JPH06287194A - New methacrylic acid copper complex and its production - Google Patents
New methacrylic acid copper complex and its productionInfo
- Publication number
- JPH06287194A JPH06287194A JP5100273A JP10027393A JPH06287194A JP H06287194 A JPH06287194 A JP H06287194A JP 5100273 A JP5100273 A JP 5100273A JP 10027393 A JP10027393 A JP 10027393A JP H06287194 A JPH06287194 A JP H06287194A
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- JP
- Japan
- Prior art keywords
- methacrylic acid
- copper
- infrared ray
- complex
- pyridine
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、下記一般式で示される
新規なメタクリル酸銅錯体及びその製造方法に関するも
のである。FIELD OF THE INVENTION The present invention relates to a novel copper methacrylic acid complex represented by the following general formula and a method for producing the same.
【０００２】Ｃｕ2 （μ−ＭＡＡ）4 Ｌ2 （式中、Ｃｕは銅金属を、μ−ＭＡＡは架橋したメタク
リル酸カルボキシラトアニオンを、Ｌは水、ピリジン、
メタクリル酸等の単座配位子を表す。）また、本発明は
赤外線領域に吸収を持つ赤外線吸収組成物に関するもの
である。Cu 2 (μ-MAA) 4 L 2 (wherein Cu is copper metal, μ-MAA is crosslinked methacrylic acid carboxylato anion, L is water, pyridine,
It represents a monodentate ligand such as methacrylic acid. The present invention also relates to an infrared absorbing composition having absorption in the infrared region.
【０００３】[0003]
【従来の技術】赤外線カットフィルター等には一般にＣ
ｕＯを含有するガラスが知られているが、割れ易く、重
いというガラスとしての問題点を有している。無機物で
あるＣｕＯは耐熱性には優れているが、有機物には溶解
しない。また重量の軽い有機物として赤外線吸収剤を含
有するポリスチレンが知られてはいるが、吸収剤が有機
物であるために耐熱性に問題があり、成形中にその赤外
線吸収効率が悪化する事が避けられなかった。また添加
する赤外線吸収剤の吸収効率が十分でないため、多量添
加する必要があり、使用中に樹脂からブリードするとと
もに、その可視光線領域の透明性が十分でないという問
題点があった。2. Description of the Related Art Generally, an infrared cut filter or the like is C
Although a glass containing uO is known, it has a problem as a glass that it is easily broken and is heavy. CuO, which is an inorganic substance, has excellent heat resistance, but does not dissolve in organic substances. Polystyrene containing an infrared absorber is known as a light weight organic substance, but since the absorber is an organic substance, there is a problem in heat resistance, and it is possible to avoid deterioration of the infrared absorption efficiency during molding. There wasn't. Further, since the absorption efficiency of the infrared absorber to be added is not sufficient, it is necessary to add a large amount, and there is a problem that the resin bleeds during use and the transparency in the visible light region is not sufficient.
【０００４】[0004]
【発明が解決しようとする課題】本発明は従来技術の有
する前記事情に鑑みてなされたものである。すなわち本
発明の目的は、４００〜６００ｎｍの可視光の透過率は
高く、６００ｎｍ以上の光は可能な限り多く吸収し、し
かも耐熱性、堅牢性に優れた、有機溶剤に可溶な、重合
性を有する赤外線吸収材料を提供する事にある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances of the prior art. That is, the object of the present invention is that the transmittance of visible light of 400 to 600 nm is high, the light of 600 nm or more is absorbed as much as possible, and the heat resistance and the fastness are excellent. An infrared absorbing material having
【０００５】また、本発明の目的は該メタクリル酸銅錯
体を効率よく、しかも高純度で製造する方法を提供する
事にある。さらに、本発明のもう一つの目的は赤外線吸
収能を有する溶解性、耐熱性に優れた安価な新規メタク
リル酸銅錯体を含有する赤外線吸収組成物を提供する事
にある。Another object of the present invention is to provide a method for efficiently producing the copper methacrylic acid complex with high purity. Further, another object of the present invention is to provide an infrared absorbing composition containing a novel copper methacrylic acid complex which has an infrared absorbing ability and is excellent in solubility and heat resistance.
【０００６】[0006]
【課題を解決するための手段】本発明者は耐熱性に優れ
る無機物を有機物に溶解する方法について鋭意検討した
結果、水溶液のｐＨを厳密に制御する事により、前記目
的を満足する化合物が得られることを見いだして本発明
を完成した。すなわちｐＨをコントロールすることによ
り、塩構造をとっていた無機銅化合物が多核錯体化して
有機溶剤に可溶性となることを見いだした。さらに詳し
くは、銅のカルボン酸塩はアルカリ性条件下でのみ安定
であるが、酸性条件下で、しかも特殊な塩濃度の下での
みカルボキシラトが架橋して銅原子が二核錯体化する事
を発見した。そしてこの反応はカルボン酸に共通ではあ
るが、メタクリル酸のみがこの条件下で沈澱として析出
し、有機溶剤に可溶性の銅二核錯体を生成することを見
いだした。そして配位子として通常は水分子が配位する
が、仕込原料中の（メタクリル酸／銅）モル比を大きく
すると、メタクリル酸が配位する。またピリジン等のＮ
配位原子を有する単座配位子を選ぶことにより、吸収波
長を調整することが可能となった。こうして銅金属を含
有する、有機溶剤への溶解性の優れた、銅含有量の高
い、重合性を有する赤外線吸収材料を提供する事が可能
となった。Means for Solving the Problems As a result of diligent studies on a method of dissolving an inorganic substance having excellent heat resistance in an organic substance, the present inventor has found that a compound satisfying the above object can be obtained by strictly controlling the pH of an aqueous solution. Then, the present invention has been completed. That is, it was found that by controlling the pH, the inorganic copper compound having a salt structure is polynuclearly complexed and becomes soluble in an organic solvent. More specifically, copper carboxylate is stable only under alkaline conditions, but under acidic conditions and under special salt concentrations, carboxylato crosslinks and copper atoms are binuclear complexed. discovered. Although this reaction is common to carboxylic acids, it was found that only methacrylic acid precipitates as a precipitate under these conditions to form a copper dinuclear complex soluble in an organic solvent. Although water molecules are usually coordinated as a ligand, methacrylic acid is coordinated when the (methacrylic acid / copper) molar ratio in the charged raw material is increased. In addition, N such as pyridine
The absorption wavelength can be adjusted by selecting a monodentate ligand having a coordinating atom. In this way, it becomes possible to provide an infrared absorbing material containing copper metal, having excellent solubility in an organic solvent, having a high copper content, and having polymerizability.
【０００７】[0007]
【作用】本発明は下記一般式で示される新規なメタクリ
ル酸含有の銅二核錯体に関するものである。The present invention relates to a novel methacrylic acid-containing copper binuclear complex represented by the following general formula.
【０００８】Ｃｕ2 （μ−ＭＡＡ）4 Ｌ2 （式中、Ｃｕは銅金属を表し、μ−ＭＡＡは架橋したメ
タクリル酸カルボキシラトアニオンを表し、Ｌは水、ピ
リジン、メタクリル酸等の単座配位子を示す。）該錯体
の生成については、ＩＲスペクトルにより観察される。
たとえば該錯体のメタクリル酸カルボキシラトアニオン
のＣ＝Ｏ伸縮振動が１５９７，１４１６ｃｍ-1に観察さ
れる。塩構造をとった場合には１５５６，１４１７ｃｍ
-1に観察され、架橋構造を取った場合にのみ、Ｃ＝Ｏの
非対称伸縮振動が高波数シフトする（Ｃｏｏｒｄ．Ｃｈ
ｅｍ．Ｒｅｖｓ．，２３，２２７（１９８０））ので、
該錯体のメタクリル酸カルボキシラトアニオンが架橋し
ている事が解る。さらに錯体構造をとる事により、Ｃｕ
2 （μ−ＭＡＡ）4 （メタクリル酸）2 の場合、２０℃
のメタクリル酸メチル（ＭＭＡ）１００ｇには、５．１
ｇ溶解するようになるが、メタクリル酸銅塩は０．１ｇ
以下の量が溶解するにすぎない。そして該錯体のアセト
ニトリル溶液の可視スペクトルにはλmax ／ｎｍ（ε／
Ｍ-1ｃｍ-1）で表すと６７７ｎｍ（５１４）の吸収が観
察される。Cu 2 (μ-MAA) 4 L 2 (wherein Cu represents a copper metal, μ-MAA represents a crosslinked methacrylic acid carboxylate anion, and L represents a monodentate compound such as water, pyridine or methacrylic acid. The formation of the complex is observed by IR spectrum.
For example, the C═O stretching vibration of the carboxylate anion of the complex is observed at 1597,1416 cm −1 . 1556,1417 cm when using a salt structure
-1 is observed, and the asymmetric stretching vibration of C = O shifts to a high wave number only when a crosslinked structure is taken (Coord. Ch.
em. Revs. , 23, 227 (1980)),
It is understood that the carboxylate methacrylate anion of the complex is crosslinked. Furthermore, by adopting a complex structure, Cu
2 (μ-MAA) 4 (methacrylic acid) 2 20 ° C
5.1 g for 100 g of methyl methacrylate (MMA)
g will dissolve, but 0.1 g of methacrylic acid copper salt
Only the following amounts dissolve. The visible spectrum of the acetonitrile solution of the complex has λ max / nm (ε /
The absorption at 677 nm (514) is observed in terms of M −1 cm −1 ).
【０００９】本発明の製造方法は水溶液中でおこなわれ
るが、溶液のｐＨを特定する必要がある。すなわち銅化
合物とメタクリル酸を混合するに際して、溶液のｐＨを
２〜５の範囲に保つ事が必要である。ｐＨが２以下では
沈澱物が生成しないし、また５を越えると沈澱は生成す
るがその構造はもはや該錯体構造をとらず、塩基性メタ
クリル酸銅塩構造を取る。メタクリル酸以外のカルボン
酸でも同種の錯体を生成するが水溶性が高く、沈澱物と
して溶液から分離出来ない。メタクリル酸のみが沈澱物
として分離でき、高純度錯体が得られる。メタクリル酸
の仕込のモル数は銅原子の２倍モル以上であればよい。
２倍モル以上とすることで配位子をメタクリル酸とする
事もできる。反応温度には特に制限はないが、室温の場
合が収量も多く望ましい。Although the production method of the present invention is carried out in an aqueous solution, it is necessary to specify the pH of the solution. That is, when mixing the copper compound and methacrylic acid, it is necessary to keep the pH of the solution within the range of 2 to 5. When the pH is 2 or less, no precipitate is formed, and when the pH is more than 5, a precipitate is formed, but the structure does not take the complex structure anymore and takes a basic copper methacrylic acid salt structure. Carboxylic acids other than methacrylic acid also produce the same type of complex, but have high water solubility and cannot be separated from the solution as a precipitate. Only methacrylic acid can be separated as a precipitate, and a high-purity complex can be obtained. The number of moles of methacrylic acid charged may be at least twice the number of moles of copper atoms.
Methacrylic acid can be used as the ligand by adjusting the amount to be 2 times or more. The reaction temperature is not particularly limited, but room temperature is desirable because of high yield.
【００１０】使用する原料化合物としては特に制限はな
く、塩化銅、硝酸銅、硫酸銅等の水溶性銅化合物が使用
できる。配位子として単座配位子が制限なく使用出来る
が、水、ピリジン、メタクリル酸が特に好ましい。The raw material compound used is not particularly limited, and water-soluble copper compounds such as copper chloride, copper nitrate and copper sulfate can be used. A monodentate ligand can be used as the ligand without limitation, but water, pyridine, and methacrylic acid are particularly preferable.
【００１１】また本発明の赤外線吸収組成物は本発明の
メタクリル酸銅錯体を含有する事により、その能力を発
揮する。その含有量に制限はないが、該錯体中の銅含有
率が高いので添加量は少なくて十分にその効果を発揮す
る。また溶解度も高いので樹脂板として使用する場合、
その厚さを薄くする事が可能となる。可視光線を透過す
る物、たとえばポリスチレン、アクリル樹脂を基体樹脂
として使用する事が特に好ましい。これらの赤外線吸収
組成物を製造するにはモノマーの段階で本発明の該銅二
核錯体を溶解して重合してもよいし、また樹脂と本発明
の赤外線吸収材料を混合成型して製造する事も出来る。The infrared absorbing composition of the present invention exhibits its ability by containing the copper methacrylate complex of the present invention. There is no limitation on the content, but since the copper content in the complex is high, the addition amount is small and the effect is sufficiently exhibited. Also, since it has high solubility, when used as a resin plate,
It is possible to reduce the thickness. It is particularly preferable to use a substance that transmits visible light, such as polystyrene or an acrylic resin, as the base resin. In order to produce these infrared absorbing compositions, the copper binuclear complex of the present invention may be dissolved and polymerized at the stage of a monomer, or a resin and the infrared absorbing material of the present invention may be mixed and molded. You can also do things.
【００１２】本発明の新規なメタクリル酸含有の銅二核
錯体は、有機溶剤への溶解性が高く、赤外線吸収能を持
つ銅原子の含有量も高く、更に重合性も兼ね備えている
ので赤外線吸収色素として実用的に使用でき、とくにカ
ラーＶＴＲカメラのフィルタ、リモコンセンサー保護用
銘板、光熱変換剤等等して使用すれば優れた効果を発揮
するものである。The novel methacrylic acid-containing copper binuclear complex of the present invention has a high solubility in an organic solvent, a high content of a copper atom having an infrared absorbing ability, and also has a polymerizability, so that it can absorb infrared rays. It can be practically used as a dye, and particularly exhibits excellent effects when used as a filter for a color VTR camera, a nameplate for protecting a remote control sensor, a photothermal conversion agent, and the like.
【００１３】[0013]
【実施例】以下、本発明を実施例によりさらに具体的に
説明するが、本発明は、その要旨を越えない限り以下の
実施例に限定されるものではない。 実施例１ 硝酸銅６水和物２４．２ｇとメタクリル酸４５．１ｇを
３００ｍｌの水に溶解する。この水溶液に水酸化ナトリ
ウム１３．０ｇを溶解した水溶液１００ｍｌを添加す
る。この時、液のｐＨは３．５で濃青色の沈澱が２９．
２ｇ生成した。EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Example 1 24.2 g of copper nitrate hexahydrate and 45.1 g of methacrylic acid are dissolved in 300 ml of water. 100 ml of an aqueous solution in which 13.0 g of sodium hydroxide is dissolved is added to this aqueous solution. At this time, the pH of the liquid was 3.5 and the dark blue precipitate was 29.
2 g was produced.
【００１４】得られた固体の元素分析値は、Ｃｕ（２
０．０％）、Ｃ（４４．１％）、Ｈ（４．９％）で、化
学式としてＣｕ2 （ＭＡＡ）4 （メタクリル酸）2 であ
った。またこのＩＲスペクトルを図１に示したが、架橋
したメタクリル酸カルボキシラトアニオンのＣ＝Ｏ伸縮
振動が１５９７，１４１６ｃｍ-1に、配位したメタクリ
ル酸の吸収が１６８０ｃｍ-1に観測され、錯体構造を取
っている事が解る。この錯体は２０℃のメタクリル酸メ
チル１００ｇには５．１ｇ溶解した。 比較例１ 硝酸銅６水和物１２．１ｇとメタクリル酸１５．１ｇを
１５０ｍｌの水に溶解した。この水溶液に水酸化ナトリ
ウム８．０ｇを添加すると１１．２ｇの白青色沈澱を得
た。溶液のｐＨは５．５であった。The elemental analysis value of the obtained solid is Cu (2
0.0%), C (44.1%), H (4.9%), and the chemical formula was Cu 2 (MAA) 4 (methacrylic acid) 2 . Also showed the IR spectrum in FIG. 1, C = O stretching vibration of the crosslinked methacrylic acid carboxy Lato anions in 1597,1416cm -1, absorption of coordinating methacrylic acid was observed at 1680 cm -1, complex structure I understand that I am taking. 5.1 g of this complex dissolved in 100 g of methyl methacrylate at 20 ° C. Comparative Example 1 12.1 g of copper nitrate hexahydrate and 15.1 g of methacrylic acid were dissolved in 150 ml of water. When 8.0 g of sodium hydroxide was added to this aqueous solution, 11.2 g of white-blue precipitate was obtained. The pH of the solution was 5.5.
【００１５】この固体のＩＲスペクトルを図２に示した
が、ＯＨの伸縮振動が３６１６ｃｍ-1に明瞭に観察さ
れ、メタクリル酸カルボキシラトアニオンの吸収が１５
５６，１４１７ｃｍ-1に観察されるので架橋構造は取っ
ていないと判断出来る。また元素分析値はＣｕ（２８．
１％）、Ｃ（２２．７％）、Ｈ（５．３％）なので、化
学式としてＣｕ（ＯＨ）ＭＡＡ・３Ｈ2 Ｏの塩基性メタ
クリル酸銅塩が生成したと判断できる。この塩のＭＭＡ
への溶解度は０．１ｇ以下であった。 実施例２ 硝酸銅６水和物１２．１ｇ、メタクリル酸１９．７ｇ、
ピリジン４．０ｇを水１００ｍｌ、メタリール５０ｍｌ
溶液に溶解する。この溶液に水酸化ナトリウム６．０ｇ
を溶解した水溶液５０ｍｌを添加すると、緑色の固体が
１４．８ｇ沈澱物として得られた。この時溶液のｐＨは
５であった。The IR spectrum of this solid is shown in FIG. 2. Stretching vibration of OH is clearly observed at 3616 cm -1 , and the absorption of methacrylic acid carboxylato anion is 15
Since it is observed at 56,1417 cm -1 , it can be judged that no crosslinked structure is taken. The elemental analysis value is Cu (28.
1%), C (22.7%), and H (5.3%), it can be judged that a basic copper methacrylic acid salt of Cu (OH) MAA.3H 2 O as a chemical formula was produced. MMA of this salt
The solubility in was 0.1 g or less. Example 2 12.1 g of copper nitrate hexahydrate, 19.7 g of methacrylic acid,
4.0 g of pyridine 100 ml of water, 50 ml of meta reel
Dissolve in solution. 6.0 g of sodium hydroxide in this solution
When 50 ml of an aqueous solution in which was dissolved was added, 14.8 g of a green solid was obtained as a precipitate. At this time, the pH of the solution was 5.
【００１６】得られた固体のＩＲスペクトルには配位し
たピリジンによる３０９７，３０６２，１１５３，１０
７２，１０３８ｃｍ-1の吸収と、架橋したメタクリル酸
カルボキシラトアニオンの１５９７，１４１６ｃｍ-1の
吸収が観察され、その元素分析値がＣｕ（２０．５
％）、Ｃ（４９．１％）、Ｈ（４．７％）、Ｎ（４．４
％）である事からＣｕ2 （ＭＡＡ）4 （ｐｙ）2 である
と解る。この錯体のＭＭＡへの溶解度は３．７ｇであっ
た。 実施例３ 実施例１で得た錯体５．０ｇを、１ｋｇのメタクリル酸
メチル（ＭＭＡ）とネオペンチルグリコールジメタクリ
レート１５ｇの混合モノマー液に溶解し、重合開始剤と
してラウロイルパーオキサイド（ＬＰＯ）０．４ｇを添
加して、既知の方法に従って、ガラス板中で６０℃で重
合し、３ｍｍ厚さのアクリル板を得た。得られたアクリ
ル板の可視スペクトルでは、４９０ｎｍの透過率が８４
％であるが、６３０〜７５０ｎｍの範囲の透過率が０％
であり、十分な赤外線吸収性能を示した。 実施例４ 実施例２で得た錯体１０．０ｇを、１ｋｇのＭＭＡとエ
チレングリコールジメタクリレート４０ｇの混合モノマ
ー液に溶解し、重合開始剤としてアゾビスイソブチロニ
トリル（ＡＩＢＮ）０．６ｇを添加して、既知の方法に
従って、ガラス板中で６０℃で重合した。得られた１ｍ
ｍ厚さのアクリル板の可視スペクトルでは、５２０ｎｍ
の透過率が８８％であったが、６５０〜８３０ｎｍ範囲
の透過率は０％であり、十分な赤外線吸収性能を有して
いた。 実施例５ 実施例１で得た錯体０．５ｇを１００ｇのスチレンに溶
解し、ＡＩＢＮを０．０８ｇ添加して、常法通りガラス
板間でバルク重合し、３ｍｍ厚さの透明なスチレン樹脂
板を得た。このポリスチレン板の可視スペクトルでは４
９５ｎｍの透過率が７９％で、６５０〜７８０ｎｍの範
囲の透過率は０％であった。The IR spectrum of the solid obtained shows 3097, 3062, 1153, 10 by pyridine coordinated.
And absorption of 72,1038Cm -1, crosslinked absorption of methacrylic acid carboxy Lato anion 1597,1416Cm -1 is observed, the elemental analysis value of Cu (20.5
%), C (49.1%), H (4.7%), N (4.4).
%), It is understood that it is Cu 2 (MAA) 4 (py) 2 . The solubility of this complex in MMA was 3.7 g. Example 3 5.0 g of the complex obtained in Example 1 was dissolved in a mixed monomer solution of 1 kg of methyl methacrylate (MMA) and 15 g of neopentyl glycol dimethacrylate, and lauroyl peroxide (LPO) 0. 4 g was added and polymerization was carried out in a glass plate at 60 ° C. according to a known method to obtain an acrylic plate having a thickness of 3 mm. In the visible spectrum of the obtained acrylic plate, the transmittance at 490 nm is 84.
%, But the transmittance in the range of 630 to 750 nm is 0%
And showed sufficient infrared absorption performance. Example 4 10.0 g of the complex obtained in Example 2 is dissolved in a mixed monomer solution of 1 kg of MMA and 40 g of ethylene glycol dimethacrylate, and 0.6 g of azobisisobutyronitrile (AIBN) is added as a polymerization initiator. And was polymerized in a glass plate at 60 ° C. according to known methods. 1m obtained
520nm in the visible spectrum of acrylic plate with m thickness
Had a transmittance of 88%, but had a transmittance of 0% in the range of 650 to 830 nm, and had sufficient infrared absorption performance. Example 5 0.5 g of the complex obtained in Example 1 was dissolved in 100 g of styrene, 0.08 g of AIBN was added, and bulk polymerization was performed between glass plates in a usual manner to obtain a transparent styrene resin plate having a thickness of 3 mm. Got 4 in the visible spectrum of this polystyrene plate
The transmittance at 95 nm was 79%, and the transmittance in the range of 650 to 780 nm was 0%.
【００１７】[0017]
【発明の効果】本発明は、銅金属とメタクリル酸を反応
させて特殊な錯体を形成せしめ、有機溶剤に可溶性の、
銅含有率の高い、重合性を有する赤外線吸収色素を提供
するものであり、本発明を実施する事により、耐熱性、
堅牢性に優れた、安価な赤外線吸収材料の提供を実現し
たものである。INDUSTRIAL APPLICABILITY The present invention allows copper metal and methacrylic acid to react with each other to form a special complex, which is soluble in an organic solvent.
