WO2011093144A1 - 造形方法 - Google Patents

造形方法 Download PDF

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Publication number
WO2011093144A1
WO2011093144A1 PCT/JP2011/050498 JP2011050498W WO2011093144A1 WO 2011093144 A1 WO2011093144 A1 WO 2011093144A1 JP 2011050498 W JP2011050498 W JP 2011050498W WO 2011093144 A1 WO2011093144 A1 WO 2011093144A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
mass
curable composition
fine particles
Prior art date
Application number
PCT/JP2011/050498
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
慶史 浦川
英雄 宮田
信幸 御手洗
繁 山木
伸晃 石井
邦夫 吉田
Original Assignee
昭和電工株式会社
Aji株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 昭和電工株式会社, Aji株式会社 filed Critical 昭和電工株式会社
Priority to JP2011551797A priority Critical patent/JP5769636B2/ja
Publication of WO2011093144A1 publication Critical patent/WO2011093144A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/021—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/04—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00278—Lenticular sheets
    • B29D11/00307—Producing lens wafers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00365—Production of microlenses
    • B29D11/00375—Production of microlenses by moulding lenses in holes through a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/04—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds
    • B29C2043/046—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds travelling between different stations, e.g. feeding, moulding, curing stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
    • B29C43/361—Moulds for making articles of definite length, i.e. discrete articles with pressing members independently movable of the parts for opening or closing the mould, e.g. movable pistons
    • B29C2043/3615—Forming elements, e.g. mandrels or rams or stampers or pistons or plungers or punching devices
    • B29C2043/3634—Forming elements, e.g. mandrels or rams or stampers or pistons or plungers or punching devices having specific surface shape, e.g. grooves, projections, corrugations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • B29C2043/525—Heating or cooling at predetermined points for local melting, curing or bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • B29L2011/0016—Lenses

Definitions

  • the present invention relates to a modeling method.
  • Patent Document 1 discloses a method of manufacturing a microlens array using a mold having a surface that forms a lens shape, and a first resin is cured on the first substrate by the mold into the lens shape.
  • a method of manufacturing a microlens array including a step of forming the substrate and a step of removing the second resin by dry etching and removing a part of the second substrate. That.
  • Patent Document 2 discloses a method of manufacturing a fine structure by sequentially transferring a fine pattern on a surface of a mother stamper, (1) fixing the mother stamper at a predetermined position with respect to a substrate; (2) supplying resin between the mother stamper and the substrate; (3) pressing the mother stamper against the resin in a vacuum; and (4) curing the resin. (5) removing the mother stamper from the cured resin; (6) moving the mother stamper or the substrate so as to change a relative position between the mother stamper and the substrate; After the step (6), there is disclosed a method for manufacturing a microstructure including a step of repeating steps (2) to (6) a predetermined number of times.
  • the conventional technique has a problem that it is difficult to form a molded article that requires a high degree of precision, such as an aspherical lens.
  • the present invention provides a modeling method capable of modeling a modeled object such as a lens made of a cured product having excellent transparency, heat resistance and environmental resistance as well as a low Abbe number as compared with conventional techniques.
  • the purpose is to do.
  • a feature of the present invention is that the object to be shaped and the transfer body on which the transfer shape is formed are brought into contact with each other, and the deformation process is performed to deform the object to be shaped in accordance with the transfer shape. And a curing process for curing at least a deformed portion of the object to be modeled, and a separating process for separating the object to be modeled and the transfer body from each other, and transferring the transferred shape to the modeled object.
  • the object to be modeled includes: (a) silica fine particles; and (b) a (meth) acrylate compound having two or more ethylenically unsaturated groups and having no ring structure.
  • silica fine particles (a) have the following general formula: Silane represented by the formula (1)
  • the shaping method is a curable composition which has been surface treated with the following general formula silane compound represented by (2) (f).
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • R3 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • a is an integer of 1 to 6
  • b is an integer of 0 to 2
  • R4 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • R5 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • c is an integer of 0 to 6
  • d is an integer from 0 to 2).
  • the modeling method means a method of manufacturing a modeled object.
  • (Meth) acrylate means acrylate and / or methacrylate.
  • the curable composition further comprises (g) a (meth) acrylate compound having one ethylenically unsaturated group and having an alicyclic structure and / or an aromatic ring structure.
  • the (meth) acrylate compound (b) is a (meth) acrylate compound having three ethylenically unsaturated groups and no ring structure.
  • the (meth) acrylate compound (c) is a compound represented by the following general formula (3) and / or a compound represented by the following general formula (4).
  • R6, R7, R8 and R9 each independently represents a hydrogen atom or a methyl group
  • X is an organic group having 6 to 30 carbon atoms having an aromatic ring
  • e and f are each independently And an integer of 0 to 3.
  • R10 and R11 each independently represent a hydrogen atom or a methyl group, and g and h are each independently an integer of 0 to 3).
  • the silica fine particles (a) are 5 to 40 parts by mass of the silane compound (e) with respect to 100 parts by mass of the silica fine particles (a) and 5 parts by mass with respect to 100 parts by mass of the silica fine particles (a).
  • Surface treatment is performed with ⁇ 40 parts by mass of the silane compound (f).
  • the glass transition temperature of each homopolymer of the (meth) acrylate compound (b), (meth) acrylate compound (c) and (meth) acrylate compound (g) is 80 ° C. or higher.
  • the curable composition has a viscosity at 25 ° C. of 30 to 10,000 mPa ⁇ s.
  • the modeled object is a lens.
  • the modeled object is a lens array.
  • modeling that is excellent in transparency, heat resistance, and environmental resistance and that can model a molded object such as a lens made of a cured product having a low Abbe number with high accuracy.
  • a method can be provided.
  • FIG.1 (a) is a top view
  • FIG.1 (b) is a left view
  • FIG. 2 is a partial cross-sectional view showing a transfer body and a wafer used in the first embodiment of the present invention
  • FIG. 5 is a partial cross-sectional view showing a first modification of a transfer body and a wafer used in the first embodiment of the present invention
  • FIG. 6 is a partial cross-sectional view showing a second modification of the transfer body and wafer used in the first embodiment of the present invention.
  • FIG. 2 is a block diagram showing a control device used in the joining device according to the first embodiment of the present invention.
  • 3 is a flowchart showing the operation of the bonding apparatus according to the first embodiment of the present invention.
  • 3 is a flowchart showing a transfer operation of the bonding apparatus according to the first embodiment of the present invention.
  • FIG. 3 is an explanatory diagram for explaining a process of the lens manufacturing method according to the first embodiment of the present invention.
  • FIG. 6 is an explanatory diagram for explaining a process of a lens manufacturing method according to a second embodiment of the present invention.
  • FIG. 1 the modeling apparatus 10 which concerns on the 1st Embodiment of this invention is shown.
  • the modeling apparatus 10 is a modeled object and is used for modeling a lens array that is an optical component.
  • the modeling apparatus 10 includes a base 12 installed on an installation surface, and a movable base 24 is supported on the base 12.
  • a support base 14 is further supported on the upper surface of the movable base 24.
  • the movable base 24 includes a lower part 26 in which a projecting part 25 having a shape projecting downward is formed, and an upper part 27 positioned above the lower part 26, and the projecting part 25 faces upward of the base 12. It is attached to the base 12 so as to be fitted in a groove (not shown) in the y-axis direction formed on the surface 12a. For this reason, the movable table 24 is guided by the groove in the y-axis direction, and can move in the y-axis direction on the surface 12a.
  • a feed screw 28 is engaged with the protruding portion 25. The feed screw 28 is rotatably supported by the base 12 using bearings 30 and 30 so that the axial direction (longitudinal direction) is the y-axis direction.
  • a y-axis motor 32 fixed to the base 12 is connected to the left end of the feed screw 28 in FIG. Therefore, by rotating the y-axis motor 32, the drive is transmitted to the projecting portion 25 via the feed screw 28, and the movable base 24 moves in the y-axis direction. Which direction of the y-axis is to be moved can be determined by controlling the rotation direction of the y-axis motor 32.
  • a ⁇ -axis motor 34 is provided on the upper portion 27 of the movable table 24.
  • the ⁇ -axis motor 34 rotates the upper portion 27 of the movable table 24 around a rotation axis in a direction perpendicular to the Z axis with respect to the lower portion 26 of the movable table 24.
  • the movable base 24 is movable in the y-axis direction as a whole, and the upper portion 27 is rotatable with respect to the lower portion 26.
  • a wafer W made of, for example, glass or the like is placed on the support base 14, and the support base 14 supports the placed wafer W from the lower side in the gravity direction.
  • the support base 14 is connected to a drive source 18 including, for example, a motor.
  • the support table 14 can be rotated integrally with the wafer W with respect to the upper portion 27 of the movable table 24, and is used when resin or the like is applied to the wafer W by so-called spin coating. It is configured as a rotary table for spin coating.
  • the support 14 can pass light emitted from the light irradiation device 60 described later, for example, using a material having optical transparency such as glass.
  • a placement / removal device made of, for example, a robot may be used. However, it may be performed manually by the operator.
  • the upper portion 27 of the movable table 24 is provided with a supply device 36 for supplying a photocurable resin used as a molding object to the wafer W.
  • a storage unit 40 that stores a photocurable resin is connected to the supply device 36 via a valve 38, and the supply device 36 converts the photocurable resin stored in the storage unit 40 into a substantially circular (circular shape). It is possible to supply the wafer W so as to be dropped from above onto a substantially central portion of the wafer W having a plate shape.
  • the photocurable resin supplied to the wafer W is diffused by a centrifugal force when the support base 14 rotates for a predetermined time, and is applied to the surface of the wafer W with a substantially uniform thickness.
  • a light irradiation device 60 used as a curing device is provided on the upper portion 27 of the movable table 24.
