CN1126704A - Optical glass - Google Patents

Optical glass Download PDF

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Publication number
CN1126704A
CN1126704A CN 95103393 CN95103393A CN1126704A CN 1126704 A CN1126704 A CN 1126704A CN 95103393 CN95103393 CN 95103393 CN 95103393 A CN95103393 A CN 95103393A CN 1126704 A CN1126704 A CN 1126704A
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China
Prior art keywords
glass
bao
mgo
zno
cao
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Granted
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CN 95103393
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Chinese (zh)
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CN1044223C (en
Inventor
森克夫
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Ohara Inc
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Ohara Inc
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Priority claimed from JP26839994A external-priority patent/JP3190215B2/en
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Publication of CN1044223C publication Critical patent/CN1044223C/en
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Abstract

The present invention provides an optical glass having optical constants such as refractive index (Nd) in the range of 1.57-1.72 and Abbe number (&nu d) in the range of 30-45, having low transition temp. characteristic and excellent chemical durability and suitable to mold press formability. Contents of indispensable constituents are, by wt.%, 48-64% SiO2 , 15-30% TiO2 , 3-12% ZrO2 , 0.5-5% Li2 O, 3-30% K2 O, 2-25% in total of RO (R is Mg, Ca, Sr, Ba and Zn).

Description

Opticglass
The present invention relates to SiO 2-TiO 2-ZrO 2-LiO-K 2(R is Mg to O-RO, Ca, Sr, Ba, Zn) class opticglass, specific refractory power in its optical constant (Nd) scope is 1.57-1.72, Abbe number (ν d) scope is 30-45, and this opticglass not only can improve the die forming of giving low transition temperature characteristic, and has excellent chemical durability.
Known have the glass of above-mentioned optical constant for containing P bThe silicates glass of O.But in order to solve the pollution problem that glass manufacturing process etc. relates to, glass should not contain deleterious P bThe O composition be the substitute is always to containing TiO 2Glass carry out all research.For example, No. 973350 German Patent communique discloses TiO 2, silicofluoric acid salt glass, SiO is disclosed and the spy opens clear 54-105119 communique 2-TiO 2-K 2O-BPO 4And/or Al (PO 3) 3Class glass, but the chemical durability of these glass is all not enough, before wherein during a kind of glass melting fluorine become branch's volatilization, be difficult to reach and homogenize.
In addition, No. 2165231 British patent gazette also discloses and contained TiO 2, Li 2The alkali metal silicate salt glass of O, this glass transformation temperature (calling Tg in the following text) is low, but chemical durability is poor.
The object of the invention provides and does not contain P bThe glass of O, this glass can improve the weak point of above-mentioned existing glass comprehensively, and has the aforementioned lights mathematic(al) constant, not only can keep the low Tg characteristic that is suitable for mold pressing, has more excellent chemical durability simultaneously again.
For achieving the above object, the inventor has carried out experimental study with keen determination, and the result has invented the SiO of specific composition scope 2-TiO 2-ZrO 2-Li 2O-K 2O-RO class glass, its compositing range are not open in the past, and this glass can keep aforementioned lights mathematic(al) constant and suitable and in the low Tg characteristic of mold pressing, but can further improve the chemical durability and the mass production of this glass simultaneously again.
Opticglass of the present invention is characterised in that wherein and comprises SiO in this glass ingredient of weight range 248-64%, B 2O 30-4%, TiO 215-30%, ZrO 23-12%, Nb 2O 50-4%, Li 2O 0.5-5%, Na 2O 0-25%, K 2O 3-30%, wherein Na 2O+K 2O 10-30%, MgO 0-10%, CaO 0-10%, SrO0-10%, BaO 0-15%, ZnO 0-10%, the optical constant scope of wherein MgO+CaO+SrO+BaO+ZnO 2-25%, and this glass is specific refractory power (Nd) 1.57-1.72 and Abbe number (ν d) 30-45.
Limit the reasons are as follows of above-mentioned each composition compositing range.
At first be SiO 2Composition, this is the effective oxide that forms glass, if its quantity not sufficient 48%, then the light transmission of glass and chemical durability are poor, are difficult to fusion and surpass 64% o'clock glass.
B 2O 3Composition can improve glass melting gives birth to, and makes with regard to the deteriorates chemical durability with regard to being unlikely, and its addition mostly is about 4% most.
TiO 2Composition can be given high dispersivity of glass or dispersiveness effectively, if its quantity not sufficient 15%, then specific refractory power is low, also is low dispersivity, and if surpass 30% o'clock light transmission and stability poor, and its preferable range can be decided to be 21-30%.
ZrO 2Composition is the important component that improves chemical durability, if its quantity not sufficient 3%, then its weak effect surpasses 12% if it is measured, and then the chemical durability of glass is poor again, and its preferable range can be decided to be maximum 10%.
Nb 2O 5For improving the effective constituent of glass refraction, consider again and keep chemical durability that its amount can be decided to be preferred 0.5-4%.
Li 2The O composition is important component owing to the effect of giving the low Tg characteristic of glass especially obviously forms, and available again this composition is kept the chemical durability of glass simultaneously, and in order to bring into play these effects, its amount can be decided to be 0.5-5%.
Na 2The O composition can improve glass melting, and with regard to being unlikely the limit that makes deteriorates chemical durability, its addition mostly is 25% most.
K 2The O composition is for can improving glass melting and improve the effective constituent of stability, if its quantity not sufficient 3%, and this DeGrain then, and if surpass 30%, then the chemical durability of glass is poor again.But, in order to keep glass melting and chemical durability, Na 2O and K 2The total amount of O composition can be decided to be 10-30%.
MgO, CaO, SrO, BaO and ZnO composition are for can keep optical constant, improve glass melting, therefore the composition of stability and light transmission is necessary to contain these compositions more than a kind, and, above-listed each composition can be decided to be maximum 10%, 10%, 10%, 15% and 10% respectively in order to reach above-mentioned effect.But, in order to reach above-mentioned effect, also be necessary the total amount more than a kind or 2 kinds of these compositions is decided to be more than 2%, and if surpass 25%, then glass can become low dispersivity again, also with regard to inaccessible desired light numeric constant.
Bringing under the situation of disadvantageous effect for each characteristic of glass of the present invention, in order to adjust the optical constant of glass, improve glass melting and chemical durability etc., can in glass of the present invention, add Al 2O 2, WO 3Deng, its amount is for maximum about 5%.And, can add As 3O 3And Sb 2O 3Each composition is as finings, and its add-on can be respectively maximum about 1%.
Embodiment
Opticglass embodiment of the present invention below is described.
