US20050197243A1 - Optical glass, precision press-molding preform, process for production thereof, optical element and process for the production thereof - Google Patents

Optical glass, precision press-molding preform, process for production thereof, optical element and process for the production thereof Download PDF

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Publication number
US20050197243A1
US20050197243A1 US11/065,279 US6527905A US2005197243A1 US 20050197243 A1 US20050197243 A1 US 20050197243A1 US 6527905 A US6527905 A US 6527905A US 2005197243 A1 US2005197243 A1 US 2005197243A1
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Prior art keywords
glass
preform
optical
molding
precision press
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Kazutaka Hayashi
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Hoya Corp
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Hoya Corp
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Publication of US20050197243A1 publication Critical patent/US20050197243A1/en
Priority to US12/007,081 priority Critical patent/US7622409B2/en
Priority to US12/588,235 priority patent/US7932197B2/en
Abandoned legal-status Critical Current

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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
    • C03C3/12—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
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/02—Special cores
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B69/00—Training appliances or apparatus for special sports
    • A63B69/0046—Training appliances or apparatus for special sports for bowling
    • 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

Definitions

  • the present invention relates to an optical glass, a precision press-molding preform formed of the above glass, a process for the production of the preform, an optical element formed of the above optical glass and a process for the production of the optical element.
  • a high-refractivity low-dispersion glass is in great demand as a material for optical elements such as various lenses.
  • a dense tantalum flint glass TaSF17 is known, which is described in “Glass Composition Hand Book” (Hiroshi Ogawa and Shin-ei Ogawa, issued by Japan Glass Product Industrial Society, 1991, page 106).
  • an optical glass comprising, as essential components, B 2 O 3 , La 2 O3, Gd 2 O 3 and ZnO and having a refractive index (nd) of over 1.86, an Abbe's number ( ⁇ d) of less than 35 and a glass transition temperature (Tg) of 630° C. or lower,
  • an optical glass comprising, by mol %, 15-45% B 2 O 3 , 5-20% La 2 O 3 , 1-20% Gd 2 O 3 , 10-45% ZnO, 0-15% WO 3 , 0-10% Ta 2 O 5 , 0-10% Nb 2 O 5 , 0-20% TiO 2 , 0-20% SiO 2 , 0-15% Li 2 O, 0-10% Na 2 O, 0-10% K 2 O, 0-10% MgO, 0-10% CaO, 0-10% SrO, 0-10% BaO 0-8% Y 2 O 3 , 0-8% Yb 2 O 3 ,
  • the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is 10 to 30%, 0-10% ZrO 2 , 0-10% Bi 2 O 3 , and 0-1% Sb 2 O 3 , and having a refractive index (nd) of over 1.86, an Abbe's number ( ⁇ d) of less than 35 and a glass transition temperature (Tg) of 630° C. or lower,
  • an optical glass comprising, by mol %, 15-45% B 2 O 3 , 5-20% La 2 O 3 , 1-20% Gd 2 O 3 , 10-45% ZnO, 0-15% WO 3 , 0-10% Ta 2 O 5 , 0-10% Nb 2 O 5 , 0-20% TiO 2 , 0-20% SiO 2 , 0-15% Li 2 O, 0-10% Na 2 O, 0-10% K 2 O, 0-10% MgO, 0-10% CaO, 0-10% SrO, 0-10% BaO 0-8% Y 2 O 3 , 0-8% Yb 2 O 3 ,
  • the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is 10 to 30%, 0-less than 0.5% ZrO 2 , 0-10% Bi 2 O 3 , and 0-1% Sb 2 O 3 , and having a refractive index (nd) of over 1.86, an Abbe's number ( ⁇ d) of 35 to less than 39.5 and a glass transition temperature (Tg) of 630° C. or lower,
  • a process for the production of a precision press-molding preform which comprises separating a molten glass gob having a predetermined weight from a molten glass flowing out of a pipe, and shaping the glass gob into a preform formed of the optical glass recited in any one of the above (1) to (3),
  • (6) a process for the production of a precision press-molding preform, which comprises forming a shaped glass from a molten glass and processing said shaped glass to produce a preform formed of the optical glass recited in any one of the above (1) to (3),
  • an optical glass which has a high refractive index and low dispersion and has a low glass transition temperature and which has the property of being softened at a low temperature so that a preform formed therefrom is precision press-moldable, and there can be obtained a precision press-molding preform formed of the above optical glass and an optical element which is formed of the above optical glass.
