JPS60260674A - Near-infrared absorber - Google Patents
Near-infrared absorberInfo
- Publication number
- JPS60260674A JPS60260674A JP59115839A JP11583984A JPS60260674A JP S60260674 A JPS60260674 A JP S60260674A JP 59115839 A JP59115839 A JP 59115839A JP 11583984 A JP11583984 A JP 11583984A JP S60260674 A JPS60260674 A JP S60260674A
- Authority
- JP
- Japan
- Prior art keywords
- infrared
- parts
- naphthol
- phthalocyanine
- infrared absorber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
Abstract
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
本発明は近赤外線吸収剤に係り、更に詳しくは、可視部
の透過を阻止することなく、８００ｎｍから１６００ｎ
ｍの近赤外部の全域にわたって吸収作用を呈する近赤外
線吸収剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Pertains] The present invention relates to a near-infrared absorber, and more specifically, it relates to a near-infrared absorber that absorbs light from 800nm to 1600nm without blocking transmission in the visible region.
The present invention relates to a near-infrared absorber that exhibits an absorption effect over the entire near-infrared region of m.
可視部では吸収を示さす８００ｎｍ −１６００ｎｍの
波長の光に対して吸収を呈する近赤外線吸収剤は、近赤
外線カットフィルター材料として種々の用途に用いられ
ている。Near-infrared absorbers that exhibit absorption in the visible range of light with wavelengths of 800 nm to 1600 nm are used in various applications as near-infrared cut filter materials.
例えば、農業用プラスチックに前記の近赤外線吸収剤を
塗布または含有せしめ、熱線をカットし、植物の生長を
調節したもの、或いはシリコンホトダイオード（ＳＰＤ
）などの半導体受光素子の分光感度比視感度曲線に近づ
ける光検出装置の近赤外線カットフィルター等の用途に
用いられている。For example, agricultural plastics coated with or containing the above-mentioned near-infrared absorber to cut heat rays and regulate plant growth, or silicon photodiodes (SPDs).
), etc. It is used for applications such as near-infrared cut filters in photodetecting devices that approximate the spectral sensitivity-to-luminous efficiency curves of semiconductor light-receiving elements.
前述の近赤外線吸収剤として、従来、一般式（伺：
（式中、Ｒ１はメチル基、水素、塩素または臭素、Ｘは
第４級アンモニウム基、Ｍは旧、Ｃｏ、 Ｐｄまたは
ｐｔである）で示される化合物、一般式（）：
（式中、Ｒ２は水素、塩素または臭素、ＸおよびＭは前
記と同じである）で示される化合物、一般式（ハ）：
（式中、Ｒ３はメチル基またはフェニル基、ＭｌはＮｉ
、 Ｍｏ５Ｐｄ、、Ｐｔまたは−である）で示される化
合物および一般式（ニ）；
（式中、×１はヨウ素またはテトラフルオロボレートで
ある）で示される化合物が知られている。Conventionally, the above-mentioned near-infrared absorber has a general formula: (where R1 is a methyl group, hydrogen, chlorine or bromine,
pt), a compound represented by the general formula (): (wherein R2 is hydrogen, chlorine or bromine, and X and M are the same as above), a compound represented by the general formula (c): (in the formula , R3 is a methyl group or phenyl group, Ml is Ni
, Mo5Pd, , Pt or -) and compounds represented by the general formula (d); (wherein x1 is iodine or tetrafluoroborate) are known.
（特開昭５７−２１４５８公報参照）。(Refer to Japanese Unexamined Patent Publication No. 57-21458).
しかし、この種の化合物は近赤外線吸収範囲が７００〜
１ｌ１００ｎであって狭く、ＳＰＤの用途には不充分で
ある。However, this type of compound has a near-infrared absorption range of 700~
The diameter is 1l100n, which is narrow and insufficient for SPD applications.
本発明の目的は可視部の透過を阻止することなく、かつ
広範囲の近赤外線吸収域、すなわち８００ないし１６０
０ｎｍの吸収領域を有する、特にｓｐｏの用 １・ １
（途に適した近赤外線吸収剤を提供することにある。The purpose of the present invention is to cover a wide range of near-infrared absorption ranges, that is, from 800 to 160, without blocking the transmission of visible light.
Especially for spo with absorption region of 0 nm 1.1
(Our objective is to provide near-infrared absorbers suitable for various applications.
