DE4404839A1 - Coating or impregnating substrates with polar cpds., esp. dyes - Google Patents

Abstract

Process for coating and/or impregnating a substrate with one or more substances selected from salts, organic acids and their conjugate bases comprises contacting the substrate with a soln. of the substance(s) in a supercritical fluid.

Description

The present invention relates to a method for Application or introduction of substances on or in sub strate and / or impregnation of substrates with substances or substance mixtures, the substances or substance mixtures are dissolved in a fluid.

DE 42 00 352 A1 relates to a method for application of substances on fiber materials and textile substrates from the fluid phase, in which the fluid is a supercritical fluid or a liquefied gas or gas mixture is used. The substances are in the liquid or supercritical Fluid dissolved and by changing the process parameters applied to the fiber material or the textile substrate and / or in the fiber material or in the textile substrate brought in. Active ingredients are used that Processing and / or usage properties of the fiber modify materials or the textile substrates. It for example, fragrances and aromas, insect repellents, light-protecting substances, such as UV absorbers, bactericides, fungicides etc. The substances that are on the fiber materials or textile substrates on or  are introduced are hydrophobic compounds, such as carbon acid ester.

DE 42 02 320 A1 relates to a method for impregnation of substrates in which an impregnating agent with a Absorbs fluid and then the substrate with the fluid for one certain time in contact. One uses as fluid a supercritical fluid, whereby the fluid during or after impregnation then in the non-critical Condition transferred. According to DE 42 02 320 A1 for Im Substances used in substrates can indeed have polar groups, but rather belong to non-polar ones Groups of organic compounds, such as esters, silicone oil derivatives, terpenes such as lemon oil, and others commonly compounds insoluble in water.

DE 39 06 724.6 relates to a method for dyeing textile substrates, in which the substrates of one of the Dye or the fluid containing dyes flowed or are flowed through. As a fluid here is an over critical fluid used. As a colorant Disperse dyes used. Are disperse dyes synthetic dyes which are sparingly soluble in water, such as azo dyes or anthraquinone derivatives, as well as Naphtol-AS- Dyes that together with dispersing agents are very fine grind for dyeing and printing acetate, polyester, Polyamide, polyacrylonitrile, PCV and polyurethane fibers be used. When dyeing, the moles penetrate into the dye bath Specially dissolved dye components by diffusion into the fiber and give real colorings.

The technical problem underlying the invention exists in heteropolar substances or substance mixtures, such as Salts and / or organic compounds with free acid groups or their conjugate bases, on substrates to bring or to impregnate substrates with them heteropolar connections as long as possible on the  Be anchored substrate or placed in the substrate become. Relatively non-polar should in particular also Substrates or polymeric substrates can be treated. The process to be provided should be economical Licher impregnation or coating the Allow substrates with substances or mixtures of substances.

Surprisingly, that is the basis of the invention Problem solved by a method with the features of Claim 1. The sub-claims 2 to 14 relate to preferred Embodiments of the method according to the invention.

According to the invention, the method for applying or on bring substances on or in substrates and / or Im impregnate substrates with substances or substance mix, the substances or substance mixtures in one Fluidum are solved, characterized in that the sub punch or mixtures of substances salt compounds and / or organic compounds with free acid groups or their are conjugate bases. These substances or substance Mixtures are taken up in a fluid, the fluid is in a supercritical state. The mixture from fluid and substances or substance mixtures with brought into contact with the substrate to be treated.

Surprisingly, heteropolar compounds, to which those to be processed in the method according to the invention Substances or mixtures of substances are to be counted, also in Absorb fluids in the supercritical state. this fact is surprising for the expert, because so far the prejudice was considered to be substances or mixtures of substances that are not in organic solvents, such as higher-chain aliphates, For example, octane can be dissolved, not in also relatively little polar supercritical fluids. Heteropolar compounds such as Verbin come as substances metal and non - metal or metal and Non-metal oxides, reciprocal salt pairs, inner salts, onium  salts, salts of organic acids, phenates, hydrohalides or other salts resulting from acid / base reactions into consideration. In particular come salts of organic acids or bases or their corresponding free acids or Bases in question.

The substrates used in the method according to the invention are preferably natural or artificial polymers re, which resisted the thermal stress of the process hen. In particular, materials such as wood, Paper, leather, textile materials of all kinds, porous, on organic materials, plastics in the form of fibers or foils Ceramics, especially porous ceramics.

The heteropolar or carboxyl-containing substances, which can be used in the process according to the invention, are in particular bactericides, fungicides, herbicides, Pesticides, pharmaceuticals, dyes, etc.

The fluid preferably contains the substances or the substance mixtures are taken up from a substance in the supercritical state, which is gaseous under standard conditions is. Comes as a gaseous substance under standard conditions especially ethylene, propane, carbon dioxide, laughing gas, ammonia or combinations thereof. However, it can also at standard conditions liquid substances such as diethyl ether, Fluorocarbons or other substances such as sulfur hexafluoride can be used.

The method according to the invention now also allows hetero polar compounds such as salt compounds or others above mentioned substances or substance mixtures in substrates or to spend on substrates. This creates new classes of substances Impregnation, dyeing and coating processes supplied.  

It may be advantageous to use the substances or substances mix together in supercritical fluids or fluid mixtures apply with moderators. In particular, as moderators especially those substances that consider the polarity of the Fluidum can increase or decrease, for example aqueous additives, ammonia, etc. Usually Concentrations of the aforementioned moderators between 1 vol .-% and about 10 vol .-%, preferably between 2 vol .-% and about 5 vol .-%, based on the volume of each used fluids or fluid mixture. Preferably after the contact of the substrate with the Substances or mixtures of substances gradually or the fluid continuously expanding. The treatment itself takes place preferably at a pressure of 130 to 500 bar, where the temperature depending on the temperature sensitive speed of the substrates to be treated and the fluid mixture, is usually kept between 25 ° C to 320 ° C.

The amount of the substance mixture or substances in the Fluidum is 0.1 to 10 wt .-% and the exposure time of the substances or substance mixtures on the substrate 1 to 180 min.

The method according to the invention is particularly advantageous suitable way, the substrates without the pretreatment Treatment process, such as impregnation or opening or closing bringing in substances.

Furthermore, the method according to the invention is advantageous because the treatment processes in high pressure systems like them also for dyeing synthetic fiber materials with dispersions dyes are known can be carried out. In particular special is carbon dioxide as a fluid in the invention Suitable method. The gaseous carbon dioxide is at for example from a diaphragm compressor on working pressure compressed or liquid from a riser CO₂ bottle filled. The method according to the invention is particularly suitable for  Coloring of all types of textile substrates including leather and skins suitable. The invention will be more apparent from the following Examples relating to the coloring of textile substrates explained in more detail.

Examples 1 to 14

The experiments described below were carried out in one High pressure system for dyeing experiments carried out. These High pressure system for dyeing synthetic fiber materials with Disperse dyes are described, for example, in DE 39 06 724 described. Gaseous carbon dioxide was from a mem Brankompressor compressed to working pressure or from a Riser tube CO₂ bottle filled in liquid. For the dyeing process was sample material of 2 to 4 g around the staining tree, a perforated stainless steel cylinder, wrapped. The powdery Dye was placed on the bottom of the autoclave. The leadership of pressure and temperature was essentially in accordance with the procedure recommended in the prior art and includes Treatment temperatures up to 130 ° C and pressures of 200 to 300 bar with dyeing times of 10 to 60 min. To Pressure relief was the sample if necessary by extraction with acetone (those with dyes C6 up to C8 also with water) from adhering dye and regarding colorimetric data and wash fastness analyzed.

The abbreviations used in the tables refer to as Sample material the following materials:

• E1) PES knitted fabrics Trevira 2000, 217 g / m²,
• E2) PA 6.6 stockings, with and without elastomer fibers in the waistband,
• E3) PA 6 plain weave fabric,
• E4) PA 6.6 plain weave fabric,
• E5) Dunova® polyacrylonitrile yarn,
• E6) "Crust" leather,
• E7) Mink fur.

The dyes mentioned under C1 to C8 were used det, where in particular:

• C1) ethyl red: 4 ′ - (N-diethylamino) -azobenzene-2-carboxylic acid- Sodium salt,
• C2) Lithium salt of 4 ′ - (N-diethylamino) -azobenzene-2-carbon acid,
• C3) Alizarin Yellow GG (C.I. 14025, Mordant Yellow 1), 5- (3- Nitrobenzolazo) salicylic acid sodium salt, approx. 50%,
• C4) lithium salt of 5- (3-nitrobenzolazo) salicylic acid,
• C5) ethyl red: 4 ′ - (N-diethylamino) -azobenzene-2-carboxylic acid,
• C6) methylene blue (hydrochloride),
• C7) Salt of perfluorooctanesulfonic acid with methylene blue Cation,
• C8) Resazurin (7-hydroxy-3H-phenoxazin-3-one-N-oxide sodium salt).

Table 1 gives parameters for the staining experiments.

Table 1

Dyeing conditions for synthetic fiber materials in supercritical fluid with dye salts; each 1% dye supply based on the sample weight; isobaric dyeing time at dyeing temperature T (in ° C) 60 min each; each pressure expansion stages of 10-15 bar over 8 min with a dwell time of 50 s on each expansion stage

Atomic spectroscopic analysis of the colored PES sample 2 Regarding the sodium content, the as washing sample as the difference to the undyed material 0.092% Na content, resulting in a dye absorption of 4.1 mg / g knitted fabrics gives.

Table 2 gives the visual assessment more conservative Coloring again, which follows the coloring after one the acetone rinse can be obtained. Table 3 shows of remission data according to the CIE-Lab system (light type D65) the staining results.

Table 2

Visual evaluation and wash fastness data of textile materials dyed with carboxyl group dyes in supercritical Co₂

Table 3

Example of reflectance data of colored samples

Claims (14)

1. A method for applying or introducing substances onto or in substrates and / or impregnating substrates with substances or mixtures of substances, the substances or mixtures of substances being dissolved in a fluid, characterized in that

• - The substances or mixtures of substances, Salzver compounds and / or organic compounds with free acid groups or their conjugate bases and
• - The in the fluid, which is in a critical condition, recorded substances or substance mixtures are brought into contact with the substrate.

2. The method of claim 1, wherein the substrates from natural or artificial polymers are built up, that reflects the thermal stress of the process stand. 3. The method according to claim 2, wherein the substrates are such Materials such as wood, paper, leather, textile All kinds of materials, porous, inorganic materia lien, plastics in fiber or film form, ceramics, include. 4. The method according to at least one of claims 1 to 3, where the substances, heteropolar compounds, such as Compounds of metals and non-metals, or Metals or non-metal oxides, reciprocal salt pairs, internal salts, onium salts, salts of organic acids, Phenolates, hydrohalides or others Salts resulting from acid / base reactions.   5. The method according to claim 4, wherein the substances salts organic acids or bases or their corresponding are free acids or bases. 6. The method according to at least one of claims 1 to 5, the substances being heteropolar or carboxyl groups active ingredients such as bactericides, fungicides, Herbicides, pesticides, pharmaceuticals, paints substances, UV / light stabilizers, antioxidants. 7. The method according to at least one of claims 1 to 6, the substances or substance mixtures in over critical fluids or fluid mixtures along with Moderators are applied. 8. The method according to at least one of claims 1 to 7, the fluid being a mixture of at standard conditions gaseous substances in supercritical Condition exists. 9. The method according to at least one of claims 1 to 8, characterized in that the fluid one or several of the substances mentioned, ethylene, propane, coal dioxide, nitrous oxide, diethyl ether, chlorofluorocarbons hydrogen (CFC), ammonia and / or sulfur hexa fluoride includes. 10. The method according to at least one of claims 1 to 9, the expansion of the fluid after completion of the Step the contact time of the substrate with the substances done wisely or continuously. 11. The method according to at least one of claims 1 to 10, wherein the pressure in treating the substrate 130 up to 500 bar and the temperature depending on the Temperature sensitivity of the substrates to be treated is usually kept at 25 to 320 ° C.   12. The method according to at least one of claims 1 to 11, the substance content of the fluid being 0.01 to 10% by weight is. 13. The method according to at least one of claims 1 to 12, the time of exposure of the substances to the sub strat is 1 to 180 minutes. 14. The method according to at least one of claims 1 to 13, the substrate being treated without pretreatment process is fed.