JP2012255914A - Curable composition for lens material, manufacturing method of lens, and lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for lens material which is dissolved in various (meth) acrylic monomers and has a higher refractive index than those of the conventional acrylic compounds.SOLUTION: A curable composition for lens material contains (A) a compound represented by the general formula (1), and (B) a photoradical initiator, where in the general formula (1), X is a sulfur atom or an oxygen atom; Rare hydrogen atoms or (meth) acryloyl groups and at least one of them is the (meth) acryloyl group; and n is an integer of 0-2.

Description

  The present invention relates to a curable composition for a lens material, a method for producing a lens using the curable composition for a lens material, and a lens obtained by the production method.

  Precisely processed lenses are used in camera modules mounted on mobile phones and modules such as optical disk pickups. Conventionally, glass is the main material for such a lens, but from the viewpoint of cost, a lens made of resin such as PMMA or a lens formed by combining this with a glass lens has come to be used. I came. For example, Patent Document 1 discloses a lens using a photosensitive resin and a manufacturing method thereof.

  Further, the optical accuracy required for these lenses is increasing, and materials having excellent optical characteristics such as refractive index, environmental resistance, and temperature stability have been developed. For example, Patent Document 2 discloses a resin composition in which a compound having a 9,9-bisphenylfluorene skeleton and a sulfur compound are combined.

JP-A-2005-070107 JP 2005-187661 A

An acrylic compound having a bisphenylfluorene skeleton is known as an acrylic material having a high refractive index. However, a derivative of an acrylic compound having a bisphenylfluorene skeleton has a high refractive index but a very high viscosity, and the use of a dilution monomer is essential. As a result, there is a problem that the refractive index of a practical composition is lowered, which is unsuitable for solventless materials.
Then, an object of this invention is to provide the curable composition for lens materials which has high refractive index compared with the conventional acrylic compound while melt | dissolving in various (meth) acrylic monomers.

（上記一般式（１）中、Ｘは硫黄原子、又は酸素原子である。Ｒ^１は水素原子、又は（メタ）アクリロイル基であり、かつ、複数存在するＲ^１のうち、少なくとも１つは（メタ）アクリロイル基である。Ｒ^２はフェニル基、ナフチル基、又はビフェニル基である。Ｒ^３は水素原子、炭素数１〜４のアルキル基、またはアリール基である。一般式（１）及びＲ^１〜Ｒ^３中の水素原子は、塩素原子、臭素原子、ヨウ素原子、シアノ基、または炭素数１〜４のアルキル基で置換されていてもよい。一般式（１）中に各々複数存在するＸ、Ｒ^１、Ｒ^２、及びＲ^３はそれぞれ異なっていても同じでもよい。ｎは０〜２の整数である。）
［２］ 前記一般式（１）中、Ｘが酸素原子、Ｒ^１がアクリロイル基またはメタクリロイル基であり、かつ、ｎが０または１である、前記［１］に記載のレンズ材用硬化性組成物。
［３］ さらに、（Ｃ）反応性希釈剤を含有する、前記［１］または［２］に記載のレンズ材用硬化性組成物であって、（Ｃ）成分が分子内に（メタ）アクリロイル基を１〜４個有する、前記（Ａ）成分以外の液状の（メタ）アクリレートであるレンズ材用硬化性組成物。
［４］ 前記（Ｃ）成分が、分子内に芳香族環を有する、前記［３］に記載のレンズ材用硬化性組成物。
［５］ 前記（Ｃ）成分が、下記一般式（２）〜（６）のいずれかで表される化合物である、前記［３］または［４］に記載のレンズ材用硬化性組成物。

（上記一般式（２）〜（６）中、ｉ、ｊ、ｋ、ｌ、ｍは、それぞれ０〜２の整数である。）
［６］ 前記（Ａ）成分を２０〜９９．５質量％含有する、前記［１］〜［５］のいずれかに記載のレンズ材用硬化性組成物。
［７］ 溶媒の含有量が１．０質量％未満である、前記［１］〜［６］のいずれかに記載のレンズ材用硬化性組成物。
［８］ 前記［１］〜［７］のいずれかに記載のレンズ材用硬化性組成物を硬化させて得られる硬化物。
［９］ 光を透過する透明樹脂製の透明型を含む複数の成形型によって形成されたキャビティーに、未硬化の前記［１］〜［７］のいずれかに記載のレンズ材用硬化性組成物を注入する注入工程と、前記透明型を介して前記レンズ材用硬化性組成物に光を照射して、レンズ材用硬化性組成物を前記キャビティー内で硬化させる硬化工程と、を含む、レンズの製造方法。
［１０］ 前記［９］に記載の方法によって製造されたレンズ。
［１１］ 前記［１０］に記載のレンズを備えた撮像装置。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a curable composition for a lens material containing a compound having a specific structure and a photo radical initiator, The present invention has been completed.
That is, the present invention provides the following [1] to [11].
[1] A curable composition for lens materials, comprising (A) a compound represented by the following general formula (1) and (B) a photoradical initiator.

(In the above general formula (1), X is a sulfur atom or an oxygen atom. R ¹ is a hydrogen atom or a (meth) acryloyl group, and at least one of the plurality of R ¹ is ( A meta) acryloyl group, R ² is a phenyl group, a naphthyl group, or a biphenyl group, and R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. The hydrogen atoms in ^{1 to} R ³ may be substituted with a chlorine atom, a bromine atom, an iodine atom, a cyano group, or an alkyl group having 1 to 4 carbon atoms, each of which is present in the general formula (1). X, R ¹ , R ² and R ³ may be different or the same, and n is an integer of 0 to 2.)
[2] The curable composition for a lens material according to [1], wherein, in the general formula (1), X is an oxygen atom, R ¹ is an acryloyl group or a methacryloyl group, and n is 0 or 1. object.
[3] The curable composition for a lens material according to [1] or [2], further comprising (C) a reactive diluent, wherein (C) component is (meth) acryloyl in the molecule. The curable composition for lens materials which is liquid (meth) acrylates other than the said (A) component which has 1-4 groups.
[4] The curable composition for lens materials according to [3], wherein the component (C) has an aromatic ring in the molecule.
[5] The curable composition for lens materials according to [3] or [4], wherein the component (C) is a compound represented by any one of the following general formulas (2) to (6).

(In the general formulas (2) to (6), i, j, k, l, and m are each an integer of 0 to 2.)
[6] The curable composition for a lens material according to any one of [1] to [5], containing 20 to 99.5% by mass of the component (A).
[7] The curable composition for lens materials according to any one of [1] to [6], wherein the content of the solvent is less than 1.0% by mass.
[8] A cured product obtained by curing the curable composition for lens materials according to any one of [1] to [7].
[9] The curable composition for a lens material according to any one of [1] to [7], which is uncured in a cavity formed by a plurality of molds including a transparent resin transparent mold that transmits light. An injection step of injecting an object, and a curing step of irradiating the lens material curable composition with light through the transparent mold to cure the lens material curable composition in the cavity. , Manufacturing method of lens.
[10] A lens manufactured by the method according to [9].
[11] An imaging apparatus including the lens according to [10].

  The curable composition for a lens material of the present invention dissolves in various (meth) acrylic monomers and has a high refractive index and excellent transparency compared to conventional acrylic compounds. It is useful as a solvent-based acrylic resin composition.

It is a figure which shows the NMR spectrum of the compound obtained by the synthesis example. It is a figure which shows typically an example of embodiment of the shaping | molding die used for the manufacturing method of a lens. It is a figure which shows typically a part of embodiment of the process of the manufacturing method of a lens. It is a figure which shows typically a part of embodiment of the process of the manufacturing method of a lens. It is a figure which shows typically a part of embodiment of the process of the manufacturing method of a lens. It is a figure which shows typically an example of embodiment of the modeling apparatus used for the manufacturing method of a lens. It is a figure which shows typically an example of embodiment of the transfer body used for the manufacturing method of a lens. It is a figure which shows typically a part of embodiment of the manufacturing method of a lens.

（上記一般式（１）中、Ｘは硫黄原子、又は酸素原子である。Ｒ^１は水素原子、又は（メタ）アクリロイル基であり、かつ、複数存在するＲ^１のうち、少なくとも１つは（メタ）アクリロイル基である。Ｒ^２はフェニル基、ナフチル基、又はビフェニル基である。Ｒ^３は水素原子、炭素数１〜４のアルキル基、またはアリール基である。一般式（１）及びＲ^１〜Ｒ^３中の水素原子は、塩素原子、臭素原子、ヨウ素原子、シアノ基、または炭素数１〜４のアルキル基で置換されていてもよい。一般式（１）中に各々複数存在するＸ、Ｒ^１、Ｒ^２、及びＲ^３はそれぞれ異なっていても同じでもよい。ｎは０〜２の整数である。）
上記一般式（１）中、Ｘは酸素原子が好ましい。Ｒ^１は反応性の観点から、好ましくはアクリロイル基、又はメタクリロイル基であり、より好ましくはアクリロイル基である。この場合、複数のＲ^１のうちアクリロイル基及びメタクリロイル基が占める割合は通常３０％以上、好ましくは４０％以上、より好ましくは５０％以上であり、残るＲ^１は水素原子である。Ｒ^２は好ましくはフェニル基またはビフェニル基であり、より好ましくはビフェニル基である。ビフェニル基は２−ビフェニル基、３−ビフェニル基、４−ビフェニル基の何れでもよく、ナフチル基は１−ナフチル基、２−ナフチル基の何れでもよい。
一般式（１）及びＲ^１〜Ｒ^３中の水素原子は、塩素原子、臭素原子、ヨウ素原子で置換されていてもよく、屈折率の観点から臭素原子が好ましい。また、一般式（１）中の芳香族環上の水素原子はシアノ基、エチル基、メチル基、プロピル基、イソプロピル基で置換されていることが好ましく、屈折率の観点からシアノ基がより好ましい。ｎは０又は１が好ましい。 The curable composition for a lens material of the present invention contains (A) a compound represented by the following general formula (1) and (B) a photo radical initiator.

(In the above general formula (1), X is a sulfur atom or an oxygen atom. R ¹ is a hydrogen atom or a (meth) acryloyl group, and at least one of the plurality of R ¹ is ( A meta) acryloyl group, R ² is a phenyl group, a naphthyl group, or a biphenyl group, and R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. The hydrogen atoms in ^{1 to} R ³ may be substituted with a chlorine atom, a bromine atom, an iodine atom, a cyano group, or an alkyl group having 1 to 4 carbon atoms, each of which is present in the general formula (1). X, R ¹ , R ² and R ³ may be different or the same, and n is an integer of 0 to 2.)
In the general formula (1), X is preferably an oxygen atom. From the viewpoint of reactivity, R ¹ is preferably an acryloyl group or a methacryloyl group, more preferably an acryloyl group. In this case, the proportion of the acryloyl group and methacryloyl group in the plurality of R ¹ is usually 30% or more, preferably 40% or more, more preferably 50% or more, and the remaining R ¹ is a hydrogen atom. R ² is preferably a phenyl group or a biphenyl group, and more preferably a biphenyl group. The biphenyl group may be any of 2-biphenyl group, 3-biphenyl group, and 4-biphenyl group, and the naphthyl group may be any of 1-naphthyl group and 2-naphthyl group.
Hydrogen atom in the general formula (1) and in R ¹ to R ³ is a chlorine atom, a bromine atom, may be substituted by an iodine atom, a bromine atom are preferable from the viewpoint of refractive index. The hydrogen atom on the aromatic ring in the general formula (1) is preferably substituted with a cyano group, an ethyl group, a methyl group, a propyl group, or an isopropyl group, and a cyano group is more preferable from the viewpoint of refractive index. . n is preferably 0 or 1.

  Specific examples of the compound represented by the general formula (1) include 9,9-bis [4- (3-phenyloxy-2-acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [ 4- (3-phenyloxy-2-methacryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [4- (3-naphthyloxy-2-acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [ 4- (3-naphthyloxy-2-methacryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [4- (3-biphenyloxy-2-acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [ 4- (3-Biphenyloxy-2-methacryloyloxypropyloxy) phenyl] fluorene 9,9-bis [4- (3-phenylthio-2-acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [4- (3-phenylthio-2-methacryloyloxypropyloxy) phenyl] fluorene, 9-bis [4- (3-naphthylthio-2-acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [4- (3-naphthylthio-2-methacryloyloxypropyloxy) phenyl] fluorene, 9,9- Bis [4- (3-biphenylthio-2-acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [4- (3-biphenylthio-2-methacryloyloxypropyloxy) phenyl] fluorene, 9- [4 -(3-Phenyloxy-2-acryloyloxypropyloxy) ) Phenyl] -9- [4- (3-phenyloxy-2-hydroxypropyloxy) phenyl] fluorene, 9- [4- (3-phenyloxy-2-methacryloyloxypropyloxy) phenyl] -9- [4 -(3-phenyloxy-2-hydroxypropyloxy) phenyl] fluorene, 9- [4- (3-biphenyloxy-2-acryloyloxypropyloxy) phenyl] -9- [4- (3-biphenyloxy-2) -Hydroxypropyloxy) phenyl] fluorene, 9- [4- (3-biphenyloxy-2-methacryloyloxypropyloxy) phenyl] -9- [4- (3-biphenyloxy-2-hydroxypropyloxy) phenyl] fluorene , 9- [4- (3-naphthyloxy-2-acryloyloxypro) Pyroxy) phenyl] -9- [4- (3-naphthyloxy-2-hydroxypropyloxy) phenyl] fluorene, 9- [4- (3-naphthyloxy-2-methacryloyloxypropyloxy) phenyl] -9- [ 4- (3-naphthyloxy-2-hydroxypropyloxy) phenyl] fluorene and the like, among which 9,9-bis [4- (3-phenyloxy-2-acryloyloxypropyloxy) phenyl] fluorene, 9-bis [4- (3-naphthyloxy-2-acryloyloxypropyloxy) phenyl] fluorene and 9,9-bis [4- (3-biphenyloxy-2-acryloyloxypropyloxy) phenyl] fluorene are preferred.

In addition, compounds represented by the following formulas (7) to (14) can also be preferably used.

  (A) Content of a component becomes like this. Preferably it is 20-99.5 mass%, More preferably, it is 30-70.0 mass%. If it is less than 20% by mass, the refractive index is hardly increased, and the effects of the present invention may not be sufficiently obtained. When it exceeds 99.5 mass%, the compounding quantity of (B) component mentioned later decreases, there exists a possibility that the fluidity | liquidity of a composition may be low and processing may become difficult.

(B) It does not specifically limit as a radical photoinitiator, A commercially available thing can be used. The photo radical initiator is not particularly limited as long as it can generate radical active species by light. Examples of the photo radical initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (for example, those described in JP-A-2001-139663, etc. ), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins, etc. Can be mentioned. More specifically, examples of photocleavable photoradical polymerization initiators include Irgacure 184 and Irgacure 907 manufactured by BASF.
(B) As for content of a component, 0.1-10 mass% is preferable.

（上記一般式（２）〜（６）中、ｉ、ｊ、ｋ、ｌ、ｍは、それぞれ０〜２の整数である。） Furthermore, the curable composition for lens materials of the present invention may contain (C) a reactive diluent. By including a reactive diluent, the viscosity and curability of the curable composition for lens materials can be adjusted, and the hardness of the resulting cured product can also be adjusted.
Here, the reactive diluent in the present invention is a liquid (meth) acrylate having 1 to 4 (meth) acryloyl groups in the molecule other than the component (A). Specific examples include phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, and thiophenoxyethyl acrylate.
Among these, from the viewpoint of refractive index, (meth) acrylate having an aromatic ring in the molecule is preferable, and any one of the following general formulas (2) to (6) as (meth) acrylate having an aromatic ring in the molecule. The compound represented by these can be illustrated. In this case, for the purpose of adjusting the viscosity of the curable composition for lens materials and the hardness of the resulting cured product, a non-aromatic compound may be included, but the content of the non-aromatic compound is 20 mass. % Or less is preferable.

(In the general formulas (2) to (6), i, j, k, l, and m are each an integer of 0 to 2.)

  The curable composition for a lens material of the present invention can be cured in a state where it is injected into a mold. Therefore, the curable composition for a lens material of the present invention is liquid, but preferably does not contain a solvent. Here, the solvent means a component that does not copolymerize with the component (A) or the component (C) and has a boiling point of 230 ° C. or less. When the amount of the solvent contained in the curable composition for a lens material of the present invention is large, there is a concern that the solvent volatilizes after being cured, thereby forming fine voids and lowering the refractive index. Therefore, content of the solvent contained in the curable composition for lens materials of this invention becomes like this. Preferably it is less than 1.0 mass%, More preferably, it is less than 0.5 mass%.

The curable composition for a lens material of the present invention may contain various additives in order to adjust the refractive index and the like. Such additives include titanium, zirconium, aluminum, indium, zinc, tin, and antimony having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less. The oxide (inorganic filler) of the at least 1 type of metal selected can be mentioned.
Furthermore, other various additives such as an antioxidant and a photosensitizer may be contained.

  The curable composition for a lens material of the present invention has a property of being cured by light. Here, light refers to electromagnetic waves such as far infrared rays, infrared rays, near infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, and the like, and is not particularly limited as long as it has a property of transmitting a transparent mold to be described later. The term “curing” as used herein means that fluidity is reduced due to reaction of molecules in the composition due to receiving light, polymerization, or cross-linking. The cured product of the composition has a specific cross-linked structure.

The cured product of the curable composition for lens materials of the present invention has a refractive index at 25 ° C. of preferably 1.60 or more, more preferably 1.62 or more. When the refractive index of the cured product is outside this range, the performance as a lens material is inferior.
Moreover, the Abbe number of the hardened | cured material of the curable composition for lens materials of this invention becomes like this. Preferably it is less than 30. In general, it can be said that a larger Abbe number is an optically superior lens material, but it is theoretically difficult to obtain a material having a high refractive index and a high Abbe number. Therefore, in practice, for the purpose of correcting chromatic aberration, it is common to use a lens group in which a lens having a high refractive index and a low Abbe number is combined with a lens having a low refractive index and a high Abbe number. Among these, the lens material of the present invention provides a material having a high refractive index and a low Abbe number. An Abbe number of 30 or more is excellent as a single lens material, but when used in combination with a lens having a low refractive index and a high Abbe number, correction of chromatic aberration may be difficult.

Although the method of manufacturing a lens using the curable composition for lens materials of the present invention is not particularly limited, for example, in addition to the following embodiments, the method described in Japanese Patent No. 426061 can be mentioned. .
Here, FIG. 2 is a diagram schematically illustrating an example of the configuration of a mold used in the method for manufacturing a lens according to the present embodiment. 3-5 is a figure which shows typically the process of the manufacturing method of the lens concerning this embodiment.

  The method for manufacturing a lens which is an example of the present embodiment is a method for manufacturing a lens 1 (see FIG. 5) having a specific shape, and includes an injection step and a curing step.

[Configuration of mold]
First, the configuration of a mold used in the lens manufacturing method of the present embodiment will be described. In this embodiment, the mold is composed of a transparent mold 10, a first support plate 12, a piece 14, a second support plate 16, a push plate 20, and a protruding plate 22 as shown in FIG. In the following, an example of the configuration of a mold used in the method for manufacturing a lens according to the present embodiment is shown, but not all of the configurations described in the following embodiments are essential constituent requirements of the present invention.

  The transparent mold 10 has a molding surface 10 a having a shape complementary to the surface finally formed on the lens 1. In the present embodiment, the transparent mold 10 has a molding surface 10a serving as a mold of the convex surface 1a (see FIG. 5) of the lens 1. The shape of the transparent mold 10 is not particularly limited as long as it has the molding surface 10a. The transparent mold 10 can be, for example, a disk shape, but may be a polygonal plate when the outer shape of the lens 1 is a polygon. The transparent mold 10 may have a shape that can be fitted into the first support plate 12 as shown in FIGS. 2 and 4.

  One function of the transparent mold 10 is to provide a molding surface 10 a for forming at least a part of the surface of the lens 1. Further, as one of the functions of the transparent mold 10, light can be introduced into the cavity 24 (see FIG. 4) formed by a plurality of molds including the transparent mold 10 through the transparent mold 10. To do so.

The transparent mold 10 is formed of a transparent resin that can transmit light for curing the curable composition for a lens material. The transparent resin is not particularly limited and includes various polymer compounds having transparency.
Examples of the polymer compound that can be suitably used for the transparent mold 10 include cellulose acylate (for example, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate), polyethylene terephthalate, poly Ethersulfone, polyacrylic, polyurethane, polyester, polycarbonate, polysulfone, polyether, polymethylpentene, polyetherketone, poly (meth) acrylonitrile, cyclic olefin (for example, JSR Corporation) Manufactured; trade name “ARTON” (norbornene-based)) and the like.

  The first support plate 12 is a plate-like member that supports the transparent mold 10. The shape of the first support plate 12 is not particularly limited as long as the transparent mold 10 can be supported. For example, it is preferable that the first support plate 12 has a hole into which the transparent mold 10 can be fitted as shown in the drawing. When the first support plate 12 has such a shape, it becomes easy to place the transparent mold 10 on the first support plate 12, and for example, the work efficiency of the method for manufacturing the lens 1 of the present embodiment can be improved. .

  The material of the first support plate 12 is not particularly limited, and an inorganic compound such as glass, metal, or metal oxide, or an organic compound such as resin can be used. The first support plate 12 may not be particularly transparent, but can be formed of a transparent material. When the first support plate 12 is formed of a transparent material, it can be made of the same material as the transparent mold 10.

  The piece 14 has a molding surface 14b having a shape complementary to the surface finally formed on the lens 1. In the present embodiment, the piece 14 has a molding surface 14b serving as a mold of the concave surface 1b (see FIG. 5) of the lens 1. The shape of the piece 14 is not particularly limited as long as it has the molding surface 14b. The piece 14 may be, for example, a disk shape, but may be a polygonal plate shape when the outer shape of the lens 1 is a polygon. Moreover, the piece 14 may have a shape that can be fitted into the second support plate 16 as shown in FIG.

