CN101613184B

CN101613184B - Optical glass

Info

Publication number: CN101613184B
Application number: CN200910151243.4A
Authority: CN
Inventors: 根岸智明; 邹学禄
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2008-06-27
Filing date: 2009-06-29
Publication date: 2013-07-24
Anticipated expiration: 2029-06-29
Also published as: JP2012096992A; JP5658132B2; JP2015091752A; JP5836471B2; CN101613184A

Abstract

The invention provides an optical glass with low dispersion, extremely high refractive index, excellent glass stability and less coloring. An optical glass which is an oxide glass characterized by comprising, when expressed in cation%: si⁴⁺：0～30％，B³⁺：10～55％，Li⁺、Na⁺And K⁺Less than 5% of total Mg²⁺、Ca²⁺And Sr²⁺Less than 5% of total Ba²⁺：0～8％，Zn²⁺：0.1～15％，La³⁺：10～50％，Gd³⁺：0～20％，Y³⁺：0～15％，Yb³⁺：0～10％，Zr⁴⁺：0～20％，Ti⁴⁺：0.1～22％，Nb⁵⁺：0～20％，Ta⁵⁺：0～8％，W⁶⁺：0～5％，Ge⁴⁺：0～8％，Bi³⁺：0～10％，Al³⁺: 0 to 10% of Si⁴⁺Content and B³⁺Cation ratio of contents Si⁴⁺/B³⁺Less than 1.0, Nb after conversion to oxide₂O₅And Ta₂O₅The total content of is less than 14 mass%, the refractive index nd is 1.92-2.2, and the Abbe number vd is 25-45.

Description

Opticglass

Technical field

The die forming usefulness glass block that the present invention relates to have the opticglass of the low dispersing characteristic of high refractive index, forms by described opticglass and the manufacture method of optical element and manufacture method and optical element blank.

Background technology

Disperse lens that glass forms by making up by high refractive index is low, and can revise aberration, and make the optical system miniaturization with the lens that form by ultralow dispersion glass.Therefore, the optical element as constituting projection optics systems such as image pickup optical system or projector occupies very important position.

Patent documentation 1 discloses the low glass that disperses of such high refractive index.

Patent documentation 1: the Japanese documentation spy opens clear 55-60039 communique.

Summary of the invention

But the amount that high refractive index is low disperses the high refractive index of glass to give composition becomes many relatively, and the amount that glass network forms composition reduces relatively, has therefore that stability, glass descends, problem such as devitrification in manufacturing processed easily.

In addition, give composition, then also have the painted significant problem that becomes of glass in case increase high refractive index.

The object of the present invention is to provide a kind of low dispersion and specific refractory power high, have good stability, glass, painted few opticglass, and provide a kind of die forming that forms by described opticglass with glass block and optical element blank and each manufacture method that a kind of optical element blank and optical element are provided.

In order to achieve the above object, the inventor attentively studies repeatedly, finds that the opticglass with specific glass composition, specific refractory power and Abbe number can achieve the above object, based on this opinion up to finishing the present invention.

That is, the invention provides following means:

(1) a kind of opticglass is oxide glass, it is characterized in that, when representing with positively charged ion %, comprising:

Si ⁴⁺：0～30％，

B ³⁺：10～55％，

Li ⁺, Na ⁺And K ⁺Total amount less than 5%,

Mg ²⁺, Ca ²⁺And Sr ²⁺Total amount less than 5%,

Ba ²⁺：0～8％，

Zn ²⁺：0.1～15％，

La ³⁺：10～50％，

Gd ³⁺：0～20％，

Y ³⁺：0～15％，

Yb ³⁺：0～10％，

Zr ⁴⁺：0～20％，

Ti ⁴⁺：0.1～22％，

Nb ⁵⁺：0～20％，

Ta ⁵⁺：0～8％，

W ⁶⁺：0～5％，

Ge ⁴⁺：0～8％，

Bi ³⁺：0～10％，

Al ³⁺：0～10％，

Wherein, Si ⁴⁺Content and B ³⁺The cation ratio Si of content ⁴⁺/ B ³⁺Less than 1.0, be converted into Nb behind the oxide compound ₂O ₅And Ta ₂O ₅Total content less than 14 quality %,

Refractive index n d is 1.92～2.2, and Abbe number ν d is 25～45.

(2) as above-mentioned (a 1) described opticglass, wherein, glass tansition temperature Tg is more than or equal to 630 ℃.

(3) as above-mentioned (1) item or (2) described opticglass, wherein, degree of staining λ 70 is less than 470nm.

(4) as each described opticglass in above-mentioned (1) to (3), wherein, part disperses to satisfy than Pg, F and Abbe number ν d the relation of following (1) formula,

Pg、F≤-0.0017×νd+0.660 …(1)。

(5) a kind of die forming glass block is characterized in that, is formed by each described opticglass in above-mentioned (1) to (4).

(6) a kind of optical element is characterized in that, is formed by each described opticglass in above-mentioned (1) to (4).

(7) a kind of manufacture method of optical element blank, described optical element blank is made into optical element by grinding, grinding, and this manufacture method is characterised in that,

Above-mentioned (5) described die forming is heated, softens with glass block, and carry out die forming.

(8) a kind of manufacture method of optical element blank, described optical element blank is made into optical element by grinding, grinding, and this manufacture method is characterised in that,

Frit is carried out fusion, resulting melten glass is carried out die forming, produce the optical element blank that forms by each described opticglass in above-mentioned (1) to (4).

(9) a kind of manufacture method of optical element is characterized in that, above-mentioned (7) item or (8) described optical element blank are carried out grinding, grinding.

The effect of invention

The present invention can provide a kind of refractive index n d more than or equal to 1.92, Abbe number ν d is high more than or equal to 25 such low dispersions and specific refractory power, have good stability, glass, painted less opticglass, and provides a kind of die forming that is formed by described opticglass with glass block and optical element blank and each manufacture method that a kind of optical element blank and optical element are provided.

According to above-mentioned optical element and by optical element, for example lens of above-mentioned die forming, by making up the optical system that also can provide small-sized aberration correction to use with high refractive index high dispersive glass lens with glass block or optical element blank manufacturing.

And the preferred mode of opticglass according to the present invention also can provide the glassy phase identical with possessing above-mentioned optical characteristics and Abbe number ν d to disperse the opticglass of littler than Pg, F, as to be suitable for high order colour correction than part.By effectively utilizing these character, and make up, the optical element of the aberration correction that is suitable for high order also can be provided with the optical element that forms by high refractive index high dispersive opticglass.

Embodiment

[opticglass]

At first, opticglass of the present invention is described.

Opticglass of the present invention is oxide glass, it is characterized in that, when representing with positively charged ion %, comprising:

Si ⁴⁺：0～30％，

B ³⁺：10～55％，

Li ⁺, Na ⁺And K ⁺Total amount less than 5%,

Mg ²⁺, Ca ²⁺And Sr ²⁺Total amount less than 5%,

Ba ²⁺：0～8％，

Zn ²⁺：0.1～15％，

La ³⁺：10～50％，

Gd ³⁺：0～20％，

Y ³⁺：0～15％，

Yb ³⁺：0～10％，

Zr ⁴⁺：0～20％，

Ti ⁴⁺：0.1～22％，

Nb ⁵⁺：0～20％，

Ta ⁵⁺：0～8％，

W ⁶⁺：0～5％，

Ge ⁴⁺：0～8％，

Bi ³⁺：0～10％，

Al ³⁺：0～10％，

Wherein, Si ⁴⁺Content and B ³⁺The cation ratio Si of content ⁴⁺/ B ³⁺Less than 1.0, be converted into oxide compound, Nb ₂O ₅And Ta ₂O ₅Total content less than 14 quality %, refractive index n d is 1.92～2.2, Abbe number ν d is 25～45.

(the qualification reason of compositing range)

Qualification reason to above-mentioned compositing range describes, short of special record, and the content of each composition, total content are represented with positively charged ion %.

Si ⁴⁺Be that mesh forms positively charged ion, and be to keep stability, glass, keep the viscosity of the shaping that is suitable for melten glass and improve chemical durability and effective composition, if its amount surpasses 30%, then be difficult to realize the specific refractory power expected, and liquidus temperature or glass tansition temperature can rise.And, can produce problems such as the Abbe number that is difficult to realize to expect, glass melting deterioration, devitrification resistance deterioration.Therefore, make Si ⁴⁺Content be 0～30%.Si ⁴⁺Content be limited to 25% on preferably, be limited to 23% on preferred, be limited to 20% on further preferred, be limited to 18% on further preferred again, be limited to 15% on further preferred, be limited to 12% on further preferred again.From obtaining containing above-mentioned Si ⁴⁺The effect aspect set out Si ⁴⁺Content preferably be limited to 1% down, be limited to 3% under preferred, further preferably be limited to 4% down, be limited to 5% under further preferred again, further be limited to 6% under preferably.

B ³⁺Being that mesh forms positively charged ion, is for keeping glass melting, reducing liquidus temperature, improve stability, glass and hang down decentralized and effective essential composition.If its amount is less than 10%, then stability, glass descends, and can't obtain above-mentioned effect, if its amount surpasses 55%, then be difficult to meet the desired specific refractory power, and chemical durability can worsen.Therefore, make B ³⁺Content be 10～55%.B ³⁺Content be limited to 50% on preferably, be limited to 48% on preferred again, be limited to 45% on preferred, be limited to 43% on further preferred, be limited to 40% on further preferred again, be limited to 35% on further preferred, be limited to 32% on further preferred again, be limited to 30% on especially preferred, B ³⁺Content preferably be limited to 13% down, be limited to 15% under preferred, further preferably be limited to 18% down, further preferably again be limited to 20% down, further be limited to 21% under preferably, further be limited to 22% under preferably again.

In addition, from keeping low dispersiveness and reducing liquidus temperature, improve devitrification resistance and improve meltbility, keep the viscosity aspect that is suitable for being shaped, Si ⁴⁺Content and B ³⁺The cation ratio Si of content ⁴⁺/ B ³⁺Less than 1.Cation ratio Si ⁴⁺/ B ³⁺Be limited to 0.5 on preferred.Cation ratio Si ⁴⁺/ B ³⁺Be limited to 0.03 under preferred.

Li ⁺, Na ⁺And K ⁺Be to have any composition that improves meltbility, reduces the effect of glass tansition temperature.If Li ⁺, Na ⁺And K ⁺Total content more than or equal to 5%, then be difficult to realize the specific refractory power expected, and liquidus temperature rises, stability, glass, chemical durability also descend, and therefore, make Li ⁺, Na ⁺And K ⁺Total content less than 5%.Li ⁺, Na ⁺And K ⁺The total content preferred range less than 3%, preferred scope is less than 2%, further preferred range does not further preferably contain above-mentioned alkali metal component less than 1%.

Mg ²⁺, Ca ²⁺And Sr ²⁺Has the effect that improves glass melting, reduces glass tansition temperature Tg.In addition, import in the glass, also can access the deaeration effect by form with nitrate, vitriol.But, if Mg ²⁺, Ca ²⁺And Sr ²⁺Total content more than or equal to 5%, then liquidus temperature rises, devitrification resistance worsens, and specific refractory power descends, chemical durability also can worsen.Therefore, make Mg ²⁺, Ca ²⁺And Sr ²⁺Total content less than 5%.Mg ²⁺, Ca ²⁺And Sr ²⁺The total content preferred range less than 3%, preferred scope is less than 2%, further preferred range is less than 1%, further preferred alkali-free great soil group metal ingredient.

Ba ²⁺Can improve glass melting, and import, also can access the deaeration effect by form with carbonate, nitrate.But, if Ba ²⁺Content surpass 8%, then liquidus temperature rises, stability, glass descends, and is difficult to realize the specific refractory power expected.And chemical durability also can worsen.Therefore, make Ba ²⁺Content be 0～8%.Ba ²⁺The content preferred range be 0～7%, preferred scope is 0～6%, further preferred range is 0～5%.In addition, from reaching purpose of the present invention aspect, can make Ba ²⁺Content smaller or equal to 3%, also can also can be 0 at last smaller or equal to 1% smaller or equal to 2%.

Zn ²⁺Be useful essential composition aspect the low dispersing characteristic of realization high refractive index, have and improve glass melting, devitrification resistance and reduce liquidus temperature or the effect of glass tansition temperature.If its amount is less than 0.1%, then specific refractory power descends, and liquidus temperature rises, and devitrification resistance worsens.On the other hand, if its amount surpasses 15%, then be difficult to realize the specific refractory power of expecting.Therefore, make Zn ²⁺Content be 0.1～15%.Zn ²⁺Content be limited to 14% on preferably, be limited to 13% on preferred again, be limited to 12% on preferred, be limited to 11% on further preferred, be limited to 10% on further preferred again, be limited to 7% on further preferred, be limited to 6% on further preferred again, be limited to 5% on especially preferred, Zn ²⁺Content preferably be limited to 0.3% down, be limited to 0.5% under preferred, be limited to 1% under further preferred.

La ³⁺Realizing that aspect the low dispersing characteristic of high refractive index be essential, also has the effect that improves chemical durability.If its amount then is difficult to the specific refractory power that obtains expecting less than 10%, if surpass 50%, then liquidus temperature rises, and devitrification resistance worsens.Therefore, make La ³⁺Content be 10～50%.La ³⁺Content be limited to 48% on preferably, be limited to 45% on preferred again, be limited to 43% on preferred, be limited to 40% on further preferred, be limited to 38% on further preferred again, be limited to 37% on further preferred, be limited to 36% on further preferred again, be limited to 35% on especially preferred, La ³⁺Content preferably be limited to 13% down, preferably again be limited to 15% down, preferredly be limited to 18% down, further preferably be limited to 20% down, further again be limited to 21% under preferably, further be limited to 22% under preferably.

Gd ³⁺By making itself and La ³⁺Coexistence and having reduce liquidus temperature, significantly improve devitrification resistance, also improve the effect of chemical durability.But if its amount surpasses 20%, then liquidus temperature rises, and devitrification resistance worsens.Therefore, make Gd ³⁺Content be 0～20%.Gd ³⁺Content be limited to 18% on preferably, be limited to 15% on preferred again, be limited to 13% on preferred, be limited to 12% on further preferred, be limited to 10% on further preferred again, be limited to 9% on further preferred, be limited to 8% on further preferred again, be limited to 7% on especially preferred, Gd ³⁺Content preferably be limited to 0.1% down, preferably again be limited to 0.5% down, preferredly be limited to 1% down, further be limited to 2% under preferably.

Y ³⁺Also by making itself and La ³⁺Coexistence and having reduce liquidus temperature, significantly improve devitrification resistance, improve the effect of chemical durability, if but its amount surpasses 15%, then liquidus temperature rises, devitrification resistance worsens.Therefore, make Y ³⁺Content be 0～15%.Y ³⁺The content preferred range be 0～13%, preferred range is 0～10% again, preferred scope is 0～8%, further preferred range is 0～7%, further preferred range is 0～5% again, further preferred range is 0～4%.

Yb ³⁺Also by making itself and La ³⁺Coexistence and having reduce liquidus temperature, significantly improve devitrification resistance, improve the effect of chemical durability.If its amount surpasses 10%, then liquidus temperature rises, and devitrification resistance worsens.Therefore, make Yb ³⁺Content be 0～10%.Yb ³⁺The content preferred range be 0～5%, preferred range is 0～3% again, preferred scope is 0～1%, does not further preferably contain Yb ³⁺

Zr ⁴⁺Has the effect that improves specific refractory power, improves chemical durability.Even if a spot of importing also can access good effect.But if its amount surpasses 20%, then glass tansition temperature and liquidus temperature can rise, and devitrification resistance can descend.Therefore, make Zr ⁴⁺Content be 0～20%.Zr ⁴⁺Content be limited to 18% on preferably, be limited to 16% on preferred again, be limited to 14% on preferred, be limited to 12% on further preferred, be limited to 10% on further preferred again, be limited to 8% on further preferred, be limited to 7%, Zr on further preferred again ⁴⁺Content preferably be limited to 1% down, be limited to 2% under preferred again, be limited to 3% under preferred.

Ti ⁴⁺Has the effect that improves specific refractory power, improves chemical durability and devitrification resistance.If its content less than 0.1%, then can't obtain above-mentioned effect, if surpass 22%, then be difficult to the Abbe number that obtains expecting, and glass tansition temperature or liquidus temperature can rise, devitrification resistance can worsen.Therefore, make Ti ⁴⁺Content be 0.1～22%.Ti ⁴⁺Content be limited to 21% on preferably, be limited to 20% on preferred again, be limited to 19% on preferred, be limited to 18% on further preferred, be limited to 17% on further preferred again, be limited to 16% on further preferred, be limited to 15% on further preferred again.Ti ⁴⁺Content preferably be limited to 1% down, preferably again be limited to 3% down, preferredly be limited to 5% down, further preferably be limited to 8% down, further be limited to 10% under preferably again, further be limited to 11% under preferably, further be limited to 12% under preferably again.

Especially, when refractive index n d more than or equal to 1.968 the time, Ti ⁴⁺Content be preferably greater than and equal 5%, be preferably greater than again and equal 10%, more preferably greater than equaling 12%, further be preferably greater than and equal 13%, further be preferably greater than again and equal 14%.But, even refractive index n d more than or equal to 1.968 situation under, from the rising that suppresses glass tansition temperature and liquidus temperature, the deterioration aspect that suppresses devitrification resistance, Ti ⁴⁺Content preferably smaller or equal to 21%, more preferably smaller or equal to 20%, be more preferably less than and equal 19%.

Nb ⁵⁺Have and improve refractive index n d and reduce liquidus temperature, improve the effect of devitrification resistance.If its amount surpasses 20%, then liquidus temperature can rise, and devitrification resistance can worsen, and is difficult to realize the Abbe number expected, and the painted of glass also can strengthen in addition.Therefore, make Nb ⁵⁺Content be 0～20%.Nb ⁵⁺Content be limited to 18% on preferably, be limited to 16% on preferred again, be limited to 14% on preferred, be limited to 12% on further preferred, be limited to 10% on further preferred again, be limited to 9% on further preferred, be limited to 8% on further preferred again.Nb ⁵⁺Content preferably be limited to 0.1% down, preferably again be limited to 1% down, preferredly be limited to 2% down, further be limited to 3% under preferably.

Ta ⁵⁺Have realize high refractive index low dispersed, also improve the effect of stability, glass.But, Ta ⁵⁺Be expensive composition, and if its content surpass 8%, then liquidus temperature can rise, devitrification resistance can descend, and therefore makes Ta ⁵⁺Content be 0～8%.Ta ⁵⁺The content preferred range be 0～6%, preferred range is 0～4% again, preferred scope is 0～3%, further preferred range is 0～2.5%, further preferred range is 0～2% again, further preferred range is 0～1%.Especially be preferably and do not contain Ta ⁵⁺

In addition, in opticglass of the present invention, in order to suppress the rising of liquidus temperature, keep devitrification resistance, with Nb ⁵⁺, Ta ⁵⁺Content be converted into oxide compound respectively, with Nb ₂O ₅And Ta ₂O ₅Total content be restricted to less than 14 quality %.From the above point of view, Nb ₂O ₅And Ta ₂O ₅The total content preferred range smaller or equal to 13 quality %.

W ⁶⁺Be to help to improve specific refractory power, reduce liquidus temperature, improve any composition of devitrification resistance, if but its amount surpasses 5%, and then liquidus temperature can rise, and devitrification resistance can worsen, and the painted of glass also can strengthen.Therefore, make W ⁶⁺Content be 0～5%.W ⁶⁺The content preferred range be 0～4%, preferred range is 0～3% again, preferred scope is 0～2%, further preferred range is 0～1%, does not more preferably contain W again ⁶⁺

Ge ⁴⁺Be that mesh forms positively charged ion, also have the effect that improves specific refractory power, be the composition that to keep stability, glass and improve specific refractory power therefore, but be very expensive composition, and be the composition of preferably controlling its amount from the cost aspect with the Ta composition.In the present invention, owing to as above determine to form, even therefore with Ge ⁴⁺Content be suppressed at below 8%, also can realize desired optical and good stability, glass simultaneously.Therefore, make Ge ⁴⁺Content be 0～8%.

Ge ⁴⁺The content preferred range be 0～6%, preferred range is 0～4% again, preferred scope is 0～2%, further preferred range is 0～1%.Especially be preferably and do not contain Ge ⁴⁺, be no Ge glass.

Bi ³⁺Have the effect that improves specific refractory power and also improve stability, glass, if but its amount surpasses 10%, and then the light transmittance in the visibility region can descend.Therefore, make Bi ³⁺Content be 0～10%.Bi ³⁺The content preferred range be 0～8%, preferred range is 0～6% again, preferred scope is 0～4%, further preferred range is 0～2%, further preferred range is 0～1%, especially is preferably not contain Bi ³⁺

Al ³⁺If have the effect that imports on a small quantity then can improve stability, glass and chemical durability, if but its amount surpasses 10%, and then liquidus temperature can rise, and devitrification resistance can worsen.Therefore, make Al ³⁺Content be 0～10%.Al ³⁺The content preferred range be 0～8%, preferred range is 0～6% again, preferred scope is 0～4%, further preferred range is 0～2%, further preferred range is 0～1% again, especially is preferably not contain Al ³⁺

Sb can add as finings, also has to suppress by a small amount of interpolation owing to sneak into the effect that impurity such as Fe causes light transmittance to descend, if but be converted into oxide compound and as Sb ₂O ₃Add under the ratio situation about representing in addition and surpass 1 quality %, then glass can be painted, perhaps because its powerful oxygenizement, and can encourage the deterioration of the forming face of model forming module when die forming.Therefore, be converted into Sb ₂O ₃, ratio represents to be preferably 0～1 quality % beyond the addition of Sb, is preferably 0～0.5 quality % again, and more preferably 0%.

Sn also can add as finings, if but be converted into SnO ₂Add above 1 quality % under the situation that ratio is represented in addition, then glass can be painted, perhaps owing to oxygenizement, can encourage the deterioration of the forming face of model forming module when precision moulded formation.Therefore, be converted into SnO ₂, ratio represents to be preferably 0～1 quality % beyond the addition of Sn, is preferably 0～0.5 quality % again.

In addition, also Ce oxide compound, vitriol, nitrate, muriate can be added as finings on a small quantity.

Opticglass of the present invention has realized that when keeping stability, glass high refractive index hangs down the dispersive optical characteristics, need not to contain Lu, Hf, Ga, In, the such composition of Sc.Because Lu, Hf, Ga, In, Sc also are expensive compositions, so Lu ³⁺, Hf ⁴⁺, Ga ³⁺, In ³⁺, Sc ³⁺Content preferably to suppress respectively be 0～1%, preferably suppressing respectively is 0～0.5% again, does not especially preferably import Lu ³⁺, do not import Hf ⁴⁺, do not import Ga ³⁺, do not import In ³⁺, do not import Sc ³⁺

In addition, consider influence, preferably also do not import As, Pb, U, Th, Te, Cd environment.

In addition, from effectively utilizing the good light transmissivity aspect of glass, preferably do not import the material that Cu, Cr, V, Fe, Ni, Co etc. become painted major cause.

Opticglass of the present invention is oxide glass, and in fact anionic component is by O ^2-Constitute.As mentioned above, also can add a spot of Cl as finings ^-, F ^-But, O ^2-Content be preferably greater than and equal 98 negatively charged ion %, be preferably greater than again and equal 99 negatively charged ion %, more preferably greater than equaling 99.5 negatively charged ion %, 100 negatively charged ion % more preferably.

(optical characteristics of opticglass)

The refractive index n d of opticglass of the present invention is 1.92～2.2.Refractive index n d preferably is limited to 1.930 down, preferably again is limited to 1.935 down, preferredly is limited to 1.940 down, is limited to 2.0 on preferably, is limited to 1.995 on preferably again, is limited to 1.990 on preferred.Improving specific refractory power is effectively in the multifunction of optical element, miniaturization, and the upper limit of restriction specific refractory power is being favourable improving aspect the stability, glass.

The Abbe number ν d of opticglass of the present invention is 25～45.When with the incompatible correction aberration of the set of lenses of high dispersive glass, Abbe number ν d is favourable greatly a bit.From such viewpoint, Abbe number ν d preferably is limited to 26 down, preferably again is limited to 27 down, preferredly is limited to 28 down, further is limited to 29 under preferably.On the other hand, the upper limit that relaxes Abbe number ν d can be brought into play advantageous effect aspect the stability, glass keeping, improve.From such viewpoint, Abbe number ν d is limited to 43 on preferably, be limited to 40 on preferred again, be limited to 38 on preferred, be limited to 36 on further preferred, be limited to 35 on further preferred again, be limited to 34 on further preferred, be limited to 33 on further preferred again, be limited to 32 on especially preferred.

Carried out the opticglass of high refractive indexization further and be suitable for use as the material of optical element, this optical element is suitable for miniaturization, the multifunction of optical systems such as image pickup optical system, projection optics system.In addition,, also can reduce the absolute value (bending is done slow) of curvature of the optical function face of lens even have in manufacturing under the situation of lens of the same focal length, therefore very favourable at aspects such as the shaping of lens, processing.On the other hand, carry out further high refractive indexization by making opticglass, the thermostability that then can demonstrate glass descends or painted increase, be the tendency that the light transmittance in the visible short wavelength region territory reduces.Therefore, from viewpoints such as purposes or productivity, also can roughly divide into to make further the preferential situation of high refractive indexization and make and improve thermostability or reduce painted preferential situation and distinguish and use opticglass of the present invention.

In opticglass of the present invention, when making that further high refractive indexization is preferential, preferred the following of refractive index n d is limited to 1.966, be limited to 1.967 under preferred again, be limited to 1.968 under preferred, the Abbe number ν d preferred range of this moment is 25～34, and preferred range is 26～33 again, and preferred scope is 27～32.Even make further under the preferential situation of specific refractory powerization, from keeping viewpoints such as stability, glass, refractive index n d is preferably smaller or equal to 2.200, more preferably smaller or equal to 2.100, is more preferably less than and equals 2.050.In opticglass of the present invention, refractive index n d is called opticglass A more than or equal to 1.966 opticglass, refractive index n d is called opticglass B less than 1.966 opticglass.

In addition, the refractive index n d that illustrates previously is more than or equal to the Ti under 1.968 the situation ⁴⁺The content preferred range also is applicable to the Ti among the opticglass A ⁴⁺The content preferred range.

Opticglass of the present invention is partly to disperse than little glass fixedly the time at Abbe number ν d, and therefore the optical elements such as lens that formed by opticglass of the present invention are suitable for the aberration correction of high order.

Here, part disperses to use g line, F line, each refractive index n g, nF of c line, nc to be expressed as (ng-nF)/(nF-nc) than Pg, F.

From the opticglass aspect of the aberration correction that is suitable for high order is provided, in opticglass of the present invention, part disperses preferably to satisfy than Pg, F and Abbe number ν d the relation of following (1) formula, preferably satisfies the relation of following (2) formula again, more preferably satisfies the relation of following (3) formula.

Pg、F≤-0.0017×νd+0.660 …(1)

Pg、F≤-0.0017×νd+0.655 …(2)

Pg、F≤-0.0017×νd+0.650 …(3)

Opticglass A and opticglass B, especially opticglass B preferably satisfies the some of above-mentioned (1) formula～(3) formula.

Below, the light transmissivity of opticglass of the present invention is described.

Opticglass of the present invention demonstrates the high light line transmissivity in the big wavelength region may of visibility region.

In the optimal way of opticglass of the present invention, λ 70 expressions are smaller or equal to the degree of staining of 470nm.70 again preferred range be smaller or equal to 465nm, preferred scope is below the 460nm, further preferred range is smaller or equal to 455nm, further preferred range is smaller or equal to 450nm again, further preferred range is smaller or equal to 445nm, and further preferred range is smaller or equal to 440nm again.

Here, λ 70 is that light transmittance is 70% wavelength in the wavelength region of 280～700nm.Here, light transmittance is to use the glass sample of the face parallel to each other with the thickness that grinds to form 10.0 ± 0.1mm, from the spectral transmission that obtains with the vertical direction incident light of the face of described grinding, be Iout/Iin, the light intensity that will incide described sample here as Iin, will be through the light intensity of described sample as Iout.Spectral transmission also comprises the reflection of light loss on the sample surfaces.In addition, above-mentioned grinding means with respect to wavelength, the surface roughness of measuring wavelength domain are smoothed and turns to enough little state.

In the preferred mode of opticglass of the present invention, in than the λ 70 close visibility regions of long wavelength side, light transmittance surpasses 70%.Identical with λ 70, can define λ 5 as follows.λ 5 is that spectral transmission is 5% wavelength.

λ 5 preferred range are smaller or equal to 380nm, and preferred range is smaller or equal to 375nm again, and preferred scope is smaller or equal to 365nm.

Above-mentioned spectral transmission is determined in the scope of wavelength 280～700nm as mentioned above, if but increase wavelength from λ 5, then light transmittance can increase, in case reach λ 70, then keeps the high-transmission rate more than or equal to 70% before wavelength 700nm.

Opticglass A and opticglass B, especially opticglass B is from obtaining the characteristic aspect preferred mode relevant with above-mentioned λ 70, λ 5.

As hereinafter described, the lens that formed by opticglass of the present invention make up by making itself and the lens that formed by ultralow dispersion opticglass, can provide the aberration capability for correcting good, small-sized and H.D optical system.In the past, in aberration correction optical system, as with the combination of ultralow dispersion glass lens, used high refractive index high dispersive glass lens, but high refractive index high dispersive glass contains more TiO ₂, Nb ₂O ₅, Bi ₂O ₃, WO ₃Give composition etc. the high refractive index high dispersive, can't obtain sufficiently high light transmittance at the short wavelength side of visibility region sometimes.In the aberration correction optical system that has made up ultralow dispersion glass lens and high refractive index high dispersive glass lens, light with respect to the short wavelength side of visibility regions such as blueness, the transmissivity of high refractive index high dispersive glass lens descends, and correspondingly the transmission of visible light of optical system integral body descends.By replacing high refractive index high dispersive glass lens to use the lens that form by opticglass of the present invention, can guarantee the optical transmittance of above-mentioned aberration correction optical system integral body in visibility region fully.

From such viewpoint, in the present invention, preferred λ 5 also is in the opticglass of above-mentioned scope.

(the glass tansition temperature of opticglass)

Opticglass of the present invention is the glass that is suitable for forming by grinding, grinding level and smooth optical function face.The adaptability of cold conditions such as grinding, grinding processing, be that cold conditions processibility indirect ground is relevant with the glass tansition temperature.The glass that the glass tansition temperature is low is compared with the cold conditions processibility and is more suitable for precision moulded formation, and the high glass of glass tansition temperature is compared with precision moulded formation and is more suitable for cold conditions processing, i.e. cold conditions excellent processability relatively therewith.Therefore, in the present invention, preferably excessively do not reduce the glass tansition temperature yet, preferably be higher than 630 ℃, be preferably greater than again and equal 640 ℃, more preferably greater than equaling 660 ℃.But if the glass tansition temperature is too high, the Heating temperature when then glass being carried out reheat, soften and being shaped uprises, and the deterioration of the mould that is used to be shaped becomes significantly, and perhaps annealing temperature also uprises, and the deterioration of annealing furnace, consumption also become remarkable.Therefore, the glass tansition temperature is preferably smaller or equal to 750 ℃, more preferably smaller or equal to 740 ℃, is more preferably less than and equals 730 ℃, further preferably smaller or equal to 725 ℃, more further preferably smaller or equal to 710 ℃.

(thermostability of opticglass)

The liquidus temperature of the preferred mode of opticglass of the present invention is smaller or equal to 1220 ℃.In addition, the liquidus temperature preferred range of opticglass A is smaller or equal to 1210 ℃, and preferred scope is smaller or equal to 1200 ℃.The liquidus temperature preferred range of opticglass B is smaller or equal to 1200 ℃, and preferred scope is smaller or equal to 1190 ℃.Like this, opticglass of the present invention is the low dispersion of high refractive index glass, and has good thermostability, therefore can stably produce high-quality opticglass.In addition, preventing the situation decline low melting glass of devitrification, the platinum or the platinum alloy that can suppress to constitute crucible are melted in the glass, therefore also can suppress, prevent because platinum ion etc. cause the painted increase of glass or sneak into platinum impurity.

(manufacture method of opticglass)

Below, the manufacture method of opticglass of the present invention is described.For example, form the raw materials of compound or the cullet material of weighing powder shaped accordingly with the glass of target and be in harmonious proportion, in the melt container of the platinum alloy system of being supplied to after, to its heat, fusion.After fully the fusion above-mentioned raw materials is gone forward side by side oozy glassization, the temperature of this melten glass is risen and clarify.Stirring by agitator makes the melten glass after the clarification carry out homogenizing, and without interruptionly flows out pipeline and flow out to glass, carries out chilling, curing, obtains glass shaping body.

In addition, even from obtaining, less colored and comprise optical characteristics aspect the glass of interior all stability of characteristics, preferred optics glass melting temperature is 1250～1400 ℃ a scope.

Then, die forming of the present invention is described with glass block.

[die forming glass block]

Die forming of the present invention is characterised in that with glass block, is formed by above-mentioned opticglass of the present invention.The shape of piece becomes according to as the shape of the die-formed product of target and the easy shape of die forming.In addition, the quality of piece also cooperates die-formed product to set.In the present invention, used the glass of excellent in stability, even therefore carry out reheat, soften and carry out die forming, glass also is difficult to devitrification, can stably produce high-quality molding.

Die forming is as follows with the Production Example of glass block.

In first Production Example, to horizontal arrangement flowing out pipeline below the mold effusive melten glass from pipeline of casting continuously, and be configured as and have the tabular of certain thickness.Glass after the shaping is pulled out to horizontal direction continuously from being arranged on the lateral peristome of mold.Carry out pulling out of plate glass molding by endless belt conveyor.Pull out by the thickness of slab constant mode of pulling out constant airspeed, glass shaping body, and can access preset thickness, the wide glass shaping body of plate according to endless belt conveyor.Glass shaping body is transported in the annealing furnace by endless belt conveyor, and by slow cooling.Glass shaping body after the slow cooling is cut off on the thickness of slab direction or cuts off, implement attrition process, perhaps implement barreling, and become the die forming glass block.

In second Production Example, replace above-mentioned mold and the melten glass of in mold cylindraceous, casting, and be configured as columned glass shaping body.Glass shaping body at the mold internal shaping is pulled out to vertical lower with constant speed from the peristome of mold bottom.The speed of pulling out is according to the melten glass liquid level constant mode in the mold is got final product.After glass shaping body is carried out slow cooling, cut off or cut off, implement attrition process or barreling, become the die forming glass block.

In the 3rd Production Example, be arranged on the below of flowing out pipeline with flowing out the forming mill that equally spaced disposes a plurality of shaping dies on the circumference of universal stage of circle of below of pipeline, universal stage is carried out the transposition rotation, with one of stop place of shaping dies as supplying melten glass to the position (casting position) of shaping dies supply melten glass, after the melten glass with supply is configured as glass shaping body, take out glass shaping body from the stop place (extracting position) of the predetermined shaping dies different with casting position.As for extracting position being made as which stop place, consider that the speed of rotation of universal stage, the speed of cooling of glass wait to determine to get final product.Can wait by following method to the shaping dies of casting position supply melten glass and to carry out, described method is meant: from the glass flows outlet of the flowing out pipeline melten glass that drips, catch glass drop with above-mentioned shaping dies; To rest on the shaping dies of casting position near the glass flows outlet, support the bottom of effusive molten glass flow, produce necking part midway in glass flows, and predetermined opportunity shaping dies is descended suddenly in vertical direction, isolate thus than necking part by under melten glass, and it is received on the shaping dies; Cut off effusive molten glass flow with cutter knife, receive isolated fused glass block with the shaping dies that rests on the casting position place.

The shaping of the glass on the shaping dies uses known method to get final product.Wherein, if upwards spraying gas from shaping dies, apply upwards blast to glass block, be shaped under the situation that glass is floated, the surface that then can prevent glass shaping body produces fold or glass shaping body owing to cracking the crack with contacting of shaping dies.

That the shape of glass shaping body can become according to the ejection mode of the selection of shaping dies shape or above-mentioned gas is spherical, the ellipsoid of revolution shape, have a target rotation axle and the shape all protruded laterally towards axial two faces of this target rotation etc.These shapes are suitable for being used for the glass block that die forming is optical elements such as lens or optical element blank.The glass shaping body that obtains like this can maintain the original state or the surface is ground or barreling and become the die forming glass block.

[optical element]

Then, optical element of the present invention is described.

Optical element of the present invention is characterised in that, is formed by above-mentioned opticglass of the present invention.Optical element of the present invention has the low dispersing characteristic of high refractive index, and the content of the composition of costlinesses such as Ta or Ge is suppressed to a small amount of or 0, therefore can provide optical elements such as the costly various lens of optics, prism with low cost.

As the example of lens, lens face can be shown be various lens such as sphere or aspheric, recessed crescent lens, protruding crescent lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.

Such lens can make up by the lens with low dispersion glass and revise aberration, are suitable for the lens that correction is used as aberration.In addition, also effective lens aspect the miniaturization of optical system.

In addition, for prism, because the specific refractory power height therefore by being assembled in the image pickup optical system, coming crooked light path and towards the direction of expecting, also can realize the optical system of small-sized and bigger field angle thus.

In addition, the film that prevents control light transmittances such as reflectance coating also can be set on the optical function face of optical element of the present invention.

[manufacture method of optical element blank]

Then, the manufacture method to optical element blank of the present invention describes.

The manufacture method of optical element blank of the present invention has two modes shown below.

(manufacture method of first optical element blank)

In the manufacture method of first optical element blank of the present invention, described optical element blank is made into optical element by grinding, grinding, this manufacture method is characterised in that, above-mentioned die forming of the present invention is heated, softens with glass block, and carry out die forming.

Optical element blank be have to added as the shape of the optical element of target the process redundancy removed by grinding, grinding, with the glass shaping body of the akin shape of shape of optical element.

When making optical element blank, prepare to have the model forming module of forming face of shape of the shape of this blank that overturn.Model forming module is by comprising mold, bed die and comprising also that as required the mold component of mould forms, make the forming face of mould up and down or when the use mould mould forming face become above-mentioned shape.

Then, be coated with Powdered releasing agents such as boron nitride at die forming equably with the surface of glass block, and it is heated, softening after, import in the bed die that has been preheated, carry out mold pressing by bed die with relative mold, and be configured as optical element blank.

Then, optical element blank is carried out the demoulding, and from model forming module, take out, anneal.By this anneal, reduce the strain of glass inside, make optical characteristics such as specific refractory power become the value of expectation.

The heating condition of glass block, die forming condition, the material etc. that is used for model forming module use known conditioned disjunction material to get final product.Above operation can be carried out in atmosphere.

(manufacture method of second optical element blank)

In the manufacture method of second optical element blank of the present invention, described optical element blank is made into optical element by grinding, grinding, this manufacture method is characterised in that, frit is carried out fusion, resulting melten glass is carried out die forming, make the optical element blank that forms by above-mentioned opticglass of the present invention.

By comprising mold, bed die and comprising also that as required the mold component of mould constitutes model forming module.As mentioned above, the forming face of model forming module is processed into the shape of the surface shape of the optical element blank that overturn.

On the bed die forming face, be coated with Powdered releasing agents such as boron nitride equably, to flow on the bed die forming face according to the manufacture method fused melten glass of above-mentioned opticglass, when the melten glass amount on bed die has just become the amount of expectation, cut off molten glass flow with the cutting knife that is called as cutter (shear).Like this, on bed die, obtain after the fused glass block, the bed die that will comprise fused glass block move into place in above the mold position of awaiting orders, by mold and bed die glass is carried out mold pressing, and is configured as optical element blank.

Then, the manufacture method to optical element of the present invention describes.

[manufacture method of optical element]

The manufacture method of optical element of the present invention is characterised in that, the optical element blank that is produced by above-mentioned method of the present invention is carried out grinding, grinding.Grinding, grinding can be used known method.

[embodiment]

Then, further describe the present invention, but the present invention is not limited by these examples at all by embodiment.Glass by the reference present embodiment, use the adjustment method of the content of above-mentioned each glass ingredient, and can access opticglass of the present invention.

(embodiment 1)

At first, in order to obtain having oxide glass No.1～36 of the composition (% represents with positively charged ion) shown in table 1-1～table 1-4, use nitrate, vitriol, oxyhydroxide, oxide compound, boric acid etc. as raw material, each raw material powder of weighing, carry out thorough mixing, become the blending raw material, should concoct raw material and put in the platinum system crucible, with 1400 ℃ heat, fusion, clarification, stirring, and become uniform melten glass.With this melten glass flow into preheating mold in, carry out chilling, after keeping under near the temperature the glass tansition temperature two hours, carry out slow cooling, thereby obtain each opticglass of oxide glass No.1～36.No matter do not find all in which kind of glass that crystalline separates out.

In addition, the anionic component of oxide glass No.1～36 all is O ^2-In addition, table 2-1～table 2-3 is the composition that the quality % by oxide glass No.1～36 represents, showing 3-1～table 3-3 is the composition of representing by mole %.

The characteristic of each glass is measured by method shown below.Measurement result is illustrated among the 1-5.

(1) refractive index n d and Abbe number ν d

To measuring with 30 ℃ cooling rate refrigerative opticglass per hour.

(2) part is disperseed than Pg, F

To measuring refractive index n g, nF, nc, calculate according to these values with 30 ℃ cooling rate refrigerative opticglass per hour.

(3) glass tansition temperature Tg

Use the thermo-mechanical analysis device under the condition of 4 ℃/minute of heat-up rates, to measure.

(4) liquidus temperature

Glass put in the stove that is heated to be preset temperature and kept two hours, after cooling off, come sight glass inside, have or not to determine liquidus temperature according to crystalline by 100 times opticmicroscopes.

(5) proportion

Measure by Archimedes's method.

(6)λ70、λ5

Use has the glass specimen of the face parallel to each other of the thickness that is ground into 10.0 ± 0.1mm, by spectrophotometer from light perpendicular to the direction incident intensity Iin of the described face that has been ground, measure the light intensity Iout that sees through sample, calculate light transmittance Iout/Iin, with light transmittance be 70% wavelength as λ 70, be that 5% wavelength is as λ 5 with light transmittance.

Table 1-1

No.		Si ⁴⁺	B ³⁺	Li ⁺	Na ⁺	K ⁺	Mg ²⁺	Ca ²⁺	Sr ²⁺
										1	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
2	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										3	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
4	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										5	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
6	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										7	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
8	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										9	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
10	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										11	Positively charged ion %	10.48	28.76	0.00	0.00	0.00	0.00	0.00	0.00
12	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										13	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
14	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										15	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
16	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										17	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
18	Positively charged ion %	10.48	28.76	0.00	0.00	0.00	0.00	0.00	0.00
										19	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
20	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
										21	Positively charged ion %	10.48	27.80	0.00	0.00	0.00	0.00	0.00	0.00
22	Positively charged ion %	10.48	27.76	0.00	0.00	0.00	0.00	0.00	0.00
										23	Positively charged ion %	10.48	26.76	0.00	0.00	0.00	0.00	0.00	0.00
24	Positively charged ion %	10.48	26.76	0.00	0.00	0.00	0.00	0.00	0.00
										25	Positively charged ion %	10.48	24.76	0.00	0.00	0.00	0.00	0.00	0.00
26	Positively charged ion %	10.48	23.76	0.00	0.00	0.00	0.00	0.00	0.00
										27	Positively charged ion %	10.48	23.76	0.00	0.00	0.00	0.00	0.00	0.00
28	Positively charged ion %	10.48	23.76	0.00	0.00	0.00	0.00	0.00	0.00
										29	Positively charged ion %	10.48	23.76	0.00	0.00	0.00	0.00	0.00	0.00
30	Positively charged ion %	10.48	23.26	0.00	0.00	0.00	0.00	0.00	0.00
										31	Positively charged ion %	10.48	23.76	0.00	0.00	0.00	0.00	0.00	0.00
32	Positively charged ion %	10.48	26.76	0.00	0.00	0.00	0.00	0.00	0.00
										33	Positively charged ion %	7.98	26.86	0.00	0.00	0.00	0.00	0.00	0.00
34	Positively charged ion %	7.96	28.00	0.00	0.00	0.00	0.00	0.00	0.00
										35	Positively charged ion %	7.96	28.00	0.00	0.00	0.00	0.00	0.00	0.00
36	Positively charged ion %	7.96	28.00	0.00	0.00	0.00	0.00	0.00	0.00

Table 1-2

No.		Ba ²⁺	Zn ²⁺	La ³⁺	Gd ³⁺	Y ³⁺	Yb ³⁺	Zr ⁴⁺	Ti ⁴⁺
										1	Positively charged ion %	4.96	3.44	23.26	3.00	1.10	0.00	4.81	15.08
2	Positively charged ion %	4.96	3.44	24.26	3.00	1.10	0.00	4.81	15.08
										3	Positively charged ion %	3.96	3.44	25.26	3.00	1.10	0.00	4.81	15.08
4	Positively charged ion %	3.96	3.44	25.26	4.00	1.10	0.00	4.81	14.08
										5	Positively charged ion %	3.96	3.44	25.26	5.00	1.10	0.00	4.81	13.08
6	Positively charged ion %	3.06	3.44	25.26	5.00	2.00	0.00	4.81	13.08
										7	Positively charged ion %	2.96	3.44	25.26	5.00	1.10	0.00	4.81	14.08
8	Positively charged ion %	3.96	3.44	24.26	3.00	1.10	0.00	4.81	16.08
										9	Positively charged ion %	1.96	3.44	25.26	6.00	1.10	0.00	4.81	14.08
10	Positively charged ion %	0.96	3.44	25.26	6.00	2.10	0.00	4.81	14.08
										11	Positively charged ion %	0.00	3.44	25.26	6.00	2.10	0.00	4.81	14.08
12	Positively charged ion %	2.06	3.44	25.26	6.00	2.00	0.00	4.81	13.08
										13	Positively charged ion %	1.06	3.44	25.26	6.00	2.00	0.00	4.81	13.08
14	Positively charged ion %	0.00	3.44	25.26	6.00	2.00	0.00	4.81	13.08
										15	Positively charged ion %	0.00	4.50	25.26	6.00	2.00	0.00	4.81	13.08
16	Positively charged ion %	0.00	4.50	26.26	6.00	2.00	0.00	4.81	13.08
										17	Positively charged ion %	0.00	4.50	25.26	6.00	3.00	0.00	4.81	13.08
18	Positively charged ion %	0.00	3.44	27.36	6.00	0.00	0.00	4.81	14.08
										19	Positively charged ion %	0.00	3.44	25.26	6.00	3.06	0.00	4.81	14.08
20	Positively charged ion %	0.96	4.44	25.26	6.00	2.10	0.00	4.81	13.08
										21	Positively charged ion %	0.00	4.44	25.26	6.00	3.06	0.00	4.81	13.08
22	Positively charged ion %	0.00	3.44	25.26	6.00	2.10	0.00	4.81	15.08
										23	Positively charged ion %	0.00	3.44	25.26	6.00	2.10	0.00	4.81	16.08
24	Positively charged ion %	0.00	2.44	25.26	6.00	2.10	0.00	4.81	17.08
										25	Positively charged ion %	0.00	2.44	27.36	6.00	1.00	0.00	4.81	17.08
26	Positively charged ion %	0.00	2.00	28.80	6.00	1.00	0.00	4.81	17.08
										27	Positively charged ion %	0.00	2.00	28.30	6.00	1.00	0.00	5.31	17.08
28	Positively charged ion %	0.00	2.00	30.80	4.00	0.25	0.00	4.81	17.83
										29	Positively charged ion %	0.00	2.00	34.80	0.00	0.25	0.00	4.81	17.83
30	Positively charged ion %	0.00	2.00	30.80	4.00	0.25	0.00	4.81	18.33
										31	Positively charged ion %	0.00	1.50	30.80	4.50	0.75	0.00	4.81	17.33
32	Positively charged ion %	0.00	2.00	30.80	4.00	0.25	0.00	4.81	14.83
										33	Positively charged ion %	0.00	1.75	30.80	4.25	0.50	0.00	4.81	16.98
34	Positively charged ion %	0.00	1.75	28.54	4.24	0.50	0.00	4.80	18.15
										35	Positively charged ion %	0.00	1.75	29.63	3.15	0.50	0.00	4.80	18.15
36	Positively charged ion %	0.00	1.75	29.63	3.15	0.50	0.00	4.80	17.15

Table 1-3

No.		Nb ⁵⁺	Ta ⁵⁺	W ⁶⁺	Ge ⁴⁺	Bi ³⁺	Al ³⁺	Add up to
									1	Positively charged ion %	4.07	2.00	0.00	0.00	0.00	0.00	100.00
2	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									3	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
4	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									5	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
6	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									7	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
8	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									9	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
10	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									11	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
12	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									13	Positively charged ion %	5.07	1.00	0.00	0.00	0.00	0.00	100.00
14	Positively charged ion %	5.07	2.06	0.00	0.00	0.00	0.00	100.00
									15	Positively charged ion %	5.07	1.00	0.00	0.00	0.00	0.00	100.00
16	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									17	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
18	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									19	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
20	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									21	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
22	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									23	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
24	Positively charged ion %	5.07	0.00	0.00	0.00	0.00	0.00	100.00
									25	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
26	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
									27	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
28	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
									29	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
30	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
									31	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
32	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
									33	Positively charged ion %	6.07	0.00	0.00	0.00	0.00	0.00	100.00
34	Positively charged ion %	6.06	0.00	0.00	0.00	0.00	0.00	100.00
									35	Positively charged ion %	6.06	0.00	0.00	0.00	0.00	0.00	100.00
36	Positively charged ion %	7.06	0.00	0.00	0.00	0.00	0.00	100.00

Table 1-4

No.		Si ⁴⁺/B ³⁺	Li ⁺+Na ⁺+K ⁺	Mg ²⁺+Ca ²⁺+Sr ²⁺	nd	νd	P _aF	Proportion
									1	Positively charged ion %	0.3770	0.00	0.00	1.95085	30.21	0.59771	4.97
2	Positively charged ion %	0.3770	0.00	0.00	1.94938	30.32	0.59534	4.91
									3	Positively charged ion %	0.3770	0.00	0.00	1.95378	30.34	0.59669	4.92
4	Positively charged ion %	0.3770	0.00	0.00	1.94958	30.96	0.59700	4.97
									5	Positively charged ion %	0.3770	0.00	0.00	1.94542	31.50	0.59214	5.02
6	Positively charged ion %	0.3770	0.00	0.00	1.94631	31.56	0.59468	5.02
									7	Positively charged ion %	0.3770	0.00	0.00	1.95348	30.94	0.59734	5.00
8	Positively charged ion %	0.3770	0.00	0.00	1.9574	29.79	0.59863	4.89
									9	Positively charged ion %	0.3770	0.00	0.00	1.95744	30.89	0.59516	5.03
10	Positively charged ion %	0.3770	0.00	0.00	1.96065	30.87	0.59512	5.03
									11	Positively charged ion %	0.3644	0.00	0.00	1.961	30.80	0.59551	5.01
12	Positively charged ion %	0.3770	0.00	0.00	1.9525	31.44	0.59208	5.05
									13	Positively charged ion %	0.3770	0.00	0.00	1.95901	31.17	0.59376	5.09
14	Positively charged ion %	0.3770	0.00	0.00	1.9656	30.82	0.59464	5.13
									15	Positively charged ion %	0.3770	0.00	0.00	1.9618	31.01	0.5909091	5.09
16	Positively charged ion %	0.3770	0.00	0.00	1.95955	31.37	0.5943119	5.07
									17	Positively charged ion %	0.3770	0.00	0.00	1.95862	31.36	0.5947007	5.05
18	Positively charged ion %	0.3644	0.00	0.00	1.96311	30.8	0.5951391	5.04
									19	Positively charged ion %	0.3770	0.00	0.00	1.96422	30.83	0.59463	5.03
20	Positively charged ion %	0.3770	0.00	0.00	1.95560	31.37	0.59324	5.04
									21	Positively charged ion %	0.3770	0.00	0.00	1.95877	31.33	0.59248	5.05
22	Positively charged ion %	0.3775	0.00	0.00	1.96693	30.28	0.59906	5.02
									23	Positively charged ion %	0.3916	0.00	0.00	1.97672	29.74	0.59866	5.02
24	Positively charged ion %	0.3916	0.00	0.00	1.98151	29.29	0.60042	5.01
									25	Positively charged ion %	0.4233	0.00	0.00	1.9939	29	0.60082	5.09
26	Positively charged ion %	0.4411	0.00	0.00	1.99794	29.11	0.60035	5.13
									27	Positively charged ion %	0.4411	0.00	0.00	1.99882	29.11	0.60187	5.12
28	Positively charged ion %	0.4411	0.00	0.00	2.00209	28.68	0.60132	5.09
									29	Positively charged ion %	0.4411	0.00	0.00	2.00224	28.72	0.60029	5.03
30	Positively charged ion %	0.4506	0.00	0.00	2.00582	28.45	0.60238	5.08
									31	Positively charged ion %	0.4411	0.00	0.00	2.00041	29.01	0.5989	5.12
32	Positively charged ion %	0.3916	0.00	0.00	1.97948	30.16	0.59575	5.07
									33	Positively charged ion %	0.2971	0.00	0.00	2.00165	29.05	0.59948	5.12
34	Positively charged ion %	0.0613	0.00	0.00	2.00392	28.25	0.60214	5.04
									35	Positively charged ion %	0.0591	0.00	0.00	2.00401	28.28	0.60394	5.02
36	Positively charged ion %	0.0591	0.00	0.00	2.00341	28.4	0.60289	5.03

Table 1-5

No.		Tg(℃)	Ts(℃)	Liquidus temperature (℃)	λ70(nm)	λ5(nm)
							1	Positively charged ion %	688	741	Less than 1180	436	363
2	Positively charged ion %	686	738	Less than 1180	434	362
							3	Positively charged ion %	690	743	Less than 1190	443	363
4	Positively charged ion %	694	744	Less than 1190	455	363
							5	Positively charged ion %	695	747	Less than 1200	431	359
6	Positively charged ion %	698	751	Less than 1180	432	360
							7	Positively charged ion %	694	742	Less than 1180	438	361
8	Positively charged ion %	687	738	Less than 1180	448	365
							9	Positively charged ion %	697	750	Less than 1180	433	361
10	Positively charged ion %	700	751	Less than 1180	434	362
							11	Positively charged ion %	697	750	Less than 1180	437	363
12	Positively charged ion %	700	753	Less than 1200	427	359
							13	Positively charged ion %	700	753	Less than 1190	431	361
14	Positively charged ion %	699	753	Less than 1220	435	362
							15	Positively charged ion %	694	749	Less than 1190	434	362
16	Positively charged ion %	698	751	Less than 1200	431	360
							17	Positively charged ion %	699	750	Less than 1190	431	360
18	Positively charged ion %	697	748	Less than 1200	433	362
							19	Positively charged ion %	702	753	Less than 1190	436	362
20	Positively charged ion %	694	746	Less than 1190	430	360
							21	Positively charged ion %	698	752	Less than 1200	431	360
22	Positively charged ion %	699	751	Less than 1180	444	365
							23	Positively charged ion %	702	752	Less than 1180	451	366
24	Positively charged ion %	707	757	Less than 1180	457	367
							25	Positively charged ion %	713	761	Less than 1180	450	367
26	Positively charged ion %	722	772	Less than 1190	450	366
							27	Positively charged ion %	713	771	Less than 1220	449	366
28	Positively charged ion %	716	766	Less than 1190	466	370
							29	Positively charged ion %	713	764	Less than 1210	464	369
30	Positively charged ion %	714	766	Less than 1200	469	371
							31	Positively charged ion %	721	772	Less than 1190	460	368
32	Positively charged ion %	713	763	Less than 1190	450	365
							33	Positively charged ion %	714	764	Less than 1190	462	368
34	Positively charged ion %	707	757	Less than 1180	468	370
							35	Positively charged ion %	707	758	Less than 1180	468	370
36	Positively charged ion %	706	756	Less than 1190	466	369

Table 2-1

No.		SiO ₂	B ₂O ₃	Li ₂O	Na ₂O	K ₂O	MgO	CaO	SrO
										1	Quality %	6.38	9.80	0.00	0.00	0.00	0.00	0.00	0.00
2	Quality %	6.47	9.95	0.00	0.00	0.00	0.00	0.00	0.00
										3	Quality %	6.47	9.94	0.00	0.00	0.00	0.00	0.00	0.00
4	Quality %	6.40	9.83	0.00	0.00	0.00	0.00	0.00	0.00
										5	Quality %	6.33	9.73	0.00	0.00	0.00	0.00	0.00	0.00
6	Quality %	6.36	9.77	0.00	0.00	0.00	0.00	0.00	0.00
										7	Quality %	6.38	9.81	0.00	0.00	0.00	0.00	0.00	0.00
8	Quality %	6.52	10.02	0.00	0.00	0.00	0.00	0.00	0.00
										9	Quality %	6.36	9.78	0.00	0.00	0.00	0.00	0.00	0.00
10	Quality %	6.39	9.82	0.00	0.00	0.00	0.00	0.00	0.00
										11	Quality %	6.46	10.28	0.00	0.00	0.00	0.00	0.00	0.00
12	Quality %	6.34	9.74	0.00	0.00	0.00	0.00	0.00	0.00
										13	Quality %	6.30	9.68	0.00	0.00	0.00	0.00	0.00	0.00
14	Quality %	6.25	9.61	0.00	0.00	0.00	0.00	0.00	0.00
										15	Quality %	6.34	9.75	0.00	0.00	0.00	0.00	0.00	0.00
16	Quality %	6.38	9.81	0.00	0.00	0.00	0.00	0.00	0.00
										17	Quality %	6.41	9.86	0.00	0.00	0.00	0.00	0.00	0.00
18	Quality %	6.39	10.17	0.00	0.00	0.00	0.00	0.00	0.00
										19	Quality %	6.41	9.86	0.00	0.00	0.00	0.00	0.00	0.00
20	Quality %	6.39	9.82	0.00	0.00	0.00	0.00	0.00	0.00
										21	Quality %	6.41	9.86	0.00	0.00	0.00	0.00	0.00	0.00
22	Quality %	6.43	9.87	0.00	0.00	0.00	0.00	0.00	0.00
										23	Quality %	6.40	9.47	0.00	0.00	0.00	0.00	0.00	0.00
24	Quality %	6.41	9.48	0.00	0.00	0.00	0.00	0.00	0.00
										25	Quality %	6.23	8.52	0.00	0.00	0.00	0.00	0.00	0.00
26	Quality %	6.13	8.05	0.00	0.00	0.00	0.00	0.00	0.00
										27	Quality %	6.14	8.06	0.00	0.00	0.00	0.00	0.00	0.00
28	Quality %	6.16	8.10	0.00	0.00	0.00	0.00	0.00	0.00
										29	Quality %	6.21	8.16	0.00	0.00	0.00	0.00	0.00	0.00
30	Quality %	6.15	7.91	0.00	0.00	0.00	0.00	0.00	0.00
										31	Quality %	6.12	8.05	0.00	0.00	0.00	0.00	0.00	0.00
32	Quality %	6.25	9.24	0.00	0.00	0.00	0.00	0.00	0.00
										33	Quality %	4.72	9.21	0.00	0.00	0.00	0.00	0.00	0.00
34	Quality %	4.82	9.83	0.00	0.00	0.00	0.00	0.00	0.00
										35	Quality %	4.83	9.85	0.00	0.00	0.00	0.00	0.00	0.00
36	Quality %	4.81	9.80	0.00	0.00	0.00	0.00	0.00	0.00

Table 2-2

No.		BaO	ZnO	La ₂O ₃	Gd ₂O ₃	Y ₂O ₃	Yb ₂O ₃	ZrO ₂	TiO ₂
										1	Quality %	7.70	2.84	38.37	5.51	1.26	0.00	6.00	12.20
2	Quality %	7.82	2.88	40.62	5.59	1.28	0.00	6.09	12.38
										3	Quality %	6.23	2.87	42.25	5.58	1.28	0.00	6.09	12.37
4	Quality %	6.17	2.85	41.82	7.37	1.26	0.00	6.02	11.43
										5	Quality %	6.11	2.82	41.39	9.12	1.25	0.00	5.96	10.51
6	Quality %	4.74	2.83	41.54	9.15	2.28	0.00	5.98	10.55
										7	Quality %	4.60	2.84	41.70	9.18	1.26	0.00	6.01	11.40
8	Quality %	6.29	2.90	40.93	5.63	1.29	0.00	6.14	13.30
										9	Quality %	3.04	2.83	41.58	10.99	1.26	0.00	5.99	11.37
10	Quality %	1.49	2.84	41.75	11.03	2.41	0.00	6.01	11.41
										11	Quality %	0.00	2.87	42.24	11.16	2.43	0.00	6.08	11.55
12	Quality %	3.18	2.82	41.43	10.95	2.27	0.00	5.97	10.52
										13	Quality %	1.63	2.80	41.15	10.87	2.26	0.00	5.93	10.45
14	Quality %	0.00	2.78	40.86	10.80	2.24	0.00	5.88	10.37
										15	Quality %	0.00	3.69	41.46	10.96	2.28	0.00	5.97	10.53
16	Quality %	0.00	3.71	43.36	11.02	2.29	0.00	6.01	10.59
										17	Quality %	0.00	3.73	41.92	11.08	3.45	0.00	6.04	10.64
18	Quality %	0.00	2.84	45.28	11.04	0.00	0.00	6.02	11.42
										19	Quality %	0.00	2.85	41.92	11.08	3.52	0.00	6.04	11.46
20	Quality %	1.49	3.67	41.75	11.03	2.41	0.00	6.01	10.60
										21	Quality %	0.00	3.68	41.91	11.08	3.52	0.00	6.04	10.64
22	Quality %	0.00	2.86	42.05	11.11	2.42	0.00	6.06	12.31
										23	Quality %	0.00	2.85	41.86	11.06	2.41	0.00	6.03	13.07
24	Quality %	0.00	2.02	41.86	11.06	2.41	0.00	6.03	13.88
										25	Quality %	0.00	1.96	44.08	10.76	1.12	0.00	5.86	13.49
26	Quality %	0.00	1.58	45.66	10.58	1.10	0.00	5.77	13.28
										27	Quality %	0.00	1.59	44.96	10.60	1.10	0.00	6.38	13.30
28	Quality %	0.00	1.59	49.13	7.10	0.28	0.00	5.80	13.94
										29	Quality %	0.00	1.61	55.90	0.00	0.28	0.00	5.84	14.04
30	Quality %	0.00	1.59	49.02	7.08	0.28	0.00	5.79	14.30
										31	Quality %	0.00	1.19	48.80	7.93	0.82	0.00	5.77	13.47
32	Quality %	0.00	1.62	49.79	7.19	0.28	0.00	5.88	11.75
										33	Quality %	0.00	1.40	49.40	7.58	0.56	0.00	5.84	13.35
34	Quality %	0.00	1.43	46.90	7.75	0.57	0.00	5.96	14.62
										35	Quality %	0.00	1.44	48.79	5.77	0.57	0.00	5.97	14.65
36	Quality %	0.00	1.43	48.52	5.74	0.57	0.00	5.94	13.77

