WO2009041707A2 - Manufacturing method of optical member, optical member manufacturing apparatus and optical member - Google Patents

Manufacturing method of optical member, optical member manufacturing apparatus and optical member Download PDF

Info

Publication number
WO2009041707A2
WO2009041707A2 PCT/JP2008/067869 JP2008067869W WO2009041707A2 WO 2009041707 A2 WO2009041707 A2 WO 2009041707A2 JP 2008067869 W JP2008067869 W JP 2008067869W WO 2009041707 A2 WO2009041707 A2 WO 2009041707A2
Authority
WO
WIPO (PCT)
Prior art keywords
optical member
droplet
thermoplastic resin
substrate
nozzle
Prior art date
Application number
PCT/JP2008/067869
Other languages
French (fr)
Other versions
WO2009041707A3 (en
Inventor
Noriko Eiha
Seiichi Watanabe
Masato Yoshioka
Original Assignee
Fujifilm Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Publication of WO2009041707A2 publication Critical patent/WO2009041707A2/en
Publication of WO2009041707A3 publication Critical patent/WO2009041707A3/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00432—Auxiliary operations, e.g. machines for filling the moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00317—Production of lenses with markings or patterns
    • B29D11/00346—Production of lenses with markings or patterns having nanosize structures or features, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00951—Measuring, controlling or regulating

