EP0662094A1 - Process for producing dye-containing polyvinyl alcohol foils and their use - Google Patents
Process for producing dye-containing polyvinyl alcohol foils and their useInfo
- Publication number
- EP0662094A1 EP0662094A1 EP94924739A EP94924739A EP0662094A1 EP 0662094 A1 EP0662094 A1 EP 0662094A1 EP 94924739 A EP94924739 A EP 94924739A EP 94924739 A EP94924739 A EP 94924739A EP 0662094 A1 EP0662094 A1 EP 0662094A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyvinyl alcohol
- dye
- containing polyvinyl
- foils
- film
- 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.)
- Withdrawn
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/221—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating pH value
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Definitions
- the invention relates to a process for the production of waterproof, dye-containing polyvinyl alcohol films and their use as a sensor membrane for determining the pH value.
- Sensor membrane consists of a mechanically stable carrier element and a hydrophilic recording layer applied thereon, which contains an indicator dye in immobilized form.
- the absorption layer consists of cellulose, gelatin, hydrogel, hydrophilic polyvinyl alcohols or mixtures of these substances. Reactive indicators are usually used as indicator dyes, i.e.
- pH indicators that have a chemical function that enables chemical bonding to the absorption layer.
- the invention has for its object to provide waterproof polyvinyl alcohol films for reversible pH measurement, which ensure rich colorations.
- an uncrosslinked polyvinyl alcohol layer can be made waterproof not only by heating with acids or aldehydes, for example, but also by reacting it directly with reactive dye solutions.
- the invention relates to a process for the production of waterproof, dye-containing polyvinyl alcohol films, which is characterized in that an uncrosslinked polyvinyl alcohol layer is reacted directly with a reactive dye solution.
- Another object of the invention is the use of the polyvinyl alcohol film thus produced as a sensor membrane for the reversible optical display of the pH value of a sample.
- a reactive dye solution By reacting an uncrosslinked polyvinyl alcohol film with a reactive dye solution and, in comparison, with a dye-free solution, it could be demonstrated that in the latter case no water resistance is achieved. It can be concluded from this that the water resistance developed is based directly on the reaction of the polyvinyl alcohol with the reactive dye. Since the number of free hydroxyl groups in the uncrosslinked polyvinyl alcohol is high, the process according to the invention results in a higher dye absorption and thus a rich color, which in turn allows more precise measurements. The covalently bound reactive dyes can no longer be washed out.
- Typical chemical structures of reactive indicators are e.g.
- the polyvinyl alcohol films obtained according to the invention are optically completely transparent and are therefore readily accessible to a photometric absorption measurement. In addition, they can be produced in large quantities at low cost. Due to the relatively thin film or indicator layer of approximately 0.1 to 20, preferably 1 to 10 ⁇ m, the film according to the invention has a very low buffer capacity, which it is used for the purpose of measuring unbuffered solution (for example when detecting acid rain) makes very suitable. The films have a fast response time because the protons can diffuse through the thin hydrophilic indicator layer much faster than through relatively thick layers.
- the polyvinyl alcohol film according to the invention can of course also be applied to a solid support element e.g. made of hydrophobic, optically transparent material such as polyester of the phthalic acid ester type, polycarbonates, polyvinyl chlorides, polyamides, silicones, crosslinked polyacrylamides or polyvinyl alcohols.
- a solid support element e.g. made of hydrophobic, optically transparent material such as polyester of the phthalic acid ester type, polycarbonates, polyvinyl chlorides, polyamides, silicones, crosslinked polyacrylamides or polyvinyl alcohols.
- the waterproof, reactive dye-containing polyvinyl alcohol film is used as a sensor membrane for visual, photometric or reflectometric determination of the pH. It is also suitable for pH measurement in very weakly buffered solutions, e.g. of surface and rain water and for measuring physiological pH values.
- Example 2 10% solution of polyvinyl alcohol applied with a coater in a film thickness of 10 ⁇ m. The layer is then dried at room temperature. This film is immersed in the coloring solution according to Example 2 for 45 minutes so that the polyvinyl alcohol film is completely covered with it. Then it is rinsed with water until it is evenly colored yellow and then dried.
- Example 2
- the film colored according to Example 1 is used for pH measurements in the range from pH 4 to 7, since it changes its color depending on the pH. If you dip pieces of the film (e.g. 2 ⁇ 10 cm) in buffer solutions, you get the following colors:
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biophysics (AREA)
- Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
A process is disclosed for producing water-resistant, dye-containing polyvinyl alcohol foils and their use as sensor membranes for the reversible optical indication of the pH value of a sample. The foils are produced by direct reaction of a non cross-linked polyvinyl alcohol layer with a reactive dyestuff solution.
Description
Verfahren zur Herstellung von Farbstoffe enthaltenden Process for the preparation of dyes
Polyvinylalkoholfolien und deren Verwendung Polyvinyl alcohol films and their use
Die Erfindung betrifft ein Verfahren zur Herstellung von wasserfesten, Farbstoffe enthaltenden Polyvinylalkoholfolien und deren Verwendung als Sensorbembran zur pH-Wert-Bestimmung. The invention relates to a process for the production of waterproof, dye-containing polyvinyl alcohol films and their use as a sensor membrane for determining the pH value.
Aus WO 93/07 483 sind ähnliche Folien zur reversiblen optischen From WO 93/07 483 are similar films for reversible optical
Anzeige des pH-Werts einer Probe bekannt. Die dort beschriebene Known pH display of a sample. The one described there
Sensormembran besteht aus einem mechanisch stabilen Trägerelement und einer darauf aufgebrachten hydrophilen Aufnahmeschicht, die einen Indikatorfarbstoff in immobilisierter Form enthält. Die Aufnahmeschicht besteht aus Cellulose, Gelatine, Hydrogel, hydrophilen Polyvinylalkoholen oder Gemischen dieser Substanzen. Als Indikatorfarbstoffe werden üblicherweise Reaktivindikatoren verwendet, d.h. Sensor membrane consists of a mechanically stable carrier element and a hydrophilic recording layer applied thereon, which contains an indicator dye in immobilized form. The absorption layer consists of cellulose, gelatin, hydrogel, hydrophilic polyvinyl alcohols or mixtures of these substances. Reactive indicators are usually used as indicator dyes, i.e.
pH-Indikatoren, die eine chemische Funktion besitzen, mit deren Hilfe eine chemische Bindung an die Aufnahmeschicht ermöglicht wird. pH indicators that have a chemical function that enables chemical bonding to the absorption layer.
Versuche mit den Folien auf der Basis von Polyvinylalkohσl haben gezeigt, daβ diese Folien für den mehrfachen Einsatz in Wasser entweder nicht genügend wasserfest sind oder nur sehr schwache Experiments with the films based on polyvinyl alcohol have shown that these films are either not sufficiently waterproof for repeated use in water or are only very weak
Färbungen entstehen.
Der Erfindung liegt die Aufgabe zugrunde, wasserfeste Polyvinylalkoholfolien zur reversiblen pH-Messung zur Verfügung zu stellen, die satte Färbungen gewährleisten. überraschenderweise wurde gefunden, daβ sich eine unvernetzte Polyvinylalkoholschicht nicht nur z.B. durch Erhitzen mit Säuren oder Aldehyden wasserfest machen läβt, sondern auch dadurch, daβ man sie direkt mit Reaktivfarbstofflösungen umsetzt. Colorings arise. The invention has for its object to provide waterproof polyvinyl alcohol films for reversible pH measurement, which ensure rich colorations. Surprisingly, it has been found that an uncrosslinked polyvinyl alcohol layer can be made waterproof not only by heating with acids or aldehydes, for example, but also by reacting it directly with reactive dye solutions.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von wasserfesten, Farbstoffe enthaltenden Polyvinylalkoholfolien, das dadurch gekennzeichnet ist, daβ man eine unvernetzte Polyvinylalkoholschicht direkt mit einer Reaktivfarbstofflösung umsetzt. The invention relates to a process for the production of waterproof, dye-containing polyvinyl alcohol films, which is characterized in that an uncrosslinked polyvinyl alcohol layer is reacted directly with a reactive dye solution.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der so hergestellten Polyvinylalkoholfolie als Sensormembran zur reversiblen optischen Anzeige des pH-Wertes einer Probe. Durch die Umsetzung einer unvernetzten Polyvinylalkoholfolie mit einer Reaktivfarbstofflösung und im Vergleich dazu mit einer farbstoffreien Lösung, konnte nachgewiesen werden, daβ im letzteren Fall keine Wasserfestigkeit erreicht wird. Daraus kann man schlieβen, daβ die ausgebildete Wasserfestigkeit unmittelbar auf der Reaktion des Polyvinylalkohols mit dem Reaktivfarbstoff beruht. Da die Zahl der freien Hydroxylgruppen im unvernetzten Polyvinylalkohol hoch ist, erfolgt nach dem erfindungsgemäβen Verfahren eine höhere Farbstoffaufnähme und damit eine satte Färbung, die ihrerseits genauere Messungen erlaubt. Die kovalent gebundenen Reaktivfarbstoffe lassen sich nicht mehr auswaschen. Another object of the invention is the use of the polyvinyl alcohol film thus produced as a sensor membrane for the reversible optical display of the pH value of a sample. By reacting an uncrosslinked polyvinyl alcohol film with a reactive dye solution and, in comparison, with a dye-free solution, it could be demonstrated that in the latter case no water resistance is achieved. It can be concluded from this that the water resistance developed is based directly on the reaction of the polyvinyl alcohol with the reactive dye. Since the number of free hydroxyl groups in the uncrosslinked polyvinyl alcohol is high, the process according to the invention results in a higher dye absorption and thus a rich color, which in turn allows more precise measurements. The covalently bound reactive dyes can no longer be washed out.
Typische chemische Strukturen von Reaktivindikatoren sind z.B. Typical chemical structures of reactive indicators are e.g.
folgende:
Die erfindungsgemäβ erhaltenen Polyvinylalkoholfolien sind optisch vollkommen transparent und somit einer photometrischen AbsorptionsMessung ohne weiteres zugänglich. Auβerdem sind sie zu geringen Kosten in groβer Menge herstellbar. Aufgrund der relativ dünnen Folie bzw. Indikatorschicht von etwa 0,1 bis 20, vorzugsweise 1 bis 10 um, besitzt die Folie nach der Erfindung eine sehr geringe Pufferkapazität, was sie für Zwecke der Messung von ungepufferten Lösung (z.B. beim Nachweis des sauren Regens) sehr geeignet macht. Die Folien haben eine schnelle Ansprechzeit, weil die Diffusion der Protonen durch die dünne hydrophile Indikatorschicht viel schneller erfolgen kann als durch relativ dicke Schichten. the following: The polyvinyl alcohol films obtained according to the invention are optically completely transparent and are therefore readily accessible to a photometric absorption measurement. In addition, they can be produced in large quantities at low cost. Due to the relatively thin film or indicator layer of approximately 0.1 to 20, preferably 1 to 10 µm, the film according to the invention has a very low buffer capacity, which it is used for the purpose of measuring unbuffered solution (for example when detecting acid rain) makes very suitable. The films have a fast response time because the protons can diffuse through the thin hydrophilic indicator layer much faster than through relatively thick layers.
Die erfindungsgemäβe Polyvinylalkoholfolie kann natürlich auch auf ein festes Trägerelement z.B. aus hydrophobem, optisch transparentem Material wie Polyester vom Typ der Phthalsäureester, Pσlycarbonate, Polyvinylchloride, Polyamide, Silicone, vernetzte Polyacrylamide oder Polyvinylalkohole aufgebracht werden. The polyvinyl alcohol film according to the invention can of course also be applied to a solid support element e.g. made of hydrophobic, optically transparent material such as polyester of the phthalic acid ester type, polycarbonates, polyvinyl chlorides, polyamides, silicones, crosslinked polyacrylamides or polyvinyl alcohols.
Die wasserfeste, Reaktivfarbstoffe enthaltende Polyvinylalkoholfolie wird als Sensormembran zur visuellen, photometrischen oder reflektometrischen Bestimmung des pH-Werts verwendet. Sie eignet sich auch zur pH-Wert-Messung in sehr schwach gepufferten Lösungen, z.B. von Oberflächen- und Regenwasser und zur Messung physiologischer pH-Werte. The waterproof, reactive dye-containing polyvinyl alcohol film is used as a sensor membrane for visual, photometric or reflectometric determination of the pH. It is also suitable for pH measurement in very weakly buffered solutions, e.g. of surface and rain water and for measuring physiological pH values.
Beispiel 1 example 1
Herstellung der Folie Production of the film
Auf eine glasklare, 75 um dicke Polyester-Trägerfσlie wird eine One is placed on a crystal-clear, 75 µm thick polyester carrier film
10 %ige Lösung des Polyvinylakohols mit einem Streichgerät in einer Filmdicke von 10 μm aufgetragen. Die Schicht wird anschlieβend bei Raumtemperatur getrocknet. Diese Folie wird 45 Minuten lang so in die Färbelösung nach Beispiel 2 eingetaucht, daβ der Polyvinylalkoholfilm vollständig damit bedeckt ist. Anschlieβend wird sie mit Wasser abgespült, bis sie gleichmäβit gelb gefärbt ist, und dann getrocknet.
Beispiel 2 10% solution of polyvinyl alcohol applied with a coater in a film thickness of 10 μm. The layer is then dried at room temperature. This film is immersed in the coloring solution according to Example 2 for 45 minutes so that the polyvinyl alcohol film is completely covered with it. Then it is rinsed with water until it is evenly colored yellow and then dried. Example 2
Färbelösung Staining solution
0.4 g des Farbstoffs 0.4 g of the dye
werden in 500 ml H2O gelöst. Nacheinander werden 40 g Natriumchlorid, 12 g Natriumcarbonat und 2.6 ml 32 %ige Natronlauge zugegeben und aufgelöst. are dissolved in 500 ml of H 2 O. 40 g of sodium chloride, 12 g of sodium carbonate and 2.6 ml of 32% sodium hydroxide solution are added and dissolved in succession.
Beispiel 3 Example 3
Anwendung der Folie Application of the film
Die nach Beispiel 1 gefärbte Folie wird für pH-Messungen im Bereich von pH 4 bis 7 eingesetzt, da sie ihre Färbung in Abhängigkeit vom pH-Wert ändert. Wenn man Stücke der Folie (z.B. 2 × 10 cm) in Puffer- lösungen eintaucht, erhält man folgende Färbungen: The film colored according to Example 1 is used for pH measurements in the range from pH 4 to 7, since it changes its color depending on the pH. If you dip pieces of the film (e.g. 2 × 10 cm) in buffer solutions, you get the following colors:
pH 4 gelb pH 4 yellow
pH 5 hellgrün pH 5 light green
pH 6 dunkelgrün pH 6 dark green
pH 7 blau.
pH 7 blue.
Claims
1. Verfahren zur Herstellung von wasserfesten, Farbstoffe enthaltenden Polyvinylalkoholfolien, dadurch gekennzeichnet, daβ man eine unvernetzte Polyvinylalkoholschicht direkt mit einer Reaktivfarbstofflösung umsetzt. 1. A process for the production of waterproof, dye-containing polyvinyl alcohol films, characterized in that an uncrosslinked polyvinyl alcohol layer is reacted directly with a reactive dye solution.
2. Verwendung der nach Anspruch 1 hergestellten Polyvinylalkoholfolie als Sensormembran zur reversiblen optischen Anzeige des pH-Wertes einer Probe. 2. Use of the polyvinyl alcohol film produced according to claim 1 as a sensor membrane for the reversible optical display of the pH of a sample.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4324991 | 1993-07-26 | ||
| DE19934324991 DE4324991A1 (en) | 1993-07-26 | 1993-07-26 | Process for the preparation of polyvinyl alcohol films containing dyes and their use |
| PCT/EP1994/002269 WO1995003340A1 (en) | 1993-07-26 | 1994-07-12 | Process for producing dye-containing polyvinyl alcohol foils and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0662094A1 true EP0662094A1 (en) | 1995-07-12 |
Family
ID=6493696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94924739A Withdrawn EP0662094A1 (en) | 1993-07-26 | 1994-07-12 | Process for producing dye-containing polyvinyl alcohol foils and their use |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0662094A1 (en) |
| JP (1) | JPH08502549A (en) |
| DE (1) | DE4324991A1 (en) |
| WO (1) | WO1995003340A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19634164A1 (en) | 1996-08-23 | 1998-02-26 | Bosch Siemens Hausgeraete | System and method for displaying alphanumeric and / or graphic characters |
| US6544794B1 (en) * | 2000-05-12 | 2003-04-08 | Shiseido Company, Ltd. | Method for visual imaging of ion distribution in tissue |
| GB2408330B (en) * | 2003-11-22 | 2008-12-03 | Advanced Gel Technology Ltd | Polymeric materials comprising pH indicators for use in wound dressings |
| CN101374915A (en) * | 2005-11-10 | 2009-02-25 | 贝克曼库尔特公司 | Covalently attached nile blue derivatives for optical sensors |
| US8242203B2 (en) | 2005-11-10 | 2012-08-14 | Eric Bakker | Covalently attached nile blue derivatives for optical sensors |
| AT515010B1 (en) * | 2013-11-06 | 2018-03-15 | Joanneum Res Forschungsgmbh | A test device for detecting the presence or absence of an analyte in a liquid sample, and methods of making the same |
| US9581551B2 (en) | 2014-07-31 | 2017-02-28 | Research & Business Foundation Sungkyunkwan University | Color-change sensor using film for detecting harmful material |
| KR101590111B1 (en) * | 2014-07-31 | 2016-02-01 | 성균관대학교산학협력단 | Color-change sensor using film for detecting harmful material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3544484A (en) * | 1967-12-18 | 1970-12-01 | American Standard Inc | Optical ph indicator comprising aromatic aminoazo dye and inert polymer containing carbonyl radicals |
| JPS4943720B2 (en) * | 1972-09-16 | 1974-11-22 | ||
| JPS5748905A (en) * | 1980-09-05 | 1982-03-20 | Kanebo Ltd | Film type pack capable of discriminating peeling time by color change |
| JPS58103584A (en) * | 1981-12-15 | 1983-06-20 | Ricoh Co Ltd | Reversible thermochromic composition |
| DE59209350D1 (en) * | 1991-09-30 | 1998-07-02 | Merck Patent Gmbh | SENSOR MEMBRANE TO DISPLAY THE pH OF A SAMPLE, THEIR PRODUCTION AND USE |
-
1993
- 1993-07-26 DE DE19934324991 patent/DE4324991A1/en not_active Withdrawn
-
1994
- 1994-07-12 JP JP7504904A patent/JPH08502549A/en active Pending
- 1994-07-12 EP EP94924739A patent/EP0662094A1/en not_active Withdrawn
- 1994-07-12 WO PCT/EP1994/002269 patent/WO1995003340A1/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9503340A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4324991A1 (en) | 1995-02-02 |
| WO1995003340A1 (en) | 1995-02-02 |
| JPH08502549A (en) | 1996-03-19 |
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