Table 2-3

No.		Nb ₂O ₅	Ta ₂O ₅	WO ₃	GeO ₂	Bi ₂O ₃	Al ₂O ₃	Add up to	Nb ₂O ₅+Ta ₂O ₅
										1	Quality %	5.48	4.47	0.00	0.00	0.00	0.00	100.00	9.95
2	Quality %	6.93	0.00	0.00	0.00	0.00	0.00	100.00	6.93
										3	Quality %	6.92	0.00	0.00	0.00	0.00	0.00	100.00	6.92
4	Quality %	6.85	0.00	0.00	0.00	0.00	0.00	100.00	6.85
										5	Quality %	6.78	0.00	0.00	0.00	0.00	0.00	100.00	6.78
6	Quality %	6.80	0.00	0.00	0.00	0.00	0.00	100.00	6.80
										7	Quality %	6.83	0.00	0.00	0.00	0.00	0.00	100.00	6.83
8	Quality %	6.98	0.00	0.00	0.00	0.00	0.00	100.00	6.98
										9	Quality %	6.81	0.00	0.00	0.00	0.00	0.00	100.00	6.81
10	Quality %	6.84	0.00	0.00	0.00	0.00	0.00	100.00	6.84
										11	Quality %	6.92	0.00	0.00	0.00	0.00	0.00	100.00	6.92
12	Quality %	6.78	0.00	0.00	0.00	0.00	0.00	100.00	6.78
										13	Quality %	6.74	2.21	0.00	0.00	0.00	0.00	100.00	8.95
14	Quality %	6.69	4.52	0.00	0.00	0.00	0.00	100.00	11.21
										15	Quality %	6.79	2.23	0.00	0.00	0.00	0.00	100.00	9.02
16	Quality %	6.83	0.00	0.00	0.00	0.00	0.00	100.00	6.83
										17	Quality %	6.86	0.00	0.00	0.00	0.00	0.00	100.00	6.86
18	Quality %	6.84	0.00	0.00	0.00	0.00	0.00	100.00	6.84
										19	Quality %	6.86	0.00	0.00	0.00	0.00	0.00	100.00	6.86
20	Quality %	6.84	0.00	0.00	0.00	0.00	0.00	100.00	6.84
										21	Quality %	6.86	0.00	0.00	0.00	0.00	0.00	100.00	6.86
22	Quality %	6.89	0.00	0.00	0.00	0.00	0.00	100.00	6.89
										23	Quality %	6.85	0.00	0.00	0.00	0.00	0.00	100.00	6.85
24	Quality %	6.85	0.00	0.00	0.00	0.00	0.00	100.00	6.85
										25	Quality %	7.98	0.00	0.00	0.00	0.00	0.00	100.00	7.98
26	Quality %	7.85	0.00	0.00	0.00	0.00	0.00	100.00	7.85
										27	Quality %	7.87	0.00	0.00	0.00	0.00	0.00	100.00	7.87
28	Quality %	7.90	0.00	0.00	0.00	0.00	0.00	100.00	7.90
										29	Quality %	7.96	0.00	0.00	0.00	0.00	0.00	100.00	7.96
30	Quality %	7.88	0.00	0.00	0.00	0.00	0.00	100.00	7.88
										31	Quality %	7.85	0.00	0.00	0.00	0.00	0.00	100.00	7.85
32	Quality %	8.00	0.00	0.00	0.00	0.00	0.00	100.00	8.00
										33	Quality %	7.94	0.00	0.00	0.00	0.00	0.00	100.00	7.94
34	Quality %	8.12	0.00	0.00	0.00	0.00	0.00	100.00	8.12
										35	Quality %	8.13	0.00	0.00	0.00	0.00	0.00	100.00	8.13
36	Quality %	9.42	0.00	0.00	0.00	0.00	0.00	100.00	9.42

Table 3-1

No.		SiO ₂	B ₂O ₃	Li ₂O	Na ₂O	K ₂O	MgO	CaO	SrO
										1	Mole %	15.10	20.03	0.00	0.00	0.00	0.00	0.00	0.00
2	Mole %	15.10	20.03	0.00	0.00	0.00	0.00	0.00	0.00
										3	Mole %	15.21	20.18	0.00	0.00	0.00	0.00	0.00	0.00
4	Mole %	15.32	20.33	0.00	0.00	0.00	0.00	0.00	0.00
										5	Mole %	15.44	20.48	0.00	0.00	0.00	0.00	0.00	0.00
6	Mole %	15.54	20.61	0.00	0.00	0.00	0.00	0.00	0.00
										7	Mole %	15.44	20.48	0.00	0.00	0.00	0.00	0.00	0.00
8	Mole %	15.10	20.03	0.00	0.00	0.00	0.00	0.00	0.00
										9	Mole %	15.55	20.63	0.00	0.00	0.00	0.00	0.00	0.00
10	Mole %	15.67	20.78	0.00	0.00	0.00	0.00	0.00	0.00
										11	Mole %	15.78	21.65	0.00	0.00	0.00	0.00	0.00	0.00
12	Mole %	15.66	20.77	0.00	0.00	0.00	0.00	0.00	0.00
										13	Mole %	15.77	20.92	0.00	0.00	0.00	0.00	0.00	0.00
14	Mole %	15.90	21.09	0.00	0.00	0.00	0.00	0.00	0.00
										15	Mole %	15.77	20.92	0.00	0.00	0.00	0.00	0.00	0.00
16	Mole %	15.77	20.92	0.00	0.00	0.00	0.00	0.00	0.00
										17	Mole %	15.77	20.92	0.00	0.00	0.00	0.00	0.00	0.00
18	Mole %	15.78	21.65	0.00	0.00	0.00	0.00	0.00	0.00
										19	Mole %	15.78	20.93	0.00	0.00	0.00	0.00	0.00	0.00
20	Mole %	15.67	20.78	0.00	0.00	0.00	0.00	0.00	0.00
										21	Mole %	15.78	20.93	0.00	0.00	0.00	0.00	0.00	0.00
22	Mole %	15.66	20.75	0.00	0.00	0.00	0.00	0.00	0.00
										23	Mole %	15.55	19.85	0.00	0.00	0.00	0.00	0.00	0.00
24	Mole %	15.55	19.85	0.00	0.00	0.00	0.00	0.00	0.00
										25	Mole %	15.55	18.37	0.00	0.00	0.00	0.00	0.00	0.00
26	Mole %	15.60	17.68	0.00	0.00	0.00	0.00	0.00	0.00
										27	Mole %	15.54	17.62	0.00	0.00	0.00	0.00	0.00	0.00
28	Mole %	15.51	17.58	0.00	0.00	0.00	0.00	0.00	0.00
										29	Mole %	15.51	17.58	0.00	0.00	0.00	0.00	0.00	0.00
30	Mole %	15.45	17.15	0.00	0.00	0.00	0.00	0.00	0.00
										31	Mole %	15.63	17.72	0.00	0.00	0.00	0.00	0.00	0.00
32	Mole %	15.86	20.25	0.00	0.00	0.00	0.00	0.00	0.00
										33	Mole %	12.14	20.42	0.00	0.00	0.00	0.00	0.00	0.00
34	Mole %	12.00	21.12	0.00	0.00	0.00	0.00	0.00	0.00
										35	Mole %	12.00	21.13	0.00	0.00	0.00	0.00	0.00	0.00
36	Mole %	12.09	21.28	0.00	0.00	0.00	0.00	0.00	0.00

Table 3-2

No.		BaO	ZnO	La ₂O ₃	Gd ₂O ₃	Y ₂O ₃	Yb ₂O ₃	ZrO ₂	TiO ₂
										1	Mole %	7.15	4.96	16.76	2.16	0.79	0.00	6.93	21.73
2	Mole %	7.15	4.96	17.48	2.16	0.79	0.00	6.93	21.73
										3	Mole %	5.75	4.99	18.33	2.18	0.80	0.00	6.98	21.89
4	Mole %	5.79	5.03	18.47	2.92	0.80	0.00	7.03	20.59
										5	Mole %	5.83	5.07	18.60	3.68	0.81	0.00	7.09	19.27
6	Mole %	4.54	5.10	18.73	3.71	1.48	0.00	7.13	19.40
										7	Mole %	4.36	5.07	18.60	3.68	0.81	0.00	7.09	20.74
8	Mole %	5.71	4.96	17.48	2.16	0.79	0.00	6.93	23.18
										9	Mole %	2.91	5.10	18.74	4.45	0.82	0.00	7.14	20.89
10	Mole %	1.44	5.14	18.88	4.49	1.57	0.00	7.19	21.05
										11	Mole %	0.00	5.18	19.02	4.52	1.58	0.00	7.24	21.20
12	Mole %	3.08	5.14	18.87	4.48	1.49	0.00	7.19	19.54
										13	Mole %	1.60	5.18	19.01	4.52	1.51	0.00	7.24	19.69
14	Mole %	0.00	5.22	19.16	4.55	1.52	0.00	7.30	19.85
										15	Mole %	0.00	6.77	19.01	4.52	1.51	0.00	7.24	19.69
16	Mole %	0.00	6.77	19.76	4.52	1.51	0.00	7.24	19.69
										17	Mole %	0.00	6.77	19.01	4.52	2.26	0.00	7.24	19.69
18	Mole %	0.00	5.18	20.61	4.52	0.00	0.00	7.24	21.20
										19	Mole %	0.00	5.18	19.02	4.52	2.30	0.00	7.24	21.20
20	Mole %	1.44	6.64	18.88	4.49	1.57	0.00	7.19	19.56
										21	Mole %	0.00	6.69	19.02	4.52	2.30	0.00	7.24	19.70
22	Mole %	0.00	5.14	18.88	4.48	1.57	0.00	7.19	22.54
										23	Mole %	0.00	5.10	18.73	4.45	1.56	0.00	7.14	23.86
24	Mole %	0.00	3.62	18.73	4.45	1.56	0.00	7.14	25.34
										25	Mole %	0.00	3.62	20.29	4.45	0.74	0.00	7.14	25.34
26	Mole %	0.00	2.98	21.43	4.47	0.74	0.00	7.16	25.42
										27	Mole %	0.00	2.97	20.98	4.45	0.74	0.00	7.87	25.33
28	Mole %	0.00	2.96	22.80	2.96	0.19	0.00	7.12	26.39
										29	Mole %	0.00	2.96	25.76	0.00	0.19	0.00	7.12	26.39
30	Mole %	0.00	2.95	22.72	2.95	0.18	0.00	7.09	27.03
										31	Mole %	0.00	2.24	22.95	3.36	0.56	0.00	7.17	25.84
32	Mole %	0.00	3.03	23.32	3.03	0.19	0.00	7.28	22.45
										33	Mole %	0.00	2.66	23.42	3.23	0.38	0.00	7.31	25.82
34	Mole %	0.00	2.63	21.52	3.20	0.38	0.00	7.23	27.36
										35	Mole %	0.00	2.63	22.34	2.37	0.38	0.00	7.23	27.36
36	Mole %	0.00	2.65	22.51	2.39	0.38	0.00	7.29	26.05

Table 3-3

No.		Nb ₂O ₅	Ta ₂O ₅	WO ₃	GeO ₂	Bi ₂O ₃	Al ₂O ₃	Add up to
									1	Mole %	2.93	1.44	0.00	0.00	0.00	0.00	100.00
2	Mole %	3.65	0.00	0.00	0.00	0.00	0.00	100.00
									3	Mole %	3.68	0.00	0.00	0.00	0.00	0.00	100.00
4	Mole %	3.71	0.00	0.00	0.00	0.00	0.00	100.00
									5	Mole %	3.73	0.00	0.00	0.00	0.00	0.00	100.00
6	Mole %	3.76	0.00	0.00	0.00	0.00	0.00	100.00
									7	Mole %	3.73	0.00	0.00	0.00	0.00	0.00	100.00
8	Mole %	3.65	0.00	0.00	0.00	0.00	0.00	100.00
									9	Mole %	3.76	0.00	0.00	0.00	0.00	0.00	100.00
10	Mole %	3.79	0.00	0.00	0.00	0.00	0.00	100.00
									11	Mole %	3.82	0.00	0.00	0.00	0.00	0.00	100.00
12	Mole %	3.79	0.00	0.00	0.00	0.00	0.00	100.00
									13	Mole %	3.82	0.75	0.00	0.00	0.00	0.00	100.00
14	Mole %	3.85	1.56	0.00	0.00	0.00	0.00	100.00
									15	Mole %	3.82	0.75	0.00	0.00	0.00	0.00	100.00
16	Mole %	3.82	0.00	0.00	0.00	0.00	0.00	100.00
									17	Mole %	3.82	0.00	0.00	0.00	0.00	0.00	100.00
18	Mole %	3.82	0.00	0.00	0.00	0.00	0.00	100.00
									19	Mole %	3.82	0.00	0.00	0.00	0.00	0.00	100.00
20	Mole %	3.79	0.00	0.00	0.00	0.00	0.00	100.00
									21	Mole %	3.82	0.00	0.00	0.00	0.00	0.00	100.00
22	Mole %	3.79	0.00	0.00	0.00	0.00	0.00	100.00
									23	Mole %	3.76	0.00	0.00	0.00	0.00	0.00	100.00
24	Mole %	3.76	0.00	0.00	0.00	0.00	0.00	100.00
									25	Mole %	4.50	0.00	0.00	0.00	0.00	0.00	100.00
26	Mole %	4.52	0.00	0.00	0.00	0.00	0.00	100.00
									27	Mole %	4.50	0.00	0.00	0.00	0.00	0.00	100.00
28	Mole %	4.49	0.00	0.00	0.00	0.00	0.00	100.00
									29	Mole %	4.49	0.00	0.00	0.00	0.00	0.00	100.00
30	Mole %	4.48	0.00	0.00	0.00	0.00	0.00	100.00
									31	Mole %	4.53	0.00	0.00	0.00	0.00	0.00	100.00
32	Mole %	4.59	0.00	0.00	0.00	0.00	0.00	100.00
									33	Mole %	4.62	0.00	0.00	0.00	0.00	0.00	100.00
34	Mole %	4.56	0.00	0.00	0.00	0.00	0.00	100.00
									35	Mole %	4.56	0.00	0.00	0.00	0.00	0.00	100.00
36	Mole %	5.36	0.00	0.00	0.00	0.00	0.00	100.00

(embodiment 2)

Then, produce the die forming glass block that each opticglass by embodiment 1 forms as follows.

At first,, frit is in harmonious proportion, it is put in the platinum system crucible, heat, fusion, clarification, stirring, obtain uniform melten glass in order to obtain above-mentioned each glass.Then, flow out melten glass with the constant flow, be cast in the mold of horizontal arrangement below the outflow pipeline, make to have certain thickness glass-pane shaping from flowing out pipeline.The sheet glass that has been shaped is pulled straight to horizontal direction from being arranged on the lateral peristome of mold, be transported in the annealing furnace, carry out slow cooling by endless belt conveyor.

Cut off or cut off slow cooling sheet glass, produce sheet glass, these sheet glass are carried out barreling, become the die forming glass block.

In addition, configuration mold cylindraceous below the outflow pipeline, the melten glass of in this mold, casting, be configured as cylindric glass, from the peristome of mold bottom with constant speed after vertical lower is pulled out, carry out slow cooling, and cut off or cut off, produce sheet glass, these sheet glass are carried out barreling, also can obtain the die forming glass block.

(embodiment 3)

Identical with embodiment 2 from flowing out pipeline outflow melten glass, catch effusive melten glass lower end by shaping dies after, the urgent shaping dies that reduces cuts off molten glass flow by surface tension, obtains the fused glass block of the amount expected on shaping dies.Then,, apply blast upwards to glass and make under its situation of floating, be configured as glass block, and from shaping dies, take out glass block, anneal from shaping dies ejection gas.Then, glass block is carried out barreling, become the die forming glass block.

(embodiment 4)

Each die forming that obtains in to embodiment 3 is coated with after the releasing agent that is formed by boron nitride powder equably with the whole surface of glass block, above-mentioned is heated, softens, and carry out die forming, thereby produce various lens, prismatical blanks such as recessed crescent lens, protruding crescent lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.

(embodiment 5)

Make melten glass in the same manner with embodiment 2, melten glass is fed to the bed die forming face of the releasing agent that has been coated with boron nitride powder equably, when the melten glass amount on bed die has just become desired amount, cut off molten glass flow with cutting knife.

By mold and bed die the fused glass block that obtains is like this carried out mold pressing on bed die, thereby produce various lens, prismatical blanks such as recessed crescent lens, protruding crescent lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.

(embodiment 6)

Each blank that produces among the embodiment 4,5 is annealed.Reduce the strain of glass inside by annealing, make optical characteristics such as specific refractory power become the value of expectation.

Then, each blank is carried out grinding, grinding, thereby produce various lens, prisms such as recessed crescent lens, protruding crescent lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.Also can prevent reflectance coating in the surface-coated of resulting optical element.

(embodiment 7)

Make sheet glass and cylindric glass in the same manner with embodiment 2, resulting glass shaping body is annealed, reduce inner strain, and make optical characteristics such as specific refractory power become the value of expectation.

Then, cut off these glass shaping bodies, and carry out grinding, grinding, produce various lens, prismatical blanks such as recessed crescent lens, protruding crescent lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.Also can prevent reflectance coating in the surface-coated of resulting optical element.

Practicality on the industry

The present invention can stablize supply and the opticglass that possesses the low dispersiveness of high refractive index that have good stability, glass, is applicable to die forming glass block, optical element blank and optical element.

Claims

1. an opticglass is oxide glass, when representing with positively charged ion %, comprising:

Si ⁴⁺：3～20％，

B ³⁺：18～35％，

Li ⁺, Na ⁺And K ⁺Total amount less than 5%,

Mg ²⁺, Ca ²⁺And Sr ²⁺Total amount less than 5%,

Ba ²⁺：0～8％，

Zn ²⁺：0.1～10％，

La ³⁺：18～40％，

Gd ³⁺：1～10％，

Y ³⁺：0～7％，

Yb ³⁺：0～10％，

Zr ⁴⁺：2～8％，

Ti ⁴⁺：8～22％，

Nb ⁵⁺：1～14％，

Ta ⁵⁺：0～6％，

W ⁶⁺：0～5％，

Ge ⁴⁺：0～6％，

Bi ³⁺：0～6％，

Al ³⁺：0～6％，

Do not comprise Te,

Wherein, Si ⁴⁺Content and B ³⁺The cation ratio Si of content ⁴+/B ³⁺Less than 1.0, be converted into Nb behind the oxide compound ₂O ₅And Ta ₂O ₅Total content less than 14 quality %,

Refractive index n d is 1.92～2.2, and Abbe number v d is 25～45,

Glass tansition temperature Tg is higher than 630 ℃.

2. opticglass as claimed in claim 1, wherein,

Degree of staining λ 70 is less than 470nm.

3. opticglass as claimed in claim 1 or 2, wherein,

The relation of following (1) formula is satisfied in the part dispersion than Pg, F and Abbe number v d:

Pg、F≤-0.0017×v d+0.660…(1)。

4. opticglass as claimed in claim 1 wherein, is converted into Sb ₂O ₃, the content of Sb is except Sb ₂O ₃0～1 quality % of outer glass ingredient.

5. opticglass as claimed in claim 1 wherein, is converted into SnO ₂, the content of Sn is except SnO ₂0～1 quality % of outer glass ingredient.

6. opticglass as claimed in claim 1, Lu ³⁺, Hf ⁴⁺, Ga ³⁺, In ³⁺And Sc ³⁺Respectively comprise 0～1%.

7. opticglass as claimed in claim 1 does not comprise As, Pb, U, Th and Cd.

8. opticglass as claimed in claim 1 does not comprise Te.

9. opticglass as claimed in claim 1 does not comprise Cu, Cr, V, Fe, Ni and Co.

10. opticglass as claimed in claim 1 comprises O ^2-Content more than or equal to 98 negatively charged ion %.

11. opticglass as claimed in claim 1, λ 5 is being less than or equal to the wavelength region may of 380nm.

12. opticglass as claimed in claim 1, liquidus temperature are 1220 ℃.

13. a die forming glass block is characterized in that,

Described die forming is formed by each described opticglass in the claim 1 to 12 with glass block.

14. an optical element is characterized in that,

Described optical element is formed by each described opticglass in the claim 1 to 12.

15. optical element as claimed in claim 14, this element are lens or prism.

16. optical element as claimed in claim 14, this element are the lens that the aberration correction is used.

17. the manufacture method of an optical element blank, described optical element blank is made into optical element by grinding, grinding, and this manufacture method is characterised in that,

The described die forming of claim 13 is heated, softens with glass block, and carry out die forming.

18. the manufacture method of an optical element blank, described optical element blank is made into optical element by grinding, grinding, and this manufacture method is characterised in that,

Frit is carried out fusion, resulting melten glass is carried out die forming, produce the optical element blank that forms by each described opticglass in the claim 1 to 12.

19. the manufacture method of an optical element is characterized in that, claim 17 or 18 described optical element blanks are carried out grinding, grinding.