Definitions

  • the present invention relates to a manufacturing method of an optical member, an optical member manufacturing apparatus, and an optical member formed by the manufacturing method, and more specifically, to an art of forming an optical member from a nanocomposite material.
  • optical devices including a mobile phone's built-in camera and optical information recording devices, such as DVD, CD and MO drives
  • developments of excellent materials and processes have been intensely desired also for optical members used in those devices, such as optical lenses or filters.
  • plastic lenses in particular are lightweight and less splintery, can be worked into various shapes and further can be produced at low cost as compared with lenses made of inorganic materials such as glass, they have rapidly come into widespread use as not only eyeglasses but also optical lenses for the foregoing uses. With this trend, it comes to be desired that the refractive indexes of raw materials themselves be heightened for the purposes of thinning lenses and stabilizing optical refractive indexes against thermal expansion, temperature changes and so on. In general, such plastic lenses are formed by charging resin materials into molds.
  • optical members notably optical members required to have high degree of transparency
  • reduction of light scattering required the inorganic fine particles to have sizes smaller than the wavelengths of light used.
  • Examples of a technique to manufacture a nanocomposite material containing a plastic resin and inorganic fine particles dispersed therein include the following.
  • the technique (1) aggregation of the particles occurs when the proportion of the particles mixed is high; as a result, the composite material obtained is lacking in transparency.
  • shape control is difficult because of a great shrinkage at the time of polymerization, and shaping cannot be performed with a precision required of, e.g., shooting lenses for miniature cameras for mobile phones, pickup lenses and the like.
  • the technique (2) though it allows manufacture of highest-quality lenses, it still takes much time to strip away the solvent used.
  • plastic lenses are formed by charging resin materials into molds, or they are formed by heat pressing with dies, changes in shapes of products involve preparation for new molds, and much time and much expense are required for making molds. Therefore, it is impossible to cope with frequent design changes in the cases where the volume of production is low and a wide variety of products are made, or prototypes are made.
  • JP-A-2006- 146063 employs an inkjet method, and provides three-dimensional microscopic asperities by utilizing shrinkage of organic materials. More specifically, two or more fluid materials for discharge are discharged in succession onto a substrate and form droplets in an incompletely-mixed state, or in a state that the fluid materials are not mixed thoroughly.
  • the three-dimensional shaping apparatus disclosed in JP-A-2005-59289 incorporates a three-dimensional shaping device by which a process of discharging a solution fed from a storage tank in droplet form from a drop-on-demand type inkjet head and then solidifying the discharged solution by drying is repeated two or more times, thereby stacking droplets and forming a three-dimensional shape, and aims at improvement of shape quality by adjusting an average speed of each droplet discharged from the inkjet head to fall within a range of 7 m/s to 4 m/s during the passage of a distance of 1 mm from the nozzle face so that the flying speed of each droplet is minimized and thereby not only the shape of each droplet arriving at the shaping stage becomes closer and closer to a sphere but also the collision energy is lessened.
  • a lens manufacturing method wherein the lens shape is formed through discharge of a resin solution in droplet form from an inkjet head
  • the methods disclosed in JP-A-2000-67449, JP-A-2006-54489, JP-A-2005-88502 and JP-A-2005-92049 can be given.
  • the droplets of a resin solution are made to land on the same position and the landed droplets are stacked to form a lens of desired size.
  • the optical surface is formed by the leveling of droplets in every one of the lens manufacturing methods disclosed in JP-A-2006- 146063, JP-A-2000-67449, JP-A-2006-54489, JP-A-2005-88502 and JP-A-2005-92049, the degree of flexibility in designing the shape is seriously low. More specifically, the forming of a lens shape by utilization of leveling has an advantage of easy forming of a general lens shape in the cases of miniature lenses including micro lenses and the like, but there is a difficulty in applying it to forming of lenses of sizes on the general camera lens level, concave lenses and high-precision lens shapes.
  • the radius of curvature of a droplet surface is unambiguously determined by the viscosity and surface tension of a resin solution used, and besides, fluctuations therein tend to occur. This respect also makes it difficult to complete the forming of a lens in a desired shape.
  • the lens manufacturing method utilizing the leveling are effective for lenses aiming to obtain only a light-gathering action, such as optical systems for projecting light, but it cannot attain profile irregularity for keeping up high resolution required of lenses in optical systems for taking pictures.
  • a first object of the invention is to provide a method of manufacturing a high-precision optical member without requiring any mold
  • a second object of the invention is to provide a manufacturing method of an optical member, wherein resin solutions containing nanocomposite materials are formed into uniform droplets and the droplets can be formed into a desired shape with stability while stripping away the solvent in a short time, and an optical member formed by this manufacturing method.
  • a manufacturing method of an optical member comprising: discharging a droplet of a solution including a transparent thermoplastic resin and solidifying the droplet on a substrate on a basis of profile data of the optical member to shape the optical member, wherein a process of discharging droplets of the solution on different positions of the substrate and solidifying the droplets by drying is repeated a plurality of times to stack the thermoplastic resin so that the stacked thermoplastic resin have a height according to the profile data; and separating the shaped optical member from the substrate.
  • an optical member when an optical member is shaped by discharging a solution of thermoplastic resin and solidifying it by drying, its thickness is controlled at many sites, whereby a concavo-convex optical surface of a desired shape is formed. In other words, while confirming discharge thicknesses at many sites, an optical member of a desired shape is formed. Thus, even when a modification is made to the product shape, no mold needs to be newly prepared, and manufacture of a high-precision optical member becomes possible with high design flexibility.
  • the height of thermoplastic resin at each time of repeated landing and stacking on the substrate is detected in succession, whereby it becomes possible to form an optical member free of deviation from the profile data, namely a high-precision optical member.
  • each plane section is stacked in succession. So, the simplified forming is possible even when the optical member has a complex shape.
  • the inkjet head allows high-accuracy setting of a uniform droplet size.
  • the inkjet head includes the nozzle, a pressure chamber communicated with the nozzle, and a piezoelectric element combined with the pressure chamber for pressurization, and wherein the inkjet head discharges the droplet of the solution of the thermoplastic resin out of the nozzle when an inside of the pressure chamber is pressurized by application of a voltage to the piezoelectric element.
  • the piezoelectric element is extended by applying a voltage to the piezoelectric element in the pressure chamber, and this extending motion pressurizes the interior of the pressure chamber; as a result, the solution can be discharged in droplet form out of the nozzle.
  • the inkjet head includes the nozzle, a fluid channel communicated with the nozzle, and a heating unit disposed on a part of the fluid channel, and wherein bubbles are produced in the fluid channel by heat supply from the heating unit so that the droplet of the solution of the thermoplastic resin is discharged out of the nozzle.
  • bubbles are produced in the solution by heat supply to the fluid channel from the heating unit to cause volumetric expansion, thereby allowing discharge of the solution out of the nozzle in droplet form.
  • the diameters of the droplets are adjusted to fall within the specified range (from 0.005 mm to 0.1 mm), thereby expediting the drying of landed droplets through evaporation of the solvent.
  • the discharged thermoplastic resin solution is formed into a desired optical shape in a short time, and that with stability.
  • the optical profile irregularity of the optical member shaped is also enhanced.
  • droplets too large in diameter require a long time for drying and the shapes thereof become coarse.
  • too small in diameter require too long time for forming, and each droplet dries up before landing. As a result, these droplets cannot stick together through blending.
  • instant fusion or semi-fusion by rapid thermal anneal treatment allows removing microscopic asperities on the optical member surface and the optical member surface is prepared in a smooth condition so as to accord with a concavo-convex optical surface of a desired shape.
  • thermoplastic resin is stacked on a spherical lens-shaped transparent body.
  • this manufacturing method of an optical member when compared with the case of stacking a thermoplastic resin on the forming substrate from the beginning, the process of repeating discharge of droplets and their solidification by drying until the amount of droplets discharged becomes equal to the volume of the transparent body is dropped off, so high-speed forming in reduced amount of discharge can be attained.
  • an aspheric surface layer is formed from the solution of the thermoplastic resin on the spherical lens-shaped transparent body.
  • an aspheric lens can be formed at a high speed only by forming of an aspherical surface layer.
  • a process of discharging droplets onto a forming substrate and solidifying them by drying is repeated, thereby shaping a halved optical member having a planar surface on the bottom side and a desired concavo-convex optical surface on the top side, and two pieces of the halved optical members are joined together in a state that their bottom surfaces face each other.
  • a process of discharging droplets onto a forming substrate and solidifying them by drying is repeated, thereby shaping a halved optical member having a planar surface on the bottom side and a desired concavo-convex optical surface on the top side, and two pieces of the halved optical members are joined together in a state that their bottom surfaces face each other.
  • thermoplastic resin is a nanocomposite material including a transparent thermoplastic resin into which fine particles having sizes of 20 nm or less are incorporated.
  • inorganic fine particles such as fine particles of a metal oxide, are dispersed homogeneously into the thermoplastic resin, whereby optical members having high refractive indexes and excellent optical characteristics can be formed with stability.
  • the surface of a lens it becomes possible to shape the surface of a lens to be a desired concavo-convex optical surface by repeating the process of discharging droplets onto a forming substrate and solidifying them by drying, whereby lenses of arbitrary shapes can be formed without any of molds and the development period for lens units can be shortened.
  • this manufacturing method of an optical member it is possible to form a lens to which a refractive index distribution is imparted in either the diameter direction, or the thickness direction, or both by mixing (on the surface of each droplet discharged) two or more kinds of resin solutions different in content of the fine particles at a ratio in accordance with at least either the diameter direction of the lens or the thickness direction of the lens.
  • resins differing in refractive index are mixed, a phase boundary is formed between them because they are not blended perfectly, and reflections of light occur thereat; as a result, white turbidity appears.
  • resin solutions differing in fine-particle content are blended uniformly, so it becomes possible to adjust the refractive index to an arbitrary value.
  • An optical member manufacturing apparatus for manufacturing an optical member by discharging a droplet of a solution of a thermoplastic resin and solidifying the droplet on a substrate by drying on a basis of profile data of the optical member, the apparatus comprising: a substrate on which the optical member is shaped; a nozzle which discharges the droplet of the solution of the thermoplastic resin; a discharge head freely-movably facing to the substrate and including the nozzle; and a control section for repeating a plurality of times a process of discharging droplets of the solution at different positions on a surface the substrate and solidifying the droplets by drying is repeated a plurality of times to stack the thermoplastic resin so that the stacked thermoplastic resin have a height according to the profile data.
  • thermoplastic resin solution is discharged onto a forming substrate as a discharge head is moved, and this discharging process is repeated until the thermoplastic resin comes to have desired heights at different positions, respectively, on the plane of the forming substrate, and it becomes possible to form a concavo-convex optical surface in a desired shape having undergone thickness control at many sites.
  • optical members of which frequent design changes are required such as low-volume diversified products, prototypes and the like, without using any of molds.
  • the discharge point passes through the center of rotation of the forming substrate, so it becomes possible to discharge onto all the positions inside a circle and to easily shape an optical member symmetric with respect to a point by movement in a radius direction.
  • optical member manufacturing apparatus as described in (18) or (19), further comprising a relative movement section which enables relative movement of the substrate and the discharge head along a direction.
  • this optical member manufacturing apparatus by moving the discharge head sequentially in a Y direction relative to the forming substrate while moving the discharge head repeatedly in an X direction relative to the forming substrate, it becomes possible to shape an optical member other than that having an axisymmetric shape, such as a cylindrical lens having a cylindrical face and its axis line in the X direction.
  • the optical member manufacturing apparatus as described in any one of (18) to (20), further comprising a measurement section that measures a height of droplets discharged out of the nozzle and landed and stacked on the substrate, wherein the control section controls for repeating the process discharging a droplet of the solution and solidifying the droplet by drying until the measured height of the stacked droplets reaches one corresponding to the profile data of the optical member.
  • the height measurement of the thermoplastic resin which is landed on the forming substrate and being stacked up is repeated in succession until the height of the thermoplastic resin stacked reaches to the height corresponding to the profile data, which allows high-precision shaping free of deviation from the profile data.
  • this optical member As to this optical member, the thickness thereof is controlled at many sites in the course of shaping, and the concavo-convex optical surface thereof is formed in a desired shape. Thus, it becomes possible to appropriate this optical member for optical members of which frequent design changes are required, such as low-volume diversified products or prototypes.
  • shaping of the optical member is performed by repeating a process of charging droplets of a thermoplastic resin solution onto different positions on the plane of a forming substrate and solidifying the droplets by drying until desired heights are reached at the different positions respectively by reference to the profile data of the optical member, thereby stacking the thermoplastic resin in a transparent condition on the substrate.
  • the optical member can be controlled in thicknesses at many sites, and does not require special preparation for a mold even when it undergoes a shape change.
  • time and cost spent on the making of a mold becomes unnecessary, and a wide variety of optical members in small quantities can be manufactured with high precision and at low cost.
  • An optical member manufacturing apparatus is equipped with a forming substrate on which the optical member is formed, a nozzle which discharges droplets of a thermoplastic resin solution, a freely-movable discharge head which faces the forming substrate and a control section for repeating a process of discharging the droplets onto different positions on a plane of the forming substrate and then solidifying them by drying until the droplets reach to desired heights at their respective positions. Therefore, the optical member shaped to have desired heights at different positions with high precision can be manufactured without using any mold; as a result, optical members involving frequent design changes, such as low-volume products and prototypes, can be manufactured with high precision and at low cost.
  • An optical member according to an aspect of the invention requires no mold for the shaping because it is manufactured by the method according to the invention. So, time and cost spent on the making of molds can be reduced, and short-time, low-cost manufacturing becomes possible.
  • Fig. 1 is a schematic block diagram showing an apparatus for manufacturing an optical member according to an aspect of the invention
  • Fig. 2 is a plan view of a forming substrate
  • Fig. 3 is a series of cross-sectional views of a discharge head which illustrates discharge situations (a), (b) and (c) of a droplet from a nozzle;
  • Fig. 4 is a flow chart describing a procedure of the manufacturing method according to an aspect of the invention.
  • Fig. 5 is an explanatory diagram showing plane section height-specific discharged areas obtained on the basis of profile data
  • Fig. 6 is a manufacturing process drawing which illustrates the shaping process of an optical member by section views (a) to (e);
  • Figs. 7(a) and 7(b) are explanatory diagrams showing, in Fig. 7(a), one structural example of a discharge head which discharges two or more kinds of resin solutions and, in Fig. 7(b), a lens having a refractive index distribution;
  • Fig. 8 is a manufacturing process drawing of an optical member made by bonding two pieces of halved optical members together;
  • Fig. 9 is a cross-sectional diagram showing one example of an irradiation device for performing a rapid thermal annealing treatment
  • Fig. 10 is an explanatory drawing of an optical member surface leveled off by removing microscopic asperities therefrom by raid thermal annealing treatment
  • Fig. 11 is a series of manufacturing process drawings (a), (b) and (c) of additional adjustment of a shaped optical member surface by means of a heat pressing
  • Fig. 12 is a set of cross-sectional views (a) and (b) of an optical member formed by raising of a glass body
  • Fig. 13 is a configuration diagram of a substantial part of an optical member manufacturing apparatus equipped with a relative movement device
  • Figs. 14(a) and 14(b) are a set of manufacturing process drawings wherein a discharge head equipped with a UV lamp is used;
  • Fig. 15 is a manufacturing process drawing of a lens formed from an optical member whose bottom alone is shaped by use of a die.
  • Fig. 1 is a schematic block diagram showing an apparatus for manufacturing an optical member according to an exemplary embodiment of the invention
  • Fig. 2 is a plan of a forming substrate
  • Fig. 3 is a series of cross-sectional views of a discharge head which illustrates discharge situations (a), (b) and (c) of a droplet from a nozzle.
  • the optical member manufacturing apparatus 100 discharges a thermoplastic resin solution in droplet form on a basis of profile data of an optical member and solidifies them by drying, thereby shaping the optical member. Additionally, in this embodiment, though a case where the optical member is a convex lens
  • lens shape can be changed as appropriate.
  • the manufacturing apparatus 100 is basically equipped with a forming substrate 13 on which a convex lens 11 is formed, a nozzle 15 discharging droplets of a thermoplastic resin solution, a freely-movable discharge head 17 incorporating a nozzle 15 and facing the forming substrate 13, and a control section 21 for repeating two or more times a process of discharging the droplets onto different positions on a plane of the forming substrate and then solidifying them by drying until desired heights are reached at the different positions respectively by referring the profile data of the convex lens 11 to a memory section 19.
  • the forming substrate 13 is supported by a lifting and lowering mechanism 25 in a condition that it can freely move up and down in such directions as to approach to and recede from the discharge head 17.
  • a rotary drive device 27 incorporating an electric motor is fastened to an upper part of the lifting and lowering mechanism 25.
  • the rotary drive device 27 rotates the forming substrate 13 fixed to a driving shaft 27a.
  • the discharge head 17 is supported in a condition of freely shuttling to and fro by means of a linear movement device 29 provided with a linear motor, a ball screw mechanism or the like.
  • the discharge head 17 is moved along a straight line 33 heading in a radius direction from the rotation center 31 of the forming substrate 13 by means of the linear movement device 29. In this way, it becomes possible to shape a convex lens 11 having a desired radius r.
  • This discharge head 17 is configured as an inkjet head which discharges droplets out of the nozzle 15. Further, in the neighborhood of the discharge head 17, a height measurement device
  • This height measurement device 37 is installed, and thereby the heights of droplets discharged out of the nozzle 15, landed on the forming substrate 13 and stacked thereat are measured.
  • This height measurement device 37 is mounted in a freely-movable sensor head 18 facing the forming substrate 13, and installed in a slanting direction so as to head its measurement direction for the landing position 1 IA of each droplet from the discharge head 17.
  • the sensor head 18, as in the case of the discharge head 17, is supported in a condition of freely shuttling to and fro by means of a linear movement device 30 provided with a linear motor, a ball screw mechanism or the like.
  • a linear movement device 30 provided with a linear motor, a ball screw mechanism or the like.
  • the sensor head 18 is moved along the straight line 33 heading in a radius direction from the rotation center 31 of the forming substrate 13 by means of the linear movement device 30.
  • the sensor head 18 may be moved in the direction opposite to the straight line 33 so that the height measurement is made at a position 36 to be reached by rotating the forming substrate 13 a half turn after the landing of a droplet.
  • the height measurement device 37 non-contact type devices, including those utilizing phase differences of laser light and the like, can be used to advantage.
  • a laser-utilized height measurement device 37 By use of a laser-utilized height measurement device 37, it becomes possible to perform non-contact, real-time, high-precision height detection of a soft thermoplastic resin just after landing on the forming substrate 13 and before complete solidification, and no damage to the convex lens 11 is caused by height measurements.
  • the discharge head 17 and the height measurement device 37 are supported separately in Fig. 2, the configuration thereof is not limited to such one, but the discharge head 17 and the height measurement device 37 may be configured to move in an integrated manner. Further, the traveling directions of the discharge head 17 and the sensor head 18 can be set arbitrarily without limited to the illustrated directions so long as they are radius directions.
  • the control section 21 repeats a process of discharging droplets and solidifying them by drying until the heights measured by the height measurement device 37 reach to heights corresponding to the profile data of the convex lens 11.
  • each of droplets is discharged out of the nozzle 15 by utilizing the deformation caused in the pressure chamber 39 by application of a voltage to the piezoelectric element 41.
  • the thermoplastic resin solution is fed from a tank 43 to an anterior pressure chamber 47 of the discharge head 17 via a feed tube 45.
  • the interior wall of the pressure chamber 39 facing the nozzle 15 is formed with diaphragm 49, and the diaphragm 49 is fastened to the piezoelectric element 41.
  • the diaphragm 49 is deformed by displacement occurring upon application of a voltage to the piezoelectric element 41.
  • the interior volume of the pressure chamber 39 varies, and thereby a droplet 51 is discharged out of the nozzle 15.
  • a minuscule droplet 51 is discharged with stability out of the nozzle 15 via a closed channel communicated with the pressure chamber 39 in a state of being favorable for drying.
  • the droplet 51 is not dry at the time of landing on the forming substrate 13, so it is dried after landing. More specifically, the first layer of the resin is dried after landing on the forming substrate, and the second layer and afterward are dried after upper and lower layers adhere to each other by blending and a phase boundary disappears. Additionally, each droplet is solidified immediately after landing because of its minuteness, so the measurement of its height H becomes possible.
  • the droplet 51 of a resin solution has a diameter of 0.005 mm to 0.1 mm.
  • the diameter of the droplet 51 to the specified range (0.005 mm to 0.1 mm)
  • the solvent evaporates from the droplet 51 landed, and thereby drying of the droplet is accelerated and the discharged thermoplastic resin solution is formed into a desired optical shape in a short time, and that wit stability. Further, the optical profile irregularity of the optical member formed is improved too. Additionally, when the droplet is too large in diameter, drying the droplet takes a long time and the optical member formed becomes coarse in shape.
  • the discharge of the droplet 51 is performed in either a vacuum, or an atmosphere of carbon dioxide, or an atmosphere of nitrogen. By doing so, it is possible to prevent occurrence of defects, including optical distortion and the like, caused by air remaining in the droplet 51 being trapped in the material under shaping into the convex lens 11 from the droplet 51.
  • Discharging droplets in a vacuum can prevent with certainty air from being trapped in the thermoplastic resin, while discharging droplets in an atmosphere of oxygen or nitrogen can prevent the gas from being trapped and remaining in the thermoplastic resin because each gas has high solubility in the thermoplastic resin.
  • discharging droplets in an atmosphere of oxygen or nitrogen can prevent the gas from being trapped and remaining in the thermoplastic resin because each gas has high solubility in the thermoplastic resin.
  • a piezoelectric inkjet head utilizing an piezoelectric element is employed.
  • an inkjet head of another system may be employed.
  • the so-called thermal inkjet head which is equipped with a nozzle, a fluid channel communicated with the nozzle and a heating unit disposed on a part of the fluid channel, and produces bubbles in the fluid channel by heat supply from the heating unit and thereby discharges droplets of the thermoplastic resin solution out of the nozzle.
  • thermoplastic resin solution is discharged onto the forming substrate 13 as the discharge head 17 is moved, and this discharging is repeated until the thermoplastic resin comes to have desired heights at different positions on the plane of the forming substrate, whereby forming the convex lens 11 with a concavo-convex optical surface of a desired shape becomes possible through thickness control at many sites.
  • a system of non-contact dispenser type may be employed in place of an inkjet system.
  • this optical member manufacturing apparatus is therefore equipped with the forming substrate 13 on which the convex lens 11 is formed, the nozzle 15 discharging droplets of a thermoplastic resin solution, the freely-movable discharge head 17 which faces the forming substrate 13, and the control section 21 for repeating a process of discharging the droplet 51 and solidifying by drying until desired heights are reached at different positions on the forming substrate plane, the convex lens 11 shaped so as to have the desired heights at different positions can be manufactured.
  • the convex lens 11 of which frequent design changes are required such as low-volume products and prototypes, can be manufactured speedily with high precision and at low cost without using any mold.
  • Fig. 4 is a flow chart describing a procedure of the manufacturing method relating to the invention
  • Fig. 5 is an explanatory diagram showing plane section height-specific discharged areas obtained on the basis of profile data
  • Fig. 6 is a manufacturing process drawing which illustrates the shaping process of an optical member by section views (a) to
  • the profile data of the convex lens 11 is captured from the memory section 19 by the control section 21 (si), converted to data as a model engineered by three-dimensional CAD and, as shown in Fig. 5, output in the form of discharge maps 23 of layers hi, h 2 , • • • h n- i, h n obtained by slicing the model into a plurality of plane sections in the direction parallel to the forming substrate (s2).
  • the control section 21 makes the setting of a target height from the discharge map 23 on the forming substrate 13 (s3).
  • control section 21 actuates the linear movement device 29 and sets the nozzle position of the discharge head 17 at the rotation center 31 (s4), and further actuates the rotary drive device 27 and rotates the forming substrate 13 (s5). And the control section 21 allows the discharge head 17 to discharge a droplet 51 while controlling the drive of the linear movement device 29 so as to increase the radius r (s6) gradually. At this time, the control section 21 allows the rotation speed of the forming substrate 13 to decrease and the interval of discharge timing from the discharge head 17 to lengthen with a gradual increase in the radius r, and thereby the constant density is kept at all the landing points.
  • the method of increasing the radius r gradually in whorls allows a smooth motion of the discharge head 17, and thereby continuous stacking can be achieved and occurrence of disarray in shape can be prevented.
  • the method of increasing the radius r stepwise after making a circuit with the same radius may be employed. In this case, the positioning of the radius r is made accurately, and shaping accuracy can be enhanced with ease.
  • the landing height is measured with the height measurement device 37 mounted in the sensor head 18 (s7).
  • the sensor head 18 is moved in the same direction as the discharge head 17 is moved in synchronization with movement of the discharge head 17 in the radius direction. In other words, both heads are moved in cooperation with each other so that the landing position of a droplet from the discharge head 17 agrees with the height measurement position of the height measurement device 37.
  • the control section 21 repeats two or more times a process of discharging the droplet 51 and solidifying through drying until the desired heights are reached at different positions on the forming substrate 13 while judging whether or not each layer comes to have its individually desired heights by reference to the profile data (s8).
  • the height of the droplet 51 landed on the forming substrate 13 and stacked thereat is measured, and the process of discharging the droplet 51 and solidifying it by drying is repeated until this measured height reaches to the height corresponding to the profile data of the convex lens 11.
  • the height of the thermoplastic resin landed repeatedly on the forming substrate 13 and being stacked thereon is detected in succession, which allows forming free of deviation from the profile data, or high-precision shaping.
  • a target height is set from the discharge map 23 of the next layer (slO). These processes are repeated until the layer stacked is detected as the final layer (topmost layer) (s9), and convex multilayer bodies 11a, l ib and lie are shaped in order as shown in Figs. 6(a) to 6(d).
  • the rotary drive device 27 is stopped (si I) 5 the discharge head 17 is evacuated (si 2), and the convex lens 11 is taken out of the forming substrate 13 as shown in Fig. 6(e), whereby the manufacturing of the lens is ended.
  • the convex lens 11 may be subjected to drying treatment for perfect removal of the solvent remaining therein.
  • vacuum drying at a temperature lower than the glass transition temperature of the thermoplastic resin is preferred. At this time, change in shape is negligibly small because the residual solvent is limited in quantity.
  • the convex lens 11 thickness control is performed at many sites in shaping the convex lens 11 by discharging a thermoplastic resin solution and solidifying it by drying, and thereby a concavo-convex optical surface of the desired shape is formed.
  • the convex lens 11 of a desired shape is formed as the discharge thicknesses at many sites are decided.
  • a volume change error does not occur when the thermoplastic resin solution is solidified, and a precise shape can be formed.
  • no mold needs to be newly prepared, and manufacture of the convex lens 11 becomes possible with high precision and high design flexibility.
  • the thermoplastic resin used in the description is a nanocomposite material which contains fine particles having sizes of 20 nm or below in a transparent thermoplastic resin. More specifically, the nanocomposite material is a material prepared by homogeneously dispersing inorganic fine particles, such as fine particles of a metal oxide, into a thermoplastic resin, has a high refractive index, and makes it possible to form optical members having excellent optical characteristics with stability. Details thereof are described hereinafter. According to this optical member manufacturing method, a process of discharging the droplet 51 and solidifying through drying is repeated until the desired heights are respectively reached at different positions on a plane by reference to the profile data of the convex lens 11, and thereby a transparent thermoplastic resin is stacked on the forming substrate 13 to perform shaping.
  • the shape of the convex lens 11 can be controlled in thicknesses at many sites, and special preparation for a mold is not required even when the product shape is changed. As a result, time and cost spent on the making of a mold becomes unnecessary, and a wide variety of convex lenses 11 in small quantities can be manufactured with high precision and at low cost. And by repetition of a process of discharging the droplet 51 onto the forming substrate 13 and solidifying it by drying, it becomes possible to shape the surface of the convex lens 11 into a desired concavo-convex optical surface, the convex lens 11 of an arbitrary shape can be easily manufactured without making any mold, and flexibility in lens design is enhanced.
  • the convex lens 11 manufactured by this manufacturing method allows offering a wide variety of lenses in small quantities in a short time and at low cost because time and cost spent for the making of a mold are cut.
  • a lens can be formed by mixing two or more kinds of the resin solutions differing in refractive index, e.g., by having different fine-particle contents at desired ratios in at least either the diameter direction of the lens or the thickness direction of the lens.
  • a refractive index distribution is imparted to at least either its diameter or thickness direction of the lens, and a variety of optical members can be formed freely.
  • FIG. 7(a) A structural example of a discharge head which discharges two or more kinds of resin solutions is shown in Fig. 7(a), and a lens having a refractive index distribution is shown in Fig. 7(b).
  • the discharge head 17A is connected to tanks 43 A and 43B, which store resin solutions A and B having different refractive indexes respectively, via feed tubes 45, and the controls of a discharge timing, discharge amount and so on are performed on a nozzle basis by a control section not shown in the figure.
  • the configuration of other parts is the same as shown in Fig. 1, so the description thereof is omitted.
  • a nozzle 15A and a nozzle 15B mounted in the discharge head 17A use a resin solution A having a refractive index of, say, 1.4 and a resin solution B having a refractive index of, say, 1.6 respectively, and shape a lens 11 having a refractive index distribution.
  • the lens 11 is formed by discharging only the resin solution A onto the central region 1 Ia of the lens and discharging only the resin solution B onto the outer region l ib of the lens.
  • the region l ie between the central region 11a and the outer region 1 Ib of the lens is formed by discharging the resin solutions A and B at mixing ratios changed as a function of, e.g., radius r.
  • the control function such as a function of radius r, may be a function of lens thickness, and can be freely chosen depending on the contents of an optical design. Thus, arbitrary refractive index distributions can be formed with ease.
  • the nozzles 15A and 15B may be mounted in an integrated state and designed movable as shown in the figure, but they are not limited to this design. They may be configured to be movable independently.
  • the height information of the lens under shaping is detected first and then, on the basis of the height information detected, a time required for each droplet to arrive the position slated for landing of the droplet on the forming substrate 13 is determined from the information of the nozzle-placed height position and the droplet discharge speed set in advance. And an amount of deviation of landing position after the forming substrate 13 is rotated by the time required for the arrival from the position slated for landing is determined. Timing of discharge of each droplet out of the nozzle 15 is corrected so as to be moved up and cancel the amount of deviation, and the landing position of the droplet is made to coincide with the position predetermined by the design.
