CN1510002A - Optical glass for molding shape - Google Patents

Optical glass for molding shape Download PDF

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Publication number
CN1510002A
CN1510002A CNA031526896A CN03152689A CN1510002A CN 1510002 A CN1510002 A CN 1510002A CN A031526896 A CNA031526896 A CN A031526896A CN 03152689 A CN03152689 A CN 03152689A CN 1510002 A CN1510002 A CN 1510002A
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glass
opticglass
die forming
composition
mould
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CN100337955C (en
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ʷ
佐藤史雄
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority claimed from JP2002373735A external-priority patent/JP4305940B2/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

To provide an optical glass for mold press, which has a refractive index (nd) of 1.75-1.85 and an Abbe's number ([upsilon]d) of >=35, has a high transmittance in a short wavelength range, and has an improved devitrification property. The optical glass has a composition of, by mass%, B<SB>2</SB>O<SB>3</SB>of 5-25%, La<SB>2</SB>O<SB>3</SB>of 15-35%, ZnO of 10-30%, Ta<SB>2</SB>O<SB>5</SB>of 15.5-25%, Li<SB>2</SB>O of 0-3.5%, Na<SB>2</SB>O of 0-10%, K<SB>2</SB>O of 0-9%, R'<SB>2</SB>O (R' is one kind or more of Li, Na, and K) of 0-10%, SiO<SB>2</SB>of 0-20%, Al<SB>2</SB>O<SB>3</SB>of 0-15%, MgO of 0-10%, CaO of 0-7%, BaO of 0-12%, SrO of 0-5%, RO (R is one kind or more of Mg, Ca, Ba, and Sr) of 0-15%, ZrO<SB>2</SB>or 0-10%, Gd<SB>2</SB>O<SB>3</SB>of 0-20%, Bi<SB>2</SB>O<SB>3</SB>of 0-5%, Sb<SB>2</SB>O<SB>3</SB>of 0-1%, TiO<SB>2</SB>of 0-0.5%, and Nb<SB>2</SB>O<SB>5</SB>of 0-0.3%. (C)2003,JPO .

Description

Die forming opticglass
Technical field
The present invention relates to die forming opticglass.
Background technology
As the optical characteristics of the glass that uses in optical pickup unit lens, video camera and the optical lens of typical CCD camera photography with lens of so-called CD, MD, DVD and other various optical disk systems, great majority require higher specific refractory power, the low dispersion.And originally to use specific refractory power (nd) in these purposes be the B more than 35 as 1.75-1.85, Abbe number (vd) always 2O 3-La 2O 3System glass.
As optical pickup unit lens and the making method of photography with lens, be known that and earlier melten glass be configured as blank, will be truncated into the method for carrying out die forming after the chunk glass grinding of suitable size and form droplet-like, be about to the so-called chunk glass that forms by drop forming and carry out grinding or not grinding and the method for mold pressing then from the nozzle tip melten glass that drips.
Correlation technique is documented in that for example the spy of Japan opens flat 8-26765 communique and the spy opens in the flat 8-26766 communique.
But, because B 2O 3-La 2O 3System glass tendency towards devitrification is strong, so melten glass is quenched casting when making blank, its property produced in batches is poor.In addition, in drop forming, melten glass is dripped, can form under the shaping viscosity of glass of drop and be limited to about 10 from nozzle tip 0.8Pool, if drip below the viscosity at this, then drop can not form, and can form thread.Therefore, have high tendency towards devitrification, that is to say 10 0.8The B of devitrification under the low viscosity below the pool 2O 3-La 2O 3System glass is not suitable for drop forming.By B 2O 3-La 2O 3-Y 2O 3The devitrification resistance of the glass that system is formed improves, but specific refractory power can reduce again in this system.
B in addition 2O 3-La 2O 3The common softening temperature of system glass (Ts) height is above 700 ℃.In the die forming method, near chunk glass being heated to softening temperature (Ts), make it to become the soft state shaping, press tool is warmed up near the temperature of Ts.When the Ts of chunk glass was high, mould also became high temperature, had promoted the deteriorations such as oxidation of mould, became the reason that causes the property produced in batches reduction.In order to reduce Ts, also proposed at B 2O 3-La 2O 3Add R ' in the system glass 2The method of O (R ' be among Na, K, the Li more than one) contains R ' in large quantities 2O can make increased devitrification resistance increase.Also produced the problem of easy and mould sticking to mould in addition.
In addition, in recent years, use short wavelengths' (390-440nm) such as blue laser the laser laser that pick-up is used as light usually, also require to improve transmittance the short wavelength for lens.
Summary of the invention
The purpose of this invention is to provide specific refractory power (nd) is more than 35 for 1.75-1.85, Abbe number (vd), at short wavelength's transmittance height, and the improved die forming opticglass of increased devitrification resistance.
