SE187479C1 - - Google Patents

Description

Inventor: P D Gagliardi Priority Required as of June 26, 1958 (USA) The invention relates to an improved dyeing process and new dyeing compositions based on the color affinity between pigments of both natural and synthetic origin or the anion dyes and substrates which can be applied to the use of aminoalkylsilecor. Among the substrates that can be used in the set according to the invention can be mentioned: Materials such as natural animal or vegetable fibers for example silk, wool (wool), cotton, hemp and jute as well as synthetic fibers Iran natural raw materials such as rayon and casein fibers. The normally good affinity of such fibers for ordinary dyes can in many cases be improved and a wider use can be achieved by agents such as pigment dyes, which have hitherto found only limited use of these substrates.

Norman black-colored substrates comprising (A) natural fibrous materials such as charges and asbestos fibers, (B) natural solids such as powdered or laminated inorganic oxides such as silica, titanium dioxide, quartz, mica, diatomaceous earth, siliceous sand and gravel and metals and spontaneously formed , (C) semi-synthetic fibrous materials comprising glass fibers and aluminosilicate fibers, (D) synthetic single fibers and continuous yarns made of polyamide fibers (various types of nylon), acrylic, vinyl and vinylidene type fibers, (orlon, acrylic, creslan, dynel, darlon, verel, zefran, velon, vinyon and reflon), polyester fibers (dacron, terylene, etc.), and polyethylene fibers and (E) blended or blended materials produced by combination spinning of selected natural semi-synthetic and synthetic fibrous materials, such as orlon-wool, nylon-nil, orlon- rayon, dynel-viscose, dacron-borne wool and dacron-nylon. Dyes which hitherto have been considered essentially to have no affinity for these DupIs. at 8 m: 10/01; 8 m: 13 materials can now be successfully dyed on these substrates.

The most significant use of satat according to the invention lies in the dyeing of black, dyeable substrates belonging to group 2 above and especially for dyeing glass fibers, synthetic fibers belonging to subgroup D and mixed fibers specified in subgroup E.

Fiberglass products represent the most black-dyed materials used today by the textile industry and the like, as there are no known dyes that have a natural affinity for these materials. In the present dyeing technique, various types of dyeing aids are widely used, including protein-type adhesives or resin-bound pigments. Most colored glass fibers produced today are dyed with printing pastes made from water- or oil-dispersible pigments and water- or oil-soluble synthetic resin binders. The color effects obtained with such medals are relatively limited, and the operating costs are significantly greater than those of competing textile materials.

With the method according to the invention Is it possible to dye glass substrates with the most common textile dyes with certain new types of textile dyes, such as so-called "cellulose fiber reactive" dyes and with organic and inorganic pigments either by penetrating the fiberglass with an aminoalkylsilicon compound or by simultaneously applying pigment or dye and the aminoalkyl silicon compound against the glass from an aqueous solution, dispersion or emulsion. In addition, these results can be achieved by using a normal dyeing and printing equipment without using highly unstable compounds, responsive reaction conditions or unusual solvents.

Synthetic organic fibers are also responsible for dyeing. Some progress has been made in the newly developed technology with printing at temperatures above 100 ° C, so that the diffusion of the dye into the fibers is facilitated, whereby thus deeper color tones are obtained after shorter dyeing periods. However, the necessary special equipment such as pressure vessels and connected control devices are expensive. In addition, various solvent systems with or without water, special metal complexes or cation dyes and the use of ultrasonic waves have been proposed.

None of these methods Concerns directly applicable to existing factory facilities.

Mixtures of synthetic organic fibers as well as natural fibers present an additional problem due to the difference in dyeing tendency of the two fibers. While after the start the number of new aids or color aids has been developed, you can only use these for a limited number of materials.

By means of the sheet according to the invention it is possible to dye such fibers which otherwise normally show poor or no affinity with a selected dye or a pigment under conditions such as applying the dye or pigment to a natural textile material. A dispersion containing a water-insoluble pigment and an aminoalkylsilicon compound can usually be applied by obtaining a uniform color on textile materials containing both natural and synthetic fibers.

The set according to the invention is also useful for coloring inorganic substrates other than glass by using standardized textile dyes and pigments. Such colored substrates were breathable as fillers and as inexpensive pigments and were more compatible with synthetic rubber oak tiles on the untreated inorganic fillers.

Finally, the kit of the invention can be used to dye metallic substrates such as tin, jam, aluminum, zinc, manganese, titanium and chromium. It is possible that the amino silicon compound is useful depending on the coatings that spontaneously form on these metallic materials.

Either method can be used to apply the aminoalkyl silicon compound to the substrate and thus improve the efficiency of the compound. In one set, the substrate is pretreated with the silicon compound. In the second, it is treated with a mixture of the silicon compound and usually from a solution or suspension of the two materials. The choice of these methods depends on the equipment and installation of the plant, the colorant, the substrate, the amino silicon compound and the presence of aids such as leveling agents or color catalysts.

Although the methods can be used in most dyeing, one of these will usually be preferred in a given work. When dyeing glass with ordinary textile colors, for example, is it more convenient to pre-treat the glass. On the other hand, it is more convenient to use a dispersion or emulsion of pigments and aminoalkyl silicon compound when fusing glass with insoluble pigment colors. The pretreatment of the substrate is usually carried out more economically by immersing the substrate in an aqueous solution of aminoalkylsilicon compound. However, the required coating of the silicon compound can be achieved fully satisfactorily by such commonly used methods as spraying. The silicon compound can be released above its normal temperature in purified aqueous (aqueous) solutions by using acids, alkalis or other release agents, or emulsions can also be used. The aminoalkyl silicon compounds can also be detached during salt formation or by introducing detaching groups into the molecule. Solutions Concerns about suspensions or emulsions are particularly difficult to treat when treating highly hydrophobic substrates so that non-uniform staining is avoided. In fact, any solvent system that is substantially non-reactive with the aminoalkylsilicon compound can be used to facilitate uniform distribution of the color aid on the substrate. Commercially available wetting agents normally used in the dyeing industry can also be used to facilitate the uniform distribution of the silicon compounds.

Reading agents which facilitate uniform distribution include alkanols and ether alcohols such as ethanol, propanol, isopropanol, methoxyethanol and ethoxyethanol, monobasic acids such as formic, attic, propionic, lactic, glyconic and glycolic acids and diglycolic acid, mineral acids, aromatic hydrocarbons , toluene and xylene and alkaline compounds. Water and water-alcohol solutions containing said monobasic organic acids were used as lasers. For example, solutions containing aqueous systems of 40 to 60 parts of water, 60 to 40 parts of ethanol or isopropanol and 5% by volume of acetic acid have been found to be satisfactory for applying the aminoalkyl silicon compounds ph to any of the above substrates.

The concentration of the aminoalkylsilicon compound treatment solution Or not critical. If glass cloth was pretreated, an increase in the concentration of the silicon compound in solution from 3 to 9% by weight (representing an increase of from 0.75-2.25% by weight of applied solid substances) was achieved, essentially no difference in the dyeing of the fabric by means of ordinary textile dyes. In general, a pretreatment of from 1 to 5% by weight of silicon compound in the solution gives 10 to 60% by weight of liquid uptake of the solid substances and this is fully sufficient for most dyes. If a substrate is to be treated with an aminoalkyl silicon compound simultaneously during the dyeing, a concentration of the silicon compound which results in a coating of 0.25 to 3.0% by weight of the substrate in a similar manner will give satisfactory results.

If aminoalkylsilicon compounds are applied to a substrate by the pretreatment method, it is appropriate if not necessary to dry the treated substrate. Drying in air at room temperature gives satisfactory results, but suitably the treated substrate is heated to a ratio It is possible that the heating system results in an improved bond between the substrate and the silicon compound. Time and temperature are inversely proportional to each other during this drying. Only a few seconds are required at temperatures as high as 200 ° C, for example. The drying temperature is of course limited by the ability of the substrate to be resistant at high temperatures. It is conveniently dried at temperatures from 95 to 177 ° C and times from 5 minutes to 1/2 hour.

If the silicon compound and the dye are applied simultaneously to Iran a single solution, the required heating periods for normal dyeing and printing are equivalent. Additional heating can of course be used if necessary.

The dyes which can be used in carrying out the set according to the invention comprise, a organic and inorganic pigments, the dyes of the anion type, i.e. the dyes containing an acidic substituent, their neutralized equivalents, the anionic dyes in the form of complexes with a metal and the dyes having substrate-reactive groups such as halogen atoms. The term "anion dyes" includes those dyes which are normally stored anionic in use, for example the dye dyes which become anionic as they are reduced during dyeing and similar "functionally anionic" dyes which can be applied in a neutralized form for possible conversion during use. Particular groups of the anion dyes used in the set according to the invention include: indigo dyes, anthral non-dye dyes, light cyan dye dyes, cyanide dye dyes, direct azo dyes, sulfur dyes, total wool or wool dyes, form-metallized acid dyes, neutral dye-colored cellulose dyes. Among usable organic and inorganic pigments may be mentioned: natural and synthetic inorganic pigments such as umbra, sienna, ocra, chromium green colors, iron blue colors, iron oxide brown colors and red colors, zinc white, titanium white, ultramarine blue, lead chromate yellow, zinc chromium quartz yellow, zinc chromium quartz yellow; and natural and synthetic organic pigments such as carmine, catechu, turmeric, yellowwood, fargtra, naphthol yellow, azorot, lithol root, azoorange, indanthrene leaf, indanthrene violet, toluidene yellow and phthalocyanine leaf. Synthetic pigments obtained when used in normal textile dyes and aminoalkyl silicon compounds on finely divided inorganic oxides such as silica, titanium dioxide and zinc oxide are also useful in the process of the invention.