  • each droplet can be landed exactly on the position slated for landing, and the optical member can be shaped with high precision.
  • the deviation of landing positions not only the positional deviation by rotation of the forming substrate 13 is corrected but also deviation of centrifugal force origin (deviation in a radiant direction from the center of rotation), which is caused by each droplet undergoing the centrifugal force generated by the rotary motion after landing, may be corrected.
  • an optical member is formed by bonding two pieces of convex lenses together, each of which is the convex lens 11, is illustrated.
  • Fig. 8 is a manufacturing process drawing of an optical member made by bonding two pieces of halved optical members together.
  • the convex lens 11 can be used alone as an optical member, two pieces of optical members, each of which is the optical member 11 whose bottoms 53 are formed into a planar shape, may be formed in one-piece optical member 1 IA by being joined together in a state that their bottoms 53 and 53 face each other for the purpose of further enhancing the flexibility of optical design. These bottoms 53 and 53 can be stuck together through blending by forming an adhesive layer 55 with, e.g., the same thermoplastic resin solution as used for the optical members.
  • the adhesion layer 55 may be formed by use of another transparent adhesive having the refractive index similar or approximate to that of the convex lens 11.
  • halved convex lenses each of which is the convex lens 11
  • halved convex lenses to be joined together each of which is the convex lens 11
  • a method of smoothing the surface of each lens is illustrated.
  • Fig. 9 is a cross-sectional diagram showing an example of an irradiation device for performing a rapid thermal annealing treatment
  • Fig. 10 is an explanatory drawing of an optical member surface leveled off by removing microscopic asperities therefrom by raid thermal annealing treatment.
  • a heat treatment unit 61 for performing rapid thermal annealing treatment has a plurality of lamps 63 and a reflector member 65 accommodated in a cabinet 67, and gathers flash irradiation beams gathered by the reflector member and forward flash irradiation light beams by means of a condenser lens 69 or a light shaper and conducts the gathered beams to the outside.
  • a light-condensing concave reflector member 65 cooled by circulating a refrigerant purified water or the like
  • a refrigerant purified water or the like
  • a light-condensing concave reflector member cooled by circulating a refrigerant (purified water or the like) is placed in the rear of a plurality of flash lamps, and flash irradiation light beams gathered by the reflector member and forward flash irradiation light beams are shaped with a light shaper (a beam homogenizer or the like), and thereby illuminance uniformity is enhanced.
  • the shaped light beams may be passed through a heat-wave reduction filter 70 or a heat-wave cutoff filter and transmitted to a desired direction when required.
  • the microscopic asperities on the surface of the convex lens 11 shown in Fig. 10 are removed by instant melting or semi-melting, and thereby the surface of the convex lens 11 is rendered smooth (leveled off) in accordance with the concavo-convex optical surface of the desired shape.
  • surface leveling of the optical member may be carried out by heat pressing too.
  • Fig. 11 is a manufacturing process drawing of additional adjustment of a shaped optical member surface by means of a heat pressing.
  • the front and rear optical surfaces of the shaped convex lens 11 are hot-pressed by means of pressing dies 71 and 73, and thereby the final adjustment of the lens shape can be made.
  • adjustment faces 71a and 73a corresponding to the front and rear optical surfaces of the convex lens 11 are formed.
  • the pressing dies 71 and 73 are positioned by guide jigs 75a and 75b, and allow pressing the front and rear sides of the convex lens 11 , respectively, while heating.
  • a transparent body (glass body) prepared beforehand is illustrated.
  • Fig. 12 shows a cross-sectional view of an optical member formed by raising of a glass body.
  • a transparent thermoplastic resin In the manufacturing method of an optical member, a transparent thermoplastic resin
  • 83 is stacked in layers on a spherical lens-shaped glass body 81 prepared beforehand, and thereby shaped into a convex lens 1 IB.
  • thermoplastic resin 83 is stacked on the forming substrate 13 from the start, because the number of repetition times of a process of discharging the droplet 51 and solidifying through drying is reduced by those required for reaching the volume of the glass body 81.
  • the working time for lens shaping can be shortened.
  • an aspheric lens can be shaped at a high speed by merely forming an aspheric surface layer through forming of an aspheric surface layer on a spherical lens-shaped glass body 81 by use of a thermoplastic resin solution.
  • the lens shaped when the glass body 81 and the thermoplastic resin are identical in refractive index, the lens shaped can have refraction performance equivalent to general aspheric lenses; while, when they are different in refractive index, the lens shaped can deliver different optical performance according to the combination of those refractive indexes.
  • the manufacturing method of an optical member are illustrated .
  • Fig. 13 shows a configuration diagram of a substantial part of an optical member manufacturing apparatus equipped with a relative movement device.
  • This manufacturing apparatus is equipped with a relative movement device 91 which allows a forming substrate 13 and a discharge head 17 to move relatively in arbitrary directions.
  • the relative movement device 91 is configured, e.g., so that a linear movement device 29 supporting the discharge head 17 so as to be freely movable in the X direction is further supported by a linear movement device 93 so as to be freely movable in the Y direction.
  • energy-curable resin can also be used as a lens material.
  • An optical member manufacturing apparatus in this case is illustrated below.
  • FIG. 14 drawings of a manufacturing process using a discharge head equipped with a UV lamp are shown.
  • a UV lamp 101 as an energy irradiation device is mounted in a discharge head 17 A.
  • the UV lamp 101 is made to move together with the discharge head 17 in the X direction through the reciprocatory motion of the discharge head 17.
  • Solidification of the energy-curable resin 84 which is discharged from the nozzle 15 and lands on the forming substrate 13 is accelerated by energy irradiation with the UV lamp 101 passing over the resin just after the landing, and thereby the resin 84 is formed into a convex lens HD.
  • a mercury lamp, gas laser, solid layer and the like can be used as the energy source.
  • a mercury lamp and a metal halide lamp can be used.
  • a GaN semiconductor UV emission device useful ecologically too may be used.
  • LED UV-LED
  • LD UV-LD
  • the energy irradiation device moves together with the reciprocatory movement of the discharge head 17 A, and irradiate the energy-curable resin 84 discharged from each nozzle 15 and landed on the forming substrate 13 with its energy.
  • solidification of the energy-curable resin 84 is accelerated and rapid shaping of the convex lens 1 ID becomes possible.
  • Fig. 15 shows a manufacturing process drawing of a lens formed from an optical member whose bottom alone is shaped by use of a die.
  • a specifically forming surface 111 is given to the substrate surface of a forming substrate 13 A, and by this forming surface the bottom of the convex lens 1 IE is shaped.
  • the surface of the convex lens 1 IE is worked so as to have an arbitrary lens shape by use of the method as described above.
  • the forming substrate 13A having such a forming surface 111 can form the surface of the convex lens HE facing the forming substrate 13A into a specified optical member surface 113. Therefore, a convex lens 1 IE with a high refractive index, which has surfaces formed into the shape of convex curve on both front and rear sides and a high refractive index, can be easily obtained without bonding two pieces of halved convex lens 11 and 11 together.
  • the invention should not be construed as being limited to the foregoing embodiments, but various changes and modifications can be made thereto as appropriate.
  • the lenses formed are not limited to convex lenses, but they may be concave lenses or gull-shaped lenses with two or more inflection points.
  • nanocomposite material (a material prepared by incorporating inorganic fine particles into a thermoplastic resin) usable in optical member manufacturing methods according to the invention is described below in detail.
  • a nanocomposite material for use in the invention contains a compound represented by the following formula (1) in combination with inorganic fine particles.
  • R 1 and R 2 each represent a substituent independently.
  • the substituent which can be taken as R 1 and R 2 each is not limited to particular ones.
  • examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (e.g., a methyl group, an ethyl group), an aryl group (e.g., a phenyl group, a naphthyl group), an alkenyl group, an alkynyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group (e.g., a methoxycarbonyl group), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group), a substituted or unsubstituted carbamoyl group (e.g., a carbamoyl group, an N-phenylcar
  • substituents may further be substituted.
  • substituents may be the same or different.
  • substituents may form a fused ring structure together with the benzene ring to which they are attached.
  • each of R 1 and R 2 is preferably a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, a sulfonamido group, an alkoxy group, an aryloxy group, an acyloxy group, a substituted or unsubstituted sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group, far preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an arylsulfonyl group, particularly preferably a halogen atom, an alkyl group, an aryl group or an aryloxy group.
  • ml and m2 each represent an integer of 0 to 5 independently. Each of ml and m2 is preferably from 0 to 3, far preferably from 0 to 2, further preferably 0 or 1. When ml and m2 are integers of 2 or above, substituents on the same benzene ring may be the same or different.
  • L represents an oxy group or a methylene group.
  • the molecular weight of a compound represented by formula (1 ) is preferably lower than 2,000, far preferably lower than 1,000, further preferably lower than 700.
  • the compounds represented by formula (1) may be synthesized according to the methods well-known to persons skilled in the art, or may be acquired by purchase on the market.
  • S-3101, S-3103, S-3105 and S-3230 produced by Matsumura Oil Research Corp. can be used.
  • the amount of a compound represented by formula (1) added to an inorganic-organic complex composition is preferably from 0.1 to 30 mass%, far preferably from 0.3 to 25 mass%, further preferably from 0.5 to 20 mass%.
  • the addition amount is 30 mass% or below, there is a trend toward easy prevention of weep of the compound during the forming and the storage.
  • the addition amount is 0.1 mass% or above, the addition of the compound tends to exhibit its effect with ease.
  • weep used herein means a phenomenon that the compound added oozes out of the formed body surface.
  • the nanocomposite material for use in the invention contains inorganic fine particles in combination with a compound represented by formula (1).
  • inorganic fine particles usable in the invention and the fine particles disclosed, e.g., in JP-A-2002-241612, JP-A-2005-298717, JP-A-2006-70069 and so on can be used.
  • fine particles of oxides such as aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, zinc oxide, magnesium oxide, tellurium oxide, yttrium oxide, indium oxide and tin oxide
  • fine particles of compound oxides such as lithium niobate, potassium niobate and lithium tantalate
  • fine particles of sulfides such as zinc sulfide and cadmium sulfide
  • crystalline fine particles of semiconductors such as zinc selenide, cadmium selenide, zinc telluride and cadmium telluride
  • fine particles of metal oxides are preferred over the others. More specifically, one metal oxide selected from the group consisting of zirconium oxide, zinc oxide, tin oxide and titanium oxide is preferred, one metal oxide selected from the group consisting of zirconium oxide, zinc oxide and titanium oxide is far preferred, and it is particularly advantgageous to use fine particles of zirconium oxide having good transparency in the visible region and low photocatalyst activity.
  • Inorganic fine particles for use in the invention may be a composite of two or more ingredients from the viewpoints of refractive index, transparency and stability.
  • the inorganic fine particles may be doped with a foreign element, or the surface layers thereof may be coated with a different kind of metal oxide, such as silica or alumina, or modified with a silane coupling agent, a titanate coupling agent, aluminate coupling agent, an organic acid (e.g., a carboxylic acid, a sulfonic acid, a phosphoric acid, a phosphonic acid) or so on for various purposes of, e.g., depression of photocatalyst activity, reduction in water absorption, and so on. Further, two or more kinds of these fine particles may be used in combination.
  • a different kind of metal oxide such as silica or alumina
  • a silane coupling agent such as silane coupling agent, a titanate coupling agent, aluminate coupling agent, an organic acid (e.g., a carboxylic acid, a sulfonic acid, a phosphoric acid, a phosphonic acid) or so on
  • the refractive index of inorganic fine particles for use in the invention have no particular limits. However, when a nanocomposite material is applied to an optical member required to have a high refractive index as in the invention, it is preferable that the inorganic fine particles have not only the thermal dependency but also high refractive index characteristics.
  • the refractive index of inorganic fine particles used is preferably from 1.9 to 3.0, far preferably from 2.0 to 2.7, particularly preferably from 2.1 to 2.5, as measured at a temperature of 22°C and a wavelength of 589 nm.
  • the refractive index of inorganic fine particles can be estimated by using, e.g., a method in which a composite composed of a thermoplastic resin used in the invention and the inorganic fine particles compounded therewith is formed into a transparent film, the refractive index of the transparent film is measured with an Abbe refractometer (e.g., DM-M4, made by ATAGO CO., LTD.), the refractive index of resin component itself is measured separately, and the refractive index of inorganic fine particles is calculated from these measured values, or a method of calculating a refractive index of fine particles by measuring the refractive indexes of fine particle dispersions differing in fine particle concentration.
  • an Abbe refractometer e.g., DM-M4, made by ATAGO CO., LTD.
  • the lower limit of the number average particle size of inorganic fine particles for use in the invention is preferably 1 nm or above, far preferably 2 nm or above, further preferably 3 nm or above, and the upper limit thereof is preferably 15 nm or below, far preferably 10 nm or below, further preferably 7 nm or below.
  • the number average particle size of inorganic fine particles in the invention is preferably from 1 nm to 15 nm, far preferably from 2 nm to 10 nm, particularly preferably from 3 nm to 7 nm.
  • inorganic fine particles for use in the invention satisfy the average particle size specified above, and besides, the particle size distribution thereof be as narrow as possible.
  • the numerically specified range as disclosed, e.g., in JP-A-2006- 160992 holds true also for preferred particle size distribution of fine particles for use in the invention.
  • the foregoing number average particle size can be measured by means of, e.g., an X-ray diffracting (XRD) device or a transmission electron microscope (TEM).
  • XRD X-ray diffracting
  • TEM transmission electron microscope
  • inorganic fine particles for use in the invention has no particular restrictions, and any of known methods can be employed.
  • desired fine particles of an oxide can be obtained by using a metal halide or a metal alkoxide as a raw material and performing hydrolysis in a reaction system containing water. Details of this method are described, e.g., in Japanese Journal of Applied
  • Examples of a solvent usable in those methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone and anisole. These solvents may use used alone or as mixtures of two or more thereof.
  • the content of inorganic fine particles in a nanocomposite material for use in the invention is preferably from 20 to 95 mass%, far preferably from 25 to 70 mass%, further preferably from 30 to 60 mass%, from the viewpoint of ensuring good transparency and a high refractive index.
  • the mass ratio between the inorganic fine particles and the thermoplastic resin (dispersion polymer) in the invention is preferably from 1:0.01 to 1:100, far preferably from 1:0.05 to 1:10, particularly preferably from 1 :0.05 to 1:5.
  • the nanocomposite material for use in the invention contains a thermoplastic resin.
  • the nanocomposite material for use in the invention contain a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond together with an inorganic fine particle at least either at a high molecular chain end thereof or in a side chain thereof.
  • the term "chemical bond" used herein is intended to include a covalent bond, an ionic bond, a hydrogen bond and a coordination bond.
  • thermoplastic resin the following three kinds of thermoplastic resins can be given.
  • each of R 11 , R 12 , R 13 and R 14 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group), -SO 3 H, -OSO 3 H, -CO 2 H, or -Si(OR !5 ) ml R 16 3-m i (wherein each of R 15 and R 16 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and ml represents an integer of 1 to 3).
  • Thermoplastic resin having in at least one end of its high molecular chain a functional group
  • R 21 , R 22 , R 23 and R 24 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group
  • R 25 and R 26 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and m2 represents an integer of 1 to 3).
  • Block copolymer including a hydrophobic segment and a hydrophilic segment.
  • the thermoplastic resin (3) in particular is described below in detail.
  • thermoplastic resin (3) usable in the invention is a block copolymer including a hydrophobic segment and a hydrophilic segment.
  • hydrophobic segment (A) refers to the segment having a property of being insoluble in water or methanol in the form of a polymer containing only the segment (A)
  • hydrophilic segment (B) refers to the segment having a property of being soluble in water or methanol in the form of a polymer containing only the segments (B).
  • type of the block copolymer include an AB type, a B 1 AB 2 type (wherein two hydrophilic segments B 1 and B 2 may be the same or different) and an A 1 BA 2 type (wherein two hydrophobic segments A 1 and A 2 may be the same or different).
  • a block copolymer of AB type or A 1 BA type block copolymer is preferred; while, in point of production suitability, a block copolymer of AB type or ABA type (or A 1 BA 2 type in which two hydrophobic segments are the same) is far preferred, and a block copolymer of AB type is especially preferred.
  • Each of the hydrophobic segment and the hydrophilic segment can be selected arbitrarily from heretofore known polymers including vinyl polymers prepared by polymerization of vinyl monomers, polyether polymers, ring-opening metathesis polymerization polymers and condensation polymers (such as polycarbonate, polyester, polyamide, polyether ketone and polyether sulfone). Of these polymers, however, those selected from vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates or polyesters are preferred as those segments, and vinyl polymers are far preferred in point of production suitability.
  • Examples of a vinyl monomer (A) forming the hydrophobic segment (A) include the following: Acrylic acid esters and methacrylic acid esters (ester groups of which are substituted or unsubstituted aliphatic ester groups or substituted or unsubstituted aromatic ester groups, such as a methyl ester group, a phenyl ester group and naphthyl ester group); acrylamides and methacrylamides, with examples including an N-monosubstituted acrylamide, an N-disubstituted acrylamide, an N-monosubstituted methacrylamide and an N-disubstituted methacrylamide (substituents of the monosubstituted and disubstituted amides are substituted or unsubstituted aliphatic groups or/and substituted or unsubstituted aromatic groups, with examples including a methyl group, a phenyl group and a naphthyl group
  • acrylic acid esters and methacrylic acid esters the ester moieties of which contain unsubstituted aliphatic groups, or substituted or unsubstituted aromatic groups; an N-monosubstituted acrylamide, an N-disubstituted acrylamide, an N-monosubstituted methacrylamide and an N-disubstituted methacrylamide, the substituents of which are unsubstituted aliphatic groups or/and substituted or unsubstituted aromatic groups; and styrene compounds are preferable to the others. Further, acrylic acid esters and methacrylic acid esters the ester moieties of which contain substituted or unsubstituted aromatic groups, and styrene compounds are preferred over the others.
  • Examples of a vinyl monomer (B) forming the hydrophilic segment (B) include acrylic acid, methacrylic acid, and acrylic acid esters and methacrylic acid esters which have hydrophilic substituents in their respective ester moieties; styrene compounds which have hydrophilic substituents in their respective aromatic ring moieties; and vinyl ether, acrylamide, methacrylamide, an N-monosubstituted acrylamide, an N-disubstituted acrylamide, an N-monosubstituted methacrylamide and an N-disubstituted methacrylamide, which each contain a hydrophilic substituent.
  • the preferred as such hydrophilic substituents are those having functional groups selected from,
  • each of R 31 , R 32 , R 33 and R 34 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group), -SO 3 H, -OSO 3 H, -CO 2 H, -OH or -Si(OR 35 ) m3 R 36 3-m3 (wherein each of R 35 and R 36 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and m3 represents an integer of 1 to 3).
  • R 31 , R 32 , R 33 , R 34 , R 35 and R 36 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group
  • preferred ranges of these groups are the same as recited as preferred ones in the description of R 11 , R 12 , R 13 and R 14 .
  • m3 is preferably 3.
  • the block copolymer has a functional group selected from
  • the hydrophilic segment (B) be formed from acrylic acid, methacrylic acid, an acrylic or methacrylic acid ester having a hydrophilic substituent in its ester moiety, or a styrene compound having a hydrophilic substituent on its aromatic ring moiety.
  • the vinyl monomer (B) may be included to the extent of having no detrimental effect on the hydrophobic property of the segment (A).
  • the mole ratio between the vinyl monomer (A) and the vinyl monomer (B) included in the hydrophobic segment (A) is preferably from
  • the vinyl monomer (A) may be included to the extent of having no detrimental effect on the hydrophilic property of the segment (B).
  • the mole ratio between the vinyl monomer (B) and the vinyl monomer (A) included in the hydrophilic segment (B) is preferably from 100:0 to 60:40.
  • each of the vinyl monomer (A) and the vinyl monomer (B) one kind thereof may be used alone, or two or more kinds thereof may be used together.
  • These vinyl monomers (A) and (B) are selected variously according to different purposes (such as acid content control, glass transition temperature (Tg) control, organic solvent or water solubility control and dispersion stability control).
  • the functional group content in the overall block copolymer is preferably from 0.05 to 5.0 mmol/g, far preferably from 0.1 to 4.5 mmol/g, particularly preferably from 0.15 to 3.5 mmol/g. Too low functional-group contents may cause poor suitability for dispersion, while too high functional-group contents may cause excessive water solubility or gelling of the organic-inorganic complex composition. Additionally, the functional group(s) in the block copolymer may combine with cationic ion(s), such as alkali metal ion(s) (e.g., Na + , K + , etc.) or ammonium ion(s), to form salt(s).
  • the molecular weight (Mn) of the block copolymer is preferably from 1,000 to
  • 100,000 far preferably from 2,000 to 80,000, particularly preferably from 3,000 to 50,000.
  • the molecular weight of the block copolymer is adjusted to 1,000 or above, there is a trend toward easy preparation of a stable dispersion, and when the molecular weight of the block copolymer is adjusted to 100,000 or below, there is a trend toward enhancement of solubility in organic solvents. So, the range of 1,000 to 100,000 is preferred.
  • the refractive index of the block copolymer for use in the invention is preferably greater than 1.50, far preferably 1.55 or greater, further preferably greater than 1.60, particularly preferably greater than 1.65. Additionally, the values of the refractive indexes specified herein are values determined by measurements with an Abbe refractometer (e.g.,
  • DM-M4 made by ATAGO CO., LTD. wherein light with a wavelength of 589 nm is used.
  • the glass transition temperature of the block copolymer for use in the invention is preferably from 80°C to 400 0 C, far preferably from 130°C to 380 0 C.
  • the glass transition temperature is adjusted to 80 0 C or higher, there is a trend toward enhancement of heat resistance; while, when the glass transition temperature is adjusted to 400 0 C or lower, there is a trend toward enhancement of workability in forming.
  • the light-beam transmittance of the block copolymer for use in the invention is preferably 80% or above, far preferably 85% or above, in terms of 1-mm thickness when measured at the wavelength of 589 nm.
  • Examples of the block copolymer (exemplified compounds Q-I to Q-20) are illustrated in the following tables. Additionally, block copolymers usable in the invention should not be construed as being limited to these examples in any way.
  • the block copolymer as illustrated above can be synthesized by utilizing living radical polymerization or living ionic polymerization and, if required, using a technique of protecting a carboxyl group or the like or a technique of introducing a functional group into a polymer. Alternatively, it can be synthesized from a polymer having an end functional group by radical polymerization, or by interlinking one polymer having an end functional group with another polymer having an end functional group. Of these syntheses, syntheses utilizing living radial polymerization and living ionic polymerization are preferred to the others from the viewpoints of molecular weight control and the yields of block copolymers obtained thereby.
  • additives can be mixed in the nanocomposite material for use in the invention as appropriate from the viewpoints of uniform dispersibility, releasability and weather resistance.
  • additives include a surface treating agent, an antistatic agent, a dispersant, a plasticizer and a releasing agent.
  • resins not having the functional groups as recited above may further be added regardless of their kinds. However, it is preferred that the resins added be similar in optical properties, thermal properties and molecular weights to the thermoplastic resin used.
  • the mixing proportion of those additives is preferably from 0 to 50 mass%, far preferably from 0 to 30 mass%, particularly preferably from 0 to 20 mass%, with respect to the sum of the inorganic fine particles and the thermoplastic resin.
  • fine particle surface modifiers other than the thermoplastic resin may be added in mixing the inorganic fine particles dispersed in water or an alcohol solvent into the thermoplastic resin in response to various purposes including the purpose of enhancing extractability and exchangeability with organic solvents, the purpose of enhancing uniform dispersibility in the thermoplastic resin, the purpose of lowering a water absorption rate of the fine particles, the purpose of improving the weather resistance, and so on.
  • the weight average molecular weight of the surface treating agent including such a surface modifier is preferably from 50 to 50,000, far preferably from 100 to 20,000, further preferably from 200 to 10,000.
  • a compound having the structure represented by the following formula (2) is preferred.
  • A represents a functional group capable of forming a chemical bond together with an inorganic fine particle surface
  • B represents a 1-30C univalent group having compatibility or reactivity with a resin matrix composed mainly of the thermoplastic resin used in the invention or a polymer.
  • the term "chemical bond” used herein is intended to include a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond and the like.
  • Examples of a group suitable as the group represented by A include the same groups as recited as examples of the functional group of the thermoplastic resin used in the invention.
  • the group represented by B it is preferred in point of compatibility that the group represented by B be identical or similar in chemical structure to that of the thermoplastic resin dominating in the resin matrix. From the viewpoint of enhancing the refractive index in particular, it is preferred that an aromatic ring be present in the chemical structure of B as in the chemical structure of the thermoplastic resin.
  • Examples of a surface treating agent suitably used in the invention include p-octylbenzoic acid, p-propylbenzoic acid, acetic acid, propionic acid, cyclopentanecarboxylic acid, dibenzyl phosphate, monobenzyl phosphate, diphenyl phosphate, di- ⁇ -naphthyl phosphate, phenylphophonic acid, phenylphosphonic acid monophenyl ester, KAYAMER PM-21 (trade name, a product of NIPPON KAYAKU CO., LTD.), KAYAMER PM-2 (trade name, a product of NIPPON KAYAKU CO., LTD.), benzenesulfonic acid, naphthalenesulfonic acid, p-octylbenzenesulfonic acid, and the silane coupling agents disclosed in JP-A-5-221640, JP-A-9-100111 and JP-A-2002- 187921
  • the ratio between the total addition amount of these surface treating agents and that of the inorganic fine particles is preferably from 0.01 to 2, far preferably from 0.03 to 1, particularly preferably from 0.05 to 0.5, on a mass basis.
  • an antistatic agent can be added.
  • inorganic fine particles themselves which are added to the nanocomposite material for the purpose of improving optical properties, contribute to antistatic effect as another effect.
  • the antistatic agent added may be an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, an amphoteric antistatic agent, a polymeric antistatic agent, or antistatic fine particles.
  • Two or more kinds of antistatic agents may also be used in combination. Examples of these antistatic agents include the compounds disclosed in JP-A-2007-4131 and JP-A-2003-201396.
  • the antistatic agents added constitute preferably 0.001 to 50 mass%, far preferably 0.01 to 30 mass%, particularly preferably 0.1 to 10 mass%, of the total solids.
  • native wax such as vegetable wax (e.g., carnauba wax, rice wax, cotton wax, Japan wax, etc.), animal wax (e.g., beeswax, lanolin, etc.), mineral wax (e.g., ozocerite, cerecin, etc.) or petroleum wax (e.g., paraffin, microcrystalline wax, petrolactam, etc.), synthetic hydrocarbon wax such as Fischer-Tropsch wax or polyethylene wax, synthetic wax such as a long-chain aliphatic amide, ester, ketone or ether (e.g., stearic acid amide, chlorin
  • degradation inhibitors of hindered phenol type, amine type, phosphorus-containing type or thioether type may further be added as appropriate.
  • the mixing proportion of such degradation inhibitors is preferably on the order of 0.1 to 5 mass% with respect to the total solids in the resin composition.
  • the nanocomposite material for use in the invention is prepared by dispersing inorganic fine particles into the thermoplastic resin molecules having functional groups in a state that the particles form chemical bonds to the resin molecules. And this process of dispersing is carried out in the presence of the compound represented by formula (1).
  • the inorganic fine particles for use in the invention is minute in particle size and high in surface energy, once they are isolated in a solid state they are difficult to disperse again. Accordingly, it is preferred that the inorganic fine particles in a state of being dispersed in a solution be mixed into the thermoplastic resin and made into a stable dispersion.
  • Examples of a manufacturing method suitable for the nanocomposite material include: [1] a method of manufacturing a composite of inorganic fine particles and a thermoplastic resin by subjecting inorganic particles to surface treatment in the presence of a surface treating agent, extracting the surface-treated inorganic fine particles with an organic solvent, and then homogeneously mixing the extracted inorganic fine particles with the thermoplastic resin and the compound represented by formula (1), and [2] a method of manufacturing a composite of inorganic fine particles and a thermoplastic resin by mixing all the ingredients including inorganic fine particles, the thermoplastic resin, the compound represented by formula (1) and other additives with the aid of a solvent in which all the ingredients can disperse homogenously or dissolve.
  • the organic solvent used is a solvent insoluble in water, such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloromethane, dichloroethane, chlorobenzene or methoxybenzene.
  • the surface treating agent used in extracting fine particles with an organic solvent may be similar or different in kind to or from the thermoplastic resin, and suitable examples thereof include those mentioned in the foregoing section ⁇ Surface Treating Agent>.
  • the compound represented by formula (1) is also added, and additives such as a plasticizer, a releasing agent or a different kind of polymer may further be added as required.
  • the solvent used is a hydrophilic polar solvent, such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, l-methoxy-2-propanol, tert-butanol, acetic acid or propionic acid, or a mixture of two or more of these polar solvents, or a mixture of a solvent insoluble in water, such as chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene or methoxybenzene, and a polar solvent as recited above.
  • a hydrophilic polar solvent such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether,
  • a dispersant other than the thermoplastic resin, a plasticizer, a releasing agent or a different kind of polymer may be added as needed.
  • a hydrophilic solvent having higher boiling point than the water-methanol mixture, in which the thermoplastic resin can be dissolved is added, then the dispersion liquid of the fine particles is replaced with the polar organic solvent by concentrating the water-methanol mixture through distillation, and thereafter the fine particles are mixed with the resin.
  • the surface treating agent may be added.
  • a zirconium oxychloride solution having a concentration of 50 g/L was neutralized with a 48% aqueous sodium hydroxide solution, thereby preparing a hydrated zirconium suspension.
  • This suspension is filtered off, and then washed with ion exchange water.
  • hydrated zirconium cake was obtained.
  • This cake was prepared into a concentration of 15 mass% in zirconium oxide terms by use of ion exchange water, placed in an autoclave, and subjected to 24-hour hydrothermal treatment at 150°C under a pressure of 150 atmospheres.
  • a fine-particle suspension of zirconium oxide was obtained.
  • Solvent replacement was carried out by adding 500 g of N,N'-dimethylacetamide to
  • a mixed solution containing 2.1 g of tert-butyl acrylate, 0.72 g of 2-bromopropionic acid tert-butyl ester, 0.46 g of Copper ⁇ bromide, 0.56 g of N,N,N',N',N", N"-pentamethyldiethylenetetramine and 9 ml of methyl ethyl ketone was prepared, and subjected to replacement with N 2 . While stirring the resulting solution for one hour at an oil-bath temperature of 80°C, 136.2 g of styrene was added thereto in a stream of nitrogen. The resulting mixture was further stirred for 16 hours at an oil-bath temperature of 90°C, and then cooled to room temperature.
  • thermoplastic resin Q-I To the dispersion of zirconium oxide dimethylacetamide, the thermoplastic resin Q-I, Compound PL-I and a surface treating agent (4-propylbenzoic acid) were added at a ZrO 2 (as a solid component)/PL-l /4-propylbenzoic acid ratio of 41.7/8.3/8.3, and mixed homogeneously with stirring, and then the dimethylacetamide solvent was concentrated by heating under reduced pressure. The thus obtained concentrated solution as a resinous solution of nanocomposite material was formed into a lens by means of the inkjet head.
  • a surface treating agent 4-propylbenzoic acid
  • various drying methods such as a heat-transfer drying method, an internal heat generation drying method and an unheated drying method, can be applied to the pretreatment of the resinous solution. More specifically, box drying, tunnel and band drying, rotary drying, through-flow rotary drying, channel agitation drying, fluidized-bed drying, spray drying, flash drying, vacuum-freeze drying, vacuum drying, infrared drying, internal heat generation drying, drum drying or so on can be given in advance. Additionally, two or more of these drying methods may be used in combination.
  • the liquid viscosity at the time of spray drying is adjusted preferably to 300 cP or below, far preferably to 100 cP or below, further preferably to 50 cP. (The liquid viscosity is adjustable by changing the concentration of the solution.)
  • a lens having a diameter ⁇ of 5 mm and a thickness of 1 mm was shaped under conditions that drying shrinkage of the resinous solution was 90%, the discharge cycle from a nozzle was 20 times per second and the number of nozzles was 20.
  • the shaping was able to reach completion within the span of 15.6 minutes at the shortest.
  • optical-member manufacturing method of an exemplary embodiment of the invention as mentioned above, high-quality optical materials can be manufactured with arbitrary shapes and arbitrary optical characteristics in a short time by use of nanocomposite materials having high refractive indexes. Therefore, the present manufacturing method has very high utility value in manufacturing optical members including miniature-sized lenses usable in, e.g., mobile phone's built-in cameras and optical information recording devices, such as DVD, CD and MO drives.

