TW201031694A - Shaping method - Google Patents

Abstract

A shaping method in which a shaped object such as a lens can be produced with higher accuracy than in conventional techniques. A shaped object, e.g., a lens array or a die for nanoimprinting, is produced by repeatedly performing a transfer step a plurality of times, the transfer step comprising: a deformation step in which a photocurable composition comprising a urethane compound having a polymerizable functional group and a polymerization initiator is brought into contact with a transfer object (62) having a shape to be transferred that is either the same as the shape of an aspherical lens part (312) or the reverse of the shape of an aspherical lens part (312), and the photocurable composition is thereby deformed so as to conform to the shape to be transferred of the transfer object (62); a curing step in which at least the deformed portion of the deformed photocurable composition is cured by irradiation with light using a light irradiator (60); and a separation step in which the photocurable composition that has been cured is separated from the transfer member.

Description

[Technical Field] The present invention relates to a method of forming a lens such as a lens array having a lens portion formed of an aspherical shape, or a shape for forming such a lens. [Prior Art] φ Patent Document 1 discloses a method of manufacturing a microlens array using a metal mold having a lens-shaped surface, which comprises curing a first resin onto the first substrate by the metal mold to form the lens shape. a step of forming a plurality of lens substrates, a step of arranging the lens substrates in an array, a step of forming a mask having a surface for performing ammonium coating on the array lens substrate, and a lens for forming the mask a step of forming a mother plate on the surface of the shape, a step of forming a shape by the mother die, and a step of curing the second resin into the lens shape by the molding type on the second φ substrate. a forming method and a method of manufacturing a microlens array in which a part of the second substrate is removed while removing the second resin by dry etching. Further, Patent Document 2 discloses a method for producing a microstructure in which a fine pattern of a surface of a mother stamper is sequentially transferred, which comprises (1) fixing the mother stamper to a substrate. a step of supplying a resin at a predetermined position, (2) a step of supplying a resin between the mother stamper and the substrate, and (3) a step of pressing the mother stamper against the resin in a vacuum, and (4) curing the foregoing a step of removing the mother stamper from the hardened resin and (6) changing the relative position of the mother stamper to the substrate to move the mother stamper or the substrate as described in (5) -5 to 201031694 And the step of repeating steps (2) to (6) a predetermined number of steps after (7) the aforementioned step (6). [Patent Document 1] JP-A-2005-4 1 1 25 (Patent Document 2) JP-A-2-3-4944

According to the techniques disclosed in Patent Document 1 and Patent Document 2, for example, it is difficult to form a shape of a lens made of an aspherical shape or the like which is required to have high precision. The present invention has been made in view of a method for forming a shape such as a lens with high precision, as compared with the prior art.

According to a feature of the present invention, there is provided a transfer formed by a transfer shape formed by forming a shape, a shape of a lens portion formed by an aspherical shape, or a shape of a lens formed by the aspherical shape. The body is brought into contact with each other, and the deformed step of deforming the shaped object in the form of the transfer shape, the hardening step of hardening the at least deformed portion of the shaped object, and the separating of the shaped object from the transfer body a separating step, a moving step of moving the transfer body relative to the other position of the object to be shaped, and a plurality of steps of forming a transfer step of transferring the transfer shape to the object to be shaped, which is the object to be shaped It is a method of forming a curable composition containing a urethane compound having a polymerizable functional group and a polymerization initiator. The curable composition preferably contains -6-201031694 (A) cerium oxide microparticles, and (B) a urethane compound represented by the following general formula (1).

(wherein Ri represents a divalent aliphatic group having a linear or branched carbon number of 1 to 12, a divalent organic group having a carbon number of 3 to 12 having an alicyclic group, and a carbon number of 6 to 30 having an aromatic ring; a divalent organic group or [-(Ch2) a-0-(CH2) b-]c (a and b each independently represent an integer of 1 to 10, and c represents an integer of 1 to 5.), and R2 represents a straight chain. Or a bivalent aliphatic group having a carbon number of 1 to 10, a divalent organic group having a carbon number of 3 to 10 having an alicyclic group, a divalent organic group having a carbon number of 6 to 30 of an aromatic ring or [-(CH2) ) d-0-(CH2) e-]f (d and e each independently represent an integer of 1 to 10, and f represents an integer of 1 to 5.), and R3 and R4 are each independently a hydrogen atom or a methyl group. C) a (meth) acrylate having an ethylenically unsaturated group and having an alicyclic structure, and (D) a polymerization initiator, wherein the cerium oxide microparticles (A) are represented by the following general formula (2) The surface treatment of the decane compound (E) is characterized by the forming method described in the first item of the patent application. [Chemical 2] R5 (2)

