JPH07159612A - Production of resin containing metal and lens consisting of that resin - Google Patents
Production of resin containing metal and lens consisting of that resinInfo
- Publication number
- JPH07159612A JPH07159612A JP30761393A JP30761393A JPH07159612A JP H07159612 A JPH07159612 A JP H07159612A JP 30761393 A JP30761393 A JP 30761393A JP 30761393 A JP30761393 A JP 30761393A JP H07159612 A JPH07159612 A JP H07159612A
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- metal
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- weight
- containing resin
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- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、透明樹脂中に金属化
合物を高濃度に導入し、高性能のフィルタ素材を製造す
る方法及びそれを用いたレンズに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-performance filter material by introducing a metal compound into a transparent resin at a high concentration, and a lens using the same.
【０００２】[0002]
【従来の技術】ＣＣＤ固体撮像素子を用いた光学機器、
例えばカメラ、バーコードリーダは、レンズを通してＣ
ＣＤ素子上に結像する光に近赤外光が含まれているとノ
イズとなるので、フィルタを、光学系内に配置し、可視
光のみをＣＣＤ素子に入射させている。また、この近赤
外光カット用のフィルタはＣＣＤ素子以外に、フォトダ
イオード等にも用いられる。2. Description of the Related Art An optical device using a CCD solid-state image sensor,
For example, a camera or a bar code reader uses C through a lens.
If near-infrared light is included in the light imaged on the CD element, it becomes noise. Therefore, a filter is arranged in the optical system and only visible light is made incident on the CCD element. Further, this filter for cutting near infrared light is used not only for CCD elements but also for photodiodes and the like.
【０００３】近赤外光カット用のフィルタは、ガラス製
のものとプラスチック製のものがある。ガラス製フィル
タは、図３の分光特性例に示すように、可視光（波長４
００nm〜７００nm）に対する透過率で略９０％、近赤外
光（波長７００nm〜）に対する透過率で略０％という良
好なフィルタ特性が得られる。このガラス製フィルタ
は、硫酸銅をシリカ中に溶かし込み、銅イオンＣｕ+を
ガラス中に分散させたものである。Filters for cutting near infrared light include those made of glass and those made of plastic. As shown in the spectral characteristic example of FIG. 3, the glass filter is used for visible light (wavelength 4
Good filter characteristics of about 90% in the transmittance for 00 nm to 700 nm) and about 0% in the transmittance for near infrared light (wavelength of 700 nm) are obtained. This glass filter is made by dissolving copper sulfate in silica and dispersing copper ions Cu + in the glass.
【０００４】しかし、ガラス製フィルタは成形性に難が
あり、平板状のフィルタとしてのみ製品化されている。
したがって、例えば組み合わせレンズに代えて用いられ
る非球面レンズの素材として使用し、近赤外光カット機
能を備えたレンズとして量産するには不適当である。However, the glass filter is difficult to form, and is only commercialized as a flat plate filter.
Therefore, it is unsuitable for mass production as a lens having a near-infrared light cutting function, which is used as a material of an aspherical lens used in place of a combination lens, for example.
【０００５】一方、プラスチック製フィルタは、射出成
形等の樹脂成形技術により任意形状にできるので、非球
面レンズも容易に量産できる。On the other hand, the plastic filter can be formed into an arbitrary shape by a resin molding technique such as injection molding, so that aspherical lenses can be easily mass-produced.
【０００６】ところが、従来のプラスチック製フィルタ
は、図２の分光特性例に示すように、フイルタ特性が、
ガラス製のものに比べて劣っていた。However, the conventional plastic filter has a filter characteristic as shown in the spectral characteristic example of FIG.
It was inferior to the one made of glass.
【０００７】プラスチック製フィルタは、透明樹脂中に
金属化合物を導入することによって得られる。このため
の従来の方法は、（メタ）アクリル酸エステルに金属塩
を添加して重合させる方法、（メタ）アクリル酸の存在
下で共重合させる方法、分子内に極性基を持ったモノマ
ーに金属塩を加えて重合させる等の方法であった。The plastic filter is obtained by introducing a metal compound into a transparent resin. The conventional methods for this are as follows: a method of adding a metal salt to (meth) acrylic acid ester to polymerize, a method of copolymerizing in the presence of (meth) acrylic acid, a method of using a monomer having a polar group in the molecule It was a method of adding a salt and polymerizing.