Landscapes

  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)

Abstract

A method for manufacturing an optical member (11) is provided and includes: discharging a droplet (51) of a solution a transparent thermoplastic resin and solidifying the droplet on a substrate (13) on a basis of profile data of the optical member to shape the optical member, in which a process of discharging droplets of the solution on different positions of the substrate and solidifying the droplets by drying is repeated a plurality of times to height according to the profile data; and separating the shaped optical member from the substrate.

Description

DESCRIPTION
MANUFACTURING METHOD OF OPTICAL MEMBER, OPTICAL MEMBER MANUFACTURING APPARATUS AND OPTICAL MEMBER
Technical Field
The present invention relates to a manufacturing method of an optical member, an optical member manufacturing apparatus, and an optical member formed by the manufacturing method, and more specifically, to an art of forming an optical member from a nanocomposite material.
Background Art
With the recent performance enhancement, miniaturization and cost reduction of optical devices including a mobile phone's built-in camera and optical information recording devices, such as DVD, CD and MO drives, developments of excellent materials and processes have been intensely desired also for optical members used in those devices, such as optical lenses or filters.
Since plastic lenses in particular are lightweight and less splintery, can be worked into various shapes and further can be produced at low cost as compared with lenses made of inorganic materials such as glass, they have rapidly come into widespread use as not only eyeglasses but also optical lenses for the foregoing uses. With this trend, it comes to be desired that the refractive indexes of raw materials themselves be heightened for the purposes of thinning lenses and stabilizing optical refractive indexes against thermal expansion, temperature changes and so on. In general, such plastic lenses are formed by charging resin materials into molds.
In the case of forming high-precision lenses, highly precise shapes are imparted to the lenses by heat pressing with dies. Furthermore, various attempts have been made to enhance optical refractive indexes of the lenses and to control thermal expansion coefficients of the lenses and temperature-dependent changes in optical refractive indexes of the lenses by using as lens materials nanocomposite materials made by dispersing inorganic fine particles, such as fine particles of metal, into plastic resins (See, e.g., JP-A-2006-343387, JP-A-2002-47425 and JP-A-2003-155415).
In the cases of forming optical members, notably optical members required to have high degree of transparency, by use of such nanocomposite materials, reduction of light scattering required the inorganic fine particles to have sizes smaller than the wavelengths of light used. Further, for reduction in the decay of transmitted light intensity by Rayleigh scattering, it was required to prepare and disperse nanoparticles having a uniform size of 15 nm or below. Examples of a technique to manufacture a nanocomposite material containing a plastic resin and inorganic fine particles dispersed therein include the following.
(1) A technique of putting inorganic fine particles directly in a plastic resin and mixing them into the resin.
(2) A technique of mixing inorganic fine particles with a plastic resin in a liquid acting as a solvent, and then stripping away the solvent by heating.
(3) A technique of mixing a monomer and inorganic fine particles together, and then polymerizing the monomer and thereby incorporating the inorganic fine particles into the polymer formed.
However, according to the technique (1), aggregation of the particles occurs when the proportion of the particles mixed is high; as a result, the composite material obtained is lacking in transparency. In the technique (3), shape control is difficult because of a great shrinkage at the time of polymerization, and shaping cannot be performed with a precision required of, e.g., shooting lenses for miniature cameras for mobile phones, pickup lenses and the like. The technique (2), though it allows manufacture of highest-quality lenses, it still takes much time to strip away the solvent used.
In addition, since plastic lenses are formed by charging resin materials into molds, or they are formed by heat pressing with dies, changes in shapes of products involve preparation for new molds, and much time and much expense are required for making molds. Therefore, it is impossible to cope with frequent design changes in the cases where the volume of production is low and a wide variety of products are made, or prototypes are made.
By contrast, the three-dimensional shape forming method disclosed in
JP-A-2006- 146063 employs an inkjet method, and provides three-dimensional microscopic asperities by utilizing shrinkage of organic materials. More specifically, two or more fluid materials for discharge are discharged in succession onto a substrate and form droplets in an incompletely-mixed state, or in a state that the fluid materials are not mixed thoroughly.
And by curing the droplets in a state that the two or more fluid materials discharged are mixed incompletely, differences in shrinkage rate are made between the cured fluid materials to contribute formation of microscopic asperities on the droplet surface of the cured fluid materials. Thus, in addition to a greatly undulating convex shape formed by droplets each being made up of the liquid materials discharged, microscopic asperities with little undulations are formed on the surface of each droplet.
In addition, the three-dimensional shaping apparatus disclosed in JP-A-2005-59289 incorporates a three-dimensional shaping device by which a process of discharging a solution fed from a storage tank in droplet form from a drop-on-demand type inkjet head and then solidifying the discharged solution by drying is repeated two or more times, thereby stacking droplets and forming a three-dimensional shape, and aims at improvement of shape quality by adjusting an average speed of each droplet discharged from the inkjet head to fall within a range of 7 m/s to 4 m/s during the passage of a distance of 1 mm from the nozzle face so that the flying speed of each droplet is minimized and thereby not only the shape of each droplet arriving at the shaping stage becomes closer and closer to a sphere but also the collision energy is lessened.
As other examples of a lens manufacturing method wherein the lens shape is formed through discharge of a resin solution in droplet form from an inkjet head, the methods disclosed in JP-A-2000-67449, JP-A-2006-54489, JP-A-2005-88502 and JP-A-2005-92049 can be given. In each of these lens shaping methods, the droplets of a resin solution are made to land on the same position and the landed droplets are stacked to form a lens of desired size.
However, because the optical surface is formed by the leveling of droplets in every one of the lens manufacturing methods disclosed in JP-A-2006- 146063, JP-A-2000-67449, JP-A-2006-54489, JP-A-2005-88502 and JP-A-2005-92049, the degree of flexibility in designing the shape is seriously low. More specifically, the forming of a lens shape by utilization of leveling has an advantage of easy forming of a general lens shape in the cases of miniature lenses including micro lenses and the like, but there is a difficulty in applying it to forming of lenses of sizes on the general camera lens level, concave lenses and high-precision lens shapes. Further, the radius of curvature of a droplet surface is unambiguously determined by the viscosity and surface tension of a resin solution used, and besides, fluctuations therein tend to occur. This respect also makes it difficult to complete the forming of a lens in a desired shape. In other words, the lens manufacturing method utilizing the leveling are effective for lenses aiming to obtain only a light-gathering action, such as optical systems for projecting light, but it cannot attain profile irregularity for keeping up high resolution required of lenses in optical systems for taking pictures.
On the other hand, in the three-dimensional shaping apparatus disclosed in JP-A-2005-59289, while melt of a thermoplastic resin is formed into droplets, the melt is unfit for formation of droplets because the resin is high in viscosity and made up of long molecules.
Disclosure of the Invention A first object of the invention is to provide a method of manufacturing a high-precision optical member without requiring any mold, and a second object of the invention is to provide a manufacturing method of an optical member, wherein resin solutions containing nanocomposite materials are formed into uniform droplets and the droplets can be formed into a desired shape with stability while stripping away the solvent in a short time, and an optical member formed by this manufacturing method.
The objects of the invention can be achieved by constitutions as described below. (1) A manufacturing method of an optical member, comprising: discharging a droplet of a solution including a transparent thermoplastic resin and solidifying the droplet on a substrate on a basis of profile data of the optical member to shape the optical member, wherein a process of discharging droplets of the solution on different positions of the substrate and solidifying the droplets by drying is repeated a plurality of times to stack the thermoplastic resin so that the stacked thermoplastic resin have a height according to the profile data; and separating the shaped optical member from the substrate.
According to this manufacturing method of an optical member, when an optical member is shaped by discharging a solution of thermoplastic resin and solidifying it by drying, its thickness is controlled at many sites, whereby a concavo-convex optical surface of a desired shape is formed. In other words, while confirming discharge thicknesses at many sites, an optical member of a desired shape is formed. Thus, even when a modification is made to the product shape, no mold needs to be newly prepared, and manufacture of a high-precision optical member becomes possible with high design flexibility.
(2) The manufacturing method of an optical member as described in (1), further comprising measuring a height of droplets of the solution landed and stacked on the substrate, wherein the process of discharging a droplet of the solution and solidifying the droplet by drying is repeated until the measured height of the stacked droplets reaches one corresponding to the profile data of the optical member.
According to this manufacturing method of an optical member, the height of thermoplastic resin at each time of repeated landing and stacking on the substrate is detected in succession, whereby it becomes possible to form an optical member free of deviation from the profile data, namely a high-precision optical member.
(3) The manufacturing method of an optical member as described in (1) or (2), wherein the discharging of the droplet is performed so that each of plane sections into which the optical member is sliced in a direction parallel to the substrate is stacked in succession, starting with a bottom plane section, on the substrate.
According to this manufacturing method of an optical member, each plane section is stacked in succession. So, the simplified forming is possible even when the optical member has a complex shape.
(4) The manufacturing method of an optical member as described in (2), wherein the measuring of the height of the droplets is performed by utilizing a phase difference of laser light.
According to this manufacturing method of an optical member, it becomes possible to carry out non-contact, high-precision height detection of a soft thermoplastic resin just after landing on the substrate and before complete solidification; as a result, no damage to the optical member is caused by height measurements.
(5) The manufacturing method of an optical member as described in any one of (1) to (4), wherein the droplet is discharged out of a nozzle of an inkjet head.
According to this manufacturing method of an optical member, the inkjet head allows high-accuracy setting of a uniform droplet size.
(6) The manufacturing method of an optical member as described in (5), wherein the inkjet head includes the nozzle, a pressure chamber communicated with the nozzle, and a piezoelectric element combined with the pressure chamber for pressurization, and wherein the inkjet head discharges the droplet of the solution of the thermoplastic resin out of the nozzle when an inside of the pressure chamber is pressurized by application of a voltage to the piezoelectric element.
According to this manufacturing method of an optical member, the piezoelectric element is extended by applying a voltage to the piezoelectric element in the pressure chamber, and this extending motion pressurizes the interior of the pressure chamber; as a result, the solution can be discharged in droplet form out of the nozzle.
(7) The manufacturing method of an optical member as described in (5), wherein the inkjet head includes the nozzle, a fluid channel communicated with the nozzle, and a heating unit disposed on a part of the fluid channel, and wherein bubbles are produced in the fluid channel by heat supply from the heating unit so that the droplet of the solution of the thermoplastic resin is discharged out of the nozzle.
According to this manufacturing method of an optical member, bubbles are produced in the solution by heat supply to the fluid channel from the heating unit to cause volumetric expansion, thereby allowing discharge of the solution out of the nozzle in droplet form.
(8) The manufacturing method of an optical member as described in any one of (1) to (7), wherein the droplet of the solution has a diameter of 0.005 mm to 0.1 mm.
According to this manufacturing method of an optical member, the diameters of the droplets are adjusted to fall within the specified range (from 0.005 mm to 0.1 mm), thereby expediting the drying of landed droplets through evaporation of the solvent. As a result, the discharged thermoplastic resin solution is formed into a desired optical shape in a short time, and that with stability. Furthermore, the optical profile irregularity of the optical member shaped is also enhanced. Additionally, droplets too large in diameter require a long time for drying and the shapes thereof become coarse. On the other hand, too small in diameter require too long time for forming, and each droplet dries up before landing. As a result, these droplets cannot stick together through blending. In particular, when the droplets are too small, not only the shape of the optical member is difficult to complete but also the landing positions becomes difficult to control. (9) The manufacturing method of an optical member as described in any one of ( 1 ) to (8), wherein the shaped optical member is subjected to a rapid thermal anneal treatment to level a surface of the optical member.
According to this manufacturing method of an optical member, instant fusion or semi-fusion by rapid thermal anneal treatment allows removing microscopic asperities on the optical member surface and the optical member surface is prepared in a smooth condition so as to accord with a concavo-convex optical surface of a desired shape.
(10) The manufacturing method of an optical member as described in any one of (1) to (9), wherein the thermoplastic resin is stacked on a spherical lens-shaped transparent body. According to this manufacturing method of an optical member, when compared with the case of stacking a thermoplastic resin on the forming substrate from the beginning, the process of repeating discharge of droplets and their solidification by drying until the amount of droplets discharged becomes equal to the volume of the transparent body is dropped off, so high-speed forming in reduced amount of discharge can be attained. (11) The manufacturing method of an optical member as described in (10), wherein an aspheric surface layer is formed from the solution of the thermoplastic resin on the spherical lens-shaped transparent body.
According to this manufacturing method of an optical member, an aspheric lens can be formed at a high speed only by forming of an aspherical surface layer.
(12) The manufacturing method of an optical member as described in any one of (1) to (11), wherein two pieces of optical members shaped to be planar at bottoms thereof are joined into one optical member in a state that their bottom surfaces face to each other.
According to this manufacturing method of an optical member, a process of discharging droplets onto a forming substrate and solidifying them by drying is repeated, thereby shaping a halved optical member having a planar surface on the bottom side and a desired concavo-convex optical surface on the top side, and two pieces of the halved optical members are joined together in a state that their bottom surfaces face each other. In this way, it becomes possible to form an optical member having desired concavo-convex surfaces on both sides respectively without using any of molds.
(13) The manufacturing method of an optical member as described in any one of (1) to (12), wherein the discharging of the droplet is performed in one of a vacuum, an atmosphere of carbon dioxide, and an atmosphere of nitrogen.
According to this manufacturing method of an optical member, discharge of droplets in a vacuum can prevent air from being trapped and remaining in the thermoplastic resin, while discharge of droplets in an atmosphere of oxygen or nitrogen can prevent the oxygen or nitrogen gas from being trapped and remaining in the thermoplastic resin because each gas has high solubility in the thermoplastic resin. Thus, it becomes possible to reduce product defects resulting from pin holes, fine hollow portions, boundaries between stacks and so on. (14) The manufacturing method of an optical member as described in any one of
(1) to (13), wherein the thermoplastic resin is a nanocomposite material including a transparent thermoplastic resin into which fine particles having sizes of 20 nm or less are incorporated.
According to this manufacturing method of an optical member, inorganic fine particles, such as fine particles of a metal oxide, are dispersed homogeneously into the thermoplastic resin, whereby optical members having high refractive indexes and excellent optical characteristics can be formed with stability.
(15) The manufacturing method of an optical member as described in any one of (1) to (14), wherein the optical member is a lens.
According to this manufacturing method of an optical member, it becomes possible to shape the surface of a lens to be a desired concavo-convex optical surface by repeating the process of discharging droplets onto a forming substrate and solidifying them by drying, whereby lenses of arbitrary shapes can be formed without any of molds and the development period for lens units can be shortened.
(16) The manufacturing method of an optical member as described in (15), wherein the lens is formed by mixing two or more kinds of resin solutions different in content of the fine particles at a ratio in accordance with at least one of a diameter direction and a thickness direction of the lens, so that a refractive index distribution is imparted to the at least one of the diameter direction and the thickness direction of the lens.
According to this manufacturing method of an optical member, it is possible to form a lens to which a refractive index distribution is imparted in either the diameter direction, or the thickness direction, or both by mixing (on the surface of each droplet discharged) two or more kinds of resin solutions different in content of the fine particles at a ratio in accordance with at least either the diameter direction of the lens or the thickness direction of the lens. In general, when resins differing in refractive index are mixed, a phase boundary is formed between them because they are not blended perfectly, and reflections of light occur thereat; as a result, white turbidity appears. On the other hand, resin solutions differing in fine-particle content are blended uniformly, so it becomes possible to adjust the refractive index to an arbitrary value.
(17) The manufacturing method of an optical member as described in (15), wherein the lens is shaped on the substrate by landing of the droplet discharged out of the nozzle on a desired position of the substrate under rotary drive, and the method further comprises: detecting height information on a height of the lens under shaping; determining an arrival time required for the droplet to arrive a first position where the droplet from the nozzle disposed at a height is to be landed, on a basis of the height information; determining an amount of deviation of a second position from the first position, the second position being a position where the droplet is landed after the substrate is rotated by the arrival time; and correcting a timing of discharging of the droplet out of the nozzle so as to cancel the amount of deviation, so that the droplet is landed at a position coinciding with the desired position.
According to this manufacturing method of an optical member, when the position slated for landing of each droplet moves during the period from discharge of the droplet out of the nozzle to landing of the droplet, the timing of discharge of the droplet is corrected (moved up) so that the moving distance is canceled as the amount of deviation. By doing so, each droplet can be landed exactly on the position slated for landing, and the optical member can be shaped with high precision.
(18) An optical member manufacturing apparatus for manufacturing an optical member by discharging a droplet of a solution of a thermoplastic resin and solidifying the droplet on a substrate by drying on a basis of profile data of the optical member, the apparatus comprising: a substrate on which the optical member is shaped; a nozzle which discharges the droplet of the solution of the thermoplastic resin; a discharge head freely-movably facing to the substrate and including the nozzle; and a control section for repeating a plurality of times a process of discharging droplets of the solution at different positions on a surface the substrate and solidifying the droplets by drying is repeated a plurality of times to stack the thermoplastic resin so that the stacked thermoplastic resin have a height according to the profile data.
According to this apparatus for manufacturing an optical member, a thermoplastic resin solution is discharged onto a forming substrate as a discharge head is moved, and this discharging process is repeated until the thermoplastic resin comes to have desired heights at different positions, respectively, on the plane of the forming substrate, and it becomes possible to form a concavo-convex optical surface in a desired shape having undergone thickness control at many sites. Thus, it becomes possible to manufacture optical members of which frequent design changes are required, such as low-volume diversified products, prototypes and the like, without using any of molds.
(19) The optical member manufacturing apparatus as described in (18), wherein the substrate is supported so as to be a freely-rotatable, and a discharge point of the discharge head is freely movable along at least a straight line passing through a center of rotation of the substrate.
According to this optical member manufacturing apparatus, the discharge point passes through the center of rotation of the forming substrate, so it becomes possible to discharge onto all the positions inside a circle and to easily shape an optical member symmetric with respect to a point by movement in a radius direction.
(20) The optical member manufacturing apparatus as described in (18) or (19), further comprising a relative movement section which enables relative movement of the substrate and the discharge head along a direction.
According to this optical member manufacturing apparatus, by moving the discharge head sequentially in a Y direction relative to the forming substrate while moving the discharge head repeatedly in an X direction relative to the forming substrate, it becomes possible to shape an optical member other than that having an axisymmetric shape, such as a cylindrical lens having a cylindrical face and its axis line in the X direction.
(21) The optical member manufacturing apparatus as described in any one of (18) to (20), further comprising a measurement section that measures a height of droplets discharged out of the nozzle and landed and stacked on the substrate, wherein the control section controls for repeating the process discharging a droplet of the solution and solidifying the droplet by drying until the measured height of the stacked droplets reaches one corresponding to the profile data of the optical member. According to this optical member manufacturing apparatus, the height measurement of the thermoplastic resin which is landed on the forming substrate and being stacked up is repeated in succession until the height of the thermoplastic resin stacked reaches to the height corresponding to the profile data, which allows high-precision shaping free of deviation from the profile data.
(22) An optical member formed by the manufacturing method of an optical member as described in any one of (l) to (15).
As to this optical member, the thickness thereof is controlled at many sites in the course of shaping, and the concavo-convex optical surface thereof is formed in a desired shape. Thus, it becomes possible to appropriate this optical member for optical members of which frequent design changes are required, such as low-volume diversified products or prototypes.
