 recorded as " composition a ".

Then, by the Gd containing 5.15 mass %₂O₃3 mass % are reduced to, by Gd₂O₃2.15 matter of decrement of content % is measured according to La₂O₃Content and Y₂O₃Content be respectively allocated to La₂O₃And Y₂O₃.Specifically, will be used 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 recorded as " composition b ".

The composition of the embodiment 7 of patent document 17, " composition a " and " forming b " are 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, By melten glass be poured into mold and the peripheral portion of molding glass, i.e. due to mold contact causing to be quickly cooled down Do not have to find the precipitation of crystal in part, but has been precipitated greatly in the central portion of glass, the i.e. cooling velocity part smaller than peripheral portion The crystal of amount.In addition, when making the glass for the embodiment that front is recorded by identical method, it is not limited to the periphery of glass Portion does not have to find the precipitation of crystal in entire scope.

Above result is regarded as indicating in mass ratio (B₂O₃/(B₂O₃+SiO₂)) glass of range recorded beyond front Make Gd in glass composition₂O₃The result that thermal stability reduces when content reduces.

(comparative example 4)

Cation ratio (the Gd of the glass of the embodiment 7 of patent document 17 (Japanese Unexamined Patent Publication 2002-284542 bulletins)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 ingredient in addition is set as fixed, to by Gd³⁺Part or all be replaced into La³⁺And Y³⁺When glass heat it is steady Qualitatively variation is verified.

First, by the Gd containing 2.31 cation %³⁺It is set as 0%, by Gd³⁺The 2.31 cation % roots of decrement 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⁺, by conduct 2.31 cation % × ((Y³⁺Content/(La³⁺Content and Y³⁺Content total content)) calculate 0.63 cation % From Gd³⁺It is replaced into Y³⁺.Hereinafter, the composition is recorded 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 Cationic % 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)) calculate 0.59 cation % be replaced into La³⁺, will 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 recorded as " composition d ".

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

【Table 105】

(unit：Cationic %, 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, By melten glass be poured into mold and the peripheral portion of molding glass, i.e. due to mold contact causing to be quickly cooled down Do not have to find the precipitation of crystal in part, but has been precipitated greatly in the central portion of glass, the i.e. cooling velocity part smaller than peripheral portion The crystal of amount.In addition, when making the glass for the embodiment that front is recorded by identical method, it is not limited to the periphery of glass Portion does not have to find the precipitation of crystal in entire scope.

Above result is regarded as indicating in cation ratio (B³⁺/(B³⁺+Si⁴⁺)) glass of range recorded beyond front Make Gd in glass composition³⁺The result that thermal stability reduces when content reduces.

Finally, it summarizes to above-mentioned each mode.

According to a mode, it is capable of providing a kind of glass (glass 1), is oxide glass, is indicated with quality %, B₂O₃With SiO₂Total content be 15~35 mass %, La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content be 45~65 mass %, but It is Yb₂O₃Content is 3 mass % hereinafter, ZrO₂Content is 3~11 mass %, Ta₂O₅Content is 5 mass % hereinafter, 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, the range of refractive index nd It is 1.800~1.850, and ranging from the 41.5~44 of Abbe number ν d.

According to a mode, it is capable of providing a kind of glass (glass 2), is oxide glass, is indicated with cationic %, 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 3% hereinafter, B³⁺Content is relative to B³⁺And Si⁴⁺Total content sun Ion ratio (B³⁺/(B³⁺+Si⁴⁺)) it is 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, ranging from the 1.800~1.850 of refractive index nd, and ranging from the 41.5~44 of Abbe number ν d.

Glass 1 and glass 2 are the 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, which is Gd, Ta and Yb content, to be reduced and can show Go out the glass of high thermal stability.

In a mode, for glass 1, from raising meltbility, the thermal stability for further improving glass, inhibition glass From the perspective of changing the reduction improvement of machining property (thus caused by) of transition temperature, improving chemical durability, preferred matter Amount is than (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+WO₃)) ranging from 0.1~3 or less.

In a mode, for glass 2, from raising meltbility, the thermal stability for further improving glass, inhibition glass It is preferably positive from the perspective of changing the reduction improvement of machining property (thus caused by) of transition temperature, improving chemical durability Ion ratio (Zn²⁺/(Nb⁵⁺+Ti⁴⁺+Ta⁵⁺+W⁶⁺)) ranging from 0.1~5 or less.

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

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

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

By glass 1 described above or glass 2, can make compression moulding glass material, optical element blank and Optical element.That is, according to other modes, it is first to provide compression moulding glass material, the optics formed by glass 1 or glass 2 Part blank and optical element.

In addition, according to another mode, can also be provided with glass 1 or glass 2 are shaped to compression moulding glass material The manufacturing method of the compression moulding glass material of the process of material.

In turn, it according to another mode, can also be provided with by the way that above-mentioned compression moulding glass material is used pressure Be made pattern be pressed and the manufacturing method that makes the optical element blank of the process of optical element blank.

In turn, it according to another mode, can also be provided with the work that glass 1 or glass 2 are shaped to optical element blank The manufacturing method of the optical element blank of sequence.

In turn, it according to another mode, can also be provided with by being at least polished above-mentioned optical element blank Make the manufacturing method of the optical element of the process of optical element.

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

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

In addition, 2 or more of item capable of making to illustrate in specification certainly or recording as preferred range are appointed The combination of meaning ground.

In addition, the case where meeting 2 both sides of glass 1 and glass there is also certain glass.

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

Claims

1. a kind of glass is oxide glass,

It is indicated with quality %,

B₂O₃And SiO₂Total content be 21~32 mass %,

La₂O₃、Y₂O₃、Gd₂O₃And Yb₂O₃Total content be 50~63 mass %, wherein Yb₂O₃Content be 1.0 mass % with Under,

ZrO₂Content is 4~10 mass %,

Ta₂O₅Content be 2 mass % hereinafter,

Li₂O、Na₂O and K₂Total content of O is 0~2.0 mass %,

Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content be 4 mass % or more,

B₂O₃Content is relative to B₂O₃And SiO₂Total content mass ratio (B₂O₃/(B₂O₃+SiO₂)) it is 0.6~0.900,

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 0.10~0.30,

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 0.95~1,

Ranging from the 1.800~1.850 of refractive index nd, and ranging from the 41.5~44 of Abbe number ν d,

Wherein, B is not included₂O₃Content is 22.380 mass %, La₂O₃Content is 45.680 mass %, Y₂O₃Content is 8.780 matter Measure %, ZnO content is 4.250 mass %, SiO₂Content is 4.680 mass %, Nb₂O₅Content is 7.880 mass % and ZrO₂ Content is the glass of 6.350 mass %.

2. glass according to claim 1, wherein

B₂O₃Content is 17 mass % or more.

3. glass according to claim 1 or 2, wherein

B₂O₃Content is 23 mass % or less.

4. glass according to claim 1 or 2, wherein

ZnO content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content mass ratio (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+ WO₃)) ranging from 0.20~1.5.

5. glass according to claim 4, wherein

ZnO content is relative to Nb₂O₅、TiO₂、Ta₂O₅And WO₃Total content mass ratio (ZnO/ (Nb₂O₅+TiO₂+Ta₂O₅+ WO₃)) ranging from 0.20~0.500.

6. glass according to claim 1 or 2, wherein

Without containing Pb.

7. glass according to claim 1 or 2, wherein

Ranging from the 1.810~1.850 of refractive index nd.

8. glass according to claim 7, wherein

Ranging from the 1.820~1.850 of refractive index nd.

9. glass according to claim 1 or 2, wherein

Degree of staining λ 5 is 335nm or less.

10. glass according to claim 1 or 2, wherein

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

d/(nd-1)≤5.70…(A)。

11. glass according to claim 1 or 2, wherein

Glass transition temperature is 640 DEG C or more.

12. a kind of compression moulding glass material, is formed by the glass described in any one of claim 1~11.

13. a kind of optical element blank, is formed by the glass described in any one of claim 1~11.

14. a kind of optical element is formed by the glass described in any one of claim 1~11.