CN101445322A - Dense crown optical glass - Google Patents

Dense crown optical glass Download PDF

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Publication number
CN101445322A
CN101445322A CNA2008103066397A CN200810306639A CN101445322A CN 101445322 A CN101445322 A CN 101445322A CN A2008103066397 A CNA2008103066397 A CN A2008103066397A CN 200810306639 A CN200810306639 A CN 200810306639A CN 101445322 A CN101445322 A CN 101445322A
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glass
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optical glass
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dense
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匡波
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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Abstract

The invention aims to provide a dense crown optical glass which is free of P2O5, has a low transition temperature (Tg) and is adaptive to precision pressure-forming process. The components in weight percentages of the dense crown optical glass are as follows: 20% to 50% of SiO2; 5% to 30% of B2O3; 0% to 12% of ZnO; 10% to 41% of MgO, CaO, SrO and BaO; 0% to 7% of La2O3, Gd2O3 and Y2O3; 5% to 15% of Li2O, Na2O and K2O; 0% to 10% of AL2O3; 0% to 2% of ZrO2; 0% to 3% of TiO2, Nb2O5 and WO3; and 0% to 0.5% of Sb2O3. The dense crown optical glass contains borosilicate components and is free of P2O5 capable of producing harmful volatile substances. The nd of the dense crown optical glass is in the range from 1.55 to 1.65, and the vd is in the range from 55 to 64. The dense crown optical glass has low raw materials cost and low manufacturing cost, and can be further processed to prefabticated optical elements or optical elements when the Tg is below 525 DEG C.