  One of the functions of the piece 14 is to provide a mold surface that forms at least a part of the surface of the lens 1. The material of the piece 14 is not particularly limited, and an inorganic compound such as glass, metal or metal oxide, or an organic compound such as resin can be used. Note that the piece 14 may not be particularly transparent, but may be formed of a transparent material. When the piece 14 is formed of a transparent material, the same material as the transparent mold 10 can be used. In this case, the piece 14 has the same function as the transparent mold 10 and can be called a transparent mold in the manufacturing method of the present embodiment. When light is to be introduced into the cavity 24 through the piece 14, the protruding plate 22 and the like need to be formed of a transparent material.

  The second support plate 16 is a plate-like member that supports the piece 14. The shape of the second support plate 16 is not particularly limited as long as the piece 14 can be supported. For example, as shown in FIGS. 2 and 4, the hole can be placed on the protruding plate 22 by fitting the piece 14. It is preferable to have. When the second support plate 16 has such a shape, it is easy to place the piece 14 on the second support plate 16 and, for example, the work efficiency of the method for manufacturing the lens 1 of the present embodiment can be improved.

Moreover, in this embodiment, the hole for fitting the piece 14 formed in the second support plate 16 penetrates the second support plate 16, and presses the protruding plate 22 against the second support plate 16. The piece 14 is formed so as to be pushed out from the second support plate 16. In this way, the formed lens 1 (formed in the cavity 24 of FIG. 4) can be easily collected from the piece 14.

  The second support plate 16 has a molding surface 16 c having a shape complementary to the surface finally formed on the lens 1. In the present embodiment, the second support plate 16 has a molding surface 16 c that serves as a mold for the side surface 1 c (see FIG. 5) of the lens 1. The shape of the second support plate 16 is not particularly limited as long as it has the molding surface 16c. The second support plate 16 can have, for example, a circular hole for fitting the piece 14, but when the outer shape of the lens 1 is a polygon, it may be a plate having a polygonal hole. Good.

  One of the functions of the second support plate 16 is to provide a mold surface that forms at least a part of the surface of the lens 1 (particularly, the side surface that forms the thickness). One function of the second support plate 16 is to facilitate handling of the piece 14 by fitting the piece 14.

  The material of the second support plate 16 is not particularly limited, and an inorganic compound such as glass, metal, or metal oxide, or an organic compound such as resin can be used. The second support plate 16 may not be particularly transparent, but can be formed of a transparent material. When the second support plate 16 is formed of a transparent material, it can be made of the same material as that of the transparent mold 10. In this case, the second support plate 16 has the same function as the transparent mold 10 and can be called a transparent mold in the manufacturing method of the present embodiment.

The pressing plate 20 is a plate-like member for pressing the transparent mold 10 toward the cavity 24 (lens 1). The shape of the pressing plate 20 is not particularly limited as long as the transparent mold 10 can be mechanically pressed, and can be, for example, a flat plate shape.
The material of the pressing plate 20 is not particularly limited, and an inorganic compound such as glass, metal, or metal oxide, or an organic compound such as resin can be used. The push plate 20 does not have to be particularly transparent. However, when the push plate 20 is formed of a material that does not have transparency, light is introduced into the transparent mold 10 from the outside as in the illustrated example. It can be formed to have an opening (window) that can be. When the push plate 20 is formed of a transparent material, it can be made of the same material as that of the transparent mold 10, and in that case, the push plate 20 may have a shape having no opening or the like.

The protruding plate 22 is a plate-like member for pressing at least the piece 14 toward the cavity 24 (lens 1). The shape of the protruding plate 22 is not particularly limited as long as the piece 14 can be mechanically pressed. For example, the shape of the protruding plate 22 may be a shape having a protrusion on the flat plate at a position corresponding to the piece 14.
The material of the protruding plate 22 is not particularly limited, and an inorganic compound such as glass, metal, or metal oxide, or an organic compound such as resin can be used.

In the present embodiment, the cavity 24 is formed by the surfaces of the transparent mold 10, the second support plate 16, and the piece 14, but other member configurations may be included. Moreover, although the case where the transparent mold | type 10 is transparent is illustrated in this embodiment, it is not limited to these.
The cavity 30 is a space having a shape complementary to the lens 1 manufactured in this embodiment. Light can be introduced into the cavity 30 through the transparent mold 10. In addition, a layer having a specific function such as a release layer for facilitating peeling of the lens 1 (molded body) may be formed on the surface surrounding the cavity 30.

[Injection process]
The injection step is a step of injecting an uncured curable composition for a lens material into the cavity 24 formed by a plurality of molds including the transparent mold 10. An uncured curable composition for a lens material refers to a curable composition for a lens material in a state having fluidity, and is a curable composition for a lens material in which no curing reaction has occurred. Alternatively, it may be a curable composition for a lens material in which a part of the curing reaction has occurred and has fluidity.

  As a specific form of injecting the uncured curable composition for a lens material into the cavity 24, for example, as shown in FIG. Before the 24 is formed, an uncured curable composition for a lens material is filled in the space in which the cavity 24 is formed, and the interval between the push plate 20 and the ejection plate 22 is reduced as shown in FIG. In this case, the cavity 24 can be formed. Moreover, filling of the space in which the cavity 24 of the curable composition for lens material is formed can be performed by a dispenser or the like, for example.

[Curing process]
The curing step is a step of irradiating the lens material curable composition with light through the transparent mold 10 to cure the lens material curable composition in the cavity 24.
The light irradiation method in the curing step is not particularly limited, but light from a device that generates light that can be cured by the curable composition for a lens material is introduced into the transparent mold 10 directly or through an optical fiber or the like. Can be done.

  The curing process can be performed at atmospheric pressure, but can also be performed in other pressure environments. For example, the curing step can be performed while applying pressure so as to be sandwiched between the push plate 20 and the ejection plate 22. Further, the curing step can be performed by a vacuum press. The vacuum press is a molding method in which, for example, the inside of the cavity 24 is brought into a state lower than the atmospheric pressure so that the pressing plate 20 and the ejecting plate 22 are stressed by the atmospheric pressure in a direction approaching each other. When the curing process is performed in such a pressure environment, for example, it is possible to make it difficult to cause defects such as bubbles in the lens.

  The lens 1 is obtained by performing the above-mentioned injection | pouring process and hardening process using the structure of the above-mentioned shaping | molding die. Since this lens 1 can be manufactured as an individual piece, a process of dividing it into individual pieces is unnecessary.

Moreover, the following method is mentioned as another example of the manufacturing method of a lens.
Here, FIG. 6 is a diagram illustrating the modeling apparatus 30 used in the method for manufacturing a lens.
The modeling apparatus 30 includes a base 31 installed on the installation surface, and a movable base 33 is supported on the base 31. A support base 32 is further supported on the upper surface of the movable base 33. The movable table 33 includes a lower portion 35 in which a protruding portion 34 having a shape protruding downward is formed, and an upper portion 36 positioned above the lower portion 35, and the protruding portion 34 is an upper surface of the base 31. It is attached to the base 31 so as to be fitted in a groove (not shown) in the y-axis direction formed in. For this reason, the movable table 33 is guided by the groove in the y-axis direction, and can move in the y-axis direction on the base 31.

A θ-axis motor 37 is provided on the upper portion 36 of the movable table 33. The θ-axis motor 37 rotates the upper part 36 of the movable table 33 around a rotation axis in a direction parallel to the Z axis with respect to the lower part 35 of the movable table 33. As described above, the movable stage 33 has the upper portion 36 that is rotatable with respect to the lower portion 35.
A wafer W made of, for example, glass or the like is placed on the support base 32, and can be rotated integrally with the wafer W with respect to the upper portion 36 of the movable base 33. It is configured as a spin coating rotary table used when applying a resin or the like by spin coating. The support base 32 can pass light emitted from a light irradiation device 44 to be described later, for example, using a material having optical transparency such as glass.

  A supply device 38 that supplies a curable composition for a lens used as a molding material to the upper portion 36 of the movable table 33 so as to drop from a top to a substantially central portion of a wafer W having a substantially circular shape (disc shape). Is provided. The lens curable composition supplied to the wafer W is diffused by centrifugal force when the support base 32 rotates for a predetermined time, and is applied to the surface of the wafer W with a substantially uniform thickness. .

  A light irradiation device 44 used as a curing device is provided on the upper portion 36 of the movable table 33. The light irradiation device 44 is used to irradiate the lens curable composition applied to the wafer W with light. In this embodiment, the light irradiation device 44 is provided on the lower side opposite to the transfer body 50 described later with respect to the applied lens curable composition. For this reason, it is possible to irradiate the lens curable composition with light without being blocked by the transfer body 50 in a state where the transfer body 50 is in contact with the lens curable composition.

A movable base 33 is mounted on the base 31 and a support post 39 is fixed. A movable unit 40 is attached to the column 39 so as to be movable in the x-axis direction with respect to the column 39.
A transfer body 50 is mounted on the right side portion of the movable unit 40 via a support member 41. The support member 41 is attached to the movable unit 40 so as to be movable in the z-axis direction. The support member 41 includes a protrusion 42 protruding to the left and a support 43 fixed to the protrusion 42. For example, a transfer body 50 used as a transfer body is mounted on the support portion 43 so as to be detachable on a downward surface.
Since the transfer body 50 can be attached to and detached from the support portion 43, another transfer body can be attached to the support portion 43 instead of the transfer body 50.
A detection device 45 used as detection means for detecting the position of the wafer W and the transfer body 50 is movable up and down independently of the support member 41 (movable in the z-axis direction) on the right side portion of the movable unit 40. ) Is installed.

  As described above, the support member 41 is attached to the movable unit 40 so as to be movable in the z-axis direction, and the movable unit 40 is attached to the support column 39 so as to be movable in the x-axis direction. Therefore, the transfer body 50 can be moved together with the support member 41 in the x-axis direction and the z-axis direction. Further, as described above, the support base 32 moves in the y-axis direction together with the movable base 33 and rotates. Therefore, the relative positional relationship between the wafer W and the light irradiation device 44 and the transfer body 50 can be changed.

Then, by changing the relative positional relationship between the wafer W and the transfer body 50, the lens curable composition applied to the wafer W and the transfer body 50 can be brought into contact with each other and separated from each other.
FIG. 7 shows the transfer body 50. The transfer body 50 is made of, for example, metal and has a substantially cylindrical main body 51 as shown in FIG. 7, and the bottom surface 52 of the main body 51 is used as a transfer portion. An optical component part forming part 53 used for forming a lens, for example, in the lens curable composition is provided in a substantially central part of the bottom surface 52 so as to protrude downward. The bottom surface 54 of the optical component part forming part 53 is formed of, for example, a spherical surface or an aspherical surface, and the spherical surface or the like is formed by mechanically processing the transfer body 50 such as cutting or polishing. The shape of the bottom surface 54 is transferred to the curable composition for lenses, and an optical component part having a shape opposite to the bottom surface 54 is formed in the curable composition for lenses.

