JP2009083326A - Manufacturing method of optical member and optical member formed by the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an optical member, which does not require the time and the cost spent on the manufacture of a mold, highly precisely and inexpensively manufactures optical members in the production of many kinds of products each in a small quantity. <P>SOLUTION: In the manufacturing method of an optical member 11, based on the profile data of the optical member 11, a solution of a thermoplastic resin is discharged as droplets and solidified to shape the optical member 11. Reference being made to the profile date, there is repeated in a plurality of times the process of discharging droplets on different positions on the flat surface and solidifying until each reaches a predetermined height, and thereby the transparent thermoplastic resin is stacked on the substrate and shaped. This shaping is realized by repetition of measuring the height formed when the droplets hit the substrate and are stacked, by discharging the droplets until the measured height reaches the one corresponding to the profile date of the optical member 11, and also by repetition of solidifying by drying. The measurement of the height is performed by utilizing the phase difference of a laser beam. The droplets are discharged from the nozzle 15 of the inkjet type head. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an optical member and an optical member formed by the manufacturing method, and more particularly to a technique for forming an optical member using a nanocomposite material.

  In recent years, as optical devices such as portable cameras and optical information recording devices such as DVDs, CDs, and MO drives increase in performance, size, and cost, optical lenses used in these devices The development of excellent materials and processes is also strongly desired for optical members such as filters.

In particular, plastic lenses are lighter and harder to break than inorganic materials such as glass, and can be processed into various shapes, so that they can be produced at a lower cost. is there. Accordingly, it is required to increase the refractive index of the material itself and to stabilize the optical refractive index against thermal expansion and temperature change in order to reduce the thickness of the lens.
In general, such a plastic lens is formed by filling a mold with a resin material, or when a highly accurate lens is formed, it is hot-pressed with a mold to obtain a highly accurate lens shape. In addition, various attempts have been made to improve the optical refractive index and suppress the temperature change of the thermal expansion coefficient and optical refractive index by using a nanocomposite material in which inorganic fine particles such as metal fine particles are dispersed in a plastic resin as a lens material. (For example, refer to Patent Documents 1 to 3).

When an optical member is formed using such a nanocomposite material, an inorganic material is used to reduce light scattering when dispersing inorganic fine particles in a plastic resin for an optical member that requires a high degree of transparency. It was necessary to make the particle size of the fine particles smaller than at least the wavelength of light to be used. Furthermore, in order to reduce the attenuation of transmitted light intensity due to Rayleigh scattering, it was necessary to prepare and disperse nanoparticles having a particle size of 15 nm or less.
JP 2006-343387 A JP 2002-47425 A JP 2003-155415 A JP 2006-146063 A JP 2005-59289 A JP 2000-67449 A JP 2006-54489 A JP 2005-88502 A JP 2005-92049 A

In order to produce a nanocomposite material in which inorganic fine particles are dispersed in a plastic resin, the following method can be mentioned.
(1) Inject and mix inorganic fine particles directly into plastic resin.
(2) After mixing the inorganic fine particles in a liquid serving as a solvent, the solvent is removed by heating.
(3) After mixing the monomer and inorganic fine particles, the monomer is polymerized to contain inorganic fine particles.

However, in the method (1), when the particle concentration is high, the particles are aggregated and are not transparent. In the method (3), the shrinkage during polymerization is large and the shape control is difficult.
There has been a problem that molding cannot be performed with the accuracy required for a photographing lens or a pickup lens of a portable small camera. The method (2) is a method that can produce a lens having the highest quality, but the conventional method still has a problem that it takes time to remove the solvent.
In addition, plastic lenses are formed by filling a resin material into a mold or by hot pressing with a mold, so it is necessary to prepare a new mold as the shape of the product changes. Since a lot of time and money is required to manufacture the mold, there is a problem that it is not possible to cope with frequent design changes such as when producing a variety of small-quantity products and prototypes.

  On the other hand, the method for forming a three-dimensional shape disclosed in Patent Document 4 uses an inkjet method to give a three-dimensional uneven shape with a fine size by utilizing the shrinkage of an organic material. That is, the plurality of ejected fluid materials that are sequentially ejected onto the substrate form droplets on the substrate in an incompletely mixed state that is not completely mixed. When the droplets in which the plurality of discharge fluid materials are incompletely mixed are cured, fine irregularities are formed on the surface of the droplets of the discharge fluid material to be cured due to the difference in shrinkage rate in the curing process. Is done. Thereby, in addition to the convex shape of the large undulation formed by the droplets of the discharge fluid material, fine irregularities having small undulations are formed on the surface of the droplet.

Further, the three-dimensional modeling apparatus disclosed in Patent Document 5 discharges a solution supplied from a storage tank as droplets from a drop-on-demand ink jet head and then solidifies the discharged solution by drying a plurality of times. Using a three-dimensional modeling machine that repeatedly laminates and forms a three-dimensional modeled object, droplets discharged from the ink jet head are average speeds of 7 m / s or less and 4 m / s or more while passing a distance of 1 mm from the nozzle surface. By setting, the flying speed of the liquid droplets is suppressed, and when reaching the modeling stage, the quality of the molded product is improved by making it as close to a sphere as possible and reducing the collision energy.
Further, as a lens manufacturing method for forming a lens shape by discharging a resin solution as droplets using an ink jet head, there are those disclosed in Patent Documents 6 to 9, for example. In these lens moldings, a resin solution is landed at the same position, and the landed resin solutions are stacked to form a lens of a desired size.

However, the lens manufacturing methods disclosed in Patent Document 4 and Patent Documents 6 to 9 all have a problem that the degree of freedom in designing the shape is extremely low because the optical surface is formed by leveling the droplets. In other words, when forming a lens shape using leveling, although there is an advantage that a rough lens shape can be easily obtained for a small lens such as a microlens, it is as large as a general camera lens. It is difficult to apply the lens to a lens, a concave lens, and a highly accurate lens shape. Further, the radius of curvature of the surface is uniquely determined by the viscosity and surface tension of the resin solution and is likely to vary. This also makes it difficult to finish the desired shape. In other words, the above-described lens manufacturing method using leveling is effective for a lens that simply obtains a condensing function, such as an optical system that projects light, but requires a high resolving power in an imaging optical system. For such a lens, the surface accuracy for maintaining the necessary resolving power cannot be obtained.
Further, the three-dimensional modeling apparatus disclosed in Patent Document 5 uses a thermoplastic resin melt as droplets, but the resin has a high viscosity and a long molecule, and thus there is a problem that it is not suitable for droplet formation. .

  The present invention has been made in view of such conventional problems, and has as its first object to provide a method for producing a highly accurate optical member without the need for a mold, and a nanocomposite material. A method for producing an optical member that can be stably molded into a desired optical shape while removing the solvent in a short time by forming the resin solution containing the liquid into uniform droplets and an optical member formed by this production method This is the second purpose.

The above object of the present invention is achieved by the following configuration.
(1) Based on the shape data of the optical member, a method for producing an optical member for forming a thermoplastic optical solution by discharging a thermoplastic resin solution as droplets and solidifying the solution on a molded substrate,
With reference to the shape data, the transparent thermoplastic resin is obtained by repeating the process of discharging the droplets to different positions on the molded substrate until they reach a predetermined height and solidifying by drying a plurality of times. A method for producing an optical member, comprising: laminating on the molded substrate, and separating the optical member from the molded substrate after completion of the lamination.

  According to this method for producing an optical member, when a solution of a thermoplastic resin is discharged and solidified by drying to form an optical member, the thickness of many portions is controlled, and an uneven optical surface having a desired shape is formed. That is, an optical member having a desired shape is formed while the discharge thicknesses at a plurality of sites are determined. Thereby, even if the shape of the product is changed, it is not necessary to prepare a new mold, and a highly accurate optical member can be manufactured with a high degree of design freedom.

(2) In the method for manufacturing an optical member according to (1), the height at which the droplets land on the substrate and are stacked is measured, and the measured height corresponds to the shape data of the optical member. A method for producing an optical member, wherein the step of discharging the liquid droplets until the height is reached and solidifying by drying is repeated.

  According to this method of manufacturing an optical member, the height of the thermoplastic resin repeatedly landed and laminated on the substrate is sequentially detected, so that there is no error with respect to the shape data, that is, high-precision modeling. It becomes possible.

(3) A method for producing an optical member according to (1) or (2),
2. The liquid droplet ejection is performed such that each slice obtained by slicing the optical member in a direction parallel to the molding substrate is sequentially stacked on the molding substrate from the lowest layer. Or the manufacturing method of the optical member of Claim 2.

  According to this method of manufacturing an optical member, even if the shape is complicated, it is possible to easily form a model by laminating the respective slices sequentially.

(4) The method for manufacturing an optical member according to (2), wherein the height measurement is performed using a phase difference of laser light.

  According to this method of manufacturing an optical member, it is possible to detect the height of a soft thermoplastic resin that has not been completely solidified immediately after landing on a substrate in a non-contact manner with high accuracy, and optically associated with height measurement. There is no damage to the member.

(5) The method for producing an optical member according to any one of (1) to (4),
The method for producing an optical member, wherein the droplet is generated by an ink jet head that discharges the droplet from a nozzle.

  According to this method of manufacturing an optical member, it is possible to accurately and uniformly set the size of the liquid droplets by the ink jet head.

(6) The method for producing an optical member according to (5),
The ink jet head includes a nozzle, a pressurizing chamber communicating with the nozzle, and a pressurizing piezoelectric element disposed in the pressurizing chamber, and the pressurizing chamber is applied by applying a voltage to the piezoelectric element. A method of manufacturing an optical member that discharges the solution as droplets from the nozzle by pressing.

According to this method for manufacturing an optical member, a voltage is applied to the piezoelectric element in the pressurizing chamber to expand the piezoelectric element, and the pressurizing chamber is pressurized by this stretching operation, and the solution is dropped as a droplet from the nozzle. Can be discharged.

(7) The method for manufacturing an optical member according to (5), wherein the ink jet head includes a nozzle, a flow path communicating with the nozzle, and a heating unit disposed in a part of the flow path. A method for producing an optical member, wherein bubbles are generated in the flow path by supplying heat from the heating means, and the solution is discharged as droplets from the nozzle.

  According to this method for manufacturing an optical member, by supplying heat from the heating means to the flow path, bubbles are generated in the solution and the volume expands, whereby the solution can be discharged as droplets from the nozzle.

(8) The method for manufacturing an optical member according to any one of (1) to (7), wherein the droplet diameter of the solution is 0.005 mm or more and 0.1 mm or less. .