I H2C==C——CΟ—(CH2)„—SiRer(OR7)3-r Ο 201031694 (In the formula (2), R5 represents a hydrogen atom or a methyl group, and R6 represents an alkyl group having 1 to 3 carbon atoms or benzene. The group, r7 represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 1 Å, wherein q represents an integer of 1 to 6, and r represents an integer of 〇 〜2.) It is preferably the aforementioned cerium oxide microparticles contained in the hardenable composition ( A) The surface treatment of 10 to 50 parts by mass of the above-described decane compound (E) is carried out for 100 parts by mass of the cerium oxide fine particles (A). Preferably, the viscosity of the aforementioned hardenable composition is 100 to 5 000 mPa. S ° According to the present invention, a method for forming a shape such as a lens with high precision can be provided as compared with the prior art. Next, an embodiment of the present invention will be described with reference to the drawings. Fig. 1 shows a first embodiment of the present invention. The shape forming device 10 is a shaped object having a lens array for use in an optical component, and the base 12' disposed on the installation surface supports the movable table 24 on the base 12. The movable table 24 is The upper side further supports the support table 14. The movable table 24 is formed by The lower side portion 26 of the protruding portion 25 of the lower side protruding shape is formed with the upper side upper side portion 27 of the lower side portion 26, and the protruding portion 25 is formed, for example, on the y-axis formed by the upward facing surface 12a of the base 12 The groove (not shown) in the direction is assembled to the base 12. Therefore, it is guided by the groove in the y-axis direction, and the movable table 24 is movable in the y-axis direction on the surface 12a. The conveying screw is inserted into the protruding portion 25. 28. The axial direction (long direction) of the conveying screw 28 is set to the y-axis direction, and is supported by the bases 12 in a freely rotatable manner by the bearings 30 and 30. The left end of the conveying screw 28 in Fig. 1 is fixed to the base. The y-axis motor 32 of 12 is coupled. Therefore, the y-axis motor 32 is rotated by -8-201031694, and the drive screw 28 is transmitted to the protruding portion 25 via the transport screw 28 to move the movable table 24 in the y-axis direction. The movable table is moved to the y-axis. The movement in any direction is determined by controlling the rotational direction of the y-axis motor 32. On the upper side portion 27 of the movable table 24, a zero-axis motor 34 is provided. The zero-axis motor 34 is the upper side portion 27 of the movable table 24, and the movable table 24 is provided. The lower side portion 26 is centered on a rotational axis perpendicular to the Z axis. The entire movable table 24 is movable in the y-axis direction, and the upper portion 27 is rotatable to the lower portion 26 at the same time φ. On the support table 14, for example, a wafer W made of glass or the like is placed. The support table 14 supports the wafer W placed on the lower side in the direction of gravity. Further, the support unit 14 is connected to a drive source 18 such as a motor. Therefore, the support table 14 can be moved. The upper portion 27 of the stage 24 is rotated integrally with the wafer W, and a spin table for spin coating which is used for coating a curable composition or the like by spin coating is formed on the wafer W. Alternatively, the support table 14 may be formed as a φ as a rotary table for spin coating, instead of being coated with a curable composition on the wafer W by spin coating, and a plurality of holes h2 formed in the wafer w (refer to the figure) 2) For example, an injection device (not shown) for injecting a curable composition as described above is provided in the forming device 10, and the injecting device may inject a curable composition into the plurality of holes h2 formed in the wafer W. . The support table 14 is made of, for example, a material having light transmittance such as glass, and is light that can be emitted by the light irradiation device 60 to be described later. In the case where the wafer W is placed on the support table 14 and the wafer W is removed in the state in which the support table 14 is placed, for example, a mounting and removing device (not shown in the figure) of a robot or the like can be used. The work can be performed by the operator by hand. A supply device 36 for supplying a photocurable composition used as a molded article to the wafer W is provided on the upper portion 27 of the movable table 24. In the supply device 36, the storage unit 40 for storing the photocurable composition is connected to the valve 3, and the supply device 36 is a photocurable composition to be stored in the storage unit 40, and is slightly circular (arc shape). The slightly center portion of the formed wafer W is dropped from above and can be supplied. The photocurable composition supplied to the wafer W is dispersed by the centrifugal force by the support stage 14 by a predetermined predetermined time, and is applied to the surface of the wafer W to have a slightly uniform thickness. Further, a light irradiation device 60 used as a curing device is provided on the upper side portion 27 of the movable table 24. The light irradiation device 60 is connected to the light source 70 by the optical fiber 68 used as the light transmitting means, and is used for light irradiation on the photocurable composition applied to the wafer W. In the embodiment, the light irradiation device 60 is provided on the support plate 14, the wafer W, and the photocurable composition applied to the wafer W on the side opposite to the side opposite to the transfer body 62 to be described later. Therefore, in a state in which the transfer body 62 is brought into contact with the photocurable composition, it is not necessary to be covered by the transfer body 62, and the photocurable composition can be irradiated with light. The base 42 is fixed to the base 12 while the movable table 24 is being mounted. The movable unit 44 which is movable in the X-axis direction with respect to the pillar 42 is assembled on the pillar 42. The movable unit 44 is formed by a left side portion 48 positioned on the left side in the drawing and a right side portion 50 fixed to the left side portion 48. The left side portion 48 is 'supported to move in the x-axis direction for the post 42 and is inserted into the -10- 201031694 delivery screw 52. The conveying screw 52 is rotatable on the strut 42 by the bearing 54 in the direction of the x-axis of the shaft. At one end of the conveying screw 52, the cymbal motor 56 assembled to the strut 42 is coupled. Therefore, when the spindle motor 56 is rotated, the drive of the spindle motor 56 is transmitted to the left portion 48 via the feed screw 52, and the left portion 48 of the movable unit 44 is integrated with the right portion 50 and moved in the x-axis direction. The movable unit 44 is moved in either direction of the x-axis direction to control the direction of rotation of the φ φ shaft motor 56. On the right side portion 50 of the movable unit 44, the transfer body 62 is attached via the supporting member 45. The support member 45 is formed by disposing the movable unit 44 in the z-axis direction, and is formed by a protruding portion 46 that protrudes to the left side in Fig. 1 and a support portion 47 that is fixed to the protruding portion 46. For example, the support portion 47 is assembled so as to be detachable from the transfer body 62, and the transfer body 62 is assembled to match the shape of the lens portion to be formed or the type of the curable composition used as the object to be formed. It can be selected from Φ which differs in size or shape from each other. The conveying screw 58 is screwed onto the projection 46. The conveying screw 58 is assembled to the right side portion 50 of the movable unit 44 so as to be rotatable in the z-axis direction by using the bearings 6A, 61. The upper end portion of the conveying screw 58 is coupled to the z-axis motor 64 for the support member. Therefore, when the z-axis motor 64 is rotated, the transfer screw 58 is driven to the support member 45, and the support member 45' and the transfer member 62 supported by the support member 45 are moved in the z-axis direction. In the right portion 50 of the movable unit 44, the detecting device 72 used as the detecting means for detecting the positions of the wafers w-11 - 201031694 and the transfer body 62 is assembled so as to be movable up and down independently of the supporting member 45 ( Move in the z-axis direction). The detecting 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 means capable of ensuring the sharpness of photographing by the photographing unit 74. Lamp 78 used. The detection device 72 is equipped with a z-axis motor 80 for the detection device, and the z-axis motor 80 for the detection device is used as a drive source for moving the detection unit 72 to the movable unit 44 in the z-axis direction, and can be moved up and down by φ. The detecting device 72 can align the focus of the photographing portion 74 with the transfer body 62 or the like. As described above, the support member 45 is assembled so as to be movable in the z-axis direction with respect to the movable unit 44, and the movable unit 44 is assembled so as to be movable in the X-axis direction with respect to the pillar 42. Therefore, by controlling the X-axis motor 56 and the support member z-axis motor 64, the support member 45 and the transfer body 62 can be simultaneously moved in the X-axis direction and the z-axis direction. Further, as described above, the support table 14 can simultaneously move and rotate the movable table 24 in the y-axis direction by driving the y-axis motor 32 and the y-axis motor 34. Thereby, the relative positional relationship with the wafer W, the light irradiation device 60, and the transfer body 62 can be changed by controlling the y-axis motor 32, the X-axis motor 56, the support member z-axis motor 64, and the boring motor 34'. . Therefore, by changing the relative positional relationship between the wafer W and the transfer body 62, the photocurable composition applied to the wafer W and the transfer body 62' can be brought into contact with each other and separated. In this embodiment, the y-axis motor 32, the X-axis motor 56, the z-axis motor 64 for the support member, and the boring motor 34 and the conveying screws 28, 5 2, 5 8 and the like are simultaneously cured by the photocurable composition. The printing body 6 2 is brought into contact with each other and separated from each other, and is used as a moving device that moves at least one of the photocurable composition and the transfer body 62. Details of the control of the y-axis motor 32, the X-axis motor 56, the support member z-axis motor 64, and the boring motor 34 will be described later. In the embodiment described above, the photocurable composition is a curable composition that can be cured by irradiation with light. Further, in the embodiment described above, a photocurable composition is used as the object to be formed, and φ is used as the object to be formed, and the contact transfer member 62 or the pressure contact transfer member 62 may be transferred to the transfer. The shape of the body 62 is deformed, and a material which can be cured while being deformed can be applied. For example, a thermosetting composition which is cured by heating by the above-mentioned curable composition can be used. Further, in the embodiment, the light irradiation device for curing the photocurable composition is used as the curing device for curing the shaped object, but the curing device may be appropriately selected by mixing the material used as the object to be molded. For example, when a thermosetting composition is used as the object to be formed as described above, a heater for heating the thermosetting φ composition can be selected as the curing means. FIG. 2 shows the details of the transfer body 62 and the wafer W. As shown in Fig. 2, the wafer W has a structure in which the holding plate W2 is overlapped above the substrate W1. The substrate W1 is made of, for example, glass which is permeable to light, and has a thickness t1 of, for example, 400 μ. The holding plate W2 is formed, for example, of a liquid, and is used when a precurable photocurable composition having high fluidity is held at a predetermined position. For example, the thickness t2 is 725 μ, and a plurality of layers are formed from above. The through hole hi is penetrated to the lower side. Each of the through holes hi is, for example, a shape that is narrowed from the top to the bottom. -13- 201031694 In this manner, the holding plate W2' disposed above the substrate W1 passes through the holding plate W2 and forms a plurality of through holes hi'. Therefore, the lower side of the through hole hi is sealed by the substrate W1, and the lower surface of the substrate W1 is The state of the plurality of holes h2 formed by forming the shape of the recess opened upward is formed. Further, at a position between the through holes h 1 adjacent to each other of the substrate W1, for example, a scriber layer (scriber portion) S is formed on the inside of the substrate W1. Since the position of the patterned layer S on which the substrate W1 is formed is weaker than the strength of the other portions, the substrate W1 is divided along the patterned layer S when the substrate W1 is divided. The transfer body 62 is made of, for example, a metal, and the lens portion formed as an aspherical shape has the same shape as the lens portion 3 1 2 (see FIG. 8 described later) used, or is opposite to the lens portion 3 1 2 . The transfer body formed by the transfer shape formed by the shape is used, and as the transfer shape, for example, the convex portion 90 is formed. Further, the transfer body 62 is used to deform the photocurable composition in the shape of the convex portion 90, and to cure the photocurable composition in a deformed state, and to form a transfer shape of the transfer body 62 to form a photocurable composition. The material is transferred. The convex portion 90 is formed by a metal working body such as a mechanical center, for example, by cutting, and is formed by mechanical processing to form an aspherical shape. The transfer shape formed into the transfer body 62 is required to be high-precision by the shape-formed object which is formed by transfer. Therefore, for example, the transfer shape formed by the transfer portion 62 as the convex portion 90 is also required to have high precision, and the convex portion 90 has an aspherical shape and is difficult to process, so that it takes a long time to process the transfer body 62. There are more cases of high costs. Therefore, in this embodiment, it is intended to shorten the processing time and suppress the cost, and the transfer shape is formed in only one place in the transfer body 62-14-201031694. The aspherical shape is generally a shape in which a part of the spherical surface is cut out. The surface shape other than the curved surface formed. Further, in the optical component of the lens portion 312, it is referred to as a shape represented by the aspherical shape shown by the following formula (1). z = C.p2/[l + {l-(l+Kl).C2.p2}1/2] Equation (1) However, C is taken as the inverse of the radius of curvature R, and p is used as the reflection The height of the optical axis of the mirror, z is the amount of sag, and κ is taken as the conic coefficient. In FIG. 2, the photocurable composition is applied by spin coating on the surface of the wafer W upward, and the applied photocurable composition flows into the hole h2 of the holding plate W2 and is held by the holding plate W2. With respect to the held photocurable composition, at least the convex portion 90 is in contact with the photocurable composition, and the φ-printed body 62 is in contact with each other. In this state, when the light irradiation device 60 is in contact with the position of the convex portion 90 of the photocurable composition and when the periphery is irradiated with light, the photocurable composition is cured, and the transfer shape forming the convex portion is transferred to Photocurable composition. After the photocurable composition is hardened, the transfer body 62 is separated from the wafer W by a two-dot chain line as shown in FIG. 2, as shown by an arrow in FIG. 2, for example, a hole for holding the hardened hardenable composition. The uncured hardenable composition held by the adjacent hole h2 of h2 moves under contact. 3 shows that the photo-curable composition is applied by spin coating instead of the wafer W facing upward, and the injection device is used in the plurality of holes -15-201031694 h2 formed by the wafer W (not In the case where the photocurable composition is injected, the photocurable composition held by the holding plate W2 is at least the convex portion 90, and the state in which the transfer body 62 is contacted is displayed. At this time, the photocurable composition held in the one hole h2 is in contact with the convex portion 90, and the light hardening composition has been injected into the hole h2 adjacent to the hole h2 at the time of light irradiation. After the photocurable composition in the hole h2 is hardened, the transfer body 62 is separated from the wafer W as shown by the two-dot chain line in FIG. 3, as shown by the arrow in FIG. 3, and the hardened composition is maintained. The uncured hardenable composition held by the adjacent hole h2 of the hole h2 of the object moves under contact. And the transfer body 62 in a state of being in contact with the hardenable composition held by the adjacent hole h2 is, before the movement of the adjacent hole h2 further adjacent to the hole h2, the light hardening is injected into the further adjacent hole h2 by the injection device. Sexual composition. In other words, as shown in FIG. 3, when the photocurable composition is injected into the hole h2 using an injection device, when the photocurable composition is deformed in the transfer body 62 (deformation step), a plurality of holes h2 are formed in advance. The wafer W is injected with a photocurable composition (injection step), and the photocurable composition injected into the hole h2 is brought into contact with the transfer body 62 (contact step). Further, when the photocurable composition is deformed, the injection of the photocurable composition of the hole h2 (injection step) and the contact with the transfer body 62 of the photocurable composition injected into the hole h2 (contact step) may be performed. Repeat several times with each other. FIG. 4 shows a first modification of the wafer W. The wafer W of the above-described embodiment is in a state in which the substrate Wi and the holding plate W2 are laminated. However, the substrate W1 of the first modification is formed only by the holding plate W2. When the substrate W1 of the first modification is used, the through hole hi is inserted from below, and the transfer body 62 is brought into contact with the holding plate W2, and is closed by the lower side, and the hole h2 formed is formed by In the upper curable composition, the photocurable composition supplied to the hole h2 is irradiated with light, and the configuration of the forming device 10 must be changed. When the wafer W related to the example is used, the light hardening injected in the hole h2 is hardened, and the through hole hi adjacent to the transfer body 62 is moved by the lower side φ, and then the through hole h 1 is closed. The formed adjacent iridium I injection device injects a photocurable composition. The same portions as those of the wafer W of the related art are given the same as those in Fig. 3. As described above, when the wafer W formed by the wafer holding plate W2 having the holding plate W2 is used, the photocurable composition protective sheet W2 is different from the case where the holding plate W2 is not held, and the photoconductor is formed. The entire surface of the wafer W does not exist in a continuous manner and is divided into a state in which a space formed by a plurality of small volumes is present. When the photocurable composition is shrunk, since the photocurable composition is a cumulative mode, the occurrence of an error in the shape of the transfer body 62 between the transferred positions can be prevented. Further, when the photocurable composition is entirely applied to the substrate W1 and the non-plate W2, the amount of the photocurable composition to be used can be reduced. FIG. 5 shows a second modification of the wafer W.