FIG. 8 shows details of the transfer body 50 and the wafer W, and describes the operation of the transfer body 50.
As shown in FIG. 8, the wafer W has a structure in which a holding plate W2 is overlaid on a substrate W1. The substrate W1 is made of, for example, glass that is a material that can transmit light.
The holding plate W2 is used to hold the curable composition for a lens having high fluidity before curing at a predetermined position. For example, the holding plate W2 is made of silicon, and a plurality of mortar-shaped through holes h penetrating from above to below are formed.
In FIG. 8, the lens curable composition is applied to the upper surface of the wafer W, and the applied lens curable composition is held by the holding plate W2 so as to flow into the through holes h of the holding plate W2. The state in which the transfer body 50 is in contact with the curable composition for lenses is shown such that at least the bottom surface 52 is in contact with the curable composition for lenses.
In this state, when the light irradiating device 44 is used to irradiate light to the position where the lens curable composition is in contact with the bottom surface 52 and its periphery, the lens curable composition is cured and the bottom surface of the transfer body 50. The shape of 52 is transferred to the curable composition for lenses. Then, after the curable composition for lenses is cured, the transfer body 50 is separated from the wafer W as indicated by a two-dot chain line in FIG. 8, and is cured, for example, as indicated by an arrow in FIG. It moves so as to contact the uncured resin held in the through hole h adjacent to the through hole h holding the resin.
After repeating this, the wafer W is divided into a plurality of lenses by a method such as cutting the wafer W.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same purposes and effects). In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

A lens made of a cured product of the curable composition for a lens material of the present invention manufactured by the above-described lens manufacturing method, etc. includes an imaging device equipped with a lens such as a small camera, an optical pickup for a recording medium, a display device, Used in optical systems such as lighting devices, copying devices, and printing devices, glasses, and contact lenses.
In addition, the surface of the lens manufactured by the above-described manufacturing method can have an arbitrary shape such as a spherical surface, an aspherical surface, a free-form surface, a convex surface, or a concave surface.

[Evaluation of the physical properties]
NMR: ¹ H-NMR was measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE500).
Refractive index: The Abbe number was determined by measuring the refractive index at 589 nm, 486 nm, and 656 nm at 25 ° C. using a refractometer equipped with a circulator (Multi-wave Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.).

[Synthesis Example 1]
9,9-bis (4-glycidyloxyphenyl) fluorene 10.00 g (0.0216 mol), 4-phenylphenol 7.36 g (0.0432 mol), tetrabutylammonium bromide 0.7 g (0.00216 mol), N- Methyl pyrrolidone (5 g) was weighed and reacted at 160 ° C. for 5 hours.
After confirming disappearance of 9,9-bis (4-glycidyloxyphenyl) fluorene and 4-phenylphenol as raw materials by GPC, tetrahydrofuran (THF) 22 g, acrylic acid chloride 5.87 g (0.0648 mol), N, 7.86 g (0.0648 mol) of N-dimethylaniline was added and reacted at a temperature of 20 ° C. or lower for 5 hours.
After the deposited salt was removed by filtration, the filtrate was diluted with 200 g of methylene chloride and washed three times with 200 g of ion-exchanged water. The organic layer was dried over anhydrous magnesium sulfate, concentrated and purified by silica gel column chromatography (developing solvent; methylene chloride). The obtained solution was concentrated and then vacuum-dried to obtain 18.8 g (yield 98%) of a white solid. The synthesis flow is shown in the following synthesis flow 1. Moreover, the NMR spectrum of the obtained compound is shown in FIG.
[Synthesis flow 1]

[Example 1]
When 50 parts by mass of the compound obtained in Synthesis Example 1, 50 parts by mass of phenoxyethyl acrylate, 1 part by mass of Irganox 1035 (manufactured by BASF) and 2 parts by mass of Irgacure 184 (manufactured by BASF) were mixed, a uniform solution was obtained. The obtained solution was applied onto a glass wafer made of borosilicate glass, and a spacer having a thickness of 0.5 mm was arranged around it, and then a mask aligner (manufactured by Karl Suss Co., Ltd.) was put on another glass wafer. MA100CC) was used to expose the entire surface (20 mW / cm ² (365 nm) for 2 minutes) to obtain a plate-like sample. The obtained cured product was colorless and transparent and had a refractive index (n _D ²⁵ ) of 1.6023 and an Abbe number (ν _D ) of 28 at 25 ° C. and 589 nm.

[Example 2]
When 60 parts by mass of the compound obtained in Synthesis Example 1, 40 parts by mass of phenoxyethyl acrylate, 1 part by mass of Irganox 1035 (manufactured by BASF) and 2 parts by mass of Irgacure 184 (manufactured by BASF) were mixed, a uniform solution was obtained. When the obtained solution was cured in the same manner as in Example 1, a colorless and transparent cured product was obtained, and the refractive index was measured. As a result, n _D ²⁵ = 1.611 and ν _D = 27.

[Example 3]
50 parts by mass of the compound obtained in Synthesis Example 1, 25 parts by mass of phenoxyethyl acrylate, 25 parts by mass of o-phenylphenoxyethyl acrylate, 1 part by mass of Irganox 1035 (manufactured by BASF), and 2 parts by mass of Irgacure 184 (manufactured by BASF) were mixed. A uniform solution was obtained. When the obtained solution was cured in the same manner as in Example 1, a colorless and transparent cured product was obtained, and the refractive index was measured. As a result, n _D ²⁵ = 1.616 and ν _D = 26.

[Example 4]
When 44 parts by mass of the compound obtained in Synthesis Example 1, 56 parts by mass of o-phenylphenoxyethyl acrylate, 1 part by mass of Irganox 1035 (manufactured by BASF) and 2 parts by mass of Irgacure 184 (manufactured by BASF) were mixed, a uniform solution was obtained. It was. When the obtained solution was cured in the same manner as in Example 1, a colorless and transparent cured product was obtained, and the refractive index was measured. As a result, n _D ²⁵ = 1.624 and ν _D = 25.

[Example 5]
When 55 parts by mass of the compound obtained in Synthesis Example 1, 45 parts by mass of thiophenoxyethyl acrylate, 1 part by mass of Irganox 1035 (manufactured by BASF) and 2 parts by mass of Irgacure 184 (manufactured by BASF) were mixed, a uniform solution was obtained. When the obtained solution was cured in the same manner as in Example 1, a colorless and transparent cured product was obtained, and the refractive index was measured. As a result, n _D ²⁵ = 1.628 and ν _D = 26.

[Comparative Example 1]
When 60 parts by mass of a compound represented by the following formula (15), 40 parts by mass of phenoxyethyl acrylate, 1 part by mass of Irganox 1035 (manufactured by BASF) and 2 parts by mass of Irgacur 184 (manufactured by BASF) are mixed, a uniform solution is obtained. It was. When the obtained solution was cured in the same manner as in Example 1, a colorless and transparent cured product was obtained, and the refractive index was measured. As a result, n _D ²⁵ = 1.599 and ν _D = 28.

[Comparative Example 2]
A reaction between 0.02 mol of isophthalic acid dichloride and 0.04 mol of 9,9-bis (4-hydroxyphenyl) fluorene was carried out in tetrahydrofuran in the presence of 0.08 mol of triethylamine to synthesize an oligomer having a terminal OH group. Thereafter, 0.04 mol of acrylic acid chloride was added to the reaction solution to cause further reaction, thereby obtaining an acrylic oligomer represented by the following formula (16). Purification was performed by washing with water and reprecipitation with methanol. The mass average molecular weight Mw measured by GPC was 2000, and the terminal acrylic group introduction rate was 90%. As a result of mixing the obtained oligomer with phenoxyethyl acrylate and o-phenylphenoxyethyl acrylate, respectively, both were insoluble.

[Comparative Example 3]
A reaction between 0.02 mol of bisphenol A bischloroformate and 0.04 mol of 9,9-bis (4-hydroxyphenyl) fluorene is carried out in tetrahydrofuran in the presence of 0.08 mol of triethylamine to synthesize an oligomer having an OH group at the end. did. Thereafter, 0.04 mol of acrylic acid chloride was added to the reaction solution to further react to obtain an acrylic oligomer represented by the following formula (17). Purification was performed by washing with water and reprecipitation with methanol. The mass average molecular weight Mw measured by GPC was 4000, and the terminal acrylic group introduction rate was 70%. As a result of mixing the obtained oligomer with phenoxyethyl acrylate, when the concentration of the oligomer exceeded 40%, the viscosity of the solution increased and the fluidity was lost. When a solution having a concentration of 40% was cured in the same manner as in Example 1, a colorless and transparent cured product was obtained, and the refractive index was measured. As a result, n _D ²⁵ = 1.594 and ν _D = 31.

DESCRIPTION OF SYMBOLS 1 Lens 1a Convex surface 1b Concave surface 1c Side surface 10 Transparent type | mold 10a Molding surface 12 1st support plate 14 Piece 14b Molding surface 16 2nd support plate 16c Molding surface 20 Push plate 22 Extrusion plate 30 Modeling apparatus 31 Base 32 Support stand 33 Movable stand 37 θ-axis motor 38 supply device 39 support 40 movable unit 44 light irradiation device 45 detection device 50 transfer body 51 main body portion 52 bottom surface 53 optical component portion formation portion 54 bottom surface

Claims (11)

(A) a compound represented by the following general formula (1), and
(B) a photo radical initiator,
The curable composition for lens materials containing this.

(In the above general formula (1), X is a sulfur atom or an oxygen atom. R ¹ is a hydrogen atom or a (meth) acryloyl group, and at least one of the plurality of R ¹ is ( A meta) acryloyl group, R ² is a phenyl group, a naphthyl group, or a biphenyl group, and R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. The hydrogen atoms in ^{1 to} R ³ may be substituted with a chlorine atom, a bromine atom, an iodine atom, a cyano group, or an alkyl group having 1 to 4 carbon atoms, each of which is present in the general formula (1). X, R ¹ , R ² and R ³ may be different or the same, and n is an integer of 0 to 2.) 2. The curable composition for a lens material according to claim 1, wherein, in the general formula (1), X is an oxygen atom, R ¹ is an acryloyl group or a methacryloyl group, and n is 0 or 1. 3.   Furthermore, (C) It is a curable composition for lens materials of Claim 1 or 2 containing a reactive diluent, Comprising: (C) component has 1-4 (meth) acryloyl groups in a molecule | numerator. A curable composition for a lens material, which is a liquid (meth) acrylate other than the component (A).   The curable composition for lens materials according to claim 3, wherein the component (C) has an aromatic ring in the molecule. The curable composition for lens materials according to claim 3 or 4, wherein the component (C) is a compound represented by any one of the following general formulas (2) to (6).

(In the general formulas (2) to (6), i, j, k, l, and m are each an integer of 0 to 2.)   The curable composition for lens materials according to any one of claims 1 to 5, comprising 20 to 99.5% by mass of the component (A).   The curable composition for lens materials according to any one of claims 1 to 6, wherein the content of the solvent is less than 1.0% by mass.   Hardened | cured material obtained by hardening the curable composition for lens materials of any one of Claims 1-7. The uncured curable composition for a lens material according to any one of claims 1 to 7 is injected into a cavity formed by a plurality of molds including a transparent mold made of a transparent resin that transmits light. An injection process;
A curing step of irradiating the lens material curable composition with light through the transparent mold to cure the lens material curable composition in the cavity; and
A method for manufacturing a lens, comprising:   A lens manufactured by the method according to claim 9.   An imaging apparatus comprising the lens according to claim 10.

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