It has been found that all the aminoalkyl silicon compounds (or aminoalkyl silicone compounds) tested can be used in the method of the invention. Although there is a variation in the effect of the particular silicon compounds depending on the substrate and the use of the dye.

It is important that the silicon compound contains at least one group of the following formula: R 'Yb N-R-Si R "marl R represents a substituted or unsubstituted carbon group having at least 3 carbon atoms between the nitrogen atom and the silicon atom, R' and R" represent hydrogen or organic radicals , namely alkyl, aminoalkyl, cyanoalkyl, hydroxyalkyl, carboalkoxyalkyl, carboxyalkyl or aryl radicals or monovalent groups: —R — Si-XZ, van i X denotes an alkoxy radical or the oxygen atom of a siloxylidine radical Si-O--, Y is a hydroxyalkoxy, alkyl or aryl radical, Z is an alcohol, alkyl or aryl radical, C 1 or 2, b is 0.1 or 2, and C plus b is a maximum of 3. The necessary group of the color aid may be a part ay a monomeric aminoalkylalkoxysilane, an aminoalkylpolysiloxane, or a copolymer or simply a mixture of an aminoalkylpolysiloxane with one or more other siloxanes. It is not necessary that these materials be used in any form, clear hydrolyzate or aqueous-alcoholic solutions in the silicon compounds to be used for applying ananooalkyl silicon groups to the substrate or in dye baths which are to be used for coloring the substrate.

The aminoalkylalkoxysilanes which can be used in the process according to the invention can be represented by the following general formula: R'Yb II N-RT SiX4- (o-Eb) van in R, R 'and R "have the same meaning as the glints above, X Or en alkoxy radical, Y Or an alkyl or aryl radical, (c) Or 1 or 2, (b) Or zero, 1 or 2, and the sum ay (cb) Or into stone On 3.

Feljande special silanes Oro illustrative of the above formula to beta-methyl-gamma-aminopropyltriethoxysilane gamma-aminopropyltriethoxysilane gamma aminopropyltripropoxisilan gamma-aminopropylmethyldiethoxysilane gamma aminopropyletyldietoxisilan gamma aminopropylfenyldietoxisilan delta aminobutyltrietcodsilan delta aminobutylmetyldietoxisilan delta aminobutylfenyldietoxisilan gamma aminobutyltrietcodsilan gamma aminoisobutylmetyldietoxisilan gamma aminobutylmetyldietoxisilan X 4 – c – b 4— 17479 - N-beta-carbethoxyethyl-gamma-aminopropyl-triethoxysilane N-beta-cyanoethyl-delta-aminobutyltriethoxysilane N-gamma-triethoxysilylpropyl-pyrrolidine N-gamma-triethoxysilylpropyl-2,2-dimethylpyrrolidine N-phenyl-N-methyl-gamma-aminopropyltriethoxysilane N-phenyl-N-methyl-delta-aminobutyltriethoxysilane N-methyl-beta-methyl-gamma-aminopropyltriethoxysilane N-beta-aminoethyl-gamma-aminopropyltrimethosilane N- gamma-aminopropyl-gamma-aminopropyl-triethoxysilane N-gamma-aminopropyl-delta-aminobutyl-methyldiethoxysilane N-ok Tyl-gamma-aminoisobutylmethyldiethoxysilane N-beta-aminoethyl-yarn-aminoisobutyl-diethoxylsilane bis (gamma-triethoxysilylpropyl) imine bis (beta-methyltriethoxysilylpropyl) imine N, N-dimethyl-gamma-aminopropyltriethoxysilane N-naphthyl -aminopropyltri-ethoxysilane N- (furfuryl) -gamma-aminopropyltriethoxysilane etc.

Aminoalkylalkoxy silanes of the type indicated above and intended to produce compounds of this structure are generally described in U.S. Pat. No. 2,832,744 and in French Pat. No. 1,184,096. In addition, these silanes which contain two. aminoquine atoms are prepared by reacting a diamine with an appropriate chloroalkylalkoxysilane.

The silane monomers used in the kit of the invention generally form stable solutions with aqueous mixtures of organic compounds. This is a particularly apt feature with regard to erasing practice in the dyeing industry. In aqueous solution, the alkoxy groups slowly hydrolyze so that the silane monomers are optionally transferred to water-soluble aminoalkyl polysiloxanes. Aqueous mixtures of such polysiloxanes with water-soluble organic compounds are sufficiently stable to be used in the dyeing industry. The aminoalkylpolysiloxanes which can be used in the kit according to the invention can be linear cyclic or space-linked. Space-linked aminoalkyl polysiloxanes are readily prepared by hydrolysis and condensation of trialkoxy-substituted silanes and may contain small amounts of silicon-bonded hydroxyl groups or silicon-bonded alkoxide groups depending on the conditions of the hydrolysis and condensation. For example, space-linked aminoalkylpolysiloxanes which substantially lack residual silicon-bonded alkoxy or hydroxyl groups can be prepared by complete hydrolysis and total condensation of an aminoalkyltrialkoxysilane. Polymers containing larger amounts of residual alkyd groups can be prepared by partial hydrolysis and total condensation of the same starting silane. Polymers containing significant amounts of residual silicon-bonded hydroxyl groups can be prepared by substantially complete hydrolysis and only partial condensation of the same starting material. Polysiloxanes of the foregoing types can be generally represented by the following structural unit formula: R 'N-R-Si (Z) dO 3 -d R "van in R, R' and R" have the meaning given above, Z represents hydroxyl or alkoxy groups and (d) has an average value of from 0 to 2 and suitably from 0 to 1. Typical such polymers include gamma-aminopropylpolysiloxane and delta-aminobutylpolysiloxane and to these obtainable hydroid- and alkyd-containing hydrolysates and condensates of these polymers.

Aminoalkoid polysiloxanes of cyclic and linear type are prepared by hydrolysis for condensation of dialkoxy-substituted silanes. These polymers can generally be represented by 101st structure: R 'N-R-SiO Rn van in R, R' and R "have the meaning given above, is an alkyl or aryl radical and (n) an integer with a value of at least 3, with the mean of frail 3-7 for cyclic polysiloxanes and higher for linear polysiloxanes.Typical cyclic polymers include the cyclic tetramer of gamma-aminopropylmethylpolysiloxane () and delta-aminobutylmethylpolysiloxane.The linear polymers amylopropylamopropylamopropylamopropyl , delta-aminobutylmethylpolysiloxane, gamma-aminobutylmethylpolysiloxane, N-beta-aminoethyl-gamma-aminopropylpolysiloxane, N-beta-aminoethyl-gamma-aminoisobutylmethylpolysiloxane and blocked polysiloxanes in which from 1 to 3 alkyl or alkyl groups or hydroxyls of molecules comprising a polymeric chain.Sadane andblocked linear polymers include methoxyandblocked gamma-aminopropylethylmethylpolysiloxane and monoethoxydimethylsilyl and blocked gamma-aminopropylphenylpolysiloxane and can be readily prepared by transferring in equilibrium cyclic aminoalkylpolysiloxanes with silicon compounds containing silicon-bonded alkoxy groups or by cohydrolysis and condensation of trialkylalkoxysiloxylanylsilanes with aminoalkylsilanylethanes. The hydroxyand-blocked polymers 2 (IV) (v) -in - can also be prepared by digesting linear or cyclic aminoalkylpolysiloxanes with water.

The copolymeric polysiloxanes which can be used in the set according to the invention may contain siloxane units consisting of one of the above typical groups in combination with one or more other carbonate-substituted siloxane units generally representing the formula: We W '-SiO3_0 2 van in W and W' are hydrocarbon radicals and (e) an integer having a value from 0 to 2. These copolymers can be prepared by cohydrolysis and condensation of aminoalkylsilanes with other carbonate-substituted silanes or by direct equilibrium reaction of a mixture of aminoalkylpolysiloxanes and other carbonate-substituted siloxanes. The linear copolymers may also contain blocking alkyl, aryl, hydroxy and alkoxy radicals. The various polymeric copolymeric materials of the kind set forth above and set forth in the preparation of these materials have been described in the aforementioned U.S. Patents.

The aminoalkylsilecyl compounds can also be used in the form of their coordinated complexes with metals such as copper, chromium and cobalt. For example, the copper complexes can be easily prepared by reaction between the silicon compounds and. copper chloride, acetate, sulphate, hydroxide or stearate. The silicon compound can be precomplexed with the metal or reacted in situ.