  According to this optical member manufacturing method, the droplet diameter is set within a certain range (0.005 mm or more and 0.1 mm or less), so that the solvent evaporates from the landed droplet and drying is accelerated. The discharged thermoplastic resin solution is formed into a desired optical shape stably in a short time. Moreover, the optical surface accuracy of the optical member to be shaped is also improved. If the diameter of the droplet is too large, drying takes time and the shape becomes rough. On the other hand, if the diameter is too small, it takes a long time to mold, and it dries before landing and does not weld. In particular, when the droplet is too small, it is difficult not only to finish the shape of the optical member, but also to control the landing position.

(9) The optical member manufacturing method according to any one of (1) to (8), wherein a rapid thermal annealing process is performed on the shaped optical member to level the surface of the optical member. Manufacturing method of member.

  According to this method of manufacturing an optical member, a rapid thermal annealing process is performed, whereby fine irregularities on the surface of the optical member are removed by instantaneous melting or semi-melting, and the optical member surface has an irregular optical surface with a desired shape. To be prepared smoothly.

(10) The method for manufacturing an optical member according to any one of (1) to (9), wherein the transparent thermoplastic resin is laminated on a spherical lens-shaped transparent body prepared in advance. Method.

  According to this method of manufacturing an optical member, compared to the case where a thermoplastic resin is laminated from the beginning on a molded substrate, the number of repeated steps of discharging droplets by the volume of the transparent body and solidifying by drying is reduced, and the discharge amount is small. Enables high-speed modeling.

(11) The method for producing an optical member according to (10),
A method for producing an optical member, comprising forming an aspheric surface layer with the thermoplastic resin solution on the spherical lens-shaped transparent body.

  According to this method of manufacturing an optical member, an aspheric lens can be formed at high speed only by forming an aspheric surface layer.

(12) The method for manufacturing an optical member according to any one of (1) to (11), wherein bottom surfaces of the two optical members each having a bottom surface formed in a planar shape are joined to each other. Manufacturing method of optical member to be formed.

According to this method of manufacturing an optical member, the process of discharging droplets onto a molded substrate and solidifying by drying is repeated, so that half of the optical surfaces have a flat bottom surface and a desired uneven optical surface. By forming the member and joining the bottom surfaces of the two halved optical members, it is possible to form an optical member in which both the front and back surfaces are the desired concavo-convex optical surfaces without using a mold.

(13) The optical member manufacturing method according to any one of (1) to (12), wherein the droplet is discharged in any one of a vacuum, a carbon dioxide atmosphere, and a nitrogen atmosphere. Manufacturing method of member.

  According to this method for manufacturing an optical member, air is not trapped and left in the thermoplastic resin by discharging the droplets in a vacuum. Further, by discharging the droplets in a carbon oxide atmosphere or a nitrogen atmosphere, the solubility of each gas in the thermoplastic resin solution is high, so that the gas does not remain trapped in the thermoplastic resin. Thereby, the product defect by generation | occurrence | production of a pinhole, a fine hollow part, a lamination | stacking boundary, etc. can be suppressed.

(14) The method for producing an optical member according to any one of (1) to (13), wherein the thermoplastic resin is a nanocomposite in which a transparent thermoplastic resin contains fine particles having a particle size of 20 nm or less. The manufacturing method of the optical member which is material.

  According to this method for producing an optical member, by uniformly dispersing inorganic fine particles such as metal oxide fine particles in a thermoplastic resin, an optical member having a high refractive index and excellent optical characteristics can be stably formed. It becomes possible.

(15) The method for producing an optical member according to any one of (1) to (14),
The manufacturing method of the optical member whose said optical member is a lens.

  According to this method of manufacturing an optical member, by repeating the steps of discharging droplets on a molded substrate and solidifying by drying, it becomes possible to form a lens whose surface has a desired concavo-convex optical surface, and an arbitrary shape The lens can be manufactured without making a mold, and the lens unit development period is shortened.

(16) The method for manufacturing an optical member according to (15), wherein a plurality of types of resin solutions having different fine particle contents are provided in a predetermined manner corresponding to at least one of a radial direction and a thickness direction of the lens. A method of manufacturing an optical member, which forms a refractive index distribution in at least one of a radial direction and a thickness direction of the lens by forming the lens by mixing at a ratio.

  According to this method for producing an optical member, a plurality of types of resin solutions are mixed (mixed on the discharge surface) in a predetermined ratio with respect to the radial direction, the thickness direction, or both directions of the lens. A lens having a refractive index distribution in one or both directions can be formed. Usually, when resins having different refractive indexes are mixed, an interface is formed because they are not completely mixed, and light is reflected at the interface, resulting in white turbidity. However, if the resin solution has a different content of fine particles, it can be adjusted to an arbitrary refractive index because it is uniformly mixed.

(17) The method for producing an optical member according to (15),
When the droplet of the resin solution discharged from the nozzle is landed on a predetermined position of the rotationally driven molded substrate, and the lens is formed on the molded substrate,
Detect the height information of the lens in the middle of modeling,
Obtaining the arrival time from the height position of the nozzle to the expected landing position of the droplet based on the height information,
Obtain the amount of deviation of the landing position from the expected landing position after the molded substrate has rotated the arrival time,
A method for manufacturing an optical member, wherein the ejection timing of droplets from the nozzle is corrected so as to cancel the deviation amount, and the landing position of the droplets is made coincident with the predetermined position.

  According to this method of manufacturing an optical member, when the expected landing position moves from when the droplet is ejected from the nozzle to when it is landed, the amount of movement is canceled as a deviation amount from the nozzle. The ejection timing of the droplet is corrected (accelerated). Thereby, the landing position of a droplet can be matched correctly and an optical member can be modeled with high precision.

(18) Based on the optical member shape data, a thermoplastic resin solution is ejected as droplets, solidified by drying, and an optical member manufacturing apparatus for modeling the optical member,
A molded substrate on which the optical member is formed;
A nozzle for discharging droplets of the thermoplastic resin;
An ejection head that is mounted with the nozzle and is movable facing the molding substrate;
With reference to the shape data, a controller that repeatedly discharges the liquid droplets to different positions on the molding substrate plane until they reach a predetermined height and solidifies by drying a plurality of times, and
An optical member manufacturing apparatus comprising:

  According to this optical member manufacturing apparatus, the thermoplastic resin solution is discharged onto the molded substrate while the discharge head is moved, and this discharge is repeated until it reaches a predetermined height at different positions on the plane of the molded substrate. It is possible to form a concavo-convex optical surface having a desired shape whose thickness is controlled in (1). This makes it possible to manufacture optical members that require frequent design changes, such as small-quantity products and prototypes, without using a mold.

(19) The optical member manufacturing apparatus according to (18),
The molded substrate is rotatably supported,
An apparatus for manufacturing an optical member, wherein a discharge point of the discharge head is movable along at least a straight line passing through a rotation center of the molded substrate.

  According to this optical member manufacturing apparatus, the discharge point passes through the center of rotation of the molded substrate, so that it is possible to discharge to all positions inside the circle, and the optical member having a point-symmetric shape can be easily obtained by moving in the radial direction. It becomes possible to form.

(20) The optical member manufacturing apparatus according to (18) or (19),
An apparatus for manufacturing an optical member, comprising: a relative movement unit that relatively moves the molded substrate and the ejection head in an arbitrary direction.

  According to this optical member manufacturing apparatus, an optical member other than an axially symmetric shape, for example, a molded substrate and a discharge head are repeatedly moved relative to each other in the X direction and sequentially moved in the Y direction. It becomes possible to form a cylindrical lens (cylindrical lens) having a cylindrical surface.

(21) The optical member manufacturing apparatus according to any one of (18) to (20),
A height measuring means for measuring the height at which the liquid droplets ejected from the nozzle landed and laminated on the molded substrate;
An apparatus for manufacturing an optical member, wherein the controller repeats a step of discharging the droplets and solidifying them by drying until the measured height reaches a height corresponding to the shape data of the optical member.

  According to this optical member manufacturing apparatus, the height of the thermoplastic resin that is landed and laminated on the molded substrate is sequentially measured until the height corresponding to the shape data is reached, and an error is detected with respect to the shape data. Highly accurate modeling is possible.

(22) An optical member formed by the method for manufacturing an optical member according to any one of (1) to (15).

  According to this optical member, the thickness of many parts is controlled during modeling, and the concave-convex optical surface is formed in a desired shape. As a result, it is possible to apply to small-quantity multi-product products and prototypes that require frequent design changes.

  According to the method for manufacturing an optical member according to the present invention, with reference to the shape data of the optical member, a step of discharging droplets to different positions on a plane until they reach a predetermined height, and solidifying by drying By repeating the process, a transparent thermoplastic resin is laminated on the substrate for modeling, so the modeling of optical members can be controlled with the thickness of many parts, and it is necessary to prepare a new mold even if the shape of the product is changed Therefore, it is possible to eliminate the time and cost spent on the production of the mold, and to manufacture a small amount of various types of optical members with high accuracy and at low cost.

  According to the optical member manufacturing apparatus of the present invention, a molded substrate on which the optical member is formed, a nozzle that ejects droplets of a thermoplastic resin solution, an ejection head that is movable facing the molded substrate, and a molding A controller that repeats the process of discharging droplets to different positions on the substrate plane until they reach a predetermined height and solidifying them by drying is provided. An optical member shaped with high accuracy at a height of 5 mm can be manufactured, and optical members that require frequent design changes, such as a small amount of products and prototypes, can be manufactured quickly, accurately, and inexpensively.

  According to the optical member of the present invention, since it is formed by the above-described optical member manufacturing method, a mold is not required for modeling, and the time and cost spent for manufacturing the mold are reduced, and the optical member is shortened. Manufacturing at a low cost is possible.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, a preferred embodiment of an optical member manufacturing method according to the invention and an optical member formed by the manufacturing method will be described with reference to the drawings.
FIG. 1 is a schematic configuration diagram showing an optical member manufacturing apparatus according to the present invention, FIG. 2 is a plan view of a molded substrate, and FIG. 3 shows droplet discharge conditions from nozzles (a), (b), (c It is sectional drawing of the discharge head represented by).
The optical member manufacturing apparatus 100 according to the present embodiment discharges a thermoplastic resin solution as droplets based on the shape data of the optical member, solidifies it by drying, and forms the optical member. In this embodiment, the case where the optical member is the convex lens 11 will be described as an example. However, the lens shape can be changed as appropriate.