In the second modification, in the second modification, at least one of the lower side of the wafer W is supplied with light, and the first modified composition of the wafer W is plugged down. H2 is saved by the above-mentioned implementation number, or by holding in the group of holding hardenability, and is compared with the shrinkage of the object, compared with the use of the holding, and the holding plate does not have the holding plate W2 of -17-201031694 It is made of the substrate W1. When the wafer W according to the second modification is used, the photocurable composition is applied by spin coating on the entire surface of the wafer W, and the photocurable composition applied to the wafer W is transferred by transfer. The body 62 is transferred. In the wafer W of the second modification, since the holding plate W2 is not provided, the photocurable composition is continuously present on the entire surface of the wafer W, and the photocurable composition is shrunk. Due to the shrinkage of the cumulative photocurable composition, there is a fear that an error occurs between the position where the transfer body 62 is transferred and the position where it is transferred. Therefore, in order to prevent the occurrence of such an error, it is preferable to change the pitch of the position where the transfer body 62 is in contact with the photocurable composition in accordance with the shrinkage of the photocurable composition to be used. In other words, the transfer body 62 is a pitch at which the transfer position is adjacent to the position and the transfer body is in contact with the other position of the photocurable composition, and the shrinkage ratio of the photocurable composition to be used is matched. It is preferable to set and change it to be wider than the desired distance after curing of the photocurable composition. The same portions as those of the wafer W according to the above-described embodiment are denoted by the same reference numerals as those in Fig. 5, and description thereof will be omitted. Figure 6 shows a grid diagram of a control device 200 having a forming device 10. As shown in Figure 6, the control device 200 has an image recognition device 202 for identifying an image captured by the detecting device 72. The output of 72 is input to the main control unit 2〇4. The main control unit 204 controls the y-axis motor 32, the X-axis motor 56, the z-axis motor 64 for the support member, and the boring motor 34 by controlling the motor control circuit 206. Further, the main control unit 204 201031694 controls the light source 70 by controlling the light source driving circuit 208. Further, the main control unit 404 controls the z-axis motor 80 for the detecting device by controlling the motor control circuit 2 10 . Further, the main control unit 204 controls the valve 38 by controlling the valve drive circuit 212. Further, the main control unit 204 controls the drive source 18 by controlling the drive source control circuit 2 1 4 . Further, when an injection device (not shown) for injecting a photocurable composition into the hole h2 formed in the wafer W is provided in the forming device 10, the control of the injection device is also carried out by the control device 200. Fig. 7 is a first flow chart showing the control of the forming apparatus 10 of the control unit 200, which shows the steps of the forming method of the lens array forming of the optical parts of the shaped object. Here, the lens array is an optical component in which a plurality of members form a plurality of lens portions. In the first flowchart, the step of applying the photocurable composition to the wafer W in total is applied, for example, by spin coating. At the beginning of the series of steps, in step S100, the placing step of the wafer W placed on the support stage 14 is carried out. Next, in the stage s 2 00, a photocurable composition coating step of applying a photocurable composition to the wafer W is carried out. In the photocurable composition application step, the main control unit 204 controls the valve drive circuit 2 12 to supply the photocurable composition to the surface of the wafer W at a predetermined time and in an open state. After the supply of the photocurable composition is completed, the main control unit 204 controls the drive source control circuit 2 1 4 to drive the drive source 18 for a predetermined time. By driving the driving source 18, the support table 14 is rotated, and the photohardenable composition supplied to the wafer W placed on the support table 14 is slightly spread by the centrifugal force on the surface of the wafer W. -19-201031694 status. In the next stage S300, a transfer step of transferring the transfer shape formed by the transfer body 62 to the photocurable composition is carried out. A detailed description of the transfer step of the stage S300 will be described later. In the next stage S 4 0 0, it is judged whether or not all the transfer steps have ended. That is, as the step S300, for example, after the transfer step of about 1,500 times to 2,400 times is repeated, it is determined whether or not the final transfer step is performed. In the step S4 00, if it is determined that the final transfer step is not the same, the process returns to the step S3 00. On the other hand, when it is determined in the step S300 that the final transfer step is made, the process proceeds to the next stage S500. In the stage S 5 00, the crystal circle W transferred to the applied photocurable composition is placed on the support table 14 and carried out of the forming apparatus 10. Further, when the forming apparatus 1 is a device such as a robot that does not have the wafer W placed on the support table 14 and the wafer W is carried out from the forming apparatus 10, the wafer W is placed on the support table 14 and the self-forming apparatus 10 is mounted. The removal of the wafer W is performed by the operator by hand, and the operations of the stages S100 and S500 by the control of the main control unit 204 are not performed. FIG. 8 shows a first flow chart of the transfer step of the control device 200. When the photocurable composition is applied to the entire wafer W by spin coating or the like, the thermosetting composition is formed on the transfer body. A detailed flowchart of the control of the transfer step (stage S 3 0 0) in which the transfer shape of the transfer is performed. At the start of the transfer step, a step of deforming the photocurable composition applied to the wafer W in the step S302 in a transfer shape formed on the transfer body 62 and deforming the same is carried out. That is, in the stage S 3 02, the main control unit 204 201031694 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 x-axis motor 34 to be applied to the crystal. The predetermined position of the photocurable composition of the circle W is in contact with the transfer body 62, and the photocurable composition is deformed to move at least the transfer member 62 and the support table 14. In the deformation step of the stage S 3 02, the detection device 7 2 detects that the image recognition device 202 performs image processing, and the transfer body 62 φ is in contact with the positive position of the photocurable composition on the support table. 1 and the transfer body 62 creates position correction data, and in accordance with the correction data, in the deformation step of at least one of the movable transfer body 62 and the support table 14 by the control of the main control unit 204, The photocurable composition is deformed in accordance with the convex portion 90 of the transfer body 62. Here, the convex portion 90 of the transfer body 62 is processed to have an inverted shape of each lens portion (optical part portion) constituting the lens array. Therefore, the photocurable composition is deformed into a shape of a lens portion formed by a concave aspherical shape by deforming the convex portion 90 from the aspherical shape. In the embodiment, the transfer body 62 having the convex portion 90 is used to form the concave lens portion. For example, the transfer member 62 having the concave portion to form the convex lens portion is used, and the optical component to be formed is used. For the shape of the portion, a transfer body 62 having a transfer portion processed into the shape of the optical component portion and the reverse shape may be selected. Further, when the transfer body 62 is selected, the shrinkage ratio of the photocurable composition to be used is selected in consideration of the type of the photocurable composition to be used, and even if the lens portion having the same final shape is formed, the phase can be selected. Different size - 21 - 201031694 A transfer body that forms a convex portion 90 or the like of a different shape. In other words, the shrinkage during the molding of the photocurable composition is changed to the transfer body 62. In the next step S3 04, a curing step of hardening the photocurable composition deformed by the transfer member 62 is carried out by contact with the transfer member 62. In other words, the main control unit 204 controls the light source driving circuit 208 to irradiate the light source 70 with a portion of the photo-curing composition that is at least deformed by contact with the transfer body 62 at a predetermined time. By the hardening step of the step S3 04, the photocurable composition is subjected to @hardening in a state of being deformed into the shape of the lens portion, and one lens portion is produced in the photocurable composition. In the next step S3 06, a separation step of separating the cured photocurable composition from the transfer body 62 is carried out. In other words, the main control unit 204 controls the motor control circuit 206 to move the transfer body 62 in a state of being in contact with the thermosetting composition to the z-axis motor 64 for the upper and lower driving support members. After the completion of the series of transfer steps by the step S302, the step S304, and the step S306 described above, the transfer step is completed, and one lens portion is formed in the photocurable composition. On the other hand, as shown in FIG. 6, the number of the lens portions formed by the 0 is repeated, and the transfer process is repeated until the transfer is completed, and the shape of the lens portion in which the photocurable composition is transferred and the number of repeated transfer steps is the same, And the lens array is manufactured. Fig. 9 is a second flow chart showing the control of the lens array forming of the optical component of the shaped object by the control of the forming device 10 of the control device 200. The first flowchart shows a step in which the photocurable composition is applied to the entire surface of the wafer W by spin coating. On the other hand, in the second flowchart, the steps of injecting the photocurable composition into the plurality of holes h2-22 to 201031694 (see Fig. 2) of the wafer w using an injection device (not shown) are shown. In the step shown in the first flowchart, in step S100, the mounting step of placing the wafer W on the support table 14 is performed, and in the step S2 00, the photo-curable composition is entirely applied to the wafer W, in the stage s 3 00. The transfer shape formed on the transfer body 62 is transferred to the photocurable composition, and in step S400, it is determined whether or not all of the transfer steps are completed, and then the wafer W is carried out in the step S5 00 outside the φ shape forming apparatus 1. On the other hand, in the step shown in the second flowchart, the wafer W in the step S200 is not coated with the photocurable composition in its entirety, and is formed in the crystal in the transfer step of the step S 3 00 described later. The hole h2 of the circle W is injected into the curable composition. Fig. 10 shows a second flow chart of the transfer step by the control device 200, which is shown in the plurality of holes h2 formed in the wafer W, and is injected into the photocurable composition using an injection device, and is transferred to the thermosetting composition. A detailed flowchart of the control of the transfer step (stage S3 00) formed on the transfer shape of the transfer body 62. At the start of the transfer step, in the step S302, the injection step (stage S3 02a) of one of the plurality of holes h2 formed in the wafer W is injected into the hole, and the step S3 02a is injected into the hole. The step of contacting (S3 02b) of the photocurable composition of one of h2 in contact with the transfer body 62 is carried out by a deformation step of deforming the photocurable composition in a transfer shape formed on the transfer body 62. In other words, in the step S302, the main control unit 204 controls the injection device to inject the -23-201031694 photocurable composition into one of the plurality of holes h2 of the wafer W, and then controls the motor control circuit 206 to inject one. At least one of the transfer body 62 and the support table 14 is moved by the hole h2 of the hole h2 in contact with the transfer body 62. In the next step S3 04, a hardening step of curing the photocurable composition which is deformed in accordance with the transfer body 62 is carried out. That is, the main control unit 204 irradiates the light source 70 with at least light irradiation of the curable composition injected into the hole h2 in the step S3 02a. By the hardening step of the step S3 04, the photocurable composition injected into the hole h2 is deformed into the shape of the lens portion to produce one through mirror portion. In the next step S306, a step of separating the photocurable composition injected from the hardened hole h2 and the transfer member 62 is performed. After the end of the series of transfer steps by the stages S302a, S302b, S304, and S306 described above, one shot of the plurality of holes h2 formed in the wafer W is hardened by the end of the transfer step. At the same time as the composition, the photocurable composition is cured in a state of being deformed in a transfer shape formed on the transfer body 62, and 1 H lens portions are formed. As shown in FIG. 9, the number of the lens portions formed is the same as the number of lens portions of the photocurable composition transfer and the repeated transfer step by repeating the transfer step until all the transfer ends. Shape to form a lens array. Fig. 11 shows a step of producing a lens of an optical component having a lens portion formed by at least one aspherical shape using the lens array 306 formed by the above-described steps. First, as shown in Fig. 11 (a) and Fig. 11 (b) - 24 - 201031694, the formed lens array is joined by a method such as bonding (joining step) as necessary. Fig. 11(a) shows three lens arrays 304 before bonding, and Fig. n(b) shows bonded lens arrays 310 of three lens arrays 34 joined. Then, the cemented lens array 3 1 0 ' joined by the joining step is divided into at least one lens portion by a cutting method or the like (dividing step). The lens is manufactured by dividing the bonded lens array 310. Here, as described above, when the patterned layer S (see Fig. 2) is formed on the wafer W, it is easy to perform the division of the bonded φ mirror array 310. Fig. 11 (c) shows a lens array 314 in which the lens array 304 is bonded to the bonded lens array 310, which is normally laminated, and cut into a lens portion 312. The lens 314 can be manufactured by, for example, being