High copper content, to provide an infrared absorbing dye having polymerizability, by carrying out the present invention, heat resistance,
It is possible to provide an inexpensive infrared absorbing material having excellent robustness.
【図１】本発明の新規メタクリル酸銅錯体のＩＲスペク
トルである。FIG. 1 is an IR spectrum of the novel copper methacrylic acid complex of the present invention.
【図２】本発明の新規メタクリル酸銅錯体のＩＲスペク
トルである。FIG. 2 is an IR spectrum of the novel copper methacrylic acid complex of the present invention.
Claims (4)
銅錯体。 Ｃｕ2 （μ−ＭＡＡ）4 Ｌ2 （式中、Ｃｕは銅金属を、μ−ＭＡＡは架橋したメタク
リル酸カルボキシラトアニオンを、Ｌは水、ピリジン、
メタクリル酸等の単座配位子を表す。）1. A novel copper methacrylic acid complex represented by the following general formula. Cu 2 (μ-MAA) 4 L 2 (wherein Cu is copper metal, μ-MAA is crosslinked carboxylate carboxylate anion, L is water, pyridine,
It represents a monodentate ligand such as methacrylic acid. )
反応させるに際して水溶液のｐＨを２〜５の範囲に保つ
事を特徴とする、請求項１記載の新規なメタクリル酸銅
錯体の製造方法。2. The method for producing a novel copper methacrylic acid complex according to claim 1, wherein the pH of the aqueous solution is maintained in the range of 2 to 5 when the copper compound and methacrylic acid are reacted in the aqueous solution.
体を含有し、６００〜９００ｎｍの範囲に吸収を持つ赤
外線吸収組成物。3. An infrared absorbing composition containing the novel copper methacrylic acid complex according to claim 1 and having an absorption in the range of 600 to 900 nm.
ル樹脂である、請求項３記載の赤外線吸収組成物。4. The infrared absorbing composition according to claim 3, wherein the base resin is transparent polystyrene or acrylic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10027393A JP3506459B2 (en) | 1993-04-02 | 1993-04-02 | Novel copper methacrylate complex and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10027393A JP3506459B2 (en) | 1993-04-02 | 1993-04-02 | Novel copper methacrylate complex and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06287194A true JPH06287194A (en) | 1994-10-11 |
| JP3506459B2 JP3506459B2 (en) | 2004-03-15 |
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ID=14269604
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10027393A Expired - Fee Related JP3506459B2 (en) | 1993-04-02 | 1993-04-02 | Novel copper methacrylate complex and method for producing the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015158657A (en) * | 2014-01-21 | 2015-09-03 | 富士フイルム株式会社 | Spectral adjustment method for near-infrared absorbing materials, near-infrared absorbing composition and manufacturing method therefor, near-infrared cut filter and manufacturing method therefor, camera module, and spectral modifier for copper compounds |
| US11555132B2 (en) | 2019-02-01 | 2023-01-17 | Samsung Electronics Co., Ltd. | Near-infrared absorbing composition, optical structure, and camera module and electronic device comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245859A (en) * | 1988-02-15 | 1989-10-02 | Henkel Kgaa | Macroporous ion selective exchange resin, and its production and use |
-
1993
- 1993-04-02 JP JP10027393A patent/JP3506459B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245859A (en) * | 1988-02-15 | 1989-10-02 | Henkel Kgaa | Macroporous ion selective exchange resin, and its production and use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015158657A (en) * | 2014-01-21 | 2015-09-03 | 富士フイルム株式会社 | Spectral adjustment method for near-infrared absorbing materials, near-infrared absorbing composition and manufacturing method therefor, near-infrared cut filter and manufacturing method therefor, camera module, and spectral modifier for copper compounds |
| US11555132B2 (en) | 2019-02-01 | 2023-01-17 | Samsung Electronics Co., Ltd. | Near-infrared absorbing composition, optical structure, and camera module and electronic device comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3506459B2 (en) | 2004-03-15 |
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