  The manufacturing apparatus 100 includes a molding substrate 13 on which a convex lens 11 is formed, a nozzle 15 that ejects droplets of a thermoplastic resin solution, and an ejection head that is mounted with the nozzle 15 and is movable facing the molding substrate 13. 17 and the shape data of the convex lens 11 are referred to in the storage unit 19, and the process of ejecting liquid droplets to different positions on the plane of the molding substrate until reaching a predetermined height and solidifying by drying is repeated a plurality of times. A control unit 21 is provided as a basic configuration.

  The molded substrate 13 is supported by an elevating mechanism 25 so as to be movable up and down in a direction approaching and separating from the ejection head 17. A rotation driving means 27 incorporating an electric motor is fixed to the upper part of the elevating mechanism 25, and the rotation driving means 27 rotates the molded substrate 13 fixed to the driving shaft 27a. The discharge head 17 is supported so as to be reciprocally movable by a linear moving means 29 including a linear motor or a ball screw mechanism.

  As shown in FIG. 2, the ejection head 17 is moved by a linear moving means 29 along a straight line 33 along the radial direction from the rotation center 31 of the molded substrate 13. Thereby, the convex lens 11 having a desired radius r can be formed. As described above, the discharge point 35 of the nozzle 15 passes through the rotation center 31 of the molded substrate 13, so that it is possible to discharge to all positions inside the circle, and the point-symmetrical convex lens 11 can be easily obtained by moving in the radial direction. Can be shaped. The discharge head 17 is an ink jet head that discharges droplets from the nozzle 15.

  Further, adjacent to the ejection head 17 is provided a height measuring means 37 for measuring the height at which the droplets ejected from the nozzle 15 land on the molded substrate 13 and are stacked. The height measuring means 37 is mounted on a sensor head 18 that is movable so as to face the molding substrate 13, and is attached with the measurement direction inclined toward the droplet landing position 11 </ b> A by the discharge head 17. Similar to the ejection head 17, the sensor head 18 is supported by a linear moving means 30 including a linear motor or a ball screw mechanism so as to be reciprocally movable. As shown in FIG. 2, the sensor head 18 is moved by the linear moving means 30 along a straight line 33 along the radial direction from the rotation center 31 of the molded substrate 13. In some cases, after the droplets have landed, they may be moved in the direction opposite to the straight line 33 so that the height is measured at a position 36 where the molded substrate 13 is half-rotated.

As the height measuring means 37, a non-contact type one such as one using a phase difference of laser light can be preferably used. By using the height measuring means 37 by laser light, it is possible to detect the height of the soft thermoplastic resin that has not completely solidified immediately after landing on the molded substrate 13 in a non-contact and real-time manner. Thus, the convex lens 11 is not damaged due to the height measurement.
In FIG. 2, the ejection head 17 and the height measuring means 37 are supported separately. However, the present invention is not limited to this, and the ejection head 17 and the height measuring means 37 may be moved together. . Further, the moving direction of the ejection head 17 and the sensor head 18 is not limited to the illustrated example, and can be arbitrarily set as long as it is in the radial direction.

  The control unit 21 repeats the process of discharging droplets and solidifying them by drying until the height measured by the height measuring unit 37 reaches the height corresponding to the shape data of the convex lens 11. In this way, the height of the thermoplastic resin that is landed and laminated on the molded substrate 13 is repeated until it reaches a height corresponding to the shape data while being measured in sequence, so that there is no error with respect to the shape data. Modeling becomes possible.

  As shown in FIG. 3, the droplet includes a nozzle 15 that discharges the droplet, a pressurizing chamber 39 that communicates with the nozzle 15, and a piezoelectric element 41 that is disposed corresponding to the pressurizing chamber 39. The discharge head 17 discharges from the nozzle 15 by utilizing the bending caused by applying a voltage to the piezoelectric element 41. The thermoplastic resin solution is supplied from the tank 43 through the supply tube 45 to the pre-pressurization chamber 47 of the discharge head 17. An inner wall of the pressurizing chamber 39 facing the nozzle 15 is formed by a diaphragm 49, and the diaphragm 49 is fixed to the piezoelectric element 41. Therefore, the diaphragm 49 bends due to the displacement caused by applying a voltage to the piezoelectric element 41, and the internal volume of the pressurizing chamber 39 is varied, whereby the droplet 51 is ejected from the nozzle 15.

  As a result, minute droplets 51 are stably ejected from the nozzle 15 through a sealed channel communicating with the pressurizing chamber 39 in a state advantageous for drying. Further, the droplet 51 is not dried at the time of landing on the molded substrate 13, but is dried after landing. That is, the first layer is landed on the molded substrate and then dried, but the second and subsequent layers are dried after the interface with the lower layer disappears and disappears. Since the droplet is small, it solidifies immediately after landing and the height H can be measured.

Here, the droplet 51 of the solution preferably has a diameter of 0.005 mm or more and 0.1 mm or less. By setting the diameter of the droplet 51 within a certain range (0.005 mm or more and 0.1 mm or less), the solvent is evaporated from the landed droplet 51 and drying is accelerated, and the discharged thermoplastic resin solution Is formed into a desired optical shape stably in a short time. Moreover, the optical surface accuracy of the optical member to be shaped is also improved. If the diameter of the droplet is too large, drying takes time and the shape becomes rough. On the other hand, if the diameter is too small, it takes a long time to mold, and it dries before landing and does not weld. In particular, when the droplet is too small, it is difficult not only to finish the shape of the optical member, but also to control the landing position.

   Further, it is preferable that the droplets 51 be discharged in any one of a vacuum, a carbon dioxide atmosphere, and a nitrogen atmosphere. That is, when modeling from the droplet 51 to the convex lens 11, the air remaining between the droplets 51 is confined in the material, and the occurrence of defects such as optical distortion can be prevented. When discharging droplets in a vacuum, it is possible to reliably prevent air from being trapped in the thermoplastic resin. When discharging droplets in a carbon dioxide atmosphere or a nitrogen atmosphere, the heat of each gas Since the solubility in the plastic resin solution is high, the gas is not trapped in the thermoplastic resin and does not remain. As a result, it is possible to eliminate product defects due to the occurrence of pinholes, fine hollow portions, lamination boundaries, and the like.

  In the above example, a piezo-type ink jet head using a piezoelectric element is used, but in addition to this configuration, for example, a nozzle, a flow path communicating with the nozzle, and heating disposed in a part of the flow path And a so-called thermal ink jet head in which bubbles are generated in the flow path by supplying heat from the heating means, and a solution of the thermoplastic resin is discharged from the nozzle as droplets.

  Thus, in the manufacturing apparatus 100 described above, the thermoplastic resin solution is discharged onto the molded substrate 13 while the discharge head 17 is moved, and this discharge is repeated at different positions on the plane of the molded substrate until a predetermined height is reached. In addition, the convex lens 11 can be formed with a concave-convex optical surface having a desired shape whose thickness is controlled at a number of sites. In addition, a non-contact dispenser type may be used instead of the inkjet method.

  Therefore, according to this optical member manufacturing apparatus, the molding substrate 13 on which the convex lens 11 is formed, the nozzle 15 that ejects droplets of the thermoplastic resin solution, and the ejection head 17 that is movable facing the molding substrate 13. And a control unit 21 that repeats a process of discharging droplets 51 to different positions on the molding substrate plane until they reach a predetermined height and solidifying them by drying, without using a mold. It is possible to manufacture a convex lens 11 that is shaped with high accuracy at a predetermined height at different positions, and to manufacture a convex lens 11 that requires frequent design changes, such as a small amount of products and prototypes, quickly, with high accuracy, and at low cost. it can.

Next, the manufacturing method of an optical member is demonstrated.
FIG. 4 is a flowchart explaining the procedure of the manufacturing method according to the present invention, FIG. 5 is an explanatory diagram showing discharge areas according to stacking heights obtained on the basis of shape data, and FIG. 6 shows a molding process of an optical member (a). It is a manufacturing-process figure represented by-(e).
In order to manufacture the convex lens 11 as an optical member using the manufacturing apparatus 100, first, the control unit 21 takes in the shape data of the convex lens 11 from the storage unit 19 (s1), and is a model designed by three-dimensional CAD or the like. As shown in FIG. 5, as a discharge map 23 of each layer h ₁ , h ₂ ,... H _n−1 , h _n obtained by slicing it into a plurality of thin sections in a direction parallel to the molded substrate. Output (s2). The control unit 21 sets the target height from the discharge map 23 from the molded substrate 13 (s3).

Next, the controller 21 drives the linear moving means 29, sets the nozzle position of the ejection head 17 to the rotation center 31 (s4), and drives the rotation driving means 27 to rotate the molded substrate 13 (s5). The controller 21 discharges the droplet 51 while driving and controlling the linear moving means 29 so that the radius r gradually increases (s6). At this time, the controller 21 keeps the density of the landing points constant by decreasing the rotation speed of the molded substrate 13 or increasing the interval of the ejection timing from the ejection head 17 as the radius r increases. As for the gradual increase of the radius r, the method of increasing the radius r little by little in a spiral manner can make the ejection head 17 operate smoothly, perform continuous lamination processing, and prevent the occurrence of shape disorder. Alternatively, the radius r may be increased stepwise after making a round with the same radius. In that case, since the radius r is accurately positioned, it is easy to improve the modeling accuracy.
Then, at the same time as droplets are ejected from the ejection head 17 as described above, the landing height is measured by the height measuring means 37 attached to the sensor head 18 (s7). The sensor head 18 is moved in the same direction as the ejection head 17 in synchronization with the movement of the ejection head 17 in the radial direction. That is, both heads are operated in cooperation so that the landing position of the droplet by the ejection head 17 and the height measurement position of the height measuring means 37 coincide.

  The control unit 21 refers to the shape data and determines whether or not each layer has reached a predetermined height at different positions on the molded substrate 13 (s8) until the predetermined height is reached. The process of discharging the droplet 51 and solidifying it by drying is repeated a plurality of times. That is, the height at which the droplet 51 landed on the molded substrate 13 is measured, and the droplet 51 is discharged and dried until the measured height reaches a height corresponding to the shape data of the convex lens 11. The solidification process is repeated. As described above, the height of the thermoplastic resin that is repeatedly landed and laminated on the repetitively molded substrate 13 is sequentially detected, so that formation without error with respect to the shape data, that is, high-precision modeling is possible. By such an operation, the cross-sectional bodies, that is, the layer bodies are sequentially stacked at an accurate height for each layer.

