JPS62100557A - Improvement of light fastness of dye - Google Patents
Improvement of light fastness of dyeInfo
- Publication number
- JPS62100557A JPS62100557A JP24008585A JP24008585A JPS62100557A JP S62100557 A JPS62100557 A JP S62100557A JP 24008585 A JP24008585 A JP 24008585A JP 24008585 A JP24008585 A JP 24008585A JP S62100557 A JPS62100557 A JP S62100557A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- cyclodextrin
- light fastness
- formula
- light resistance
- 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は着色剤に用いる染料の耐光性に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to the light resistance of dyes used as colorants.
従来、染料の光退色を防ぐ方法としては一般的に紫外線
吸収剤や酸化防止剤が用いられてきた。Conventionally, ultraviolet absorbers and antioxidants have generally been used to prevent photobleaching of dyes.
第２図は例えば「化学と工業」誌第３８巻第１２２頁（
１９８５年発行）に記載された酸化防止剤を用いる従来
の光退色防止法を施された感熱記録紙の断面図であｌ）
％（１）は染料、（４）は支持体、（５）は酸化防止剤
、（６）は着色層である。次に動作について説明する。Figure 2 shows, for example, ``Chemistry and Industry'', Vol. 38, page 122 (
This is a cross-sectional view of thermal recording paper subjected to the conventional photofading prevention method using an antioxidant described in 1985 (published in 1985).
% (1) is the dye, (4) is the support, (5) is the antioxidant, and (6) is the colored layer. Next, the operation will be explained.
染料（式中りと略す）は光照射により励起−重積（式中
ＩＤと略す）→励起三重積（式中３Ｄ ）と略す）→分
解物（式中ｐｒｏｄｕｃｔと略す）という経路で分解す
る。即ち、下式（１）〜（６）で表わすことができる。The dye (abbreviated as RI in the formula) is decomposed by light irradiation through the following route: excitation-superposition (abbreviated as ID in the formula) → excited triple stack (abbreviated as 3D in the formula) → decomposition product (abbreviated as product in the formula) . That is, it can be expressed by the following formulas (1) to (6).
Ｄ ｂν ’Ｄ （１）−一−
−→
’Ｄ ｋｏ Ｄ （２）−一
一一一−Ｎ
１Ｄ 上１Ｄ ＋ ｈν （３）”Ｄ
ｌ（，４ｍＯｃ“）
’Ｄ ｋｏ’ Ｄ （５）−
一一一→
”＋０” ｍ ｐｒｏｄｕｃｔ （６）式
中、ｋＯは一重項から基底状態への無輻射遷移の速度定
数、
ｋｐハ螢光による一重項から基底状態への遷移の速度定
数、
ｋ、は三重積染料と酸素との反応速度定数である。D bν 'D (1)-1-
−→ 'D ko D (2) −1111−N 1D upper 1D + hν (3)”D
l(,4mOc") 'D ko' D (5)-
111 → "+0" m product (6) In the formula (6), kO is the rate constant of non-radiative transition from a singlet to the ground state, kp is the rate constant of the transition from a singlet to the ground state due to fluorescence, k, is the reaction rate constant between the triple stack dye and oxygen.
上記退色を防止する方法として、従来は酸化防止剤（式
中ＡＨと略す）が用いられ、下式（７） 、 （８）で
示すように退色を防止していた。As a method for preventing the above-mentioned fading, an antioxidant (abbreviated as AH in the formula) has conventionally been used to prevent fading as shown in the following formulas (7) and (8).
３Ｄ＋０１ ｋ、 ＤＯＯ（７）ＤＯＯ＋４ＡＨ
ｋｔ Ｄ＋４Ａ・＋２ Ｈｚ Ｏ（ｓ＋式中、ｋＩは
８重項染料と酸素との結合速度定数、ｋｔは染料過酸化
物の分解速度定数である。3D+01k, DOO(7)DOO+4AH
kt D+4A·+2 Hz O(s+ In the formula, kI is the binding rate constant between the octet dye and oxygen, and kt is the decomposition rate constant of the dye peroxide.
〔発明が解決しようとする問題点〕
上記従来のように、酸化防止剤により光退色を防止する
場合、下式のような酸化防止剤による還元退色により逆
に退色が促進するという問題点があった。[Problems to be Solved by the Invention] When photofading is prevented using an antioxidant as described above, there is a problem in that the reductive fading caused by the antioxidant accelerates the fading as shown in the formula below. Ta.
３Ｄ ＋ ＡＨ→ ＤＨ＋ Ａ・ （９）この
発明は、かかる問題点を解決するためになされたもので
、染料の耐光性を向上することを目的とする。3D+AH→DH+A・ (9) This invention was made to solve this problem, and its purpose is to improve the light resistance of dyes.
この発明の染料の耐光性改善方法は、染料とシクロデキ
ストリンとの包接化合物を形成するものである。The method of improving the light resistance of a dye according to the present invention involves forming an inclusion compound between a dye and a cyclodextrin.
この発明におけるシクロデキストリン（式中ＣＤと略す
）は染料と包接化合物を形成し、染料の一重項を下式〇
Ｇ、αυに示すように消光する。即ち、００式がおこる
か（２）式のｋｏの値が大きくなる。The cyclodextrin (abbreviated as CD in the formula) in this invention forms an inclusion compound with the dye, and quenches the singlet of the dye as shown in the following formulas 〇G and αυ. That is, either equation 00 occurs or the value of ko in equation (2) increases.
’Ｄ ＋ Ｃ！Ｉ）机Ｄ＋１０Ｄ Ｑｔ１’Ｃ
Ｄ ｋＩ； ＣＤ （１１）
−声
式中ｋｑは一重項染料からシクロデキストリンへのエネ
ルギー移動速度定数、
ｋｏは一重項シクロデキストリンの無輻射遷移の速度定
数である。'D + C! I) Desk D+10D Qt1'C
DkI; CD (11)
- In the equation, kq is the rate constant of energy transfer from singlet dye to cyclodextrin, and ko is the rate constant of nonradiative transition of singlet cyclodextrin.
＋ＣＤはＣＤの励起−重積である。+CD is the excitation-contamination of CD.
この時、染料の退色速度は下式（至）〜αηで示される
。At this time, the fading rate of the dye is expressed by the following formula (to) ~αη.
＋ｋｏ’（ｓＤ）＋ｋｑ（’Ｄ） （ＣＤ’ｌ
（ｌａｋｓｒ（’Ｄ）ｋｑ（”Ｄ）（ＣＤ）
０３定常状態よりｄ（”Ｄ）／ｄｔ＝０ 、 ｄ
（’Ｄ：］／ｄｔ ＝ 。+ko'(sD)+kq('D) (CD'l
(laksr('D)kq(”D)(CD)
03 From the steady state, d(”D)/dt=0, d
('D:]/dt = .
（１５、９４９式を（２）式に代入して（ロ）式を得る
。(Substituting equation (15,949) into equation (2) yields equation (b).
ａＶ式から、ｋｏ、 ｋＦ、 ｋｑ、 ＣＯＤ〕カ増加
ｆレバ、退色速度が減少することが解り、そのため、シ
クロデキストリンを添加するのである。From the aV formula, it can be seen that as ko, kF, kq, COD] increases, the fading rate decreases, and that is why cyclodextrin is added.
第１図は、この発明の一実施例の染料とシクロデキスト
リンとの包接化合物の構成図であり１（１）ハ染料、（
２）はシクロデキストリン、（３）は包接化合物、であ
る。FIG. 1 is a structural diagram of a clathrate compound of a dye and a cyclodextrin according to an embodiment of the present invention.
2) is a cyclodextrin, and (3) is an inclusion compound.
この発明に係わるシクロデキストリンとしては、例えば
β−シクロデキストリン、β−シクロデキストリン、γ
−シクロデキストリン、２，４．５−トリス−Ｏ−メチ
ル−γ−シクロデキストリン、および水溶性シクロデキ
ストリン含有重合体（公開特許公報５８−１６７６１８
に記載）などが用いられる。Examples of the cyclodextrin according to the present invention include β-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.
-Cyclodextrin, 2,4.5-tris-O-methyl-γ-cyclodextrin, and water-soluble cyclodextrin-containing polymer (Publication Patent Publication No. 58-167618
) etc. are used.
この発明に係わる染料としては、例えばメチレンフルー
、マラカイトグリーン、ベーシックオレンチ２１、ヘー
シックレッド１３、ベーシックブルー２５１およびベー
シックブラウン１などが用いられる。Examples of the dyes used in the present invention include methylene flu, malachite green, Basic Orange 21, Hessick Red 13, Basic Blue 251, and Basic Brown 1.