Die forming opticglass of the present invention is specific refractory power (nd) for 1.75-1.85, Abbe number (vd) are, softening temperature is, lead-free die forming opticglass more than 35 below 700 ℃, is characterised in that Δ T={ forming temperature is (10 0.8Temperature under the pool)-and liquidus temperature } be more than 20 ℃, reduce less than 0.10% according to the weight in the powder method water tolerance of Japanese optics nitre industry meeting specification JOGIS, reduce less than 0.35% according to the weight in the powder method acid resistance of Japanese optics nitre industry meeting specification JOGIS, the internal transmittance of 400nm wavelength (t=10mm) is more than 90.0%, and the basicity of glass is below 11.
Die forming of the present invention in addition is characterised in that to have in quality %, 5-25%B with opticglass 2O 3, 15-35%La 2O 3, 10-30%ZnO, 15.5-25%Ta 2O 5, 0-3.5%Li 2O, 0-10%Na 2O, 0-9%K 2O, 0-10%R ' 2O (R ' be among Li, Na, the K more than one), 0-20%SiO 2, 0-15%Al 2O 3, 0-10%MgO, 0-7%CaO, 0-12%BaO, 0-5%SrO, 0-15%RO (R is more than one among Mg, Ca, Ba, the Sr), 0-10%ZrO 2, 0-20%Gd 2O 3, 0-5%Bi 2O 3, 0-1%Sb 2O 3, 0-0.5%TiO 2, 0-0.3%Nb 2O 5Composition.
Die forming opticglass of the present invention is that specific refractory power (nd) is the glass more than 35 for 1.75-1.85, Abbe number (vd).Softening temperature is below 700 ℃ in addition, and glass ingredient is difficult to volatilization.In addition, (Δ T={ forming temperature is (10 owing to operating temperature range 0.8Temperature under the pool)-liquidus temperature }) be more than 20 ℃, in the fusion of chunk glass and forming process, do not produce the problem of devitrification pit and striped, can pass through the drop forming mass production.And, reduce less than 0.10% according to the weight in the powder method water tolerance of Japanese optics nitre industry meeting specification JOGIS, reduce less than 0.35% according to the weight in the powder method acid resistance of Japanese optics nitre industry meeting specification JOGIS, have high weather proofing.The internal transmittance of 400nm wavelength (t=10mm) is more than 90.0%, and short wavelength's absorption is little.And basicity is (preferred below 9.5) below 11, can prevent the sticking to mould of glass and press tool when die forming.
Embodiment
In the present invention, so-called basicity is defined as (summation of the summation of the mole number of Sauerstoffatom/cationic intensity of field (Field Strength)) X100.Intensity of field in the formula (Field Strength) (below be labeled as F.S.) can be obtained by following formula.
F.S.＝Z/r 2
Z represents the ion valence mumber, and r represents ionic radius.Z among the present invention, the numerical value of r are with reference to " chemical brief guide basis is adapted and ordered 2 editions (kind Co., Ltd. of ball in 1975 distribution) ".According to the inventor's opinion, basicity is low more, is difficult to more and the mould sticking to mould.The mechanism that regards to the basicity control sticking to mould of glass down describes.
The basicity of glass is had the index of much degree attraction by the positively charged ion in the glass for the electronics of oxygen in the expression glass.In the high glass of basicity, a little less than the electronics attraction of the positively charged ion in the glass to oxygen.Therefore, the glass that basicity is high is being inclined to strong positively charged ion (mould composition) when contacting with the demand electronics, and the glassy phase ratio low with basicity causes that easily positively charged ion is by the intrusion of mould in glass.If invade (diffusion) in glass as the positively charged ion of mould composition, then the mould constituent concentration in the glassy phase of near interface increases.Glassy phase and mould composition difference mutually reduces thus, so affinity between the two increases the glass easy wet mold that becomes.Can think according to such mechanism glass and mould sticking to mould.Therefore basicity is low more, and the mould composition is difficult to invade in the glass more, and glass and mould are got over not sticking to mould.
Specifically, can think if the basicity of glass is below 11, preferred below 9.5, then do not cause sticking to mould.If the basicity of glass surpasses 9.5, then show the tendency of carrying out sticking to mould with mould, if surpass 11, then, damaged the surface accuracy of product because glass and mould carry out sticking to mould, the property produced in batches significantly worsens.
As the concrete compositional system of the glass with above-mentioned characteristic, that suitable is B 2O 3-La 2O 3-ZnO-Ta 2O 5System glass.More specifically, preferably by having in quality %, 5-25%B 2O 3, 15-35%La 2O 3, 10-30%ZnO, 15.5-25%Ta 2O 5The glass of essentially consist form.Usually at B 2O 3-La 2O 3In the system glass,, make it contain a large amount of La in order to obtain high refractive index 2O 3, this is the reason of the easy devitrification of this system glass.Therefore in glass of the present invention, use Ta 2O 5Replace the La of part 2O 3, pass through B simultaneously 2O 3With ZnO amount optimization, can keep high specific refractory power, improve increased devitrification resistance simultaneously.By improving increased devitrification resistance, can add the composition R ' that softening temperature is reduced of requirement in addition 2O.
Narration limits the reason of each composition range as mentioned above.
B 2O 3Be the framework ingredient of glass, have the effect that improves devitrification resistance.Be the composition that improves Abbe number in addition, softening temperature is reduced.B 2O 3Also have the effect that reduces glass basicity, also have the glass that prevents in the die forming and the effect of mould sticking to mould.Its amount is 5-25%, preferred 10-21.5%, more preferably 10-20%, particularly 15-20%.If B 2O 3Surpass 25%, then when glass melting by B 2O 3-R ' 2It is many that the volatile matter that O forms becomes, and encouraged the growth of striped.When contour forming, also produce volatilization in addition and polluted mould, shortened the life-span of mould greatly.And weather proofing significantly worsens.If littler than 5%, then devitrification resistance reduces, and can not fully guarantee operating temperature range.
La 2O 3Be composition, have the effect that does not make Abbe number reduce and improve specific refractory power in addition in order to ensure enough operating temperature ranges.And also have the rising that suppresses softening temperature, and the effect that improves weather proofing.If but a large amount of addings in order to obtain high specific refractory power, then increased devitrification resistance increases, so be necessary to use Ta 2O 5Deng its part is replaced.La 2O 3Amount be 15-35%, preferred 15-29.5%, more preferably 18-29.5%.If La 2O 3Surpass 35%, then increased devitrification resistance uprises, and liquidus temperature rises, so operability reduces significantly.If littler than 15%, then specific refractory power reduces, and weather proofing also worsens in addition.
ZnO has the raising specific refractory power, suppresses B simultaneously 2O 3-La 2O 3The effect of the increased devitrification resistance that system glass is high.Its amount is 10-30%, preferred 15-25%.If ZnO surpasses 30%, then the phase-splitting of glass tendency grow is difficult to obtain uniform glass.If littler than 10%, then specific refractory power reduces, and can not obtain to suppress the devitrification effect in addition, and liquidus temperature rises, and can not fully guarantee operating temperature range.
Ta 2O 5Has the effect that does not make Abbe number reduce and improve specific refractory power.Therefore by with La 2O 3Replacement can improve devitrification resistance.In addition, by an amount of adding, has the B of being suppressed at 2O 3-La 2O 3The effect of phase-splitting takes place in-ZnO system the glass easily.And because few,, also can reduce transmittance hardly, promptly be used in the lens that short wavelength laser uses and also can not cause problem even contain in a large number in the absorption of ultraviolet region.Its amount is preferably 15.5-25%, particularly 15.5-20%.If Ta 2O 5Surpass 25%, then increased devitrification resistance uprises, and operating temperature range narrows down.If littler than 15.5%, then specific refractory power reduces, and the phase-splitting of glass tendency grow is difficult to obtain uniform glass simultaneously.
For softening temperature is reduced, glass of the present invention can contain R ' 2O (R ' be among Li, Na, the K more than one).In the present invention, because can be by using Ta 2O 3Replace the La of part 2O 3Improve increased devitrification resistance, so even contain R ' in large quantities 2O also is difficult to devitrification.
R ' 2O is that its total amount is 0-15% for the composition that softening temperature is reduced, preferred 0-10%, more preferably 0.1-5%.If R ' 2O surpasses 15%, and then liquidus temperature significantly rises, and operating temperature range narrows down, and brings detrimentally affect for the property produced in batches.Weather proofing also significantly worsens in addition.
At R ' 2Li among the O 2The effect maximum that O reduces softening temperature.Its amount is 0-3.5%, preferred 0-3%, more preferably 0.1-3%, but Li 2O has the tendency that increased devitrification resistance height, liquidus temperature uprise, operability worsens, and F.S. reduces in addition, has improved the basicity of glass, causes the sticking to mould with mould when drawing, so be limited in below 3.5%.
Na 2O, K 2O has the effect that softening temperature is reduced, if but contain in large quantities, then when fusion by B 2O 3-R ' 2It is many that the volatile matter that O forms becomes, and encouraged the generation of striped.When contour forming, also produce volatilization in addition and polluted mould, shortened the life-span of mould greatly.Therefore, Na 2The amount of O is restricted to 0-10%, preferred 0-5%, more preferably 0-3%.K similarly 2The amount of O is restricted to 0-9%, preferred 0-5%, more preferably 0-3%.
Glass of the present invention in addition can contain SiO 2, Al 2O 3, MgO, CaO, BaO, SrO, ZrO 2, Gd 2O 3, Bi 2O 3, Sb 2O 3, TiO 2, Nb 2O 5Deng.
Below mentioned component is elaborated.
SiO 2Be the composition that constitutes the glass skeleton, have the effect that improves devitrification resistance, enlarges operating restraint.Also has the effect that improves weather proofing in addition.Its amount is 0-10%, preferred 0.5-8%, more preferably 3-6.5%.If SiO 2Surpass 10%, then specific refractory power significantly reduces, and softening temperature may be above 700 ℃.
Al 2O 3Be and SiO 2Constitute the composition of glass skeleton together, have the effect that improves weather proofing.Preferred its amount is 0-15%, and particularly 0-10% further is 0-5%, the scope that 0-3% is best suited for.Al 2O 3Have the tendency that tendency towards devitrification is increased, but, then be difficult to devitrification, because meltbility does not worsen,, can satisfy in addition as the calling hierarchy of lens with glass so striped and bubble can not remain in the glass if below 15%.
RO (R is Mg, Ca, Ba, Sr) uses as flux, simultaneously at B 2O 3-La 2O 3-ZnO-Ta 2O 5In the system glass, has the effect that Abbe number is reduced and improve specific refractory power.Its total amount is 0-15%, preferred 0-10%.If the RO total amount surpasses 15%, then in preliminary shaping glass melting, forming process, separate out the devitrification pit easily, liquidus temperature raises, and operating temperature range narrows down, and produces the difficulty that becomes in batches.And become acutely by the stripping of glass in grinding washing water and various washing soln, become significantly the rotten of many wet conditions of high temperature lower-glass surface in addition, weather proofing significantly worsens.
MgO is the composition that improves specific refractory power, and for the phase-splitting tendency of reinforced glass, preferably its amount is restricted to below 10%, below 5%, further is 0-2% particularly.
CaO is the composition that improves specific refractory power, and is same with MgO, and for the phase-splitting tendency of reinforced glass, preferably its amount is restricted to below 7%, below 6%, further is below 5% particularly, the scope that 0-3% is best suited for.
BaO is the composition that improves specific refractory power, also has the effect that makes liquidus temperature reduce, improve operability in addition in this glass system.But, owing under the many wet conditions of high temperature, significantly increase by the amount of separating out of glass surface RO composition than other, so if it is contained in a large number, weather proofing that then can the obvious damage the finished product.Therefore, preferably its amount is 0-12%, particularly 0-11%, further is 0-10%, the scope that 0-3% is best suited for.
SrO is the composition that improves specific refractory power, compares with other RO composition, has the effect that reduces liquidus temperature, therefore can enlarge operating temperature range.Compare with BaO in addition, under the many wet conditions of high temperature by glass surface to separate out degree little, can obtain the weather proofing good quality production.But SrO and MgO and CaO are same, if contain in large quantities, then the phase-splitting of glass tendency grow is difficult to obtain uniform glass.The amount of preferred SrO is 0-5%, particularly 0-4.5%, further is 0-2%.
ZrO 2It is the composition that improves specific refractory power, improves weather proofing.In addition, owing to form glass, also has the effect that improves devitrification resistance as intermidate oxide.If but ZrO 2To contain quantitative change many, then softening temperature rises, press formability worsens.ZrO 2Amount be 0-10%, preferred 0-9.5%, more preferably 0.1-9%, the scope that 1-4% is best suited for.
Gd 2O 3It is the composition that improves specific refractory power, improves weather proofing.In addition with ZrO 2Equally, be to have the effect that improves devitrification resistance, the composition that can enlarge operating temperature range, if still contain in large quantities, then the phase-splitting of glass tendency grow is difficult to obtain uniform glass.Gd 2O 3Amount be 0-20%, preferred 5-15%, more preferably 7-13%.
Bi 2O 3Be the composition that improves specific refractory power, in die forming, have the effect that prevents glass and mould sticking to mould, the heating when still being shaped makes the tendency grow of glass coloring, and therefore preferred its amount is below 5%, below 3%, further is below 3% particularly.
Can also add Sb 2O 3As finings.Excessively painted for fear of to glass, Sb 2O 3Amount be below 1%.
TiO 2Adjusting composition as optical constant can contain 0-0.5%.If TiO 2Surpass 0.5%, then will cause Abbe number to reduce, increased devitrification resistance uprises simultaneously, and liquidus temperature rises, and operability reduces.In addition, since big in the absorption of ultraviolet region, so reduce, can hinder the use with lens as the short wavelength in the transmittance of 390nm-440nm.Therefore, preferably do not contain in the present invention as far as possible.
Nb 2O 5Adjusting composition as optical constant can contain 0-0.3%, preferred 0-0.2%.If Nb 2O 5Surpass 0.3%, then increased devitrification resistance uprises, and liquidus temperature rises, and operability significantly reduces.In addition, with TiO 2Equally, big in the absorption of ultraviolet region, if surpass 0.3%, then short wavelength's transmittance reduces.Therefore, in the present invention with TiO 2Equally, preferably do not contain as far as possible.
Except above-mentioned, in the scope of not damaging feature of the present invention, also can add WO 3, P 2O 5Wait other composition.
