CN1211548A - Optical glass - Google Patents

Optical glass Download PDF

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CN1211548A
CN1211548A CN 98119983 CN98119983A CN1211548A CN 1211548 A CN1211548 A CN 1211548A CN 98119983 CN98119983 CN 98119983 CN 98119983 A CN98119983 A CN 98119983A CN 1211548 A CN1211548 A CN 1211548A
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composition
glass
sio
cao
bao
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CN1155528C (en
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中原宗雄
坂本刚弘
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Ohara Inc
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Ohara Inc
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Abstract

The object is to provide stable optical glass having an optical constant in a prescribed range and satisfactory chemical durability, excellent in devitrification resistance and meltability and without contg. components of expensive starting materials such as Gd2 O3 and Ta2 O5 or without requiring the components as essential components. The optical glass consists of a compsn. contg., by weight, >5% to 20% SiO2 , 35-55% B2 O3 , 0 to <10% Al2 O3 , 10-30% La2 O3 , 0.5-15% Y2 O3 , 10-30% CaO, >0 to <0.5% Li2 O, 0-5% MgO< 0-5% SrO, 0-15% BaO, 0-15% ZnO, 0-3% TiO2 , 0-5% ZrO2 , 0-5% Nb2 O5 , 0-5% Ta2 O5 , 0-5% WO3 and 0-1% Sb2 O3 .