  • the light irradiation device 60 is connected to a light source 70 by an optical fiber 68 used as a light transmission means, and is used for irradiating light to a photocurable resin applied to the wafer W.
  • the light irradiation device 60 is provided on the lower side, which is opposite to the transfer body 62 described later, with respect to the support base 14, the wafer W, and the photocurable resin applied to the wafer W. Yes. For this reason, it is possible to irradiate the photocurable resin with light without being blocked by the transfer body 62 while the transfer body 62 is in contact with the photocurable resin.
  • a movable base 24 is mounted on the base 12 and a support 42 is fixed.
  • a movable unit 44 is attached to the column 42 so as to be movable in the x-axis direction with respect to the column 42.
  • the movable unit 44 includes a left side portion 48 located on the left side in the drawing and a right side portion 50 fixed to the left side portion 48.
  • the left portion 48 is supported so as to be movable in the x-axis direction with respect to the support column 42, and the feed screw 52 is engaged with the left portion 48.
  • the feed screw 52 is rotatably attached to the column 42 by a bearing 54 so that the axis direction is the x-axis direction.
  • the x-axis motor 56 attached to the column 42 is connected to one end of the feed screw 52. Therefore, when the x-axis motor 56 is rotated, the drive of the x-axis motor 56 is transmitted to the left portion 48 via the feed screw 52, and the left portion 48 and the right portion 50 of the movable unit 44 are integrated in the x-axis direction. Moving. Which direction in the x-axis direction the movable unit 44 is moved can be determined by controlling the rotation direction of the x-axis motor 56.
  • a transfer body 62 is mounted on the right side portion 50 of the movable unit 44 via a support member 45.
  • the support member 45 is attached to the movable unit 44 so as to be movable in the z-axis direction.
  • the support member 45 includes a protrusion 46 that protrudes to the left in FIG. 1 and a support 47 that is fixed to the protrusion 46.
  • the transfer body 62 is attached to the support portion 47 so that the transfer body 62 can be attached to and detached from the downward surface.
  • a feed screw 58 is screwed into the protruding portion 46.
  • the feed screw 58 is rotatably attached to the right side portion 50 of the movable unit 44 using bearings 61 and 61 so that the axial direction becomes the z-axis direction.
  • the upper end of the feed screw 58 is connected to the support member z-axis motor 64. Therefore, when the support member z-axis motor 64 is rotated, the drive is transmitted to the support member 45 via the feed screw 58, and the support member 45 and the transfer body 62 supported by the support member 45 are integrated into the z-axis. Move in the direction.
  • a detection device 72 used as detection means for detecting the position of the wafer W and the transfer body 62 is movable up and down independently of the support member 45 (movable in the z-axis direction). Is attached).
  • the detection device 72 is, for example, a photographing unit 74 formed of a CCD camera, a lens unit 76 provided on the wafer W side of the photographing unit 74, and an illumination unit that ensures brightness for good photographing by the photographing unit 74. And a light 78 to be used.
  • a z-axis motor 80 for detecting device is attached to the detecting device 72, and the z-axis motor 80 for detecting device is used as a drive source for moving the detecting device 72 in the z-axis direction with respect to the movable unit 44. Then, by moving the detection device 72 up and down, the photographing unit 74 can be focused on the transfer body 62 and the like.
  • the support member 45 is attached to the movable unit 44 so as to be movable in the z-axis direction, and the movable unit 44 is attached to the support column 42 so as to be movable in the x-axis direction. Therefore, by controlling the x-axis motor 56 and the support member z-axis motor 64, the transfer member 62 can be moved in the x-axis direction and the z-axis direction together with the support member 45. Further, as described above, the support base 14 moves in the y-axis direction together with the movable base 24 and rotates by driving the y-axis motor 32 and the ⁇ -axis motor 34.
  • the y-axis motor 32 controls the y-axis motor 32, the x-axis motor 56, the support member z-axis motor 64, and the ⁇ -axis motor 34, the relative positional relationship between the wafer W, the light irradiation device 60, and the transfer body 62. Can be changed.
  • the photocurable resin applied to the wafer W and the transfer body 62 can be brought into contact with each other and separated from each other.
  • the y-axis motor 32, the x-axis motor 56, the support member z-axis motor 64, and the ⁇ -axis motor 34 together with the feed screws 28, 52, 58, etc. It is used as a moving device that moves at least one of the photocurable resin and the transfer body 62 so as to abut against and separate from each other. Details of control of the y-axis motor 32, the x-axis motor 56, the support member z-axis motor 64, and the ⁇ -axis motor 34 will be described later.
  • photocurable resin contains resin hardened
  • a photocurable resin is used as the object to be modeled.
  • the transfer body 62 abuts or the transfer body 62 is pressed.
  • a material that can be deformed according to the shape of the transfer body 62 and can be cured while maintaining the deformed state can be used as appropriate.
  • a thermosetting resin that is cured by heating can be used.
  • a light irradiation device for curing a photocurable resin is used as a curing device for curing the object to be modeled, but the curing device is appropriately selected according to the material used as the object to be modeled.
  • a thermosetting resin is used as the object to be modeled as described above, a heater that heats the thermosetting resin is selected as the curing device.
  • FIG. 2 shows details of the transfer body 62 and the wafer W.
  • the wafer W has a structure in which a holding plate W2 is overlaid on a substrate W1.
  • the substrate W1 is made of, for example, glass that is a material that can transmit light, and the thickness t1 thereof is, for example, 400 ⁇ m.
  • the holding plate W2 is made of, for example, a liquid, and is used for holding a photocurable resin before curing with high fluidity at a predetermined position.
  • the holding plate W2 is made of, for example, silicon, and has a thickness t2 of, for example, 725 ⁇ m, A plurality of through holes h penetrating downward from the bottom are formed.
  • Each through-hole h has, for example, a mortar shape that narrows from the top to the bottom.
  • a scribe layer (notched portion) S is formed inside the substrate W1 at a position between the adjacent through holes h of the substrate W1. Since the position where the scribe layer S of the substrate W1 is formed is weaker than other portions, the substrate W1 is divided along the scribe layer S when dividing the substrate W1.
  • the transfer body 62 is made of, for example, metal, and a transfer shape is formed on the surface of the convex portion 90, for example.
  • the photocurable resin is deformed in accordance with the shape of the transfer shape formed on the surface of the convex portion 90, and the photocurable resin is cured in the deformed state, so that the transfer shape formed on the surface of the convex portion 90 is Transferred to photo-curing resin.
  • the transfer shape formed on the convex portion 90 is, for example, a spherical surface or an aspheric surface, and is formed by mechanically processing the transfer body 62, for example.
  • the object to be modeled requires accuracy. For this reason, accuracy is also required for the transfer shape formed on the convex portion, and in general, the processing for forming the surface shape often requires a long time and high cost. Therefore, in this embodiment, in order to shorten the processing time and suppress the cost, the transfer body 62 is formed with a transfer shape only at one place.
  • a photocurable resin is applied to the upward surface of the wafer W, and the applied photocurable resin is held and held by the holding plate W2 so as to flow into the through holes h of the holding plate W2.
  • a state in which the transfer body 62 is in contact with the photocurable resin so that at least the convex portions 90 are in contact with the photocurable resin is shown.
  • the photocurable resin is cured and the transferred shape formed on the convex portion is light. Transferred to a cured resin.
  • the transfer body 62 is separated from the wafer W as indicated by a two-dot chain line in FIG. 2, and, for example, as shown by an arrow in FIG. It moves so as to be in contact with the uncured resin held in the through hole h adjacent to the through hole h to be held.
  • FIG. 3 shows a first modification of the wafer W.
  • the wafer W according to the above-described embodiment is configured such that the substrate W1 and the holding plate W2 are stacked.
  • the substrate W1 according to the first modification includes only the holding plate W2.
  • the transfer body 62 is brought into contact with the holding plate W2 from below so as to close at least one of the through holes h from below, and the penetration blocked from below. It is necessary to change the configuration of the modeling apparatus 10 so that the photocurable resin can be supplied to the hole h from above and the photocurable resin supplied to the through hole h can be irradiated with light from above. Note that the same portions as those of the wafer W according to the above-described embodiment are denoted by the same reference numerals in FIG.
  • FIG. 4 shows a second modification of the wafer W. While the wafer W according to the above-described embodiment is configured such that the substrate W1 and the holding plate W2 are stacked, in this second modification, the wafer W does not have the holding plate W2. And the substrate W1. Note that the same portions as those of the wafer W according to the above-described embodiment are denoted by the same reference numerals in FIG.
  • FIG. 5 is a block diagram illustrating a control device 200 included in the modeling apparatus 10.
  • the control device 200 includes a main control unit 204 to which an output from the detection device 72 is input via an image recognition device 202 that recognizes an image captured by the detection device 72.
  • the main control unit 204 controls the y-axis motor 32, the x-axis motor 56, the support member z-axis motor 64, and the ⁇ -axis motor 34 by controlling the motor control circuit 206.
  • the main control unit 204 controls the light source 70 by controlling the light source driving circuit 208.
  • the main control unit 204 controls the z-axis motor 80 for the detection device by controlling the motor control circuit 210.
  • the main control unit 204 controls the valve 38 by controlling the valve drive circuit 212.
  • the main control unit 204 controls the drive source 18 by controlling the drive source control circuit 214.
  • FIG. 6 is a flowchart showing the control of the modeling apparatus 10 by the control apparatus 200, and shows a process of a modeling method for modeling a lens array that is a modeled object and an optical component.
  • the lens array refers to an optical component in which a plurality of lens portions are formed on one member.
  • the main control unit 204 controls the drive source control circuit 214 to drive the drive source 18 for a predetermined time.
  • the drive source 18 is driven, the support table 14 rotates, and the photocurable resin supplied to the wafer W placed on the support table 14 is diffused substantially uniformly on the surface of the wafer W by centrifugal force. It becomes.
  • step S300 a transfer process for transferring the transfer shape formed on the transfer body 62 to the photocurable resin is executed. Details of the transfer process in step S300 will be described later.
  • next step S400 it is determined whether or not all the transfer processes have been completed. That is, as step S300, for example, it is determined whether or not it is the last transfer process among the transfer processes repeated about 1500 to 2400 times. If it is determined in step S400 that it is not the last transfer process, the process returns to step S300. On the other hand, if it is determined in step S300 that it is the last transfer process, the process proceeds to the next step S500.
  • step S ⁇ b> 500 the wafer W transferred to the applied photocurable resin is unloaded from the modeling apparatus 10 from the state of being placed on the support base 14.
  • the modeling apparatus 10 does not have a device such as a robot that places the wafer W on the support table 14 and carries the wafer W out of the modeling apparatus 10, the wafer W is placed on the support table 14.
  • the removal of the wafer W from the modeling apparatus 10 is performed manually by the operator, and the operations of Step S100 and Step S500 under the control of the main control unit 204 are not performed.
  • FIG. 7 is a flowchart showing details of control in the transfer step (step S300) in which the control device 200 transfers the transfer shape formed on the transfer body 62 to the thermosetting resin.
  • a deforming process is performed in which the photocurable resin applied to the wafer W is deformed in accordance with the transfer shape formed on the transfer body 62 in step S302. That is, in step S302, the main control unit 204 controls the motor control circuit 206 to drive the y-axis motor 32, the x-axis motor 56, the support member z-axis motor 64, and the ⁇ -axis motor 34, and thereby the wafer W. At least one of the transfer body 62 and the support 14 is moved so that the transfer body 62 comes into contact with a predetermined position of the photocurable resin applied to the transfer body 62 and deforms the photocurable material.
  • step S302 based on the data detected by the detection device 72 and subjected to image processing by the image recognition device 202, the support base 14 and the transfer body so that the transfer body 62 comes into contact with an appropriate position of the photocurable resin.
  • Position correction data may be created in 62, and at least one of the transfer body 62 and the support base 14 may be moved under the control of the main control unit 204 based on the correction data.
  • step S302 the photocurable resin is deformed following the convex portion 90 of the transfer body 62 as described above.
  • the convex part 90 of the transfer body 62 is processed so as to have the opposite shape of each lens part (optical component part) constituting the lens array.
  • the photocurable resin is deformed into the shape of the concave lens portion by being deformed following the convex portion 90.
  • the transfer body 62 having the convex portion 90 is used to form the concave lens portion.
  • the transfer body 62 having the concave portion for forming the convex lens portion is used.
  • a transfer body 62 having a transfer portion processed into a shape opposite to the shape of the optical component portion is used in accordance with the shape of the optical component portion to be formed.
  • a curing process is performed in which the photocurable resin deformed following the transfer body 62 is cured by contacting the transfer body 62.
  • the main control unit 204 controls the light source driving circuit 208 to cause the light source 70 to irradiate light that has been deformed in contact with at least the transfer body 62 of the photo-curing resin for a predetermined time.
  • the photocurable resin is cured in a state of being deformed into the shape of the lens portion, and one lens portion is formed in the photocurable resin.
  • a divorce process for separating the cured photocurable resin and the transfer body 62 is executed. That is, the main control unit 204 controls the motor control circuit 206 to drive the support member z-axis motor 64 so as to move the transfer body 62 in contact with the thermosetting resin upward, for example.
  • a series of transfer processes are completed by steps S302, S304, and S306 described above, and one lens portion is formed in the photocurable resin by completing the transfer process. Then, as shown in FIG. 6, by repeating the transfer process until all the transfer is completed according to the number of lens parts to be formed, the same number of lens parts as the number of transfer processes repeated on the photo-curing resin. The shape is transferred and a lens array is formed.
  • FIG. 8 illustrates a process of manufacturing a lens, which is an optical component, having at least one lens unit, using the lens array 304 that has been shaped by the process described above.
  • the formed lens array is bonded by a method such as bonding a plurality of sheets as necessary (bonding step).
  • 8A shows three lens arrays 304 before being joined
  • FIG. 8B shows a joined lens array 310 in which three lens arrays 304 are joined.
  • the cemented lens array 310 joined in the joining process is divided by a method such as cutting so as to have at least one lens portion (dividing process).
  • a lens is manufactured by dividing the cemented lens array 310. If the scribe layer S (see FIG. 2) is formed on the wafer W as described above, the cemented lens array 310 can be easily divided.
  • FIG. 8C shows a lens 314 manufactured by cutting the cemented lens array 310 joined so that the lens arrays 304 are laminated so as to include one lens portion 312.
  • a camera can be manufactured by attaching the lens 314 to a light receiving element such as a CMOS sensor, for example, and the manufactured camera is used as a camera built in a mobile phone, for example.
  • a process of forming a lens array 314 having a plurality of lens portions by forming a cemented lens array by joining a plurality of lens arrays 304 and dividing the cemented lens array 310 has been described. However, by dividing the plurality of lens arrays 304 without joining them, a single layer lens 314 can be formed. Further, the lens array 304 and the cemented lens array 310 can be used as the lens array 304 and the cemented lens array 310 without being divided.
  • the lens array 304 (see FIG. 8) is modeled using the modeling apparatus 10 (see FIG. 1), whereas in the second embodiment, the modeling apparatus 10 is used.
  • the mold used to mold the lens array is formed.
  • the mold is shaped through the placement process in step S100, the photocurable resin coating process in step S200, the transfer process in step S300, and the wafer unloading process in step S500. The transfer process is repeated according to the number of lens portions of the lens array to be finally molded.
  • the transfer body 62 having a transfer portion processed into a shape opposite to the lens portion formed in the lens array 304 is used as the transfer body 62 (see FIG. 2).
  • a transfer body 62 having a lens portion processed into the same shape as the lens portion of the lens array finally formed is used. For this reason, the shape of the lens portion 312 of the lens array 304 to be finally formed is transferred to the lens molding die to be shaped.
  • FIG. 9 shows a step of molding a lens array as a primary optical component using a mold modeled using the modeling apparatus 10 in the second embodiment of the present invention, and the molded lens array is divided. A process for manufacturing a lens as a secondary optical component is described.
  • a mold 300 manufactured using the modeling apparatus 10 is used.
  • the lens array 304 is molded using a nanoimprint technique (molding process).
  • two molds 300 are prepared, and the two molds 300 and 300 are arranged so that the surfaces on which the shape of the transfer body 62 (see FIG. 2) is transferred face each other.
  • the material of the lens array such as resin is supplied using the supply device 302, and the material such as resin is cured in a deformed state following the shape of the molds 300 and 300, and is opposite to the shape of the transfer surface of the mold 300.
  • a lens array having a shape is molded.
  • the resin when a photocurable resin is used as a material for the lens array, the resin can be cured by irradiating light as in the case of manufacturing the mold 300.
  • the two molds 300 are arranged so that the surfaces on which the shape of the transfer body 62 is transferred face each other, and the material of the lens array is supplied between the molds 300, 300.
  • a lens array material may be supplied between the mold 300 and the flat plate by disposing the surface on which the shape of the body 62 is transferred and a flat plate having a flat surface.
  • the formed lens array is bonded as necessary as shown in FIG. 9B (bonding step).
  • 9 (c) is a cemented lens array 310, and the cemented lens array 310 is divided so as to have at least one lens portion (dividing step), and as shown in FIG. 9 (d),
  • a lens 314 having one lens portion 312 is manufactured.
  • the lens 314 can be manufactured by attaching the lens 314 to a light receiving element such as a CMOS sensor, for example. Used as a built-in camera.
  • the lens array 304 manufactured in the second embodiment can be divided into a single layer without joining, thereby forming a lens 314 composed of a single layer. it can. Further, the lens array 304 and the cemented lens array 310 can be used as the lens array 304 and the cemented lens array 310 without being divided.
  • the molded object that can be formed is not limited to an optical component such as a lens array or a mold for molding the optical component, and for example, an electroforming mother mold used in electroforming and a tank model can be formed.
  • the curable composition used in one embodiment of the present invention comprises (a) silica fine particles, and (b) a (meth) acrylate compound having two or more ethylenically unsaturated groups and having no ring structure (hereinafter referred to as “a”). And (c) a (meth) acrylate compound having two or more ethylenically unsaturated groups and having an aromatic ring structure (hereinafter simply referred to as “reaction (meth) acrylate (b)”). And (d) polymerization initiator, and the silica fine particles (a) are surface-treated with specific silane compounds (e) and (f). It is characterized.
  • the curable composition used in one embodiment of the present invention has a (meth) acrylate compound (g) having one ethylenically unsaturated group and having an alicyclic structure and / or an aromatic ring structure (hereinafter referred to as “a”). , Or simply “reactive (meth) acrylate (g)”) as well as various additives.
  • a ethylenically unsaturated group
  • a alicyclic structure and / or an aromatic ring structure
  • a aromatic ring structure
  • silica fine particles (a) As the silica fine particles (a) used in one embodiment of the present invention, those having an average particle diameter of 1 to 100 nm can be suitably used. If it is less than 1 nm, the viscosity of the prepared curable composition increases, the content of the silica fine particles (a) in the curable composition is limited, and the dispersibility in the curable composition deteriorates. There is a tendency that sufficient transparency and heat resistance cannot be obtained in a cured product obtained by curing the curable composition (hereinafter also simply referred to as “cured product”). On the other hand, if it exceeds 100 nm, the transparency of the cured product may deteriorate.
  • the average particle diameter of the silica fine particles (a) is more preferably 1 to 50 nm, further preferably 5 to 50 nm, and most preferably 5 to 40 nm from the viewpoint of the balance between the viscosity of the curable composition and the transparency of the cured product. It is.
  • the average particle size of the silica fine particles (a) was determined by observing the silica fine particles with a high-resolution transmission electron microscope (H-9000 type, manufactured by Hitachi, Ltd.), and arbitrarily selecting 100 silica particles from the observed fine particle image. This is a value obtained by selecting a particle image and obtaining the number average particle diameter by a known image data statistical processing technique.
  • silica fine particles having different average particle diameters may be mixed and used.
  • porous silica sol, or a composite metal oxide of aluminum, magnesium, zinc or the like and silicon may be used as the silica fine particles (a).
  • the content of the silica fine particles (a) in the curable composition is preferably 20 to 80% by mass as the surface-treated silica fine particles, and the balance between the heat resistance of the cured product and the viscosity of the curable composition. Therefore, the content is more preferably 20 to 60% by mass. If it is this range, since the fluidity
  • silica fine particles (a) it is preferable to use silica fine particles dispersed in an organic solvent from the viewpoint of dispersibility in the curable composition.
  • organic solvent organic components contained in the curable composition (reactive (meth) acrylate (b), reactive (meth) acrylate (c), reactive (meth) acrylate (g), etc.) described later) It is preferable to use a material that dissolves.
  • organic solvent examples include alcohols, ketones, esters, and glycol ethers.
  • alcohol-based organic solvents such as methanol, ethanol, isopropyl alcohol, butyl alcohol and n-propyl alcohol
  • ketone-based organic solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferred.
  • isopropyl alcohol is particularly preferable.
  • silica fine particles (a) dispersed in isopropyl alcohol are used, the viscosity of the curable composition after desolvation is lower than when other solvents are used, and the curable composition having a low viscosity is stabilized. Can be produced.
  • Such silica fine particles dispersed in an organic solvent can be produced by a conventionally known method, and are commercially available, for example, under the trade name Snowtech IPA-ST (manufactured by Nissan Chemical Co., Ltd.).
  • silica fine particles (a) used in one embodiment of the present invention are surface-treated with a silane compound (e) and a silane compound (f).
  • a silane compound (e) and a silane compound (f) are surface-treated with a silane compound (e) and a silane compound (f).
  • silane compound (e) is a compound represented by the following general formula (1).
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • R3 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • a Is an integer from 1 to 6
  • b is an integer from 0 to 2.
  • two R2s may be the same or different.
  • a plurality of R3s may be the same or different.
  • a substituent may be bonded to the phenyl group as long as the effects of the present invention are not impaired.
  • preferable R2 is a methyl group
  • preferable R3 is a methyl group
  • preferable a is 3, and preferable b is 0.
  • the silane compound (e) reduces the viscosity of the curable composition and reacts with the reactive (meth) acrylate (b) described later, thereby improving the dispersion stability of the silica fine particles (a) in the curable composition. It is used for improving and reducing curing shrinkage when curing the curable composition, and imparting moldability to the cured product. That is, when the silica fine particles (a) are not surface-treated with the silane compound (e), the viscosity of the curable composition is increased, the curing shrinkage during curing is increased, the cured product becomes brittle, and the cured product becomes Since cracks are generated, it is not preferable.
  • silane compound (e) examples include ⁇ -acryloxypropyldimethylmethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, ⁇ -acryloxypropyldiethylmethoxysilane, ⁇ -acryloxypropylethyldimethoxysilane, and ⁇ -acryloxy.
  • ⁇ -acryloxypropyldimethylmethoxysilane and ⁇ -acryloxypropylmethyldimethoxysilane are used.
  • ⁇ -methacryloxypropyldimethylmethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane are preferable, and ⁇ -methacryloxypropyltrimethoxy is more preferable.
  • Silane and ⁇ -acryloxypropyltrimethoxysilane may be used alone or in combination of two or more.
  • Such a silane compound (e) can be produced by a known method and is commercially available.
  • the amount of the silane compound (e) used in the surface treatment of the silica fine particles (a) is usually 5 to 40 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the silica fine particles (a).
  • the amount of the silane compound (e) used is less than 5 parts by mass, the viscosity of the curable composition is increased, and the dispersibility of the silica fine particles (a) in the curable composition is deteriorated to cause gelation. there is a possibility.
  • it exceeds 40 mass parts aggregation of a silica fine particle (a) may be caused.
  • the mass of the silica fine particles (a) refers to the mass of the silica fine particles themselves dispersed in the organic solvent. The same applies thereafter.
  • the surface treatment of the silica fine particles (a) will be described later.
  • the curable composition contains a large amount of acrylate (reactive acrylate (b), reactive acrylate (c) and reactive acrylate (g) described later), an acrylic group is added as the silane compound (e).
  • a silane compound represented by the general formula (1) in which R1 is a hydrogen atom is added to a methacrylate (reactive methacrylate (b), reactive methacrylate (c) and reactive methacrylate (described later) in a curable composition.
  • R1 reactive methacrylate
  • c reactive methacrylate
  • reactive methacrylate described later
  • silane compound (f) used in one embodiment of the present invention is a compound represented by the following general formula (2).
  • R 4 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • c is an integer of 0 to 6
  • d 2
  • two R4s may be the same or different
  • d is 1 or less
  • a plurality of R5s may be the same or different.
  • a substituent may be bonded to the phenyl group as long as the effects of the present invention are not impaired.
  • preferable R4 is a methyl group
  • preferable R5 is a methyl group
  • preferable c is 0 or 1
  • preferable d is 0.
  • the silica fine particles (a) react with the silane compound (f)
  • hydrophobicity is imparted to the surface of the silica fine particles (a)
  • the dispersibility of the silica fine particles in the organic solvent is improved. Therefore, the compatibility with the reactive (meth) acrylate (c) is improved, whereby the viscosity of the curable composition is reduced, and the storage stability of the curable composition can be further improved.
  • silane compound (f) examples include phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, phenyldimethylethoxysilane, phenylmethyldiethoxysilane, and phenyldiethylethoxysilane.
  • phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane are preferable. Trimethoxysilane and diphenyldimethoxysilane are more preferable. These silane compounds may be used alone or in combination of two or more.
  • Such a silane compound (f) can be produced by a known method and is commercially available.
  • the amount of the silane compound (f) used in the surface treatment of the silica fine particles (a) is usually 5 to 40 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the silica fine particles (a).
  • the usage-amount of a silane compound (f) is less than 5 mass parts, the viscosity of a curable composition may become high, gelling may be produced, or the heat resistance of hardened
  • it exceeds 40 mass parts aggregation of a silica fine particle (a) may be caused.
  • the surface treatment of the silica fine particles (a) will be described later.
  • the amount of the treating agent is too large. ) May cause aggregation and gelation due to a reaction between the silica fine particles during the surface treatment.
  • Examples of the (meth) acrylate compound (b) having two or more ethylenically unsaturated groups and having no ring structure used in one embodiment of the present invention include trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meta ) Acrylate and the like.
  • the number of ethylenically unsaturated groups is usually 6 or less.
  • those having three ethylenically unsaturated groups are preferred from the viewpoint of heat resistance of the cured product, and those having a glass transition temperature of a homopolymer of 80 ° C. or more are preferred.
  • trimethylolpropane tri (meth) acrylate having a glass transition temperature of a homopolymer of 200 ° C. or higher and relatively low curing shrinkage among polyfunctional (meth) acrylates is most preferable.
  • the glass transition temperature of the said homopolymer is 300 degrees C or less normally.
  • the glass transition temperature of the homopolymer is measured by the following method.
  • the glass transition temperature is determined from the peak temperature of the tan ⁇ value measured with MS6100 (manufactured by Seiko Denshi Kogyo Co., Ltd.) in a tensile mode, a temperature range of 30 ° C. to 300 ° C., a heating rate of 2 ° C./min, and a frequency of 1 Hz.
  • the amount of the reactive (meth) acrylate (b) used in one embodiment of the present invention is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the silica fine particles (a) before the surface treatment, From the viewpoint of the viscosity of the curable composition, the dispersion stability of the silica fine particles (a) in the curable composition, and the heat resistance of the cured product, it is more preferably 30 to 300 parts by mass, still more preferably 50 to 200 parts by mass. Part. If the blending amount is less than 20 parts by mass, the viscosity of the curable composition is increased, and gelation may occur. When the blending amount exceeds 500 parts by mass, shrinkage at the time of curing of the curable composition is increased, and the cured product may be warped or cracked.
  • the reactive (meth) acrylate (c) used in one embodiment of the present invention is a compound having two or more ethylenically unsaturated groups and an aromatic ring structure, and the reactive (meth) acrylate (c). Is contained in the curable composition used in one embodiment of the present invention, the Abbe number of the resulting cured product can be lowered. In the reactive (meth) acrylate (c) used in the present invention, the number of ethylenically unsaturated groups is usually 6 or less.
  • the reactive (meth) acrylate (c) for example, a compound represented by the following general formula (3) can be used.
  • R6, R7, R8 and R9 each independently represent a hydrogen atom or a methyl group
  • X is an organic group having 6-30 carbon atoms having an aromatic ring
  • e and f are each independently It is an integer from 0 to 3. when e is 2 or more, a plurality of R8 may be the same or different; When f is 2 or more, a plurality of R9 may be the same or different.
  • the aromatic ring is an unsaturated cyclic structure in which atoms having ⁇ electrons are arranged in a ring, and the above “carbon number is 6 to 30” means that the number of carbon atoms including the aromatic ring carbon is 6 to 6 30.
  • R6, R7, R8 and R9 are preferably methyl groups from the viewpoint of improving the heat resistance of the resulting cured product.
  • e and f are each independently preferably 0 or 1 from the viewpoint of improving the heat resistance of the resulting cured product and the availability of raw materials. It is more preferable that
  • the carbon number of X is 7 to 24 from the viewpoint of reducing the Abbe number and the viscosity of the curable composition used in one embodiment of the present invention. Is more preferably 7 to 19, and further preferably 7 to 15.
  • X include the following (i) to (p).
  • aromatic group-containing (meth) acrylate compound (1) represented by the following general formula (5) (hereinafter also referred to as “aromatic group-containing (meth) acrylate compound (1)”) and a general formula (6) described later.
  • aromatic group-containing (meth) acrylate compounds shown are particularly preferred as reactive (meth) acrylate (c).
  • R6, R7, R8 and R9 are each independently a hydrogen atom or a methyl group, and e and f are each independently an integer of 0 to 3.
  • e is 2 or more, a plurality of R8 may be the same or different, and when f is 2 or more, a plurality of R9 may be the same or different.
  • R6, R7, R8 and R9 are preferably methyl groups from the viewpoint of improving the heat resistance of the resulting cured product.
  • e and f are each preferably 0 or 1 independently from the viewpoint of improving the heat resistance of the resulting cured product and the availability of raw materials. More preferably.
  • the carbonyl group in the naphthoyl group is more preferably bonded to the ⁇ -position of naphthalene.
  • aromatic group-containing (meth) acrylate compound (hereinafter referred to as “aromatic group-containing”) represented by the following general formula (6), wherein X in the general formula (3) is a compound having a phenylbenzoyl skeleton. (Meth) acrylate compound (2) ”) is also particularly preferred.
  • R6, R7, R8 and R9 are each independently a hydrogen atom or a methyl group, and e and f are each independently an integer of 0 to 3.
  • e is 2 or more, a plurality of R8 may be the same or different, and when f is 2 or more, a plurality of R9 may be the same or different.
  • R6, R7, R8 and R9 are preferably methyl groups from the viewpoint of improving the heat resistance of the resulting cured product.
  • e and f are each preferably 0 or 1 independently from the viewpoint of improving the heat resistance of the resulting cured product and the availability of raw materials. It is more preferable that
  • the carbonyl group in the phenylbenzoyl group is more preferably bonded to the 4-position carbon of biphenyl.
  • the structure shown below is particularly preferable.
  • R10 and R11 each independently represent a hydrogen atom or a methyl group
  • g and h are each independently an integer of 0 to 3.
  • R10 and R11 are preferably hydrogen atoms from the viewpoint of availability of raw materials.
  • g and h are each preferably 0 or 1, more preferably 1, from the viewpoint of easy availability of raw materials.
  • Specific examples of the reactive (meth) acrylate (c) represented by the above general formula (4) include 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene, 9,9- Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxyethoxy) phenyl] fluorene, products manufactured by Osaka Gas Chemical Co., Ltd.
  • the names Ogsol EA-0200, EA-1000, EA-F5003, EA-F5503 and the like can be mentioned.
  • the reactive (meth) acrylate (c) described above may be used alone or in combination of two or more.
  • the reactive (meth) acrylate (c) has a glass transition temperature of 80 homopolymer.
  • a (meth) acrylate compound having a temperature of 0 ° C. or higher is preferred.
  • the method for measuring the glass transition temperature of the homopolymer is the same as described above.
  • the glass transition temperature of the homopolymer is usually 300 ° C. or lower.
  • the (meth) acrylate compound represented by the above general formula (3) and the above general formula (4) from the viewpoint of low Abbe number of the cured product and heat resistance.
  • the amount of the reactive (meth) acrylate (c) used in one embodiment of the present invention is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the silica fine particles (a) before the surface treatment, From the viewpoint of reducing the viscosity of the curable composition, the dispersion stability of the silica fine particles (a) in the curable composition, the heat resistance of the cured product, and the Abbe number of the cured product, more preferably 10 to 200 parts by mass. More preferably, it is 20 to 150 parts by mass. If the blending amount is less than 5 parts by mass, the Abbe number may not be sufficiently low. If the amount exceeds 400 parts by mass, the cured product may be colored.
  • Polymerization initiator (d) examples include a photopolymerization initiator that generates radicals and a thermal polymerization initiator.
  • photopolymerization initiator examples include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxy-phenylphenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine. Oxides and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide. These photopolymerization initiators may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator in the curable composition may be an amount that allows the curable composition to be appropriately cured, and is 0.01 to 10% by mass relative to 100% by mass of the curable composition. It is preferably 0.02 to 5% by mass, more preferably 0.1 to 2% by mass.
  • the content of the photopolymerization initiator is too large, the storage stability of the curable composition is lowered, colored, or the crosslinking when obtaining a cured product by crosslinking is rapidly progressed, such as cracks during curing. Problems may occur.
  • a curable composition may not fully be hardened.
  • thermal polymerization initiator examples include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and the like.
  • the content of the thermal polymerization initiator in the curable composition is preferably 2% by mass or less with respect to 100% by mass of the curable composition.
  • the curable composition used in one embodiment of the present invention is a (meth) acrylate compound having one ethylenically unsaturated group and having an alicyclic structure and / or an aromatic ring structure in addition to the above components ( g) may be contained.
  • the reactive (meth) acrylate (g) is used to impart heat resistance to the cured product and to reduce shrinkage during curing of the curable composition.
  • the alicyclic structure is a structure in which an aromatic ring structure is excluded from a structure in which carbon atoms are bonded in a ring, and the aromatic ring is as described in the description of the reactive (meth) acrylate (c). .
  • the reactive (meth) acrylate (g) is, for example, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Cycloalkyl (meth) acrylates such as pentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecane dimethanol diacrylate, and adamantyl (meth) acrylate Benzyl (meth) acrylate, phenyl (meth) acrylate, o-tolyl (meth) acrylate, m-tolyl (meth) acrylate, phenethyl (meth) acrylate, phenoxyprop (Meth) acrylate
  • the reactive (meth) acrylate (g) is preferably a (meth) acrylate compound whose homopolymer has a glass transition temperature of 80 ° C. or higher.
  • the method for measuring the glass transition temperature of the homopolymer is the same as described above.
  • the glass transition temperature of the homopolymer is usually 300 ° C. or lower.
  • dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, and benzyl (meth) acrylate are preferable from the viewpoint of transparency and heat resistance of the cured product.
  • adamantyl (meth) acrylate and benzyl (meth) acrylate which have a high glass transition temperature.
  • the amount of (meth) acrylate (g) used in one embodiment of the present invention is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the silica fine particles (a) before the surface treatment, and is curable. From the viewpoint of the viscosity of the composition, the dispersion stability of the silica fine particles (a) in the curable composition, and the heat resistance of the cured product, it is more preferably 10 to 200 parts by mass, and still more preferably 10 to 100 parts by mass. is there. When the blending amount is less than 5 parts by mass, the viscosity of the curable composition is increased, and gelation may occur. If the blending amount exceeds 400 parts by mass, the cured product may be cracked or the heat resistance of the cured product may be reduced.
  • the curable composition used in one embodiment of the present invention is a polymerization inhibitor and a leveling agent as long as the viscosity of the composition and the properties of the cured product, such as transparency and heat resistance, are not impaired.
  • the polymerization inhibitor is used to prevent the components of the curable composition from causing a polymerization reaction during storage.
  • examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, 2,6-di-t-butyl-4-methylphenol, and the like.
  • the addition amount of the polymerization inhibitor is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the curable composition from the viewpoint of the transparency of the composition and the heat resistance of the cured product.
  • the polymerization inhibitor may be used alone or in combination of two or more.
  • leveling agent examples include polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, and polyether. Examples thereof include a modified methylalkylpolysiloxane copolymer.
  • ⁇ Leveling agents may be used alone or in combination of two or more.
  • the antioxidant is a compound having a function of capturing an oxidation promoting factor such as a free radical.
  • the antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.
  • antioxidants may be used alone or in combination of two or more.
  • phenolic antioxidant examples include Irganox 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals.
  • Irganox 1076 (Irganox 1076: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by Ciba Specialty Chemicals)
  • Irganox 1330 (Irganox 1330: 3, 3) ', 3'',5,5' , 5 ′′ -hexa-t-butyl-a, a ′, a ′′-(mesitylene-2,4,6-triyl) Tri-p-cresol, manufactured by Ciba Specialty Chemicals Co., Ltd.
  • Irganox 3114 1,3,5-tris (3,5-di-t-butyl-4- Hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by Ciba Specialty Chemicals)
  • Irganox 3790 (Irganox 3790: 1,3,5-Tris) ((
  • Examples of the phosphorus antioxidant include Irgafos 168 (Irgafos 16). 8: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by Ciba Specialty Chemicals), Irgafos 12 (Irgafos 12: Tris [2-[[2,4 , 8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6-yl] oxy] ethyl] amine, manufactured by Ciba Specialty Chemicals), Irgaphos 38 ( Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by Ciba Specialty Chemicals), ADK STAB 329K (manufactured by ADEKA), ADK STAB PEP36 (Manufactured by
  • sulfur-based antioxidant examples include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl, and ⁇ -alkyl mercaptopropion of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane.
  • dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl
  • ⁇ -alkyl mercaptopropion of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane.
  • acid ester compounds examples include acid ester compounds.
  • the above-mentioned ultraviolet absorber is a compound that can absorb ultraviolet rays having a wavelength of about 200 to 380 nm, change them into energy such as heat and infrared rays, and release them.
  • the ultraviolet absorber is not particularly limited as long as it is generally used industrially, and is not limited to benzotriazole, triazine, diphenylmethane, 2-cyanopropenoate, salicylate, anthranilate, Acid derivative-based, camphor derivative-based, resorcinol-based, oxalinide-based, coumarin derivative-based ultraviolet absorbers, and the like can be used.
  • ultraviolet absorbers may be used alone or in combination of two or more.
  • benzotriazole ultraviolet absorber examples include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4- And methyl-6- (tert-butyl) phenol.
