JPH0665712B2 - Near infrared absorber - Google Patents
Near infrared absorberInfo
- Publication number
- JPH0665712B2 JPH0665712B2 JP59115839A JP11583984A JPH0665712B2 JP H0665712 B2 JPH0665712 B2 JP H0665712B2 JP 59115839 A JP59115839 A JP 59115839A JP 11583984 A JP11583984 A JP 11583984A JP H0665712 B2 JPH0665712 B2 JP H0665712B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- compound
- phthalocyanine
- near infrared
- infrared
- 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.)
- Expired - Fee Related
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
Landscapes
- Protection Of Plants (AREA)
- Greenhouses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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1600nm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。Description: TECHNICAL FIELD The present invention relates to a near-infrared absorber, and more specifically, to a near-infrared absorption region of 800 nm to 1600 nm without blocking transmission in the visible region. The present invention relates to a near infrared ray absorbent.
可視部では吸収を示さず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
イ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 do not absorb in the visible region but absorb light with a wavelength of 800 nm to 1600 nm are used for various applications as a near-infrared cut filter material.
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, a plastic for agricultural use coated with or containing the above-mentioned near-infrared absorber, heat rays are cut, and the growth of plants is controlled, or silicon photodiode (SPD)
It is used as a near-infrared cut filter of a photodetector that approximates the spectral sensitivity ratio luminosity curve of a semiconductor light receiving element.
前述の近赤外線吸収剤として、従来、一般式 （イ）： （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Ni、Co、PdまたはPtである）
で示される化合物、一般式 （ロ）： （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エニル基、M1はNi、Mo、
Pd、PtまたはＷである）で示される化合物および一般式
（ニ）： （式中、X1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。（特開昭57−21
458公報参照）。As the above-mentioned near-infrared absorbing agent, conventionally, the general formula (a): (In the formula, R 1 is a methyl group, hydrogen, chlorine or bromine, X is a quaternary ammonium group, and M is Ni, Co, Pd or Pt.)
A compound represented by the general formula (b): (In the formula, R 2 is hydrogen, chlorine or bromine, X and M are the same as the above), the general formula (C): (In the formula, R 3 is a methyl group or a phenyl group, M 1 is Ni, Mo,
Pd, Pt or W) and the general formula (d): A compound represented by the formula (wherein X 1 is iodine or tetrafluoroborate) is known. (JP-A-57-21
458).
しかし、この種の化合物は近赤外線吸収範囲が700〜110
0nm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 to 110.
It is 0 nm and narrow, which is not sufficient 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1600nmの
吸収領域を有する、特にSPDの用途に適した近赤外線吸
収剤を提供することにある。An object of the present invention is to provide a near-infrared absorber which is suitable for SPD applications, in particular, which has a wide near-infrared absorption region without blocking transmission in the visible region, that is, an absorption region of 800 to 1600 nm. .
前述の目的を達成するため、本発明によれば、波長800
ないし1600nmに至る近赤外線領域で吸収をもつ、例えば
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。In order to achieve the above-mentioned object, according to the present invention, a wavelength of 800
It is characterized in that the active ingredient is an azo compound having absorption in the near-infrared region up to 1600 nm and having, for example, a phthalocyanine skeleton represented by the general formula (I).
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、Alであり、ＡはナフトールAS系カッ
プリング成分である。 However, n is an integer of 2 to 4, M is 2 hydrogen atoms or Cu, Fe, Co, Cr, Al, and A is a naphthol AS-based coupling component.
以下、本発明を具体的に詳述する。 Hereinafter, the present invention will be described in detail.
本発明の前記一般式（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
ンノ体、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系のカッ
プリング成分とをカッ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 (I) of the present invention is a monoamino phthalocyanine such as a metal-free phthalocyanine, a copper phthalocyanine, an iron phthalocyanine, a cobalt phthalocyanine, a chromium phthalocyanine and an aluminum phthalocyanine, a diamineno compound, a triamino compound. And a diamino compound obtained by diazotizing a tetraamino compound with a naphthol AS-based coupling component are obtained.
前記ナフトールAS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 AS-based coupling component include the following.
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100重
量部中に加え、室温で撹拌した後、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。得られた瀘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。 Example-1 Tetraamino copper phthalocyanine 9.4 parts by weight was added to concentrated hydrochloric acid 100 parts by weight, and 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,
Filtered. Borofluoric acid was added dropwise to the obtained filtrate,
The resulting blue-green precipitate was filtered off, washed and dried to obtain 11.7 parts of 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160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。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100重
量部中に加え、室温で撹拌した後、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。得られた瀘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。Next, 3.2 parts (by weight) of 2-hydroxy-3-naphthoic acid anilide (naphthol AS) and triethanolamine 3.6.