Description

Opticglass
The opticglass of the present invention relates to have specific refractory power (nd) 1.60～1.68, the optical constant of Abbe number (vd) more than 55.
In the past, as the opticglass with above-mentioned scope optical constant, known have for example with SiO 2, B 2O 3And BaO is as the glass of basal component.The glass of this compositional system, though the excellent in stability during fusion, but the non-constant of weather resistance of chemistry, in the grinding and washing procedure of glass, or as eyeglass through use over a long time in, glass surface Yi Fashengyin is burnt or weathering and the erosion that causes, and therefore the glass in above-mentioned past needs in processing and when using to note especially.In addition, the glass in above-mentioned past contains the BaO composition of comparison volume, so proportion has the tendency that becomes big, have again, and in the time will concocting raw materials melt, SiO 2Composition is easy to be separated to molten surface, is difficult to obtain the glass of homogeneous.
The objective of the invention is to, eliminate each shortcoming that is shown in the above-mentioned prior art, provide a kind of optical constant with afore mentioned rules scope and good chemical durability, that devitrification resistance and meltbility are good and do not contain Gd 2O 3And Ta 2O 5Such high cost of material composition or not with its stable opticglass as neccessary composition.
The inventor has carried out repetition test research for solving above-mentioned problem, found that, by the SiO in the specific composition scope 2-B 2O 3-CaO-La 2O 3Be to add Li in the glass 2O and Y 2O 3As neccessary composition, just can achieve the above object, thereby finish the present invention.
That is, the opticglass of the present invention that achieves the above object is characterized in that, in weight %, is made of following ingredients:
SiO 2????5＜～20％、
B 2O 3??35～55％、
Al 2 O 30～less than 10%,
La 2O 3?10～30％、
Y 2O 3??0.5～15％、
CaO??????10～30％、
Li 2O 0＜～less than 0.5%,
MgO??????0～5％、
SrO??????????0～5％、
BaO??????????0～15％、
ZnO??????????0～15％、
TiO 2???????0～3％、
ZrO 2???????0～5％、
Nb 2O 5?????0～5％、
Ta 2O 5?????0～5％、
WO 30～5% and Sb 2O 30～1%.
In addition, it is further characterized in that, in weight %, is made of following ingredients: SiO 26～15%,
B 2O 3??????40～50％、
Al 2O 3?????0.3～5％、
La 2O 3?????10～25％、
Y 2O 31～12%, but La 2O 3+ Y 2O 315～30%,
CaO??????????18～25％、
Li 2O 0＜～less than 0.5%,
MgO??????????0～5％、
SrO??????????0～5％、
BaO??????????0～10％、
ZrO??????????0～10％、
ZrO 2??????0～5％、
Ta 2O 50～5% and Sb 2O 30～0.5%, do not contain TiO 2, Nb 2O 5And WO 3In addition, it is further characterized in that again, in weight %, is made of following ingredients:
SiO 2??????6～15％、
B 2O 340～50%, but SiO 2+ B 2O 3More than 50%,
Al 2O 3?????0.3～5％、
La 2O 3?????10～25％、
Y 2O 31～12% but La 2O 3+ Y 2O 315～30%,
CaO??????????18～25％、
Li 2O 0＜～less than 0.5%,
MgO??????0～5％、
SrO??????0～5％、
BaO??????0～10％、
ZnO??????0～10％、
ZrO 2???0～5％、
Ta 2O 50～5% and Sb 2O 30～0.5%, do not contain TiO 2, Nb 2O 5And WO 3
Below be described in the opticglass of the present invention, each composition is limited to reason in the above-mentioned compositing range.
SiO 2And B 2O 3Composition is a network former, in the present invention, is effective for enlarging the vitrifying scope and making the viscosity that has appropriateness in the glass.SiO 2Composition, its amount is insufficient in 5% above-mentioned effect when following, and the meltbility variation above 20% o'clock mixing raw material easily generates not melts.In addition, B 2O 3Composition, when its quantity not sufficient 35% and above 55% o'clock, the glass that is difficult to obtain having desirable specific refractory power.In particular for obtaining the good glass of uniformity, with SiO 2The amount of composition is decided to be 6～15%, with B 2O 3The amount of composition is decided to be 40～50% for good.And for to obtain more stable glass, with SiO 2Composition and B 2O 3The total amount of composition fixes on more than 50% better.
Al 2O 3Composition to the raising of glass chemistry weather resistance and the adjustment of viscosity, and has effect to the stabilization of devitrification.But its amount makes the increased devitrification resistance increase on the contrary 10% when above, thereby not good.Better amount is 0.3～5%.
La 2O 3Composition improves the chemical durability of glass and devitrification resistance, disperses to improve specific refractory power under the excessive situation not making simultaneously, is the effective composition for the stabilized glass that obtains to have high refractive index.During its quantity not sufficient 10%, the chemical durability and the devitrification resistance of glass are insufficient, can not get desired specific refractory power and surpass at 30% o'clock.For obtaining to have desired optical constant, and the glass of the homogeneous of devitrification not, La 2O 3The amount of composition is at 10～25% scope Nei Gengjia.