Because WO 3Forming glass as intermidate oxide, have the effect that improves devitrification resistance, in addition, also is the composition that improves specific refractory power.Its amount is 0-10%, preferred 0-8%, more preferably 0.1-5%.
P 2O 5In die forming, have the effect that prevents glass and mould sticking to mould and reduce liquidus temperature, but because the phase-splitting of glass tendency grow has the tendency that water tolerance reduces, so preferably be restricted to below 5%, particularly below 3%.
PbO and As 2O 3Not preferred aspect environmental protection, Ag and halogen are light reversible color carrier in addition, so preferably do not use in the present invention.Add Y 2O 3, then increased devitrification resistance uprises, and liquidus temperature rises, and operability reduces, so preferably do not contain in the present invention.Contain TeO in a large number 2, then absorbing the tendency grow of short-wavelength light such as blue laser, transmittance reduces, so preferably its amount is limited in below 5%.Lu 2O 3With Y 2O 3Equally, strengthened the tendency towards devitrification of glass.Because price is very high, be not suitable for industrial actual the use in addition.Therefore preferably do not contain in the present invention.
The following describes and use die forming of the present invention to make optical pickup unit lens, photography method with lens etc. with opticglass.
At first will carry out fusion, make melten glass by the composition blended frit of hope.Then drip melten glass and be configured as droplet-like (drop forming) and obtain chunk glass by nozzle tip.Again with the chunk glass grinding that is shaped, perhaps do not carry out grinding and carry out mold pressing, obtain the lens of regulation shape.
Also can adopt melten glass is configured as blank, will be truncated into the method for carrying out mold pressing after the chunk glass grinding of suitable size then and replace carrying out drop forming.
Below, according to embodiment the present invention is described.
Table 1-3 represents embodiments of the invention (sample No.1-13), and table 4 is represented comparative example (sample No.14,15) respectively.
Table 1
????1 ????2 ????3 ????4 ????5
Glass is formed (quality %) B 2O 3??La 2O 3??ZnO ??Ta 2O 5??Li 2O ??Na 2O ??K 2O ??SiO 2??Al 2O 3??MgO ??CaO ??BaO ??SrO ??ZrO 2??Gd 2O 3??Bi 2O 3??Sb 2O 3??WO 3??∑R’ 2O ??∑RO ??11.7 ??23.0 ??22.5 ??17.4 ??1.0 ??- ??- ??5.9 ??1.0 ??- ??1.2 ??1.7 ??- ??1.8 ??12.8 ??- ??- ??- ??1.0 ??2.9 ??13.6 ??22.8 ??22.7 ??17.7 ??1.8 ??- ??- ??5.9 ??- ??- ??- ??1.0 ??- ??2.1 ??12.4 ??- ??- ??- ??1.8 ??1.0 ??16.8 ??21.0 ??19.8 ??18.0 ??0.5 ??2.2 ??- ??4.2 ??2.5 ??- ??- ??0.7 ??1.5 ??1.2 ??9.8 ??0.5 ??0.1 ??1.2 ??2.7 ??2.2 ??17.2 ??21.4 ??20.1 ??17.5 ??0.8 ??- ??1.5 ??3.6 ??- ??0.7 ??2.2 ??- ??- ??1.6 ??10.9 ??1.5 ??- ??1.0 ??2.3 ??2.9 ??17.7 ??22.4 ??21.5 ??18.8 ??1.9 ??- ??- ??6.1 ??1.6 ??- ??- ??1.2 ??- ??1.6 ??7.2 ??- ??- ??- ??1.9 ??1.2
Refractive index n d ??1.8315 ??1.8147 ??1.7795 ??1.7760 ??1.7755
Abbe number vd ??41.3 ??42.1 ??43.8 ??44.7 ??43.8
Softening temperature T s(℃) ??645 ??634 ??663 ??667 ??632
Forming temperature T w(℃) ??1075 ??1055 ??1075 ??1082 ??1050
Liquidus temperature T L(℃) ??1043 ??1028 ??972 ??962 ??992
Operating temperature range Δ T (℃) ??32 ??27 ??103 ??120 ??58
Water tolerance (%) ??0.06 ??0.06 ??0.07 ??0.08 ??0.07
Acid resistance (%) ??0.12 ??0.11 ??0.17 ??0.16 ??0.17
Internal transmittance (%) ??91.1 ??92.2 ??91.5 ??91.7 ??92.5
Basicity ??10.97 ??10.32 ??9.48 ??9.49 ??9.21
Table 2
????6 ????7 ????8 ????9 ????10