If it is confirmed by the height measurement that the layer being formed has reached the predetermined height, the target height is set from the discharge map 23 of the next layer (s10). These steps are repeated until the final layer (uppermost layer) is detected (s9), and as shown in FIGS. 6A to 6D, the convex laminates 11a, 11b, and 11c are sequentially laminated. And then modeling. After the final layer stacking process is completed, the rotation driving means 27 is stopped (s11), the ejection head 17 is retracted (s12), and the convex lens 11 is taken out from the molded substrate 13 as shown in FIG. 6 (e). To complete the lens manufacturing.
In addition, in order to completely remove the solvent remaining on the convex lens 11, a drying process may be further performed. In this case, it is desirable to vacuum dry below the glass transition point of the thermoplastic resin. At this time, since the amount of residual solvent is small, the shape change is negligible.

  In this method of manufacturing the convex lens 11, when the convex lens 11 is formed by discharging a thermoplastic resin solution and solidifying by drying, the thickness of many portions is controlled, and a concave / convex optical surface having a desired shape is formed. That is, the convex lens 11 having a desired shape is formed while the discharge thicknesses at a plurality of sites are determined. Thus, an accurate shape can be generated without causing an error due to a volume change when the thermoplastic resin solution is solidified. Further, even if the shape of the product is changed, it is not necessary to prepare a new mold, and the convex lens 11 with high design freedom and high accuracy can be manufactured.

  The thermoplastic resin used in the above description is a nanocomposite material in which fine particles having a particle size of 20 nm or less are contained in a transparent thermoplastic resin. The nanocomposite material is a material in which inorganic fine particles such as metal oxide fine particles are uniformly dispersed in a thermoplastic resin, and an optical member having a high refractive index and excellent optical characteristics can be stably formed. Details thereof will be described later.

  Therefore, according to this method of manufacturing an optical member, the process of discharging the droplets 51 to different positions on the plane with reference to the shape data of the convex lens 11 until reaching respective predetermined heights and solidifying by drying. By repeating the above, a transparent thermoplastic resin is laminated on the molded substrate 13 for modeling, so that the convex lens 11 can be modeled with a large number of thicknesses, and a new mold is prepared even if the shape of the product is changed This eliminates the need for the time and expense required to manufacture the mold, and makes it possible to manufacture a small amount of various types of convex lenses 11 with high accuracy and at low cost. Then, by repeating the steps of discharging the droplets 51 onto the molded substrate 13 and solidifying by drying, it becomes possible to form the convex lens 11 whose surface is a desired concavo-convex optical surface, and the convex lens 11 having an arbitrary shape is a mold. It can be easily manufactured without fabrication, and the degree of freedom in lens design is improved.

  Further, according to the convex lens 11 manufactured by this manufacturing method, the time and cost spent on the production of the mold can be reduced, and a lens of high-mix low-volume production can be provided in a short time and at a low cost. Is possible.

  Further, a plurality of types of resin solutions having different refractive indexes due to differences in the content of inorganic fine particles are mixed at a predetermined ratio corresponding to at least one of the radial direction and the thickness direction of the lens, and the lens It can also be formed. In that case, a refractive index distribution can be given to at least one of the radial direction and the thickness direction of the lens, and various optical members can be freely produced.

Here, a method for manufacturing a lens by selectively switching a plurality of resin solutions having different refractive indexes as described above will be described.
FIG. 7 shows a configuration example (a) of a discharge head that discharges a plurality of types of resin solutions, and a lens (b) having a refractive index distribution.
As shown in FIG. 7A, the discharge head 17A is connected to tanks 43A and 43B for storing resin solutions A and B having different refractive indexes via supply tubes 45, and discharge timing and The discharge amount and the like are controlled for each head. The other configuration is the same as the configuration shown in FIG.

The nozzles 15A and 15B mounted on the discharge head 17A include, for example, a lens 11 having a refractive index distribution using a resin solution A having a refractive index of 1.4 and a resin solution B having a refractive index of 1.6. Model. As shown in FIG. 7B, the lens 11 is formed by discharging only the resin solution A at the lens central portion 11a and discharging only the resin solution B at the lens outer peripheral portion 11b. Further, in the region 11c between the lens center portion 11a and the lens outer peripheral portion 11b, the resin solutions A and B are formed, for example, by changing the mixing ratio of the resin solutions A: B as a function of the diameter r. Such a control function such as a function of the diameter r may be a function of the lens thickness, and can be freely set according to the contents of the optical design, and an arbitrary refractive index distribution can be freely formed.
As described above, by selectively discharging different types of resin solutions from the nozzles 15A and 15B of the discharge head 17A, the degree of freedom in lens design can be further improved. The nozzles 15A and 15B may be integrally mounted and movable as in the illustrated example. However, the nozzles 15A and 15B are not limited to this and may be configured to be movable separately.

  Here, when the droplet of the resin solution discharged from the nozzle is landed on a predetermined position of the rotationally driven molded substrate and the optical member is formed on the molded substrate, the droplet is ejected after being ejected. During this period, the molding substrate is driven to rotate, and the landing position of the droplet changes. Therefore, it is preferable to perform ejection while correcting the deviation of the landing position.

In order to correct the displacement of the landing position, first, the height information of the lens in the middle of modeling is detected, and based on this height information, the height position information where the nozzle is arranged and the preset liquid The arrival time from the droplet discharge speed to the planned landing position of the droplet on the molded substrate 13 is determined. Then, the arrival time and the deviation amount of the landing position from the planned landing position after the molded substrate 13 rotates are obtained. Correction is made so that the discharge timing of the droplet from the nozzle 15 is advanced so that the deviation amount is canceled, and the landing position of the droplet is made to coincide with a predetermined position as designed. Thereby, the landing position of a droplet can be matched correctly and an optical member can be modeled with high precision.
As for the amount of deviation of the landing position, in addition to the correction of the positional deviation due to the rotation of the forming substrate 13, a deviation corresponding to the centrifugal force received after the droplets land due to the centrifugal force generated by the rotating operation (radiation direction from the rotation center) May be corrected.

Next, an example in which an optical member is formed by bonding two convex lenses 11 will be described.
FIG. 8 is a manufacturing process diagram of an optical member obtained by bonding halved optical members together.
The convex lens 11 is used as an optical member by itself, but in order to further increase the degree of freedom in optical design, the bottom surfaces 53 and 53 of the two optical members 11 having the bottom surface 53 formed in a planar shape are joined to each other. It can be formed on the member 11A. The bottom surfaces 53 and 53 can be welded together by the adhesive layer 55 made of the same material, for example, by using the above-described thermoplastic resin solution. In this way, the process of discharging the droplets 51 onto the molded substrate 13 and solidifying by drying is repeated, so that the half-convex convex lens 11 whose bottom surface 53 is flat and whose surface is a desired uneven optical surface is formed. In this case, the bottom surfaces 53 and 53 of the two half-convex lenses 11 are joined to each other, so that an optical member 11A in which both the front and back surfaces become desired concave and convex optical surfaces can be easily formed without using a mold. It becomes. In addition to the thermoplastic resin, other transparent adhesives having the same refractive index as the convex lens 11 or an approximate range can be used as the adhesive layer 55. Furthermore, the adhesive layer 55 may be bonded to the half-convex lenses 11 by applying heat to melt the surfaces, or by ultrasonic welding. Note that the half-convex lens 11 to be joined may be lenses made of different materials in order to obtain a desired optical performance.

Next, a method for smoothing the surface of each lens will be described.
FIG. 9 is a cross-sectional view showing an example of irradiation means for performing a rapid thermal annealing process, and FIG. 10 is an explanatory view of the surface of an optical member to be smoothed by removing minute irregularities by the rapid thermal annealing process.
In the manufacturing method of the optical member described above, it is preferable to perform a rapid thermal annealing process on the shaped convex lens 11 and level the surface of the convex lens 11. A heat treatment apparatus 61 that performs a rapid thermal annealing process includes a plurality of lamps 63 and a reflecting member 65 housed in a casing 67, and the flash irradiation light reflected and collected and the flash irradiation light forward are collected by a condensing lens 69 or light. Guided through a shaper.

  Specifically, when irradiating with a belt-like flash light, a concave condensing reflecting member 65 cooled with a circulating refrigerant (pure water or the like) is disposed behind the plurality of flash lamps 63, and the reflected and condensed flash. The irradiation light and the front flash irradiation light are further squeezed by the condenser lens 69 to obtain a belt-like flash irradiation light with improved illuminance. In addition, when large area batch irradiation is performed with a square or rectangular flash irradiation light, a reflecting member cooled with a circulating refrigerant (such as pure water) is arranged behind the plurality of flash lamps, and the reflected flash irradiation light and The front flash irradiation light is shaped by a light shaper (such as a beam homogenizer) to improve illuminance uniformity. At this time, the light may be projected in a predetermined direction via the heat ray reducing filter 70 or the heat ray blocking filter as necessary.

  By performing this rapid thermal annealing treatment, the fine unevenness on the surface of the convex lens 11 shown in FIG. 10 is removed by instantaneous melting or semi-melting, and the surface of the convex lens 11 is made smooth according to the uneven optical surface of the desired shape. It is adjusted (smoothed).

The surface smoothing of this optical member can also be performed by hot pressing.
FIG. 11 is a manufacturing process diagram of additional adjustment by hot pressing of the surface of the optical member that has been shaped.
In this optical member manufacturing method, the final lens shape can be adjusted by heating and pressing the optical front and back surfaces of the shaped convex lens 11 with the pressing dies 71 and 73. Adjusting surfaces 71 a and 73 a corresponding to the optical front and back surfaces of the convex lens 11 are formed on the opposing surfaces of the pressing dies 71 and 73. The pressing dies 71 and 73 are positioned by the guide jigs 75a and 75b so that the convex lens 11 can be pressed while being heated from the front and back.

Next, an example in which an optical member is formed using a transparent body (glass body) prepared in advance will be described.
FIG. 12 shows a cross-sectional view of an optical member formed by raising a glass body.
In the manufacturing method of the optical member described above, a transparent thermoplastic resin 83 is laminated on a spherical lens-shaped glass body 81 prepared in advance to form the convex lens 11B.
According to such a manufacturing method using the glass body 81, compared to the case where the thermoplastic resin 83 is laminated on the molded substrate 13 from the beginning, the droplet 51 is ejected by the volume of the glass body 81 and solidified by drying. This reduces the number of repetitive steps to be performed, and enables high-speed modeling with a small discharge amount. Thereby, the processing time for lens molding is shortened. Then, by forming the aspheric surface layer with the thermoplastic resin solution on the spherical lens-shaped glass body 81, the aspheric lens can be formed at high speed only by forming the aspheric surface layer. If the refractive index is the same, the glass body 81 and the thermoplastic resin can obtain the same refractive performance as a normal aspheric lens, and if they are different from each other, they exhibit different optical performance depending on the combination of refractive indexes. it can.