In the set according to the invention, colored substrates are obtained which have an excellent affinity for elastomeric polymers which are used to a large extent as pigment binders and as textile preparation agents. For example, a cotton swab treated with an aminoalkyl silicon burn was pigmented in one step using an acrylic polymer as a textile finish. The fabric exhibited wash resistance, abrasion and degradation resistance as well as light resistance which were decidedly better than in a cotton fabric not treated with an aminoalkyl silicon compound. In the same way, a normally pigmented glass fiber fabric treated with an acrylic polymer did not exhibit the same excellent degradation or probing resistance and creasing resistance as a glass fabric first treated with an aminoalkyl silicon impurity.

Elastic polymers which are more effective formulation materials when applied to colored substrates and which are prepared according to the invention are polymers which have a shark or two-dimensional structure which may contain attached reactive groups such as carboxy, ethoxy, methylolamide or vinylsilyl groups. These can be applied to the substrate after the dyeing has ended or they can be mixed with the pigment and applied to the silicon compound-treated substrate or the elastomer, pigment and silicon compound can be applied together.

In an embodiment of the set according to the invention, dyeing can be carried out using a silicone vat together with the aminoalkyl silicon compound and the dye, thereby improving improvements e.g. in the form of a better mixture of the silicon compound and the colorant, better. application of the silicon compound to the substrate and whereby a colored substrate is obtained as a better grip.

These silicone wipes can be used in admixture with the aminoalkyl silicon compound or in admixture with the color aid or in admixture with both. The silicone wipes can also be used for the treatment of substrates after they have been dyed by a set according to the invention. When used in the form of an after-treatment, the silicone wipes are suitably used in combination with the elastomers which are usually used as pigment binders or as textile preparations.

The silicone wipes which are most useful in modifying the invention are polysiloxane oils such as dimethylpolysiloxane, beta-phenylethylpolysiloxane, diethylpolysiloxane and oils containing both dimethylsiloxane units and methylethylsiloxane, diethylsiloxylsiloxane, diethylsiloxylsiloxanes, These silicone wipes also include copolymers of linear or branched polysiloxanes and polyoxyalkylene polymers.

The amount of silicone liquid used to make the colored substrates can vary widely. For example, the amount of silicone fluid applied to the substrate Iran is one quarter to four times the weight of the applied aminoalkylsilicon compound. This can be achieved by using baths which contain a quantity of silicone liquid lying between a quarter and four times the amount of weight compound. If the aminoalkyl silicon compound and the silicone liquid are applied from separate baths or in the silicone liquid anyandes in more than one bath, the total quantity of silicone liquid used in all baths is suitably within the above range. Man Ink note that the quantity of silicone wadding beyond the above range is not Or disadvantageous. However, a further advantage does not seem to emerge with higher quantities.

The silicone wipes are suitably added to the treatment bath in the form of an emulsion, for example a water emulsion containing Iran 10 to 60% by weight of a polysiloxane oil.

In addition to silicone waders, small amounts of known organic casting agents for textile materials can be used as emulsions of long chain fatty acids, epoxidized soybean oil, quaternary amine compounds with long chains e.g. octadecyltrimethylammonium chloride, octadecylethyleneimine and the like. Such plasticizers, even if de Oro usable, do not, however, show such generally favorable effects as the silicone waders.

Further improvement of the grip of the fabric or fabric dyed with a pigment and an aminoalkylsilicon compound as a coloring agent appears after washing, pulling or stretching of the fabric.

The coating can be carried out with water or with a mixture of water and a surfactant such as whey or a synthetic detergent. For example, after dyeing, the fabric can be rinsed with water, washed with an aqueous soap solution and finally separated one or more times with water. Pulling or stretching is carried out in standard devices.

The following examples illustrate the invention. For the sake of simplicity, it is found in the examples to use the aminoalkyl silicon compounds in the form of code numbers according to Table 1 below.

Table 1.

Code number for auxiliary purification or composition of the agents 1gamma-aminopropyltriethoxysilane 2delta-aminobutyltriethoxysilane 3scopolymer ay gamma-arninopropyltriethoxysilane and phenyltriethoxysilane (30% solids) 430% ethanol solution propyl-amoloxylaminooxyl of gamma-aminopropyl-triethoxysilane and phenyltriethoxysilane (30% ethanol solution) 7 N-phenyl-N-methyl-gamma-aminopropyltriethoxysilane 8 copolymer silicone oil containing 95.2% trimethylsiloxyand-blocked dimethylsiloxyl silicone oil containing 75% trimethylsiloxyandblocked dimethylsiloxane and 25% delta-aminobutylmethylsiloxy group 11 copolymer silicone oil containing gamma-aminopropyltriethoxysilane and vinyltriethoxysilane (25% solids) 12scopolymer siliconyltriethylamethane rtser) 13 cobalt chelate of gamma-aminopropyl-triethoxysilane (17% in H 2 O) 14 copolymer silicone oil containing 83.3% trimethylsiloxyand-blocked dimethylsiloxane and 16% gamma-aminopropylsiloxy groups gamma-aminopropylpolysilopane / gamma naphthyl-gamma-aminopropyltriethoxysilane Code number for color aid compound or composition 17 copolymer containing 50% trimethylsiloxyand-blocked dimethylsiloxane and 50% delta-aminobutylmethylsiloxy groups 18scopolymer containing 70% trimethylsiloxysiloxane and silica ) - delta-aminobutylmethylsiloxy groups 19 copolymer containing 25% trimethylsiloxyandblocked dimethylsiloxane, 40 ° X, diphenylsiloxy groups and 33% delta-aminobutylmethylsiloxy groups copolymer containing 68.5% trimethylsiloxyaniloxylsiloxyl-dimoxyloxylmethylsiloxyl triethoxysilylpropylpyrrole i-denhydrochloride 22N-beta-cyanoethyl-delta-aminobutyl-triethoxysilane 23 N, N-dimethyl-gamma-amino-propyltriethoxysilane hydroiodide 24 beta-methyl-gamma-aminopropyltriethoxysilane bis- (beta-methyltriethoxysilylpropyl) imine 26 N-methyl-methyl -gamma-aminopropyltriethoxysilane 27 N-beta-carbethoxyethyl-gamma-aminopropyltriethoxysilane 28N-beta-cyanoethyl-delta-aminobutyl-methylpolysiloxane (mainly cyclic) 29N- (beta-furfury1) -gamma-aminopropylbutylethyloethodiloxyl-amyltyldoxysilan The product is otherwise comparable to 9 above prepared genorn hydrolysing agent ay 30) 32Same as 31 but prepared by solvent hydrolysis 33delta-aminobutylmethylpolysiloxane incompletely condensed and thus probably containing silicon-bonded ethoxy or hydroxyl groups (60% solids amine-ethanol-amethoethylamine gamma-aminopropyltriethoxysilane 36 copolymer silicone containing 60 °, trimethylsiloxyand-blocked dimethylsiloxane and 40% N-beta-amine oethyl-gamma-aminoisobutylmethylsiloxy groups 37 N-beta-aminoethyl-gammaaminopropyltrimethoxysilane 38 N, N-bis (beta-hydroxypropyl) -gammaaminopropylpolysiloxane - - 1Code number for coloring compound or composition containing 39s copolymer siliconexyl hydroxy-stearyl-gamma-aminoisobutylmethyl-siloxane units N-octyl-gamma-aminoisobutylmethyldietcaisilane The reaction product of propylene oxide with N-beta-aminoethyl-ganama-aminopropyltriethoxysilane copolymers of color auxiliaries described as copolymers and siloxylsiloxanes containing dimopolymers and silicones; which is usually prepared by equilibrium reaction of a trimethylsilmand tooth blocked dimethylpolysiloxane with a cyclic or linear silicone composed of the specific siloxane units referred to therein. Salunda aro such materials are trimethylsiloxyandblocked polymers containing dimethylsiloxane units as well as one or more units of the particular kind.

Example 1.

Aminoalkyl silica dyes 9 and 17 were clumped into glass webs from solutions of the following composition:% dye 5% acetic acid% isopropanol 45% water At a moisture uptake of 33%, 1.65 ° /, silicon compound was applied to the web by the graft. The samples were dried for 10 minutes at a temperature of 149 ° C.

Dye baths were then prepared with the following three cellulosic reactive dyes: Procion yellow R Procion brilliant trout 2B Procionblatt 3G Each dye bath contained 5% by weight of dye and 0.25% sodium alkyl sulphate as a wetting agent in the water.

The dyes and wetting agents were transferred in paste form into cold water and then diluted with water at 30 to 49 ° C. The dyes were applied by chipping at 20 ° C. A sample from each dye bath was immediately rinsed with water to determine the reaction between the treated glass cloth and the procion dye had entered immediately or if the reaction required a considerable time for completion. Another sample for habit dye bath was dried for 5 minutes at a temperature of 121 ° C. The bathed groups of colored tissues were rinsed in water at 35 to 41 ° C and then in boiling water and then in hot water containing sodium alkyl sulfate anhydrous and then in a final water rinse at 35 to 41 ° C. After final drying for 5 minutes at 121 ° C, the quality and color intensity of the samples were examined and judged arbitrarily by the color depth, with a rating of 3 to 5 representing a very good coloration: Mummer 5 = very deep hue Mummer 4 = deep hue Mummer 3 - medium hue Mummer 2 = light hue Mummer I = only light shade 0 = no coloring - the sample remained white The assessment can be found in Table 2 below.