Glass is formed (quality %) B 2O 3????La 2O 3????ZnO ????Ta 2O 5????Li 2O ????Na 2O ????K 2O ????SiO 2????Al 2O 3????MgO ????CaO ????BaO ????SrO ????ZrO 2????Gd 2O 3????Bi 2O 3????Sb 2O 3????WO 3????∑R’ 2O ????∑RO ??18.0 ??21.2 ??21.0 ??17.7 ??1.3 ??0.8 ??0.6 ??4.3 ??- ??1.2 ??- ??- ??1.0 ??1.2 ??11.7 ??- ??- ??- ??2.7 ??2.2 ????18.2 ????23.3 ????17.9 ????18.0 ????2.3 ????- ????- ????4.7 ????- ????- ????- ????- ????- ????3.8 ????10.3 ????- ????- ????1.5 ????2.3 ????- ??18.2 ??28.4 ??16.4 ??17.2 ??2.2 ??- ??- ??4.7 ??- ??- ??- ??- ??- ??1.4 ??7.8 ??- ??- ??3.7 ??2.2 ??- ????18.5 ????26.2 ????17.2 ????16.9 ????1.0 ????- ????- ????4.9 ????- ????- ????- ????- ????- ????3.0 ????11.3 ????- ????- ????1.0 ????1.0 ????- ????18.7 ????21.9 ????21.0 ????18.2 ????2.3 ????- ????- ????5.0 ????- ????- ????- ????- ????- ????1.4 ????11.5 ????- ????- ????- ????2.3 ????-
Refractive index n d ??1.7798 ????1.8014 ??1.7994 ????1.8072 ????1.7855
Abbe number vd ??44.2 ????42.5 ??42.4 ????43.0 ????43.5
Softening temperature T s(℃) ??646 ????621 ??619 ????652 ????614
Forming temperature T w(℃) ??1063 ????1030 ??1033 ????1080 ????1028
Liquidus temperature T L(℃) ??1011 ????974 ??962 ????934 ????1006
Operating temperature range Δ T (℃) ??52 ????56 ??71 ????146 ????22
Water tolerance (%) ??0.07 ????0.06 ??0.07 ????0.05 ????0.06
Acid resistance (%) ??0.17 ????0.16 ??0.17 ????0.13 ????0.18
Internal transmittance (%) ??92.0 ????92.3 ??92.2 ????91.4 ????92.4
Basicity ??9.27 ????9.21 ??9.21 ????9.01 ????9.06
Table 3
????11 ????12 ????13
Glass is formed (quality %) B 2O 3????La 2O 3????ZnO ????Ta 2O 5????Li 2O ????Na 2O ????K 2O ????SiO 2????Al 2O 3????MgO ????CaO ????BaO ????SrO ????ZrO 2????Gd 2O 3????Bi 2O 3????Sb 2O 3????WO 3????∑R’ 2O ????∑RO ????18.8 ????27.6 ????16.3 ????17.0 ????1.2 ????- ????- ????5.1 ????- ????- ????- ????- ????- ????2.8 ????11.2 ????- ????- ????- ????1.2 ????- ????18.9 ????22.0 ????24.1 ????15.9 ????2.2 ????- ????- ????4.2 ????- ????- ????- ????- ????- ????1.5 ????11.2 ????- ????- ????- ????2.2 ????- ????19.2 ????18.5 ????23.7 ????19.7 ????2.0 ????- ????- ????4.5 ????- ????- ????- ????- ????- ????1.7 ????10.7 ????- ????- ????- ????2.0 ????-
Refractive index n d ????1.8032 ????1.7849 ????1.7853
Abbe number vd ????43.6 ????43.6 ????42.9
Softening temperature T s(℃) ????650 ????599 ????618
Forming temperature T w(℃) ????1071 ????1038 ????1040
Liquidus temperature T L(℃) ????946 ????1017 ????983
Operating temperature range Δ T (℃) ????125 ????21 ????57
Water tolerance (%) ????0.05 ????0.06 ????0.07
Acid resistance (%) ????0.15 ????0.17 ????0.20
Internal transmittance (%) ????91.6 ????91.7 ????92.2
Basicity ????8.94 ????9.08 ????9.98
Table 4
????14 ????15
Glass is formed (quality %) B 2O 3??La 2O 3??ZnO ??Ta 2O 5??Li 2O ??Na 2O ??K 2O ??SiO 2??Al 2O 3??MgO ??CaO ??BaO ??SrO ??ZrO 2??Gd 2O 3??Bi 2O 3??Sb 2O 3??WO 3??Yb 2O 3??As 2O 3??∑R’ 2O ??∑RO ????15.9 ????37.5 ????15.7 ????16.3 ????2.1 ????- ????- ????2.9 ????- ????- ????- ????- ????- ????1.2 ????8.4 ????- ????- ????- ????- ????- ????2.1 ????- ????26.0 ????22.5 ????5.7 ????13.3 ????1.9 ????- ????- ????- ????- ????- ????- ????1.1 ????- ????6.8 ????20.6 ????- ????- ????- ????2.0 ????0.2 ????1.9 ????1.1
Refractive index n d ????1.8279 ????1.7948
Abbe number vd ????43.2 ????45.3
Softening temperature T s(℃) ????621 ????650
Forming temperature T w(℃) ????＜1100 ????＜1070
Liquidus temperature T L(℃) ????1100 ????1070
Operating temperature range Δ T (℃) ????× ????×
Water tolerance (%) ????0.04 ????0.09
Acid resistance (%) ????0.10 ????0.30
Internal transmittance (%) ????90.3 ????91.2
Basicity ????9.90 ????7.92
Each sample is following to be prepared.Composition at first as shown in Table mixes frit, uses platinum crucible 1400 ℃ of following fusions 3 hours.After the fusion, liquation is flowed on carbon plate, after annealing, make the sample that is fit to each mensuration again.