Description

Dense-crown optical glass
Technical field
The present invention relates to a kind of opticglass, particularly relate to a kind of specific refractory power (nd) between 1.55～1.65, Abbe number (vd) between 55～64, transition temperature (Tg) is at the dense-crown optical glass below 525 ℃.
Background technology
Along with the highly integrated and multifunction development of optical system, but portable class optical electron product such as digital camera, digital camera camera cell phone etc. obtain rapid popularization and application.In order to realize the high pixel of optical system, small portable, cheaply requirement, use the accurate die pressing technology development innovation that non-spherical lens carries out optical design and adopts direct weighting moulding optical glass device (mainly being non-spherical lens).Carry out secondary press with traditional glass blank spare that utilizes, and then the method for carrying out grinding and polishing manufacturing optical element is compared, opticglass accurate die pressing technology obtains the final finished element by directly the accurate prefabricated component of melten glass or glass being carried out precision press formation, after having omitted moulding lens are ground, step of polishing, thereby reduced manufacturing cost, alleviated carrying capacity of environment, and the method for accurate die pressing has unrivaled technology of traditional diamond-making technique and cost advantage on the manufacturing aspherical optical element, therefore the demand for the low softening point opticglass that is applicable to this precise compression molding method also increases sharply.Temperature in the time of can reducing mold pressing by the low glass of use transition temperature (Tg) reduces the die surface oxidation, prolongs die life, thereby reduces manufacturing cost.
JP2004315324 discloses a kind ofly to have low chromatic dispersion, low glass transformation temperature, is used in the optical glass that extrusion forming is used, nd is between 1.55～1.72, vd is 57～70, Tg is below 550 ℃, glass transition temperature (Ts) contains 28～50% P below 600 ℃ during its prescription forms 2O 5(mol%); CN1495142A discloses a kind of dense-crown optical glass of lead and arsenic free, its nd between 1.55～1.60, vd be 54～63, Tg below 500 ℃, but also contain a large amount of P2O5 in the component, its content has been up to 56wt%.
P 2O 5In Improving Glass Manufacturing Processes, can produce the volatilization of harmful substance P, be easy to cause acid pollution, with respect to SiO 2And B 2O 3, use P 2O 5Generate cognition as glass the cost of glass is obviously increased, be unfavorable for realizing the cost degradation of product.In addition, contain a large amount of P 2O 5Glass weather resistance poor.
CN1105955A discloses a kind of opticglass that is suitable for compression molding, and its nd is between 1.55～1.65, and vd is 55～63, and Tg is 600 ℃.Except glass transformation temperature than the height, B2O3 content is worked as B at 16～40wt% in its compositing formula 2O 3During too high levels, the volatilization in the fusion process can cause constant of glass and striped fluctuation, reduces the quality stability of glass, thereby causes complex manufacturing.
Summary of the invention
Technical problem to be solved by this invention provides a kind of P that do not contain 2O 5, have low transition temperature, be suitable for carrying out the dense-crown optical glass of precision press formation.
The technical scheme that technical solution problem of the present invention adopts is: dense-crown optical glass, the weight percent content of its constituent is: SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
Further, the weight percent content of its constituent is: SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, Li 2O:4～10%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
Further, the weight percent content of its constituent is: SiO 2: 30～47%, B 2O 3: 5～30%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, Li 2O:4～10%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
Further, the weight percent content of its constituent is: SiO 2: 20～50%, B 2O 3: 6～26%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, Li 2O:4～10%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
Further, the weight percent content of its constituent is: SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:2～9%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3: 0～7%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 1～8%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%.
Further, the weight percent content of its constituent is: SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:2～9%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3: 1～5%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 3～7%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%.
Further, the weight percent content of its constituent is: SiO 2: 30～47%, B 2O 3: 6～26%, ZnO:2～9%, BaO:3～38%, La 2O 3: 1～5%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 3～7%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%.
Further, the weight percent content of its constituent is: SiO 2: 30～47%, B 2O 3: 6～26%, ZnO:2～9%, BaO:10～35%, La 2O 3: 1～5%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 3～7%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%
Further, the weight percent content of its constituent is: SiO 2: 20～50%, B 2O 3: 5～30%, BaO:3～38%, Li 2O:4～10%.
Further, the weight percent content of its constituent is: SiO 2: 30～47%, B 2O 3: 6～26%, BaO:10～35%, Li 2O:4～10%.
The invention has the beneficial effects as follows: adopt the borosilicate system component, do not add the P that can produce the harmful substance volatilization 2O 5, nd is between 1.55～1.65, and vd is between 55～64.Frit of the present invention and low cost of manufacture, Tg can be made into optical precast product or optical element below 525 ℃.
Embodiment
Each component introducing reason of opticglass of the present invention and weight percent content setting range are as follows:
SiO 2Be the neccessary composition that forms glass network, SiO 2Can improve high temperature viscosity, devitrification resistance and the chemical stability of glass, its content range is set in 20～50%, when its content is lower than 20%, the chemical stability variation of glass, optical constant is difficult to reach the invention requirement, when content surpassed 50%, the glass melting variation was difficult to the softening temperature that keeps low.So SiO 2Content is set between 20～50%, and preferred content is 30～47%.
B 2O 3Also be the neccessary composition that consists of glass network, an amount of introducing can improve the meltdown property of glass, is conducive to glass and has low softening temperature, improves the resistance to water of glass, and B 2O 3When content is lower than 5%, the obvious variation of the meltdown property of glass, refractive index reduces, and when content was higher than 30%, the Abbe number of glass can not reach the chemical stability variation of desired value and glass, so B 2O 3Content is 5～30%, and preferred content is 6～26%.
ZnO can reduce glass melting temperature, liquidus temperature and glass transformation temperature, improves the chemical durability of glass, reduces the tendency towards devitrification of glass, and its content is 0～12%, and preferred content is 2～9%.
The importing of alkaline earth oxide MgO, CaO, SrO and BaO can be adjusted optical constant, improves the stability of glass, and reduces the glass high temperature viscosity, increases the low temperature viscosity of glass, so that glass is easy to produce.Wherein BaO has outstanding role to improving glass refraction, improve devitrification resistance and reducing liquidus temperature, and it is with low cost, so the alkaline earth metal oxide total content is controlled at 10～41%, and wherein BaO content is 3～38%, and preferred content is 10～35%.
La 2O 3Having higher refractive index and lower chromatic dispersion, is the active ingredient that improves glass refraction, with B 2O 3Mix and have the devitrification resistance property that can also improve glass, improve the chemical stability of glass.Gd 2O 3And Y 2O 3Have and La 2O 3Identical effect, but the too high meeting of use amount causes glass transition temperature to raise, thereby La of the present invention 2O 3, Gd 2O 3And Y 2O 3Total content be 0～7%, La wherein 2O 3Content is 0～7%, and preferred content is 1～5%.
Li 2O can significantly reduce the transition temperature of glass, improve glass melting, when its content less than 4% the time, can not reach transition temperature required for the present invention, but too much importing can make the devitrification resistance and the obvious variation of chemical stability of glass, so its content is controlled at 4～10%.Except adding Li 2Interpolation Na that also can be suitable beyond the O 2O and K 2O reduces the transition temperature of glass, but its effect is not as Li 2O, Na 2O content is controlled at 0～5%, K 2O is controlled at 0～5%, Li 2O, Na 2O, K 2The total content of O is 5～15%.
AL 2O 3Be intermediate oxide, an amount of introducing can improve glass high temperature viscosity and chemical durability, and can reduce the tendency towards devitrification of liquidus temperature and glass, AL 2O 3When content surpassed 10%, the refractive index of glass reduced and devitrification resistance stability obviously descends, and transition temperature and softening temperature raise, AL 2O 3Content is controlled at 0～10%, and is preferred 1～8%, and more preferably 3～7%.
ZrO 2The chemical stability of glass can be increased in the present invention, and when using the zirconia refractory molten glass, corrosion can be alleviated refractory materials, but ZrO 2Use glass transformation temperature will be raise, therefore limiting its content is 0～2%.
In glass, introduce TiO 2, Nb 2O 5And WO 3Can significantly improve refractive index and chromatic dispersion, and can improve the chemical stability of glass, but these composition use amounts too much can make the softening temperature of glass raise, and the ultraviolet permeability of glass is descended, therefore its total content is defined as 0～3%.
Sb 2O 3Can be used as the fining agent of glass, if but add the life-span that too much can affect pressurizing mould.Therefore, its content is set in 0～0.5%, preferred〉0～0.1%.
Below narrate embodiments of the invention, but the present invention not merely is defined in these embodiment.
Table 1, table 2 and table 3 are 15 embodiment of the present invention, have listed the prescription of each embodiment in the table and have formed pairing specific refractory power (nd), Abbe number (vd), glass transition temp (Tg), glass transition temperature (Ts).
Table 1
Figure A200810306639D00081
Table 2
Figure A200810306639D00091
Table 3
Figure A200810306639D00101
With the raw material of 15 embodiment component correspondences shown in the table for example oxide compound, oxyhydroxide, carbonate, nitrate etc. respectively in accordance with regulations ratio weigh, be mixed into admixtion, put in the platinum crucible, according to the meltbility of forming, under 1050～1400 ℃ of temperature through fusing, clarification, stir, after homogenizing, just can obtain melten glass of the present invention
As can be seen from the above embodiments, the nd of opticglass of the present invention is 1.55～1.65, and vd is 55～64, and Tg can reach below 525 ℃, demonstrates fabulous low softening character, is suitable as optical glass for precision profiling.Use optical glass of the present invention, can make prefabricated part for precise compression molding, and the optical element that is made of optical glass of the present invention such as various lens etc. can be provided.