incorporated in a light-receiving element such as a CMOS sensor, and the manufactured camera can be used, for example, as a camera incorporated in a mobile phone. Further, in the manufacturing step of the lens described above, the step of manufacturing the lens 3 1 4 having the plurality of lens portions by dividing the bonded lens φ array 3 10 by bonding the complex lens array 306 to the bonded lens array is performed. Although the division is performed directly under a single layer without joining the complex lens array 304, the lens 314 can be formed by a single layer. Further, the undivided lens array 304 and the bonded lens array 310 can also be used as the lens array 304 and the bonded lens array 310. Next, a second embodiment of the present invention will be described. In the first embodiment, the lens array 30 (see Fig. 1) is formed by using the forming device 10 (see Fig. 1). In the second embodiment, the forming device 1 is used to form the lens array. The formation of the model -25-201031694 was used. In the same manner as in the first embodiment, the model is formed by the step of placing the stage S 1 00, the step of applying the photocurable composition in the step S200, the transfer step of the step S300, and the wafer unloading step of the stage S500. The transfer step of S300 is repeated in accordance with the number of lens portions of the finally formed lens array. In the first embodiment, the transfer body 62 having the aspherical shape formed by the lens array 304 and the transfer portion 62 processed in the reverse shape are used as the transfer body 62 (see Fig. 2). On the other hand, in the second embodiment, the transfer body 62 having the lens portion processed in the same shape as the lens portion of the finally formed lens array is used. Therefore, in the model for forming the lens, the shape of the lens portion 31 of the finally formed lens array 304 is transferred. In the second embodiment of the present invention, in the second embodiment of the present invention, a step of forming a lens array as a primary optical component and a process of dividing a molded lens array into a secondary optical component are used. The steps of the lens are explained. When a lens is manufactured using a model formed by the forming device 10 and a lens array is formed, first, as shown in Fig. 12(a), the forming device 10 is used and the model 300 is formed (formation step), and the shaped model 300 is used, for example, using a nai. The technique of nanoimprint, forming lens array 304 (lens array forming step). For example, two models 300 are prepared, and the side surfaces of the two models 300 and 300 which are transferred to the shape of the transfer body 62 (see FIG. 2) are arranged in opposite directions to each other, and are used between the models 300 and 300. The supply device 308, for example, 201031694 material for supplying a lens array such as a curable composition, is formed by having a material such as a curable composition deformed in a shape deformed by the shape of the model 300 and 3 Ο 0. 00 The transfer surface shape and the lens array of the opposite shape. In this case, for example, when the photocurable composition is used as the material of the lens array in the same manner as in the case of the manufacture of the model 300, the curable composition can be cured by irradiation of light. Further, instead of arranging the two models 300 to the shape of the transfer body 62, the transfer side faces are opposed to each other, and the material for supplying the lens array between the models 300 and 300 is configured as a model 3 0 0 The shape of the transfer body 62 is transferred to the side opposite to the flat plate, and the material of the lens array can be supplied between the mold 300 and the flat plate. The lens array formed is the same as the lens array formed in the first embodiment, and the plurality of sheets are joined as necessary as shown in Fig. 12 (b) (joining step), as shown in Fig. 12 (c). The lens array 310 is divided into the bonded lens arrays 310 to have at least one lens portion (dividing step). As shown in FIG. 12(d), a lens Φ 3 1 4 having one lens portion 312 is manufactured. In the same manner as the lens manufactured in the first embodiment, the lens 3 14 can be manufactured by, for example, being incorporated in a light-receiving element such as a CMOS sensor, and the camera can be used as a camera incorporated in a mobile phone, for example, in the first embodiment. Similarly, the lens array 304 manufactured in the second embodiment can be divided into a single layer without being bonded, so that a lens 314 made of a single layer can be formed. Further, in the first embodiment described above, the lens array 304 and the cemented lens array 3 1 0 can be used as the lens array 304 and the cemented lens array 3 1 0, and the lens array can be formed. In the second embodiment, an example in which a mold to be formed into a lens array is molded is described. However, the shape in which the forming device 1 is used for forming is not limited to an optical component such as a lens array to be formed. The model for the optical component or the optical component may, for example, be an electroforming mother mold or a grooved model used for electroforming. The hardenable composition used in the present invention will be described in detail below. [Curable composition] The curable composition used in the present invention contains a urethane compound having a polymerizable functional group and a polymerization initiator, preferably (A) cerium oxide microparticles, and (B) has a specific structure. a urethane compound (hereinafter may be simply referred to as "urethane compound (B)"), (C) a (meth) acrylate having an ethylenically unsaturated group and having an alicyclic structure (hereinafter may be referred to simply as reactivity) The (meth) acrylate (C)) and (D) polymerization initiator are characterized in that the cerium oxide microparticles (A) are surface-treated with a specific decane compound. Each component will be described below. Further, the term "(meth)acrylate" means methacrylate and/or acrylate. <(A) cerium oxide microparticles> As the cerium oxide microparticles (A) used as the curable composition, those having an average particle diameter of 1 to 10 nm can be used. When the average particle diameter is less than 1 nm, the viscosity of the curable composition to be produced is increased, and the content of the curable composition of the cerium oxide microparticles -28 - 201031694 (A) is limited, and the curable composition is The dispersibility is deteriorated, and the cured product obtained by curing the curable composition (hereinafter simply referred to as a cured product) tends to have insufficient transparency and heat resistance. Further, when the average particle diameter exceeds 100 nm, the transparency of the cured product may deteriorate. The average particle diameter of the cerium oxide microparticles (A) is preferably from 1 to 50 nm, more preferably from 5 to 50 nm, most preferably from 5 to 40 nm, from the balance between the viscosity of the curable composition and the transparency of the cured product. . Further, the average particle diameter of the silica sand fine particles (A) was observed by a high-decomposition energy transmission electron microscope (H-9000 type manufactured by Hitachi, Ltd.), and the fine particle images observed were randomly selected from 100. The cerium oxide particle image is obtained by a known image data statistical processing method to obtain a numerical average particle diameter. In the curable composition, in order to increase the amount of the hardened material of the cerium oxide microparticles (A), the cerium oxide microparticles having an average particle diameter difference may be mixed and used. Further, as the cerium oxide fine particles (A), porous φ-type cerium oxide rubber or a composite metal oxide of aluminum, magnesium, zinc or the like may be used. The content of the cerium oxide microparticles (A) in the curable composition is preferably 20 to 80% by mass as the surface-treated cerium oxide microparticles, and the heat resistance, environmental resistance and curability of the cured product. The viscosity balance of the composition is preferably from 40 to 60% by mass. If it is in this range, the fluidity of the curable composition and the dispersibility of the cerium oxide microparticles (A) in the curable composition are good. Therefore, if such a curable composition is used, it is easy to produce sufficient strength and A cured product of heat resistance and environmental resistance. -29- 201031694 Further, as the cerium oxide fine particles (A), it is preferred to use cerium oxide microparticles dispersed in an organic solvent from the viewpoint of dispersibility in the curable composition. As the organic solvent, it is preferred to use an organic component (hereinafter referred to as a urethane compound (B) or a (meth) acrylate (C)) to be dissolved in the curable composition. Examples of the organic solvent include alcohols, ketones, esters, and glycol ethers. The ease of desolvation in the solvent removal step of removing the organic solvent from the mixture of the cerium oxide microparticles (A), the urethane compound (B), and the (meth) acrylate (C) described later, with methanol and ethanol An alcohol such as isopropyl alcohol, butyl alcohol or η-propyl alcohol, or a ketone-based organic solvent such as methyl ethyl ketone or methyl isobutyl ketone is preferred. Among them, isopropyl alcohol is also preferred. When the cerium oxide fine particles (A) dispersed in isopropyl alcohol are used, the viscosity of the curable composition after solvent removal is lower than when other solvents are used, and a hardening composition having a low viscosity can be produced by stability. The cerium oxide fine particles dispersed in such an organic solvent can be produced by a conventionally known method, and, for example, commercially available under the trade name Snow-TechIPA-ST (manufactured by Seiko Chemical Co., Ltd.) or the like can be used. When the cerium oxide fine particles dispersed in the organic solvent as the cerium oxide fine particles (A) are used, the content of the cerium oxide fine particles (A) in the curable composition of the present invention is expressed only in the composition. The content of the cerium oxide microparticles themselves. Further, the cerium oxide microparticles (A) used in the curable composition of the present invention are surface-treated with a decane compound (E). The following describes the decane compound. 201031694 <(E) decane compound> The aforementioned decane compound (E) is represented by the following general formula (2). [Chemical 3] R6 H2C=C-C--〇(CH2)e——SiR6r(OR7)3_r (2) Ο φ (In the formula (2), R5 represents a hydrogen atom or a methyl group, and R6 represents a carbon number of 1 ～3 alkyl or phenyl, R7 represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 10, q represents an integer of 1 to 6, and r represents an integer of 0 to 2.) The viscosity of the curable composition is reduced, and the stability is preserved. From the viewpoint of nature, R6 is preferably a methyl group, R7 is preferably a methyl group, q is preferably 3, and hydrazine is preferably a decane compound (E) for reducing the viscosity of the curable composition, and by The urethane compound (B) to be described later is subjected to a reaction, and the dispersion stability in the curable composition of the cerium oxide micro φ particle (A) and the hardening shrinkage at the time of curing the hardenable composition are increased, and the cured product is to be imparted. Formability and user. In other words, when the cerium oxide microparticles (A) are not surface-treated with the decane compound (E), the viscosity of the curable composition is increased, and the hardening shrinkage at the time of hardening is increased, the hardened material becomes brittle, and cracks are formed in the cured product. Not good. Examples of the decane compound (E) include r-propyleneoxypropyldimethylmethoxydecane, γ-acryloxypropylmethyldimethoxydecane, and γ-acryloxypropyldiethyl. Methoxymethoxydecane, γ-propyleneoxypropylethyl-31 - 201031694 dimethoxydecane, γ-propyleneoxypropyltrimethoxydecane, γ-propyleneoxypropyldimethylethoxy Decane, γ-acryloxypropylmethyldiethoxydecane, γ-propyleneoxypropyldiethylethoxydecane, γ-acryloxypropylethyldiethoxydecane, γ-propylene Oxypropyl triethoxy decane, γ-methacryloxypropyl dimethyl methoxy decane, γ-methacryloxypropyl methyl dimethoxy decane, γ-methyl propyleneoxy Propyl diethyl methoxy decane, γ-methyl propyloxypropyl ethyl dimethoxy decane, γ-methyl propyloxypropyl trimethoxy decane, γ-methyl propyleneoxy propyl Dimethylethoxydecane, γ-methacryloxypropylmethyldiethoxydecane, γ-methacryloxypropyldiethylethoxysilane, γ-methylpropoxypropane Base B The coagulation of the curable composition of the cerium oxide microparticles (A) and the viscosity of the curable composition are reduced by the bismuth ethoxy decane, γ-methyl propyloxypropyl triethoxy decane, and the like. From the standpoint of improving stability, 'r-propoxypropyldimethylmethoxydecane, γ-acryloxypropylmethyldimethoxydecane, γ-methylpropoxypropyldi Methyl methoxy decane, γ-methacryloxypropyl methyl dimethoxy decane, γ-acryloxypropyl trimethoxy decane, γ-methyl propyloxypropyl trimethoxy decane Preferably, it is r-propyleneoxypropyltrimethoxydecane. Moreover, these can be used in two or more types. Further, such a decane compound (E) can be produced by a known method and can be sold. The amount of the decane compound (E) used for surface treatment of the cerium oxide microparticles (A) is -32 to 201031694, generally 10 to 50 parts by mass, preferably 20, for the cerium oxide microparticles A) 100 parts by mass. ~ 40 parts by mass, more preferably 24 to 36 parts by mass. When the amount of the decane compound (E) is less than 10 parts by mass, the viscosity of the curable composition is increased, and the dispersibility in the curable composition of the cerium oxide microparticle (A) is deteriorated to cause gelation. . Further, when it exceeds 50 parts by mass, aggregation of the cerium oxide microparticles (A) is caused. When the cerium oxide fine particles dispersed as an organic solvent in the cerium oxide fine particles (A) are used, the mass φ of the cerium oxide fine particles (A) indicates the mass of only the cerium oxide fine particles themselves dispersed in the organic solvent. Further, the surface treatment of the cerium oxide microparticles (A) will be described later. When the curable composition contains a large amount of acrylate (the urethane compound (B) and the reactive acrylate (C) described later), the decane compound (E) has a propylene group, in other words, R1 is a hydrogen atom. 1) When the decane compound or the curable composition is a large amount of methacrylate (the urethane compound (B) and the methacrylate (C) described later), the methyl group is used as the decane compound (E). The propylene group is preferably a decane compound represented by the general formula (1) wherein R1 is a methyl group. In this case, the hardening reaction of the present invention is likely to cause a hardening reaction. <(B) urethane compound> The (B) urethane compound (hereinafter referred to simply as "(B) urethane compound") used in the present invention has two or more molecules as shown in the following general formula (1). Polymeric unsaturated bond. -33- 201031694 〔化4〕