Next, another embodiment of the optical member manufacturing apparatus will be described.
The principal part block diagram of the manufacturing apparatus of the optical member provided with the relative displacement means was shown in FIG.
This manufacturing apparatus is provided with relative movement means 91 for relatively moving the molding substrate 13 and the discharge head 17 in an arbitrary direction. The relative moving unit 91 is configured, for example, by supporting a linear moving unit 29 that supports the ejection head 17 so as to be movable in the X direction, and further supports the linear moving unit 93 so as to be movable in the Y direction.
If the discharge head 17 is movably supported by the relative moving means 91, optical members other than the axially symmetric shape, for example, the molded substrate 13 and the discharge head 17 are repeatedly moved relative to each other in the X direction, and sequentially in the Y direction. By being moved, it becomes possible to form a cylindrical lens (cylindrical lens) 11C having a cylindrical surface whose X direction is the axial direction.

Further, an energy curable resin can be used as the lens material. An optical member manufacturing apparatus in that case will be described.
FIG. 14 shows a manufacturing process diagram of an ejection head provided with a UV lamp.
In this manufacturing apparatus, a UV lamp 101 serving as an energy irradiation unit is provided in the ejection head 17A. The UV lamp 101 is moved together in the X direction by the reciprocating movement of the discharge head 17. The energy curable resin 84 ejected from the nozzle 15 and landed on the molded substrate 13 is immediately solidified by the energy irradiation of the UV lamp 101 passing therethrough, and formed on the convex lens 11D.

  As an energy source, a mercury lamp, a gas / solid laser, or the like can be used. When using an ultraviolet light curable resin, a mercury lamp or a metal halide lamp can be used. A GaN-based semiconductor ultraviolet light emitting device that is also environmentally useful may be used. Furthermore, LED (UV-LED) and LD (UV-LD) are small in size, have a long life, have high efficiency, and are low in cost, and can be suitably used as a radiation source for energy curable resins.

  According to the manufacturing apparatus provided with such an energy irradiation means (UV lamp 101 or the like) in the ejection head 17A, the energy irradiation means moves together with the reciprocating movement of the ejection head 17A, and is ejected from each nozzle 15 to be molded substrate 13. Since energy is irradiated to the energy curable resin 84 that lands on the top, solidification of the energy curable resin 84 can be promoted, and rapid modeling of the convex lens 11D can be achieved.

Next, an example will be described in which an optical member having a bottom surface with a specified lens shape is additionally processed on the surface in order to obtain desired lens performance.
FIG. 15 shows a manufacturing process diagram of a lens for an optical member in which only the bottom surface is molded by a mold.
In this manufacturing apparatus, a fixed molding surface 111 is formed on the substrate surface of the molding substrate 13A, and the bottom surface of the convex lens 11E is formed by this molding surface. Then, the surface of the convex lens 11E is processed into an arbitrary lens shape by the same method as described above.
In the molding substrate 13A provided with such a molding surface 111, the surface facing the molding substrate 13A of the convex lens 11E can be formed on the fixed optical member surface 113, so that the two half-convex lenses 11, 11 are not bonded together. It is possible to easily obtain a convex lens 11E having a high refractive index in which both front and back surfaces are formed as convex curved surfaces.

  In addition, this invention is not limited to each embodiment mentioned above, A deformation | transformation, improvement, etc. are possible suitably. For example, the lens is not limited to a convex lens but may be a concave lens or a gull-type lens having a plurality of inflection points.

Next, a nanocomposite material (a material in which inorganic fine particles are contained in a thermoplastic resin) used in the method for producing an optical member of the present invention will be described in detail below.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Compound represented by general formula (1)]
The nanocomposite material of the present invention contains a compound represented by the following general formula (1) together with inorganic fine particles.

  In general formula (1), R1 and R2 each independently represent a substituent. The substituent that R1 and R2 can adopt is not particularly limited, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (for example, a methyl group, an ethyl group), and an aryl group (for example, Phenyl group, naphthyl group), alkenyl group, alkynyl group, cyano group, carboxyl group, alkoxycarbonyl group (eg methoxycarbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl group), substituted or unsubstituted carbamoyl group (eg carbamoyl) Group, N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group), alkylcarbonyl group (eg acetyl group), arylcarbonyl group (eg benzoyl group), nitro group, acylamino group (eg acetamido group, ethoxycarbonylamino group) , Sul Amide group (eg methanesulfonamide group), imide group (eg succinimide group, phthalimide group), imino group (eg benzylideneamino group), alkoxy group (eg methoxy group), aryloxy group (eg phenoxy group), acyloxy group ( For example, acetoxy group, benzoyloxy group), alkylsulfonyloxy group (for example, methanesulfonyloxy group), arylsulfonyloxy group (for example, benzenesulfonyloxy group), sulfo group, substituted or unsubstituted sulfamoyl group (for example, sulfamoyl group, N -Phenylsulfamoyl group), alkylthio group (eg methylthio group), arylthio group (eg phenylthio group) alkylsulfonyl group (eg methanesulfonyl group), arylsulfonyl group (eg benzenesulfo group) Le group), a formyl group, and the like heterocyclic compounds. These substituents may be further substituted. When there are a plurality of substituents in the molecule represented by the general formula (1), each substituent may be the same or different. The substituent may form a condensed ring structure with the benzene ring. As the substituent for R1 and R2, a halogen atom, alkyl group, aryl group, cyano group, alkoxycarbonyl group, aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, alkylcarbonyl group, arylcarbonyl group, sulfonamide group are preferable. , Alkoxy group, aryloxy group, acyloxy group, substituted or unsubstituted sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, more preferably halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, aryl A sulfonyl group, particularly preferably a halogen atom, an alkyl group, an aryl group, or an aryloxy group.

  m1 and m2 each independently represents an integer of 0 to 5. m1 and m2 are preferably 0-3, more preferably 0-2, and even more preferably 0-1. When m1 and m2 are integers of 2 or more, the substituents on the same benzene ring may be the same or different.

  a represents 0 or 1; When a is 0, it means that the benzene rings are single-bonded. When a is 1, the benzene rings are connected by L. L represents an oxy group or a methylene group. As described above, the benzene rings of the compound represented by the general formula (1) are bonded to each other by a single bond, an oxy group or a methylene group, but a single bond or an oxy group is preferable.

  The molecular weight of the compound represented by the general formula (1) is preferably less than 2000, more preferably less than 1000, and still more preferably less than 700.

  Although the specific example of a compound represented by General formula (1) below is shown, the compound of General formula (1) which can be used by this invention is not limited to these.

  The compound represented by the general formula (1) may be synthesized according to a method well known to those skilled in the art or may be obtained from the market. For example, S-3101, S-3103, S-3105, S-3230 manufactured by Muramatsu Oil Research Co., Ltd. can be used.

  The amount of the compound represented by the general formula (1) added to the organic-inorganic composite composition is preferably 0.1 to 30% by mass, more preferably 0.3 to 25% by mass, and further preferably It is 0.5-20 mass%. If the addition amount is 30% by mass or less, there is a tendency to prevent crying during molding or storage, and if the addition amount is 0.1% by mass or more, the effect of adding tends to be easily obtained. is there. In addition, crying out here means the phenomenon in which the added compound oozes out on the surface of a molded object.

[Inorganic fine particles]
The nanocomposite material of the present invention contains inorganic fine particles together with the compound represented by the general formula (1). The inorganic fine particles used in the present invention are not particularly limited, and for example, fine particles described in JP-A Nos. 2002-241612, 2005-298717, 2006-70069 and the like can be used.

Specifically, fine oxide particles (aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, zinc oxide, magnesium oxide, tellurium oxide, yttrium oxide, indium oxide, tin oxide, etc.), double oxide fine particles (lithium niobate, Potassium niobate, lithium tantalate, etc.), sulfide fine particles (zinc sulfide, cadmium sulfide, etc.), other semiconductor crystal fine particles (zinc selenide, cadmium selenide, zinc telluride, cadmium telluride, etc.), or LiAlSiO ₄ , PbTiO ₃ , Sc ₂ W ₃ O ₁₂ , ZrW ₂ O ₈ , AlPO ₄ , Nb ₂ O ₅ , LiNO _{3 and the} like can be used.

  Among these, metal oxide fine particles are particularly preferable, and among these, any one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide, and titanium oxide is preferable, and includes zirconium oxide, zinc oxide, and titanium oxide. More preferably, it is any one selected from the group, and it is particularly preferable to use zirconium oxide fine particles having good visible range transparency and low photocatalytic activity.

  The inorganic fine particles used in the present invention may be a composite of a plurality of components from the viewpoints of refractive index, transparency, stability, and the like. In addition, for various purposes such as reducing photocatalytic activity and water absorption, the inorganic fine particles are doped with different elements, the surface layer is coated with different metal oxides such as silica and alumina, silane coupling agents, titanate cups. The surface may be modified with a ring agent, an aluminate coupling agent, an organic acid (such as a carboxylic acid, a sulfonic acid, a phosphoric acid, or a phosphonic acid). Furthermore, these two or more types may be used in combination depending on the purpose.

  The refractive index of the inorganic fine particles used in the present invention is not particularly limited. However, when the nanocomposite material is used for an optical member that requires a high refractive index as in the present invention, the inorganic fine particles have the above-described thermal temperature dependency. In addition, it is preferable to have a high refractive index characteristic. In this case, the refractive index of the inorganic fine particles used is preferably 1.9 to 3.0 at 22 ° C. and a wavelength of 589 nm, more preferably 2.0 to 2.7, and particularly preferably 2.1. ~ 2.5. If the refractive index of the fine particles is 3.0 or less, the difference in refractive index from the resin is relatively small, so that Rayleigh scattering tends to be easily suppressed. If the refractive index is 1.9 or more, the effect of increasing the refractive index tends to be easily obtained.

  The refractive index of the inorganic fine particles is obtained by, for example, molding a composite compounded with the thermoplastic resin used in the present invention into a transparent film, and measuring the refractive index with an Abbe refractometer (for example, “DM-M4” manufactured by Atago Co., Ltd.). It can be estimated by a method of calculating from the refractive index of only the resin component separately measured or a method of calculating the refractive index of the fine particles by measuring the refractive index of the fine particle dispersion having different concentrations.

  If the number average particle size of the inorganic fine particles used in the present invention is too small, the characteristics specific to the substance constituting the fine particles may change. Conversely, if the number average particle size is too large, the influence of Rayleigh scattering is significant. Thus, the transparency of the organic-inorganic composite composition may be extremely reduced. Therefore, the lower limit of the number average particle size of the inorganic fine particles used in the present invention is preferably 1 nm or more, more preferably 2 nm or more, further preferably 3 nm or more, and the upper limit is preferably 15 nm or less, more preferably 10 nm. Hereinafter, it is more preferably 7 nm or less. That is, the number average particle size of the inorganic fine particles in the present invention is preferably 1 nm to 15 nm, more preferably 2 nm to 10 nm, and particularly preferably 3 nm to 7 nm.