Advantageous Effects In accordance with the present method of manufacturing an optical member, shaping of the optical member is performed by repeating a process of charging droplets of a thermoplastic resin solution onto different positions on the plane of a forming substrate and solidifying the droplets by drying until desired heights are reached at the different positions respectively by reference to the profile data of the optical member, thereby stacking the thermoplastic resin in a transparent condition on the substrate. In this way, the optical member can be controlled in thicknesses at many sites, and does not require special preparation for a mold even when it undergoes a shape change. As a result, time and cost spent on the making of a mold becomes unnecessary, and a wide variety of optical members in small quantities can be manufactured with high precision and at low cost. An optical member manufacturing apparatus according to an aspect of the invention is equipped with a forming substrate on which the optical member is formed, a nozzle which discharges droplets of a thermoplastic resin solution, a freely-movable discharge head which faces the forming substrate and a control section for repeating a process of discharging the droplets onto different positions on a plane of the forming substrate and then solidifying them by drying until the droplets reach to desired heights at their respective positions. Therefore, the optical member shaped to have desired heights at different positions with high precision can be manufactured without using any mold; as a result, optical members involving frequent design changes, such as low-volume products and prototypes, can be manufactured with high precision and at low cost.
An optical member according to an aspect of the invention requires no mold for the shaping because it is manufactured by the method according to the invention. So, time and cost spent on the making of molds can be reduced, and short-time, low-cost manufacturing becomes possible.
Brief Description of the Drawings
Fig. 1 is a schematic block diagram showing an apparatus for manufacturing an optical member according to an aspect of the invention;
Fig. 2 is a plan view of a forming substrate; Fig. 3 is a series of cross-sectional views of a discharge head which illustrates discharge situations (a), (b) and (c) of a droplet from a nozzle;
Fig. 4 is a flow chart describing a procedure of the manufacturing method according to an aspect of the invention;
Fig. 5 is an explanatory diagram showing plane section height-specific discharged areas obtained on the basis of profile data;
Fig. 6 is a manufacturing process drawing which illustrates the shaping process of an optical member by section views (a) to (e);
Figs. 7(a) and 7(b) are explanatory diagrams showing, in Fig. 7(a), one structural example of a discharge head which discharges two or more kinds of resin solutions and, in Fig. 7(b), a lens having a refractive index distribution;
Fig. 8 is a manufacturing process drawing of an optical member made by bonding two pieces of halved optical members together;
Fig. 9 is a cross-sectional diagram showing one example of an irradiation device for performing a rapid thermal annealing treatment; Fig. 10 is an explanatory drawing of an optical member surface leveled off by removing microscopic asperities therefrom by raid thermal annealing treatment;
Fig. 11 is a series of manufacturing process drawings (a), (b) and (c) of additional adjustment of a shaped optical member surface by means of a heat pressing; Fig. 12 is a set of cross-sectional views (a) and (b) of an optical member formed by raising of a glass body;
Fig. 13 is a configuration diagram of a substantial part of an optical member manufacturing apparatus equipped with a relative movement device;
Figs. 14(a) and 14(b) are a set of manufacturing process drawings wherein a discharge head equipped with a UV lamp is used; and
Fig. 15 is a manufacturing process drawing of a lens formed from an optical member whose bottom alone is shaped by use of a die.
Best Mode for Carrying Out the Invention Exemplary embodiments of the optical member manufacturing method and the optical member formed by this manufacturing method are illustrated below by reference to drawings.
Fig. 1 is a schematic block diagram showing an apparatus for manufacturing an optical member according to an exemplary embodiment of the invention, Fig. 2 is a plan of a forming substrate, and Fig. 3 is a series of cross-sectional views of a discharge head which illustrates discharge situations (a), (b) and (c) of a droplet from a nozzle.
The optical member manufacturing apparatus 100 according to this embodiment discharges a thermoplastic resin solution in droplet form on a basis of profile data of an optical member and solidifies them by drying, thereby shaping the optical member. Additionally, in this embodiment, though a case where the optical member is a convex lens
11 is illustrated as an example, the lens shape can be changed as appropriate.
The manufacturing apparatus 100 is basically equipped with a forming substrate 13 on which a convex lens 11 is formed, a nozzle 15 discharging droplets of a thermoplastic resin solution, a freely-movable discharge head 17 incorporating a nozzle 15 and facing the forming substrate 13, and a control section 21 for repeating two or more times a process of discharging the droplets onto different positions on a plane of the forming substrate and then solidifying them by drying until desired heights are reached at the different positions respectively by referring the profile data of the convex lens 11 to a memory section 19. The forming substrate 13 is supported by a lifting and lowering mechanism 25 in a condition that it can freely move up and down in such directions as to approach to and recede from the discharge head 17. To an upper part of the lifting and lowering mechanism 25, a rotary drive device 27 incorporating an electric motor is fastened. The rotary drive device 27 rotates the forming substrate 13 fixed to a driving shaft 27a. The discharge head 17 is supported in a condition of freely shuttling to and fro by means of a linear movement device 29 provided with a linear motor, a ball screw mechanism or the like.
As shown in Fig. 2, the discharge head 17 is moved along a straight line 33 heading in a radius direction from the rotation center 31 of the forming substrate 13 by means of the linear movement device 29. In this way, it becomes possible to shape a convex lens 11 having a desired radius r. By passage of a discharge point 35 of the nozzle 15 through the rotation center 31 of the forming substrate 13, it becomes possible to discharge onto all the positions inside a circle, and the movement in the radius direction allows simple shaping of the convex lens 11 in a form of point symmetry. This discharge head 17 is configured as an inkjet head which discharges droplets out of the nozzle 15. Further, in the neighborhood of the discharge head 17, a height measurement device
37 is installed, and thereby the heights of droplets discharged out of the nozzle 15, landed on the forming substrate 13 and stacked thereat are measured. This height measurement device 37 is mounted in a freely-movable sensor head 18 facing the forming substrate 13, and installed in a slanting direction so as to head its measurement direction for the landing position 1 IA of each droplet from the discharge head 17. The sensor head 18, as in the case of the discharge head 17, is supported in a condition of freely shuttling to and fro by means of a linear movement device 30 provided with a linear motor, a ball screw mechanism or the like. In addition, as shown in Fig. 2, the sensor head 18 is moved along the straight line 33 heading in a radius direction from the rotation center 31 of the forming substrate 13 by means of the linear movement device 30. Alternatively, in some cases, the sensor head 18 may be moved in the direction opposite to the straight line 33 so that the height measurement is made at a position 36 to be reached by rotating the forming substrate 13 a half turn after the landing of a droplet. As the height measurement device 37, non-contact type devices, including those utilizing phase differences of laser light and the like, can be used to advantage. By use of a laser-utilized height measurement device 37, it becomes possible to perform non-contact, real-time, high-precision height detection of a soft thermoplastic resin just after landing on the forming substrate 13 and before complete solidification, and no damage to the convex lens 11 is caused by height measurements.
Additionally, though the discharge head 17 and the height measurement device 37 are supported separately in Fig. 2, the configuration thereof is not limited to such one, but the discharge head 17 and the height measurement device 37 may be configured to move in an integrated manner. Further, the traveling directions of the discharge head 17 and the sensor head 18 can be set arbitrarily without limited to the illustrated directions so long as they are radius directions.
The control section 21 repeats a process of discharging droplets and solidifying them by drying until the heights measured by the height measurement device 37 reach to heights corresponding to the profile data of the convex lens 11. By repeating the process until the height of the thermoplastic resin landed and being stacked on the forming substrate 13 reaches to a height corresponding to the profile data while measuring the height sequentially, high-precision shaping becomes possible without deviation from the profile data.
As shown in Fig. 3, by using a discharge head 17 which is equipped with a discharge nozzle 15 for discharging droplets, a pressure chamber 39 communicated with the nozzle 15 and a piezoelectric element 41 combined with the pressure chamber 39, each of droplets is discharged out of the nozzle 15 by utilizing the deformation caused in the pressure chamber 39 by application of a voltage to the piezoelectric element 41. The thermoplastic resin solution is fed from a tank 43 to an anterior pressure chamber 47 of the discharge head 17 via a feed tube 45. The interior wall of the pressure chamber 39 facing the nozzle 15 is formed with diaphragm 49, and the diaphragm 49 is fastened to the piezoelectric element 41. Therefore, the diaphragm 49 is deformed by displacement occurring upon application of a voltage to the piezoelectric element 41. As a result, the interior volume of the pressure chamber 39 varies, and thereby a droplet 51 is discharged out of the nozzle 15. In this way, a minuscule droplet 51 is discharged with stability out of the nozzle 15 via a closed channel communicated with the pressure chamber 39 in a state of being favorable for drying. Additionally, the droplet 51 is not dry at the time of landing on the forming substrate 13, so it is dried after landing. More specifically, the first layer of the resin is dried after landing on the forming substrate, and the second layer and afterward are dried after upper and lower layers adhere to each other by blending and a phase boundary disappears. Additionally, each droplet is solidified immediately after landing because of its minuteness, so the measurement of its height H becomes possible.
Herein, it is preferable that the droplet 51 of a resin solution has a diameter of 0.005 mm to 0.1 mm. By adjusting the diameter of the droplet 51 to the specified range (0.005 mm to 0.1 mm), the solvent evaporates from the droplet 51 landed, and thereby drying of the droplet is accelerated and the discharged thermoplastic resin solution is formed into a desired optical shape in a short time, and that wit stability. Further, the optical profile irregularity of the optical member formed is improved too. Additionally, when the droplet is too large in diameter, drying the droplet takes a long time and the optical member formed becomes coarse in shape. On the other hand, when the droplet is too small in diameter, forming the optical member takes a long time, and besides, the droplets discharged cannot stick together through blending because they dry up before landing. In particular, too small droplets make it difficult not only to complete shaping of the optical member but also to control the landing positions. Further, it is preferable that the discharge of the droplet 51 is performed in either a vacuum, or an atmosphere of carbon dioxide, or an atmosphere of nitrogen. By doing so, it is possible to prevent occurrence of defects, including optical distortion and the like, caused by air remaining in the droplet 51 being trapped in the material under shaping into the convex lens 11 from the droplet 51. Discharging droplets in a vacuum can prevent with certainty air from being trapped in the thermoplastic resin, while discharging droplets in an atmosphere of oxygen or nitrogen can prevent the gas from being trapped and remaining in the thermoplastic resin because each gas has high solubility in the thermoplastic resin. Thus, it becomes possible to reduce product defects resulting from pin holes, fine hollow portions, boundaries between stacks and so on.
In the case described above, a piezoelectric inkjet head utilizing an piezoelectric element is employed. Alternatively, an inkjet head of another system may be employed. For example, it is possible to use the so-called thermal inkjet head which is equipped with a nozzle, a fluid channel communicated with the nozzle and a heating unit disposed on a part of the fluid channel, and produces bubbles in the fluid channel by heat supply from the heating unit and thereby discharges droplets of the thermoplastic resin solution out of the nozzle.
In the manufacturing apparatus 100, as mentioned above, a thermoplastic resin solution is discharged onto the forming substrate 13 as the discharge head 17 is moved, and this discharging is repeated until the thermoplastic resin comes to have desired heights at different positions on the plane of the forming substrate, whereby forming the convex lens 11 with a concavo-convex optical surface of a desired shape becomes possible through thickness control at many sites. Alternatively, a system of non-contact dispenser type may be employed in place of an inkjet system.
Because this optical member manufacturing apparatus is therefore equipped with the forming substrate 13 on which the convex lens 11 is formed, the nozzle 15 discharging droplets of a thermoplastic resin solution, the freely-movable discharge head 17 which faces the forming substrate 13, and the control section 21 for repeating a process of discharging the droplet 51 and solidifying by drying until desired heights are reached at different positions on the forming substrate plane, the convex lens 11 shaped so as to have the desired heights at different positions can be manufactured. Thus, the convex lens 11 of which frequent design changes are required, such as low-volume products and prototypes, can be manufactured speedily with high precision and at low cost without using any mold.
Next, the manufacturing method of an optical member is described.
Fig. 4 is a flow chart describing a procedure of the manufacturing method relating to the invention, Fig. 5 is an explanatory diagram showing plane section height-specific discharged areas obtained on the basis of profile data, and Fig. 6 is a manufacturing process drawing which illustrates the shaping process of an optical member by section views (a) to
(e). In order to manufacture the convex lens 11 as an optical member by use of the manufacturing apparatus 100, first of all, the profile data of the convex lens 11 is captured from the memory section 19 by the control section 21 (si), converted to data as a model engineered by three-dimensional CAD and, as shown in Fig. 5, output in the form of discharge maps 23 of layers hi, h2, • • • hn-i, hn obtained by slicing the model into a plurality of plane sections in the direction parallel to the forming substrate (s2). The control section 21 makes the setting of a target height from the discharge map 23 on the forming substrate 13 (s3).
Next, the control section 21 actuates the linear movement device 29 and sets the nozzle position of the discharge head 17 at the rotation center 31 (s4), and further actuates the rotary drive device 27 and rotates the forming substrate 13 (s5). And the control section 21 allows the discharge head 17 to discharge a droplet 51 while controlling the drive of the linear movement device 29 so as to increase the radius r (s6) gradually. At this time, the control section 21 allows the rotation speed of the forming substrate 13 to decrease and the interval of discharge timing from the discharge head 17 to lengthen with a gradual increase in the radius r, and thereby the constant density is kept at all the landing points. Additionally, as to the gradual increase of the radius r, the method of increasing the radius r gradually in whorls allows a smooth motion of the discharge head 17, and thereby continuous stacking can be achieved and occurrence of disarray in shape can be prevented. Alternatively, the method of increasing the radius r stepwise after making a circuit with the same radius may be employed. In this case, the positioning of the radius r is made accurately, and shaping accuracy can be enhanced with ease.
Simultaneously with the discharge of a droplet from the discharge head 17, the landing height is measured with the height measurement device 37 mounted in the sensor head 18 (s7). The sensor head 18 is moved in the same direction as the discharge head 17 is moved in synchronization with movement of the discharge head 17 in the radius direction. In other words, both heads are moved in cooperation with each other so that the landing position of a droplet from the discharge head 17 agrees with the height measurement position of the height measurement device 37. The control section 21 repeats two or more times a process of discharging the droplet 51 and solidifying through drying until the desired heights are reached at different positions on the forming substrate 13 while judging whether or not each layer comes to have its individually desired heights by reference to the profile data (s8). In other words, the height of the droplet 51 landed on the forming substrate 13 and stacked thereat is measured, and the process of discharging the droplet 51 and solidifying it by drying is repeated until this measured height reaches to the height corresponding to the profile data of the convex lens 11. In this way, the height of the thermoplastic resin landed repeatedly on the forming substrate 13 and being stacked thereon is detected in succession, which allows forming free of deviation from the profile data, or high-precision shaping. By these operations, each plane section, or each layer body, is stacked in succession at its accurate height.
When it is ascertained by height measurement that the layer formed reaches the desired height, a target height is set from the discharge map 23 of the next layer (slO). These processes are repeated until the layer stacked is detected as the final layer (topmost layer) (s9), and convex multilayer bodies 11a, l ib and lie are shaped in order as shown in Figs. 6(a) to 6(d). After the stacking process of the final layer is completed, the rotary drive device 27 is stopped (si I)5 the discharge head 17 is evacuated (si 2), and the convex lens 11 is taken out of the forming substrate 13 as shown in Fig. 6(e), whereby the manufacturing of the lens is ended.
Additionally, the convex lens 11 may be subjected to drying treatment for perfect removal of the solvent remaining therein. In this case, vacuum drying at a temperature lower than the glass transition temperature of the thermoplastic resin is preferred. At this time, change in shape is negligibly small because the residual solvent is limited in quantity.
According to this manufacturing method of the convex lens 11 , thickness control is performed at many sites in shaping the convex lens 11 by discharging a thermoplastic resin solution and solidifying it by drying, and thereby a concavo-convex optical surface of the desired shape is formed. In other words, the convex lens 11 of a desired shape is formed as the discharge thicknesses at many sites are decided. By doing so, a volume change error does not occur when the thermoplastic resin solution is solidified, and a precise shape can be formed. In addition, even when changes in product shape are made, no mold needs to be newly prepared, and manufacture of the convex lens 11 becomes possible with high precision and high design flexibility.
The thermoplastic resin used in the description is a nanocomposite material which contains fine particles having sizes of 20 nm or below in a transparent thermoplastic resin. More specifically, the nanocomposite material is a material prepared by homogeneously dispersing inorganic fine particles, such as fine particles of a metal oxide, into a thermoplastic resin, has a high refractive index, and makes it possible to form optical members having excellent optical characteristics with stability. Details thereof are described hereinafter. According to this optical member manufacturing method, a process of discharging the droplet 51 and solidifying through drying is repeated until the desired heights are respectively reached at different positions on a plane by reference to the profile data of the convex lens 11, and thereby a transparent thermoplastic resin is stacked on the forming substrate 13 to perform shaping. Therefore, the shape of the convex lens 11 can be controlled in thicknesses at many sites, and special preparation for a mold is not required even when the product shape is changed. As a result, time and cost spent on the making of a mold becomes unnecessary, and a wide variety of convex lenses 11 in small quantities can be manufactured with high precision and at low cost. And by repetition of a process of discharging the droplet 51 onto the forming substrate 13 and solidifying it by drying, it becomes possible to shape the surface of the convex lens 11 into a desired concavo-convex optical surface, the convex lens 11 of an arbitrary shape can be easily manufactured without making any mold, and flexibility in lens design is enhanced.
The convex lens 11 manufactured by this manufacturing method allows offering a wide variety of lenses in small quantities in a short time and at low cost because time and cost spent for the making of a mold are cut.
Alternatively, a lens can be formed by mixing two or more kinds of the resin solutions differing in refractive index, e.g., by having different fine-particle contents at desired ratios in at least either the diameter direction of the lens or the thickness direction of the lens. In this case, a refractive index distribution is imparted to at least either its diameter or thickness direction of the lens, and a variety of optical members can be formed freely.
Then, a method of manufacturing a lens by selectively switching between two or more resin solutions having different refractive indexes is illustrated.
A structural example of a discharge head which discharges two or more kinds of resin solutions is shown in Fig. 7(a), and a lens having a refractive index distribution is shown in Fig. 7(b).
As shown in Fig. 7(a), the discharge head 17A is connected to tanks 43 A and 43B, which store resin solutions A and B having different refractive indexes respectively, via feed tubes 45, and the controls of a discharge timing, discharge amount and so on are performed on a nozzle basis by a control section not shown in the figure. The configuration of other parts is the same as shown in Fig. 1, so the description thereof is omitted.
A nozzle 15A and a nozzle 15B mounted in the discharge head 17A use a resin solution A having a refractive index of, say, 1.4 and a resin solution B having a refractive index of, say, 1.6 respectively, and shape a lens 11 having a refractive index distribution. As shown in Fig. 7(b), the lens 11 is formed by discharging only the resin solution A onto the central region 1 Ia of the lens and discharging only the resin solution B onto the outer region l ib of the lens. In addition, the region l ie between the central region 11a and the outer region 1 Ib of the lens is formed by discharging the resin solutions A and B at mixing ratios changed as a function of, e.g., radius r. The control function, such as a function of radius r, may be a function of lens thickness, and can be freely chosen depending on the contents of an optical design. Thus, arbitrary refractive index distributions can be formed with ease.
As mentioned above, different kinds of resin solutions are selectively discharged out of the nozzles 15A and 15B in the discharge head 17A, respectively, and thereby the flexibility in designing lenses can be enhanced. Additionally, the nozzles 15 A and 15B may be mounted in an integrated state and designed movable as shown in the figure, but they are not limited to this design. They may be configured to be movable independently.
When an optical member is shaped on the forming substrate through landing of resin solution droplets discharged out of the nozzle on desired positions of the forming substrate under rotary drive, the landing position of each droplet varies through the rotary drive of the forming substrate during the time between the discharge and landing of the droplet. Therefore, it is preferred that the discharge be carried out while correcting the deviation of landing positions.
In order to correct this deviation of landing positions, the height information of the lens under shaping is detected first and then, on the basis of the height information detected, a time required for each droplet to arrive the position slated for landing of the droplet on the forming substrate 13 is determined from the information of the nozzle-placed height position and the droplet discharge speed set in advance. And an amount of deviation of landing position after the forming substrate 13 is rotated by the time required for the arrival from the position slated for landing is determined. Timing of discharge of each droplet out of the nozzle 15 is corrected so as to be moved up and cancel the amount of deviation, and the landing position of the droplet is made to coincide with the position predetermined by the design. In this way, each droplet can be landed exactly on the position slated for landing, and the optical member can be shaped with high precision. As to the deviation of landing positions, not only the positional deviation by rotation of the forming substrate 13 is corrected but also deviation of centrifugal force origin (deviation in a radiant direction from the center of rotation), which is caused by each droplet undergoing the centrifugal force generated by the rotary motion after landing, may be corrected. Next, a case where an optical member is formed by bonding two pieces of convex lenses together, each of which is the convex lens 11, is illustrated.