【０００８】これらの方法では、少量の金属が導入され
るだけであり、図２の分光特性例に見られるように、銅
の金属錯体である染料の濃度が小さいと（プラスチック
素材に対する重量比で０.０２％）、近赤外光（７００n
m〜）のカット率が悪くなり、染料の濃度を大きくする
と（重量比で０.１％）、可視光（４００〜７００nm）
の透過率が２５％以下と低下する。赤外線のカット率を
犠牲にして、可視光の透過率を最大にしても７０％程度
にしかできない。In these methods, only a small amount of metal is introduced, and as shown in the spectral characteristic example of FIG. 2, when the concentration of the dye, which is a metal complex of copper, is small (the weight ratio to the plastic material is 0.02%), near infrared light (700n
When the cut rate of m-) becomes worse and the concentration of dye is increased (0.1% by weight), visible light (400-700 nm)
Transmittance is reduced to 25% or less. Even if the transmittance of visible light is maximized at the sacrifice of the cutoff rate of infrared rays, it can only be about 70%.
【０００９】この点で、プラスチックフィルタは、近赤
外光を略１００％カットしながら可視光の透過率を９０
％程度にできる図３のガラス製フィルタには及ばず、Ｃ
ＣＤ素子を用いた光学機器において、レンズ自体に近赤
外光のカット機能を持たせ、構造の簡素化を図ること
は、性能上実現できなかった。In this respect, the plastic filter has a visible light transmittance of 90% while cutting almost 100% of near infrared light.
%, Which does not reach the glass filter shown in FIG.
In an optical device using a CD element, it was not possible in terms of performance to provide the lens itself with a function of cutting near-infrared light so as to simplify the structure.
【００１０】[0010]
【発明が解決しようとする課題】そこで、この発明は、
ガラス製フィルタと同様の特性を持つ金属含有樹脂の製
造方法を提供し、ＣＣＤ素子を用いた光学機器に用いる
レンズに近赤外光カット機能を持たせ、その構成の簡素
化を図ることを目的とする。Therefore, the present invention is
An object of the present invention is to provide a method for producing a metal-containing resin having the same characteristics as a glass filter, and to make a lens used in an optical device using a CCD element have a function of cutting near-infrared light to simplify the configuration. And
【００１１】[0011]
【００１２】(1) 本発明が提供する金属含有樹脂の製造
方法は、次の工程からなる。 金属イオン存在下、ポリアクリル酸（ＰＡＡ）水溶
液中で、メタクリル酸２−ヒドロキシエチル（２ＨＥＭ
Ａ）を重合させてヒドロゲルを生成し、水分を除去す
る。 で生成したヒドロゲルに、メタクリル酸メチル
（ＭＭＡ）を加えて重合させ金属含有樹脂を得る。(1) The method for producing a metal-containing resin provided by the present invention comprises the following steps. 2-hydroxyethyl methacrylate (2HEM) in an aqueous solution of polyacrylic acid (PAA) in the presence of metal ions.
A) is polymerized to form a hydrogel and water is removed. Methyl methacrylate (MMA) is added to the hydrogel produced in the above to polymerize to obtain a metal-containing resin.
【００１３】(2) 上記(1)の製造方法で用いる原料の配
合の具体例は、次のようになる。 ヒドロゲル生成工程で使用する原料 硝酸銅３水和物 ２〜３重量部 ポリアクリル酸水溶液（２５％） ３〜４重量部 メタクリル酸２−ヒドロキシエチル １重量部 水溶性重合開始剤 ０.４重量部 最終反応で使用する原料 メタクリル酸メチル ３重量部 最終反応用の重合開始剤 ０.０６重量部(2) A specific example of blending the raw materials used in the production method of the above (1) is as follows. Raw materials used in hydrogel production step Copper nitrate trihydrate 2-3 parts by weight Polyacrylic acid aqueous solution (25%) 3-4 parts by weight 2-hydroxyethyl methacrylate 1 part by weight Water-soluble polymerization initiator 0.4 parts by weight Raw material used in final reaction Methyl methacrylate 3 parts by weight Polymerization initiator for final reaction 0.06 parts by weight
【００１４】(3) 上記(1)の製造方法で、使用する原料
の代替物質として、以下のものが使用できる。すなわ
ち、ポリアクリル酸（ＰＡＡ）水溶液の代りにポリメタ
クリル酸水溶液、メタクリル酸２−ヒドロキシエチル
（２ＨＥＭＡ）の代りに、アクリル酸２−ヒドロキシエ
チル、（メタ）アクリル酸２−ヒドロキシプロピル、又
は（メタ）アクリル酸テトラヒドロフルフリルのいずれ
か１つ、メタクリル酸メチル（ＭＭＡ）の代りにアクリ
ル酸メチルである。(3) In the production method of the above (1), the following substances can be used as substitute substances for the raw materials used. That is, an aqueous solution of polymethacrylic acid instead of an aqueous solution of polyacrylic acid (PAA), 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, or (meth ) Any one of tetrahydrofurfuryl acrylate, methyl acrylate instead of methyl methacrylate (MMA).
【００１５】これらの代替物質は、１種以上を任意に組
み合わせて使用可能である。These alternative substances can be used in any combination of one or more.
【００１６】(4) 上記(1)(2)の製造方法で、使用される
金属イオン生成用の金属化合物の具体例としては、硝酸
銅３水和物〔Ｃｕ（ＮＨ3）・３Ｈ2Ｏ〕がある。(4) Specific examples of the metal compound for producing metal ions used in the production methods (1) and (2) include copper nitrate trihydrate [Cu (NH 3 ) .3H 2 O ]]
【００１７】(5) 上記本発明方法によって製造された
金属含有樹脂を素材として、金型内重合によってレンズ
を製作し、近赤外光カット機能を持たせる。(5) Using the metal-containing resin produced by the method of the present invention as a raw material, a lens is produced by in-mold polymerization to have a near infrared light cutting function.
【００１８】[0018]
【作用】上記製法は、金属塩の存在下、ポリアクリル酸
（ＰＡＡ）水溶液中で、メタクリル酸２−ヒドロキシエ
チル（２ＨＥＭＡ）を水溶性重合剤で重合させ、水分を
除いて、ヒドロゲルを得る工程により、金属イオンを高
濃度に含有させることができ、可視光の透過率を高くす
ることができる。The above process is a step of polymerizing 2-hydroxyethyl methacrylate (2HEMA) with a water-soluble polymerizing agent in a polyacrylic acid (PAA) aqueous solution in the presence of a metal salt to remove water and obtain a hydrogel. Thereby, the metal ions can be contained at a high concentration, and the transmittance of visible light can be increased.
【００１９】[0019]
【実施例】以下、具体的実施例を説明する。EXAMPLES Specific examples will be described below.
【００２０】実施例１：冷却管、窒素導入管、かき混ぜ
装置付き４つ口フラスコに、２５％ポリアクリル酸（Ｐ
ＡＡ）水溶液４０ｇ、メタクリル酸２−ヒドロキシエチ
ル（２ＨＥＭＡ）６ｇ、硝酸銅３水和物〔Ｃｕ（Ｎ
Ｈ3）・３Ｈ2Ｏ〕３３.８ｇ、過硫酸カリウム（ＫＰ
Ｓ）０.０５ｇを仕込み、窒素気流下、７０°Ｃで１５
時間重合を行う。この結果物は乳青色水溶液となる。こ
の水溶液から水分を除去して、ヒドロゲルを得る。Example 1 In a four-necked flask equipped with a cooling tube, a nitrogen introducing tube and a stirring device, 25% polyacrylic acid (P
AA) aqueous solution 40 g, 2-hydroxyethyl methacrylate (2HEMA) 6 g, copper nitrate trihydrate [Cu (N
H 3 ) / 3H 2 O] 33.8 g, potassium persulfate (KP
S) 0.05 g was charged, and under nitrogen flow at 70 ° C for 15
Polymerize for a period of time. The result is a milky blue aqueous solution. Water is removed from this aqueous solution to obtain a hydrogel.
【００２１】次に、このヒドロゲルに、２ＨＥＭＡを４
ｇを加えて、２４時間かき混ぜた後に、不溶部を除き、
ヒドロゲル−ＨＥＭＡ溶液とする。Next, 2 HEMA was added to this hydrogel 4 times.
g, and after stirring for 24 hours, remove the insoluble part,
This is a hydrogel-HEMA solution.