前述の目的を達成するため、本発明によれば、波長８０
０ないし１６００ｎｍに至る近赤外線領域で吸収をもつ
、一般式（Ｉ）で示されるフタロシアニン骨格を有する
アゾ化合物を有効成分とすることを特徴とする。To achieve the above object, according to the invention, the wavelength 80
It is characterized by containing as an active ingredient an azo compound having a phthalocyanine skeleton represented by general formula (I), which absorbs in the near infrared region from 0 to 1600 nm.
ただし、ｎは２ないし４の整数、Ｍは水素原子２個また
はＣｕＳＦｅ、 Ｃｏ−Ｃｒ、＾１であり、Ａはナフト
ールＡＳ系カンプリング成分である。However, n is an integer of 2 to 4, M is two hydrogen atoms or CuSFe, Co-Cr, ^1, and A is a naphthol AS-based camping component.
以下、本発明を具体的に詳述する。 Hereinafter, the present invention will be specifically explained in detail.
本発明の前記一般式Ｎ）で示されるフタロシアニン骨格
を有するアゾ化合物は、無金属フタロシアニン、銅フタ
ロシアニン、鉄フタロシアニン、コバルトフタロシアニ
ン、クロムフタロシアニンおよびアルミニウムフタロシ
アニン等のフタロシアニン類のモノアミノ体、ジアミノ
体、トリアミノ体、テトラアミノ体をジアゾ化して得ら
れるジアゾニウム化合物と、ナフトールＡＳ系のカンプ
リング成分とをカンプリングすることによって得られる
。The azo compound having a phthalocyanine skeleton represented by the general formula N) of the present invention is a monoamino, diamino, or triamino form of phthalocyanine such as metal-free phthalocyanine, copper phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, chromium phthalocyanine, and aluminum phthalocyanine. , is obtained by campling a diazonium compound obtained by diazotizing a tetraamino compound and a naphthol AS-based campling component.
前記ナフトール＾Ｓ系のカップリング成分としては例え
ば以下のものが挙げられる。Examples of the naphthol^S-based coupling components include the following.
ＯＣＨ３
ＯＣ１ｌ＋
ナフトール ＭＳ −Ｓ
ナフトール ＭＳ −ＢＲ
ナフトール ΔＳ −ＫＮ
ナフトール ＡＳ −ＢＴ（ＭＳ −ＤＢ）ｃｎｉ
■
ナフトール ＭＳ −５Ｇ
ＣＩｌｉ ナフトール ＡＳ −Ｇ
ナフト−ＩＬＭＳ−ＬＧ
１
Ｃ１１３
ナフトール ＭＳ −１，３Ｇ
Ｎ す丹−ル ＡＳ −Ｌ４Ｇ
０
実施例−１
テトラアミノ銅フタロシアニン９．４重量部を濃塩酸１
００重量部中に加え、室温で攪拌した後、氷１３０重量
部と、亜硝酸ナトリウム４．６部を水２０部に溶かした
ものを加え、濾過した。得られた濾液にホウフッ化水素
酸を滴下し、生じた青緑色の沈澱を濾別し、洗浄、乾燥
し、１１．７部の安定化ジアゾニウム塩を得た。OCH3 OC1l+ Naphthol MS -S Naphthol MS -BR Naphthol ΔS -KN Naphthol AS -BT (MS -DB) cni ■ Naphthol MS -5G CIli Naphthol AS -G Naphthol -ILMS-LG 1 C113 Naphthol MS -1,3G N Sutan -L AS -L4G 0 Example-1 9.4 parts by weight of tetraamino copper phthalocyanine was added to 1 part by weight of concentrated hydrochloric acid.
After stirring at room temperature, 130 parts by weight of ice and 4.6 parts of sodium nitrite dissolved in 20 parts of water were added and filtered. Hydrofluoroboric acid was added dropwise to the obtained filtrate, and the resulting blue-green precipitate was filtered off, washed, and dried to obtain 11.7 parts of a stabilized diazonium salt.
次に２−ヒドロキシ−３−ナフトエ酸アニリド（ナフト
ールＡＳ） ３．２部（重量）およびトリエタノールア
ミン３．６部をＮＮ’−ジメチルホルムアミド５００部
に溶解し、５℃以下に冷却し、そこへ上記安定化ジアゾ
ニウム塩３．７部をＮ、Ｗ−ジメチルホルムアミド１６
０部に溶かした溶液を滴下し、滴下終了後熟成を行った
。生成した黒紫色沈澱を濾別、洗浄、乾燥し、目的のフ
タロシアニン骨格を有するアゾ化合物５．５部を得た。Next, 3.2 parts (by weight) of 2-hydroxy-3-naphthoic acid anilide (naphthol AS) and 3.6 parts of triethanolamine were dissolved in 500 parts of NN'-dimethylformamide, cooled to below 5°C, and then 3.7 parts of the above stabilized diazonium salt was added to 16 parts of N,W-dimethylformamide.
A solution dissolved in 0 parts was added dropwise, and after the addition was completed, ripening was performed. The produced black-purple precipitate was filtered, washed and dried to obtain 5.5 parts of the desired azo compound having a phthalocyanine skeleton.
収率９５．２％実施例−２
テトラアミノ銅フタロシアニン９．４重量部を濃塩酸１
００重量部中に加え、室温で攪拌し、た後、氷１３０重
量部と、亜硝酸ナトリウム４．６部を水２０部に溶かし
たものを加え、濾過した。得られた濾液にホウフッ化水
素酸を滴下し、生した青緑色の沈澱を濾別し、洗浄、乾
燥し、１１．７部の安定化ジアゾニウム塩を得た。Yield 95.2% Example-2 9.4 parts by weight of tetraamino copper phthalocyanine was dissolved in 1 part by weight of concentrated hydrochloric acid.
After stirring at room temperature, 130 parts by weight of ice and 4.6 parts of sodium nitrite dissolved in 20 parts of water were added and filtered. Hydrofluoroboric acid was added dropwise to the obtained filtrate, and the blue-green precipitate formed was filtered off, washed, and dried to obtain 11.7 parts of a stabilized diazonium salt.
次に、２−ヒドロキシ−Ｎ−（４−メトキシ−２−メチ
ルフェニル） −１１Ｈベンゾ［ａ）カルハソ゛−ル−
３−カルボキシアミド（八Ｓ−５Ｒ） ４．７６部及び
トリエタノールアミン３．６部をＮ、１１−ジメチルホ
ルムアミド５００部に溶解し、５℃以下に冷却し、そこ
へ上記安定化ジアゾニウム塩３．７部をＮ、Ｎ−ジメチ
Ｊレホルムアミドｏ；ｏｓｃこン容かした？容液を滴下
し、滴下終了後熟成を行った。生成した紫色沈澱を濾別
、洗浄、乾燥し、目的のフタロシアニン骨格を有するア
ゾ化合物４．８部を得た。収率７２．４％
応用例
実施例１．２で得たフタロシアニン骨格を有す ・ １
（るアゾ化合物３重量部を７重量部のＤＢＰ （可塑剤
、ジブチルフタレート）に混線分散させ、さらに１
これを２００重量部のメチルメタアクリレートプレポリ
マーに混ぜ、良く分散させたものをガラス板鋳型に注入
した。６０℃の温度で２４時間、さらに８０℃の温度で
３時間加熱して、透明な成形板を作った。Next, 2-hydroxy-N-(4-methoxy-2-methylphenyl)-11H benzo[a) calhasol-
4.76 parts of 3-carboxamide (8S-5R) and 3.6 parts of triethanolamine were dissolved in 500 parts of N,11-dimethylformamide, cooled to below 5°C, and the above stabilized diazonium salt 3 was added thereto. .7 parts were mixed with N,N-dimethyleneformamide o;osc? The solution was added dropwise, and after the addition was completed, ripening was performed. The produced purple precipitate was filtered, washed and dried to obtain 4.8 parts of the desired azo compound having a phthalocyanine skeleton. Yield 72.4% Application Example Having the phthalocyanine skeleton obtained in Example 1.2 1
3 parts by weight of an azo compound (3 parts by weight) are cross-dispersed in 7 parts by weight of DBP (plasticizer, dibutyl phthalate), then mixed with 200 parts by weight of methyl methacrylate prepolymer, and the well-dispersed mixture is molded into a glass plate mold. A transparent molded plate was prepared by heating at a temperature of 60°C for 24 hours and then at a temperature of 80°C for 3 hours.