  • triazine-based ultraviolet absorber examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4,6-tris. -(Diisobutyl 4'-amino-benzalmalonate) -s-triazine, 4,6 -Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy) -4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-
  • diphenylmethane ultraviolet absorber examples include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone, 4-dodecyloxydiphenylmethanone, 4-benzyloxydiphenylmethanone, 4,2 ′ , 4'-trihydroxydiphenylmethanone, 2'-hydroxy-4,4'-dimethoxydiphenylmethanone, 4- (2-ethylhexyloxy) -2-hydroxy-diphenylmethanone, methyl o-benzoylbenzoate, benzoin Examples include ethyl ether.
  • Examples of the 2-cyanopropenoic acid ester ultraviolet absorber include ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylpropenoate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylpropenoate, and the like.
  • salicylic acid ester UV absorber examples include isocetyl salicylate, octyl salicylate, glycolic salicylate, and phenyl salicylate.
  • anthranilate-based UV absorber examples include menthyl anthranilate.
  • Examples of the cinnamic acid derivative-based ultraviolet absorber include ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, diisopropylmethyl cinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl- ⁇ -carbomethoxycinnamate. And methyl- ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate.
  • camphor derivative ultraviolet absorber examples include benzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, terephthalidene dicamphor sulfonic acid, polyacrylamide methylbenzylidene camphor, and the like.
  • resorcinol ultraviolet absorber examples include dibenzoyl resorcinol, bis (4-tert-butylbenzoyl resorcinol), and the like.
  • Examples of the oxalinide ultraviolet absorber include 4,4′-di-octyloxy oxanilide, 2,2′-diethoxyoxy oxanilide, and 2,2′-di-octyloxy-5,5 ′.
  • Examples of the coumarin derivative ultraviolet absorber include 7-hydroxycoumarin.
  • the light stabilizer is a compound having an effect of reducing auto-oxidative decomposition due to radicals generated by light energy and suppressing resin deterioration.
  • the light stabilizer is not particularly limited as long as it is generally used industrially, and a hindered amine compound (abbreviated as “HALS”), a benzophenone compound, a benzotriazole compound, and the like can be used.
  • HALS hindered amine compound
  • benzophenone compound a benzotriazole compound, and the like can be used.
  • These light stabilizers may be used alone or in combination of two or more.
  • HALS examples include N, N ′, N ′ ′, N ′ ′-tetrakis- (4,6- Bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine , 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [ ⁇ (1,1,3,3- Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6 -Tetramethyl-4-piperidyl) imino ⁇ ], 1,6-hexanediamine-N, N′-bis (2,2 , 6,6
  • the curable composition used in one embodiment of the present invention may further contain a solvent. By mixing the solvent, dispersion of each component in the curable composition can be assisted.
  • the solvent used in the curable composition used in one embodiment of the present invention include esters such as ethyl acetate, butyl acetate and isopropyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Cyclic ethers such as tetrahydrofuran and dioxane; Amides such as N, N-dimethylformamide; Aromatic hydrocarbons such as toluene; Halogenated hydrocarbons such as methylene chloride; Ethylene glycol, ethylene glycol methyl ether, ethylene glycol mono -N-propyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Ethylene glycols such as no ethyl ether acetate; propylene glycol, propylene glycol,
  • the above solvents may be used alone or in combination of two or more.
  • the amount of the solvent used is not particularly limited, but is usually 50 to 200 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the curable composition.
  • filler or pigment examples include calcium carbonate, talc, mica, clay, Aerosil (registered trademark), barium sulfate, aluminum hydroxide, zinc stearate, zinc white, bengara, azo pigment, and the like.
  • Viscosity at 25 ° C. of the curable composition used in one embodiment of the present invention containing such various components, as measured with a B-type viscometer DV-III ULTRA (manufactured by BROOKFIELD), is usually from 30 to 10,000 mPa ⁇ s, preferably 100 to 8000 mPa ⁇ s, and the curable composition used in one embodiment of the present invention has an appropriate viscosity even when it does not contain a solvent, and has good handling properties. .
  • the curable composition used in one embodiment of the present invention includes, for example, a step of surface-treating colloidal silica (silica fine particles (a)) dispersed in an organic solvent with silane compounds (e) and (f) (step 1). Add the reactive (meth) acrylate (b), the reactive (meth) acrylate (c) and, if necessary, the reactive (meth) acrylate (g) to the surface-treated silica fine particles (a), and mix uniformly.
  • Step (step 2) silica fine particles (a) obtained in step 2, reactive (meth) acrylate (b), reactive (meth) acrylate (c) (and reactive (meth) acrylate (g))
  • step 3 A step of distilling off and removing the organic solvent and water from the homogeneous mixed solution (step 3), adding a polymerization initiator (d) to the composition desolvated in step 3, and uniformly mixing the curable composition Step (step 4) It can be produced by Ukoto.
  • step 3 silica fine particles (a) obtained in step 2
  • reactive (meth) acrylate (b) reactive (meth) acrylate (c) (and reactive (meth) acrylate (g)
  • step 3 A step of distilling off and removing the organic solvent and water from the homogeneous mixed solution (step 3), adding a polymerization initiator (d) to the composition desolvated in step 3, and uniformly mixing the curable composition Step (step 4) It can be produced by Ukoto.
  • step 1 the silica fine particles (a) are surface treated with the silane compounds (e) and (f).
  • the silica fine particles (a) are put into a reactor, and while stirring, the silane compounds (e) and (f) are added, mixed with stirring, and water necessary for further hydrolyzing the silane compound.
  • the silane compound is hydrolyzed and subjected to condensation polymerization on the surface of the silica fine particles (a).
  • silica fine particles dispersed in an organic solvent as the silica fine particles (a).
  • the disappearance due to hydrolysis of the silane compound can be confirmed by gas chromatography.
  • a non-polar column DB-1 manufactured by J & W
  • gas chromatography manufactured by Agilent, Model 6850
  • the temperature is 50 to 300 ° C.
  • the heating rate is 10 ° C./min
  • He is used as the carrier gas. Since the residual amount of the silane compound can be measured by an internal standard method using a flame ionization detector at a flow rate of 1.2 cc / min, the disappearance due to hydrolysis of the silane compound can be confirmed.
  • the amount of the silane compound (e) used in the surface treatment of the silica fine particles (a) is usually 5 to 40 parts by mass, preferably 10 to 30 parts per 100 parts by mass of the silica fine particles (a). Part by mass.
  • the amount of the silane compound (f) used is usually 5 to 40 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the silica fine particles (a).
  • the lower limit of the amount of water necessary for carrying out the hydrolysis reaction is 1 times the total number of moles of alkoxy groups and hydroxy groups bonded to the silane compounds (e) and (f), and the upper limit is 10 times. . If the amount of water is too small, the hydrolysis rate may become extremely slow, resulting in lack of economic efficiency, or the surface treatment may not proceed sufficiently. Conversely, if the amount of water is excessively large, the silica fine particles (a) may form a gel.
  • a catalyst for the hydrolysis reaction When performing the hydrolysis reaction, a catalyst for the hydrolysis reaction is usually used.
  • a catalyst include, for example, inorganic acids such as hydrochloric acid, acetic acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid and maleic acid
  • Alkaline catalysts such as potassium hydroxide, sodium hydroxide, calcium hydroxide and ammonia; organic metals; metal alkoxides; organotin compounds such as dibutyltin dilaurate, dibutyltin dioctylate and dibutyltin diacetate; aluminum tris (acetylacetonate); Titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate),
  • hydrochloric acid, acetic acid, maleic acid, and boron compounds are preferable from the viewpoints of solubility in water and sufficient hydrolysis rate.
  • These catalysts can be used alone or in combination of two or more.
  • a water-insoluble catalyst may be used, but a water-soluble catalyst is preferably used.
  • a water-soluble catalyst for hydrolysis reaction it is preferable to dissolve the water-soluble catalyst in an appropriate amount of water and add it to the reaction system because the catalyst can be uniformly dispersed.
  • the addition amount of the catalyst used for the hydrolysis reaction is not particularly limited, but is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the silica fine particles (a).
  • the mass of the silica fine particles (a) refers to the mass of only the silica fine particles themselves dispersed in the organic solvent.
  • the catalyst may be used in the hydrolysis reaction as an aqueous solution dissolved in water. In this case, the addition amount of the catalyst represents the addition amount of the entire aqueous solution.
  • the reaction temperature of the hydrolysis reaction is not particularly limited, but is usually in the range of 10 to 80 ° C, preferably in the range of 20 to 50 ° C. If the reaction temperature is excessively low, the hydrolysis rate may become extremely slow, resulting in lack of economic efficiency, and the surface treatment may not proceed sufficiently. When the reaction temperature is excessively high, the gelation reaction tends to occur.
  • the reaction time for performing the hydrolysis reaction is not particularly limited, but is usually in the range of 10 minutes to 48 hours, preferably 30 minutes to 24 hours.
  • the surface treatment with the silane compound (e) and the silane compound (f) in step 1 may be performed sequentially, but it is preferable to perform the surface treatment at the same time in terms of simplification and efficiency of the reaction process.
  • Step 2 the surface-treated silica fine particles (a) are mixed with the reactive (meth) acrylate (b), the reactive (meth) acrylate (c), and, if necessary, the reactive (meth) acrylate (g).
  • the method used there are no particular restrictions on the method used, but, for example, mixing with a mixer such as a mixer, ball mill, or three rolls at room temperature or under heating conditions, or continuous stirring in the reactor in which Step 1 was performed
  • a method of adding and mixing reactive (meth) acrylate (b) and reactive (meth) acrylate (c) (and reactive (meth) acrylate (g)) can be mentioned.
  • step 3 the organic solvent and the homogeneous mixture of silica fine particles (a), reactive (meth) acrylate (b), reactive (meth) acrylate (c) (and reactive (meth) acrylate (g))
  • solvent reactive (meth) acrylate
  • step 3 the organic solvent and the homogeneous mixture of silica fine particles (a), reactive (meth) acrylate (b), reactive (meth) acrylate (c) (and reactive (meth) acrylate (g)
  • desolvent it is preferable to heat in a reduced pressure state.
  • the temperature is preferably maintained at 20 to 100 ° C., and more preferably 30 to 70 ° C., and further preferably 30 to 50 ° C. in terms of the balance between aggregation gelation prevention and the solvent removal speed. If the temperature is raised too much, the fluidity of the curable composition may be extremely lowered or may be gelled.
  • the degree of vacuum at the time of depressurization is usually 10 to 4,000 kPa, more preferably 10 to 1,000 kPa, and most preferably 10 to 500 kPa, in order to balance the solvent removal speed and prevention of aggregation gelation. is there. If the value of the degree of vacuum is too large, the desolvation speed becomes extremely slow and the economy is lacking.
  • the composition after desolvation contains substantially no solvent.
  • substantially means that when a cured product is actually obtained using the curable composition used in one embodiment of the present invention, it is not necessary to go through a step of removing the solvent again.
  • the remaining amount of the organic solvent and water in the curable composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. Means.
  • a polymerization inhibitor may be added to 100 parts by mass of the composition after desolvation before desolvation.
  • the polymerization inhibitor can be used to prevent a component contained in the composition from causing a polymerization reaction during the solvent removal process or during the storage of the composition and the curable composition after the solvent removal.
  • Step 3 is a uniform mixed solution of silica fine particles (a) having undergone Step 2 and reactive (meth) acrylate (b), reactive (meth) acrylate (c) (and reactive (meth) acrylate (g)). Can be carried out by transferring it to a dedicated apparatus, and if step 2 is carried out using the reactor carried out in step 1, it can be carried out in the reactor subsequent to step 2.
  • step 4 there is no particular limitation on the method of adding and uniformly mixing the polymerization initiator (d) to the composition desolvated in step 3, but for example, mixing a mixer, ball mill, three rolls, etc. at room temperature And a method of adding and mixing the polymerization initiator (d) with continuous stirring in the reactor in which Steps 1 to 3 have been performed.
  • the curable composition obtained by adding and mixing such a polymerization initiator (d) may be filtered as necessary. This filtration is performed for the purpose of removing foreign substances such as dust in the curable composition.
  • the filtration method is not particularly limited, but a method of pressure filtration using a membrane type or cartridge type filter having a pressure filtration pore size of 1.0 ⁇ m is preferable.
  • the curable composition used in one embodiment of the present invention manufactured as described above is cured to provide an optical lens, an optical disk substrate, a plastic substrate for a liquid crystal display element, a substrate for a color filter, an organic EL It becomes the hardened
  • a cured product is obtained by curing the curable composition used in one embodiment of the present invention.
  • the curing method include a method of cross-linking ethylenically unsaturated groups by irradiation with active energy rays, a method of thermally polymerizing ethylenically unsaturated groups by applying heat, and these can be used in combination.
  • a photopolymerization initiator is contained in the curable composition in Step 4 described above.
  • a thermal polymerization initiator is contained in the curable composition.
  • the cured product used in one embodiment of the present invention is, for example, applied by applying the curable composition used in one embodiment of the present invention onto a substrate such as a glass plate, a plastic plate, a metal plate, or a silicon wafer. After forming the film, it can be obtained by irradiating the curable composition with active energy rays or heating. For curing, both irradiation with active energy rays and heating may be performed.
  • Examples of the application method of the curable composition include application by a bar coater, applicator, die coater, spin coater, spray coater, curtain coater, roll coater, etc., application by screen printing, and application by dipping.
  • the coating amount on the base material of the curable composition used in one embodiment of the present invention is not particularly limited and can be appropriately adjusted according to the purpose, and is a curing treatment by active energy ray irradiation and / or heating.
  • the film thickness of the coating film obtained later is preferably 1 to 1,000 ⁇ m, more preferably 10 to 800 ⁇ m.
  • the active energy ray used for curing is preferably an electron beam or light in the ultraviolet to infrared wavelength range.
  • an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet rays
  • a metal halide light source or a halogen light source can be used for visible rays
  • a halogen light source can be used for infrared rays. Can be used.
  • the irradiation amount of the active energy ray is appropriately set according to the type of the light source, the film thickness of the coating film, etc., but preferably reactive (meth) acrylate (b), reactive (meth) acrylate (c), and
  • the reaction rate of the ethylenically unsaturated group of the reactive (meth) acrylate (g) can be appropriately set so as to be 80% or more, more preferably 90% or more.
  • the reaction rate is calculated from the change in the absorption peak intensity of the ethylenically unsaturated group before and after the reaction by infrared absorption spectrum.
  • curing may be further advanced by heat treatment (annealing treatment).
  • the heating temperature at that time is preferably in the range of 80 to 220 ° C.
  • the heating time is preferably in the range of 10 minutes to 60 minutes.
  • the heating temperature is preferably in the range of 80 to 200 ° C, more preferably 100 to 150 ° C. Range.
  • the heating temperature is lower than 80 ° C., it is necessary to lengthen the heating time, and there is a tendency that it is not economical. Therefore, it tends to lack economic efficiency.
  • the heating time is appropriately set according to the heating temperature, the film thickness of the coating film, etc., but preferably the reactive (meth) acrylate (b), the reactive (meth) acrylate (c), and the curable composition.
  • the reaction rate of the ethylenically unsaturated group of the reactive (meth) acrylate (g) can be appropriately set so as to be 80% or more, more preferably 90% or more.
  • the reaction rate is calculated from the change in the absorption peak intensity of the ethylenically unsaturated group before and after the reaction by infrared absorption spectrum.
  • the cured product used in one embodiment of the present invention is excellent in transparency, heat resistance and environmental resistance, an optical lens, a liquid crystal display element plastic substrate, a color filter substrate, an organic EL display element plastic substrate, It can be suitably used as an optical material such as a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED sealing material.
  • the refractive index of the cured product can be appropriately selected depending on the application. And since the hardened
  • the cured product used in an embodiment of the present invention has a low Abbe number, usually an Abbe number of 50 or less, preferably 45 or less. Therefore, an optical material with little chromatic aberration can be obtained by combining the cured product used in one embodiment of the present invention with a material having a high Abbe number, such as a polymethyl methacrylate resin.
  • the Abbe number is calculated from the refractive indexes of wavelengths 486 nm, 589 nm, and 656 nm measured at 25 ° C.
  • the cured product used in one embodiment of the present invention is excellent in heat resistance, and therefore the change in the refractive index before and after heating is small, so the change in the Abbe number before and after heating is also small.
  • the 5% weight reduction temperature when heated in a nitrogen atmosphere is usually 300 ° C. or higher, preferably 320 ° C. or higher, more preferably 350 °C or more.
  • the 5% weight loss temperature when heated is below 300 ° C., for example, when this cured product is used for an active matrix display element substrate, problems such as warpage and deflection, and in some cases, generation of cracks occur in the manufacturing process. There is a fear.
  • the cured product used in one embodiment of the present invention is preferably a reactive (meth) acrylate (b), a reactive (meth) acrylate (c) (and a reactive (meta) having a high glass transition temperature of the homopolymer. ) Since it is obtained by curing a curable composition containing acrylate (g)), it has excellent heat resistance.
  • the cured product used in one embodiment of the present invention has a high glass transition temperature.
  • the glass transition temperature of the cured product is determined from the peak temperature of the loss tangent tan ⁇ value measured at a frequency of 1 Hz using a dynamic viscoelasticity measurement method, and is usually 150 ° C. or higher, preferably 160 ° C. or higher.
  • cured material is 300 degrees C or less normally.
  • the light transmittance at a wavelength of 400 nm with a cured film thickness of 200 ⁇ m is preferably 80% or more, and is used in one embodiment of the present invention. Since the cured product is excellent in heat resistance, the amount of change in transmittance at a wavelength of 400 nm before and after performing heat treatment at 270 ° C. for 1 minute three times is usually 5% or less. When the light transmittance at a wavelength of 400 nm is 80% or less, the efficiency of using light is lowered, which is not preferable for applications where light efficiency is important.
  • the total light transmittance in a cured film thickness of 200 ⁇ m is preferably 85% or more, and is used in one embodiment of the present invention. Since the cured product is excellent in heat resistance, the amount of change in the total light transmittance before and after performing heat treatment at 270 ° C. for 1 minute three times is usually 5% or less.
  • the cured product used in an embodiment of the present invention has an absolute value of a refractive index temperature dependency coefficient of 10.0 ⁇ 10 ⁇ 5 / ° C. or less, preferably 9.0 ⁇ 10 ⁇ 5 / ° C. or less. .
  • a refractive index temperature dependency coefficient exceeds 10.0 ⁇ 10 ⁇ 5 / ° C., for example, when applied to an optical lens or an optical waveguide, the focal length of light changes when the temperature changes under the use environment. This is not preferable because the image accuracy is lowered and the light propagation efficiency is lowered.
  • As a material conventionally used for an optical lens or the like there is polycarbonate, but the absolute value of the refractive index temperature dependency coefficient is 10.7 ⁇ 10 ⁇ 5 / ° C., and the change with temperature is large.
  • the refractive index temperature dependency coefficient is a cured product used in one embodiment of the present invention by changing the temperature in steps of 5 ° C. from 30 to 60 ° C. using MODEL 2010M PRISM COUPLER (manufactured by Metricon). Is the slope when the refractive index at a wavelength of 594 nm is plotted against the temperature.
  • Curable composition (B-1) In a separable flask, 100 parts by mass of isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, average particle size 10-20 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Co., Ltd.) is placed. 5.4 parts by mass of ⁇ -methacryloxypropyltrimethoxysilane and 3.6 parts by mass of phenyltrimethoxysilane were mixed with stirring, and 2.9 parts by mass of an HCl solution having a concentration of 0.1825% by mass was further added. The silica fine particles were surface-treated by stirring for 24 hours at ° C.
  • Example 2 Curable composition (B-2)
  • a curable composition (B-2) was prepared in the same manner as in Example 1 except that the methacrylate compound (A-2) synthesized in Synthesis Example 2 was used instead of the acrylate compound (A-1). )
  • Example 3 Curable composition (B-3)
  • Example 2 in place of diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, t-butylperoxy (2-ethylhexanoate) (trade name perbutyl O;
  • a curable composition (B-3) was obtained in the same manner as in Example 2 except that (Oil Co., Ltd.) was used.
  • Curable composition (B-4) In a separable flask, 100 parts by mass of isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, average particle size 10-20 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Co., Ltd.) is placed. In addition, 9.0 parts by mass of ⁇ -methacryloxypropyltrimethoxysilane and 6.0 parts by mass of phenyltrimethoxysilane were added, mixed by stirring, and further 2.9 parts by mass of HCl solution having a concentration of 0.1825% by mass was added. The silica fine particles were surface-treated by stirring for 24 hours at ° C.
  • Example 5 Curable composition (B-5)
  • the amount of ⁇ -methacryloxypropyltrimethoxysilane used was 5.4 parts by mass
  • the amount of phenyltrimethoxysilane used was 3.6 parts by mass
  • the amount of trimethylolpropane triacrylate used was 33.
  • a curable composition (B-5) was obtained in the same manner as in Example 4 except that the amount of adamantyl methacrylate used was changed to 8 parts by mass and 11.3 parts by mass.
  • Example 6 Curable composition (B-6) In Example 5, curing was performed in the same manner as in Example 5 except that the amount of ⁇ -methacryloxypropyltrimethoxysilane used was changed to 6.0 parts by mass and the amount of phenyltrimethoxysilane used was changed to 9.0 parts by mass. Sex composition (B-6) was obtained.
  • Example 7 Curable composition (B-7)
  • Example 4 curing was carried out in the same manner as in Example 4 except that the amount of ⁇ -methacryloxypropyltrimethoxysilane used was changed to 5.4 parts by mass and the amount of phenyltrimethoxysilane used was changed to 3.6 parts by mass.
  • Sex composition (B-7) was obtained.
  • Curable composition (B-8) In a separable flask, 100 parts by mass of isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, average particle size 10-20 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Co., Ltd.) is placed. 5.4 parts by mass of ⁇ -methacryloxypropyltrimethoxysilane and 3.6 parts by mass of phenyltrimethoxysilane were mixed with stirring, and 2.9 parts by mass of an HCl solution having a concentration of 0.1825% by mass was further added. The silica fine particles were surface-treated by stirring for 24 hours at ° C.
  • trimethylolpropane triacrylate (trade name: TMPTA; manufactured by Nippon Kayaku Co., Ltd., Tg> 250 ° C. of homopolymer) is uniformly added to 39 parts by mass of the surface-treated silica fine particles. Mixed. Thereafter, the mixture was heated under reduced pressure at 40 ° C. and 100 kPa with stirring to remove volatile components.
  • EA-F5503 manufactured by Osaka Gas Chemical Co., Ltd., homopolymer Tg: 115 ° C.
  • functional (meth) acrylate (c) pentamethylpiperidinyl methacrylate (trade name FA-711MM; Hitachi) 1 part by mass of Kasei Co., Ltd., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (trade name Perocta O; manufactured by NOF Corporation) as a thermal polymerization initiator 7 parts by mass, 0.3 parts by mass of t-butylperoxyneodecanoate (trade name perbutyl ND; manufactured by NOF Corporation) were dissolved, and the membrane filter (pore size) .0Myuemu) in a pressurized filtration (pressure 0.2 MPa) A curable composition was obtained (B-8).
  • Curable composition (B-9) In Example 1, a curable composition (B--) was used in the same manner as in Example 1 except that o-phenylphenoxyethyl acrylate (manufactured by Toagosei Co., Ltd.) was used instead of the acrylate compound (A-1). 9) was obtained.
  • Curable composition (B-10) 50 parts by mass of the methacrylate compound (A-2) synthesized in Synthesis Example 2, 50 parts by mass of trimethylolpropane triacrylate (trade name: Biscote # 295; manufactured by Osaka Organic Chemical Co., Ltd.), diphenyl as a photopolymerization initiator -Dissolve 1 part by mass of (2,4,6-trimethylbenzoyl) phosphine oxide (trade name Lucirin TPO-L; manufactured by BASF Japan Ltd.) and apply pressure filtration (pressure) with a membrane filter (pore size: 1.0 ⁇ m) 0.2 MPa) to obtain a curable composition (B-10).
  • Curable composition (B-12) 29 parts by mass of trimethylolpropane triacrylate (trade name: TMPTA; manufactured by Nippon Kayaku Co., Ltd.), 29 parts by mass of adamantyl methacrylate (trade name: ADMA; Osaka Organic Chemical Co., Ltd.), EA-F5503 (Osaka Gas Chemical) Co., Ltd., 42 parts by mass of homopolymer Tg: 115 ° C., 1 part by mass of pentamethylpiperidinyl methacrylate (trade name FA-711MM; manufactured by Hitachi Chemical Co., Ltd.) as HALS, 1 as thermal polymerization initiator , 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (trade name Perocta O; manufactured by NOF Corporation) 0.7 parts by mass, t-butylperoxyneodecanoate (trade name) Perbutyl ND (manufactured by NOF Corporation) 0.3
  • Comparative Example 5 As Comparative Example 5, a polycarbonate resin (manufactured by Partec Co., Ltd.) that is generally used as an optical material and is commercially available was used.
  • the curable composition (B-3) prepared in Example 3 was applied onto a glass substrate so that the thickness of the cured film was 200 ⁇ m, and the coating film was cured by heat treatment at 140 ° C. for 25 minutes. I let you. Thereafter, annealing was performed at 180 ° C. for 30 minutes.
  • the curable compositions (B-4) to (B-8), (B-11), and (B-12) prepared in Examples 4 to 8 and Comparative Examples 3 and 4 were each on separate glass substrates.
  • the cured film was applied so that the thickness of the cured film was 200 ⁇ m, and the coating film was cured by heat treatment at 130 ° C. for 30 minutes. Thereafter, annealing was performed at 180 ° C. for 30 minutes.
  • Viscosity The viscosity of the curable compositions (B-1) to (B-12) is a B-type viscometer DV-III ULTRA. (BROOKFIELD) was used and measured at 25 ° C. The results are shown in Tables 1 and 2.
  • the curable composition has better handling properties as the viscosity is moderately low.
  • the handling properties are good.
  • the cured product used in one embodiment of the present invention has a low Abbe number, and can effectively reduce chromatic aberration by combining with a material having a high Abbe number.
  • the cured product used in one embodiment of the present invention is excellent in heat resistance, and has little change in transmittance (400 nm) and total light transmittance before and after performing heat treatment at 270 ° C. for 1 minute three times, and transparency. Is good.
  • the absolute value of the refractive index temperature dependency coefficient of the cured product shown in the examples is 10.0 ⁇ 10 ⁇ 5 / ° C. or less. That is, the change in refractive index with respect to temperature is small, and the environment resistance is excellent.
  • Comparative Examples 1 and 2 have good handling properties and a low Abbe number, but are inferior in heat resistance and thus have low transmittance after heat treatment and poor transparency.
  • Comparative Examples 3 and 4 also have good handling properties and a low Abbe number, but the absolute value of the refractive index temperature dependency coefficient is large and the environment resistance is poor.
  • the polycarbonate resin shown in Comparative Example 5 is conventionally used in optical lenses and has excellent transparency and low Abbe number, but is inferior in heat resistance.
  • the absolute value of the refractive index temperature dependency coefficient is 10.7 ⁇ 10 ⁇ 5 / ° C., which is inferior in environmental resistance.
  • the present invention is, for example, an optical component such as a lens array, a modeling method for modeling a modeled object such as a mother die used for electroforming, a camera including a light receiving element such as a CMOS sensor, and the like.
  • the present invention can be applied to an optical component manufacturing method for manufacturing optical components such as lenses used in the present invention.
  • the curable composition used in the present invention containing silica fine particles surface-treated with two specific silane compounds, two specific (meth) acrylates, and a polymerization initiator has an appropriate viscosity. And handling is good.
  • a cured product obtained by curing the curable composition is excellent in transparency and heat resistance, has a low Abbe number, and can effectively reduce chromatic aberration by a combination with a material having a high Abbe number.
  • the cured product includes a transparent plate, an optical lens, an optical disk substrate, a plastic substrate for a liquid crystal display element, a substrate for a color filter, a plastic substrate for an organic EL display element, a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED sealing material. It can use suitably for etc.
  • the cured product used in the present invention has a small change in refractive index with respect to a change in temperature and is excellent in environmental resistance, and can be suitably used for an optical lens, an optical waveguide, or the like.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ophthalmology & Optometry (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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KR20160140578A (ko) 2014-03-31 2016-12-07 닛산 가가쿠 고교 가부시키 가이샤 반응성 함불소 실리콘 화합물을 포함하는 중합성 조성물
JP2017043652A (ja) * 2015-08-24 2017-03-02 株式会社菱晃 透明光学部材用硬化性樹脂組成物、硬化物、透明光学部材、レンズ及びカメラモジュール
TWI614107B (zh) * 2015-07-15 2018-02-11 趙崇禮 透鏡陣列的模具設備及其使用方法

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KR20160140578A (ko) 2014-03-31 2016-12-07 닛산 가가쿠 고교 가부시키 가이샤 반응성 함불소 실리콘 화합물을 포함하는 중합성 조성물
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JP2017043652A (ja) * 2015-08-24 2017-03-02 株式会社菱晃 透明光学部材用硬化性樹脂組成物、硬化物、透明光学部材、レンズ及びカメラモジュール

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