Patent Application
20100313603
This application is based on Japanese Patent Application No. 2009-140842 filed on Jun. 12, 2009, in Japan Patent Office, the entire content of which is hereby incorporated by reference.
The present invention relates to methods for manufacturing a molding die, use for manufacturing a glass gob or a glass molded article, from a dropped molten glass droplet, and a method for manufacturing a glass gob and a glass molded article utilizing a molding die manufactured by the manufacturing method.
In recent years, an optical element made of glass has been utilized in a wide range of applications as a lens such as a digital camera, an optical pick up lens for a DVD, a camera lens for a cell phone and a coupling lens for optical communication. As such an optical element made of glass, a molded glass article manufactured by press molding of a glass material by use of a molding die is generally utilized.
As such a manufacturing method of a molded glass article, proposed is a method in which a molten glass droplet at a temperature higher than a lower die is dropped on a lower die which is heated at a predetermined temperature, and the dropped molten glass droplet is subjected to press molding with a lower die and an upper die facing to the lower die to prepare a molded glass article (hereinafter, also referred to as “a liquid drop molding method”). This method has been noted because time necessary for one shot of molding can be made very short because it is possible to manufacture a molded glass article directly from a molten glass droplet.
Further, also known is a method for manufacturing a glass molded article in which a molten glass droplet dropped on a lower die is cooled and solidified without any additional treatment to prepare a glass gob (glass block), and the prepared glass gob is heated together with a molding die to be subjected to press molding (a reheat press method).
However, in these methods, there was a problem that minute concave parts are formed in the central neighborhood of the bottom surface of a molten glass droplet (the contact surface with the lower die) at the time of a dropped molted glass drop collides against the lower die, and air immersed into the concave part (air bubble) is sealed to remain in the concave part on the bottom surface of a glass molded article (air bubbles).
To solve such a problem, proposed is a method utilizing a molding die comprising a substrate on which a cover layer is formed and the surface of the cover layer is roughened to prevent an air bubble from remaining by securing a flow path for air having been immersed into concave parts (refer to PCT International Application Publication No. 2009/016993). Further, in PCT International Application Publication No. 2009/016993, described is a method to deposit a cover layer to be roughened, by a sputtering method.
However, in the case of a molding surface on which cover layer is to be formed has a convex form or a concave form, when the cover layer is formed by a sputtering method as described in PCT International Application Publication No. 2009/016993, film properties and film thickness of the cover layer deposited vary between the central portion and circumferential portion of a molding surface. Therefore, there is a problem that roughening excessively proceeds in the circumferential part to easily generate film peeling in the circumferential portion of the cover layer at the time of roughening processor during manufacturing of a glass molded article.
This invention has been made in view of a technical problem such as described above and an object of this invention is to provide a method for manufacturing a molding die which is possible to prevent generation of film peeling and having excellent durability, and is possible to effectively prevent generation of air bubbles. Further, another object of this invention is to provide a method for stably manufacturing a glass gob and a glass molded article.
In view of forgoing, one embodiment according to one aspect of the present invention is a method for manufacturing a molding die to be used for manufacturing a glass gob or a glass molded article, the method comprising the steps of:
forming, in a substrate, a molding surface having a predetermined shape;
forming a cover layer on the molding surface by a sputtering method, while the substrate is being held by a substrate holding member which is being rotated about a predetermined rotation axis, and a relative position between a sputtering target and the substrate holding member is being changed so as to temporarily change an angle between a normal line of a surface of the sputtering target and the rotation axis; and
roughening a surface of the cover layer by an etching method.
According to another aspect of the present invention, another embodiment is a method for manufacturing a glass gob, the method comprising the steps of:
dropping a molten glass droplet on a first molding die; and
cooling the dropped molten glass droplet on the first molding die;
wherein the first molding die is manufactured by the above-mentioned method for manufacturing a molding die.