Part was dissolved in 500 parts of NN'-dimethylformamide, and the temperature was 5 ° C.
After cooling to below, a solution prepared by dissolving 3.7 parts of the above-mentioned stabilized diazonium salt in 160 parts of N, W-dimethylformamide was added dropwise, and aging was carried out after completion of the addition. The black-purple precipitate formed was filtered off, washed and dried to obtain 5.5 parts of the desired azo compound having a phthalocyanine skeleton. Yield 95.2% Example-2 Tetraaminocopper phthalocyanine (9.4 parts by weight) was added to concentrated hydrochloric acid (100 parts by weight) and stirred at room temperature, and then ice (130 parts by weight) and sodium nitrite (4.6 parts) were dissolved in water (20 parts). And add
Filtered. Borofluoric acid was added dropwise to the obtained filtrate,
The resulting blue-green precipitate was filtered off, washed and dried to obtain 11.7 parts of stabilized diazonium salt.
次に、２−ヒドロキシ−Ｎ−（４−メトキシ−２−メチ
ルフエニル）−11Hベンゾ〔ａ〕カルバゾール−３−カ
ルオキシアミド（AS−SR）4.76部及びトリエタノールア
ミン3.6部をN,W−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−ジメチルホルムアミド160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）に混練分散させ、さらにこれを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) -11Hbenzo [a] carbazole-3-caroxyamide (AS-SR) 4.76 parts and triethanolamine 3.6 parts were added to N, W-dimethyl. A solution of 3.7 parts of the above-mentioned stabilized diazonium salt dissolved in 160 parts of N, N-dimethylformamide was added dropwise to 500 parts of formamide and cooled to 5 ° C or lower, and aging was carried out after the completion of the addition. The purple precipitate formed was filtered, washed and dried to obtain 4.8 parts of the desired azo compound having a phthalocyanine skeleton. Yield 72.4% Application Example 3 parts by weight of the azo compound having a phthalocyanine skeleton obtained in Examples 1 and 2 was kneaded and dispersed in 7 parts by weight of DBP (plasticizer, dibutyl phthalate), and further 200 parts by weight of methyl meta. What was mixed with the acrylate prepolymer and well dispersed was poured into a glass plate mold. A transparent molded plate was prepared by heating at a temperature of 60 ° C. for 24 hours and further at a temperature of 80 ° C. for 3 hours.
この試料について（株）日立製作所330型分光光度計を
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。第１図ならびに第２図か
ら、いずれも800〜1600nm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。The near-infrared absorption region of this sample was measured using a Hitachi Ltd. Model 330 spectrophotometer. 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. It can be seen from FIGS. 1 and 2 that they both absorb near infrared rays in the wavelength range of 800 to 1600 nm and have a shielding effect.
以上のとおり、本発明の近紫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の近赤外線
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イルタ材料としてきわめて有用であ
る。As described above, the near-ultraviolet absorber of the present invention does not block the transmission of light in the visible region, has a low transmittance absorption over the entire range of near-infrared rays of 800 to 1600 nm, and cuts near-infrared rays such as a photodetector. It is extremely useful as a filter material.
第１図および第２図はそれぞれ、実施例１ならびに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。FIG. 1 and FIG. 2 are graphs showing the measurement results of the near infrared absorption region for each of the samples of Examples 1 and 2.
Claims (1)
ナフトールAS系カップリング成分とをカップリングして
得られる、波長800nmから1600nmに至る近赤外線領域で
吸収をもつ次の一般式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、Alであり、ＡはナフトールAS系カッ
プリング成分である。1. A phthalocyanine skeleton represented by the following general formula, which is obtained by coupling a diazonium compound of a phthalocyanine compound and a naphthol AS-based coupling component and has absorption in the near infrared region from wavelength 800 nm to 1600 nm. A near infrared absorber containing an azo compound as an active ingredient. However, n is an integer of 2 to 4, M is 2 hydrogen atoms or Cu, Fe, Co, Cr, Al, 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 JPS60260674A (en) | 1985-12-23 |
| JPH0665712B2 true 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) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2590109B2 (en) * | 1987-07-03 | 1997-03-12 | 三井東圧化学株式会社 | Sulfur-containing urethane resin for near infrared absorption |
| JP2636657B2 (en) * | 1993-01-26 | 1997-07-30 | 光陽プラスチック株式会社 | Semi-negative plant cultivation house sheet |
| GB9613476D0 (en) * | 1996-06-27 | 1996-08-28 | British Polythene Ltd | Improvements in or relating to films and/or coatings |
| WO2001065914A2 (en) * | 2000-03-09 | 2001-09-13 | Ciba Specialty Chemicals Holding Inc. | Pigment concentrates for coloring seeds |
-
1984
- 1984-06-06 JP JP59115839A patent/JPH0665712B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60260674A (en) | 1985-12-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |