DE2515105A1 - Textile dyeing by spraying with solid particles of polymer contg dye - gives spots, stripes or streaks - Google Patents

Abstract

Materials of hydrophobic and/or hydrophilic fibres are dyed in spots, stripes or streaks by spraying with solid preps. contg. (A) non-ionic dye(s), (B) a polymeric material and opt. (C) other additives, and subsequently fixing the dye. Multicolour effects can be obtd. by a single spraying process. The solid prepns do not give up their colour in water and can be applied in an aq. dye bath to give a coloured background. Spots of controlled size with sharply-defined edges are obtd.

Description

Coloring method by means of spraying solid particles The present The invention relates to a new method for coloring textiles or the like Materials made from hydrophobic fibers or from mixtures of hydrophobic and hydrophilic Fibers are made, creating colored spots, stripes or strokes in a more regular manner or arbitrarily with a dye preparation according to the Swiss Patent application no.

8802/73 can be produced.

There has not yet been a satisfactory method of manufacture colored spots, stripes or lines on textiles, especially those made of hydrophobic ones Fibers, available. In a conventional method in which a dispersion a non-ionic disperse dye sprayed on in an aqueous medium different colors cannot be mixed together. You need to be sprayed on separately to achieve dots of different colors. Self then receives by overlapping the dots, a mixture of the Colours. It is not possible to use an ionic compound or an ionic dye admit, since these dispersions are very sensitive to ions. Farther the textile material must be dry in order to get spots with sharp delimitations, and it is impossible to spray the dots and a color for the fund together like this that you get colored spots on a colored background. The size of the spots is determined in such a process by the size of the droplets, and it is difficult to apply dots in changing sizes as desired. Additives like Reducing agents, caustic agents, burnout agents, oxidizing agents etc. cannot be added to the dispersions of non-ionic dyes because of the undesired modification of the dye or the dispersion caused by this Treatment can occur.

In the German Auslegeschrift No. 2 122 714 describes a method after which a solid preparation of a soluble dye is sprayed onto a material is, and using a liquid auxiliary in which the dye preparation is dissolved to form a homogeneous coloring medium on the material to be colored is transferred, the dye transfer taking place from the liquid phase.

The dye preparation consists of one dye and another substance soluble in the aid. The liquid phase is an essential item this procedure. Their concentration, temperature and composition can determine the final color yield influence. The color preparation loses its identity when it is mixed with the liquid Phase comes into contact. The remaining, unreacted dye is washed off, supplies a colored wastewater and can stain the white ground.

The present invention shows that the dye preparations according to the Swiss patent application No. 8802/73 are extremely useful for Production of special effects that were previously not achievable by conventional methods was. For example, the preparations can be applied to a substance in dry form sprayed, which can be wet or dry. The substance is then, if necessary, dried and heat-set, or under pressure or at atmospheric pressure Fixation of the dye attenuated. The dye preparation can also be based on a Carrier such as a metal foil, paper, wire mesh, foil or any other Material that has no affinity for the dye is sprayed on, and the textile material can be in contact with this support by known methods using hot vapors, steam or air will. The support can be dry or wet and the dye formulation can be solid or keep in loose form.

The dye preparations are preferably in an aqueous Suspended liquor or printing paste and then padding or printing applied to the material to be colored.

The dye preparations do not easily dust when dry during spraying so that they are carried away by the air. The on Excess preparation present in the substance can be easily separated off and can be used again after collecting. The dye preparations give the Color only off if suitable coloring conditions are available. The preparations are in Insoluble in water, do not swell in water and do not stick to the surfaces.

The paint formulations used in the present invention are Subject of the applicant's Swiss patent application No. 8802/73, in which the advantages of these preparations for use in conventional Zårbe processes are shown. These preparations put the dye in an aqueous bath not free under normal spray temperatures. Dye preparations can now be used different colors can be easily mixed and applied together without the identity of the individual colors is lost. The dye preparations are not very sensitive to salts, acids, alkali, oxidizing or reducing agents. They can be in different particle sizes or in a uniform particle size can be obtained, and the size of the color dots on textiles can be predetermined and can be easily controlled. If the dye preparations are suspended in a liquid and then sprayed on is the size of the liquid drop in which the Dye preparation is suspended, does not affect the size of the on the colored material.

In fact, the size of the resulting spot of color remains the same, if the dye preparation is sprayed or from an aqueous suspension on dry Fabric foulardier.

or as a powder (by sieve or air blowing) on wet Fabric is dusted and dried and heat set in the usual way.

According to the present invention, the problems associated with the Procedures of the known process (DAS 2 122 714) are repealed as a solid preparation of an insoluble dye, as such or in dispersed form Form, sprayed onto a textile material by any conventional method or applied, which may be dry or covered with a liquid phase is to the movement of the particles of the dye preparation on narrow the point where it will be sprayed on without the dye dissolving. The color transfer takes place essentially in the dry state without involvement the possibly existing liquid phase instead. The dye is essentially present in a polymeric material and is only used under suitable color conditions Approved. The polymeric material is inert to the dye in the sense that that it does not react with the dye or with the material intended for coloring. The liquid phase on the material is not an essential part of the process and in the case of organic solvents, the polymeric material can at best swell without leaching noticeable amounts of the dye from the preparation will. The identity of the dye preparations is revealed even in contact with the liquid Maintain phase, in contrast to the situation with conventional dye preparations.

The sharpness of the colored points is not affected by the volume of the liquid phase on the textile material or in the suspension of the dye preparation influenced. Washing of the material is not essential in the given procedure Step. The residual dye in the preparation does not adhere to the textile Material. The residue can be removed in a mechanical manner, for example by suction, dedusting, Brushing or similar procedures. Of the Fond is not colored during the cleaning process as the remaining color is not released from the preparation during wet or dry cleaning. The wash liquors remain almost colorless and the dye preparation can be removed from the Waste water: to be filtered off, which is the case with disperse dyes or soluble dyes not possible.

According to the method of the present invention, it is possible to use the To mix dye preparations with conventional disperse dyes, whereby colored dots on colored ground are obtained in one step. The mesh can also be padded with the disperse dye, and the dye preparation can be sprayed on the wet material. During the heat setting, both Dyes fixed on hydrophobic fibers. When mixtures of hydrophilic with hydrophobic Fibers used in the textiles can toffziib soluble dyes of the dye preparation can be added to color the hydrophilic fibers.

In accordance with the present invention, the dyes of the following provide Classes (classified according to chemical criteria) good results: Msonoazo- and diazo dyes, anthraquinone, naphthoperinone, quinophthalone, oxazine, phthalocyanine and methine dyes including styryl, azomethine and azostyryl dyes, Benzanthrone, anthraquinone derivatives, anthrone derivatives, indigoid and thioindigoid dyes, Sulfur dyes, Sulphurous copper dyes, as well as metal complex compounds of azo and formazan dyes. From the standpoint of coloring, the following types of dyes are preferred: Those so named Disperse dyes, defined in the Color Index, especially vat dyes and others organic dyes that are free from groups that give the dye solubility in dyeing media, especially in aqueous media, imparting, fiber-rtoactive dyes, as far as they are soluble in organic media and almost insoluble in water, metal-free Dyes that are free from groups that give the dyes solubility in water give (these dyes referred to in the Color Index as "Solvent Dyes" will). Mixtures of dyes of different types can be used in the present Procedure to be used.

The following types of dyes are particularly suitable for this Purpose: water-soluble, acidic dyes, similarly leveling acidic dyes, those for coloring in the presence of acetic or formic acid or in a neutral one Dye bath can be used until the aqueous dye bath is exhausted, pre-metallized Dyes in which the metal: dye ratio can be 1: 1 or 1: 2, the Groups may contain, but not necessarily contain, the dye Give solubility in water, basic dyes, fiber reactive dyes, Direct dyes and their mixtures. The selection of the particular dye is not determined by the type of material to be colored and by the desired color. Mixtures of Dyes from different classes can be prepared according to the method of this invention for one-step dyeing of different types of fibers and blended fabrics can be used to obtain colored dots on colored ground.