【００２２】さらに、このヒドロゲル−ＨＥＭＡ溶液
１.４ｇに、メタクリル酸メチル（ＭＭＡ）０.６ｇ、重
合開始剤（ｔ−ａｍｙｌｐｅｒｏｘｙ ２−ｅｔｈｙｌ
ｈｅｘａｎｏａｔｅ）０.０１ｇを混入し、成形用のガ
ラス製セルの中に入れ、６０°Ｃのオーブンで４時間過
熱し、赤外線カットフィルタを得た。Further, 1.4 g of this hydrogel-HEMA solution was added with 0.6 g of methyl methacrylate (MMA) and a polymerization initiator (t-amylperoxy 2-ethyl).
Hexanoate) (0.01 g) was mixed, placed in a glass cell for molding, and heated in an oven at 60 ° C. for 4 hours to obtain an infrared cut filter.
【００２３】このフィルタの分光特性は、図１に示すよ
うになる。The spectral characteristic of this filter is as shown in FIG.
【００２４】上記実施例は、図１において、ヒドロゲル
−ＨＥＭＡ溶液に混入するメタクリル酸メチル（ＭＭ
Ａ）の混入比率を（３／７）とした場合であり、可視光
領域において９０％程度の透過率、近赤外領域で０％の
透過率となっている。The above-mentioned embodiment is shown in FIG. 1 in which methyl methacrylate (MM) mixed with the hydrogel-HEMA solution is mixed.
This is a case where the mixing ratio of A) is (3/7), and the transmittance is about 90% in the visible light region and 0% in the near infrared region.
【００２５】他の実施例：上記１の実施例で、使用した
原料の代替物質として以下のものを使用する。Other Examples: The following substances are used as substitutes for the raw materials used in the above Example 1.
【００２６】すなわち、ポリアクリル酸（ＰＡＡ）水溶
液の代りにポリメタクリル酸水溶液、メタクリル酸２−
ヒドロキシエチル（２ＨＥＭＡ）の代りに、アクリル酸
２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロ
キシプロピル、又は（メタ）アクリル酸テトラヒドロフ
ルフリルのいずれか１つ、メタクリル酸メチル（ＭＭ
Ａ）の代りにアクリル酸メチルである。That is, instead of the polyacrylic acid (PAA) aqueous solution, a polymethacrylic acid aqueous solution, methacrylic acid 2-
Instead of hydroxyethyl (2HEMA), any one of 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, or tetrahydrofurfuryl (meth) acrylate, methyl methacrylate (MM
It is methyl acrylate instead of A).
【００２７】これらの代替物質は、１種以上を任意に組
み合わることが、その物性により可能となる。The physical properties of these alternative substances make it possible to arbitrarily combine one or more thereof.
【００２８】上記実施例１及び他の実施例で製造した金
属含有樹脂は、例えばガラス製セルの形状を、所定のレ
ンズ形状とすることにより、非球面レンズを含む任意形
状のレンズを、近赤外光カットフィルタの機能を持たせ
て製作することができる。これによって、ＣＣＤ素子を
持つ光学機器の光学系を簡素化でき、光学性能を低下さ
せないでコスト低減が可能になる。The metal-containing resin produced in the above-mentioned first embodiment and other embodiments is capable of producing a lens having an arbitrary shape, including an aspherical lens, in a near red color by making a glass cell into a predetermined lens shape. It can be manufactured with the function of an external light cut filter. As a result, the optical system of the optical device having the CCD element can be simplified, and the cost can be reduced without lowering the optical performance.
【００２９】[0029]
【発明の効果】本発明によれば、ガラス製フィルタと同
等の特性を持つプラスチック製フィルタを製造でき、プ
ラスチックの成形容易性を生かして、近赤外光カット機
能を持つ任意形状のレンズを製作できる。According to the present invention, a plastic filter having the same characteristics as a glass filter can be manufactured, and a lens having an arbitrary shape having a near-infrared light cutting function can be manufactured by utilizing the ease of molding of plastic. it can.
【図１】本発明により製造された金属含有樹脂の分光特
性図FIG. 1 is a spectral characteristic diagram of a metal-containing resin produced by the present invention.
【図２】従来のプラスチックフィルタの分光特性図FIG. 2 is a spectral characteristic diagram of a conventional plastic filter.