この発明に係わるシクロデキストリンと染料トの包接化
合物を形成する方法としては、適当な溶媒、例えばジメ
チルスルフオキシド等などに、シフロブキス）Ｕンと染
料を溶解させておいて後乾燥することによるものがある
。The method for forming the clathrate compound of cyclodextrin and dyest according to the present invention is to dissolve the cyclodextrin and dye in a suitable solvent such as dimethyl sulfoxide, and then dry the mixture. There is something.
以下実施例によりこの発明を具体的に説明する。The present invention will be specifically explained below with reference to Examples.
実施例１
メチレンブルー０．０１重量部とβ−シクロデキストリ
ン１重量部をジメチルスルホキシド１００ ｌｉｉ部に
溶かし、口紙をそのものの中に浸漬して引き上げ乾燥す
る。この口紙を２．５，７．１０分間超高圧水銀灯光を
照射した時の反射濃度Ｃ０Ｄ）変化を示す特性図を第３
図（ａｌに示す。図において、縦軸はＯＤ （Ｏｐｔｉ
ｃａｌ Ｄｅｎｓｉｔｙで表わす反射濃度を、横軸は分
で表わす照射時間（分）である。Example 1 0.01 parts by weight of methylene blue and 1 part by weight of β-cyclodextrin are dissolved in 100 parts by weight of dimethyl sulfoxide, and a slip is dipped into the solution and pulled up and dried. The characteristic diagram showing the change in reflection density C0D) when this cover sheet was irradiated with ultra-high pressure mercury lamp light for 2.5, 7.10 minutes is shown in Figure 3.
Figure (shown in al. In the figure, the vertical axis is OD (Opti
The reflection density is expressed as cal density, and the horizontal axis is the irradiation time (minutes) expressed in minutes.
比較例
メチレンブルー０．０１重量部のみをジメチルスルホキ
シド１００重量部に溶かし、口紙をそのものの中に浸漬
して引き上げ乾燥する。この口紙に２゜５．７．１０分
間超高圧水銀灯光を照射すると反射濃度は第３図（ｂ）
のようになった。Comparative Example Only 0.01 part by weight of methylene blue is dissolved in 100 parts by weight of dimethyl sulfoxide, and a paper is immersed in the solution and pulled up and dried. When this slip is irradiated with ultra-high pressure mercury lamp light for 2°5.7.10 minutes, the reflection density is as shown in Figure 3 (b).
It became like this.
上記第３図（ａ）と（ｂ）を比べると明らかなように、
（ａ）の方が耐光性が改善されていることが解る。As is clear from comparing Figure 3 (a) and (b) above,
It can be seen that (a) has improved light resistance.
以上説明したとおり、この発明は染料とシクロデキスト
リンとの包接化合物を形成することにより、染料の耐光
性を改善することができる。As explained above, the present invention can improve the light resistance of a dye by forming an inclusion compound between a dye and a cyclodextrin.
第１図はこの発明の一実施例の包接化合物の溝成図、第
２図は、従来の感熱記録紙の断面図、第３図はこの発明
の一実施例に係わる染料の耐光性と従来の染料のそれを
比較する耐光性を示す特性図である。
図において、（１）は染料、（２）はシクロデキストリ
ン、（３）は包接化合物である。
なお、図中同一符号は同−又は相当部分を示す。Fig. 1 is a groove diagram of an clathrate compound according to an embodiment of the present invention, Fig. 2 is a cross-sectional view of a conventional thermosensitive recording paper, and Fig. 3 is a diagram showing the light fastness of a dye according to an embodiment of the present invention. FIG. 2 is a characteristic diagram showing the light fastness compared with that of conventional dyes. In the figure, (1) is a dye, (2) is a cyclodextrin, and (3) is an inclusion compound. Note that the same reference numerals in the figures indicate the same or equivalent parts.
Claims (4)
することを特徴とする染料の耐光性改善方法。(1) A method for improving the light resistance of a dye, which comprises forming an inclusion compound of a dye and a cyclodextrin.
ある特許請求の範囲第１項記載の染料の耐光性改善方法
。(2) The method for improving light resistance of a dye according to claim 1, wherein the cyclodextrin is β-cyclodextrin.
メチル−γ−シクロデキストリンである特許請求の範囲
第１項記載の染料の耐光性改善方法。(3) Cyclodextrin is 2,4,5-tris-O-
A method for improving the light resistance of a dye according to claim 1, which is methyl-γ-cyclodextrin.
項ないし第３項の何れかに記載の染料の耐光性改善方法
。(4) Claim 1 in which the dye is methylene blue
A method for improving light resistance of a dye according to any one of items 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60240085A JPH0615673B2 (en) | 1985-10-25 | 1985-10-25 | Method for producing dye inclusion compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60240085A JPH0615673B2 (en) | 1985-10-25 | 1985-10-25 | Method for producing dye inclusion compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62100557A true JPS62100557A (en) | 1987-05-11 |
| JPH0615673B2 JPH0615673B2 (en) | 1994-03-02 |
Family
ID=17054258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60240085A Expired - Lifetime JPH0615673B2 (en) | 1985-10-25 | 1985-10-25 | Method for producing dye inclusion compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615673B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808189A (en) * | 1987-02-04 | 1989-02-28 | Hoyu Co., Ltd. | Powdered hair dye containing cyclodextrin inclusion complex |
| WO1996019502A1 (en) * | 1994-12-20 | 1996-06-27 | Kimberly-Clark Worldwide, Inc. | Improved mutable composition |
| WO1996022335A1 (en) * | 1995-01-17 | 1996-07-25 | Kimberly-Clark Worldwide, Inc. | Novel colorants and colorant modifiers |
| WO1997001605A1 (en) * | 1995-06-28 | 1997-01-16 | Kimberly-Clark Worldwide, Inc. | Novel colorants and colorant modifiers |
| JP2008088201A (en) * | 2006-09-29 | 2008-04-17 | Toppan Printing Co Ltd | Ink for oxygen indicator and packaging material using the same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5064320A (en) * | 1973-10-09 | 1975-05-31 | ||
| JPS53114987A (en) * | 1977-03-17 | 1978-10-06 | Toppan Printing Co Ltd | Printing of structure comprising cellulose fiber and fiber containing said cellulose fiber |
| JPS54117536A (en) * | 1978-03-04 | 1979-09-12 | Kawashima Fumio | Stabilization of natural coloring material |
| JPS573861A (en) * | 1980-06-11 | 1982-01-09 | Sumitomo Chem Co Ltd | Preparation of carotenoid pharmaceutical |
| JPS60156761A (en) * | 1984-01-26 | 1985-08-16 | Yamagataken | Preparation of dyestuff of safflower green powder |
| JPS60192729A (en) * | 1984-03-14 | 1985-10-01 | Ichiro Shibauchi | Production of concentrated color pellet for synthetic resin |
| JPS6187760A (en) * | 1984-06-30 | 1986-05-06 | Wako Pure Chem Ind Ltd | Method for improving solubility of methyl orange dye in solvent |
-
1985
- 1985-10-25 JP JP60240085A patent/JPH0615673B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5064320A (en) * | 1973-10-09 | 1975-05-31 | ||
| JPS53114987A (en) * | 1977-03-17 | 1978-10-06 | Toppan Printing Co Ltd | Printing of structure comprising cellulose fiber and fiber containing said cellulose fiber |
| JPS54117536A (en) * | 1978-03-04 | 1979-09-12 | Kawashima Fumio | Stabilization of natural coloring material |
| JPS573861A (en) * | 1980-06-11 | 1982-01-09 | Sumitomo Chem Co Ltd | Preparation of carotenoid pharmaceutical |
| JPS60156761A (en) * | 1984-01-26 | 1985-08-16 | Yamagataken | Preparation of dyestuff of safflower green powder |
| JPS60192729A (en) * | 1984-03-14 | 1985-10-01 | Ichiro Shibauchi | Production of concentrated color pellet for synthetic resin |
| JPS6187760A (en) * | 1984-06-30 | 1986-05-06 | Wako Pure Chem Ind Ltd | Method for improving solubility of methyl orange dye in solvent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808189A (en) * | 1987-02-04 | 1989-02-28 | Hoyu Co., Ltd. | Powdered hair dye containing cyclodextrin inclusion complex |
| WO1996019502A1 (en) * | 1994-12-20 | 1996-06-27 | Kimberly-Clark Worldwide, Inc. | Improved mutable composition |
| WO1996022335A1 (en) * | 1995-01-17 | 1996-07-25 | Kimberly-Clark Worldwide, Inc. | Novel colorants and colorant modifiers |
| WO1997001605A1 (en) * | 1995-06-28 | 1997-01-16 | Kimberly-Clark Worldwide, Inc. | Novel colorants and colorant modifiers |
| JP2008088201A (en) * | 2006-09-29 | 2008-04-17 | Toppan Printing Co Ltd | Ink for oxygen indicator and packaging material using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0615673B2 (en) | 1994-03-02 |
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