The textiles or similar materials are preferably made of hydrophobic, hydrophilic and / or a mixture of hydrophobic and hydrophilic Material such as cotton, regenerated rayon, cellulose triacetate, Cellulose acetate, wool, silk, acrylic or acrylonitrile fibers, polyacrylonitrile fibers and copolymers of acrylonitrile and other vinyl compounds such as acrylic esters, Acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanethylene or vinyl acetate, as well as acrylonitrile block copolymers, fibers of polyurethanes, polyolefins, polyamides, such as nylon-6, nylon-6.6, nylon-II, ylon-6.10 (Hexamethylenediamine and sebacic acid) and nylon 6-6.6 (copolymer of hexamethylenediamine, Adipic acid and caprolactam) and especially aromatic polyesters, such as those from Terephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane, copolymers of terephthalic acid and isophthalic acid and Ethylene glycol, as well Mixtures of these fibers, such as cellulose fibers, e.g. building wool, regenerated cellulose polyester fibers, I? Ollv polyester fibers or wool-polyamide fibers, cellulose triacetate-viscose- 5 Mix the eide fiber.

The textile material can be in any form, for example in the form of loose material, as fleeces, yarns, as knitted, woven material or non woven, as carpets and thread materials in short or long lengths. The textile Material can also be in the form of ready-made clothing.

Such polymeric material is used to produce the dye preparation suitable, which is inert towards the dye in the sense that it is the dye not chemically modified, the dye being homogeneous with the polymeric material Medium forms. Such polymeric materials include synthetic fiber-forming materials Polymers of the following classes: hydrocarbons (polyolefins), w; e polyethylene, Polypropylene, chlorinated hydrocarbons such as polyvinyl chloride or polyvinylidene chloride or polytetrafluoroethylene, acrylics such as polyacrylonitrile, nitriles such as dinitrile fibers, Polyalcohols such as polyvinyl alcohol, polyamides such as nylon 6, nylon 6.6, nylon 11, Nylon 6-6.6, polyureas or polyester, such as polyethylene terephthalate, or polymers of natural origin that are chemically modified, such as starch derivatives, e.g. starch esters and ethers, cellulose esters such as cellulose acetate, cellulose ethers and resins (gums) of different types Origin.

The dye preparation can be carried out by any suitable method be produced, which is a homogeneous mixture of the dye and the polymeric material such as by having the dye and polymeric material mixes with each other. One can also use the polymeric material in a suitable solvent dissolve, whereby a spinning liquid is formed, and the dye through it Mix stirring. This mixture is then milled for a time to be homogeneous To obtain a solution of the dye and the polymer and, if necessary, heated, after which the solvent is removed by any conventional method. The homogeneous mixture can also be dripped into a diluent, or it can an additive can be mixed with the homogeneous mixture, creating the dye preparation is precipitated. Fusing the polymeric material and the dye is one another way to mix these two. The homogeneous mixture is then in a brought to a suitable shape e.g. wire, rope, thread, pearls, shavings, films or powder.

The usual aids useful for staining can be used also added to the dye preparation during or after its production or they can optionally be the liquor containing the preparations contains as usual, to be added. For example, carriers, dispersants, surface-active agents Agents, buffers, salts, acids, alkalis, acidic and alkaline binders, mild Oxidizing or reducing agents are mixed with the dye preparation, to maintain the proper properties of the dye bath.

It was found that the solid dye preparations in polymeric Materials for the dry spray process are better suited than microdispersed ones Dyes or non-ionic dye pigments. The new preparation of dyes tends to form a monolayer on the surface of the fabric. For spraying dry dye preparations, the material to be dyed is advantageous with padding or impregnated padding liquids, which contain e.g. the following components: 1. Organic solvents, such as ethyl methyl ketone, 2. Polymer solutions, such as Polyvinyl alcohol in water, 3. thickener solutions such as sodium alginate in water, 4. Water or 5. Emulsions as used in textile printing.

The dye preparation is applied to the dry or wet material sprayed on using conventional spray technology, e.g. using compressed air, sieves, etc. After spraying on, any liquid that may be present will penetrate dry removed and the dye on the fabric by any conventional method fixed as by heating at elevated temperatures in the usual way or by steam treatment.

It is also possible to make the dye preparation on a dry or wet inert carrier material either by wet or dry spraying or to be applied by padding or printing processes. The dye will then be on the textiles or similar materials by means of the usual sublimation transfer processes transfer.

The invention is illustrated by the following examples, wherein, unless otherwise stated, parts and percentages are by weight and the temperatures are given in degrees Celsius.

Example 1 2 parts of dye are dissolved in a spinning solution of 3 parts of nylon 6 in 20 parts of formic acid with stirring in a ball mill overnight at 20 ° C. 150 parts of water are slowly added to precipitate the colored nylon 6 solid in a fine powder form. The solid is filtered off, washed free of acid, dried at room temperature and ground into a fine powder using the following dyes: Dye color yellow orange red pink blue The solid dye preparation is sprayed onto fabric made of polyester tapel fiber, which has been padded with a solution of sodium alginate (0.8%), using a fine sieve and / or a jet of compressed air. The fabric is dried at 100 to 1100 before being heated to 205 ° for 60 seconds to fix the dyes. The heat-set fabric is washed, cleaned by reduction, soaped and dried to obtain a fabric with many colored spots.

In another example, the staple fiber fabric in the above Example instead of padding with the alginate solution printed to the multicolored Achieve polka dot prints on the fabric. In another example, the fabric is made of staple fibers covered with a metal foil, the holes in Has geometric patterns before the solid dye preparation is spun to achieve multi-colored polka dot patterns on the fabric. In another For example, the fabric is padded with an alginate solution that has a blue microdisperse Dye 1,4-di (methylamino) anthraquinone, 1 part in 99 parts alginate thickener contains, as a result of which a fabric with multicolored polka dots on a blue background is obtained.

Example 2 2 parts of colored pigments, 3 parts of ethyl cellulose and 50 parts Ethyl methyl ketone are poured into a rod mill to form a homogeneous mixture touched. The solvent is removed by spray drying under vacuum, and the thus obtained solid dye preparation ground to a fine powder. she will as used in example 1, except that the temperature of the heat setting 200 ° be wears, creating brilliantly colored dots on polyester and nylon 6 fabric obtained from staple fibers and filament yarn.

The following dyes are used: Dye Color yellow Red Blue nylon 6 fabric is washed in hot and cold water, while the polyester fabric is treated as in Example 1. According to this procedure nylon-6 and polyester fabrics with brilliantly colored polka dots are obtained.

Example 3 2.5 parts of starch triacetate are dissolved in 50 parts of glacial acetic acid stirred, whereby a spinning liquid is obtained in which 2.5 parts of the color pigment is dissolved by stirring for 30 minutes in a ball mill. The solution will be slowly diluted, making a solid powdered dye preparation such as described in Example 1, is obtained. The following dyes are used.

Dye color yellow orange pink yellow brown blue yellow brown blue These preparations are used as in Example 1, resulting in a fabric with multicolored polka dots on a white background.

In another example, the substance is replaced by an ethyl methyl ketone or a 2.5% polyvinyl alcohol solution is padded instead of the sodium alginate solution. A fabric with multicolored polka dots and stripes is obtained. example 4 The dye preparations of Examples 1 to 3 are sprayed onto paper, that was covered with a polyester staple fiber and the whole thing is in one hot press heated at 200 ° for 60 seconds, creating a fabric with multicolored Received polka dots on a white background. The paper with the dye preparation can be restored can be used to obtain a fabric with pale colored polka dots.