Claims (10)

  1. [claim 1] dense-crown optical glass is characterized in that, the weight percent content of its constituent is: SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
  2. [claim 2] dense-crown optical glass as claimed in claim 1 is characterized in that, the weight percent content of its moiety is:
    SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, Li 2O:4～10%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
  3. [claim 3] dense-crown optical glass as claimed in claim 1 is characterized in that, the weight percent content of its moiety is:
    SiO 2: 30～47%, B 2O 3: 5～30%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, Li 2O:4～10%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
  4. [claim 4] dense-crown optical glass as claimed in claim 1 is characterized in that, the weight percent content of its moiety is:
    SiO 2: 20～50%, B 2O 3: 6～26%, the total content sum of ZnO:0～12%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3, Gd 2O 3And Y 2O 3The total content sum be 0～7%, Li 2O, Na 2O and K 2The total content sum of O is 5～15%, Li 2O:4～10%, AL 2O 3: 0～10%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.5%.
  5. [claim 5] dense-crown optical glass as claimed in claim 1 is characterized in that, the weight percent content of its moiety is:
    SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:2～9%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3: 0～7%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 1～8%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%.
  6. [claim 6] dense-crown optical glass as claimed in claim 1 is characterized in that, the weight percent content of its moiety is:
    SiO 2: 20～50%, B 2O 3: 5～30%, the total content sum of ZnO:2～9%, MgO, CaO, SrO and BaO be 10～41%, BaO:3～38%, La 2O 3: 1～5%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 3～7%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%.
  7. [claim 7] dense-crown optical glass as claimed in claim 1 is characterized in that, the weight percent content of its moiety is:
    SiO 2: 30～47%, B 2O 3: 6～26%, ZnO:2～9%, BaO:3～38%, La 2O 3: 1～5%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 3～7%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%.
  8. [claim 8] dense-crown optical glass as claimed in claim 1 is characterized in that, the weight percent content of its moiety is:
    SiO 2: 30～47%, B 2O 3: 6～26%, ZnO:2～9%, BaO:10～35%, La 2O 3: 1～5%, Li 2O:4～10%, Na 2O:0～5%, K 2O:0～5%, AL 2O 3: 3～7%, ZrO 2: 0～2%, TiO 2, Nb 2O 5And WO 3The total content sum be 0～3%, Sb 2O 3: 0～0.1%.
  9. [claim 9] dense-crown optical glass as claimed in claim 1 is characterized in that the weight percent content of its moiety is: SiO 2: 20～50%, B 2O 3: 5～30%, BaO:3～38%, Li 2O:4～10%.
  10. [claim 10] dense-crown optical glass as claimed in claim 1 is characterized in that the weight percent content of its moiety is: SiO 2: 30～47%, B 2O 3: 6～26%, BaO:10～35%, Li 2O:4～10%.
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CN102311228A (en) * 2011-06-30 2012-01-11 湖北新华光信息材料有限公司 Optical glass
CN105271724A (en) * 2015-10-22 2016-01-27 成都光明光电股份有限公司 Optical glass and optical element
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CN105271714A (en) * 2014-06-26 2016-01-27 成都光明光电股份有限公司 Optical glass and optical element
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CN105884192A (en) * 2016-04-05 2016-08-24 湖北戈碧迦光电科技股份有限公司 Special glass and preparation method and application thereof
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CN111018342B (en) * 2019-12-24 2022-04-15 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN111204969A (en) * 2020-03-06 2020-05-29 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN114853336A (en) * 2022-06-22 2022-08-05 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN115028354A (en) * 2022-06-22 2022-09-09 成都光明光电股份有限公司 Optical glass and optical element
CN114853336B (en) * 2022-06-22 2023-09-05 成都光明光电股份有限公司 Optical glass, glass preform, optical element, and optical instrument
CN115028354B (en) * 2022-06-22 2023-09-05 成都光明光电股份有限公司 Optical glass and optical element

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