The untreated glass cloth was not stained in any way and in all cases the samples treated with silicon dye aids were deep and brilliantly colored. The test results also show that the effect of color aids must be immediate as there is no significant difference between the samples that were immediately rinsed (0. S. in Table 2) and those heated to 120 ° C (U in Table 2). The dye no. 9 seems to give the deepest coloring with all the Irish colors.

Table 2.

Glasvav- Glasvavnadnad be- treated by hand with means 17hjalpme- O. S. U.del 9 O. S. U.

Yellow R 0 0 3 3 4 Brilliant Trott 2B 0 0 4 4 Blue 3G 0 0 3 3 4 4 Example 2.

Either alkali or heat or hada must be used to catalyze the reaction between cellulosic fiber reactive dyes and cellulosic hydroxyl groups. To determine if alkali was necessary when the substrate was first treated with an aminoalkyl silicon compound and to test these dyes in a dye jig, the following samples were made.

The dye aids 9 and 17 were applied to glass tissues according to Example 1. The samples were then stained with the following water bath containing:% dye (calculated on the weight of the fabric) 3% Na.2SO 10 I-1.0 0.4 cyo sodium alkyl sulfate at 10: 1 = bath : tissue condition shaved as volume.

The treated and untreated glass tissue sample was placed in the dye solutions and licked at 27 ° C for 75 minutes with periodic stirring. They were then rinsed in water at 36 ° C, washed in water at 71-76 ° C, washed in hot water containing a wetting agent, rinsed in water again at 30-36 ° C and allowed to air dry to dryness.

Procion dye Untreated glass cloth O. S. U. 8— - A total of four different procion dyes were used according to Table 3.

- A second series of jig staining is challenged with the first three procion dyes listed in Table 3 using the same treated and untreated glass fabrics. Here, however, 1% Na 2 CO 3 was added to the dye bath after 45 minutes and the total residence time in the bath was 90 minutes. The samples were rinsed, washed and dried as above.

The same evaluation scale as in Example 1 was used to examine the samples and the results are shown in Table 3 below. The untreated glass cloth was not stained in any of the experiments. Both the silica-treated products showed satisfactory results and if no alkali was used, alien was used if the No. 9-treated substrates showed the clearest color tones. The presence of alkali had no flake effect in glass tissue treatment with No. 17. Yid treatment of the glass tissue with No. 9 it was observed that a reduced quantity of dye had been taken up by the tissue by alkali treatment.

Table 3.

Procion farganane Untreated glass cloth AlkaliNo alkali With silicon compound 17 treated glass cloth AlkaliNo alkali With silicon compound 9 treated glass cloth AlkaliNo alkali Yellow R 3 3 2 Brilliant trout 2B 0 0 4 4 2 Blue 3G 0 0 4 4 2 Brilliant blue _ Brilliant blue Example 3.

Aminoalkyl silicon compounds of Table 4 were used as color aids by applying them to glass cloths of Example 1. Samples of treated and untreated glass cloths were then stained at room temperature with the cellulose fiber reactive procian dyes listed in Table 4 according to the procedure described in Example 2. The total color time was 90 minutes and no alkali was used.

Table 4 shows the result as an assessment scale according to Example 1. All aminoalkyl silicon compounds resulted in a staining of the glass fabric and most produced a color tone Iran medium to very deep. Some of the samples were striped and uniformly colored. Improved results are obtained at higher dyeing temperatures due to better watering and increased reactivity.

Table 4.

Color aidsProcion (Table 1) brilliant- Oct 2 B Color depth Procion brilliant- blue R Procion brilliant- yellow 6 G 9 4 17 3 4 4 4 1 3 3 4 3 2 14 2 3 3 11 3 2 2 3 2 3 6 2 2 1 Control (untreated) 0 0 0 Example 4.

Another series of stainings on glass fabrics treated according to Example 1 with the stain aids listed in Table 5 are challenged. The three procion dyes listed in Example 3 were also used in these experiments. The dye samples were immersed in an aqueous solution containing:% dye (calculated on the weight of the fabric) 3% glauber salt 0.5% dioctyl sodium sulfosuccinate (water agent) Volume ratio between bath and fabric = = 15: 1.

After 60 minutes at 71 ° C, the samples were rinsed, washed and dried according to Example 2.

The results are shown in Table 5 below using the color scheme set forth in Example 1. All samples in this series had been dyed more uniformly than the fabrics dyed at the lower temperature of 26 ° C according to Example 3. While the dyeing aids which produced medium deep or very deep hues when dyed at 26 ° C also showed good results at 71 ° C. ° C whereby some of the aids which had been less effective at 26 ° C were much more effective at 71 ° C. The results of Tables 4 and 5 also show that monomeric silanes are in some cases less effective than polysiloxanes if equivalent concentrations are applied to the tissue ( 1.65%). This is shown, for example, by the respective assessments for the color aid No. 1 in comparison with No. 4 (Table 4), or No. 5 in comparison with No. 15 (Tables 4 and 5). Arylsilanes constituting derivatives of N-methylaniline (No. 7) and naphthylamine (No. 16) showed a relatively similar effect in this sample. This is probably due to the steric effect of the aryl groups and to the fact that these aids are secondary and tertiary amines. Several tertiary and secondary amino-substituted silanes (Nos. 18, 22 and 23) provided good staining under these conditions.

Table 5.

Aminoalkyl silicone dye-Procion medium brilliant- (Table 1) root 2 B Color depth Procion brilliant-blue R Procion brilliant-yellow 6 G 9 4 4 4 12 4 4 17 4 4 4 3 3 11 4 3 3 6 4 3 3 19 4 22 4 1 4 3 3 18 3 3 4 3 23 3 14 2 3 3 16 1 7 1 Control (untreated) 0 0 0 The stiffness or grip of a vavilad after staining is an important criterion for the overall applicability of a paint treatment and Table 6 shows stiffness assessments for the samples stained as above. Such data can be crucial in choosing between otherwise equally effective color aids for a given color.

Paint aids which provide a soft grip 1 4 6 9 11 15 20 23 Table 6.

Dyestuffs which provide a medium rigid grip 12 14 18 22 7 Dyestuffs which provide a rigid grip 17 19 In samples similar to those carried out as described above, glass fabrics pretreated with aminoalkyl silicon compounds listed in Table 1 were dyed with dye baths containing direct-acting cellulose dyes. ), direct dyes (superlite fast fracture 3BL, orange LLLWF, blue G1 and yellow EFC), acid wool dyes (Metro Alizarine Sapphire BN, Metro cid Phloxine G and Metrocid PMO area GRC), wax dyes (Metrovat Jade Green BD Double Paste , Ponsol Brown RBT, Ponsol Red 2B, Pon-. Sol Khaki Dbl).

Example 5.

The effect of the concentration ay in the aminoalkyl silica dye aids listed in Table 1 was examined in a series of samples in which in hot purified glass vesicles; where dyed with different anion dyes. The aminoalkyl silicon compounds were applied to the tissues of aqueous brine baths containing 3.6 and 9% silica compound and 0.1% sodium alkyl sulfate. The baths used with dyes 9, 12 and 17 contained 5% acetic acid for solubilization of the silicon compounds in water. The moisture uptake in the water was 25 ° / n and the concentrations of the applied color aids were thus 0.75, 1.50 and 2.25%, respectively. After chipping, all samples were dried after 10 minutes at one. temperature of 149 ° C.

The staining of the aminoalkyl silica compound treated web was accomplished with ten different dyes by the following methods. The results of these stainings are found in Table 7 below.

(A) Direct-acting and developing dyes: Dye: Metromind-diazo-black bra 125% (CI 401) Dye bath: 5% dye calculated on the weight of the fabric, 0.5% dioctyl sodium sulfosuceinate - 75% Bath ratio: 30: 1.

The dye (5% metromindia-diazo-black bra calculated on the weight of the fabric) was spread in paste with. a small amount of hot water and 0.5% dioctyl sodium sulfosuccinate wetting agent were added thereto to obtain a dye bath. The glass cloth previously dissolved with water was introduced into the dye bath at 50 ° C. The bath was heated to 82 ° C for a 15 minute period after which 1.5 ml of a 10% sodium chloride solution was added per gram of cloth. After an additional 15 minutes at 82 ° C, the same amount of sodium chloride was added to the bath. After a further 15 minutes, the samples were rinsed with cold water. 3% sodium nitrite 6% HCl (37%) (all calculated by weight of fabric) Bath ratio 30: 1.

The washed glass tissue samples were placed in a diazotization bath containing 3% NaNO, and 6% HCl. The ratio of bath volume to tissue volume was 30: 1. After 10 minutes at 10-15 ° C, the samples were taken, developed in a solution of 1% beta-naphthol and 0.5% sodium hydroxide at 50 ° C for 10 minutes, separated in cold water, washed with 0.5% of an anionic detergent (fatty methyl tauride) at 71 ° C, rinsed anyo with cold water and dried in air at room temperature. Kyp dye: The dye (3% metrovat jade-grout BD Dbl. Pst based on the weight of the fabric) was transferred in paste form with 1.5% dioctyl sodium sulfosuccinate and a small amount of hot water and added to a sufficient amount of water so that a volume ratio between water and the volume of the cloth was 30: 1. NaOH (1%) was added and the temperature was raised to 49 ° C. While stirring the bath, 1.5% sodium hydrosulfite was slowly added and the bath was then milled for 15 minutes at 49 ° C. Samples of the glass cloth was diluted with 0.1% sodium alkyl sulfate solution and introduced into the bath. After 15 minutes, 1 ml of 10% NaCl solution per gram of tissue was added. After an additional 5 minutes, the same amount of NaCl solution was added. After an additional 5 minutes, the glass cloth was removed from the Iran dye bath, rinsed in cold water and oxidized in 0.5% hydrogen superoxide solution. They were then washed at 71 ° C, rinsed and dried.

Kypester dye: The dye (3% metrosol green IBW based on the weight of the fabric) was transferred in paste form with 0.5% dioctyl sodium sulfosuccinate and then diluted with a sufficient amount of cold water so that a volume ratio between liquid and fabric was 30: 1, the fabric was watered with 0.1% solution of sodium alkyl sulfate and introduced into the dye bath. The temperature was then raised to 60 ° C. After 10 minutes, 0.5% glauber salt was added. 2% sodium nitrite was added. The bath was stirred for 10 minutes and then cooled to 38 ° C. In this case, 0.5% of 1-12 SO 4 previously mixed with 4 parts of water was added. The color was allowed to develop for 10 minutes after which the stained glass cloth was rinsed in water and dried with a 0.5% solution of fatty methyl tauride at 71 ° C. After a rinse in cold water, the cloth was air dried.

Direct dye - 1: Glass tissues are washed with a solution of 0.1% sodium alkyl sulphate wetting agent and immersed in a dye bath at 71 ° C containing 0.3% metromine sky leaf FF Ex. Cone and 0.5% dioctyl sodium sulfosuccinate. The volume ratio of had to weave was 30: 1. The bath temperature was raised to 82 ° C over a 15 minute period and 1 ml per gram of weave of 10% sodium chloride solution was added. After 15 minutes, the same amount of sodium chloride was added. After another 10 minutes, another equal amount of NaCl was added to Ater. After an additional 10 minutes, the samples were rinsed in a 10% sodium chloride solution at 35 ° C, washed with 0.5% fatty methyl tauride solution, rinsed twice with cold water and air dried.

Direct dye - 2: This method is challenged in exactly the same way as indicated under (D) except that cuprofixbordeaux-BL dye is used.

Naftol dye: Color name: (base) Naftol AS (Pr. 302) (dye salt) fast-acting scarlet root R-salt (C. I. 118).

The dye base (3.0 grams of naphthol AS per 5 grams of tissue) was transferred in paste form and added to 250 cc of water per 5 grams of tissue. 4 cc of 28% NaOH solution and 2 cc of methoxyethanol were added per gram of tissue. The tissue was washed with a 0.1% solution of sodium alkyl sulfate solvent and added to the solution with the naphthol AS base. After an additional 10 minutes at 20 ° C, 10% NaCl shaved on the weight of the fabric was added. After a further 10 minutes, the samples were clumped so that excess liquid was removed and dried for 5 minutes at 121 ° C.

The dry samples were then clumped with an aqueous solution containing 5% fast-acting scarlet R-salt. The Milos 30 seconds in air to develop the color () eh were then rinsed in cold water, rinsed again in warm water, washed in a 2% solution containing 1% Na 2 CO 3, rinsed with water and dried.

Cellulose fiber reactive dye: The glass wafers were washed with a 0.1% solution of sodium alkyl sulphate solvent and immersed in a dye bath at 20 ° C containing 3.0% procion-brillilant 2B dye, 2.0% glauber salt and 0.5% dioctyl sodium sulfosuccinate, all calculated by weight of the fabric. The ratio was shaved as volume between bard and weave and was 15: 1. The temperature was raised to 71 ° C over a 30 minute period and maintained at 71 ° C for an additional 30 minutes. The tissue was rinsed in cold water, rinsed in water at 60 ° C, washed in a 0.1% solution of sodium alkyl sulfate at 60 ° C, rinsed in cold water and dried in lit.

The results of these tests can be found in Table 7 below with assessment figures according to Example 1.

Table 7.

Treatment and color management AB CDEF G No. 9 3% 4 4 4 3 3 6% 4 4 5 4 3 9% 5 4 5 5 4 No. 17 3% 4 5 3 1 3 6% 4 5 3 2 4 9% 5 5 3 2 No. 12 3% 2 4 4 1 9 6% 3 4 5 1 3% 3 4 5 1 3 No. 5 3% 2 3 3 1 2 6% 2 2 3 1 1 9% 2 2 3 1 2 No. 4 3% 2 2 2 1 0 6% 1 1 1 1 1 0 9% 1 0 2 1 0 Nr 1 3% 1 2 2 1 0 6% 1 0 1 1 0 9% 1 0 2 1 0 Control - mget 1 1 2 1 0 Silicon Purity 2 4 2 4 2 3 4 4 4 3 3 4 4 4 3 4 13 1 3 1 4 1 2 1 2 1 2 12 12 1 3 11 - - It appears from the above experimental data that a Wining mom concentration limits in this experiment of the amount of aminoalkylsilicon compound applied to the fabric has no significant effect on the color that develops on the fabric in a subsequent color operation. The test results also confirm the conclusions drawn from the examples given above, namely that 9 and 17 are the most generally acceptable color aids and that a choice of a color aid depends on the fabric and faun used.

The results of the above examples have shown that aminoalkylsilicon compound No. 9 was one of the most commonly used color aids in the kit of the invention. A test series was performed to determine if the delta-aminobutyl group would exhibit the same degree of efficacy if present in other silicon compounds. The color aid No. 30 was a monomer from which No. 9 was prepared. Color aids Nos. 31, 32 and 33 were used as representatives of relatively red and therefore less expensive hydrolysates, while color aids No. 2 were a monomeric trifuction functional silane. Glass tissue previously treated with the dye aids was stained with a form metallized acid dye (Wooncolan Orange RL), cellulosic fiber reactive dyes (pro ion ion broth 2B and cibacron-turquoise blue G), acid dyes (Wooncester gypsum Phycloid); (metrosal-green IBW and Woon-cosol-red-violet W 12 R), the direct dyes (Cuprofix-marinblatt 2B and Cuprofix-direkt-bordeaux BL), a direct and development dye (Metromine-diazo-black bra) and a sulfur-dye (sulfur-reddish-brown WOE). The results showed that the crude hydrolysates (Nos. 31, 32 and 33) all showed results comparable to those obtained with No. 9. The monomers (Nos. 1 and 30) resulted in the same staining of the glass cloth even though the colors obtained were as deep as those that emerged with the polymeric dyes.

Example 6.

The various dyes listed below were applied to glass cloth pretreated with an aqueous solution of dye aid No. 9 containing 5% acetic acid. Table 8 shows the concentrations of dye used based on the weight of the fabric dyed and the color assessment of the dyed fabric. In practice, the recommended salt was used for each dye.

(A) Sulfur dyes: I) Sulfur brown-yellow WRCF Sulfur-marine leaf 2CF 150% Sulfur-reddish-brown W9R Metrolan sulfur-yellow BG (B) Loose cypress-yellow dyes: Wooncosol-golden-yellow WIGK Metrosal-green IBW Wooncosol-red-violet-WIZR Cos-WroZB ) Reguljara kypfargamnen: Metrovat-jadegront BD Dbl. Pst Ponsol-brown RBT Pst Ponsol-khaki 2G Dbl. Pst Calcosol-golden yellow GKWP Ponsol-black Ba Pst Metrovat-brilliant map R Ponsol-blue BF Dbl. Pst Calcosol leaf 2B Dbl. Pst Ponsol-gratt 2B Pst Ponsol-gold-orange RRT Pst Ponsol-yellow PG Dbl. Pst Table 8.

Percent color Tint depth 34 3 3 34 3 3.4, 3.3, 34 4 32 34 33 32 33 33 3 33 32 3 3 34 Example 8.

A series of powdered oxides, aluminosilicate, titanium dimeth, silica gel, silica gel, alumina and calcium carbonate were treated by placing 5 grams of powder in 100 grams of a treatment solution containing 5 grams of color aid No. 9, 5 grams of glacial acetic acid, 90 grams of water and 0.1 grams of sodium alkyl sulfate.

(When grating the calcium carbonate, the attic acid and water were replaced by 95 grams of a mixture of equal parts water and isopropanol). The powder was stirred in the solution for 30 minutes at room temperature, removed by filtration, applied to a glass plate and dried by heating at 149 ° C for 15-25 minutes.

The treated powders were then dispersed in a dye bath containing 0.5 grams of procion broth dye, 0.1 grams of sodium alkyl sulfate anhydrous and 99.5 grams of water. With stirring, the temperature was slowly raised to 71 ° C and kept there for 30 minutes. The colored powders were taken out. Colored Sulfur yellow-brown Sulfur-blue Sulfur-brown Sulfur-green Kypestergult Kypestergront Kypester-violet Kypester-star Map Kypesteroli-green Kypesterblatt Kypgront Kypbrunt Kypkhaki Kypgult Kypsvatt Kypskart Kypblatt Kypblatt Kypblatt Kypblatt Kypgblatt. The wet filter cake was dried at 110 ° C.

The staining was repeated with powder as a joke treated with the aminoalkyl silica staining aid. According to Table 9, the dye aids ensured that these dyes could be dyed.