Fig. 8 is a manufacturing process drawing of an optical member made by bonding two pieces of halved optical members together.
Although the convex lens 11 can be used alone as an optical member, two pieces of optical members, each of which is the optical member 11 whose bottoms 53 are formed into a planar shape, may be formed in one-piece optical member 1 IA by being joined together in a state that their bottoms 53 and 53 face each other for the purpose of further enhancing the flexibility of optical design. These bottoms 53 and 53 can be stuck together through blending by forming an adhesive layer 55 with, e.g., the same thermoplastic resin solution as used for the optical members. In this way, when a halved convex lens 11 having a planar surface as the bottom 53 and a desired concavo-convex optical surface as the top surface is shaped by repeating a process of discharging the droplet 51 onto the forming substrate 13 and solidifying through drying, two pieces of the halved the convex lens 11 thus shaped are joined together in a state that their bottom surfaces 53 and 53 face each other, and thereby the optical member HA having the intended concavo-convex optical surfaces on the both sides can be obtained with ease without using any mold. Instead of using the thermoplastic resin, the adhesion layer 55 may be formed by use of another transparent adhesive having the refractive index similar or approximate to that of the convex lens 11. Alternatively, two pieces of halved convex lenses, each of which is the convex lens 11, may be joined together through surface melting by application of heat, or ultrasonic adhesion. In addition, halved convex lenses to be joined together, each of which is the convex lens 11, may be lenses having different material properties in order to achieve the aimed optical performance. Next, a method of smoothing the surface of each lens is illustrated. Fig. 9 is a cross-sectional diagram showing an example of an irradiation device for performing a rapid thermal annealing treatment, and Fig. 10 is an explanatory drawing of an optical member surface leveled off by removing microscopic asperities therefrom by raid thermal annealing treatment.
In the manufacturing method of an optical member, it is preferable that rapid thermal annealing treatment is given to the convex lens 11 shaped and thereby the surface of the convex lens 11 is leveled off. A heat treatment unit 61 for performing rapid thermal annealing treatment has a plurality of lamps 63 and a reflector member 65 accommodated in a cabinet 67, and gathers flash irradiation beams gathered by the reflector member and forward flash irradiation light beams by means of a condenser lens 69 or a light shaper and conducts the gathered beams to the outside.
More specifically, in the case of irradiating with strip-shaped flash light beams, a light-condensing concave reflector member 65 cooled by circulating a refrigerant (purified water or the like) is placed in the rear of a plurality of flash lamps 63, and flash irradiation light beams gathered by the reflector member and forward flash irradiation light beams are further focused by a condenser lens 69 into a strip-shaped flash light beams. Alternatively, in the case of performing large-area blanket irradiation with square- or rectangle-shaped flash irradiation light beams, a light-condensing concave reflector member cooled by circulating a refrigerant (purified water or the like) is placed in the rear of a plurality of flash lamps, and flash irradiation light beams gathered by the reflector member and forward flash irradiation light beams are shaped with a light shaper (a beam homogenizer or the like), and thereby illuminance uniformity is enhanced. At this time, the shaped light beams may be passed through a heat-wave reduction filter 70 or a heat-wave cutoff filter and transmitted to a desired direction when required. By giving such rapid thermal annealing treatment, the microscopic asperities on the surface of the convex lens 11 shown in Fig. 10 are removed by instant melting or semi-melting, and thereby the surface of the convex lens 11 is rendered smooth (leveled off) in accordance with the concavo-convex optical surface of the desired shape.
Additionally, surface leveling of the optical member may be carried out by heat pressing too.
Fig. 11 is a manufacturing process drawing of additional adjustment of a shaped optical member surface by means of a heat pressing.
In the manufacturing method of this optical member, the front and rear optical surfaces of the shaped convex lens 11 are hot-pressed by means of pressing dies 71 and 73, and thereby the final adjustment of the lens shape can be made. At the facing surfaces of the pressing dies 71 and 73, adjustment faces 71a and 73a corresponding to the front and rear optical surfaces of the convex lens 11 are formed. The pressing dies 71 and 73 are positioned by guide jigs 75a and 75b, and allow pressing the front and rear sides of the convex lens 11 , respectively, while heating. Next, a case where an optical member is formed by using a transparent body (glass body) prepared beforehand is illustrated.
Fig. 12 shows a cross-sectional view of an optical member formed by raising of a glass body. In the manufacturing method of an optical member, a transparent thermoplastic resin
83 is stacked in layers on a spherical lens-shaped glass body 81 prepared beforehand, and thereby shaped into a convex lens 1 IB.
According to the manufacturing method using such a glass body 81, high-speed shaping at a low discharge rate becomes possible as compared with the case where the thermoplastic resin 83 is stacked on the forming substrate 13 from the start, because the number of repetition times of a process of discharging the droplet 51 and solidifying through drying is reduced by those required for reaching the volume of the glass body 81. Thus, the working time for lens shaping can be shortened. And an aspheric lens can be shaped at a high speed by merely forming an aspheric surface layer through forming of an aspheric surface layer on a spherical lens-shaped glass body 81 by use of a thermoplastic resin solution. Additionally, when the glass body 81 and the thermoplastic resin are identical in refractive index, the lens shaped can have refraction performance equivalent to general aspheric lenses; while, when they are different in refractive index, the lens shaped can deliver different optical performance according to the combination of those refractive indexes. Next, other embodiments of the manufacturing method of an optical member are illustrated .
Fig. 13 shows a configuration diagram of a substantial part of an optical member manufacturing apparatus equipped with a relative movement device.
This manufacturing apparatus is equipped with a relative movement device 91 which allows a forming substrate 13 and a discharge head 17 to move relatively in arbitrary directions. The relative movement device 91 is configured, e.g., so that a linear movement device 29 supporting the discharge head 17 so as to be freely movable in the X direction is further supported by a linear movement device 93 so as to be freely movable in the Y direction. When the discharge head 17 is supported by such a relative movement device 91 so as to be freely movable, it becomes possible to shape an optical member other than those having axisymmetric shapes, e.g., a cylindrical lens 11C having a cylindrical face and its axis line in the X direction, by moving the discharge head 17 sequentially in a Y direction relative to the forming substrate 13 while moving the discharge head 17 repeatedly in an X direction relative to the forming substrate 13.
Further, energy-curable resin can also be used as a lens material. An optical member manufacturing apparatus in this case is illustrated below.
In Fig. 14, drawings of a manufacturing process using a discharge head equipped with a UV lamp are shown.
In this manufacturing apparatus, a UV lamp 101 as an energy irradiation device is mounted in a discharge head 17 A. The UV lamp 101 is made to move together with the discharge head 17 in the X direction through the reciprocatory motion of the discharge head 17. Solidification of the energy-curable resin 84 which is discharged from the nozzle 15 and lands on the forming substrate 13 is accelerated by energy irradiation with the UV lamp 101 passing over the resin just after the landing, and thereby the resin 84 is formed into a convex lens HD.
As the energy source, a mercury lamp, gas laser, solid layer and the like can be used.
When a UV-curable resin is used, a mercury lamp and a metal halide lamp can be used. Alternatively, a GaN semiconductor UV emission device useful ecologically too may be used.
Further, LED (UV-LED) and LD (UV-LD) are compact, long-life, high-efficiency and low-cost devices, so they can be used suitably as radiation sources for energy-curable resins.
According to the manufacturing apparatus having such an energy irradiation device (e.g., a UV lamp 101) in the discharge head 17A, the energy irradiation device moves together with the reciprocatory movement of the discharge head 17 A, and irradiate the energy-curable resin 84 discharged from each nozzle 15 and landed on the forming substrate 13 with its energy. As a result, solidification of the energy-curable resin 84 is accelerated and rapid shaping of the convex lens 1 ID becomes possible.
Next, an example of a case where an optical member whose bottom is made so as to have a specified shape undergoes an additional surface working for the purpose of achieving desired lens performance is illustrated.
Fig. 15 shows a manufacturing process drawing of a lens formed from an optical member whose bottom alone is shaped by use of a die. In this manufacturing apparatus, a specifically forming surface 111 is given to the substrate surface of a forming substrate 13 A, and by this forming surface the bottom of the convex lens 1 IE is shaped. And the surface of the convex lens 1 IE is worked so as to have an arbitrary lens shape by use of the method as described above.
The forming substrate 13A having such a forming surface 111 can form the surface of the convex lens HE facing the forming substrate 13A into a specified optical member surface 113. Therefore, a convex lens 1 IE with a high refractive index, which has surfaces formed into the shape of convex curve on both front and rear sides and a high refractive index, can be easily obtained without bonding two pieces of halved convex lens 11 and 11 together. The invention should not be construed as being limited to the foregoing embodiments, but various changes and modifications can be made thereto as appropriate. For instance, the lenses formed are not limited to convex lenses, but they may be concave lenses or gull-shaped lenses with two or more inflection points.
Then, a nanocomposite material (a material prepared by incorporating inorganic fine particles into a thermoplastic resin) usable in optical member manufacturing methods according to the invention is described below in detail.
Although some of the following descriptions of constituent factors are made on the basis of representative embodiments of the invention, the invention should not be construed as being limited to such embodiments. Additionally, the word "to" used for expressing a range of numerical values in this specification means that the values described in front of and behind "to" are included in the range as the lower limit and the upper limit.
<Compound Represented by Formula (1)>
A nanocomposite material for use in the invention contains a compound represented by the following formula (1) in combination with inorganic fine particles. Formula (1)
Figure imgf000030_0001
In formula (1), R1 and R2 each represent a substituent independently. The substituent which can be taken as R1 and R2 each is not limited to particular ones. And examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (e.g., a methyl group, an ethyl group), an aryl group (e.g., a phenyl group, a naphthyl group), an alkenyl group, an alkynyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group (e.g., a methoxycarbonyl group), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group), a substituted or unsubstituted carbamoyl group (e.g., a carbamoyl group, an N-phenylcarbamoyl group, an N,N-dimethylcarbamoyl group), an alkylcarbonyl group (e.g., an acetyl group), an arylcarbonyl group (e.g., a benzoyl group), a nitro group, an acylamino group (e.g., an acetamido group, an ethoxycarbonylamino group), a sulfonamido group (e.g., a methanesulfonamido group), an imido group (e.g., a succinimido group, a phthalimido group), an imino group (e.g., a benzylideneamino group), an alkoxy group (e.g., a methoxy group), an aryloxy group (e.g., a phenoxy group), an acyloxy group (e.g., an acetoxy group, a benzoyloxy group), an alkylsulfonyloxy group (e.g., a methanesulfonyloxy group), an arylsulfonyloxy group (e.g., a benzenesulfonyloxy group), a sulfo group, a substituted or unsubstituted sulfamoyl group (e.g., a sulfamoyl group, an N-phenylsulfamoyl group), an alkylthio group (e.g., a methylthio group), an arylthio group (e.g., a phenylthio group), an alkylsulfonyl group (e.g., a methanesulfonyl group), an arylsulfonyl group (e.g., a benzenesulfonyl group), a formyl group, and a heterocyclic group. These substituents may further be substituted. When two or more substituents are present in a molecule represented by formula (1), they may be the same or different. And the substituents may form a fused ring structure together with the benzene ring to which they are attached. The substituent as each of R1 and R2 is preferably a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, a sulfonamido group, an alkoxy group, an aryloxy group, an acyloxy group, a substituted or unsubstituted sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group, far preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an arylsulfonyl group, particularly preferably a halogen atom, an alkyl group, an aryl group or an aryloxy group. ml and m2 each represent an integer of 0 to 5 independently. Each of ml and m2 is preferably from 0 to 3, far preferably from 0 to 2, further preferably 0 or 1. When ml and m2 are integers of 2 or above, substituents on the same benzene ring may be the same or different. The subscript a represents 0 or 1. The case of a=0 means that the benzene rings are linked by a single bond. When a is 1, the benzene rings are linked by L. Herein, L represents an oxy group or a methylene group. Although the benzene rings of a compound represented by formula (1) are linked by a single bond, an oxy group or a methylene group as specified above, the preferred linkage is a single bond or an oxy group. The molecular weight of a compound represented by formula (1 ) is preferably lower than 2,000, far preferably lower than 1,000, further preferably lower than 700.
Examples of a compound represented by formula (1) are illustrated below, but compounds represented by formula (1) and usable in the invention should not be construed as being limited to these examples.
Figure imgf000032_0001
PL-I
PL-2 PL-3
Figure imgf000032_0002
PL-4 PL-5 PL-6
Figure imgf000032_0003
Figure imgf000032_0004
PL- 12 PL- 13 PL-14 SO2NHPh
Figure imgf000032_0005
Figure imgf000032_0006
PL-17 PL-18 PL-19
Figure imgf000033_0001
PL-23 PL-24 PL-25
Figure imgf000033_0002
PL-26
PL-27 PL-28
Figure imgf000033_0003
PL-29 PL-30 PL-31
Figure imgf000033_0004
Figure imgf000033_0005
S-3103, synthetic lubricating oil of tetraphenyl ether type, produced by Matsumura Oil Research Corp.
S-3105, synthetic oil of pentaphenyl ether type, produced by Matsumura Oil Research Corp.
S-3101, synthetic lubricating oil of monoalkyltetraphenyl ether type, produced by Matsumura Oil Research Corp.
S-3230, synthetic lubricating oil of dialkyltetraphenyl ether type, produced by Matsumura Oil Research Corp.
The compounds represented by formula (1) may be synthesized according to the methods well-known to persons skilled in the art, or may be acquired by purchase on the market. For example, S-3101, S-3103, S-3105 and S-3230 produced by Matsumura Oil Research Corp. can be used.
The amount of a compound represented by formula (1) added to an inorganic-organic complex composition is preferably from 0.1 to 30 mass%, far preferably from 0.3 to 25 mass%, further preferably from 0.5 to 20 mass%. When the addition amount is 30 mass% or below, there is a trend toward easy prevention of weep of the compound during the forming and the storage. When the addition amount is 0.1 mass% or above, the addition of the compound tends to exhibit its effect with ease. Additionally, the term "weep" used herein means a phenomenon that the compound added oozes out of the formed body surface. <Inorganic Fine Particles>
The nanocomposite material for use in the invention contains inorganic fine particles in combination with a compound represented by formula (1). There is no particular restriction as to inorganic fine particles usable in the invention, and the fine particles disclosed, e.g., in JP-A-2002-241612, JP-A-2005-298717, JP-A-2006-70069 and so on can be used.
More specifically, fine particles of oxides (such as aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, zinc oxide, magnesium oxide, tellurium oxide, yttrium oxide, indium oxide and tin oxide), fine particles of compound oxides (such as lithium niobate, potassium niobate and lithium tantalate), fine particles of sulfides (such as zinc sulfide and cadmium sulfide), and crystalline fine particles of semiconductors (such as zinc selenide, cadmium selenide, zinc telluride and cadmium telluride) or LiAlSiO4, PbTiO3, Sc2W3Oi2, ZrW2O8, AlPO4, Nb2O5, LiNO3 etc. can be used.
Of the fine particles of those kinds, fine particles of metal oxides are preferred over the others. More specifically, one metal oxide selected from the group consisting of zirconium oxide, zinc oxide, tin oxide and titanium oxide is preferred, one metal oxide selected from the group consisting of zirconium oxide, zinc oxide and titanium oxide is far preferred, and it is particularly advantgageous to use fine particles of zirconium oxide having good transparency in the visible region and low photocatalyst activity. Inorganic fine particles for use in the invention may be a composite of two or more ingredients from the viewpoints of refractive index, transparency and stability. In addition, the inorganic fine particles may be doped with a foreign element, or the surface layers thereof may be coated with a different kind of metal oxide, such as silica or alumina, or modified with a silane coupling agent, a titanate coupling agent, aluminate coupling agent, an organic acid (e.g., a carboxylic acid, a sulfonic acid, a phosphoric acid, a phosphonic acid) or so on for various purposes of, e.g., depression of photocatalyst activity, reduction in water absorption, and so on. Further, two or more kinds of these fine particles may be used in combination.
The refractive index of inorganic fine particles for use in the invention have no particular limits. However, when a nanocomposite material is applied to an optical member required to have a high refractive index as in the invention, it is preferable that the inorganic fine particles have not only the thermal dependency but also high refractive index characteristics. In this case, the refractive index of inorganic fine particles used is preferably from 1.9 to 3.0, far preferably from 2.0 to 2.7, particularly preferably from 2.1 to 2.5, as measured at a temperature of 22°C and a wavelength of 589 nm. When the refractive index of inorganic fine particles used is lower than 3.0, there is a trend toward easy suppression of Rayleigh scattering because of a relatively small difference in refractive index from a resin used together. On the other hand, when the refractive index is higher than 1.9, effect of enhancing the refractive index tends to be achieved with ease. The refractive index of inorganic fine particles can be estimated by using, e.g., a method in which a composite composed of a thermoplastic resin used in the invention and the inorganic fine particles compounded therewith is formed into a transparent film, the refractive index of the transparent film is measured with an Abbe refractometer (e.g., DM-M4, made by ATAGO CO., LTD.), the refractive index of resin component itself is measured separately, and the refractive index of inorganic fine particles is calculated from these measured values, or a method of calculating a refractive index of fine particles by measuring the refractive indexes of fine particle dispersions differing in fine particle concentration. When the number average particle size of inorganic fine particles for use in the invention is too small, properties inherent in the material constituting the fine particles vary in some cases. On the other than, when the number average particle size is too large, influence of Rayleigh scattering becomes pronounced and transparency of the organic-inorganic complex composition is sometimes reduced in the extreme. Therefore, the lower limit of the number average particle size of inorganic fine particles for use in the invention is preferably 1 nm or above, far preferably 2 nm or above, further preferably 3 nm or above, and the upper limit thereof is preferably 15 nm or below, far preferably 10 nm or below, further preferably 7 nm or below. In other words, the number average particle size of inorganic fine particles in the invention is preferably from 1 nm to 15 nm, far preferably from 2 nm to 10 nm, particularly preferably from 3 nm to 7 nm.
In addition, it is preferred that inorganic fine particles for use in the invention satisfy the average particle size specified above, and besides, the particle size distribution thereof be as narrow as possible. Although there are various ways to define such monodisperse particles, the numerically specified range as disclosed, e.g., in JP-A-2006- 160992 holds true also for preferred particle size distribution of fine particles for use in the invention.
The foregoing number average particle size can be measured by means of, e.g., an X-ray diffracting (XRD) device or a transmission electron microscope (TEM).
The manufacturing method of inorganic fine particles for use in the invention has no particular restrictions, and any of known methods can be employed. For example, desired fine particles of an oxide can be obtained by using a metal halide or a metal alkoxide as a raw material and performing hydrolysis in a reaction system containing water. Details of this method are described, e.g., in Japanese Journal of Applied
Physics, vol. 37, pp. 4603-4608 (1998), or Langmuir, vol. 16, No. 1, pp. 241-246 (2000). As a method other than the method of carrying out hydrolysis in water, the method of forming inorganic fine particles in an organic solvent or an organic solvent in which a thermoplastic resin as used in the invention is dissolved may be adopted. In forming them, various surface treating agents (such as a silane coupling agent, an aluminate coupling agent and a titanate coupling agent and organic acids (such as a carboxylic acid, sulfonic acid and a phosphonic acid)) may be incorporated into the organic solvent.
Examples of a solvent usable in those methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone and anisole. These solvents may use used alone or as mixtures of two or more thereof.
In addition to the foregoing methods, various general synthesis methods disclosed, e.g., in JP-A-2006-70069, including the methods of utilizing vacuum processes such as molecular beam epitaxy and CVD, can be adopted as methods for synthesis of inorganic fine particles.
The content of inorganic fine particles in a nanocomposite material for use in the invention is preferably from 20 to 95 mass%, far preferably from 25 to 70 mass%, further preferably from 30 to 60 mass%, from the viewpoint of ensuring good transparency and a high refractive index. Further, in point of dispersibility, the mass ratio between the inorganic fine particles and the thermoplastic resin (dispersion polymer) in the invention is preferably from 1:0.01 to 1:100, far preferably from 1:0.05 to 1:10, particularly preferably from 1 :0.05 to 1:5. <Thermoplastic Resin>
The nanocomposite material for use in the invention contains a thermoplastic resin. In particular, it is preferable that the nanocomposite material for use in the invention contain a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond together with an inorganic fine particle at least either at a high molecular chain end thereof or in a side chain thereof. The term "chemical bond" used herein is intended to include a covalent bond, an ionic bond, a hydrogen bond and a coordination bond. As suitable examples of such a thermoplastic resin, the following three kinds of thermoplastic resins can be given. (1) Thermoplastic resin having in a side chain thereof a functional group chosen from the following:
OR11 OR13
Figure imgf000038_0001
0 , 0
(wherein each of R11, R12, R13 and R14 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group), -SO3H, -OSO3H, -CO2H, or -Si(OR!5)mlR16 3-mi (wherein each of R15 and R16 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and ml represents an integer of 1 to 3). (2) Thermoplastic resin having in at least one end of its high molecular chain a functional group chosen from the following:
OR21 OR23
Figure imgf000038_0002
I l I l
0 , 0
(wherein each of R21, R22, R23 and R24 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group),
-SO3H, -OSO3H, -CO2H, or -Si(OR25)m2R26 3-m2 (wherein each of R25 and R26 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and m2 represents an integer of 1 to 3).
(3) Block copolymer including a hydrophobic segment and a hydrophilic segment. The thermoplastic resin (3) in particular is described below in detail.
<Thermoplastic Resin (3)>
The thermoplastic resin (3) usable in the invention is a block copolymer including a hydrophobic segment and a hydrophilic segment.