The inorganic fine particles used in the present invention desirably satisfy the above average particle size and have a narrow particle size distribution. There are various ways of defining such monodisperse particles. For example, the numerical value ranges described in JP-A-2006-160992 also apply to the preferable particle size distribution range of the fine particles used in the present invention. .
Here, the above-mentioned number average particle size can be measured by, for example, an X-ray diffraction (XRD) apparatus or a transmission electron microscope (TEM).

The method for producing inorganic fine particles used in the present invention is not particularly limited, and any known method can be used.
For example, desired oxide fine particles can be obtained by using a metal halide or an alkoxy metal as a raw material and hydrolyzing in a reaction system containing water. Details of this method are described in, for example, Japanese Journal of Applied Physics, 37, 4603-4608 (1998), or Langmuir, 16: 1, 241-246 (2000). ing.

Further, as a method other than the method of hydrolyzing in water, a method of preparing inorganic fine particles in an organic solvent or an organic solvent in which the thermoplastic resin in the present invention is dissolved may be employed. In this case, various surface treatment agents (silane coupling agents, aluminate coupling agents, titanate coupling agents, organic acids (carboxylic acids, sulfones, phosphonic acids, etc.)) may be allowed to coexist as necessary. Good.
Examples of the solvent used in these methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. These may be used alone or as a mixture of two or more.

  As a method for synthesizing inorganic fine particles, in addition to the above, various general fine particle synthesizing methods described in, for example, JP-A-2006-70069 and the like, such as a method of producing by a vacuum process such as a molecular beam epitaxy method or a CVD method. Can be mentioned.

  The content of the inorganic fine particles in the nanocomposite material of the present invention is preferably 20 to 95% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass from the viewpoint of transparency and high refractive index. . In addition, the mass ratio of the inorganic fine particles and the thermoplastic resin (dispersed polymer) in the present invention is preferably 1: 0.01 to 1: 100, more preferably 1: 0.05 to 1:10, from the viewpoint of dispersibility. A ratio of 1: 0.05 to 1: 5 is particularly preferable.

[Thermoplastic resin]
The nanocomposite material of the present invention contains a thermoplastic resin. In particular, the nanocomposite material of the present invention preferably contains a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at least at the terminal or side chain of the polymer chain. The chemical bond here is defined to include a covalent bond, an ionic bond, a hydrogen bond, and a coordination bond. Preferred examples of such thermoplastic resins include the following three types of thermoplastic resins.
(1) Thermoplastic resin having a functional group selected from the following in the side chain

[R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently 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 group. Represents an aryl group. _{], - SO 3 H, -OSO} 3 H, -CO 2 H or _{^{-Si (OR 15) m1 R 16}} 3-m1 [R 15, R 16 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and m1 represents an integer of 1 to 3. ];

(2) A thermoplastic resin having a functional group selected from the following at least at one end of the polymer end

[R ²¹ , R ²² , R ²³ and R ²⁴ are each independently 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 group. Represents an aryl group. _{], -SO 3 H, -OSO 3 H} , -CO 2 H, _{^{and, -Si (OR 25) m2 R}} 26 3-m2 ^{[R 25, R 26} are each independently a hydrogen atom, a substituted or unsubstituted An alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group is represented. m2 represents an integer of 1 to 3. ];

(3) Block copolymer composed of hydrophobic segment and hydrophilic segment Hereinafter, the thermoplastic resin (3) will be described in detail.

<Thermoplastic resin (3)>
The thermoplastic resin (3) used in the present invention is a block copolymer composed of a hydrophobic segment and a hydrophilic segment.

Here, the hydrophobic segment (A) refers to a segment having a characteristic that a polymer composed only of the segment (A) does not dissolve in water or methanol, and the hydrophilic segment (B) includes only the segment (B). A segment in which the polymer has the property of being dissolved in water or methanol. The block copolymer types include AB type, B ¹ AB ² type (two hydrophilic segments B ¹ and B ² may be the same or different) and A ¹ BA ² type (two hydrophobic types). Segments A ¹ and A ² may be the same or different), and from the viewpoint of good dispersion characteristics, AB type or A ¹ BA ² type block copolymers are preferable, from the viewpoint of production suitability, AB type or ABA type (a type in which two hydrophobic segments of A ¹ BA ² type are the same) is more preferable, and AB type is particularly preferable.

  The hydrophobic segment and the hydrophilic segment are each a vinyl polymer, polyether, ring-opening metathesis polymer, and condensation polymer (polycarbonate, polyester, polyamide, polyetherketone, polyethersulfone, etc.) obtained by polymerization of vinyl monomers. However, vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates, and polyesters are preferable, and vinyl polymers are more preferable from the viewpoint of production suitability.

As a vinyl monomer (A) which forms the said hydrophobic segment (A), the following are mentioned, for example.
Acrylic acid esters and methacrylic acid esters (the ester group is a substituted or unsubstituted aliphatic ester group, a substituted or unsubstituted aromatic ester group, such as a methyl group, a phenyl group, or a naphthyl group);

  Acrylamides, methacrylamides, specifically, N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides, N-disubstituted methacrylamides (substituents of mono- and di-substituted products are A substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, and examples of the substituent include a methyl group, a phenyl group, and a naphthyl group);

  Olefins, specifically, dicyclopentadiene, norbornene derivatives, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, vinylcarbazole and the like; Styrenes, specifically styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, tribromo styrene, vinyl benzoate Acid methyl ester, etc .;

  Vinyl ethers, specifically methyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, methoxyethyl vinyl ether, etc .; other monomers include 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-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylene malononitrile, vinylidene, diphenyl 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxy Chiruhosufeto, dioctyl-2-methacryloyloxyethyl phosphate.

  Among them, acrylic esters and methacrylic esters in which the ester group is an unsubstituted aliphatic group, substituted or unsubstituted aromatic group; the substituent is an unsubstituted aliphatic group, substituted or unsubstituted aromatic group N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides and N-disubstituted methacrylamides; styrenes; preferred are acrylic esters and methacrylic esters in which the ester group is a substituted or unsubstituted aromatic group Acid esters; styrenes are more preferred.

As a vinyl monomer (B) which forms the said hydrophilic segment (B), the following are mentioned, for example.
Acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters having a hydrophilic substituent at the ester moiety; styrenes having a hydrophilic substituent at the aromatic ring portion; vinyl ethers having a hydrophilic substituent, acrylamide , Methacrylamide, N-monosubstituted acrylamide, N-disubstituted acrylamide, N-monosubstituted methacrylamide and N-disubstituted methacrylamide.
As the hydrophilic substituent,

[However, R ³¹ , R ³² , R ³³ , R ³⁴ are each independently 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 An unsubstituted aryl group is represented. _{], -SO 3 H, -OSO 3 H} , -CO 2 H, -OH, _{^{and, -Si (OR 35) m3 R}} 36 3-m3 ^[However, R ^{35, R 36} are each independently a hydrogen atom Represents 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. m3 represents an integer of 1 to 3. It preferably has a functional group selected from the group consisting of
R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl When it is a group, these preferable ranges are the same as those described as the preferable ranges of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ . M3 is preferably 3.
As the functional group,

-CO ₂ H ^{_{or,, -Si (OR 35) m3}} R 36 3-m3 is preferred,

And -CO ₂ H are more preferable,

Is particularly preferred.
In the present invention, in particular, the lock copolymer is

It has a functional group selected from —SO ₃ H, —OSO ₃ H, —CO ₂ H, —OH, and —Si (OR ³⁵ ) _m3 R ³⁶ _3-m3, and the content of the functional group is 0.00. It is preferable that they are 05 mmol / g or more and 5.0 mmol / g or less.

  Among them, as the hydrophilic segment (B), acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters having a hydrophilic substituent at the ester site, and styrenes having a hydrophilic substituent at the aromatic ring portion Is preferred.

  The vinyl monomer (A) forming the hydrophobic segment (A) may contain the vinyl monomer (B) as long as the hydrophobic properties are not hindered. The molar ratio of the vinyl monomer (A) and the vinyl monomer (B) contained in the hydrophobic segment (A) is preferably 100: 0 to 60:40.

  The vinyl monomer (B) forming the hydrophilic segment (B) may contain the vinyl monomer (A) as long as the hydrophilic property is not hindered. The molar ratio of the vinyl monomer (B) and the vinyl monomer (A) contained in the hydrophilic segment (B) is preferably 100: 0 to 60:40.

  Each of the vinyl monomer (A) and the vinyl monomer (B) may be used alone or in combination of two or more. The vinyl monomer (A) and the vinyl monomer (B) are used for various purposes (for example, adjustment of acid content, adjustment of glass transition point (Tg), adjustment of solubility in organic solvents and water, and adjustment of dispersion stability. ).

The content of the functional group is preferably 0.05 to 5.0 mmol / g, more preferably 0.1 to 4.5 mmol / g, based on the entire block copolymer. It is particularly preferably 15 to 3.5 mmol / g. If the content of the functional group is too small, the dispersibility may be reduced. If the content is too large, the water solubility may be too high, or the organic-inorganic composite composition may be gelled. In the block copolymer, the functional group may form a salt with a cationic ion such as an alkali metal ion (for example, Na ⁺ or K ⁺ ) or an ammonium ion.

  The molecular weight (Mn) of the block copolymer is preferably 1000 to 100,000, more preferably 2000 to 80000, and particularly preferably 3000 to 50000. When the molecular weight of the block copolymer is 1000 or more, a stable dispersion tends to be easily obtained, and when it is 100000 or less, the solubility in an organic solvent tends to be improved.

The block copolymer used in the present invention preferably has a refractive index of more than 1.50, more preferably 1.55 or more, further preferably more than 1.60,
It is particularly preferred that it is greater than 1.65. Here, the refractive index is a value measured with respect to light having a wavelength of 589 nm using an Abbe refractometer (Atago "DR-M4").

  The block copolymer used in the present invention preferably has a glass transition temperature of 80 ° C to 400 ° C, more preferably 130 ° C to 380 ° C. When the glass transition temperature is 80 ° C. or higher, the heat resistance tends to be improved, and when the glass transition temperature is 400 ° C. or lower, the moldability tends to be improved.

  The block copolymer used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 80% or more, and more preferably 85% or more.