Table 9.

Staining of metal oxide substrates with cellulose fiber reactive dye (procion-brittle trout 2B) Substrate material Staining depth of treatment Silica gel (treated) Alumina (treated) Calcium carbonate (treated) 4 Silica (treated) 3 Titanium dioxide (treated) 2 Aluminum treated (2) Aluminum treated ) 2 Silica gel (untreated) 1 Calcium carbonate (untreated) 0 Titanium dioxide (untreated) 0 Silica (untreated) 0 Aluminum silicate (untreated) 0 Example 9.

Samples of asbestos fabric were treated with the dye aids 9 and 17 by chipping from the following solutions so that moisture uptake of 66% was obtained. 5.0% dye aid 5.0% glacial acetic acid 0.1% sodium alkyl sulphate wadding agent 89.9% water After drying for 20 minutes at 149 ° C, the asbestos fabric was dyed with two cellulose fiber reactive dyes (procion-brittle trot 2B and procion-brilliant-green R). The dye bath had the following composition: 3% dye calculated on the weight of the fabric 2% glauber salt 0.5% dioctyl sodium sulfosuccinate Volume ratio between bath and weave: 15: 1.

The wadded asbestos cloths were placed in the bath. The temperature Ades for 30 minutes to 71 ° C and Wills at this temperature for another 30 minutes. The colored samples were then rinsed with cold water, rinsed in water of 60 ° C, rinsed in water containing 0.1% sodium alkyl sulfate water at 60 ° C, rinsed in cold water and dried. Samples of the asbestos fabric as a joke pre-treated with the dye aid were dyed in the same manner. The treated asbestos fabrics showed a color rating of 4-5 with both dyes while the color rating of the untreated fabric was 21 in both cases.

Example 10.

Samples of Dynel fabric, acetate rayon, spun orlon and daeron challis were treated with block solutions consisting of 5% dye aid 9, 5% acetic acid and 90% water. After chipping, the Dynel and acetate fabrics were dried at 121 ° C for 5 minutes. Dacron and orlon were dried for 5 minutes at 149 ° C.

Treated and untreated tissue samples were stained with 3% dye concentrations of the following dyes in the manner indicated above: Sulfur reddish brown W9R Metrovat jade green Bd Ponsol golden orange RRT Pat Metromine sky blue FF Metrolan-rOtt 2GL Cibacron-brown-purple The color assessments showed that the color uptake of the treated fabric was 2 to 5 points higher than that of the untreated fabric.

Example 11.

In the above examples, in all cases, dyeing with soluble or detached dyes containing acidic groups on a substrate which has been pretreated with one of the dyeing aids according to the invention. This experiment shows the application of these color aids when coating with water-insoluble organic pigments on the substrate.

A heat-purified fiberglass swab was chipped by an aqueous solution containing 5% color aid 31 and 5% acetic acid. After staining and curing at 149 ° C for 10 minutes, the treated glass cloth was crushed to absorb 30% liquid through aqueous dispersions containing 3% of the following pigments: Microfix brilliant green G paste Microfix brilliant blue 4G paste Microfix root R paste.

Untreated glass cloth was passed through the same pigment bath as a control. The pigmented samples were dried for 10 minutes at 149 ° C, rinsed in cold water, rinsed in hot water of 60 ° C, washed at 60 ° C with water containing sodium alkyl sulfate, rinsed with cold water and air dried. Through these rinses, the untreated glass cloths lost all color and were as white as if they had not passed through a dye bath at all. The treated fabrics were dyed excellently with very even tones. The stained treated tissues were then washed with water solution at 71 ° C. The brilliant color remained and the wash water lacked pigment. It should be noted that the fabric is excellently colored if rinsing and washing flakes that follow drying of the colored fabrics at 149 ° C are avoided, but it becomes much stiffer (has a somewhat pleasant grip).

In a similar test, heat-purified glass cloth was treated with color aids and pigments simultaneously by blocking through aqueous solutions containing 5% of color aids, 33%, 5% acetic acid and 5% of the above pigments.

After drying for 10 minutes at 149 ° C, the samples were treated as above. All samples were stained excellently and retained their color after washing in soap solutions.

Similar samples with color aids 12, 17 and 32 and with microfix blue pigment produced tissue dyes which retained their color after three dry cleaning with perchlorethylene.

Example 12.

A series of samples are challenged to demonstrate the additional technique of applying dye at the same time as the dye aid on glass cloth. The following dye bath and set were used.

Kyp dye: 3% Metrovat-jade-green BD 5% Color aid no. 31 5% Attic acid 87% Water The heat-purified glass cloth was scraped through the dye solution and dried for 10 minutes at 149 ° C.

Loose wax ester dye: 3% Metrosal-green IBW 5% Color aid no. 31 5% Attic acid 87% Water The glass cloth was clogged and dried at 149 ° C for 10 minutes. The web was then clumped by a 0.1% solution of sodium nitrite and then by a 0.25% solution of sulfuric acid so that the kypester was oxidized. The tissue was then rinsed and dried.

Sulfur dye: 3% Sulfur red-brown VV9R 3% NaiS% Color aid no. 31 89% of a solution of equal parts water and methanol.

The sulfur dye and sodium sulfide were dissolved in boiling water and the solution was cooled to room temperature. The dye aid dissolved in methanol was added in the form of a solution which was chipped on the glass cloth. The tissue was dried for 10 minutes at 149 ° C.

Formallized direct dye: 3% Cuprofix-bordeaux B1 5% Color aid no. 31 46% Methanol 46% Water Sevron »cationic» dye: 3% Sevron blue G% Color aid no. 31 46% Methanol 46% Water Acetate »dispersed» dye: 3% Calcoxyn green 2B (per 229)% Color aid no. 31 46% Methanol 46% Water Acidic dye: 3% Metrolan root 2GL% Color aid no. 31 46% Methanol 46% Water Imperse pigment: 3% Imp erse green 5% Color aid no. 31 cyo Attic acid.

In each of the four dyes from D to H, the glass cloth was clumped through the solution and dried at 149 ° C for 10 minutes. I-L in another series of dyes with direct-acting, sevron-acetate and acid dyes, the following solution without alcohol was used: 3% Dyestuff% Dyestuff No. 31% Attic acid 87% Water Again, this series was stained with the glass cloth and dried for 10 minutes at 149 °. C.

All colored fabrics were washed with soap solution at 71 ° C. Both the cationic sevron-colored fabric and the acetate-dispersed colored fabric lost their color on washing, which confirms previous conclusions that cationic and dispersed dyes are not useful in the method according to the method. The remaining anionic dye is much better than all of them and shows an excellent initial coloration with very good resistance to washing.

These experiments clearly show that soluble dyes can be applied by treatment with a single bath before dyeing.

Example 13

The following Alta dyes were introduced into printing pastes with the following composition: Paste: 5% dye ° / ,, dye auxiliary no. 32 4.5% sodium alginate cy ,, urea 65.5% water Dyes: Procion-brilliant yellow 6G Procion-brilliant trout 2B Procion-brilliant-blue Cibacron brilliant orange G Procion yellow R Microfix brilliant green G paste Cibacron turquoise leaf G Cibaeron seharlakan color 2G 14— 7 479 - Obtained print pastes were applied to the following glass fabrics: Sample A) Untreated - uncoloured fabric; Sample B) Tissue pretreated with 5% dye aid 32; Sample C) Tissue pre-treated and pigmented in a single bath with 1% microfix brilliant-leaf 4G 1% dye aid no. 9 1% acetic acid and Sample D) Tissue pretreated and pigmented in a single bath with 1% microfix-brilliant-leaf 4G 3 ° / „ color aid no. 9 3% acetic acid In all cases, the silk-screen method was used for printing. After printing, the oven was dried for 10 minutes at 149 ° C, washed with soap solutions at 71 ° C and dried for 5 minutes at 121 ° C.

All samples showed good resistance to washing. These samples show that one can either pre-treat the substrates with aminoalkyl silicon paint aids and then print them or also simply by printing them directly on the untreated substrates with printing pastes containing the paint aids.

Example 14.

Synthetic yarns: Dyes with cellulosic fiber-reactive dyes from colloidal dispersions.

A series of dyeings were performed on various synthetic hydrophobic fabrics pretreated with a combination of colloidal silica and dye aid No. 31. The pretreatment is challenged as a block so that 60% of the liquid was taken up from a bath with the following composition:% ay containing a colloidal silica 30%. 5% color aid no. 31% acetic acid The treated fabrics were a Dynel taffeta, a dacron challis and an orlon challis. After chipping, the tissues were dried for 10 minutes at 121 ° C.

The dried fabrics were stained with a breath of 3% of the following dyes shaved on the surface of the yarn: Cibacron-turquoise leaf G Cibacron-brilliant-red B Cibacron-yellow 3G Procion-brilliant-blue R Procion-leaf 3G Cibacron-scarlet-yellow Cibacrone-yellow Cibacjron room temperature using a 30: 1 volume ratio of bath to wrapper. The temperature was raised to 71 ° C for 30 minutes. After an additional 20 minutes at 71 ° C, 1% glauber salt was added. Almost all dye baths were either partially or completely depleted at the end of this dye period, which shows that the dyes have a high affinity for the treated fibers. The samples were then washed with a neutral soap solution.

All samples of the two types of fibers were dyed very deeply and a comparison with previous wash dyes and dyes of this kind shows that the silica increases the amount of dye applied to the fabric.

Example 15.

Samples of a polyethylene fabric were chipped by the following dye mixtures:% pigment% dye auxiliary no. 32 5% acetic acid Filming pigments otherandes: Imperse-Marcyrott (naphthol-rat) Imperse-yellow B (benzidine-yellow) Imperse-green (phthalocyanine-green) Imperse-blatt ( -blatt) After chipping three times with a water uptake of 40%, the samples were dried for 10 minutes at 104 ° C. Highly pronounced even colors were recovered. The samples were then dry cleaned in perchlorethylene for 5 minutes with a Wining rather than a reduction in color strength.

The surfaces that were not treated with the coloring agent showed much similar results.

The same polyethylene freshness pretreated with acidic solution of dyes Auxiliaries Nos. 9 and 17 was dried at 104 ° C for 10 minutes and stained with 5% Procion-briliantrot 2B as above. Both treated samples were deeply stained while untreated control samples were colorless. No color loss could be demonstrated if the treated samples were washed or dried.

Table 10.

Use color Imperse sheet and Color depth assessment FranTorren- MilangjordWashed aid no. 32 4 4 Imperse yellow and aid no. 32 4 4 Imperse green and aid no. 32 4 4 Imperse root and aid no. 32 4 4 Microfix sheet and aid no. 17 4 4 Microfix sheet and auxiliary no. 9 4 3 Microfix primer and - 187 auxiliary no. 9 4 —3 Pro cion root and aid no.

Two. Aluminum plates (5 cm square) were cleaned with sandpaper and rinsed with hot water containing a small amount of sodium alkyl sulfate. After drying, each spot was painted on the lower half on both sides with a solution of the following composition:% color aid No. 9 25% acetic acid 50% isopropanol The plates were heated for 15 minutes at 121 ° C, rinsed in hot water and air dried. Then they were immersed in a dye bath at 66 ° C for 10 minutes. The dye baths contained the following cellulosic fiber reactive dyes with the indicated concentrations:% Cibacron scarlet 2G% Cibracron turquoise leaf G After 10 minutes of dyeing, the plates were taken up, rinsed with hot water. In all cases, the upper part of the plate as a joke had been treated with the dye had not been dyed. The treated lower part was in both cases blue. After drying, a strongly adhered color film remained which could not be removed by further rinsing in hot water.

Example 17. • A piece of white untreated lacer was clogged with an aqueous solution containing 5% color alp agent No. 9 and 5% acetic acid. The lader was heated for 15 minutes at 104 ° C after which part became slightly yellowed and stiff. It was then chipped by a 3% solution in water of some cellulosic fiber reactive dye procion-broth 3-B and a piece of untreated charger was stained in this way. Both pieces were allowed to stand in air for 5 minutes before rinsing in a neutral soap solution, rinsing with water at 20 ° C and drying in air. The treated lader had a deep red color while the untreated showed only a faint flake fling.

Example 18.

Heat-cleaned glass cloth was treated with dye aid No. 17 by blocking samples thereof by one of the following solutions or suspensions% dye aid no. 17 5% acetic acid 90% water% dye aid no. 86% water After drying and curing, the treated glass tissue samples were clumped through aqueous dispersions containing 3% microfix-blue 4G paste and dried. The samples of the glass cloths treated with mixture (a) and (b) samples treated with mixture (b) had the same distinct color. However, the samples treated with mixture (b) were softer (had a better grip) than those treated with mixture (a).

Samples of hada colored tissues were rinsed in cold water, rinsed in hot water at 60 ° C, washed at 60 ° C with water and sodium alkyl sulfate detergent and finally in cold water by rinsing and air dried. Delta sat resulted in a softening of the grips of the fabrics which were pretreated with both mixtures (a) and (b). However, the fabric treated with (b) still had a better grip.

Example 19.

The dye aids Nos. 9 and 17 in Table 1 were applied to samples of heat-cleaned glass cloths by crushing the cloths by a solution having the following composition:% dye aid% silicone liquid (silicone emulsion containing about 35% by weight of dimethylsiloxane) then acetic acid 85% water and acid acid 85% cured for 10 minutes at a temperature of 149 ° C.

Stain baths were then treated with the procion dyes brilliant trout 2B, yellow R and blue 2G according to 1 and the treated fabrics were dyed according to Example 1. After washing and drying it was found that the colored fabrics had the same distinctive color as given in Example 1. The wraps produced according to this example, however, they were softer than those of Example 1.

The fabrics dyed according to this example using the aid # 17 were then chipped by a dispersion containing 10% by weight of an acrylate polymer emulsion and 5% by weight of a silicone emulsion (water emulsion of polysiloxane oil). After curing, it was observed that the application of the silicone acrylate emulsion did not affect the color of the fabrics and slightly improved the grip.

Example 20.

Samples of heat-cleaned fiberglass drapery wrap were clumped with a 20% liquid uptake by water dispersion containing 2% by weight of aurasperse phthaloblatt (phthalocyanine leaf) with varying amounts of color aid No. 17 and varying amounts of either lactic acid or attic acid. weight percent) 1.0 2.0 3.0 5.0 Attic acid 100% (weight percent) 0.1.0 1.2, Dispersion 6 7 8 Color aids (weight percent) 1.0 2.0 3.0 5.0 Lactic acid 85% aqueous solution (% by weight) 0,1,0 1,2 a neutral aqueous 0.5% soap solution at 49 ° C. The colored pieces of fabric were stirred in the soap solution for 5 minutes and then rinsed in cold water and dried. The color removal was demonstrated by examining the specimen and the twine. The following table shows the resistance to washing for each sample by examining the dispersion to be colored.

Dispersion 1 2 3 4 5 6 7 8 Durability 4 4 4 3 3 2 2 1 Durability code: In this example, the numbers 1-4 show the degree of wash resistance. The durability figure 4 shows a significant loss of color in the Iranian coat of arms and a significant staining of the twine. The durability figure 1 shows that no color was lost from the fabric and that the soap solution was not colored. Resistance numbers 2 and 3 are between resistance numbers 1 and 4.

The soapy water sample used is particularly black and represents a very large number of normal washes. All colored pieces of fabric that were tested showed excellent moisture retention compared to fiberglass fabric which has been pigmented according to the hitherto known method. In addition, the pieces of fabric dyed with the dispersion containing lactic acid even showed better color retention than the pieces dyed with dispersions containing acetic acid. Stained pieces of fabric dyed according to this example were also tested for color retention after response cleaning with solvent, especially using dry cleaning. All samples showed excellent color retention compared to fiberglass fabrics dyed so far and those dyed with dispersions containing lactic acid retain the color to a greater extent than those dyed with dispersions containing acetic acid. Together with a corolarium for this phenomenon, less color aids with lactic acid than with acetic acid are required to achieve equivalent results.

Gluconic acid and diglycolic acid also act in the same way as lactic acid. It is clear that lactic acid, glyconic acid and diglycolic acid have a synergistic effect cla the results obtained with the color aid and the acid together are unexpectedly better On those which would have been assumed frail results using only one.

The following materials exhibit similar overall color retention after water and dry cleaning and enhance the effect of the color aid: water-soluble epoxy compounds, such as vinylcyclohexene dioxide, diglycidyl ether of 1,4-butanediol, and polyglycidyl ethers of glycerol, water-soluble aminomolaldehyde ethylene trimethylamethyldimethoformene salts of di- and tribasic acids such as alum, metylolstearamid, oktadekylketendimer, ammonium zirconyl carbonate, melaminformaldehydstearamider as the reaction product of trimetoximetylmelamin and metylolstearamid, copolymers of acrylic resins in the form of emulsions such etylakrylatglycidylmetakrylatsampolymer, etylakrylatitakonsyrametylmetakrylatterpolymer, etylakrylatvinyltrietoxisilansampolymer and ethyl acrylate-acrylamide copolymer, ethyleneimine as is trietyleniminfosfinoxid (CH, CH 2 N β-alkylolphosphonium halides such as tetramethylolphosphonium chloride [C1P (C1-120H) 4] .

These synergistic agents also show excellent results when added to dye baths as described in other examples.

The synergist can be added to the pigment dispersion or dye bath with the dye aid or it can also be applied after dyeing the fabric. In some cases, the synergist will react spontaneously with the color aid if baths are added to the dispersion or color bath at the same time. In such cases, it is appropriate to apply the synergist at a later date.

Claims (48)

Patent claim: A method of staining solid, fibrous and powdery substrate materials with an anionic dye or a pigment dye, characterized in that an aminoalkylsilicon compound having a group = NRSivan in R Or a substituted or unsubstituted alkylene radical is applied to the substrate material. 2. A kit according to claim 1, characterized in that the aminoalkyl silicon compound is applied to the substrate before the anionic dye or pigment dye is applied thereto. 3. A kit according to claim 1, characterized in that the aminoalkyl silicon compound and the anionic dye or pigment primer are applied to the substrate simultaneously. Salt according to claims 1-3, characterized in that the substrate consists of a hydrophobic synthetic organic fibrous material, a hydrophobic synthetic inorganic fibrous material, an inorganic oxide, a metal. 5. sat according to claim 4, can be characterized (Wray, that the substrate is made of glass fiber. 6. According to claim 1-4, there is a claim that the substrate is coated with an anionic substantive dye. 7. A method according to claims 1-4, characterized in that the substrate is dyed with a cellulose fiber reactive dye. 8. A kit according to claims 1-7, characterized in that the aminalkyl silicon compound is applied from a solution, suspension or emulsion thereof. 9. A method according to claims 1-8, characterized in that the aminoalkylsilicon compound is applied to Iran a solution of water in it and an alcohol. 10. A claim according to claim 8, characterized in that the silicon compound (silicon) is present in colloidal form in the solution, suspension or emulsion of the aminoalkyl silicon compound. 11. A method according to claims 1-10, characterized in that the aminoalkyl silicon compound is formed from a monomeric silane, a hydrolyzate of monomeric silanes or a polymeric copolymer or simple mixture of an organofunctional silicon compound containing at least one functional group of the formula R R-Si-X4 – c – b LR "van in R represents a substituted or unsubstituted carbon group having at least three carbon atoms between the nitrogen atom and the silicon atom, R 'and R" represent hydrogen or alkyl, amino-alkyl, cyanoalkyl, hydroxyalkyl- , carboxyalkyl, carboalkoxyalkyl or aryl radicals or a one-yard group —R — Si — X Zr wherein X represents an alkoxy radical or the oxygen atom of a siloxylidine radical Y dr a hydroxy, alkoxy, alkyl or aryl radical, Z dr an alkoxy , alkyl or aryl radical, c dr 1 or 2, b dr 0, 1 or 2 and c plus b dr hogst 3. 12. A method according to claim 11, characterized in that X is an alkoxy radical and Y is an alkyl or aryl radical. 13. A claim according to claim 11, Unsubscribed claim, that X where the acid atom has a siloxylidine radical and Y where an alkoxy or hydroxy radical. 14. According to claim 13, characterized in that Y is an alkyl or aryl radical, c is 1, b Or 1 and the aminoalkyl silicon compound is a polysiloxane of the formula: R 'Y N-11-510 - R "Jn wherein n Or an integer of at least 3. 15. According to claim 11, characterized in that the aminoalkyl silicon compound consists of a copolymer polysiloxane containing siloxane ethers represented by the formula in claim 11 of Y Or an alkyl or aryl and X Or the acid atom of a siloxilidine and at least one other siloxane unit represented by W '—SiO3 – e 2 _ van in W and W' Oro piston radicals and (e) Or an integer from 0 to 2. 16. According to claims 13 and 14, it can be clarified that the aminoalkylsilphene drainage exists as a mixture with at least one other organopolysiloxane having the unit formula: We W'-SiO3e I 2 _I van i W and W 'Oro piston radicals and (e) On an integer frail 0 to 2. 17. Salt according patentanspraket 11, wherein, sodium ddrav that aminoalkylkiselforeningen Dr. deltaaminobutylmetylpolysiloxan, a copolymer CONTAINING approximately equal parts trimetylsiloxidndblockerad dimethylsiloxane and deltaaminobutylmetylsiloxigrupper, a copolymer of gammaaminopropyl triethoxysilane and amyltrietoxisilan, gamma-aminopropylmethyldiethoxysilane, N-betaaminoethyl-gamma-aminopropyltrimethoxysilane, a copolymer innehdllande dimethylsiloxane units and N-beta-aminoethyl-gamma-aminoisobutylmethylsiloxane units or a rahydrolyzate of deltaaminobutylmethyldiethoxysilane. 18. A kit according to claims 1-17, characterized in that the anion dye is an indigo-dye dye, an anthraquinone-dye dye, a loose dye dye substance, a sulfur dye substance, an acid wool dye substance, a formaletallic acidic dye or a dye, development dye, a naphthol dye, a cellulosic fiber reactive dye or a cyanide dye dye. 19. A salt according to claims 1-17, characterized in that the pigment dye is an insoluble pigment dye comprising a finely divided inorganic oxide substrate which has attached thereto an anionic dye by means of an aminoalkyl silicon compound. 20. A method according to claim 8, characterized in that the aminoalkyl silicon compound is applied from an aqueous alkaline solution. 21. According to patent claim 8, Urine Leeknat, in that the aminoalkyl silicon compound is applied from an aqueous acidic solution. 22. According to claim 8, characterized in that the aminoalkyl silicon compound is applied from a neutral aqueous solution, 23. & It according to patent claims 8, 9 and 21, 18— t874 - can be characterized & ray, that the solution contains a monobasic organic acid. 24. Set according to claims 1, 3-7, 11-17 and 19, characterized in that the insoluble pig soil is applied to the substrate simultaneously with the aminoalkyl silicon compound in the form of a printing paste. Salt according to claim 2, characterized in that the substrate to which the aminoalkyl silicon compound has been applied is heated before the process. 26. A kit according to claim 3, characterized in that the substrate to which the aminoalkyl silicon compound and the colorant are applied is simultaneously heated. 27. According to claim 1-12, Untietecknat & ray, that the aminoalkylsilicon compound is mixed with a silicone vat. Salt according to claims 1-27, characterized in that a polymer elastomer and a silicone wadding are applied to the colored substrate. 29. Set according to patent claims 1-17, characterized in that the colored substrate is washed. 30. Set according to claims 1-11, characterized in that the aminoalkylsilicon compound is applied in the presence of lactic acid, gluconic acid or diglycolic acid. A coloring composition containing as coloring aid a monomeric silane, a crude hydrolyzate of a monomeric silane, or a polymer, copolymer or simple mixture of organofunctional silicon compounds containing at least one functional group of the formula rft'Yb van in R is a substituted or unsubstituted three-membered carbon group carbon atoms between the nitrogen atom and the silicon atom, R 'and R "represent hydrogen or alkyl, aminoalkyl, cyanoalkyl, hydroxyalkyl, carboxyalkyl, carboalkoxyalkyl or aryl radicals or a monovalent group: -R-Si-XZ, van in X Or a alkoxy radical or the acid atom of a siloxylidine radical [—O — SiY dr a hydroxy, alkoxy, alkyl or aryl radical, Z Or an alkoxy, alkyl or aryl radical, c Or 1 or 2, b Or 0, 1 or 2 and c plus b Or hogst 3, as dye an anionic dye or pigment dye and an inboard compatible hair medium containing dyeing aid and the dye in intimate mixture. 32. A composition according to claim 31, characterized in that the carrier medium is water. 33. A composition according to claim 32, characterized in that the water contains an acid. 34. A composition according to claim 32, characterized in that the water contains an alkali. 35. A composition according to claim 31, characterized in that the bar medium Or is an alcohol. 36. A composition according to claim 31, characterized in that the carrier medium contains a solution of alcohol and water. Composition according to claims 31, 32, 33, 35 and 36, characterized in that the carrier medium contains an aqueous solution of a monobasic acid. 38. A composition according to claim 31, characterized in that the bar medium contains a colloidal suspension of the coloring aid and the coloring agent. 39. A composition according to claim 31, characterized in that the bar medium contains an aqueous dispersion of the coloring agent and the colorant. 40. A composition according to claim 31, characterized in that the bar medium comprises an emulsion-in-water of the coloring aid and the coloring agent. Composition according to Claim 31, characterized in that X Or is an alkoxy radical and Y Or is an alkyl or aryl radical. 42. A composition according to claim 31, characterized in that X Or is the acid atom of a siloxylidine radical and Y Or is an alkoxy or hydroxy radical. A composition according to claim 42, characterized in that Y Or is an alkyl or aryl radical, c Or 1, b Or 1 and the aminoalkyl silicon compound are a polysiloxane of the formula: R 'YN-R — SiO R "n van in Or an integer with a value of at least 3. 44. A composition according to claim 31, characterized in that the aminoalkyl silicon compound. Or a copolymer of polysiloxane containing siloxane units represented by the formula in claim 31 van in Y Or the alkyl or aryl and X Or the acid atom of a siloxilidine radical and at least one other siloxane unit represented by the formula: We - SiO3_e 2 van in W and W 'Oro carbon radicals and ( e) Or an integer from 0 to 2. 45. A composition according to claims 42 and 43, characterized in that the aminoalkylsilicon compound is present as a mixture of drips with at least one other organopolysiloxane having the unit formula: We 2 N-R-Si-X 4_ c_h ii drawn piston radicals and (e) is an integer from 0 to 2. 46. The composition according patentanspraket 31, characterized in that farghjalpmedlet comprises delta aminobutylmetylpolysiloxan, a copolymer silicone CONTAINING approximately equal parts trimetylsiloxidndblockerad dimethylsiloxane and deltaaminobutylmetylsiloxigrupper, a copolymer of gamma-aminopropyltriethoxysilane and amyltrietoxisilan, a homopolymer ay gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane or hydrolyzate and delta-aminobontylmethyl dithoxysilane. 47. A composition according to claims 31-46, characterized in that it additionally contains a thickener. 48. A coloring composition according to claim 31, characterized in that the on-board compatible bar medium contains lactic acid, glyconic acid and diglycolic acid. Request publications: Patents frcin United Kingdom 654 450, 786 452, 789 950.