According to another aspect of the present invention, another embodiment is a method for manufacturing a glass molding article, the method comprising the steps of:
dropping a molten glass droplet on a first molding die; and
press-molding the dropped molten glass droplet with the first molding die and a second molding die facing the first molding die,
wherein at least one of the first molding die and the second molding die is manufactured by the above-mentioned method for manufacturing a molding die.
a, 1b and 1c are cross-sectional views to show a molding die in each step of a process;
a and 6b are schematic drawings to explain the meaning of an etching rate;
In the following, an embodiment of this invention will be detailed in reference to
First, a method for manufacturing a molding die will be explained in reference to
(Substrate)
On substrate 11 which will be a substrate of a molding die to be manufactured, molding surface 15 having a predetermined form corresponding to a shape of a glass gob or a glass molded article to be manufactured is formed in advance (
In this embodiment, it is not necessary to roughen substrate 11 before deposition of cover layer 12 because cover layer 12 deposited on substrate 11 is subjected to a roughening process. Therefore, materials of substrate 11 can be selected without considering ease of roughening and durability after roughening and can be appropriately selected depending on the conditions among materials well known in the art as materials for a molding die for press molding of a molten glass droplet. Materials preferably utilized include, for example, various heat-resistant alloys (such as stainless), super hard materials comprising tungsten carbide as a primary component, various ceramics (such as silicon carbide and silicon nitride) and complex materials containing carbon. Further, utilized may be these materials the surface of which is provided with a minutely processed layer such as CVD silicon carbide film.
(Deposition Process)
Next, cover layer 12 is deposited on molding surface 15 by a sputtering method (
An example of sputtering system 30 utilized in this embodiment is shown in
At the time of deposition of cover layer 12, firstly, substrate 11 is attached to substrate holding member 34 with molding surface 15 facing downward. The number of substrates 11 may be either one or plural. Next, valve 41 is opened to evacuate the inside of vacuum chamber 31 down to a predetermined vacuum degree by displacement pump 42. It is generally preferable to evacuate down to a pressure of not more than 1×10−3 Pa. Further, it is also preferable to provide a heater in substrate holding member 34 to heat substrate 11 at a predetermined temperature. After evacuating the inside of vacuum chamber 31 down to a predetermined vacuum degree, flow rate controlling valve 43 is opened to introduce a sputtering gas from gas bottle 44, and a predetermined voltage is applied to sputtering target 32 by sputtering power supply 33 to generate plasma in the neighborhood of the upper surface of sputtering target 32. Thereby, ions of sputtering gas collide against sputtering target 32 to spatter composite elements of sputtering target as sputtering particles. The sputtered sputtering particles reach substrate 11, which is arranged above, and are accumulated to form cover layer 12 on molding surface 15.
In this embodiment, cover layer 12 is deposited while performing the above-described rotation and tilt drive. Rotation and tilt drive will be explained in reference to
The tilt drive is to vary the relative positioning of sputtering target 32 and substrate holding member 34 so as to temporarily vary angle α between normal 23 of sputtering target 32 and rotation axis 21, and in this embodiment, substrate holding member 34 is driven in the direction of arrow Q in the drawing by tilt drive part 36. The magnitude of angle α and the rate of drive may be appropriately set depending on the holding position of substrate 11, the form of molding surface 15 and the distance between sputtering target 32 and substrate 11. For example, it is preferable to set angle α to be 10°-45° for left and right each and to repeatedly drive at a rate of 0.5-2 rpm. Angle α of tilt drive is preferably α>βmax/4.5 and more preferably α>βmax/2.5 when the maximum value of inclination angle β of molding surface 15 is βmax. Further, instead of driving substrate holding member 34 by tilt drive part 36, sputtering target 32 may be driven in the direction of arrow Q as shown in
The material of cover layer 12 is not specifically limited; however, it is preferably that materials are easily roughened by etching and have low reactivity with glass. Among them, metal chromium, metal aluminum, metal titanium, oxide and nitride thereof, or mixture thereof can be preferably utilized. A film of these materials can be easily deposited and can be easily roughened by etching. Further, chromium, aluminum and titanium has a characteristic that when one of those is contained in cover layer 12, it is oxidized by heating in atmosphere to form a stable oxide layer on the surface. Since these oxides have small standard free energy of formation (standard Gibb's energy of formation) and are very stable, there is a great advantage of not easily reacting even in contact with high temperature molten glass droplet. Among them, it is more preferable to provide cover layer 12 containing chromium element, since its oxide is very stable.
