DE102009008999A1 - Dye-composite useful e.g. as lacquer for coloring material surfaces and for producing indicator strips and sensors, comprises a soluble organic dye and a complexing agent, which are homogeneously embedded in a metal oxide gel - Google Patents

Abstract

Dye-composite comprises a soluble organic dye and a complexing agent, which are homogeneous gel embedded in a metal oxide gel. Independent claims are also included for the preparation of the dye-composite comprising: producing a metal oxide nanosol consisting of silicon dioxide, silicon compound of formula (R-SiO 3/2), aluminum oxide, titanium dioxide or zirconium oxide, mixing organic dye and a complexing, coating a material surface by dipping, spraying or roller coating and drying or producing a metal oxide nanosol, gelatinizing by neutralizing or heating, drying the gel and grinding or producing a metal oxide nanosol, aluminum oxide, titanium dioxide or zirconium oxide and spraying the composite sols. R : alkyl, fluoroalkyl, epoxyalkyl, aminoalkyl, trialkyl ammonium alkyl or acryloyloxy alkyl.

Description

The The invention relates to the preparation and use of more stable washing Dye composites. The dye composites consist of a soluble organic dye and a complexing agent, the are homogeneously embedded in a metal oxide gel

It It is known that the use of water-soluble organic Dyes for coloring of objects measures for immobilization requires to unwanted out-diffusion or to prevent washing out.

For this purpose, different immobilization techniques have been used: most well-known examples of adsorptive immobilization are so-called substrate colors consisting of a color-donating component and a more or less colorless pigment (the substrate), both components being largely bound to one another in a manner that is insoluble in water and binder. Already in the Middle Ages, by using chalk or lead white, soluble plant dyes were fixed, which were complexed by aluminum compounds (alum). Newer variants use z. B. the addition of SiO ₂ particles ( FR 2831178 . FR 2831179 ) or ceramic particles ( NZ 541793 ) or modify the dyes by reactive groups, the z. B. react with fibers, (see. DE 10 2006 003 864 A1 ). The so-called inclusion immobilization encapsulates the dyes in a closed reaction space, eg. B. by organic binders (shellac, acrylates); for the food sector were z. B. natural swellable polysaccharides ( DE-A-602004004529 ) proposed. Due to the swellability, however, only a limited immobilization is achieved.

One Disadvantage of the mentioned methods is that they are from food law Reasons mostly not for the immobilization of water-soluble Food dyes are suitable because z. T. not allowed Additives are used or in the case of a chemical modification the dyes of unchecked use in the food industry is not allowed.

The Object of the following invention was therefore an easy way to find water-soluble food colors such as brilliant blue (E133, C.I., 42090), tartrazine (E102, C.I., 18140), azorubin (E112; I. 14720) u. a. effective with regard to health safety to immobilize to the mentioned disadvantages of the prior art to avoid.

These Object is achieved by a dye composite according to claim 1 and the description of the method according to claim 8-10 solved. Further aspects and preferred embodiments of the Invention are the subject of further claims.

It surprisingly showed that dye composites according to claim 1, characterized by homogeneous embedding of a soluble organic dye and a complexing agent in a metal oxide gel show a drastically reduced washout behavior, as documented in the exemplary embodiments (Table 1) becomes.

The Homogeneous embedding by a sol-gel process in a metal oxide matrix already dramatically reduces the leaching of water-soluble Dyes containing at least one sulfonic acid or carboxylic acid group contain. The effect can be due to the additional effect co-immobilized complexing agent can be amplified and at optimal compositions to a complete Immobilization of the originally slightly soluble Dyes lead, making the dye composites practical Get pigment character and numerous new applications Offer.

When Complexing agents are on the one hand di- or trivalent Metal salts, preferably magnesium, calcium, zinc, aluminum or iron salts added in stoichiometric amounts become.

On the other hand, water-soluble polymeric ammonium salts prove to be alternative and extremely effective complexing agents. Suitable examples are for. B Eudragit ^® RL 100 / Fa. Degussa as pH-independent swelling, insoluble cationic polymers which are commercially available as Tablettierungshilfsmittel or commercial polycationic compounds based on polydimethyl-diallylammonium chloride, polyvinylamines, polyacrylamides and corresponding copolymers, which are used in cosmetics and in the treatment of water.