【図３】ガラス製フィルタの分光特性図FIG. 3 is a spectral characteristic diagram of a glass filter.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 板谷 義典 大阪府大阪市東淀川区南江口３丁目２番30 号 日本非球面レンズ株式会社内 (72)発明者 徳村 啓雨 大阪府大阪市東淀川区南江口３丁目２番30 号 日本非球面レンズ株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yoshinori Itaya, 3-2-30 Minamieguchi, Higashiyodogawa-ku, Osaka City, Osaka Prefecture Japan Aspherical Lens Co., Ltd. (72) Inamu Kei Tokumura Minami, Higashiyodogawa-ku, Osaka City, Osaka Prefecture Eguchi 3-chome 2-30 Japan Aspherical Lens Co., Ltd.
Claims (5)
液中で、メタクリル酸２−ヒドロキシエチルを重合させ
てヒドロゲルを生成し、水分を除去した後、このヒドロ
ゲルにメタクリル酸メチルを加えて重合させ金属含有樹
脂を得ることを特徴とする金属含有樹脂の製造方法。1. A hydrogel is produced by polymerizing 2-hydroxyethyl methacrylate in an aqueous solution of polyacrylic acid in the presence of metal ions to remove water, and then methyl methacrylate is added to the hydrogel to polymerize the metal. A method for producing a metal-containing resin, which comprises obtaining a resin containing a metal.
製造方法。2. A compounding ratio of a metal compound for producing metal ions 2-3 parts by weight, an aqueous polyacrylic acid solution (25%) 3-4 parts by weight 2-hydroxyethyl methacrylate 1 part by weight, and a water-soluble polymerization for producing hydrogel. Initiator 0.4 parts by weight Methyl methacrylate 3 parts by weight Polymerization initiator for final reaction 0.06 parts by weight The method for producing a metal-containing resin according to claim 1, wherein:
クリル酸水溶液、メタクリル酸２−ヒドロキシエチルの
代りに、アクリル酸２−ヒドロキシエチル、（メタ）ア
クリル酸２−ヒドロキシプロピル、又は（メタ）アクリ
ル酸テトラヒドロフルフリルのいずれか１つ、メタクリ
ル酸メチルの代りにアクリル酸メチルを代替物質とし、
これらの代替物質が１種以上任意の組み合わせで含まれ
る配合で、金属含有樹脂を製造することを特徴とする請
求項１記載の金属含有樹脂の製造方法。3. A polymethacrylic acid aqueous solution instead of the polyacrylic acid aqueous solution, and 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, or (meth) acrylic acid instead of 2-hydroxyethyl methacrylate. Any one of tetrahydrofurfuryl, methyl acrylate instead of methyl methacrylate as a substitute substance,
The method for producing a metal-containing resin according to claim 1, wherein the metal-containing resin is produced in a composition containing one or more of these alternative substances in an arbitrary combination.
銅３水和物を使用したことを特徴とする請求項１〜３に
記載した金属含有樹脂の製造方法。4. The method for producing a metal-containing resin according to claim 1, wherein copper nitrate trihydrate is used as the metal compound for producing metal ions.
造された金属含有樹脂を素材とするレンズ。5. A lens made of a metal-containing resin produced by the production method according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30761393A JPH07159612A (en) | 1993-12-08 | 1993-12-08 | Production of resin containing metal and lens consisting of that resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30761393A JPH07159612A (en) | 1993-12-08 | 1993-12-08 | Production of resin containing metal and lens consisting of that resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07159612A true JPH07159612A (en) | 1995-06-23 |
Family
ID=17971146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30761393A Withdrawn JPH07159612A (en) | 1993-12-08 | 1993-12-08 | Production of resin containing metal and lens consisting of that resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07159612A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106814417A (en) * | 2017-03-14 | 2017-06-09 | 浙江博达光电有限公司 | The optical low-pass filter and its manufacture method of day and night type |
-
1993
- 1993-12-08 JP JP30761393A patent/JPH07159612A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106814417A (en) * | 2017-03-14 | 2017-06-09 | 浙江博达光电有限公司 | The optical low-pass filter and its manufacture method of day and night type |
| CN106814417B (en) * | 2017-03-14 | 2023-05-09 | 浙江博达光电有限公司 | Day and night dual-purpose optical low-pass filter and manufacturing method thereof |
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