In the above general formula (1), Ri is a divalent aliphatic group having a linear or branched carbon number of 1 to 12, a divalent organic group having an alicyclic group having 3 to 12 carbon atoms, and a carbon number having an aromatic ring. a valence organic group of 6 to 30 or [-(CH2) a-〇-(CH2) b-]^ (a and b each independently represent an integer of 1 to 10, and c represents an integer of 1 to 5). R i is derived from the viewpoint of the curability of the curable group of the present invention described later, and the balance between the hardness and the curl of the cured product obtained by curing the curable composition (hereinafter simply referred to as "cured material"). Look, a divalent aliphatic group having a carbon number of 1 to 6 or [-(CH2) a-0-(CH2) b-]c (a and b each independently represent an integer of 1 to 5, and c represents 1 to 3; In the case of an integer), it is preferably a divalent aliphatic group having 2 to 4 carbon atoms or [-(CH2) a-0-(CH2) b-]c (a and b each independently represent an integer of 2 to 4, and c represents It is preferably 1 or 2), more preferably a divalent aliphatic group having 2 or 3 carbon atoms or -(CH2) 2-0-(CH2) 2-. In the above general formula (1), r2 represents a divalent aliphatic group having a linear or branched carbon number of 1 to 10, a divalent organic group having a carbon number of 3 to 10 having an alicyclic group, and a carbon having an aromatic ring. A divalent organic group of 6 to 30 or [-(CH2)d-0-(CH2)e-]f (however, d and e each independently represent an integer of 1 to 10, and f represents an integer of 1 to 5). 112 is a divalent aliphatic group having a carbon number of 1 to 6 from the viewpoint of the curability of the curable composition of the present invention and the balance between the hardness of the cured product obtained by curing the curable composition and the curling property. Or a divalent organic group having an aromatic ring having a carbon number of 6 to 30 or -34-201031694 (-(CH2) d-〇-(CH2)e-]f (d and e each independently represent an integer of 1 to 5, f An integer of 1 to 3 is preferable, and a divalent aliphatic group having a carbon number of 2 to 4, a divalent organic group having a carbon number of 6 to 30 of a benzene ring or [_(CH2)d-〇-(CH2) E-]f (d and e each independently represent an integer of 2 to 4, and f represents 1 or 2), preferably a divalent aliphatic group having 2 or 3 carbon atoms or -(CH2) 2-0- ( In the above formula (1), each of R3 and R4 is independently a hydrogen atom or a methyl group. From the viewpoint of hardenability at which φ is hardened at a low exposure amount, a hydrogen atom is preferred. When the (B) urethane compound is used as the curable composition, a cured product having excellent balance of surface hardness, transparency, and curling property can be obtained. That is, high quality of various products made of the cured product of the present invention can be achieved. Hardening of the invention The content of the (B) urethane compound in the composition 1 part by mass is preferably 10 to 99 parts by mass, preferably 20 to 99 parts by mass, more preferably 3 to 99 parts by mass. (B) Urea When the content of the compound is within the above range, a resin having excellent curability, pencil hardness, scratch resistance, curling property Φ, and balance between strength and flexibility can be obtained. The urea represented by the above general formula (1) used in the present invention The alkane compound may contain a polymerizable unsaturated group-containing alcohol compound represented by the following general formula (3) (hereinafter also referred to as "compound (1)"), and a polymerizable unsaturated group represented by the following general formula (4). The isocyanate compound (hereinafter also referred to as "compound (2)") is synthesized by contact. [Chemical 5]