For the sample that obtains, measure specific refractory power (nd), Abbe number (vd), softening temperature (T s), forming temperature (T w), liquidus temperature (T L), operating temperature range (Δ T), water tolerance and acid resistance, the internal transmittance under wavelength 400nm (t=10mm).Calculate basicity in addition.These results have been expressed in each table.
As seen from the table, embodiments of the invention are that the specific refractory power of each sample of No.1-13 is 1.7755-1.8315, and Abbe number is more than 41.3, and softening temperature is below 667 ℃.Operating temperature range is more than 21 ℃ in addition, and operability is good.And the weight in the water tolerance is reduced to below 0.08%, and the weight in the acid resistance is reduced to below 0.20%, and weather proofing is good., good for the internal transmittance (t=10mm) of wavelength 400nm for seeing through of short-wavelength light also more than 91%.Basicity can be thought to be difficult to cause and the mould sticking to mould below 10.97 in addition.
In contrast, comparative example is that No.14,15 can not guarantee operating temperature range.
Specific refractory power (nd) is used the measured value of the d line (587.6nm) of helium lamp is represented.
The value of the specific refractory power of the C line (656.3nm) of the specific refractory power of the above-mentioned d line of Abbe number (vd) use and the F line (486.1nm) of hydrogen lamp, identical hydrogen lamp is calculated by Abbe number (v d)={ (nd-1)/(nF-nC) } formula.
Softening temperature T sMeasure by fiber elongation method according to JIS R-3104.
As follows the obtaining of operating temperature range Δ T.At first measure forming temperature T by the lifting the ball method w, obtain and be equivalent to 10 0.8The temperature of pool.Liquidus temperature T in addition LBy sample is pulverized is the Powdered of 297-500 μ m, in the boat of the platinum system of packing into after the sieve grain, keeps cooling off in air after 24 hours in having the electric furnace of thermograde, and the use opticmicroscope is obtained the position of separating out of devitrification and measured.The forming temperature T that obtains like this wWith liquidus temperature T LDifference as operating temperature range Δ T.
Water tolerance and acid resistance are according to Japanese optics nitre industry meeting specification 06-1975, it is granularity 420-590 μ m that glass specimen is pulverized, in its proportion gram of weighing and the platinum cage of packing into, put it in the flask that reagent is housed and handled 60 minutes in the boiling water-bath, the quality of calculating the powder glass after the processing reduces (weight %).The reagent that uses in the water tolerance evaluation is the pure water of pH regulator to 6.5-7.5, and the reagent that uses in the acid resistance evaluation is the aqueous nitric acid that is adjusted to 0.01N.
The transmittance of glass is represented with the internal transmittance that does not contain reflection loss.Internal transmittance uses following formula to calculate by the transmittance of the reflection loss of the sample that comprises thickness t=3mm and 10mm.
Internal transmittance=EXP[(1nT 3mm-1nT 10mm)/Δ t * L]
T 3mm: the transmittance of the sample of t=3mm (comprising reflection loss)
T 10mmThe transmittance of the sample of t=10mm (comprising reflection loss)
Δ t: the thickness difference of sample (mm)
L：10mm
Mensuration is two kinds of thickness that glass specimen are processed as 30 * 30 * 3mm and 30 * 30 * 10mm, and the face of injecting and the outgoing plane with transmitted light carries out mirror grinding respectively.
Basicity is to calculate according to the formula of (summation of the summation of the mole number of Sauerstoffatom/cationic intensity of field (FieldStrength)) * 100.Intensity of field in the formula (Field Strength) (below be labeled as F.S.) is obtained by following formula.
F.S.＝Z/r 2
Z represents the ion valence mumber, and r represents ionic radius.And the numerical value of the Z among the present invention, r is with reference to " chemical brief guide basis is adapted and ordered 2 editions (kind Co., Ltd. of ball in 1975 distribution) ".