Herein, the term "hydrophobic segment (A)" refers to the segment having a property of being insoluble in water or methanol in the form of a polymer containing only the segment (A), and the term "hydrophilic segment (B)" refers to the segment having a property of being soluble in water or methanol in the form of a polymer containing only the segments (B). Examples of the type of the block copolymer include an AB type, a B1AB2 type (wherein two hydrophilic segments B1 and B2 may be the same or different) and an A1BA2 type (wherein two hydrophobic segments A1 and A2 may be the same or different). In point of superiority in dispersing property, a block copolymer of AB type or A1BA type block copolymer is preferred; while, in point of production suitability, a block copolymer of AB type or ABA type (or A1BA2 type in which two hydrophobic segments are the same) is far preferred, and a block copolymer of AB type is especially preferred. Each of the hydrophobic segment and the hydrophilic segment can be selected arbitrarily from heretofore known polymers including vinyl polymers prepared by polymerization of vinyl monomers, polyether polymers, ring-opening metathesis polymerization polymers and condensation polymers (such as polycarbonate, polyester, polyamide, polyether ketone and polyether sulfone). Of these polymers, however, those selected from vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates or polyesters are preferred as those segments, and vinyl polymers are far preferred in point of production suitability.
Examples of a vinyl monomer (A) forming the hydrophobic segment (A) include the following: Acrylic acid esters and methacrylic acid esters (ester groups of which are substituted or unsubstituted aliphatic ester groups or substituted or unsubstituted aromatic ester groups, such as a methyl ester group, a phenyl ester group and naphthyl ester group); acrylamides and methacrylamides, with examples including an N-monosubstituted acrylamide, an N-disubstituted acrylamide, an N-monosubstituted methacrylamide and an N-disubstituted methacrylamide (substituents of the monosubstituted and disubstituted amides are substituted or unsubstituted aliphatic groups or/and substituted or unsubstituted aromatic groups, with examples including a methyl group, a phenyl group and a naphthyl group); olefins, with examples including dichloropentadiene, norbornene derivatives, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene and vinylcarbazole; styrene compounds, with examples including styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, tribromostyrene and vinylbenzoic acid methyl ester; vinyl ethers, with examples including methyl vinyl ether, butyl vinyl ether, phenyl vinyl ether and methoxyethyl vinyl ether; and other monomers including butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyloxazolidone, N-vinylpyrrolidone, vinylidene chloride, methylene malononitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and dioctyl-2-methacryloyloxyethyl phosphate.
Of these monomers, acrylic acid esters and methacrylic acid esters the ester moieties of which contain unsubstituted aliphatic groups, or substituted or unsubstituted aromatic groups; an N-monosubstituted acrylamide, an N-disubstituted acrylamide, an N-monosubstituted methacrylamide and an N-disubstituted methacrylamide, the substituents of which are unsubstituted aliphatic groups or/and substituted or unsubstituted aromatic groups; and styrene compounds are preferable to the others. Further, acrylic acid esters and methacrylic acid esters the ester moieties of which contain substituted or unsubstituted aromatic groups, and styrene compounds are preferred over the others.
Examples of a vinyl monomer (B) forming the hydrophilic segment (B) include acrylic acid, methacrylic acid, and acrylic acid esters and methacrylic acid esters which have hydrophilic substituents in their respective ester moieties; styrene compounds which have hydrophilic substituents in their respective aromatic ring moieties; and vinyl ether, acrylamide, methacrylamide, an N-monosubstituted acrylamide, an N-disubstituted acrylamide, an N-monosubstituted methacrylamide and an N-disubstituted methacrylamide, which each contain a hydrophilic substituent. The preferred as such hydrophilic substituents are those having functional groups selected from,
OR31 OR33
Figure imgf000041_0001
0 , O
(wherein each of R31, R32, R33 and R34 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group), -SO3H, -OSO3H, -CO2H, -OH or -Si(OR35)m3R36 3-m3 (wherein each of R35 and R36 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and m3 represents an integer of 1 to 3). When each of R31, R32, R33, R34, R35 and R36 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, preferred ranges of these groups are the same as recited as preferred ones in the description of R11, R12, R13 and R14. And m3 is preferably 3. As to the functional groups, OR31 OR33
Figure imgf000042_0001
O , O
-CO2H and -Si(OR3i)m3R363-m3 are preferred,
OR3 OR33
Figure imgf000042_0002
Il Il O O and -CO2H are far preferred, and
OR31 OR33
Figure imgf000042_0003
O O are especially preferred.
In the invention, it is especially preferable that the block copolymer has a functional group selected from
OR31 OR33
Figure imgf000042_0004
Il I l O O -SO3H, -OSO3H, -CO2H, -OH or -Si(OR35)m3R36 3-m3 and the functional group content therein is from 0.05 mmol/g to 5.0 mmol/g.
It is particularly preferred that the hydrophilic segment (B) be formed from acrylic acid, methacrylic acid, an acrylic or methacrylic acid ester having a hydrophilic substituent in its ester moiety, or a styrene compound having a hydrophilic substituent on its aromatic ring moiety.
In the hydrophobic segment (A) formed from the vinyl monomer (A), the vinyl monomer (B) may be included to the extent of having no detrimental effect on the hydrophobic property of the segment (A). The mole ratio between the vinyl monomer (A) and the vinyl monomer (B) included in the hydrophobic segment (A) is preferably from
100:0 to 60:40.
In the hydrophilic segment (B) formed from the vinyl monomer (B), the vinyl monomer (A) may be included to the extent of having no detrimental effect on the hydrophilic property of the segment (B). The mole ratio between the vinyl monomer (B) and the vinyl monomer (A) included in the hydrophilic segment (B) is preferably from 100:0 to 60:40.
As to each of the vinyl monomer (A) and the vinyl monomer (B), one kind thereof may be used alone, or two or more kinds thereof may be used together. These vinyl monomers (A) and (B) are selected variously according to different purposes (such as acid content control, glass transition temperature (Tg) control, organic solvent or water solubility control and dispersion stability control).
The functional group content in the overall block copolymer is preferably from 0.05 to 5.0 mmol/g, far preferably from 0.1 to 4.5 mmol/g, particularly preferably from 0.15 to 3.5 mmol/g. Too low functional-group contents may cause poor suitability for dispersion, while too high functional-group contents may cause excessive water solubility or gelling of the organic-inorganic complex composition. Additionally, the functional group(s) in the block copolymer may combine with cationic ion(s), such as alkali metal ion(s) (e.g., Na+, K+, etc.) or ammonium ion(s), to form salt(s). The molecular weight (Mn) of the block copolymer is preferably from 1,000 to
100,000, far preferably from 2,000 to 80,000, particularly preferably from 3,000 to 50,000.
When the molecular weight of the block copolymer is adjusted to 1,000 or above, there is a trend toward easy preparation of a stable dispersion, and when the molecular weight of the block copolymer is adjusted to 100,000 or below, there is a trend toward enhancement of solubility in organic solvents. So, the range of 1,000 to 100,000 is preferred.
The refractive index of the block copolymer for use in the invention is preferably greater than 1.50, far preferably 1.55 or greater, further preferably greater than 1.60, particularly preferably greater than 1.65. Additionally, the values of the refractive indexes specified herein are values determined by measurements with an Abbe refractometer (e.g.,
DM-M4, made by ATAGO CO., LTD.) wherein light with a wavelength of 589 nm is used.
The glass transition temperature of the block copolymer for use in the invention is preferably from 80°C to 4000C, far preferably from 130°C to 3800C. When the glass transition temperature is adjusted to 800C or higher, there is a trend toward enhancement of heat resistance; while, when the glass transition temperature is adjusted to 4000C or lower, there is a trend toward enhancement of workability in forming.
The light-beam transmittance of the block copolymer for use in the invention is preferably 80% or above, far preferably 85% or above, in terms of 1-mm thickness when measured at the wavelength of 589 nm. Examples of the block copolymer (exemplified compounds Q-I to Q-20) are illustrated in the following tables. Additionally, block copolymers usable in the invention should not be construed as being limited to these examples in any way.
Table 1
4AjfB-h
Figure imgf000045_0001
Table 2
4-A+hB-h
Figure imgf000046_0001
The block copolymer as illustrated above can be synthesized by utilizing living radical polymerization or living ionic polymerization and, if required, using a technique of protecting a carboxyl group or the like or a technique of introducing a functional group into a polymer. Alternatively, it can be synthesized from a polymer having an end functional group by radical polymerization, or by interlinking one polymer having an end functional group with another polymer having an end functional group. Of these syntheses, syntheses utilizing living radial polymerization and living ionic polymerization are preferred to the others from the viewpoints of molecular weight control and the yields of block copolymers obtained thereby. Manufacturing methods of the block copolymers are described in books, e.g., Kobunshi no Gosei to Hanno (1), compiled by The Society of Polymer Science, Japan, published by Kyoritsu Shuppan Co., Ltd. in 1992, Seimitsu Jugo, compiled by The Chemical Society of Japan, published by Japan Scientific Societies Press in 1993, and Kobunshi no Gosei-Hanno (1), compiled by The Society of Polymer Science, Japan, published by Kyoritsu Shuppan Co., Ltd. in 1995; R. Jerome et al., Prog. Polym. ScL, vol. 16, pp. 837-906 (1991), entitled "Telecheric Polymer: Synthesis, Properties and Applications"; Y. Yagch et al., Prog. Polym. ScL, vol. 15, pp. 551-601 (1990), entitled "Light-based Synthesis of Block Copolymers and Graft Copolymers"; and U.S. Patent No. 5085698; and so on. These block copolymer resins may be used alone or as mixtures of two or more thereof.
Other Additives>
In addition to the compound represented by the formula (1), the inorganic fine particles and the thermoplastic resin as recited above, various kinds of additives can be mixed in the nanocomposite material for use in the invention as appropriate from the viewpoints of uniform dispersibility, releasability and weather resistance. Examples of such additives include a surface treating agent, an antistatic agent, a dispersant, a plasticizer and a releasing agent. In addition to the thermoplastic resin as recited above, resins not having the functional groups as recited above may further be added regardless of their kinds. However, it is preferred that the resins added be similar in optical properties, thermal properties and molecular weights to the thermoplastic resin used.
The mixing proportion of those additives, though varies depending on the purposes, is preferably from 0 to 50 mass%, far preferably from 0 to 30 mass%, particularly preferably from 0 to 20 mass%, with respect to the sum of the inorganic fine particles and the thermoplastic resin.
<Surface Treating Agent>
In the invention, as mentioned below, fine particle surface modifiers other than the thermoplastic resin may be added in mixing the inorganic fine particles dispersed in water or an alcohol solvent into the thermoplastic resin in response to various purposes including the purpose of enhancing extractability and exchangeability with organic solvents, the purpose of enhancing uniform dispersibility in the thermoplastic resin, the purpose of lowering a water absorption rate of the fine particles, the purpose of improving the weather resistance, and so on. The weight average molecular weight of the surface treating agent including such a surface modifier is preferably from 50 to 50,000, far preferably from 100 to 20,000, further preferably from 200 to 10,000.
As the surface treating agent, a compound having the structure represented by the following formula (2) is preferred.
Formula (2) A - B
In the formula (2), A represents a functional group capable of forming a chemical bond together with an inorganic fine particle surface, and B represents a 1-30C univalent group having compatibility or reactivity with a resin matrix composed mainly of the thermoplastic resin used in the invention or a polymer. The term "chemical bond" used herein is intended to include a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond and the like.
Examples of a group suitable as the group represented by A include the same groups as recited as examples of the functional group of the thermoplastic resin used in the invention. On the other hand, it is preferred in point of compatibility that the group represented by B be identical or similar in chemical structure to that of the thermoplastic resin dominating in the resin matrix. From the viewpoint of enhancing the refractive index in particular, it is preferred that an aromatic ring be present in the chemical structure of B as in the chemical structure of the thermoplastic resin. Examples of a surface treating agent suitably used in the invention include p-octylbenzoic acid, p-propylbenzoic acid, acetic acid, propionic acid, cyclopentanecarboxylic acid, dibenzyl phosphate, monobenzyl phosphate, diphenyl phosphate, di-α-naphthyl phosphate, phenylphophonic acid, phenylphosphonic acid monophenyl ester, KAYAMER PM-21 (trade name, a product of NIPPON KAYAKU CO., LTD.), KAYAMER PM-2 (trade name, a product of NIPPON KAYAKU CO., LTD.), benzenesulfonic acid, naphthalenesulfonic acid, p-octylbenzenesulfonic acid, and the silane coupling agents disclosed in JP-A-5-221640, JP-A-9-100111 and JP-A-2002- 187921, but they should not be construed as being limited to these compounds. These surface treating agents may be used alone or as combinations of two or more thereof.
The ratio between the total addition amount of these surface treating agents and that of the inorganic fine particles is preferably from 0.01 to 2, far preferably from 0.03 to 1, particularly preferably from 0.05 to 0.5, on a mass basis. <Antistatic Agent>
In order to control the voltage of electrostatic charge on the nanocomposite material for use in the invention, an antistatic agent can be added. In some cases, inorganic fine particles themselves, which are added to the nanocomposite material for the purpose of improving optical properties, contribute to antistatic effect as another effect. The antistatic agent added may be an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, an amphoteric antistatic agent, a polymeric antistatic agent, or antistatic fine particles. Two or more kinds of antistatic agents may also be used in combination. Examples of these antistatic agents include the compounds disclosed in JP-A-2007-4131 and JP-A-2003-201396. Although those antistatic agents are various in addition amount, the antistatic agents added constitute preferably 0.001 to 50 mass%, far preferably 0.01 to 30 mass%, particularly preferably 0.1 to 10 mass%, of the total solids. <Others> In addition to the compounds recited above, it is also possible to add substances of the kind which can enhance releasing effect and further increase the flowability at the time of forming, with examples including native wax, such as vegetable wax (e.g., carnauba wax, rice wax, cotton wax, Japan wax, etc.), animal wax (e.g., beeswax, lanolin, etc.), mineral wax (e.g., ozocerite, cerecin, etc.) or petroleum wax (e.g., paraffin, microcrystalline wax, petrolactam, etc.), synthetic hydrocarbon wax such as Fischer-Tropsch wax or polyethylene wax, synthetic wax such as a long-chain aliphatic amide, ester, ketone or ether (e.g., stearic acid amide, chlorinated hydrocarbon, etc.), silicone oil such as dimethylsilicone oil or methylphenylsilicone oil, and fluorotelomers such as Zonyl FSN and Zonyl FSO produced by DuPont. For the purpose of improving light resistance and thermal degradation, known degradation inhibitors of hindered phenol type, amine type, phosphorus-containing type or thioether type may further be added as appropriate. The mixing proportion of such degradation inhibitors is preferably on the order of 0.1 to 5 mass% with respect to the total solids in the resin composition.
<Preparation Method of Inorganic-Organic Complex Composition> The nanocomposite material for use in the invention is prepared by dispersing inorganic fine particles into the thermoplastic resin molecules having functional groups in a state that the particles form chemical bonds to the resin molecules. And this process of dispersing is carried out in the presence of the compound represented by formula (1).
Since the inorganic fine particles for use in the invention is minute in particle size and high in surface energy, once they are isolated in a solid state they are difficult to disperse again. Accordingly, it is preferred that the inorganic fine particles in a state of being dispersed in a solution be mixed into the thermoplastic resin and made into a stable dispersion. Examples of a manufacturing method suitable for the nanocomposite material include: [1] a method of manufacturing a composite of inorganic fine particles and a thermoplastic resin by subjecting inorganic particles to surface treatment in the presence of a surface treating agent, extracting the surface-treated inorganic fine particles with an organic solvent, and then homogeneously mixing the extracted inorganic fine particles with the thermoplastic resin and the compound represented by formula (1), and [2] a method of manufacturing a composite of inorganic fine particles and a thermoplastic resin by mixing all the ingredients including inorganic fine particles, the thermoplastic resin, the compound represented by formula (1) and other additives with the aid of a solvent in which all the ingredients can disperse homogenously or dissolve. When a composite of the inorganic fine particles and the thermoplastic resin is manufactured according to the method [1], the organic solvent used is a solvent insoluble in water, such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloromethane, dichloroethane, chlorobenzene or methoxybenzene. The surface treating agent used in extracting fine particles with an organic solvent may be similar or different in kind to or from the thermoplastic resin, and suitable examples thereof include those mentioned in the foregoing section <Surface Treating Agent>.
In mixing the inorganic fine particles extracted with the organic solvent into the thermoplastic resin, the compound represented by formula (1) is also added, and additives such as a plasticizer, a releasing agent or a different kind of polymer may further be added as required.
When the foregoing method [2] is adopted, it is advantageous for the solvent used to be a hydrophilic polar solvent, such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, l-methoxy-2-propanol, tert-butanol, acetic acid or propionic acid, or a mixture of two or more of these polar solvents, or a mixture of a solvent insoluble in water, such as chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene or methoxybenzene, and a polar solvent as recited above. At the time of mixing, a dispersant other than the thermoplastic resin, a plasticizer, a releasing agent or a different kind of polymer may be added as needed. When fine particles dispersed in a water-methanol mixture are used, it is preferable that a hydrophilic solvent having higher boiling point than the water-methanol mixture, in which the thermoplastic resin can be dissolved, is added, then the dispersion liquid of the fine particles is replaced with the polar organic solvent by concentrating the water-methanol mixture through distillation, and thereafter the fine particles are mixed with the resin. At this time, the surface treating agent may be added.
Examples
Features of the invention are more specifically illustrated below by reference to the following examples. Additionally, various changes and modifications can be made as appropriate with respect to the ingredients, the amounts and proportions of ingredients used, details of treatment, order of procedures and so on as presented in the following examples unless they depart from the spirit of the invention. Therefore, the scope of the invention should not be construed as being limited to the following examples. Preparation of Dispersion Liquid of Fine Particles>
(1) Synthesis of Fine Particles of Zirconium Oxide
A zirconium oxychloride solution having a concentration of 50 g/L was neutralized with a 48% aqueous sodium hydroxide solution, thereby preparing a hydrated zirconium suspension. This suspension is filtered off, and then washed with ion exchange water. Thus, hydrated zirconium cake was obtained. This cake was prepared into a concentration of 15 mass% in zirconium oxide terms by use of ion exchange water, placed in an autoclave, and subjected to 24-hour hydrothermal treatment at 150°C under a pressure of 150 atmospheres. Thus, a fine-particle suspension of zirconium oxide was obtained. And it was ascertained by TEM that zirconium oxide fine particles having a number average particle size of 5 run was formed. The refractive index of these fine particles was found to be 2.1.
(2) Preparation of Zirconium Oxide Dimethylacetamide Dispersion
Solvent replacement was carried out by adding 500 g of N,N'-dimethylacetamide to
500 g of the zirconium oxide fine particle suspension (concentration: 15 mass%) prepared in
(1) and then concentrating them under reduced pressure until the total weight was reduced to about 500 g or below, and thereafter N,N'-dimethylacetamide was added for concentration adjustment, thereby preparing a 15 mass% dispersion of zirconium oxide dimethylacetamide.
<Synthesis of Thermoplastic Resin>
Synthesis of Thermoplastic Resin Q-I:
A mixed solution containing 2.1 g of tert-butyl acrylate, 0.72 g of 2-bromopropionic acid tert-butyl ester, 0.46 g of Copper© bromide, 0.56 g of N,N,N',N',N", N"-pentamethyldiethylenetetramine and 9 ml of methyl ethyl ketone was prepared, and subjected to replacement with N2. While stirring the resulting solution for one hour at an oil-bath temperature of 80°C, 136.2 g of styrene was added thereto in a stream of nitrogen. The resulting mixture was further stirred for 16 hours at an oil-bath temperature of 90°C, and then cooled to room temperature. Thereto, 100 ml of ethyl acetate and 30 g of alumina were added, and further stirred for 30 minutes. This reaction solution was filtered, and the filtrate was added dropwise to excessive methanol. The thus formed precipitate was filtered off, washed with methanol and dried, thereby yielding 61 g of resin. This resin was dissolved in 300 ml of toluene, and thereto 6 g of p-toluenesulfonic acid monohydrate was added. The resulting solution was heated under reflux for 3 hours. This reaction solution was added dropwise to excessive methanol. The precipitate formed was filtered off, washed with methanol and dried, thereby yielding 55 g of the block copolymer Q-I listed in Table 1. By GPC measurement, it was found that the thus obtained resin had a number average molecular weight of 32,000 and a weight average molecular weight of 35,000. And the refractive index of the resin was found to be 1.59 as measured with an Abbe refractometer. <Production of Solution of Nanocomposite Material>
To the dispersion of zirconium oxide dimethylacetamide, the thermoplastic resin Q-I, Compound PL-I and a surface treating agent (4-propylbenzoic acid) were added at a ZrO2 (as a solid component)/PL-l /4-propylbenzoic acid ratio of 41.7/8.3/8.3, and mixed homogeneously with stirring, and then the dimethylacetamide solvent was concentrated by heating under reduced pressure. The thus obtained concentrated solution as a resinous solution of nanocomposite material was formed into a lens by means of the inkjet head.
Additionally, at the occasion of forming droplets by the inkjet technique, various drying methods, such as a heat-transfer drying method, an internal heat generation drying method and an unheated drying method, can be applied to the pretreatment of the resinous solution. More specifically, box drying, tunnel and band drying, rotary drying, through-flow rotary drying, channel agitation drying, fluidized-bed drying, spray drying, flash drying, vacuum-freeze drying, vacuum drying, infrared drying, internal heat generation drying, drum drying or so on can be given in advance. Additionally, two or more of these drying methods may be used in combination.
When the material is concentrated before the lens is shaped by the inkjet technique, the liquid viscosity at the time of spray drying is adjusted preferably to 300 cP or below, far preferably to 100 cP or below, further preferably to 50 cP. (The liquid viscosity is adjustable by changing the concentration of the solution.)
A lens having a diameter φ of 5 mm and a thickness of 1 mm was shaped under conditions that drying shrinkage of the resinous solution was 90%, the discharge cycle from a nozzle was 20 times per second and the number of nozzles was 20. By adjusting the droplet size to 0.1 mm in diameter, the shaping was able to reach completion within the span of 15.6 minutes at the shortest.
Industrial Applicability
According to an optical-member manufacturing method of an exemplary embodiment of the invention, as mentioned above, high-quality optical materials can be manufactured with arbitrary shapes and arbitrary optical characteristics in a short time by use of nanocomposite materials having high refractive indexes. Therefore, the present manufacturing method has very high utility value in manufacturing optical members including miniature-sized lenses usable in, e.g., mobile phone's built-in cameras and optical information recording devices, such as DVD, CD and MO drives.
The present application claims foreign priority based on Japanese Patent Application No. JP2007-256811 filed September 28, 2007, the contents of which is incorporated herein by reference.