  • FIG. 1 is a schematic drawing of a precision press-molding apparatus used in Examples of the present invention.
  • optical glass of the present invention will be explained first.
  • the optical glass of the present invention includes three embodiments of the optical glass.
  • the optical glass characteristically comprises B 2 O 3 , La 2 O 3 , Gd 2 O 3 and ZnO as essential components and has a refractive index (nd) of over 1.86, an Abbe's number ( ⁇ d) of less than 35 and a glass transition temperature (Tg) of 630° C. or lower.
  • B 2 O 3 is an essential component for constituting a glass network
  • La 2 O 3 and Gd 2 O 3 are essential components for imparting the optical glass with high-refractivity low-dispersion properties. When these two components are co-present, the glass is more improved in stability.
  • ZnO is an essential component for imparting the glass with the property of being softened at a low temperature without decreasing the refractive index.
  • the optical glass according to the first embodiment of the present invention contains the above essential components, so that it has optical properties represented by a refractive index (nd) of over 1.86, preferably 1.861 or more and an Abbe's number ( ⁇ d) of less than 35, preferably 25 to less than 35, and that it has high glass stability and the property of being softened at a low temperature as is suitable for precision press-molding, or a glass transition temperature (Tg) of 630° C. or lower, preferably 620° C. or lower, more preferably less than 600° C.
  • a refractive index (nd) of over 1.86, preferably 1.861 or more and an Abbe's number ( ⁇ d) of less than 35, preferably 25 to less than 35
  • Tg glass transition temperature
  • optical glass according to a second embodiment of the present invention will be explained below.
  • optical glass according to the second embodiment of the present invention is included in (or a variant of) the above optical glass according to the first embodiment of the present invention, and the optical glass according to the second embodiment of the present invention comprises, by mol %, 15-45% B 2 O 3 , 5-20% La 2 O 3 , 1-20% Gd 2 O 3 , 10-45% ZnO, 0-15% WO 3 , 0-10% Ta 2 O 5 , 0-10% Nb 2 O 5 , 0-20% TiO 2 , 0-20% SiO 2 , 0-15% Li 2 O, 0-10% Na 2 O, 0-10% K 2 O, 0-10% MgO, 0-10% CaO, 0-10% SrO, 0-10% BaO 0-8% Y 2 O 3 , 0-8% Yb 2 O 3 ,
  • the total content of La 2 O3, Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is 10 to 30%, 0-10% ZrO 2 , 0-10% Bi 2 O 3 , and 0-1% Sb 2 O 3 , and has a refractive index (nd) of over 1.86, an Abbe's number ( ⁇ d) of less than 35 and a glass transition temperature (Tg) of 630° C. or lower.
  • B 2 O 3 is an essential component for forming the glass network. When it is introduced to excess, the refractive index (nd) of the glass is decreased, so that the content thereof is 15 to 45%.
  • the content of B 2 O 3 is preferably 18 to 43%, more preferably 20 to 40%.
  • La 2 O 3 is an essential component for imparting the glass with high-refractivity low-dispersion properties. When it is introduced to excess, the stability of the glass is decreased, so that the content thereof is 5 to 20%.
  • the content of La 2 O 3 is preferably 6 to 19%, more preferably 7 to 18%.
  • Gd 2 O 3 is also an essential component for imparting the glass with high-refractivity low-dispersion properties. When it is introduced to excess, however, the glass stability is decreased, so that the content thereof is 1 to 20%. As is already explained, Gd 2 O 3 , being co-present with La 2 O 3 , has the effect of improving the glass stability more than it is present alone.
  • the content of Gd 2 O 3 is preferably 1 to 18%, more preferably 1 to 16%.
  • ZnO is an essential component for imparting the glass with the property of being softened at a low temperature while maintaining the high-refractivity. However, when it is introduced to excess, the glass is degraded in stability, so that the content thereof is adjusted to 10 to 45%.
  • the content of ZnO is preferably 12 to 43%, more preferably 15 to 40%.
  • WO 3 works to improve the glass stability and decrease the liquidus temperature of the glass. However, when it is introduced to excess, the glass is degraded in stability and is colored, so that the content of WO 3 is adjusted to 0 to 15%.
  • the content of WO 3 is preferably 1 to 15%, more preferably 2 to 13%.
  • Ta 2 O 5 is a component for increasing the refractive index of the glass. However, when it is introduced to excess, the glass is degraded in stability, so that the content thereof is adjusted to 0 to 10%.
  • the content of Ta 2 O 5 is preferably 0 to 8%, more preferably 0 to 7%.
  • Nb 2 O 5 is also a component for increasing the refractive index of the glass. However, when it is introduced to excess, the glass is degraded in stability, and the liquidus temperature of the glass is increased, so that the content thereof is adjusted to 0 to 10%.
  • the content of Nb 2 O 5 is preferably 0 to 8%, more preferably 0 to 7%.
  • TiO 2 is also a component for increasing the refractive index of the glass. However, when it is introduced to excess, the glass is degraded in stability and is also colored, so that the content thereof is adjusted to 0 to 20%.
  • the content of TiO 2 is preferably 0 to 19%, more preferably 1 to 18%.
  • the total content of WO 3 , Ta 2 O 5 , Nb 2 O 5 and TiO 2 is adjusted preferably to over 10% by weight, more preferably to 11% by weight or more, particularly preferably to 12% by weight or more.
  • SiO 2 works to improve the glass in stability. However, when it is introduced to excess, the refractive index of the glass is decreased, and the glass transition temperature is increased. The content thereof is therefore adjusted to 0 to 20%.
  • the content of SiO 2 is preferably 0 to 15%, more preferably 0 to 10%.
  • the molar ratio of the content of B 2 O 3 to the total content of B 2 O 3 and SiO 2 is adjusted to from 0.80 to 1.00, more preferably to from 0.82 to 1.00.
  • Li 2 O highly effectively decreases the glass transition temperature. However, when it is introduced to excess, the refractive index of the glass is decreased, and the glass is also degraded in stability. It is therefore preferred to adjust the content of Li 2 O to 0 to 15%. When priority is given to imparting the glass with the property of being softened at a low temperature, it is more preferred to adjust the content thereof to 0.1 to 15%. Further, when priority is given to the property of high refractivity, Li 2 O may not be introduced. It can be therefore determined depending upon purposes whether or not Li 2 O is to be introduced.
  • Na 2 O and K 2 O work to improve the glass in meltability. However, when they are introduced to excess, the glass is degraded in refractivity and stability, so that the content of each of these is adjusted to 0 to 10%.
  • the content of each of these is preferably 0 to 8%, more preferably 0 to 6%.
  • MgO, CaO and SrO also work to improve the glass in meltability. However, when they are introduced to excess, the glass is degraded in refractivity and stability, so that the content of each of these is adjusted to 0 to 10%.
  • the content of each of these is preferably 0 to 8%, more preferably 0 to 6%.
  • BaO works to increase the refractive index of the glass. However, when it is introduced to excess, the glass is degraded in stability, so that the content thereof is adjusted to 0 to 10%.
  • the content of BaO is preferably 0 to 8%, more preferably 0 to 6%.
  • Y 2 O 3 and Yb 2 O 3 work to impart the glass with the properties of high-refractivity and low-dispersion. However, when they are introduced to excess, the glass is degraded in stability, so that the content thereof is adjusted to 0 to 8%.
  • the content of each of these is preferably 0 to 7%, more preferably 0 to 6%.
  • Y 2 O 3 and Yb 2 O 3 work to promote the improvement of the glass in stability.
  • the total content of rare earth oxides in the glass is adjusted to 10 to 30 mol %.
  • it is preferred to preclude Lu 2 O 3 since Lu 2 O 3 is an expensive component.
  • the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is adjusted to 10 to 30%.
  • the above total content is preferably 11 to 28%, more preferably 12 to 24%.
  • ZrO 2 works to increase the refractive index of the glass. However, when it is introduced to excess, the glass is degraded in stability, and the liquidus temperature of the glass is increased, so that the content thereof is adjusted to 0 to 10%.
  • the content of ZrO 2 is preferably 0 to 9%, more preferably 0 to 8%.
  • the total content of WO 3 , Ta 2 O 5 , Nb 2 O 5 , TiO 2 and ZrO 2 is adjusted to 2 to 40 mol %, more preferably, to 5 to 35 mol %.
  • Bi 2 O 3 works to increase the refractive index of the glass and improve the glass in stability. However, when it is introduced to excess, the glass is colored, so that the content thereof is adjusted to 0 to 10%.
  • the content of Bi 2 O 3 is preferably 0 to 8%, more preferably 0 to 5%.
  • the total content of the above glass components including a refining agent is adjusted to over 95%, more preferably to over 98%, still more preferably to over 99%, and particularly preferably to 100%.
  • GeO 2 and Ga 2 O 3 work to increase the refractive index of the glass and improve the glass in stability. Since, however, they are expensive components, it is preferred to adjust the content of each of these to 0 to 10%, more preferably to 0 to 1%, and it is still more preferred to introduce none of these.
  • a refining agent may be added in a total amount of 0 to 1%.
  • a refining agent may be added to excess, the molding surface of a press mold, particularly a mold release film, may be damaged during precision press-molding. It is therefore required to be careful in adding the refining agent.
  • the refining agent can be selected, for example, from Sb 2 O 3 or As 2 O 3 . In view of environmental concerns, it is imperative to avoid the use of As 2 O 3 .
  • the content of Sb 2 O 3 is preferably 0 to 1%.
  • F can be introduced as well.
  • F is volatilized from the glass to cause the occurrence of striae and make the optical constants vary, so that it is preferred not to introduce F.
  • Cu, Fe, Cr, etc. are not introduced.
  • Cd is not introduced.
  • the optical glass according to the second embodiment of the present invention has optical properties represented by a refractive index (nd) of over 1.86, preferably 1.861 or more and an Abbe's number ( ⁇ d) of less than 35, preferably 25 to less than 35, and it has high glass stability and the property of being softened at a low temperature as is suitable for precision press-molding, or a glass transition temperature (Tg) of 630° C. or lower, preferably 620° C. or lower, more preferably less than 600° C.
  • nd refractive index
  • ⁇ d Abbe's number
  • the optical glass according to a third embodiment of the present invention comprises, by mol %, 15-45% B 2 O 3 , 5-20% La 2 O 3 , 1-20% Gd 2 O 3 , 10-45% ZnO, 0-15% WO 3 , 0-10% Ta 2 O 5 , 0-10% Nb 2 O 5 , 0-20% TiO 2 , 0-20% SiO 2 , 0-15% Li 2 O, 0-10% Na 2 O, 0-10% K 2 O, 0-10% MgO, 0-10% CaO, 0-10% SrO, 0-10% BaO 0-8% Y 2 O 3 , 0-8% Yb 2 O 3 ,
  • the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is 10 to 30%, 0-less than 0.5% ZrO 2 , 0-10% Bi 2 O 3 , and 0-1% Sb 2 O 3 , and has a refractive index (nd) of over 1.86, an Abbe's number ( ⁇ d) of 35 to less than 39.5 and a glass transition temperature (Tg) of 630° C. or lower.
  • the optical glass according to the third embodiment of the present invention differs from the optical glass according to the second embodiment of the present invention only in that the content of ZrO 2 in the glass composition is 0 to less than 0.5 mol %.
  • ZrO 2 is one of components that impart the glass with the properties of high-refractivity and low-dispersion, it also works to increase the liquidus temperature of the glass.
  • an optical glass having the property of relatively low dispersion represented by an Abbe's number ( ⁇ d) of less than 35 it is required to add a large amount of rare earth components such as La 2 O 3 , Gd 2 O 3 , and the like.
  • the rare earth components such as La 2 O 3 , Gd 2 O 3 , and the like are also components that increase the liquidus temperature.
  • ZrO 2 is added to a glass containing a large amount of the above rare earth components, the liquidus temperature of the glass is further increased, so that the viscosity of the glass during shaping is decreased, which impairs the shapeability.
  • the Abbe's number ( ⁇ d) is required to be less than 35, therefore, it is preferred to adjust the content of ZrO 2 to less than 0.5 mol %, and it is more preferred to introduce no ZrO 2 .
  • the optical glass according to the third embodiment of the present invention has optical properties represented by a refractive index (nd) of over 1.86, preferably 1.861 or more and an Abbe's number ( ⁇ d) of 35 to less than 39.5 and has high glass stability and the property of being softened at a low temperature as is suitable for precision press-molding, or a glass transition temperature (Tg) of 630° C. or lower, preferably 620° C. or lower, more preferably less than 600° C.
  • nd refractive index
  • ⁇ d Abbe's number
  • the upper limit of the refractive index (nd) is not critical, while the upper limit of the refractive index (nd) is preferably 1.92 or less for obtaining a glass having excellent stability.
  • the optical glass according to any one of the first to third embodiments of the present invention can be preferably used for producing a precision press-molding preform and for producing an optical element.
  • the precision press-molding preform (the preform for precision press-molding, to be referred to as “preform” hereinafter), provided by the present invention, is formed of the optical glass according to any one of the first, second and third embodiments of the present invention.
  • the preform is a shaped glass material having a weight equivalent to the weight of a press-molded product, and it has a proper form to which the optical glass is shaped depending upon the form of a press-molded product. Examples of the form include the form of a sphere, the form of an ellipsoid of revolution, and the like.
  • the preform is heated so as to have a viscosity that permits press-molding, and then subjected to press-molding.
  • the form of the preform including the above ellipsoid of revolution preferably has one axis of rotation symmetry.
  • the above form having one axis of rotation symmetry includes a form having a smooth contour free of any corner or dent in a cross section including the above axis of rotation symmetry, such as a form having the contour of an ellipse in which the minor axis corresponds to the axis of rotation symmetry in the above cross section.
  • the angle ⁇ monotonously increases from 90°, then decreases monotonously and then decreases monotonously to come to be 90° at the other point where the contour crosses the axis of revolution symmetry.
  • the above preform may have a thin film such as a mold release film on its surface as required.
  • a mold release film include a carbon-containing film and a self-assembled film.
  • the above preform can be press-molded to give an optical element having the predetermined optical constants.
  • the process for the production of a preform includes two embodiments of the process.
  • the first embodiment of the process comprises separating a molten glass gob having a predetermined weight from a molten glass flowing out of a pipe and shaping the above glass gob into a preform formed of the optical glass according to the first, second or third embodiment of the present invention.
  • the preform is shaped at a stage when the glass in a molten state is cooled.
  • the glass can be shaped into the preform that can be used as such without processing the glass with a machine after the glass solidifies.
  • the above process has advantages that machine processing procedures such as cutting, grinding and polishing are not required.
  • the preform can be shaped as a preform having a smooth surface. Further, the entire surface is a surface formed by solidification of the glass in a molten state, so that a smooth surface free of fine scratches caused by polishing or latent scratches can be obtained.
  • the preform surface is preferably free of any cutting mark called “shear mark”.
  • the shear mark is generated when a molten glass flowing out of a pipe is cut with a cutting blade.
  • shear mark remains at a stage after the preform is precision press-molded, such a mark portion is defective. It is therefore preferred to preclude the shear mark at a stage where the preform is shaped.
  • the method for separating a molten glass gob using no cutting blade so that no shear mark is formed includes a method in which a molten glass is dropped from a flow pipe, or a method in which the forward end portion of a molten glass flow from a flow pipe is supported and the support is removed at a time when a molten glass gob having a predetermined weight can be separated (to be referred to as “descent-separation method”).
  • the molten glass gob is separated at a narrow portion formed between the forward end portion and the flow pipe side portion of the molten glass flow, and the molten glass gob having a predetermined weight can be obtained.
  • the molten glass gob is shaped into a form suitable for press-molding, whereby the preform can be obtained.
  • the thus-separated molten glass gob having a predetermined weight is shaped into a preform while the gob is caused to float by applying air (gas) pressure or while the gob is caused to nearly float so that the contact of the gob to a shaping mold is reduced (to be referred to as “float-shaping” hereinafter). Since the float-shaping can decrease a contact between a high-temperature glass and a shaping mold, cracking of the preform can be prevented. Further, a preform of which the entire surface is a free surface can be produced.
  • the second embodiment of the process comprises forming a shaped glass from a molten glass and processing the above shaped glass to produce a preform formed of the optical glass according to the first, second or third embodiment of the present invention.
  • the above process may employ a constitution in which a molten glass is cast into a mold (die) to form a shaped glass material formed of the above optical glass and the shaped glass material is processed with a machine to obtain a preform having a predetermined weight. Before processed with a machine, the glass may be annealed to fully remove strains so that the glass is not broken.
  • high-quality preforms free of defects such as devitrification, striae, scratches, breaking, etc. can be produced from a glass in a molten state since the optical glass according to any one of the first, second and third embodiments of the present invention has high glass stability.
  • optical element of the present invention will be explained below.
  • the optical element of the present invention has a characteristic feature that it is formed of the optical glass according to any one of the first, second and third embodiments of the present invention.
  • various optical elements based on optical properties that the optical glasses according to the first to third embodiments of the present invention have.
  • the optical elements include various lenses such as a spherical lens, an aspherical lens, a microlens, etc., a diffraction grating, a lens with a diffraction grating, a lens array, a prism, and the like.
  • the optical element may be provided with an optical thin film such as an anti-reflection film, a total reflection film, a partial reflection film or a film having spectral characteristics as required.
  • an optical thin film such as an anti-reflection film, a total reflection film, a partial reflection film or a film having spectral characteristics as required.
  • the process for the production of an optical element comprises heating the above preform and precision press-molding the preform.
  • optical-function surface for example, an aspherical surface of an aspherical lens or a spherical surface of a spherical lens corresponds to the optical-function surface.
  • the optical-function surface can be formed by precisely transferring the molding surface of a press mold to a glass, and the processing procedures with a machine such as grinding, polishing, etc., are not required for finishing the optical-function surface.
  • the process for the production of an optical element is suitable for producing a lens, a lens array, a diffracting grating, a prism, etc., and is the most suitable for highly productively producing aspherical lenses.
  • each optical glass has a low glass transition temperature (Tg), and the temperature for the press-molding can be therefore decreased, so that damage to the molding surface of a press mold can be reduced and that the lifetime of the press mold can be increased.
  • Tg glass transition temperature
  • the glass constituting the preform has high stability, the devitrification of the glass in re-heating and pressing steps can be effectively prevented. Further, a series of steps starting at melting of the glass and ending with obtaining of a final product can be highly productively carried out.
  • a non-oxidizing atmosphere is employed as an atmosphere for the precision press-molding for maintaining the molding surface of a press mold in an excellent state.
  • the non-oxidizing gas is preferably selected from nitrogen or a gas mixture of nitrogen with hydrogen.
  • the precision press-molding for use in the process for the production of an optical element in the present invention includes two embodiments of the process, and the two embodiments will be explained below.
  • the process as a first embodiment comprises heating a press mold and a preform together and pressing the preform with the press mold.
  • a precision press-molded product is cooled to a temperature at which the above glass exhibits a viscosity of 10 12 dPa ⁇ s or higher, preferably 10 14 dPa ⁇ s or higher, more preferably 10 16 dPa ⁇ S or higher before it is taken out of the press mold.
  • the form of molding surface of the press mold can be precisely transferred to the glass, and a precision press-molded product can be taken out of the press mold without any deformation.
  • the process as a second embodiment comprises introducing a preform preheated separately from a press mold into the preheated press mold, and precision press-molding the preform.
  • the preform is preheated before it is introduced into the press mold, so that optical elements free of surface defects and excellent in surface accuracy can be produced while the cycle time can be decreased.
  • the temperature for preheating the press mold is set at a temperature lower than the temperature for preheating the preform.
  • the attrition of the above press mold can be reduced.
  • the preform is preheated to a temperature at which the glass constituting the preform exhibits a viscosity of 10 9 dPa ⁇ S or less, more preferably less than 10 9 dPa ⁇ S.
  • the preform is preheated while it is caused to float. Further, more preferably, the preform is preheated to a temperature at which the glass constituting the preform exhibits a viscosity of 10 5.5 to 10 9 dPa ⁇ S, still more preferably at least 10 5.5 but less than 10 9 dPa ⁇ S.
  • the cooling of the glass is started concurrently with the start of the pressing or during the pressing.
  • the temperature of the press mold is adjusted to a temperature lower than the temperature employed for preheating the above preform.
  • the temperature of the press mold can be set approximately at a temperature at which the above glass exhibits a viscosity of 10 9 to 10 12 dPa ⁇ S.
  • a precision press-molded product is taken out of the press mold after it is cooled to a temperature at which the glass exhibits a viscosity of 10 12 dPa ⁇ S or more.
  • the optical element obtained by the precision press-molding is taken out of the press mold and gradually cooled as required.
  • the precision press-molded product is an optical element such as a lens
  • the product is surface-coated with an optical thin film as required.
  • Oxides, hydroxides, carbonates, nitrates, etc. were used as corresponding raw materials of each glass, these raw materials were weighed so that the composition shown in Tables 1 to 3 was obtained after the formation of the glass, and these raw materials were fully mixed. Then, the mixture was poured into a platinum crucible and melted with stirring in an electric furnace in a temperature range of 1,200 to 1,250° C. in atmosphere for 2 to 4 hours. A homogenized and refined glass melt was cast into a 40 ⁇ 70 ⁇ 15 mm mold made of carbon, and a cast glass was gradually cooled to a transition temperature.
  • optical glasses were obtained.
  • Tables 1 and 2 correspond to the optical glass according to the first or second embodiment of the present invention
  • the glasses shown in Table 3 correspond to the optical glass according to the third embodiment of the present invention.
  • the obtained optical glasses were measured for a refractive index (nd), an Abbe's number ( ⁇ d), a glass transition temperature (Tg) and a sag temperature as follows, and Tables 1 to 3 show the results.
  • a refined and homogenized molten glass corresponding to any one of the above optical glasses was caused to flow out of a pipe formed of platinum that was temperature-adjusted to a temperature range in which stable flow of the glass was permitted without causing the devitrification of the glass.
  • a molten glass gob having an intended preform weight was separated by a dropping method or a descent-separation method and received with a receiving support having a gas ejection port in a bottom thereof, and the molten glass gob was shaped into a preform while it was caused to float by ejecting a gas from the gas ejection port.
  • each molten glass was cast into a mold to form a plate-like glass, and the plate like glass was annealed and then cut. The thus-obtained pieces were ground and polished to give preforms whose surfaces were all smooth.
  • the above-obtained preforms whose surfaces were formed by solidification of the optical glasses in a molten state and the above-obtained preforms obtained by polishing their surfaces were precision press-molded with a pressing apparatus shown in FIG. 1 , to give aspherical lenses.
  • a preform 4 was placed between a lower mold member 2 and an upper mold member 1 of a press mold having the upper mold member 1 , the lower mold member 2 and a sleeve member 3 , and then a nitrogen atmosphere was introduced into a quartz tube 11 .
  • a heater 12 was electrically powered to heat an inside of the quartz tube 11 .
  • the temperature inside the press mold was set at a temperature at which each glass to be precision press-molded exhibited a viscosity of 10 8 to 10 10 dPa ⁇ S, and while such a temperature was maintained, a pressing rod 13 was caused to move downward to press the preform set in the mold.
  • the pressing was carried out at a pressure of 8 MPa for 30 seconds. After the pressing, the pressing pressure was released, and while the press-molded glass product was in contact with the lower mold member 2 and the upper mold member 1 , it was gradually cooled to a temperature at which the glass exhibited a viscosity of 10 12 dPa ⁇ S or more. Then, the product was rapidly cooled to room temperature, and the product was taken out of the press mold, to give an aspherical lens.
  • the thus-obtained aspherical lenses were lenses having remarkably high surface accuracy.
  • the aspherical lenses obtained by the precision press-molding were provided with an antireflection film as required.
  • the same preforms as the above preforms were precision press-molded according to another process. Specifically, in this process, a preform was preheated to a temperature at which the glass constituting the preform exhibited a viscosity of 10 8 dPa ⁇ S while the preform was caused to float. On the other hand, a press mold having an upper mold member, a lower mold member and a sleeve member was heated up to a temperature at which the above glass exhibited a viscosity of 10 9 to 10 12 dPa ⁇ S, and the preheated preform was introduced into the cavity of the press mold to carry out precision press-molding of the preform. The pressing pressure was set at 10 MPa.
  • the aspherical lenses obtained by the precision press-molding were provided with an antireflection film as required.
  • optical elements formed of optical glasses having excellent climate resistance and having high internal quality were highly productively and highly accurately produced.
  • optical glasses having high-refractivity low-dispersion properties, having a low glass transition temperature and having the property of being softened at a low temperature so that a preform therefrom is precision press-moldable, and there can be produced preforms for precision press-molding and optical elements such as various lenses, and the like from the above optical glasses.

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US11/065,279 2004-03-02 2005-02-25 Optical glass, precision press-molding preform, process for production thereof, optical element and process for the production thereof Abandoned US20050197243A1 (en)

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US12/588,235 US7932197B2 (en) 2004-03-02 2009-10-08 Optical glass, precision press-molding preform, process for production thereof, optical element and process for the production thereof

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US7622409B2 (en) 2009-11-24
US20080167172A1 (en) 2008-07-10
CN1663923A (zh) 2005-09-07
KR101203031B1 (ko) 2012-11-20
JP4124749B2 (ja) 2008-07-23
US20100035744A1 (en) 2010-02-11
US7932197B2 (en) 2011-04-26
CN100575288C (zh) 2009-12-30
KR20060043309A (ko) 2006-05-15
CN101570395A (zh) 2009-11-04
JP2005247613A (ja) 2005-09-15

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