Y 2O 3Composition is with La 2O 3Composition is same, is to improve, make the effective composition that improves specific refractory power and proportion is diminished under the not excessive situation disperseing for chemical durability and the devitrification resistance that makes glass.Above-mentioned effect is insufficient during its quantity not sufficient 0.5%, and surpasses at 15% o'clock, makes crystalline separate out temperature on the contrary and rises, makes glass be easy to devitrification.Y 2O 3Becoming the better scope of component is 1～12%.
In addition, in the present invention, in order to obtain more stable glass, with La 2O 3Composition and Y 2O 3The total amount of composition tailor-made 15～30% is good.
The CaO composition produces effect to the meltbility of the chemical durability, devitrification resistance and the frit that improve glass.Above-mentioned effect is insufficient during the quantity not sufficient 10% of CaO composition, and is difficult to obtain desired optical constant.But its amount surpasses at 30% o'clock, and the tendency of devitrificationization increases on the contrary, thereby not good.The better amount of CaO composition is 18～25%.
Li 2The O composition be the effective neccessary composition of fused for the promotion frit in the present invention, but in order to obtain above-mentioned effect, its quantity not sufficient 0.5% is just enough.And can be with Li 2The part of O composition is by Na 2O and K 2One of O composition person or the two are replaced.
Each composition of MgO, SrO, BaO and ZnO, specific refractory power and the adjustment of Abbe number, the raising of frit meltbility and the improvement of devitrification resistance to glass are effective, can be respectively MgO and SrO composition be added to the most nearly 5%, respectively BaO and ZnO composition be added to the most nearly 15%.Respectively the amount of BaO and ZnO composition is decided to be the most nearly 10% then better.
In glass of the present invention,, can choose wantonly and add TiO for the adjustment of specific refractory power and Abbe number or the raising of stability, glass 2, ZrO 2, Nb 2O 5, Ta 2O 5And WO 3Each composition, but their amount: TiO 2Composition reaches 3% most, ZrO 2, NbO 5, Ta 2O 5And WO 3Each composition is nearly 5% just the most enough respectively.But, TiO 2, Nb 2O 5And WO 3Composition, because the tendency of the light penetration step-down that makes shortwave side glass is arranged, the situation that does not therefore contain these compositions is better.
Sb 2O 3Composition, the finings during as glass melting can randomly add, but its amount just enough below 1%, more suitable amount is below 0.5%.
In addition, in glass of the present invention, except that mentioned component, even add fluorochemical or the P that is contained in the metallic element in above-mentioned each metal oxide composition with 5% ratio the most nearly 2O 5There is not obstruction Deng composition yet.
Embodiment
Below, with the embodiment No.1 of opticglass of the present invention～No.4) and the comparative example (No.A) of glass in the past, with the specific refractory power (nd) of these glass, Abbe number (vd), devitrification temperature (℃), proportion and Y 2O 3With respect to La 2O 3Weight ratio be shown in table 1 simultaneously, with the foregoing description (No.1～No.4) and the Y of comparative example (No.A) glass 2O 3The content of composition and the relation of devitrification temperature are shown in Fig. 1.What above-mentioned devitrification temperature was represented is: the flinders of resulting each glass is placed on the vesicle that is located on the platinum plate, in temperature gradient furnace fusion and keep 30 minutes after, be fetched into outside the stove result who obtains with microscopic examination crystallization generation situation.(No.5～No.26) is shown in table 2, table 3 and table 4 with the specific refractory power (nd) and the Abbe number (vd) of these glass and with other embodiment of opticglass of the present invention.[table 1] (weight %)
????No． Embodiment Comparative example
????1 ????2 ????3 ????4 ????A
?SiO 2 ?10.00 ?10.00 ?10.00 ?10.00 ?10.00
?B 2O 3 ?43.00 ?43.00 ?43.00 ?43.00 ?43.00
?Al 2O 3 ?1.00 ?1.00 ?1.00 ?1.00 ?1.00
?La 2O 3 ?22.75 ?19.75 ?16.75 ?13.75 ?25.75
?Y 2O 3 ?3.00 ?6.00 ?9.00 ?12.00
?CaO ?20.00 ?20.00 ?20.00 ?20.00 ?20.00
?Li 2O ?0.20 ?0.20 ?0.20 ?0.20 ?0.20
?Sb 2O 3 ?0.05 ?0.05 ?0.05 ?0.05 ?0.05
?Y 2O 3/La 2O 3 ?0.13 ?0.30 ?0.54 ?0.87
?nd ?1.6593 ?1.6567 ?1.6540 ?1.6514 ?1.6620
?vd ?58.4 ?58.2 ?57.9 ?57.7 ?58.6
Devitrification temperature (℃) ?978 ?969 ?957 ?952 ?985
Proportion ?3.20 ?3.17 ?3.15 ?3.13 ?3.22
[table 2] (weight %)
?No. Embodiment
????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12
?SiO 2 ?11.00 ?15.00 ?8.00 ??7.00 ??12.35 ??6.00 ??6.50 ??8.50
?B 2O 3 ?46.73 ?42.00 ?43.50 ??43.75 ??50.00 ??44.00 ??45.50 ??48.73
?Al 2O 3 ?1.20 ?0.30 ?4.00 ??0.48 ??2.50 ??3.00 ??1.00 ??1.20
?La 2O 3 ?16.57 ?20.50 ?22.95 ??25.00 ??10.00 ??22.00 ??20.40 ??17.07
?Y 2O 3 ?3.00 ?2.00 ?1.00 ??5.00 ??5.00 ??1.50 ??8.00 ??3.00
?CaO ?21.25 ?20.00 ?20.00 ??18.45 ??19.85 ??23.00 ??18.00 ??21.25
?Li 2O ?0.20 ?0.10 ?0.45 ??0.30 ??0.20 ??0.20 ??0.30 ??0.20
?Sb 2O 3 ?0.05 ?0.10 ?0.10 ??0.02 ??0.10 ??0.30 ??0.30 ??0.05
?nd ?1.6380 ?1.6464 ?1.6517 ??1.6712 ??1.6143 ??1.6603 ??1.6626 ??1.6395
?vd ?60.0 ?59.7 ?58.4 ??58.1 ??61.7 ??57.7 ??58.4 ??60.0
[table 3] (weight %)
?No. Embodiment
????13 ????14 ????15 ????16 ????17 ????18 ????19 ????20 ????21
?SiO 2 ?13.00 ?7.50 ?10.00 ?10.00 ?7.50 ?9.00 ?8.50 ?7.50 ?7.50
?B 2O 3 ?42.50 ?40.00 ?43.50 ?43.00 ?44.00 ?44.00 ?45.00 ?42.50 ?42.50
?Al 2O 3 ?1.50 ?2.00 ?2.00 ?1.00 ?5.00 ?1.00 ?1.25 ?1.00 ?1.00
?La 2O 3 ?14.10 ?20.00 ?14.60 ?10.75 ?20.00 ?18.75 ?17.00 ?16.75 ?16.75
?Y 2O 3 ?4.00 ?10.00 ?4.40 ?15.00 ?2.00 ?6.00 ?3.00 ?3.50 ?3.50
?CaO ?24.20 ?19.80 ?25.00 ?20.00 ?21.00 ?19.00 ?20.00 ?18.50 ?18.50
?Li 2O ?0.30 ?0.20 ?0.40 ?0.20 ?0.40 ?0.20 ?0.20 ?0.20 ?0.20
?Sb 2O 3 ?0.40 ?0.50 ?0.10 ?0.05 ?0.10 ?0.05 ?0.05 ?0.05 ?0.05
?MgO ?2.00
?SrO ?5.00
?BaO ?10.00
?ZnO ?10.00
?nd ?1.6432 ?1.6759 ?1.6480 ?1.6488 ?1.6472 ?1.6575 ?1.6486 ?1.6644 ?1.6614
?vd ?59.2 ?56.7 ?58.4 ?57.5 ?57.9 ?58.6 ?59.2 ?58.1 ?57.4
[table 4] (weight %)
????No. Embodiment
????22 ????23 ????24 ????25 ????26
?SiO 2 ?10.00 ?8.00 ?8.00 ?10.00 ?8.00
?B 2O 3 ?43.00 ?43.00 ?43.00 ?43.00 ?41.50
?Al 2O 3 ?1.00 ?1.00 ?1.00 ?1.00 ?1.00
?La 2O 3 ?17.75 ?2275 ?23.75 ?19.75 ?21.75
?Y 2O 3 ?3.00 ?3.00 ?3.00 ?5.00 ?5.00
?CaO ?20.00 ?20.00 ?19.00 ?20.00 ?19.50
?Li 2O ?0.20 ?0.20 ?0.20 ?0.20 ?0.20
?Sb 2O 3 ?0.05 ?0.05 ?0.05 ?0.05 ?0.05
?Ta 2O 5 ?5.00
?Nb 2O 5 ?2.00
?WO 3 ?2.00
?TiO 2 ?1.00
?BaF 2 ?3.00
?nd ?1.6604 ?1.6763 ?1.6602 ?1.6627 ?1.6605
?vd ?58.0 ?56.2 ?56.9 ?56.9 ?58.3
[table 5] (weight %)
???No. Embodiment
????27 ????28 ????29 ????30 ????31 ????32 ????33 ????34
?SiO 2 ?20.00 ?5.10 ?6.00 ?11.00 ?7.00 ?11.00 ?9.80 ?6.00
?B 2O 3 ?35.00 ?50.00 ?5.00 ?44.98 ?45.00 ?45.00 ?45.00 ?43.00
?Al 2O 3 ?2.00 ?2.00 ?2.00 ?9.80 ?2.00 ?2.00 ?1.00 ?1.00
?La 2O 3 ?17.78 ?13.00 ?15.00 ?18.00 ?30.00 ?17.80 ?13.00 ?16.00
?Y 2O 3 ?5.00 ?10.00 ?6.00 ?3.00 ?1.00 ?5.00 ?5.00 ?7.80
?CaO ?20.00 ?19.68 ?15.78 ?13.00 ?14.78 ?14.00 ?11.00 ?11.00
Li 2O ?0.20 ?0.20 ?0.20 ?0.20 ?0.20 ?0.20 ??0.20 ?0.20
?MgO ?5.00
?BaO ??15.00
?ZnO ?15.00
?Sb 2O 3 ?0.02 ?0.02 ?0.02 ?0.02 ?0.02
?nd ?1.6439 ?1.6454 ?1.6242 ?1.6077 ?1.6623 ?1.6275 ?1.6368 ?1.6466
?vd ?58.4 ?59.4 ?62.5 ?61.1 ?58.4 ?61.0 ?60.8 ?55.6
[table 6] (weight %)]
?No. Embodiment
????35 ????36 ????37 ????38 ????39 ????40 ????41
?SiO 2 ?8.00 ?7.00 ?9.80 ?6.00 ?11.00 ?11.00 ?11.00
?B 2O 3 ?45.00 ?46.80 ?45.00 ?48.30 ?45.00 ?47.00 ?45.00
?Al 2O 3 ?2.00 ?2.00 ?0.50 ?1.50 ?1.00 ?2.00
?La 2O 3 ?20.80 ?16.00 ?16.00 ?15.00 ?19.30 ?19.80 ?21.30
?Y 2O 3 ?6.00 ?7.00 ?7.00 ?10.00 ?2.00 ?1.00 ?0.50
?CaO ?16.00 ?16.00 ?20.00 ?15.00 ?20.00 ?20.00 ?20.00
?Li 2O ?0.20 ?0.20 ?0.20 ?0.20 ?0.20 ?0.20 ?0.20
?TiO 2 ?2.00
?ZrO 2 ?5.00
?Nb 2O 5 ?2.00
?WO 3 ?5.00
?Sb 2O 3 ?1.00
?nd ?1.6627 ?1.6560 ?1.6182 ?1.6575 ?1.6481 ?1.6399 ?1.6433
?vd ?55.1 ?57.4 ?57.3 ?57.3 ?59.2 ?59.3 ?59.6
By table 1 and Fig. 1 as can be known, the glass of the embodiment of the invention, with the glassy phase ratio of comparative example, devitrification temperature is low, and devitrification resistance is more good, and proportion is also little.And the foregoing description all obtained the homogeneous glass that meltbility is good, do not have bubble and striped, and chemical durability is also good.In addition, the glass of the embodiment of the invention shown in table 2～table 4 is that devitrification resistance, meltbility and chemical durability are good too, and proportion is little.
The glass of above-mentioned table 1 of the present invention～table 4 embodiment, can easily make by following method: the raw material weighing of the opticglass that oxide compound, carbonate, oxyhydroxide, nitrate and fluorochemical etc. are common is mixed, use platinum crucible, descended about 2 to 4 hours at about 1200 ℃ to 1400 ℃, after fusion, clarification, the stirring, be cast in the metal pattern of preheating, carry out slow cooling again.
As mentioned above, opticglass of the present invention is the SiO in the specific composition scope 2-B 2O 3-CaO-La 2O 3Be in the glass, add Li as neccessary composition 2O and Y 2O 3Glass, can obtain to have specific refractory power (nd) 1.60～1.68, the opticglass of the optical constant of Abbe number (ν d) 55 above scopes, that devitrification resistance and meltbility are good, stable and homogeneous with good chemical weather resistance.And opticglass of the present invention does not contain the high Gd of cost of material 2O 3Composition is not with Ta 2O 5Composition is as neccessary composition, and can cheaply make, and these advantages all are favourable.
Fig. 1 is expression Y 2O 3The content of composition and devitrification temperature (℃) the figure of relation.

Claims (3)

1. opticglass is characterized in that, in weight %, is made of following ingredients:
SiO 2?????5＜～20％、
B 2O 3???35～55％、
Al 2O 30～less than 10%,
La 2O 3??10～30％、
Y 2O 3???0.5～15％、
CaO???????10～30％、
Li 2O 0＜～less than 0.5%,
MgO???????0～5％、
SrO???????0～5％、
BaO???????0～15％、
ZnO???????0～15％、
TiO 2?????0～3％、
ZrO 2?????0～5％、
Nb 2O 5??0～5％、
Ta 2O 5??0～5％、
WO 30～5% and Sb 2O 30～1%.
2. the described opticglass of claim 1 is characterized in that, in weight %, is made of following ingredients:
SiO 2?????6～15％、
B 2O 3???40～50％、
Al 2O 3??0.3～5％、
La 2O 3??10～25％、
Y 2O 31～12%, but La 2O 3+ Y 2O 315～30%,
CaO???????18～25％、
Li 2O 0＜～less than 0.5%,
MgO???????0～5％、
SrO???????0～5％、
BaO????????0～10％、
ZnO??????0～10％、
ZrO 2????0～5％、
Ta 2O 50～5% and Sb 2O 30～0.5%, do not contain TiO 2, Nb 2O 5And WO 3
3. the described opticglass of claim 1 is characterized in that, in weight %, is made of following ingredients:
SiO 2????6～15％、
B 2O 340～50%, but SiO 2+ B 2O 3More than 50%,
Al 2O 3?0.3～5％、
La 2O 3?10～25％、
Y 2O 31～12% but La 2O 3+ Y 2O 315～30%,
CaO??????18～25％、
Li 2O 0＜～less than 0.5%,
MgO??????0～5％、
SrO??????0～5％、
BaO??????0～10％、
ZnO??????0～10％、
ZrO 2????0～5％、
Ta 2O 50～5% and Sb 2O 30～0.5%, do not contain TiO 2, Nb 2O 5And WO 3
CNB981199836A 1997-09-01 1998-09-01 Optical glass Expired - Fee Related CN1155528C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP251288/1997 1997-09-01
JP25128897 1997-09-01
JP251288/97 1997-09-01

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Publication Number Publication Date
CN1211548A true CN1211548A (en) 1999-03-24
CN1155528C CN1155528C (en) 2004-06-30

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295410A (en) * 2010-06-15 2011-12-28 富士胶片株式会社 Optical glass
CN109415240A (en) * 2016-06-29 2019-03-01 株式会社小原 Optical glass, preform and optical module
CN110128005A (en) * 2019-05-23 2019-08-16 成都光明光电股份有限公司 Optical glass
CN113415991A (en) * 2021-07-28 2021-09-21 成都光明光电股份有限公司 Optical glass and optical element

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295410A (en) * 2010-06-15 2011-12-28 富士胶片株式会社 Optical glass
CN102295410B (en) * 2010-06-15 2015-04-08 富士胶片株式会社 Optical glass
CN109415240A (en) * 2016-06-29 2019-03-01 株式会社小原 Optical glass, preform and optical module
CN109415240B (en) * 2016-06-29 2022-07-22 株式会社小原 Optical glass, preform and optical module
CN110128005A (en) * 2019-05-23 2019-08-16 成都光明光电股份有限公司 Optical glass
CN110128005B (en) * 2019-05-23 2021-12-07 成都光明光电股份有限公司 Optical glass
CN113415991A (en) * 2021-07-28 2021-09-21 成都光明光电股份有限公司 Optical glass and optical element

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