As mentioned above, opticglass of the present invention has the optical pickup unit lens that are used for CD, MD, DVD and other various optical disk systems, video camera and typical CCD camera photography with the specific refractory power (nd) of the 1.75-1.85 of optical lenses such as lens, the Abbe number (vd) more than 35.Softening temperature is low in addition, and glass ingredient is difficult to volatilization, so the deterioration and the pollution of forming accuracy reduction and mould can not take place.And operating temperature range is wide, and the batch process of preliminary shaping glass is good, and weather proofing is good simultaneously, so rerum natura deterioration and envenomation can not take place in the use of manufacturing process and product.In addition owing to few, so short wavelength's transmittance is good in the absorption of ultraviolet region.And because basicity is low, with mould sticking to mould not, batch process property is very good when punching press.Therefore be suitable as die forming opticglass.

Claims (9)

1, die forming opticglass, it is a specific refractory power (nd) for 1.75-1.85, Abbe number (vd) are, softening temperature is, lead-free die forming opticglass more than 35 below 700 ℃, is characterised in that Δ T={ forming temperature is (10 0.8Temperature under the pool)-and liquidus temperature } be more than 20 ℃, reduce less than 0.10% according to the weight in the powder method water tolerance of Japanese optics nitre industry meeting specification JOGIS, reduce less than 0.35% according to the weight in the powder method acid resistance of Japanese optics nitre industry meeting specification JOGIS, the internal transmittance of 400nm wavelength (t=10mm) is more than 90.0%, and the basicity of glass is below 11.
2. the die forming opticglass of claim 1 is characterised in that by B 2O 3-La 2O 3-ZnO-Ta 2O 5System glass is formed.
3. the die forming opticglass of claim 2 is characterised in that to have in quality %, 5-25%B 2O 3, 15-35%La 2O 3, 10-30%ZnO, 15.5-25%Ta 2O 5Composition.
4. die forming opticglass is characterised in that, uses in the opticglass at the die forming of claim 3, also has in quality %, 0-10%R ' 2The composition of O (R ' be among Li, Na, the K more than one).
5. die forming opticglass is characterised in that, uses in the opticglass at the die forming of claim 3, also has in quality %, 0-3.5%Li 2O, 0-10%Na 2O, 0-9%K 2The composition of O.
6. die forming opticglass is characterised in that, uses in the opticglass at the die forming of claim 3, also has in quality %, 0-10%SiO 2, 0-15%Al 2O 3, 0-10%MgO, 0-7%CaO, 0-12%BaO, 0-5%SrO, 0-10%ZrO 2, 0-20%Gd 2O 3, 0-5%Bi 2O 3, 0-1%Sb 2O 3Composition.
7. die forming opticglass is characterised in that, uses in the opticglass at the die forming of claim 3, also has in quality % the composition of 0-15%RO (R is more than one among Mg, Ca, Ba, the Sr).
8. die forming opticglass is characterised in that, uses in the opticglass at the die forming of claim 3, also has in quality %, 0-0.5%TiO 2, 0-0.3%Nb 2O 5Composition.
9. die forming opticglass is characterised in that, has in quality %, 5-25%B 2O 3, 15-35%La 2O 3, 10-30%ZnO, 15.5-25%Ta 2O 5, 0-3.5%Li 2O, 0-10%Na 2O, 0-9%K 2O, 0-10%R ' 2O (R ' be among Li, Na, the K more than one), 0-20%SiO 2, 0-15%Al 2O 3, 0-10%MgO, 0-7%CaO, 0-12%BaO, 0-5%SrO, 0-15%RO (R is more than one among Mg, Ca, Ba, the Sr), 0-10%ZrO 2, 0-20%Gd 2O 3, 0-5%Bi 2O 3, 0-1%Sb 2O 3, 0-0.5%TiO 2, 0-0.3%Nb 2O 5Composition.
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WO2006115183A1 (en) * 2005-04-22 2006-11-02 Ohara Inc. A glass composition
CN102171153A (en) * 2008-10-21 2011-08-31 日本电气硝子株式会社 Optical glass
CN109415240A (en) * 2016-06-29 2019-03-01 株式会社小原 Optical glass, preform and optical module
CN110835233A (en) * 2018-08-16 2020-02-25 Hoya株式会社 Optical glass, optical element blank and optical element

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CN86106629A (en) * 1986-09-27 1988-04-06 中国科学院上海光学精密机械研究所 Glass of high refractive index
JP2001159702A (en) * 1999-12-01 2001-06-12 Nippon Sheet Glass Co Ltd Distributed index lens
JP4093524B2 (en) * 2001-02-20 2008-06-04 Ｈｏｙａ株式会社 Optical glass, press-molding preform and optical parts

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006115183A1 (en) * 2005-04-22 2006-11-02 Ohara Inc. A glass composition
US8507394B2 (en) 2005-04-22 2013-08-13 Ohara Inc. Glass composition
CN102171153A (en) * 2008-10-21 2011-08-31 日本电气硝子株式会社 Optical glass
CN109415240A (en) * 2016-06-29 2019-03-01 株式会社小原 Optical glass, preform and optical module
CN110835233A (en) * 2018-08-16 2020-02-25 Hoya株式会社 Optical glass, optical element blank and optical element

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