The matrix used are metal oxide gels of SiO ₂ , R-SiO _3/2 , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or mixtures thereof, where R = alkyl, fluoroalkyl, epoxyalkyl, aminoalkyl, trialkylammoniumalkyl or acryloxyalkyl. The metallic oxide produced by sol-gel conversion from the corresponding nanosols that are either commercially available (eg. B. Sebosil ^® / Kallies Fine Chemicals AG Sebnitz, Ludox ^® / Helm AG Hamburg, Nyacol ^® / Akzo Nobel, Levasil ^® / Bayer) or by hydrolysis of the corresponding silicon or metal alkoxides or metal halides can be easily prepared. In the case of the use of dye composites in the food sector, a pure and harmless SiO ₂ matrix (eg in combination with Ca salts) is favored whose weight fraction in the composite should be at least 50% by weight. In contrast, the proportion of complexing agent is to minimize depending on the dye used and should be less than 30 wt .-%.

• (1) Herstellung (oder Kauf) eines Nanosols, das aus SiO₂, R-SiO_3/2, Al₂O₃, TiO₂ oder ZrO₂ besteht,
• (2) Zumischung des organischen Farbstoffs und einem Komplexierungsmittel,
• (3) Beschichtung einer Materialoberfläche durch Tauchen, Sprühen oder Walzenauftrag, (4) Trocknen.

The preparation of the dye composite according to the invention as a pure coating takes place in the following manner:

• (1) preparation (or purchase) of a nanosol consisting of SiO ₂ , R-SiO _3/2 , Al ₂ O ₃ , TiO ₂ or ZrO ₂ ,
• (2) admixing of the organic dye and a complexing agent,
• (3) coating a material surface by dipping, spraying or roller coating, (4) drying.

such Coatings can be used as a color coat for coloring material surfaces and used for the production of indicator strips and sensors become.

• (2) Zumischung des organischen Farbstoffs und einem Komplexierungsmittel
• (3a) eine Sprühtrockung oder alternativ
• (3b) Gelieren durch Neutralisieren, Zugabe verdünnter NaF-Lösung oder Erwärmen,
• (4) Trocknen des Gels und Mahlen.

For the production of bulk products (powder, granules) takes place after

• (2) admixture of the organic dye and a complexing agent
• (3a) spray-drying or alternatively
• (3b) gelling by neutralizing, adding dilute NaF solution or heating,
• (4) Dry the gel and grind.

In Analogy to insoluble color pigments increases with increasing Milling degree of the dye composite the color strength.

micronized or spray-dried dye composites easily dispersed in polymeric binders and as a lake be used for coloring of material surfaces.

Furthermore can be dispersed in powdered dye composites Form for coloring food, cosmetic or pharmaceutical preparations or for coloring be used polymeric products.

embodiments The invention will be described in more detail below.

applications

The components listed in Table 1 are mixed in a beaker with rapid stirring. The homogeneous mixture is then either spray-dried in a BUCHI spray-drying plant at 140 ° C./N ₂ as carrier gas or gelled by addition of 1-2 drops of 2% NaF solution. The gel is comminuted after 12 hours and dried to constant weight at 80 ° C.

Testing the washout stability:

• ¹⁾ Farbstoff = Brilliantblau (E133; C. I. 42090), 10% in Wasser
• ²⁾ Sebosil H ist ein kommerzielles SiO₂-Nanosol der Fa. Kallies Feinchemie AG Sebnitz. Feststoffgehalt ca. 16% SiO₂ in Ethanol.
• ³⁾ Sebosil HP ist ein kommerzielles SiO₂-Nanosol der Fa. Kallies Feinchemie AG Sebnitz. Feststoffgehalt ca. 16% SiO₂ + 4% Polyacrylat in Ethanol.
• ⁴⁾ Hersteller: Degussa
• ⁵⁾ Hersteller: CIBA
• ⁶⁾ Allied Colloids GmbH Hamburg
• ⁷⁾ Aldrich (mittl. Molgewicht 100 000 ... 200 000)
• ⁸⁾ sprühgetrocknetes Pulver

100 mg of triturated dye composite are mixed with 10 ml of dist. Stirred for 1 h at room temperature; 1 ml of the supernatant solution diluted 1: 100 and the absorbance at 630 nm determined by UV spectroscopy. On the basis of a calibration line, the concentration of the liberated dye can be determined. Table 1 Composition and washout rates of the dye composites recipe washout nanosol Dye ¹⁾ complexing in % 20 ml Sebosil H ²⁾ 3 ml (Solution) 100 20 ml of Sebosil H 3 ml 35.9 20 ml Sebosil HP ³⁾ 5 ml 15.6 20 ml of Sebosil H 3 ml 3 ml 5% CaCl ₂ 1.99 24 ⁸⁾ 20 ml of Sebosil H 3 ml 5 ml of 5% CaCl ₂ 5.5 20 ml of Sebosil H 3 ml 5 ml 5% Eudragit RL100 ⁴⁾ 0 20 ⁸⁾ 20 ml of Sebosil H 3 ml 3 ml 5% Alcostat 567 ⁵⁾ 5.95 20 ml of Sebosil H 3 ml 5 ml 5% Alcostat 567 ⁵⁾ 1.7 20 ml of Sebosil H 3 ml 3 ml 5% Fixacol 110 ⁶⁾ 0 20 ml of Sebosil H 3 ml 5 ml 5% Fixacol 158 ⁶⁾ 0 20 ml of Sebosil H 3 ml 3 ml polydimethyldiallylammonium chloride ⁷⁾ 4.8 20 ml of Sebosil H 3 ml 5 ml polydimethyldiallylammonium chloride ⁷⁾ 3.3

• ¹⁾ Dye = Brilliant Blue (E133; CI 42090), 10% in water
• ²⁾ Sebosil H is a commercial SiO ₂ nanosol from Kallies Feinchemie AG Sebnitz. Solids content about 16% SiO ₂ in ethanol.
• ³⁾ Sebosil HP is a commercial SiO ₂ nanosol from Kallies Feinchemie AG Sebnitz. Solids content about 16% SiO ₂ + 4% polyacrylate in ethanol.
• ⁴⁾ Manufacturer: Degussa
• ⁵⁾ Manufacturer: CIBA
• ⁶⁾ Allied Colloids GmbH Hamburg
• ⁷⁾ Aldrich (average molecular weight 100,000 ... 200,000)
• ⁸⁾ spray dried powder

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• FR 2831178 [0003]
• FR 2831179 [0003]
• - NZ 541793 [0003]
• - DE 102006003864 A1 [0003]
• - DE 602004004529 [0003]

Claims (14)

Dye composite, consisting of a soluble organic dye and a complexing agent that is homogeneous embedded in a metal oxide gel Dye composite according to claim 1, wherein the soluble organic dye at least one sulfonic acid or carboxylic acid group Dye composite according to claims 1 and 2, wherein the complexing agent of one or more two- or trivalent metal salts Dye composite according to claims 1 and 2, wherein the complexing agent of one or more cationic Consists of polymers Dye composite according to claim 1-4, wherein the metal oxide gel of SiO ₂ , R-SiO _3/2 , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or mixtures thereof, wherein R = alkyl, fluoroalkyl, epoxyalkyl, aminoalkyl, trialkylammonium or Acryloxyalkyl can be. Dye composite according to claim 1-5, wherein the weight fraction of the metal oxide matrix is at least 50%. Dye composite according to claims 1-6, wherein the weight ratio of the complexing agent is at most 30%. A process for the preparation of dye composites according to claim 1-7 characterized by the steps of (a) preparing a metal oxide nanosol consisting of SiO ₂ , R-SiO _3/2 , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or mixtures thereof (b) admixing the organic dye and a complexing agent, (c) coating a material surface by dipping, spraying or roller coating, (d) drying A process for the preparation of dye composites according to claim 1-7 characterized by the steps of (a) preparing a metal oxide nanosol consisting of SiO ₂ , R-SiO _3/2 , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or mixtures thereof (b) admixing the organic dye and a complexing agent, (c) gelling by neutralizing and heating, (d) drying the gel, and milling A process for the preparation of dye composites according to claim 1-7 characterized by the steps of (a) preparing a metal oxide nanosol consisting of SiO ₂ , R-SiO _3/2 , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or mixtures thereof (b) admixing the organic dye and a complexing agent, (c) spray-drying the composite sol Dye composite according to claims 1-10, wherein the dye-Kompositsol as color lacquer for coloring of Material surfaces and for the production of indicator strips and sensors is used. Dye composite according to claims 1-10, wherein the dye composite disperses in a polymeric binder and as a color coat for coloring material surfaces is used. Dye composite according to claim 1-12, wherein the dye composite in dispersed form for coloring of food, cosmetic or pharmaceutical preparations is being used. Dye composite according to claim 1-12, wherein the dye composite in dispersed form for coloring used by polymeric products.