In the case of depositing cover layer 12 containing two kinds of elements or more, deposition may be performed utilizing sputtering target 32 containing both element at a predetermined ratio, or deposition by complex sputtering may be performed utilizing plural sputtering targets 32 containing each element.
The cover layer 12 may have at least an enough thickness for the micro roughness to be formed by roughening by etching, and is generally preferably not less than 0.05 μm. On the contrary, when cover layer 12 is excessively thick, defects such as film peeling may be easily generated. Therefore, the thickness of cover layer 12 is preferably 0.05-5 μm and specifically preferably 0.1-1 μm. Further, in the case of molding surface 15 has a concave or convex form symmetric about central axis 22, the thickness of cover layer 12 over the whole range of molding surface 15 is preferably not less than 0.8 times and not more than 1.2 times, and more preferably not less than 0.9 times and not more than 1.1 times, of the film thickness at the position of central axis 22, from the point of view of sufficiently decreasing the difference of progress of roughening between the central portion and circumferential portion of molding surface 15 and assuring the effect to prevent excessive roughening in the circumferential portion.
Further, if the number of diffraction peaks or the magnitude relation of strength in the diffraction peaks, of cover layer 12, detected in the evaluation with XRD (X-ray diffraction) vary in different positions, a difference in etching rate may be caused, and a difference of the proceeding rate of roughening may be thus produced. In such a point of view, the conditions of rotation and tilt drive at the time of deposition of cover layer 12 are preferably set so as to make the number of diffraction peaks or the magnitude relation of strength between the diffraction peak of cover layer 12 detected with XRD substantially identical over the whole molding surface 15. For example, in the case of utilizing chromium film as cover layer 12, it is effective to make equal magnitude relation between the two diffraction peaks: the peak of (110) plane appearing in the vicinity of 2θ=44°, and the peak of (200) plane appearing in the vicinity of 2θ=64°. The measurement of diffraction peaks measured with XRD may be conducted by use of a general X-ray diffractometer (such as X-ray diffractometer RINT 2500 manufactured by Rigaku Co., Ltd.), and the measurement conditions may be appropriately selected depending on the object. For example, in the case of utilizing chromium film as cover layer 12, measurement may be performed under the conditions of the range of 0-80° based on a θ-2θ method, a sampling width of 0.02° and a scanning rate of 5°/min.
(Roughening Process)
Next, roughening by etching of the surface of cover layer 12 is performed (
Etching may be performed either by wet etching utilizing liquid or dry etching utilizing gas. Among them, wet etching utilizing liquid is preferable because it requires no expensive facilities and enables easy formation of uniform roughness.
In the case of wet etching, a reactive etching solution is brought in contact with cover layer 12 to make reaction, whereby cover layer 12 is subjected to roughening to form roughness in the surface. Cover layer 12 may be immersed in an etching solution stored in a vessel or a predetermined amount of etchant may be supplied on cover layer 12. Further, a method to spray an etchant in a mist form is also possible. As an etchant, an etchant well known in the art matching the material of cover layer 12 can be appropriately selected. For example, in the case of cover layer 12 being chromium film, an acidic solution containing ammonium ceric nitrate or an alkaline solution containing potassium ferricyanate and potassium hydroxide is preferably utilized.
Further, in the case of dry etching, an etching gas is introduced into a vacuum chamber and plasma is generated by application of high frequency waves, whereby cover layer 12 is subjected to roughening by ions and radicals generated by plasma. This method is also referred to as plasma etching or reactive ion etching (RIE). It is a preferable method because of such as small environmental load due to no generation of effluent, little contamination of the surface by foreign matters and excellent reproducibility of the process. As a dry etching system, a parallel plate type, a barrel (cylindrical) type, a magnetron type and an ECR type and the like may be appropriately selected from systems well known in the art, and there is no specific limitation. As an etching gas, either an inert gas such as Ar or a highly reactive gas containing halogen such as F, Cl and Br may be utilized. Among them, a gas containing halogen such as F, Cl and Br (for example, such as CF4, SF6, CHF3, Cl2, BCl3 and HBr) shows high reactivity and enables processing in a short time. Further, these gases may be used in combination with O2 or N2 and the like.
In either one of the above-described methods, difference in etching rate will be generated if film properties of cover layer 12 are different between the central part and the circumferential part of molding surface 15. However, since film properties and film thickness of cover layer 12 is made to be uniform in this embodiment, the difference in roughening is small. The etching rate of cover layer 12 varies depending on the magnitude of energy possessed by sputtering particles reaching the deposition surface at the time of deposition of cover layer 12 by sputtering, and can be controlled by the conditions of rotation and tilt drive. In such a view point, it is preferable to set the conditions of rotation and tilt drive at the time of deposition of cover layer 12 so as to make the etching rate of cover layer 12 as uniform as possible. In particular, it is preferable to set the etching rate of cover layer 12 over the whole region to not less than 0.5 times and not more than 5 times of the etching rate at the position of central axis 22 of molding surface 15.
The meaning of an etching rate in this description will now be explained in reference to
Roughening by etching is preferably peg formed so as to make the arithmetic mean roughness (Ra) of the surface of cover layer 12 be 0.01-0.2 μm and the mean length of roughness curve elements (RSm) be not more than 0.5 μm. By making the arithmetic mean roughness (Ra) and the mean length of roughness curve elements (RSm) in these ranges, it is possible to more effectively prevent generation of air bubbles in a glass molded article to be generated. Herein, the arithmetic mean roughness (Ra) and the mean length of roughness curve elements (RSm) are roughness parameters defined in JIS B 0601:2001. In this embodiment, measurement of these parameters is performed by use of a measurement system such as an AFM (an atomic force microscope) having a spatial resolution of not more than 0.1 μm.
Here, the whole surface of cover layer is not necessarily roughened etching, and it is enough that at least the region to contact with molten glass droplet 50 is roughened. Further, in this embodiment, an example in which cover layer 12 is constituted by a single layer was explained; however, cover layer 12 may have a multi-layered structure constituted by two layers or more. For example, an intermediate layer to enhance adhesion between substrate 11 and cover layer 12 may be provided, and a protective layer to protect the surface may be provided on cover layer on which roughness has been formed by a roughening treatment.
(Method for Manufacturing Glass Molded Article)
Next, a method for manufacturing a glass molded article will be explained in reference to
The manufacturing system of a glass molded article shown in
Lower die 10A and upper die 10B are constituted so as to be heated at a predetermined temperature by a heating section which is not shown in the drawing. As a heating section, a heating section well known in the art can be utilized by appropriate selection. For example, there can be used a cartridge heater which is utilized being berried in the inside, a sheet form heater which is utilized in contact with the outside surface, an infrared heater and a high frequency induction heater. It is preferable to adopt a constitution in which temperature can be controlled independently for lower die 10A and upper die 10B. Lower die 10A is arranged to be moved along guide 54 between the position to receive molten glass droplet 50 (dropping position P1) and the position to perform press molding (pressing position P2) by a drive section which is not shown in the drawing. Further, upper die 10B is arranged to be moved in the direction to press molten glass droplet 50 (the up-and-down direction in the drawing) by a drive section which is not shown in the drawing.
In the following description, each process of a method for manufacturing glass molded article 55 will be explained in order according to the flow chart shown in
First, lower die 10A and upper die 10B are heated at a predetermined temperature (step S101). As the predetermined temperature, appropriately selected is a temperature at which a good surface can be transferred on a glass molded article by press molding. The heating temperatures of lower die 10A and upper die 10B may be the same or different from each other. A suitable temperature is appropriately set depending on various conditions such as the type, form, and size of glass; and the material and the size of a molding die for molding glass. Generally, the temperature is preferably set at approximately from Tg−100° C. to Tg+100° C., when glass transition temperature of utilized glass is Tg.
Next, lower die 10A is moved to dropping position P1 (step S102) and molten glass droplet 50 is dropped from dropping nozzle 53 (step S103) (refer to
The mass of molten glass droplet 50 dropped from dropping nozzle 53 can be adjusted depending on the outer diameter of the top portion of dropping nozzle 53, and it is possible to drop molten glass droplet 50 of approximately 0.1-2 g although it depends on a kind of glass. Further, molten glass droplet 50 dropped from dropping nozzle 53 may be once made to collide against a member having penetrating micro pores so that the part of molten glass droplet having collided passes through the penetrating micro pores, whereby micronized molten glass droplets may be dropped on lower die 10A. By utilizing such a method, since a molten glass droplet, for example, as minute as 0.001 g can be prepared, it is possible to manufacture a more minute molded glass article compared to the case of directly receiving molten glass droplet 50 dropping from dropping nozzle 53 on lower die 10A.
The kind of glass utilized is not specifically limited and glass well known in the art can be appropriately selected depending on the application and be used. Examples include optical glass such as borosilicate glass, silicate glass, phosphate glass and lanthanum type glass is listed.
Next, lower die 10A is moved to pressing position P2 (step S104) and upper die 10B is moved downward, whereby molten glass droplet 50 is press-molded with lower die 10A and upper die 10B (step S105) (refer to
The load applied to press molten glass droplet 50 may be temporarily kept constant or varied with time. The magnitude of the load applied may be appropriately set depending on the size of molded glass article 55 to be manufactured. The drive means to vertically move upper die 10B is not specifically limited and a drive section well known in the art such as an air cylinder, an oil pressure cylinder and an electric cylinder employing a servo motor can be utilized by appropriate selection.
Thereafter, upper die 10B is moved upward, and molded glass article 55 having been solidified is picked up (step S106) to complete manufacture of molded glass article 55. Then, in the case of successive manufacturing of molded glass article 55, lower die 10A is moved to dropping position P1 again (step S102) and processes to continue thereto is repeated. Here, a method for manufacturing a molded glass article of this embodiment may includes processes other than those explained here. For example, provided may be a step to inspect the form of molded glass article 55 before picking up molded glass article 55, or a step to clean lower die 10A or upper die 10B after picking up molded glass article 55.
According to a method for manufacturing a glass molded article of this embodiment, since molding die 10, in which cover layer 12 has been deposited while performing rotation and tilt drive, is utilized as at least one of lower die 10A and upper die 10B, the film properties and the film thickness are made uniform, and difference in roughening between the central part and circumferential part of molding surface 15 is small. Thus, it is possible to prevent generation of air bubbles at the time of receiving molten glass droplet 50 and performing press molding, and possible to restrain film peeling of cover layer 12. Therefore, a glass molded article without air bubbles can be stably manufactured.
Glass molded article 55 manufactured by a manufacturing method of this embodiment can be utilized as various optical elements such as a picture-taking lens of a digital camera, an optical pickup lens of a DVD and a coupling lens for optical communication.
Here, in the case of utilizing molding die 10 as lower die 10A, it is also possible to prepare a glass gob (glass block) by cooling and solidifying molten glass droplet 50 dropped on lower die 10A in step S103 as is without press-molding. Also in this case, it is possible to prevent generation of film peeling in cover layer 12, and possible to effectively prevent generation of air bubbles at the time of receiving molten glass droplet 50, whereby a glass gob without air bubbles can be stably manufactured. The details of each step are similar to the steps in the case of manufacturing a glass molded article. A glass gob manufactured can be utilized as a raw material glass (a glass pre-form) for manufacturing an optical element by a reheat method.
According to this embodiment, since a substrate is held by a substrate holding member and a cover layer is deposited while varying the relative positioning of a sputtering target and the substrate holding member so as to vary the angle between the normal line of the surface of a sputtering target and the rotation axis as well as rotating the substrate holding member around a predetermined rotation axis, it is possible to decrease differences in film properties and film thickness of a cover layer between the central portion and circumferential portion of a molding surface. Whereby, a difference in roughening between the central portion and circumferential portion of a molding surface will be also decreased, and excessive roughening will be controlled in the circumferential portion. Therefore, film peeling is decreased, and air bubbles will also be decreased, whereby a molding die of excellent durability is manufactured. Further, by utilizing a molding die manufactured by the above-described method, a glass gob and a glass molded article without air bubbles are stably manufactured.
In the following, examples conducted to confirm the advantages of this invention will be explained; however, this invention is not limited thereto.
According to steps shown in
Substrate 11 was attached on substrate holding member 34 of sputtering system 30 shown in
Thereafter, substrate 11 is heated up to 200° C. while evacuating the inside of vacuum chamber 31 with valve 41 opened. After the inside of vacuum chamber 31 reached a high vacuum of 10−3 Pa, a sputtering gas of 1 Pa was introduced from gas bottle 44 by opening flow rate controlling valve 43. Argon gas was utilized as a sputtering gas. Then, a high frequency electric power of 300 W was applied to the sputtering target while performing rotation and tilt drive by operation rotation drive member 35 and tilt drive part 36, whereby chromium film (cover layer 12) of 0.5 μm was deposited. The rotation rate of the rotation was set to 5 rpm. Further, tilt drive made the substrate back and forth continuously at a rate of 1 rpm and an angle of 30° toward left and right each.
After finishing deposition, substrate 11 was taken out from vacuum chamber 31 and the surface of cover layer 12 was roughened by etching. As the etching solution, a chromium etching solution containing ammonium eerie nitrate available on the market (ECR-2), manufactured by Nacali Tesque Co., Ltd.), was utilized. The surface of cover layer 12 after roughening showed arithmetic mean roughness Ra of 0.1 μm and mean length of a roughness curve elements RSm of 0.1 μm both in the central portion and in the circumferential portion. Here, arithmetic mean roughness Ra and mean length of a roughness curve elements RSm were measured by an AFM (D3100, manufactured by Digital Instruments).
Molding die 10 prepared in the above manner was utilized as lower die 10A and upper die 10B, and a glass molded article was manufactured according to the flow chart shown in
Each process was repeated to prepare 1,000 pieces of glass molded articles and the prepared glass molded articles were observed to evaluate the presence or absence of air bubbles and film peeling of cover layer 12. In this embodiment, with respect to all the 1,000 pieces of glass molded articles, no generation of air bubbles and no film peeling of cover layer 12 were observed.
Different from the example, cover layer 12 was deposited in the state where molding surfacr 15 and sputtering target 32 were stationarily facing each other without performing rotation and tilt drive. The film thickness of cover layer was 0.5 μm. Other conditions were identical to those of the example. After finishing deposition, roughening by etching was performed similarly to the example. However, because progress of roughening was faster in the circumferential portion of molding surface 15 compared to the central portion, and film peeling was generated in the circumferential portion before the roughness at the central portion reached the similar roughness to the example, these dies were not utilized for manufacturing glass molded articles.
In a similar manner to comparative example 1, cover layer 12 was deposited in a state where molding surface 15 and sputtering target 32 were stationarily facing each other without performing rotation and tilt drive. It should be noted that the film thickness of cover layer 12 was set to 1.5 μm. After finishing deposition, roughening by etching was performed similarly to the example. Progress of roughening was faster in the circumferential portion of molding surface 15 compared to the central portion, and arithmetic mean roughness Ra in the circumferential portion was 0.3 μm when arithmetic mean roughness Ra in the central portion reached 0.1 μm. Thereafter, the presence and absence of air bubbles and film peeling of cover layer 12 were evaluated by preparing glass molded articles similarly to the example. In comparative example 2, although generation of air bubbles could be reduced, film peeling in the circumferential portion of molding surface 15 was generated at a time of molding of 100 shots, and glass molded articles manufactured after that time did not satisfy the required quality because of the poor external appearance.
As described above, in the cases of comparative examples 1 and 2, since rotation and tilt drive were not performed during deposition of cover layer 12, the difference of progress of roughening between the central portion and circumferential portion of molding surface 15 was large resulting in excessive roughening in the circumferential portion, which disabled stable manufacturing of a glass molded article. On the contrary, in the example, the difference of progress of roughening between the central portion and circumferential portion of molding surface 15 was decreased by performing rotation and tilt drive during deposition. Whereby, generation of film peeling in the circumferential portion has been restrained, and the durability of a molding die was improved, and glass molded articles without air bubbles were stably manufactured.
| Number | Date | Country | Kind |
|---|---|---|---|
| JP2009-140842 | Jun 2009 | JP | national |