In another example, 0.8% of the sodium alginate thickener is made up the paper in a regular or random manner by means of rollers or screen printing processes upset. The paint preparation is sprayed onto the wet paper and onto the paper dried. Using this paper in the example above, one obtains Fabrics with regularly or randomly printed multicolored polka dots.

In another example, the paper is replaced by a 2.5% polyvinyl alcohol solution padded and sprayed the dye preparation onto the paper. The paper is drizzled, cut into different shapes and sizes, on the fabric and the whole thing, as described above, heated, whereby one fabric with regular or random design and shaping with multicolored Polka dots. If a previously colored Substance is used a fabric with multicolored polka dots on a colored background. The dye preparations but can also be ground to a fine powder, dispersed in water and on a filter paper can be sprayed on. The filter paper is dried and used it for coloring fabrics as in the previous examples.

Example 5 The dye preparations described in Examples 1 to 3 are sprayed onto polyester fabric which is heated to 200 ° for 2 minutes and then washed as usual. A fabric with multicolored polka dots is obtained.

One can use the heat setting process in the previous example by steaming for 15 minutes at 1300 under pressure with saturated steam substitute.

In another example, nylon 6 carpet is used with the dye formulations printed in a similar way3 except that the daupfing treatment is 15 minutes 99 to 100 "is performed.

Example 6 The paint preparations described in Examples 1 to 3 are ground to a fine powder and a solution of an anionic wetting agent (0.1 to 20 parts / 100 parts of water) was added. The dispersion is left to dry Fabric made of a polyester-cotton (67/33) mixture sprayed on, wobci the dyeing process is carried out as follows: 1) Undyed, dry fabric 2) Fabric, dyed in yellow or red shade (1 g / kg shade) using vat dyes for construction rolls and disperse dyes for the polyester part of the fabric.

The fabric is dried, heat set at 210 ° for 1 minute before washing (the washing was done as usual), creating multicolored spots on it white, yellow and red ground. If you use microdisperse dyes instead of the dye preparations in the above example, they are only mixed colored spots on a tint, where the size of the spots depends on the size of the drops the dispersion was determined.

Example 7 The fine powder of those used in Examples 1-3 Dye preparations are made with an anionic wetting agent (10 parts per 100 parts Preparation) and in the sodium alginate thickening (2.5%, 20 parts in 100 Parts of water) stirred in, creating pad baths with different concentrations of dye preparation contains. The polyester or nylon 66 fabric is made with the Bath padded, which is stirred during the padding, then the fabric dried at 100 "for 2 minutes and at 2100 before washing, which was done as usual, Heat set for 1 minute. A fabric with multicolored polka dots is obtained. The addition of an orange microdisperse dye to the pad bath provides dots on orange colored ground.

If in the previous example microdisperse dyes or water-soluble acidic metal complex dyes instead of the dye preparations uniformly dyed nylon 66 fabrics are obtained.

Example 8 The dye preparations described in Example 2 are sprayed on a fiberglass, with a 2.5% poly-rinylaLkohol- Solution padded and then dried. The fiberglass fabric is then on a polyester fabric and hot air through the fiberglass-polyester fabric for 60 seconds at 2100 passed through at a rate of 2.0 liters / cm2 / minute, creating multicolored Dots on the polyester fabric. The fiberglass is then washed and used again.

In a similar way, you can make a nylon 6 carpet with the dye preparations, which are located on the fiberglass, printing, for which hot air is used for 120 seconds passes through and receives a multicolored carpet without any wet treatment, in which the color has penetrated deeply.

Example 9 2 parts of dye are dissolved in a nylon dope as in Example 1, whereby a colored solution of the dye in the dope is obtained. The solution is slowly poured into water with vigorous stirring to precipitate the dye preparation in fiber form. The dye preparation is collected as in Example 1. The following dyes are used: Dye Color yellow brown purple t pink-red The fibrous powder of the dye preparation is sprayed onto a polyester fiber gauze which is padded with sodium alginate (0.8%) thickener containing 0.1% of an anionic dispersant. The fabric is dried, heat set at 2100 for 1 minute, as in Example 1, yielding a fabric with multicolored polka dots.

Similar colorations are also observed on cellulose triacetate, The theno fixation is carried out at 200 ° and the washing with water at 40 to 500 degrees will.

Example 10 1 part dye-starch acetate preparation as described below is mixed with 100 parts of emulsion thickener which is still 0.5-1 parts of one contains finely dispersed dye. A polyethylene terephthalate is made with this liquor Fabric impregnated on the padder, dried and for 60 seconds at 210 ° thermoset.

The fabric is then rinsed with cold and warm water, reductively cleaned, soaped at 100 "for 20 minutes, washed and dried.

A polyester fabric is obtained which has an evenly distributed> has finely colored dots on a colored background.

The fabric looks similarly colored as one that is obtained, when mixing dyed fibers together before spinning and weaving.

The liquor can also be applied by film printing. One dries heat-set, washes as indicated above and obtains localized, multicolored Pattern on the hydrophobic textile material.

The dye-starch acetate preparations are prepared according to the method described in Example 3, using the following dyes: Yellow dyes Orange dyes Red dyes Blue dyes The dye preparations are pulverized, sieved through a fine-meshed sieve and stirred into the emulsion thickener.

Depending on the color of the finely dispersed dye and the color of the dye-starch acetate preparations may affect the color on the fabric can be varied as required.

The emulsion thickening is prepared using customary methods from the following components: Sodium alginate paste (5%) 600 parts of emulsifier (Lyoprint EV 12.5%) 25 parts of water 225 parts of heavy gasoline (added with vigorous stirring) 150 parts of 1000 parts Example 11 The mixture is stirred 2.5 parts of dye starch acetate preparation in 80 parts of emulsion thickener and 10 parts of polyethylene glycol and gives 1 part of the blue dye of the formula R = mixture of NH and 0 to. A mixed fabric of polyester / cotton (67:33) is impregnated with this liquor on the padder, dried, heat-set for 60 seconds at 205 °, rinsed with cold and warm water, soaped for 20 minutes at 80-90 ° and rinsed again. A mixed fabric is obtained which has orange-brown dots evenly distributed on a colored background.

The dye-starch acetate preparation is prepared according to Example 3 using the dye of the formula The same emulsion thickening as in Example 10 was used.

Claims (9)

Claims 1. Process for producing colored spots, stripes or lines on material made from hydrophobic or hydrophilic fibers or from mixtures of hydrophobic fibers and hydrophilic material, characterized in that the material is fixed Color preparations, which consist of at least one nonionic dye together with polymeric material and, if necessary, auxiliary products exist, so that Spots, stripes or lines are created and then the dye is fixed. 2. The method according to claim 1, characterized in that the Material impregnated with a solution or printing paste, which is the solid RSrbepreparate contains as a suspension. 3. The method according to claim 1, characterized in that the Applying F coloring preparations in dry form to wet or dry textile material and then fixed the dye by harvesting heat or steam treatment. 4. The method according to claim 1, characterized in that the coloring preparations on a carrier that no affinity for the dye has, applies and then the textile material in contact with this carrier heated. 5. Process according to Claims 1 to 4, characterized in that dye preparations of different colors are applied to the material at the same time. 6. The method according to claims 1 to 5, characterized in that dyeing preparations are used which contain such a polymeric material, which is not fixed on the material to be colored. 7. The method according to claims 1 to 6, characterized in that the dye preparations are applied to a material which has previously been treated with a dispersion a disperse dye padded in water or an organic solvent became. 8. The method according to claims 1 to 7, characterized in that the coloring preparations together with a dispersion of a disperse dye brings up. 9. According to the method of claims 1 to 8 in dots, strips or strokes colored material.