-35- (4) 201031694 In the formula (3), Ri and R3 are the same as described above.

In the formula (4), R2 and R4 are the same as described above.

Examples of the compound (1) ' include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxyl group. Butyl (meth) acrylate and the like. These may be used alone or in combination of two or more. Preferred is 2-hydroxyethyl (meth) acrylate. In general, when R3 is a hydrogen atom, that is, when the compound (1) has an acrylate structure, and the ratio R3 is a methyl group, that is, when the compound (1) has a methacrylate structure, the resulting sulfamate-containing compound has curability. The hardenability of the composition tends to be better. Further, the description of "(meth) acrylate" in the present specification means methacrylate and/or acrylate. R2 of 〇CN-R2- of the isocyanate compound having one or more unsaturated groups in the molecule represented by the formula (4) is the same as R2 in the compound represented by the above general formula (1), but as 〇CN-R2- Specific examples thereof include the following (a) to (e) and the like. 〔化7〕 la) —(CHj)

CO * &lt;b) —(CH2), JCH2 (—

•NCO &lt;c) NCO-卜一 * -36- 201031694 (e) —{•{CHJi—0-)^-

❹ In the above formula, * is a structure containing an isocyanato group 'hydrogen, a (meth) propylene group, a hydrocarbon group, or an aromatic ring. Each * can be the same or different. (a) is a structure containing a divalent saturated aliphatic group having a linear or branched structure, an alicyclic group or an aromatic ring, and h is a part of the portion from which the isocyanate group is removed, and is an integer satisfying the condition of 1 or more and 1 Torr or less. . (b) is a structure containing a divalent saturated aliphatic group, an alicyclic group or an aromatic ring having a linear or branched structure, and the number of carbons in the portion where 1 is an isocyanate group is an integer satisfying the condition of 1 or more and 10 or less. (c) The structure in which the ring of the ring is used as the main skeleton, and the carbon number of the portion from which the isocyanate group is removed is 6 or more and 10 or less. (d) is a structure in which a benzene ring is used as a main skeleton. The carbon number of the portion from which the isocyanate group is removed is 6 or more and 1 or less. (e) is a structure having an acid skeleton. The number of carbon atoms in the portion where the isocyanate group is removed is an integer satisfying the condition of 1 or more and 100 or less. In the above general formula (4), 'R4 is a hydrogen atom or a methyl group' is preferably a hydrogen atom. Preferred specific examples of the above compound (2) are shown below. Examples of the structure having the above (a) include 2-(meth)acryloxyethyl isocyanate, 3-(meth)acryloxypropyl isocyanate, and 4-(methyl)propene. Butyl butyl isocyanate, 5-(methyl) propyl decyl pentyl isocyanate, 6-(methyl) propylene methoxy hexyl isocyanate, 2-(methyl) propylene methoxy propyl isocyanate, 1 , 1-bis(acryloxymethyl)-37- 201031694 ethyl isocyanate, as the structure having the above (b), 3-isocyanyl-2-methylpropyl (meth)acrylic acid The ester, as the structure having the above (c), may be exemplified by 3-isocyanylcyclohexyl (meth) acrylate or 4-isocyanatocyclohexyl (meth) acrylate. The structure of the structure is exemplified by 3-isocyanatophenyl (meth) acrylate, 4-isocyanatophenyl (meth) acrylate, 3,5-diisocyanato group _ 2- Methylphenyl (meth) acrylate, as the structure which has the said (e), is 2-(isocytyl ethoxy) ethyl (meth) acrylate. In general, when R4 is a hydrogen atom, that is, the compound (2) has a propylene carbonate structure, and when the ratio R4 is a methyl group, that is, the compound (2) has a methacrylate structure, the obtained urethane is contained. The curability of the curable composition of the compound tends to be more excellent. The molar ratio when the above compound (1) is reacted with the compound (2) is the compound (1): the compound (2) = 1 : 1 to 1: 1.5. When the above compound (1) is reacted with the above compound (2), it is preferred to use a urethanized catalyst. By using a urethane catalyst, the reaction can be significantly accelerated. Specific examples of the urethanization catalyst include dibutyltin dilaurate, copper naphthalate, cobalt naphthalate, zinc naphthalate, triethylamine, and 1,4-diazabicyclo[2.2.2] Octane, 2,6,7-trimethyl-1,4-diazabicyclo[2.2_2]octane, and the like. These urethane catalysts may be used singly or in combination of two or more. The amount of the urethane-catalyzed catalyst to be added is preferably 0.01 to 5 parts by mass, preferably 0.1 to 1 part by mass, per 100 parts by mass of the compound (2). When the amount is less than 0.01 parts by mass, the reactivity may be lowered. On the other hand, -38- 201031694, when the amount is more than 5 parts by mass, a side reaction may occur during the reaction. The reaction temperature in the reaction of the above compound (1) with the compound (2) is preferably -10 to 100 ° C, more preferably 〇 to 60 ° C. Very good for 10~30 °C. The above reaction can be carried out in hexane containing BHT (2,6-di-t-butyl-4-methylphenol). The hexane containing BHT can be used as a washing solvent immediately after the completion of the reaction. Therefore, the environmental load can be reduced when the above reaction is carried out. The BHT content in the BHT-containing hexane at this time is 1 to 10,000 ppm, preferably 50 to 500 ppm', more preferably 1 to 400 ppm. When the reaction is carried out under the above-mentioned amount ratio and temperature conditions, the side reaction can be suppressed, and the (B) urethane compound can be obtained in a good yield and purity. Further, since the reaction can be carried out in the vicinity of room temperature, the possibility of polymerization of (B) urethane compounds can be reduced. ((C) (meth) acrylate> The (meth) acrylate (C) having an ethylenically unsaturated group and having a lipid • ring structure in the curable composition has an effect of reducing shrinkage at the time of hardening The shape followability of the model can be improved during the formation, and examples thereof include cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, and dicyclopentyl (meth) acrylate. Dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, borneol (meth) acrylate, isobornyl (meth) acrylate, tricyclodecyl ( Rings such as methyl) acrylate, adamantyl (meth) acrylate, dicyclopentyl di(meth) acrylate, tricyclodecane dimethanol diacrylate, and adamantyl di(meth) acrylate Alkyl (meth) acrylate-39- 201031694 class. In the above-exemplified (meth) acrylate, 'having two ethyl septic unsaturated groups from the viewpoint of the shape followability of the metal mold Methyl) acrylate is preferred as dicyclopentyldi(a) The propyl acrylate is the most preferable. The alicyclic structure is a structure in which a carbon atom is bonded to a cyclic structure and the aromatic ring structure is removed. The (meth) acrylate used in the curable composition (c) The amount of the combination is preferably from 5 to 400 parts by mass, preferably from 10 to 200 parts by mass, more preferably from 20 to 100 parts by mass per 100 parts by mass of the cerium oxide microparticles (A) before the surface treatment. When the amount of the compound is less than 5 parts by mass, the shape followability of the metal mold is lowered. When the amount exceeds 400 parts by mass, the adhesion to the substrate is lowered, and 'use as the silica sand fine particles (A When the cerium oxide fine particles dispersed in the organic solvent, the mass of the cerium oxide fine particles (A) indicates the mass of only the cerium oxide fine particles dispersed in the organic solvent. ® <(D) polymerization initiator> The polymerization initiator (D) used for the curable composition is exemplified by a photopolymerization initiator which generates a radical and a thermal polymerization initiator. As the photopolymerization initiator, for example, benzophenone is mentioned. Benzoin methyl ether, benzoin propyl ether , diethoxyacetophenone, 1-hydroxy-phenyl phenyl ketone, 2,6-dimethylbenzimidyl diphenylphosphine oxide, 2,4,6-trimethylbenzylidene Diphenylphosphine oxide and diphenyl-(2,4,6-trimethylbenzone-40-201031694 mercapto)phosphine oxide. These photopolymerization initiators can also be used in more than two types. The content of the curable composition in the polymerization initiator may be an amount which can only moderately cure the curable composition. It is preferably 0.01 to 10 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the curable composition. It is 2 to 5 parts by mass, more preferably 0.1 to 2 parts by mass. When the amount of the photopolymerization initiator is too large, the storage stability of the curable composition is lowered, or colored, or crosslinked. Crosslinking at the time of hardening is rapidly progressed, causing problems such as splitting φ at the time of hardening. Further, when the amount of the photopolymerization initiator added is too small, the curable composition cannot be sufficiently cured. Examples of the thermal polymerization initiator include benzammonium peroxide, diisopropyl peroxycarbonate, t-butylperoxy (2-ethylhexanoate), and the like. The content of the curable composition of the thermal polymerization initiator is preferably 2 parts by mass or less, and preferably 0.1 to 2 parts by mass, per 100 parts by mass of the curable composition. In addition, the curable composition used in the present invention may contain a flattening agent, an antioxidant, an ultraviolet absorber, a solvent, or the like, as long as it does not impair the viscosity of the composition and the transparency and heat resistance of the cured product. Fillers such as pigments and other inorganic materials, reactive diluents, other modifiers, and the like. As the pingping agent, for example, a polyether-denatured dimethyl polyoxyalkylene copolymer, a polyester-denatured dimethyl polyoxyalkylene copolymer, and a polyether-denatured methyl alkyl polyoxyalkylene copolymer are exemplified. And aralkyl modified methyl alkyl polyoxyalkylene copolymer, polyether modified methyl alkyl polyoxyalkylene copolymer, and the like. Examples of the chelating agent or pigment include calcium carbonate, talc, mica, clay, Aerosil (registered trademark), barium sulfate 'aluminum hydroxide, stearic acid-41 - 201031694 zinc, zinc oxide, iron oxide, azo. Pigments, etc. The curable composition of the present invention containing such various components is generally 100 to 5000 mPa*s as measured by a cone-and-plate type viscometer DV-IIIULTRA (manufactured by BROOKFIELD Co., Ltd.), 25 ° C, and Spindle No. CP-41. Even if it does not contain a solvent, it has a low viscosity and good handleability. The reason for this is that the surface of the above-mentioned cerium oxide microparticles (A) is highly compatible with the urethane compound (B) and the (meth) acrylate (C) of the cerium oxide microparticle (A), and the urethane compound. High dispersion stability of the cerium oxide microparticles (A) in (B) and (meth) acrylate (C). <Method for Producing Curable Composition> The curable composition used in the present invention is, for example, a colloidal cerium oxide (cerium oxide fine particles (A)) dispersed in an organic solvent as a decane compound (E). a step of surface treatment (step 1), a step of uniformly mixing the urethane compound (B) and the (meth) acrylate (C) in the surface-treated cerium oxide microparticles (A), and a step of uniformly mixing (step 2), a step (step 3) of distilling and desolvating the organic solvent and water by a homogeneous mixture of the cerium oxide microparticles (A) obtained in the step 2 and the urethane compound (B) and the (meth) acrylate (C), In the step 3, the polymerization initiator (D) is added to the composition obtained by distillation and desolvation, and the mixture is uniformly mixed and then produced as a step of the curable composition (step 4). The steps are explained below. • 42- 201031694 (Step 1) In step 1, the cerium oxide microparticles (A) are surface-treated with a decane compound (E). In the surface treatment, the cerium oxide microparticles (A) are placed in the reactor, and the decane compound (E) is added while stirring, and the mixture is stirred and mixed, and water and a catalyst necessary for the hydrolysis of the decane compound are added. The decane compound is generally hydrolyzed by stirring, and the polycondensation of the cerium oxide microparticles (A) is carried out by condensation polymerization. Further, as the above-mentioned diox φ 矽 矽 fine particles (A), cerium oxide fine particles dispersed in an organic solvent are preferably used, as described above. Further, the disappearance of hydrolysis by the aforementioned decane compound can be confirmed by gas chromatography. By gas chromatography (Agilent type 6850), a non-polar column DB-1 (manufactured by J&amp;W) was used at a temperature of 50 to 300 ° C, and the temperature was raised at 10 ° C/min. When He is used as a carrier gas, the flow rate is 1.2 cc/min, and the residual ion amount Φ of the decane compound can be measured by an internal standard method under the flame ionization detector, so that the disappearance of hydrolysis by the decane compound can be confirmed. . Further, the amount of the decane compound (E) used in the surface treatment of the cerium oxide microparticles (A) as described above is generally 10 to 50 parts by mass for the bismuth dioxide microparticles (A) of 1 part by mass. Preferably, it is 20 to 40 parts by mass, more preferably 24 to 36 parts by mass. The lower limit 水 of the amount of water necessary for the hydrolysis reaction is 1 times the total number of moles of the alkoxy group and the hydroxyl group bonded to the decane compound (E), and the upper limit 値 is 10 times. When the amount of water is too small, the rate of hydrolysis will be extremely slow. 'Lack of economy, there is a concern that the surface treatment cannot be fully performed. Conversely, if '43-201031694 is too much water', the cerium oxide microparticles (A) may form a gel. When the hydrolysis reaction is carried out, a catalyst for the hydrolysis reaction is generally used. Specific examples of such a catalyst include inorganic acids such as hydrochloric acid, acetic acid, sulfuric acid, and phosphoric acid; and organic acids such as formic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, and maleic acid; An alkali catalyst such as potassium hydroxide, sodium hydroxide, calcium hydroxide or ammonia; an organic metal ♦ a metal alkoxide; an organic tin compound such as dibutyltin dilaurate, dibutyltin dioctanoate or dibutyltin diacetate; Aluminum ginseng (ethionyl pyruvate), titanium bismuth (acetyl acetonate), titanium bis (butoxy) bis (ethyl acetonate), titanium bis (isopropoxy) double (B Metal chelating compounds such as mercaptopyruvate, pin bis(butoxy)bis(ethyl phthalate), zirconium bis(isopropoxy) bis(ethyl phthalate); Boron compounds such as boric acid; Among them, hydrochloric acid, acetic acid, maleic acid, and boron compounds are preferred from the viewpoints of solubility in water and sufficient hydrolysis rate. These catalysts can be used alone or in combination of two or more. In the step 1, in the hydrolysis reaction of the decane compound (E), a water-insoluble catalyst can be used, but a water-soluble catalyst is preferably used. When a water-soluble catalyst for hydrolysis is used, it is preferred to dissolve the water-soluble catalyst in an appropriate amount of water -44-201031694 after it is added to the reaction system to uniformly disperse the catalyst. The amount of the catalyst to be used in the hydrolysis reaction is not particularly limited, and is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the cerium oxide fine particles (a). When the cerium oxide microparticles (A) are used as the cerium oxide microparticles dispersed in the organic solvent, the mass of the cerium oxide microparticles (A) described above indicates the mass of the cerium oxide microparticles themselves dispersed in the organic solvent.