Claims

1. A method for manufacturing an optical member, comprising: discharging a droplet of a solution including a transparent thermoplastic resin and solidifying the droplet on a substrate on a basis of profile data of the optical member to shape the optical member, wherein a process of discharging droplets of the solution on different positions of the substrate and solidifying the droplets by drying is repeated a plurality of times to stack the thermoplastic resin so that the stacked thermoplastic resin have a height according to the profile data; and separating the shaped optical member from the substrate.
2. The method according to claim 1, further comprising measuring a height of droplets of the solution landed and stacked on the substrate, wherein the process of discharging a droplet of the solution and solidifying the droplet by drying is repeated until the measured height of the stacked droplets reaches one corresponding to the profile data of the optical member.
3. The method according to claim 1 wherein the discharging of the droplet is performed so that each of plane sections into which the optical member is sliced in a direction parallel to the substrate is stacked in succession, starting with a bottom plane section, on the substrate.
4. The method according to claim 2, wherein the measuring of the height of the droplets is performed by utilizing a phase difference of laser light.
5. The method according to claim 1, wherein the droplet is discharged out of a nozzle of an inkj et head.
6. The method of according to claim 5, wherein the inkjet head includes the nozzle, a pressure chamber communicated with the nozzle, and a piezoelectric element combined with the pressure chamber for pressurization, and wherein the inkjet head discharges the droplet of the solution of the thermoplastic resin out of the nozzle when an inside of the pressure chamber is pressurized by application of a voltage to the piezoelectric element.
7. The method according to claim 5, wherein the inkjet head includes the nozzle, a fluid channel communicated with the nozzle, and a heating unit disposed on a part of the fluid channel, and wherein bubbles are produced in the fluid channel by heat supply from the heating unit so that the droplet of the solution of the thermoplastic resin is discharged out of the nozzle.
8. The method according to claim 1, wherein the droplet of the solution has a diameter of0.005 mm to 0.1 mm.
9. The method according to claim 1, wherein the shaped optical member is subjected to a rapid thermal anneal treatment to level a surface of the optical member.
10. The method according to claim 1, wherein the thermoplastic resin is stacked on a spherical lens-shaped transparent body.
11. The method according to claim 1 , wherein an aspheric surface layer is formed from the solution of the thermoplastic resin on the spherical lens-shaped transparent body.
12. The method according to claim 1, wherein two pieces of optical members shaped to be planar at bottoms thereof are joined into one optical member in a state that their bottom surfaces face to each other.
13. The method according to claim 1, wherein the discharging of the droplet is performed in one of a vacuum, an atmosphere of carbon dioxide, and an atmosphere of nitrogen.
14. The method according to claim 1, wherein the thermoplastic resin is a nanocomposite material including a transparent thermoplastic resin into which fine particles having sizes of 20 run or less are incorporated.
15. The method according to claim 1, wherein the optical member is a lens.
16. The method according to claim 15, wherein the lens is formed by mixing two or more kinds of resin solutions different in content of the fine particles at a ratio in accordance with at least one of a diameter direction and a thickness direction of the lens, so that a refractive index distribution is imparted to the at least one of the diameter direction and the thickness direction of the lens.
17. The method according to claim 15, wherein the lens is shaped on the substrate by landing of the droplet discharged out of the nozzle on a desired position of the substrate under rotary drive, and the method further comprises: detecting height information on a height of the lens under shaping; determining an arrival time required for the droplet to arrive a first position where the droplet from the nozzle disposed at a height is to be landed, on a basis of the height information; determining an amount of deviation of a second position from the first position, the second position being a position where the droplet is landed after the substrate is rotated by the arrival time; and correcting a timing of discharging of the droplet out of the nozzle so as to cancel the amount of deviation, so that the droplet is landed at a position coinciding with the desired position.
18. An apparatus for manufacturing an optical member by discharging a droplet of a solution of a thermoplastic resin and solidifying the droplet on a substrate by drying on a basis of profile data of the optical member, the apparatus comprising: a substrate on which the optical member is shaped; a nozzle which discharges the droplet of the solution of the thermoplastic resin; a discharge head freely-movably facing to the substrate and including the nozzle; and a control section for repeating a plurality of times a process of discharging droplets of the solution at different positions on a surface the substrate and solidifying the droplets by drying is repeated a plurality of times to stack the thermoplastic resin so that the stacked thermoplastic resin have a height according to the profile data.
19. The apparatus according to claim 18, wherein the substrate is supported so as to be a freely-rotatable, and a discharge point of the discharge head is freely movable along at least a straight line passing through a center of rotation of the substrate.
20. The apparatus according to claim 18, further comprising a relative movement section which enables relative movement of the substrate and the discharge head along a direction.
21. The apparatus according to claim 1, further comprising a measurement section that measures a height of droplets discharged out of the nozzle and landed and stacked on the substrate, wherein the control section controls for repeating the process discharging a droplet of the solution and solidifying the droplet by drying until the measured height of the stacked droplets reaches one corresponding to the profile data of the optical member.
2. An optical member formed by a method according to claim 1.
PCT/JP2008/067869 2007-09-28 2008-09-25 Manufacturing method of optical member, optical member manufacturing apparatus and optical member WO2009041707A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007256811A JP2009083326A (en) 2007-09-28 2007-09-28 Manufacturing method of optical member and optical member formed by the same
JP2007-256811 2007-09-28

Publications (2)

Publication Number Publication Date
WO2009041707A2 true WO2009041707A2 (en) 2009-04-02
WO2009041707A3 WO2009041707A3 (en) 2009-06-25

Family

ID=40512009

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/067869 WO2009041707A2 (en) 2007-09-28 2008-09-25 Manufacturing method of optical member, optical member manufacturing apparatus and optical member

Country Status (3)

Country Link
JP (1) JP2009083326A (en)
TW (1) TW200914256A (en)
WO (1) WO2009041707A2 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9592690B2 (en) 2011-01-06 2017-03-14 Luxexcel Holding B.V. Print head, upgrade kit for a conventional inkjet printer, printer and method for printing optical structures
EP3311994A1 (en) * 2016-10-21 2018-04-25 Carl Zeiss Vision International GmbH Method, in particular 3d printing method, for the production of a spectacle lens
EP3312662A1 (en) * 2016-10-21 2018-04-25 Carl Zeiss Vision International GmbH Brillenglas und verfahren zu dessen herstellung
EP3473418A1 (en) * 2017-10-19 2019-04-24 Essilor International Method for manufacturing an ophthalmic lens, support and manufacturing system
WO2020169688A1 (en) * 2019-02-20 2020-08-27 Luxexcel Holding B.V. Method for printing a three-dimensional optical component
WO2021058077A1 (en) * 2019-09-23 2021-04-01 Micro Resist Technology Gesellschaft Für Chemische Materialien Spezieller Photoresistsysteme Mbh Production process of an isolated monolithic micro optical component
US11084205B2 (en) 2015-07-13 2021-08-10 Stratasys Ltd. Operation of printing nozzles in additive manufacture and apparatus for cleaning printing nozzles
CN114630721A (en) * 2019-11-11 2022-06-14 三菱电机株式会社 Laminated shaping device
US11370175B2 (en) 2017-06-19 2022-06-28 Essilor International Optical element, assembly comprising such an optical element and method of manufacturing an optical element
US11897186B2 (en) 2014-07-13 2024-02-13 Stratasys Ltd. Method and system for rotational 3D printing
EP4385735A1 (en) * 2022-12-12 2024-06-19 Essilor International Method for additively manufacturing an ophthalmic device and manufacturing system configured to carry out such a method

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011008121A (en) * 2009-06-26 2011-01-13 Sony Corp Varifocal lens, camera module, and electronic equipment
FR2964753B1 (en) * 2010-09-14 2012-09-28 Commissariat Energie Atomique METHOD FOR MANUFACTURING A SEGMENTED OPTICAL STRUCTURE
JP2015092201A (en) * 2012-02-21 2015-05-14 パナソニック株式会社 Optical element, and imaging device provided with the same
JP2015092203A (en) * 2012-02-23 2015-05-14 パナソニック株式会社 Optical element, and imaging device provided with the same
FR2996160B1 (en) * 2012-09-28 2016-07-29 Essilor Int METHOD FOR MANUFACTURING AN OPHTHALMIC LENS COMPRISING A MARKING STEP FOR PERMANENT BRANDS ON THE OPHTHALMIC LENS
FR3006623B1 (en) * 2013-06-07 2016-02-05 Essilor Int METHOD FOR MANUFACTURING AN OPHTHALMIC LENS
FR3008196B1 (en) * 2013-07-08 2016-12-30 Essilor Int METHOD FOR MANUFACTURING AT LEAST ONE OPHTHALMIC LENS
FR3014355B1 (en) * 2013-12-11 2016-02-05 Essilor Int METHOD FOR MANUFACTURING AN OPHTHALMIC LENS
JPWO2017212529A1 (en) * 2016-06-06 2019-03-28 オリンパス株式会社 METHOD FOR MANUFACTURING OPTICAL ELEMENT, AND APPARATUS FOR MANUFACTURING OPTICAL ELEMENT
WO2017216967A1 (en) * 2016-06-17 2017-12-21 オリンパス株式会社 Phantom, apparatus for producing laminated resin structure, and method for producing laminated resin structure
JP6758130B2 (en) * 2016-08-31 2020-09-23 株式会社ニコン・エシロール Manufacturing method of blocking ring and manufacturing method of spectacle lens
JP6811934B2 (en) * 2016-09-15 2021-01-13 株式会社リコー Manufacturing method of three-dimensional model, three-dimensional modeling device
WO2018095837A1 (en) * 2016-11-23 2018-05-31 Atheneum Optical Sciences, Llc Three-dimensional printing of optical devices
JP2020026101A (en) * 2018-08-14 2020-02-20 野村マイクロ・サイエンス株式会社 Manufacturing method of three-dimensional shaped article
JP6964801B2 (en) * 2018-11-09 2021-11-10 三菱電機株式会社 Laminated modeling equipment
CN112955270B (en) * 2018-11-09 2024-02-13 三菱电机株式会社 Lamination shaping device
JP6765569B1 (en) * 2019-08-07 2020-10-07 三菱電機株式会社 Laminated modeling equipment, laminated modeling method, and laminated modeling program
US20230294170A1 (en) * 2020-08-26 2023-09-21 Mitsubishi Electric Corporation 3d printing apparatus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010048968A1 (en) * 2000-02-16 2001-12-06 Cox W. Royall Ink-jet printing of gradient-index microlenses
DE10060304A1 (en) * 2000-12-04 2002-06-06 Rolf Danzebrink Production of coatings with structured thickness, especially micro-lens grids for scanning or 3D-imaging, involves metering droplets of prehydrolysed silane-based starting material onto substrate and hardening droplets
JP2004177243A (en) * 2002-11-27 2004-06-24 Dainippon Printing Co Ltd Volume measuring method for infinitesimal droplet and substrate for infinitesimal droplet collection used therefor
JP2005001131A (en) * 2003-06-09 2005-01-06 Seiko Epson Corp Method and apparatus for manufacturing lens
WO2006022217A1 (en) * 2004-08-23 2006-03-02 Kabushiki Kaisha Ishiihyoki Ink jet printer discharge amount control method, ink droplet spread check method, and orientation film formation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010048968A1 (en) * 2000-02-16 2001-12-06 Cox W. Royall Ink-jet printing of gradient-index microlenses
DE10060304A1 (en) * 2000-12-04 2002-06-06 Rolf Danzebrink Production of coatings with structured thickness, especially micro-lens grids for scanning or 3D-imaging, involves metering droplets of prehydrolysed silane-based starting material onto substrate and hardening droplets
JP2004177243A (en) * 2002-11-27 2004-06-24 Dainippon Printing Co Ltd Volume measuring method for infinitesimal droplet and substrate for infinitesimal droplet collection used therefor
JP2005001131A (en) * 2003-06-09 2005-01-06 Seiko Epson Corp Method and apparatus for manufacturing lens
WO2006022217A1 (en) * 2004-08-23 2006-03-02 Kabushiki Kaisha Ishiihyoki Ink jet printer discharge amount control method, ink droplet spread check method, and orientation film formation method

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9592690B2 (en) 2011-01-06 2017-03-14 Luxexcel Holding B.V. Print head, upgrade kit for a conventional inkjet printer, printer and method for printing optical structures
US11897186B2 (en) 2014-07-13 2024-02-13 Stratasys Ltd. Method and system for rotational 3D printing
US11084205B2 (en) 2015-07-13 2021-08-10 Stratasys Ltd. Operation of printing nozzles in additive manufacture and apparatus for cleaning printing nozzles
EP3311994A1 (en) * 2016-10-21 2018-04-25 Carl Zeiss Vision International GmbH Method, in particular 3d printing method, for the production of a spectacle lens
EP3312662A1 (en) * 2016-10-21 2018-04-25 Carl Zeiss Vision International GmbH Brillenglas und verfahren zu dessen herstellung
WO2018073397A1 (en) * 2016-10-21 2018-04-26 Carl Zeiss Vision International Gmbh 3d printing process for producing a spectacle lens
WO2018073398A1 (en) * 2016-10-21 2018-04-26 Carl Zeiss Vision International Gmbh Spectacle lens and method for producing same
US10670884B2 (en) 2016-10-21 2020-06-02 Carl Zeiss Vision International Gmbh Spectacle lens and method for producing same
US11400668B2 (en) 2016-10-21 2022-08-02 Carl Zeiss Vision International Gmbh 3D printing process for producing a spectacle lens
US11370175B2 (en) 2017-06-19 2022-06-28 Essilor International Optical element, assembly comprising such an optical element and method of manufacturing an optical element
EP3473418A1 (en) * 2017-10-19 2019-04-24 Essilor International Method for manufacturing an ophthalmic lens, support and manufacturing system
WO2019077068A1 (en) * 2017-10-19 2019-04-25 Essilor International Method for manufacturing an ophthalmic lens, support and manufacturing system
WO2020169688A1 (en) * 2019-02-20 2020-08-27 Luxexcel Holding B.V. Method for printing a three-dimensional optical component
US20220134636A1 (en) * 2019-02-20 2022-05-05 Luxexcel Holding B.V. Method for printing a three-dimensional optical component
WO2021058077A1 (en) * 2019-09-23 2021-04-01 Micro Resist Technology Gesellschaft Für Chemische Materialien Spezieller Photoresistsysteme Mbh Production process of an isolated monolithic micro optical component
CN114630721A (en) * 2019-11-11 2022-06-14 三菱电机株式会社 Laminated shaping device
CN114630721B (en) * 2019-11-11 2024-04-16 三菱电机株式会社 Lamination shaping device
EP4385735A1 (en) * 2022-12-12 2024-06-19 Essilor International Method for additively manufacturing an ophthalmic device and manufacturing system configured to carry out such a method
WO2024126334A1 (en) * 2022-12-12 2024-06-20 Essilor International Method for additively manufacturing an ophthalmic device and manufacturing system configured to carry out such a method

Also Published As

Publication number Publication date
JP2009083326A (en) 2009-04-23
WO2009041707A3 (en) 2009-06-25
TW200914256A (en) 2009-04-01

Similar Documents

Publication Publication Date Title
WO2009041707A2 (en) Manufacturing method of optical member, optical member manufacturing apparatus and optical member
US20100225013A1 (en) Method for producing optical member and optical member formed by the production process
JP2007238884A (en) Optical article
JP5701474B2 (en) Inorganic fine particle dispersion, organic-inorganic composite composition, molded article and optical component
CN102741715A (en) Diffractive optical element and manufacturing method thereof
KR20100014686A (en) Manufacturing preform for an optical member
JP2009199072A (en) Lens device
US20100041807A1 (en) Optical member manufacturing method, optical member manufacturing apparatus and optical member
JP2009242486A (en) Organic-inorganic composite composition and method for producing the same, shaped article, and optical component
JP2010235658A (en) Organic inorganic complex composition, molded product, optical component, and moist heat resistance improver
JP5244343B2 (en) ORGANIC-INORGANIC COMPOSITE MATERIAL, OPTICAL COMPONENT AND METHOD FOR PRODUCING THEM
US20100055454A1 (en) Dispersion liquid of metal oxide fine particles,and molded products using the same
JP2010043191A (en) Optical component and plastic lens
WO2009028732A1 (en) Method and apparatus for molding optical member and optical member
WO2009096606A1 (en) Preform for press working and manufacturing method thereof
JP5345302B2 (en) Organic-inorganic composite composition and optical component
JP2009298945A (en) Inorganic powder, organic/inorganic composite composition and method for producing the same, molding, and optical component
JP5345294B2 (en) Organic-inorganic composite material, manufacturing method thereof, and optical component
JP5114272B2 (en) Pressure molding apparatus and pressure molding method
JP2021151780A (en) Method for manufacturing optical component
JP2009221246A (en) Organic-inorganic composite composition, transparent molded item, optical goods and lens
JP2007213022A (en) Transparent molded article and method for producing it, and lens substrate
JP5279306B2 (en) Organic-inorganic composite composition, molded body and optical component
JP2009221433A (en) Organic inorganic composite composition, molded article and optical part
JP2010043205A (en) Organic inorganic composite material, method for manufacturing molded article, and an optical component

Legal Events

Date Code Title Description
NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08833749

Country of ref document: EP

Kind code of ref document: A2