Table 1 has been listed the composition embodiment (No.1-No.10) of opticglass of the present invention and the composition comparative example (No.A, No.B) of existing glass, has also listed the specific refractory power (Nd) of these glass in the table, Abbe number (ν d), Tg and acid resistance (SR) value.Above-mentioned SR value is to measure and ecbatic according to the measuring method of the International Organization for Stand ISO 8424,1987 (E).Here, the SR value is subjected to 0.1 μ m according to glass specimen and corrodes needed time rating in used pickling agent.SR value=4 and 5 o'clock, with the salpeter solution of pH0.3, show its erosion time be respectively 0.1-1h (hour) and below the 0.1h.SR value=5,51,52 and 53 o'clock, use the acetate buffer solution of pH4.6 respectively, show that its erosion time is respectively more than the 10h, 1-10h, 0.1-1h and below the 0.1h.
As can be seen from Table 1, compare with the glass No.A and the No.B of the composition comparative example that has substantially the same optical constant respectively, the SR value that the present invention forms embodiment No.6 and No.9 all is improved, and demonstrates more excellent chemical durability.Other glass display of forming embodiment of the present invention goes out the SR value of same excellence.And the devitrification resistance of these glass is all excellent, also easily homogenizes.Therefore, the foregoing description glass is made easily, is suitable for mold pressing, and has excellent chemical durability.
The glass that the invention described above is formed embodiment all can obtain according to a conventional method, wherein with nitrate, carbonate, opticglass raw material weighing commonly used such as oxide compound, mixing, again with platinum oil crucible with its fusion deaeration of about 2-5 hour under 1100-1350 ℃, after stirring it is poured in the metal pattern and slowly and cools off.
As mentioned above, opticglass of the present invention has SiO 2-TiO 2-ZrO 2-Li 2O-K 2Special composition of O-RO class and specific refractory power (Nd) scope are 1.57-1.72, and Abbe number (ν d) scope is optical constant and low Tg such as 30-45, and does not contain deleterious P bThe O composition, but compare with known glass, having excellent chemical durability again, mass production is also very excellent.
[table 1]
Unit: weight %
????No Embodiment
??????1 ??????2 ?????3 ?????4
????SiO 2????B 2O 3????TiO 2????ZrO 2????Nb 2O 5????Li 2O ????Na 2O ????K 2O ????MgO ????CaO ????SrO ????BaO ????ZnO ????Al(PO 3) 3????Sb 2O 3 ????48.5 ????21.6 ????3.0 ????0.5 ????0.5 ????3.2 ????12.0 ????3.0 ????7.5 ????0.2 ????54.0 ????24.0 ????4.5 ????1.0 ????2.0 ????4.0 ????6.5 ????3.8 ????0.2 ????56.5 ????22.0 ????3.5 ????1.5 ????3.5 ????10.0 ????0.8 ????2.0 ????0.2 ????48.0 ????23.5 ????3.0 ????1.5 ????2.5 ????11.0 ????7.5 ????2.8 ????0.2
????Nd ???νd ????Tg(℃) ????SR ????1.64564 ????39.8 ????530 ????4 ????1.65841 ????36.7 ????500 ????4 ????1.64335 ????38.5 ????49?0 ????5 ????1.65401 ????39.2 ????480 ????5
[table 1]
Unit: weight %
????No Embodiment
??????5 ??????6 ??????7 ?????8
????SiO 2????B 2O 3????TiO 2????ZrO 2????Nb 2O 5????Li 2O ????Na 2O ????K 2O ????MgO ????CaO ????SrO ????BaO ????ZnO ????Al(PO 3) 3????Sb 2O 3 ????49.0 ????22.5 ????4.0 ????1.8 ????1.0 ????7.5 ????9.0 ????4.5 ????0.5 ????0.2 ????52.0 ????25.2 ????4.5 ????0.5 ????2.5 ????1.8 ????9.0 ????2.0 ????2.5 ????54.0 ????21.0 ????3.0 ????0.5 ????0.5 ????5.3 ????10.0 ????0.5 ????5.0 ????0.2 ????50.0 ????22.0 ????3.0 ????2.0 ????1.0 ????18.8 ????3.0 ????0.2
????Nd ????νd ????Tg(℃) ????SR ????1.64858 ????39.0 ????540 ????4 ????1.66502 ????36.2 ????490 ????4 ????1.62537 ????40.5 ????550 ????4 ????1.63126 ????40.1 ????530 ????4
[table 1]
Unit: weight %
????No Embodiment Comparative example
?????9 ?????10 ??????A ?????B
????SiO 2????B 2O 3????TiO 2????ZrO 2????Nb 2O 5????Li 2O ????Na 2O ????K 2?O ????MgO ????CaO ????SrO ????BaO ????ZnO ????Al(PO 3) 3????Sb 2O 3 ????51.5 ????21.5 ????4.5 ????1.5 ????1.5 ????4.3 ????10.0 ????5.0 ????0.2 ????53.0 ????22.0 ????3.0 ????1.0 ????3.0 ????5.8 ????8.0 ????4.0 ????0.2 ????40.0 ????25.0 ????6.5 ????21.5 ????7.0 ????As 2O 30.5 ????50.0 ????24.0 ????11.0 ????15.0
????Nd ????νd ????Tg(℃) ????SR ????1.64276 ????39.7 ????490 ????4 ????1.64503 ????39.6 ????480 ????5 ????1.6661 ????29.8 ????-- ????51 ????1.6462 ????36.3 ????480 ????53

Claims (5)

1. opticglass is characterized in that comprising SiO in this glass ingredient of weight range 248-64%, B 2O 30-4%, TiO 215-30%, ZrO 23-12%, Nb 2O 50-4%, Li 2O 0.5-5%, Na 2O 0-25%, K 2O 3-30%, wherein Na 2O+K 2O 10-30%, MgO 0-10%, CaO 0-10%, SrO0-10%, BaO 0-15%, ZnO 0-10%, the optical constant scope of wherein MgO+CaO+SrO+BaO+ZnO 2-25%, and this glass is specific refractory power (Nd) 1.57-1.72 and Abbe number (ν d) 30-45.
2. the opticglass of claim 1 is characterized in that comprising SiO in this glass ingredient of weight range 248-64%, B 2O 30-4%, TiO 215-30%, ZrO 23-10%, Nb 2O 50.5-4%, Li 2O 0.5-5%, Na 2O 0-25%, K 2O3-30%, wherein Na 2O+K 2O 10-30%, MgO 0-10%, CaO0-10%, SrO 0-10%, BaO 0-15%, ZnO 0-10%, wherein MgO+CaO+SrO+BaO+ZnO 2-25%.
3. the opticglass of claim 1 is characterized in that comprising SiO in this glass ingredient of weight range 248-64%, TiO 215-30%, ZrO 23-10%, Nb 2O 50.5-4%, Li 2O 0.5-5%, Na 2O 0-25%, K 2O 3-30%, wherein Na 2O+K 2O 10-30%, MgO 0-10%, CaO 0-10%, SrO0-10%, BaO 0-15%, ZnO 0-10%, wherein MgO+CaO+SrO+BaO+ZnO 2-25%.
4. the opticglass of claim 1 is characterized in that comprising SiO in this glass ingredient of weight range 248-64%, TiO 221-30%, ZrO 23-10%, Nb 2O 50.5-4%, Li 2O 0.5-5%, Na 2O 0-25%, K 2O 3-30%, wherein Na 2O+K 2O 10-30%, MgO 0-10%, CaO 0-10%, SrO0-10%, BaO 0-10%, ZnO 0-10%, wherein MgO+CaO+SrO+BaO+ZnO 2-25%.
5. claim 1,2,3 or 4 opticglass, the transition temperature that it is characterized in that above-mentioned glass is below 550 ℃.
CN95103393A 1994-10-06 1995-05-08 Optical glass Expired - Fee Related CN1044223C (en)

Applications Claiming Priority (2)

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JP26839994A JP3190215B2 (en) 1994-07-14 1994-10-06 Optical glass
JP268399/94 1994-10-06

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CN1126704A true CN1126704A (en) 1996-07-17
CN1044223C CN1044223C (en) 1999-07-21

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071718C (en) * 1997-06-03 2001-09-26 株式会社小原 Optical glass for mould pressing
CN102686526A (en) * 2010-09-30 2012-09-19 Hoya株式会社 Optical glass,glass material for press molding,and optical element
CN109626813A (en) * 2019-01-07 2019-04-16 成都光明光电股份有限公司 Optical glass, optical precast product, optical element and optical instrument
CN109867442A (en) * 2019-04-24 2019-06-11 成都光明光电股份有限公司 Optical glass
CN109896740A (en) * 2019-04-24 2019-06-18 成都光明光电股份有限公司 Optical glass and optical element
CN109912195A (en) * 2019-04-24 2019-06-21 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument
CN110342813A (en) * 2019-07-22 2019-10-18 成都光明光电股份有限公司 Optical glass, optical element and optical instrument

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050028558A1 (en) * 2003-08-06 2005-02-10 Hoya Corporation Process for producing glass molded lens

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5886064A (en) * 1981-11-16 1983-05-23 Kazunori Seki Preparation of rolled fish meat product and apparatus therefor
CA2061502A1 (en) * 1991-02-19 1992-08-20 Kawamoto Toru Chemical resistant glass fiber composition
US5320987A (en) * 1992-10-06 1994-06-14 Kabushiki Kaisha Ohara Optical glass

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071718C (en) * 1997-06-03 2001-09-26 株式会社小原 Optical glass for mould pressing
CN102686526A (en) * 2010-09-30 2012-09-19 Hoya株式会社 Optical glass,glass material for press molding,and optical element
CN102686526B (en) * 2010-09-30 2017-02-15 Hoya株式会社 Optical glass,glass material for press molding,and optical element
CN109626813A (en) * 2019-01-07 2019-04-16 成都光明光电股份有限公司 Optical glass, optical precast product, optical element and optical instrument
CN109626813B (en) * 2019-01-07 2021-08-31 成都光明光电股份有限公司 Optical glass, optical preform, optical element and optical instrument
CN109867442A (en) * 2019-04-24 2019-06-11 成都光明光电股份有限公司 Optical glass
CN109896740A (en) * 2019-04-24 2019-06-18 成都光明光电股份有限公司 Optical glass and optical element
CN109912195A (en) * 2019-04-24 2019-06-21 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument
CN109912195B (en) * 2019-04-24 2021-12-07 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN110342813A (en) * 2019-07-22 2019-10-18 成都光明光电股份有限公司 Optical glass, optical element and optical instrument
CN110342813B (en) * 2019-07-22 2022-02-11 成都光明光电股份有限公司 Optical glass, optical element and optical instrument

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