The reaction temperature of the φ hydrolysis reaction is not particularly limited, but is generally in the range of 1 〇 8 (TC), preferably 20 to 50 ° C. When the reaction temperature is excessively low, the hydrolysis rate is extremely slow, and the economy is lacking. 'There is a concern that the surface treatment cannot be sufficiently performed. If the reaction temperature is too high, the gelation reaction tends to occur. Further, the reaction time for the hydrolysis reaction is not particularly limited, and is generally 10 minutes to 48 hours. Preferably, the range is from 30 minutes to 24 hours. φ (Step 2) Step 2, the method of mixing the surface treated cerium oxide microparticles (A) with the urethane compound (B) and the (meth) acrylate (C) Although it is not particularly limited, for example, a method of mixing by a mixer such as a stirrer, a bead honing machine, or a three-roller at room temperature or under heating, or continuous stirring in the reactor of the step 1 may be employed. A method in which a urethane compound (B) and a (meth) acrylate (C) are added and mixed. (Step 3) -45- 201031694 In step 3, the cerium oxide microparticles (A) and the urethane compound (B) are used. And (meth)acrylic acid When the organic solvent and the water are distilled off and desolventized (hereinafter collectively referred to as desolvation), it is preferred to heat the mixture in a reduced pressure. The temperature is preferably maintained at 20 to 100 ° C. The balance between the gelation prevention and the solvent removal speed is preferably 30 to 70 ° C, more preferably 30 to 50 ° C. If the temperature is excessively increased, the fluidity of the curable composition is extremely lowered, or the curable composition is The object will become gelatinous. @ Vacuum under reduced pressure is generally 10~4000kPa, to achieve the balance between desolvation speed and agglutination gelation prevention, more preferably 10~l〇〇〇kPa, optimally 10~ 50 OkP a. When the degree of vacuum is too large, the solvent removal rate is extremely slow and economical. The composition after solvent removal is preferably not substantially contained in the solvent. When the cured product is actually obtained, it is not necessary to pass the step of removing the solvent again. Specifically, the organic solvent and the residual amount of water in the curable composition are preferably 1% by mass or less, and more preferably 0.5% by mass. Hereinafter, it is more preferably 0.1% by mass or less. In the third step, before the solvent is removed, 0.1 part by mass or less of a polymerization inhibitor may be added to 1 part by mass of the composition after the solvent removal. The polymerization inhibitor is used in the solvent removal process or after solvent removal. In the storage of the composition and the curable composition, the polymerization reaction is prevented when the components contained in the composition are prevented. Examples of the polymerization inhibiting agent include hydroquinone, hydroquinone monomethyl ether, benzoquinone, and pt-butyl tea. Phenol, 2,6-di-t-butyl-4-methylphenol, etc., may be used in combination of one or two or more kinds. -46 - 201031694 Step 3 is that cerium oxide can be obtained in step 2. The uniform mixture of the microparticles (A) and the urethane compound (B) and the (meth) acrylate (C) is transferred to a sputum apparatus, and if the step 2 is carried out in the reactor of the step 1, the step can be carried out. 2 is then carried out in the reactor. (Step 4) In the step 4, the method of adding the polymerization initiator (D) to the solvent-decomposed composition in Step 3 and uniformly mixing is not particularly limited, for example, at room temperature by a stirrer or a bead mill. A method of mixing a mixer such as a mill or a three-roller or a method of adding the polymerization initiator (D) while stirring in a continuous manner in the reactors of the steps 1 to 3 may be mentioned. Further, the curable composition obtained by adding and mixing the polymerization initiator (D) can be filtered as necessary. This filtration is carried out for the purpose of removing foreign matter such as garbage in the hardening composition. The filtration method is not particularly limited, and a method of pressurizing filtration using a membrane having a pressure filtration pore size of 1. Ομιη, a filter type, and the like can be used. The curable composition used in the present invention can be produced by the above steps. The curable composition is treated with a specific decane compound by the cerium oxide fine particles (A) of the constituent component, and the viscosity is low and the workability is good even if the solvent is not contained. [Cured material] The curable composition used in the present invention is used as an optical lens, an optical lens molding type optical disk substrate, a liquid crystal display device, and a color filter for a color filter. A cured product used for a substrate, a plastic substrate for an organic EL display device, a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED sealing material. Among them, the hardening shrinkage ratio is small, and it can be used for various molding models, and is particularly suitable for use as a mold for use as an optical component such as a molded lens array. <Method for Producing Hardened Material> @ A hardened material can be obtained by curing the curable composition used in the present invention. As a curing method, there is a method of crosslinking an ethylenically unsaturated group of a urethane compound (B) and a (meth) acrylate (C) by irradiation with an active energy ray, and heating to thermally polymerize an ethylenically unsaturated group. The method, etc., these methods can also be applied. When the curable composition is cured by an active energy ray such as ultraviolet rays, in the above step 4, a photopolymerization initiator is contained in the curable composition. ❹ When the curable composition is heated and hardened, in the above step 4, the curable composition contains a thermal polymerization initiator. The cured product of the curable composition used in the present invention may be formed by applying a curable composition to a substrate such as a glass plate, a plastic plate, a metal plate or a tantalum wafer to form a coating film. The object is irradiated with an active energy ray or obtained by heating. For hardening, both the irradiation and heating of the active energy ray can be performed. Examples of the coating method of the curable composition include a bar coating-48-201031694 cloth applicator, an applicator, a slit applicator, a spin coater, an inkjet applicator, and a curtain coating method. Coating by a cloth, a roll coater, or the like, coating by a mesh coater or the like, coating by dipping or the like. The coating amount on the substrate of the curable composition used in the present invention is not particularly limited, and can be appropriately adjusted depending on the purpose. From the viewpoint of moldability, the film thickness of the coating film obtained by the treatment of the active energy ray irradiation and/or the heat treatment is preferably from 1 to 200 μm, preferably from 5 to ΙΟΟμηη. As the active energy ray used for hardening, it is preferred to use electron beams or light in the wavelength range from ultraviolet to infrared. As the light source, for example, an ultra-high pressure mercury light source or a metal halogen light source can be used as the ultraviolet light. For the visible light, a metal halogen light source or a halogen light source can be used, and if it is an infrared light, a halogen light source can be used, and other light sources such as lasers and LEDs can be used. The irradiation amount of the active energy ray should be set according to the type of the light source, the thickness of the coating film, etc., and preferably the reaction rate of the ethylenic unsaturated compound of the urethane compound (B) and the (meth) acrylate (C). It can be set to 80% or more, preferably 90% or more. Further, after the active energy ray is irradiated and hardened, it may be subjected to heat treatment (calcination treatment) as necessary and further cured. The heating temperature at this time is preferably in the range of 80 to 200 °C. The heating time is preferably in the range of 10 minutes to 60 minutes. When the curable composition used in the present invention is thermally polymerized by heat treatment during curing, the heating temperature is preferably in the range of 80 to 200 ° C, and -49 to 201031694 is preferably 100 to 15 ° °C. range. When the heating temperature is lower than 80 ° C, the heating time must be lengthened, so there is a lack of economy. If the heating temperature is higher than 200 ° C, energy costs will be incurred, and a longer heating and heating time and a cooling time are required. Therefore, there is a tendency to lack economics. The heating time can be appropriately set depending on the heating temperature, the film thickness of the coating film, etc., and the reaction rate of the ethylenically unsaturated group of the urethane compound (B) and the (meth) acrylate (C) is preferably set to 80%. In the above, it is preferably 90% or more, and the curable composition is cured by thermal polymerization, and may be further subjected to heat treatment (calcination treatment) if necessary. The heating temperature at this time is preferably in the range of 150 to 200 °C. The heating time is preferably in the range of 5 minutes to 60 minutes. <Cured material> The cured product of the curable composition used in the present invention has excellent transparency, hardenability, shape followability, and substrate adhesion, and is used for forming a mold used for forming optical components such as a lens array. It is better. Since the cured product has excellent transparency, the light transmittance at a wavelength of 400 nm at a thickness of 100 μm of the cured film is preferably 85 % or more. When the light transmittance at a wavelength of 400 nm is 85% or less, the efficiency of light utilization is lowered, so that the hardenability at the time of photohardening is impaired. When there is a lack of hardenability, the part which is in contact with the air cannot be hardened by oxygen resistance, so when the shape is not obtained or hardened, it is necessary to irradiate a large amount of light or the heating time becomes long, so from the viewpoint of productivity In the case of not being -50-201031694, since the cured product has excellent hardenability, when it is subjected to photohardening or thermal hardening in the air, it is not affected by oxygen and it is easy to obtain a cured product. The cured product is formed by applying a curable composition to a substrate such as glass, and the curable composition is in contact with the transfer body, and the curable composition is formed in a state in which the shape of the transfer body is deformed to form a curable composition. The object is obtained by hardening by light irradiation or the like, and the transfer shape forming the transfer body is transferred into a cured product. The cured product has excellent shape followability to the transfer body. Here, "excellent shape followability" of φ means that the shape of the transfer body is directly transferred as the shape of the cured material, and it is difficult to cause collapse or crack on the surface of the cured product. In the cured product, a curable composition is applied to a substrate such as glass, and the curable composition is in contact with the transfer member, and the curable property is irradiated by light irradiation in a state in which the shape of the transfer member is deformed and the curable composition is deformed. After the composition or the like is hardened, it is separated by the transfer body. When this separation is carried out, it is necessary to keep the substrate side adhered, but the cured product has excellent substrate adhesion. When the substrate Φ is inferior in adhesion, the cured product is removed from the transfer body side, and the cured product is peeled off from the substrate. Therefore, for example, the model used for molding the optical component may lose the function. [Embodiment] [Example 1] Hereinafter, the curable composition used in the present invention will be described in detail by way of examples, but the curable composition is not limited to the above, and is not limited to the following examples. _ _ _ _ _ Tert-butyl-4-methylphenol (BHT, manufactured by Pure Chemical Co., Ltd.) 200 ppm hexane (manufactured by Pure Chemical Co., Ltd.) 142 parts, dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.8 parts and stirred. Thereafter, 122 parts of 2-propenyloxyethyl isocyanate (trade name Calends (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.) was slowly dropped, and stirred at room temperature. Under the high-speed liquid chromatography, it was confirmed that the peak of 2-hydroxyethyl acrylate almost disappeared, and the reaction was terminated. Then, 203 parts of hexane containing 200 ppm of BHT was used, and the urethane compound (B-1) was obtained by washing four times. (Synthesis Example 2) <Uranane Compound (B-2)> In the synthesis example 1, 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd.) was used instead of 2-propenyloxyethyl isocyanate. The urethane compound (B-2) was obtained in the same manner as in Synthesis Example 1 except for the trade name of Calends (registered trademark) MOI. [Preparation of curable composition] (Preparation Example 1) A isopropyl alcohol-dispersed colloidal cerium oxide was placed in a separate flask (di-52-201031694 cerium oxide content of 30% by mass, average particle diameter 丨〇~ 20 nrn, trade name Snow-TechIPA-ST; manufactured by Nissan Chemical Co., Ltd.), 100 parts by mass of 7-methacryloxypropyltrimethoxydecane in the separation flask, and stirred and mixed. The surface treatment of the cerium oxide microparticles was carried out by adding 9.2 parts by mass of a 0.1825 mass% HCl solution and stirring at 24 ° C for 24 hr. Further, 'the disappearance of the water φ solution by r-methacryloxypropyltrimethoxydecane' was confirmed by gas chromatography (Agilent's model 68 5 0). Using a non-polar column DB-1 (manufactured by J &amp; W) at a temperature of 50 to 300 ° C 'temperature rising rate l 〇 ° C / min, using He as a carrier gas, flow rate 1.2 cc / min, flame The internal standard method was used for the measurement under the Flame ionization detector. The methacryloxypropyltrimethoxydecane disappeared after 8 hours from the addition of the above HCl solution. Next, the surface-treated cerium oxide microparticles are added to the urethanization compound (B-1) 22.0 parts by mass and dicyclopentadienyl diacrylate (trade name lamp acrylate DCP-A; Kyoeisha Chemical Co., Ltd. (Stock)) 14.7 parts by mass and uniformly mixed. Thereafter, while stirring, it was 40. (:, the pressure-reduction heating was carried out at 10 kPa to remove the volatile component. The removal amount of the volatile component was 72.0 parts by mass. In 76.6 parts by mass of the mother liquid obtained by removing the volatile matter, it was dissolved as a photopolymerization initiator. D1173 (trade name: DAROCURE 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.766 parts by mass and MBF (Methylbenzhydryl-53-201031694 formate manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: DAROCURE MBF) 1.532 parts by mass of a transmembrane filter (aperture Ι.ΟμπΟ pressure filtration (pressure 0.2 MPa) gave a curable composition 1. The viscosity of the curable composition 1 was 3700 mPa a · s ° (Preparation Example 2) In the preparation example 1, the curable composition 2 was obtained in the same manner as in Preparation Example 1 except that the urethane compound (B-1) was used instead of the urethane compound (B-1). The viscosity of the curable composition 2 was 3 3 . 00mPa·S. _ (Comparative Preparation Example 1) In the preparation example 1, in place of the urethane compound (B-1), ethylene oxide-modified trimethylolpropane triacrylate (product of Osaka Organic Chemical Co., Ltd.) was used. In the same manner as in Modification Example 1, except for the name Bis-coat #3 60 ) 3. The composition of the hard actinic curable composition viscosity of 3 to 3 OOOmP a · S.

(Comparative Preparation Example 2) In the same manner as in Preparation Example 1, except for the urethane compound (B-1), the ethyl adamantyl acrylate (trade name: EtADA, manufactured by Osaka Organic Chemical Co., Ltd.) was used. The curable composition 4 was obtained. The viscosity of the hardening composition 4 was 4,100 mPa·s. The composition of each component used in the preparation of the curable composition described above is shown in Table 1 below. -54- 201031694 [Table 1] Preparation Example 1 Preparation Example 2 Comparative Preparation Example 1 Comparative Preparation Example 2 Curable Curable Curable Curable Composition 1 Composition 2 Composition 3 Composition 4 Composition of Colloidal Ceria 100.0 100.0 100.0 100.0 7 -Methyl propyl oxypropyltrimethoxy decane (MPS) 9.0 9.0 9.0 9.0 0.05NHC1 solution 2.9 2.9 2.9 2.9 urethane compound B-1 22.0 - - - urethane compound B-2 - 22.0 - - Ethylene oxide to trimethylolpropane triacrylate - 22.0 - Ethyl adamantane acrylate. - 22.0 Dicyclopentadiene diacrylate 14/7 14.7 14.7 14.7 [Modification of hardened film] <Activity Energy ray hardening> In the examples and comparative examples, the curable composition was applied to a respective glass substrate (50 mm x 50 mm), and the thickness of the cured film was ΙΟΟμηη, and 4 J/cm 2 was carried out under an exposure apparatus equipped with an ultrahigh pressure mercury lamp. Exposure and hardening of the film. [Performance Evaluation Method] <Transmittance> The light transmittance of the obtained cured film having a wavelength of 400 nm was measured in accordance with JIS-K7105 using a spectrophotometer (UV3100 manufactured by JASCO Corporation). The results are shown in Table 2. It is a cured film having a higher transmittance and a higher transparency. Further, the total light transmittance of the obtained cured film was measured using a color turbidity meter (COH 4 00 manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 2. It is that the greater the total light transmittance, the better the transparency -55-201031694 cured film. <Shape Followability> As shown in FIG. 3, the above-described curable composition is injected onto the wafer W using an injection device, and the curable composition is brought into contact with the transfer member 62 to bring the convex portion 90 into contact with the photocurable composition. The exposure was performed at 4 J/cm 2 under an exposure apparatus equipped with an ultrahigh pressure mercury lamp and hardened. Thereafter, the transfer body 62 is separated from the wafer W. The above operation was repeated 1 time to obtain a cured product which was transferred by the shape of one transfer body 62. The shape of the one hardened material was evaluated by an optical microscope to evaluate the presence or absence of cracks or cracks. The evaluation criteria are shown below, and the results are shown in Table 2. A: Completely free of gussets and cracks. B: No breaks occurred. The frequency of cracks is 90/1 00 or more. C: No breaks occurred. The frequency of cracks is 50/100 or more and less than 90/100 D: not produced. The frequency of the break and the crack is less than 50/100. <Substrate Adhesion> As shown in FIG. 3, the curable composition is injected onto the wafer W using an injection device, and the curable composition is contacted with the transfer body 62. The convex portion 90 was brought into contact with the photocurable composition, and exposed to 4 J/cm 2 under an exposure apparatus equipped with an ultrahigh pressure mercury lamp. Thereafter, the transfer body 62 is separated from the wafer W. The above operation was repeated 100 times. When the transfer body 62 is separated from the wafer W, if the substrate adhesion of the cured product is poor, the hard material adheres to the transfer body 62 side and is peeled off by the wafer W. The results obtained by evaluating the number of wafers W in the 100 hardened materials -56-201031694 as the substrate adhesion are shown in Table 2. For example, 90 out of 100 when the wafer W is dense ’ represents the evaluation result of 90/1 00. <Curing and shrinking ratio> A resin solution was applied onto a tantalum wafer by a spin coater method. The coated substrate was measured by an optical film thickness meter. This film thickness was made into the initial film thickness. Thereafter, exposure was carried out under a nitrogen atmosphere to form a cured film, and the film thickness was measured in the same manner. This film thickness was made into the film thickness after exposure. The hardening shrinkage ratio was determined by the following formula. Further, the measurement was carried out at 5 places and the average enthalpy was calculated. (Initial film thickness - film thickness after exposure) / initial film thickness χΐ 00 <%> [Table 2] Preparation Example 1 Preparation Example 2 Comparative Preparation Example 1 Comparative Preparation Example 2 Curable Composition 1 Curable Composition 2 Curable Composition 3 The 400 nm transmittance of the cured composition 4 cured product. /〇 91 90 91 90 Total light transmittance of hardened material % 93 92 93 93 Shape followability B A C D Substrate adhesion 100/100 100/100 100/100 84/100 Hardening shrinkage 〇/〇 5.65 5.50 -

As is apparent from Table 2, the curable compositions of Modification Examples 1 and 2 have excellent shape followability, substrate adhesion, and transparency, and thus can be applied to molding of a mold used for molding optical components such as a lens array. -57-201031694 On the other hand, the curable composition of the comparative example 1 has excellent substrate adhesion and transparency, but the shape followability is inferior, and collapse or cracking is caused, which is not preferable. Further, although the curable composition of the preparation example 2 has excellent transparency, shape followability and substrate adhesion are inferior, and peeling of the substrate occurs, and even if it is adhered to the substrate, collapse or crack occurs. Not good. (Embodiment © Using the curable compositions 1 and 2 produced by the methods shown in Preparation Examples 1 and 2 of the above-described curable composition, the steps shown in Figs. 10, 11 and 12 can be obtained. A model for forming a good lens array and a lens. In particular, the shape of the model used for forming the lens is good in shape followability and substrate adhesion. [Industrial Applicability] As described above, the present invention is applicable. For example, a lens such as a lens array having a lens portion formed by an aspherical shape, or a shape forming method such as a model used for forming such a lens is formed. [Simplified description of the drawing] [Fig. 1] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1(a) is a plan view and FIG. 1(b) is a left side view. FIG. 2 is a view showing a first embodiment of the present invention. A partial cross-sectional view of the ink-58-201031694 and the wafer. [Fig. 3] shows a modification of the step of injecting the photo-curable composition onto the hole formed in the wafer used in the first embodiment of the present invention. An illustration of an example. [Fig. 4] A partial cross-sectional view showing a first modification of the transfer body and the wafer used in the first embodiment of the present invention. [Fig. 5] shows a transfer body φ used in the first embodiment of the present invention. And a partial cross-sectional view of a second modification of the wafer. Fig. 6 is a block diagram showing a control device used in the forming device according to the first embodiment of the present invention. [Fig. 7] shows a first embodiment of the present invention. Fig. 8 is a first flowchart showing a transfer operation of the forming device according to the first embodiment of the present invention. Fig. 9 shows a first embodiment of the present invention. Fig. 10 is a second flowchart showing the transfer operation of the forming device according to the first embodiment of the present invention. Fig. 11 is a view showing the first aspect of the present invention. Fig. 12 is an explanatory view showing a procedure of a lens manufacturing method according to a second embodiment of the present invention. [Description of main component symbols] -59- 201031694 1 〇: Shaped equipment Setting 14: Support table 1 8 : Drive source 24: Movable table 3 2 : Y-axis motor 34 : Clamp motor 3 6 : Supply device 44 : Movable unit _ 5 6 : X-axis motor 60 : Light irradiation device 62 : Transfer Body 64: Z-axis motor 68 for supporting member: Optical fiber 70: Light source 72: Detection device 74: Photographing unit © 76: Lens unit 90: Projection 2 0 0: Control device 2 04: Main control unit 3 0 0 : Model 3 04 : lens array 3 1 0 : cemented lens array 3 1 2 : lens portion - 60 - 201031694 3 14 : lens W : wafer W 1 : substrate W2 : holding plate h 1 : through hole h2 : hole

Claims (1)

201031694 VII. Patent application scope: 1. A forming method which has a deformation step of causing a shaped object to be in contact with a transfer body forming a transfer shape to deform a shaped object in accordance with the transfer shape, a hardening step of hardening at least a deformed portion of the shaped object, and a separating step of separating the shaped object from the front transfer member, and repeating the forming of the transfer step of transferring the transfer shape to the shaped object a plurality of times The method is characterized in that the object to be formed is composed of a curable composition containing a urethane compound having a polymerizable functional group and a polymerization initiator. 2. The method according to the first aspect of the invention, wherein the hardening composition is (A) cerium oxide microparticles, (B) a urethane compound represented by the following general formula (1), [Chem. 1] (wherein R! represents a divalent aliphatic group having a linear or branched carbon number of 1 to 12, a divalent organic group having a carbon number of 3 to 12 having an alicyclic group, and a carbon number of 6 to 30 having an aromatic ring; A divalent organic group or [-(CH2) a_〇_(Ch2) b_]^ (a and b each independently represent an integer of 1 to l〇, and c represents an integer of 1 to 5) R2 represents a straight chain or a branch a divalent aliphatic group having 1 to 10 carbon atoms, a divalent organic group having 3 to 10 carbon atoms having an alicyclic group, a 2-valent organic group having an aromatic ring of -62 to 201031694 and having a carbon number of 6 to 30 or [- (CH2) d-〇-(cH2) e·]f (d and e each independently represent an integer of 1 to l〇 'f represents an integer of 1 to 5), and R3 and R4 are each independently a hydrogen atom or a methyl group) (C) (meth) acrylate having an ethylenically unsaturated group and having an alicyclic structure, and (D) a polymerization initiator "The aforementioned cerium oxide microparticles (A) are represented by the following general formula (2) The surface treatment of the decane compound (E); Φ [Chemical 2] R5 I H2C=C ——C—Ο1 (CH2). 1~SiRer(OR7)3„r (2) Ο (In the formula (2), R5 represents a hydrogen atom or a methyl group, and R6 represents an alkyl group having a carbon number of 1 to 3 or a phenyl group. R7 represents a hydrogen atom or a carbon number of 1 The hydrocarbon group 'q represents an integer of 1 to 6, and r represents an integer of 0 to 2.) 3. The method of forming the second aspect of the patent application, wherein the (φ meth) acrylate (C) has 2 ethylene 4. The method for forming a shape according to the second or third aspect of the patent application, wherein the cerium oxide microparticle (A) is 1 for the mass fraction of the cerium oxide microparticle (A) The method for forming a surface of the above-mentioned decane compound (E), wherein the viscosity of the hardening composition is 100 to 5, as described in any one of claims 1 to 4. 000mPa.s -63-