  Specific examples of the block copolymer (Exemplary Compounds Q-1 to Q-20) are listed below. In addition, the block copolymer used for this invention is not limited to these specific examples at all.

  The block copolymer can be synthesized using living radical polymerization and living ion polymerization using a technique for protecting a carboxyl group or the like as required or introducing a functional group into the polymer. Moreover, it can synthesize | combine by the radical polymerization from a terminal functional group polymer, and the connection of terminal functional group polymers. Among them, it is preferable to use living radical polymerization and living ion polymerization from the viewpoint of molecular weight control and the yield of the block copolymer. As for the production method of the block copolymer, for example, “Synthesis and Reaction of Polymer (1) (Edited by Polymer Society, Kyoritsu Publishing Co., Ltd. (1992))”, “Precision Polymerization (Edited by Chemical Society of Japan, (Published by Academic Publishing Center (1993)) ”,“ Synthesis and Reaction of Polymers (1) (Edited by Polymer Society, Kyoritsu Publishing Co., Ltd. (1995)) ”,“ Telechelic Polymers: Synthesis, Properties, Applications (R) Jerome et al., Prog. Polym. Sci. Vol 16.837-906 (1991)), “Synthesis of block and graft copolymers by light (Y. Yagch et al., Prog. Polym. Sci. Vol 15.551-601). Page (1990)), US Pat. No. 5,085,698 and the like.

  These resins may be used alone or in combination of two or more.

[Other additives]
In addition to the compound represented by the above general formula (1), the inorganic fine particles, and the thermoplastic resin, the nanocomposite material of the present invention may appropriately include various additives from the viewpoint of uniform dispersibility, releasability, weather resistance, and the like. May be blended. For example, a surface treatment agent, an antistatic agent, a dispersant, a plasticizer, a release agent, and the like can be given. In addition to the resin, a resin having no functional group may be added, and there is no particular limitation on the kind of the resin, but the resin has the same optical properties, thermophysical properties, and molecular weight as the thermoplastic resin. Is preferred.
Although the blending ratio of these additives varies depending on the purpose, it is preferably 0 to 50% by mass and more preferably 0 to 30% by mass with respect to the total amount of the inorganic fine particles and the thermoplastic resin. 0 to 20% by mass is particularly preferable.

<Surface treatment agent>
In the present invention, as described later, when inorganic fine particles dispersed in water or an alcohol solvent are mixed with a thermoplastic resin, the objective is to improve the extractability or substitution into an organic solvent, and the uniform dispersibility to the thermoplastic resin. Depending on various purposes such as increasing the water absorption, decreasing the water absorption of the fine particles, or increasing the weather resistance, a fine particle surface modifier other than the thermoplastic resin may be added. The surface treatment agent preferably has a weight average molecular weight of 50 to 50,000, more preferably 100 to 20,000, and still more preferably 200 to 10,000.

As said surface treating agent, what has a structure represented by following General formula (2) is preferable. General formula (2)
AB

  In the general formula (2), A represents a functional group capable of forming a chemical bond with the surface of the inorganic fine particles used in the present invention, and B is compatible with the resin matrix mainly composed of the thermoplastic resin used in the present invention. Alternatively, it represents a monovalent group or polymer having 1 to 30 carbon atoms having reactivity. Here, “chemical bond” refers to, for example, a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond, and the like.

Preferred examples of the group represented by A are the same as those described above as the functional group of the thermoplastic resin used in the present invention.
On the other hand, the chemical structure of the group represented by B is preferably the same as or similar to the chemical structure of the thermoplastic resin that is the main component of the resin matrix from the viewpoint of compatibility. In the present invention, particularly from the viewpoint of increasing the refractive index, it is preferable that the chemical structure of B together with the thermoplastic resin has an aromatic ring.

  Examples of the surface treatment agent preferably used in the present invention include, for example, p-octylbenzoic acid, p-propylbenzoic acid, acetic acid, propionic acid, cyclopentanecarboxylic acid, dibenzyl phosphate, monobenzyl phosphate, diphenyl phosphate, diphosphate phosphate. -Α-naphthyl, phenylphosphonic acid, phenylphosphonic acid monophenyl ester, KAYAMER PM-21 (trade name; manufactured by Nippon Kayaku Co., Ltd.), KAYAMER PM-2 (trade name; manufactured by Nippon Kayaku Co., Ltd.), benzenesulfonic acid, Naphthalenesulfonic acid, paraoctylbenzenesulfonic acid, or silane coupling agents described in JP-A-5-221640, JP-A-9-100111, JP-A-2002-187721, and the like, are limited thereto. It is not a thing.

These surface treatment agents may be used alone or in combination of two or more.
The total amount of addition of these surface treatment agents is preferably 0.01 to 2 times, more preferably 0.03 to 1 time, and more preferably 0.05 to 0. A ratio of 5 times is particularly preferable.

<Antistatic agent>
In order to adjust the charged voltage of the nanocomposite material of the present invention, an antistatic agent can be added. In the nanocomposite material of the present invention, the inorganic fine particles added for the purpose of improving optical properties may contribute to the antistatic effect, which is another effect. In the case of adding an antistatic agent, an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, a zwitterionic antistatic agent, a polymeric antistatic agent, or a charging fine particle may be mentioned. Two or more types may be used in combination. Examples thereof include compounds described in JP2007-4131A and JP2003201396A.
The addition amount of the antistatic agent varies, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, and particularly preferably 0.1 to 10% by mass of the total solid content. % By mass.

<Others>
Other than the above compounds, animal waxes such as carnauba wax, rice wax, cotton wax, and wood wax, beeswax, lanolin, etc. for the purpose of enhancing the mold release effect and further improving the fluidity during molding. In addition to mineral waxes such as wax, ozokerite, and ceresin, and natural waxes such as paraffin, microcrystalline, and petrolatum, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, stearamide, and chlorinated carbonization Synthetic waxes such as long-chain aliphatic amides such as hydrogen, esters, ketones and ethers, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and fluorine telomers such as Zonyl FSN and Zonyl FSO manufactured by DuPont It can also be added That. In addition, for the purpose of improving light resistance and thermal degradation, known degradation inhibitors such as hindered phenols, amines, phosphoruss, and thioethers may be appropriately added. When these are blended, the resin composition About 0.1-5 mass% is preferable with respect to the total solid of.

[Method for producing organic-inorganic composite composition]
The nanocomposite material of the present invention is preferably produced by chemically bonding inorganic fine particles with the thermoplastic resin having the functional group and dispersing in the resin. At this time, the compound represented by the general formula (1) is allowed to exist.
Since the inorganic fine particles used in the present invention have a small particle size and high surface energy, it is difficult to re-disperse when isolated as a solid. Therefore, it is preferable that the inorganic fine particles are mixed with the thermoplastic resin in a state dispersed in a solution to form a stable dispersion. As a preferred method for producing the nanocomposite material,
[1] Inorganic particles are surface-treated in the presence of the surface treatment agent, the surface-treated inorganic fine particles are extracted into an organic solvent, and the extracted inorganic fine particles are extracted from the thermoplastic resin and the general formula (1). A method for producing a composite of inorganic fine particles and a thermoplastic resin by uniformly mixing with a compound represented by
[2] Inorganic fine particles and thermoplastic resin and the compound represented by the general formula (1) and other additives are uniformly mixed or mixed using a solvent capable of uniformly dispersing or dissolving the inorganic fine particles and the thermoplastic resin. A method for producing a composite is mentioned.

In the case of producing a composite of inorganic fine particles and a thermoplastic resin by the method of [1] above, water-insoluble such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloroethane, dichloroethane, chlorobenzene, methoxybenzene and the like as an organic solvent. These solvents are used. The surface treatment agent used for extraction of the fine particles into the organic solvent and the thermoplastic resin may be the same or different, but the surface treatment agent preferably used is described above Those described in the column of> are mentioned.
When mixing the inorganic fine particles extracted into the organic solvent and the thermoplastic resin, the compound represented by the general formula (1) is also added, and further, a plasticizer, a release agent, or another kind of polymer is added. You may add an agent as needed.

  When the method [2] is employed, dimethylacetamide, dimethylformamide, dimethylsulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, tert-butanol, acetic acid, propionic acid are used as the solvent. A hydrophilic polar solvent such as a single solvent or a mixed solvent, or a mixed solvent of a water-insoluble solvent such as chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene and the above polar solvent. Preferably used. In this case, a dispersant, a plasticizer, a mold release agent, or another type of polymer may be added as necessary in addition to the above-described thermoplastic resin. When using fine particles dispersed in water / methanol, after adding a hydrophilic solvent which has a higher boiling point than water / methanol and dissolves the thermoplastic resin, the water / methanol is concentrated and distilled to disperse the fine particles. After replacing the liquid with a polar organic solvent, it is preferable to mix with the resin. At this time, the surface treatment agent may be added.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Preparation of fine particle dispersion]
(1) Synthesis of zirconium oxide fine particles A zirconium oxychloride solution having a concentration of 50 g / L was neutralized with a 48% aqueous sodium hydroxide solution to obtain a hydrated zirconium suspension. The suspension was filtered and then washed with ion exchanged water to obtain a hydrated zirconium cake. This cake was adjusted to a concentration of 15% by mass in terms of zirconium oxide using ion-exchanged water as a solvent, placed in an autoclave, and hydrothermally treated at 150 ° C. and 150 ° C. for 24 hours to obtain a zirconium oxide fine particle suspension. Formation of zirconium oxide fine particles having a number average particle size of 5 nm was confirmed by TEM. The refractive index of the fine particles was 2.1.

(2) Preparation of Zirconium Oxide Dimethylacetamide Dispersion Add 500 g of N, N′-dimethylacetamide to 500 g of the zirconium oxide fine particle suspension (concentration: 15% by mass) prepared in (1) above, and reduce the pressure to about 500 g or less. After concentration and solvent replacement, the concentration was adjusted by adding N, N′-dimethylacetamide to obtain a 15 mass% zirconium oxide dimethylacetamide dispersion.

[Synthesis of thermoplastic resin]
Synthesis of thermoplastic resin Q-1
2.1 g of tert-butyl acrylate, 0.72 g of 2-bromopropionic acid tert-butyl ester, 0.46 g of copper (I) bromide, N, N, N ′, N ′, N ″, N ″ -pentamethyldiethylene A liquid mixture consisting of 0.56 g of tetramine and 9 ml of methyl ethyl ketone was prepared and purged with nitrogen. The mixture was stirred for 1 hour at an oil bath temperature of 80 ° C., and 136.2 g of styrene was added under a nitrogen stream. The mixture was stirred at an oil bath temperature of 90 ° C. for 16 hours, and after returning to room temperature, 100 ml of ethyl acetate and 30 g of alumina were added and stirred for 30 minutes. The reaction solution was filtered, and the filtrate was added dropwise to excess methanol. The resulting precipitate was collected by filtration, washed with methanol, and dried to obtain 61 g of resin. This resin was dissolved in 300 ml of toluene, 6 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux for 3 hours. The reaction solution was added dropwise to excess methanol. The resulting precipitate was collected by filtration, washed with methanol, and dried to obtain 55 g of a block copolymer Q-1 shown in Table 1. The number average molecular weight of the resin measured by GPC was 32,000, and the weight average molecular weight was 35,000. The refractive index of the resin measured with an Abbe refractometer was 1.59.

[Production of nanocomposite solution]
The mass ratio of the thermoplastic resin Q-1, compound PL-1, and surface treatment agent (4-propylbenzoic acid) to the zirconium oxide dimethylacetamide dispersion is ZrO ₂ solid content / PL-1 / 4-propylbenzoic acid. After adding benzoic acid = 41.7 / 8.3 / 8.3 and stirring and mixing uniformly, the dimethylacetamide solvent was concentrated under heating and reduced pressure. Using this concentrated solution as a resin solution of the nanocomposite material, a lens was formed by the ink jet head described above.
In addition, when forming droplets by inkjet, various drying methods such as a heat transfer drying method, an internal heat generation drying method, and a non-heating drying method can be applied as a pretreatment of the resin solution. Specifically, box drying, tunnel and band drying, rotary drying, aeration rotary drying, grooved stirring drying, fluidized bed drying, spray drying layer equipment, airflow drying, vacuum freeze drying, vacuum drying, infrared drying, internal heat generation You may give drying, a cylindrical drying apparatus, etc. Two or more of the above drying methods may be combined.

  When the material is concentrated before forming the lens by the inkjet, the liquid viscosity at the time of spray drying is preferably 300 cP or less, more preferably 100 cP or less, further preferably 50 cP or less (the liquid viscosity is the concentration of the solution Can be adjusted by).

A lens having a diameter of 5 mm and a thickness of 1 mm was molded using a resin solution having a drying shrinkage ratio of 90%, an ejection cycle from the nozzle of 20 times / second, and 20 nozzles.
By setting the droplet size to a diameter of 0.1 mm, molding could be completed in 15.6 minutes at the shortest.

  As described above, in the method for manufacturing an optical member of the present invention, a high-quality optical material can be manufactured in a short time as an arbitrary shape and arbitrary optical characteristics using a nanocomposite material having a large refractive index. When manufacturing optical members such as small lenses that can be used in optical information recording devices such as type cameras, DVDs, CDs, and MO drives, they are extremely useful.

It is a schematic block diagram showing the manufacturing apparatus of the optical member which concerns on this invention. It is a top view of a shaping | molding board | substrate. It is sectional drawing of the discharge head which represented the discharge condition of the droplet from a nozzle by (a), (b), (c). It is the flowchart explaining the procedure of the manufacturing method which concerns on this invention. It is explanatory drawing showing the discharge area according to lamination | stacking height obtained based on shape data. It is a manufacturing-process figure which represented the modeling process of the optical member by (a)-(e). It is explanatory drawing which shows one structural example (a) of the discharge head which discharges multiple types of resin solutions, and the lens (b) which has refractive index distribution. It is a manufacturing-process figure of the optical member obtained by bonding together half-split optical members. It is sectional drawing which shows an example of the irradiation means to perform a thermal rapid annealing process. It is explanatory drawing of the optical member surface by which a micro unevenness | corrugation is removed and smooth | blunted by a thermal rapid annealing process. It is manufacturing process figure (a), (b), (c) of the additional adjustment by the hot press of the shape | molded optical member surface. It is sectional drawing (a), (b) of the optical member formed by raising using a glass body. It is a principal part block diagram of the manufacturing apparatus of the optical member provided with the relative movement means. It is manufacturing process figure (a), (b) by the discharge head provided with UV lamp. It is a manufacturing-process figure of the optical member by which only a bottom face is shape | molded with a metal mold | die.

Explanation of symbols

11 Convex lens (optical member)
11A One optical member 13 Molded substrate 15 Nozzle 17 Discharge head 21 Control unit 31 Rotation center of molded substrate 33 Straight line passing through the rotation center of molded substrate 35 Discharge point 37 Height measuring means 39 Pressurizing chamber 41 Piezoelectric element 51 Droplet 53 Bottom surface 81 Spherical lens-shaped glass body 83 Thermoplastic resin 91 Relative moving means 100 Optical member manufacturing apparatus

Claims (22)

Based on the optical member shape data, a thermoplastic resin solution is discharged as droplets and solidified on a molded substrate.
With reference to the shape data, the transparent thermoplastic resin is obtained by repeating the process of discharging the droplets to different positions on the molded substrate until they reach a predetermined height and solidifying by drying a plurality of times. A method for producing an optical member, comprising: laminating on the molded substrate, and separating the optical member from the molded substrate after completion of the lamination. It is a manufacturing method of the optical member according to claim 1, Comprising:
A step of measuring the height at which the droplets land on the substrate and stacking the droplets, discharging the droplets until the measured height is a height corresponding to the shape data of the optical member, and solidifying by drying The manufacturing method of the optical member which repeats. It is a manufacturing method of the optical member according to claim 1 or 2,
2. The liquid droplet ejection is performed such that each slice obtained by slicing the optical member in a direction parallel to the molding substrate is sequentially stacked on the molding substrate from the lowest layer. Or the manufacturing method of the optical member of Claim 2. It is a manufacturing method of the optical member according to claim 2,
The height measurement is a method of manufacturing an optical member that uses a phase difference of laser light to measure. It is a manufacturing method of the optical member according to any one of claims 1 to 4,
The method for producing an optical member, wherein the droplet is generated by an ink jet head that discharges the droplet from a nozzle. It is a manufacturing method of the optical member according to claim 5,
The ink jet head includes a nozzle, a pressurizing chamber communicating with the nozzle, and a pressurizing piezoelectric element disposed in the pressurizing chamber, and the pressurizing chamber is applied by applying a voltage to the piezoelectric element. A method for producing an optical member, wherein the thermoplastic resin solution is ejected as droplets from the nozzle by pressing. It is a manufacturing method of the optical member according to claim 5,
The inkjet head includes a nozzle, a flow path communicating with the nozzle, and a heating unit disposed in a part of the flow path, and generates bubbles in the flow path by supplying heat from the heating unit. A method for producing an optical member, wherein the solution of the thermoplastic resin is ejected as droplets from the nozzle. It is a manufacturing method of the optical member according to any one of claims 1 to 7,
A method for producing an optical member, wherein the droplet of the solution has a diameter of 0.005 mm or more and 0.1 mm or less. It is a manufacturing method of the optical member according to any one of claims 1 to 8,
A method of manufacturing an optical member, which performs a rapid thermal annealing process on the shaped optical member and leveles the surface of the optical member. It is a manufacturing method of the optical member according to any one of claims 1 to 9,
A method for producing an optical member, in which a transparent thermoplastic resin is laminated on a spherical lens-shaped transparent body prepared in advance. It is a manufacturing method of the optical member according to claim 10,
A method of manufacturing an optical member, wherein an aspheric surface layer is formed on the spherical lens-shaped transparent body with a solution of the thermoplastic resin. It is a manufacturing method of the optical member according to any one of claims 1 to 11,
A method of manufacturing an optical member, wherein the bottom surfaces of two optical members each having a flat bottom surface are joined together to form one optical member. It is a manufacturing method of the optical member according to any one of claims 1 to 12,
A method for manufacturing an optical member, wherein the droplets are discharged in a vacuum, in a carbon dioxide atmosphere, or in a nitrogen atmosphere. It is a manufacturing method of the optical member according to any one of claims 1 to 13,
The said thermoplastic resin is a manufacturing method of the optical member which is a nanocomposite material which made the transparent thermoplastic resin contain the microparticles | fine-particles with a particle size of 20 nm or less. It is a manufacturing method of the optical member according to any one of claims 1 to 14,
The manufacturing method of the optical member whose said optical member is a lens. It is a manufacturing method of the optical member according to claim 15,
A plurality of types of resin solutions having different fine particle contents are mixed at a predetermined ratio corresponding to at least one of a radial direction and a thickness direction of the lens to form the lens, thereby forming the lens diameter. The manufacturing method of the optical member which provides refractive index distribution with respect to at least any one of a direction and a thickness direction. It is a manufacturing method of the optical member according to claim 15,
When the droplet of the resin solution discharged from the nozzle is landed on a predetermined position of the rotationally driven molded substrate, and the lens is formed on the molded substrate,
Detect the height information of the lens in the middle of modeling,
Obtaining the arrival time from the height position of the nozzle to the expected landing position of the droplet based on the height information,
Obtain the amount of deviation of the landing position from the expected landing position after the molded substrate has rotated the arrival time,
A method for manufacturing an optical member, wherein the ejection timing of droplets from the nozzle is corrected so as to cancel the deviation amount, and the landing position of the droplets is made coincident with the predetermined position. Based on the shape data of the optical member, a thermoplastic resin solution is ejected as droplets, solidified by drying, and an optical member manufacturing apparatus for shaping the optical member,
A molded substrate on which the optical member is formed;
A nozzle for discharging droplets of the thermoplastic resin solution;
An ejection head that is mounted with the nozzle and is movable facing the molding substrate;
With reference to the shape data, a controller that repeatedly discharges the liquid droplets to different positions on the molding substrate plane until they reach a predetermined height and solidifies by drying a plurality of times, and
An optical member manufacturing apparatus comprising: The apparatus for manufacturing an optical member according to claim 18,
The molded substrate is rotatably supported,
An apparatus for manufacturing an optical member, wherein a discharge point of the discharge head is movable along a straight line passing through at least the rotation center of the molded substrate. The optical member manufacturing apparatus according to claim 18 or 19,
An apparatus for manufacturing an optical member, comprising: a relative movement unit that relatively moves the molded substrate and the ejection head in an arbitrary direction. An apparatus for manufacturing an optical member according to any one of claims 18 to 20,
A height measuring means for measuring the height at which the liquid droplets ejected from the nozzle landed and laminated on the molded substrate;
An apparatus for manufacturing an optical member, wherein the controller repeats a step of discharging the droplets and solidifying them by drying until the measured height reaches a height corresponding to the shape data of the optical member.   The optical member formed by the manufacturing method of the optical member of any one of Claims 1-15.

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