この試料について（株）日立製作所３３０型分光光度針
を用い、近赤外吸収域を測定した。第１図は実施例１の
化合物を用いた測定結果であり、第２図は実施例２の化
合物を用いた測定結果である。The near-infrared absorption region of this sample was measured using a spectrophotometric needle model 330 manufactured by Hitachi, Ltd. FIG. 1 shows the measurement results using the compound of Example 1, and FIG. 2 shows the measurement results using the compound of Example 2.
第１図ならびに第２図から、いずれも８００〜１６００
ｎｍの波長範囲の近赤外線を良く吸収し、遮へい効果を
有することがわかる。From Figure 1 and Figure 2, both are 800 to 1600.
It can be seen that it well absorbs near-infrared rays in the nm wavelength range and has a shielding effect.
以上のとおり、本発明の近赤外線吸収剤は可視部の光の
透過を阻止することなく、８００ないし１６００ｎｍの
近赤外部の全域にわたって低透過率の吸収を有し、光検
出装置等の近赤外線カットフィルタ材料としてきわめて
有用である。As described above, the near-infrared absorbent of the present invention has low transmittance absorption over the entire near-infrared region from 800 to 1600 nm without blocking the transmission of light in the visible region, and can be used in near-infrared rays such as photodetectors. It is extremely useful as a cut filter material.
第１図および第２図はそれぞれ、実施例１なら２
びに２の各試料についての近赤外吸収域の測定結果を表
したグラフである。
特許出願人 大日精化工業株式会社FIG. 1 and FIG. 2 are graphs showing the measurement results of the near-infrared absorption region of each sample of Examples 1, 2, and 2, respectively. Patent applicant: Dainichiseika Kagyo Co., Ltd.
Claims (1)
吸収をもつ、一般式（１）で示されるフタロシアニン骨
格を有するアゾ化合物を有効成分とする近赤外線吸収剤
。 ただし、ｎは２ないし４の整数、Ｍは水素原子２個また
はＣｕ、 Ｆｅ、 Ｃｏ、 Ｃｒ、＾ｌであり、Ａはナ
フトールＡＳ系カップリング成分である。[Scope of Claims] A near-infrared absorber containing as an active ingredient an azo compound having a phthalocyanine skeleton represented by general formula (1), which absorbs in the near-infrared region of wavelengths from 800 nm to 1600 nm. However, n is an integer of 2 to 4, M is two hydrogen atoms or Cu, Fe, Co, Cr, ^l, and A is a naphthol AS-based coupling component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59115839A JPH0665712B2 (en) | 1984-06-06 | 1984-06-06 | Near infrared absorber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59115839A JPH0665712B2 (en) | 1984-06-06 | 1984-06-06 | Near infrared absorber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60260674A true JPS60260674A (en) | 1985-12-23 |
| JPH0665712B2 JPH0665712B2 (en) | 1994-08-24 |
Family
ID=14672394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59115839A Expired - Fee Related JPH0665712B2 (en) | 1984-06-06 | 1984-06-06 | Near infrared absorber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665712B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6411153A (en) * | 1987-07-03 | 1989-01-13 | Mitsui Toatsu Chemicals | Near infrared-absorbing polymer composition |
| JPH06217649A (en) * | 1993-01-26 | 1994-08-09 | Koyo Plast Kk | Sheet for semi-shade plant-culturing house |
| GB2314844B (en) * | 1996-06-27 | 2000-03-22 | British Polythene Ltd | Improvements in or relating to films and/or coatings |
| US6688041B2 (en) * | 2000-03-09 | 2004-02-10 | Ciba Specialty Chemicals Corporation | Pigment concentrates for coloring seeds |
-
1984
- 1984-06-06 JP JP59115839A patent/JPH0665712B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6411153A (en) * | 1987-07-03 | 1989-01-13 | Mitsui Toatsu Chemicals | Near infrared-absorbing polymer composition |
| JPH06217649A (en) * | 1993-01-26 | 1994-08-09 | Koyo Plast Kk | Sheet for semi-shade plant-culturing house |
| GB2314844B (en) * | 1996-06-27 | 2000-03-22 | British Polythene Ltd | Improvements in or relating to films and/or coatings |
| US6688041B2 (en) * | 2000-03-09 | 2004-02-10 | Ciba Specialty Chemicals Corporation | Pigment concentrates for coloring seeds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665712B2 (en) | 1994-08-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |