CH343360A - Stable aqueous emulsion usable for the preparation of compositions intended for the printing of textiles and process for the preparation of this emulsion - Google Patents

Description

Stable aqueous emulsion usable for the preparation of compositions intended for the printing of textiles and process for the preparation of this emulsion The object of the present invention is a stable aqueous emulsion usable for the preparation of compositions intended for the printing of textiles, - comprising a water-soluble cellulose ether and a water-immiscible hydrocarbon or mixture of hydrocarbons; the emulsion is of the oil-in-water type and is suitable as a diluent for pigmented color concentrates in the form of an oil-in-water emulsion and as a dye carrier in the vat in the printing process. The invention also relates to a process for preparing this emulsion.

Emulsions according to the invention, which will also be referred to hereinafter as filler pastes, comprise 1) water; 2) a water-soluble cellulose ether having in 2% aqueous solution, at 200°C, a viscosity of at least 1200 cps in the proportion of (0.5 to 1.7 parts by weight per 100 parts of water), 3) a hydrocarbon or a mixture of hydrocarbons immiscible with water in the proportion of (62.5 to 108 parts by weight, per 100 parts of water), Other optional ingredients are 4) a concentrated aqueous emulsion of a resin soluble in organic solvents, as a reinforcing agent, particularly useful in pastes intended for pigment printing; 5) surfactants in low proportion; 6) sulfoxylate, if pressure relief is desired using vat dye pigments or if a reducing agent is required in the paste; 7) an antifoaming agent.

These emulsions are preferably prepared by dissolving the cellulose ether in water and emulsifying the hydrocarbon(s) used in this solution.

<I>Nature and</I> proportions <I>of</I> ingredients Cellulose <I>ethers As cellulose ethers, methylcellulose or carboxymethylcellulose are usually used. The preferred grade of methylcellulose is that which has a viscosity of 4000 cps. The carboxymethylcellulose is used in the form of a water-soluble salt, especially in the form of the sodium salt, the ammonium salt or the triethanolamine salt. Preference is given to the sodium salt and the highest viscosity obtainable.

When the emulsion is intended for the preparation of RTI ID="0001.0266" WI="20" HE="4" LX="1167" LY="2341"> compositions for printing with pigments, it is methyl cellulose which is preferred because it gives brighter color and greater yardage. In the process of printing with vat dyes, most of the vat dye pigments give better color yield with sodium carboxymethylcellulose, and a small number of them better yield with sodium carboxyl cellulose. methylcellulose. In charge printing comprising the presence of sodium formaldehyde sulfoxylate or its corresponding zinc salt in the pulp, it is advantageous to use sodium carboxymethylcellulose rather than methylcellulose, the sodium salts of carboxymethylcellulose having apparently a greater tolerance to 6electrolytes and not causing the flocculation of the Pigments by addition of 61ectrolytes. Hydrocarbons As hydrocarbons, preference is given to aliphatic petroleum fractions having boiling temperatures between 99 and 1660 C (ASTM D-1078 or ASTM D-86) and flash points between 2 and 460 C (ASTM D-56-36), Kauri butanol numbers between 33 and 46 (ASTM D-1133-50T-5) and specific weights between 0.729 and 0.815 at 15.6o C. These limits include: most gasoline fractions for paints and varnishes (VM & P Naphtha) and mineral spirits up to high flash points. In order to avoid the risk of fire, it is preferable not to use hydrocarbons with a flash point lower than 380 C.

Also very suitable are aromatic hydrocarbons with boiling points between 121 and 1600 C, flash points between 27 and 570 C, Kauri butanol indices between 75 and 98.5 and specific weights at 15.6o C between 0.828 and 0.869. Among them are xylene, solvent naphtha with a high flash point (Hi-Flash-Naphtha) and aromatic hydrocarbons obtained from petroleum and which generally contain a certain amount of aliphatic compounds. Toluene is also very suitable.

Generally speaking, hydrocarbons which evaporate before the water in the emulsion easily give clear and vivid impressions while slow evaporating hydrocarbons which remain in the filler paste after most of the water has evaporated cause temporary haze as a result of the deposition of cellulose ether on the surface of the print, which haze moreover disappears if the print is subjected to steaming or soaping. If the prints are not exposed to the action of steam or water and if the printed fabric is sold direct, it may be necessary to use faster evaporating hydrocarbons to avoid clouding. Gasoline for paints and varnishes and xylene are examples of such hydrocarbons which escape before the water during coevaporation. In contrast, mineral spirits fractions and high flash point naphthas allow water to evaporate first during coevaporation.

EnRTI ID="0002.0271" WI="4" HE="4" LX="398" LY="2496"> as far as the vividness of the colors is concerned, it is better with aliphatic hydrocarbons than with aromatic hydrocarbons.

In general, it is preferred to have a hydrocarbon content of at least 80 parts by weight per 100 parts water because it achieves lower color intensity and less gloss by using a lower hydrocarbon content. Concentrated Emulsions <I>of</I> Resin in Water <I>as</I> Reinforcing Agents The addition of concentrated resin emulsions to the emulsions according to the invention is particularly advantageous. The hydrocarbons and water evaporate and the methylcellulose or carboxymethylcellulose remains on the fibers. Both are water soluble and Premiere is more water soluble. It is necessary to insolubilize them to preserve the full intensity of the coloration obtained. The binding part of the emulsion of the pigmented color concentrate can produce this insolubilization for a certain time by employing relatively high proportions of color concentrate, but this effect is not lasting. It is therefore advantageous to incorporate resinous emulsions in the emulsions according to the invention when they are used as filler pastes for printing.

For this purpose, one can use from 0.25 to 3.5% by weight of resinous emulsion which has the ability to insolubilize the cellulose ether, for 99.75 - 96.5% of filler paste. . Such resinous emulsions for concentrates are described in Swiss Patent No. 328397 and in the present patent. Surfactants In the present filler pastes, the cellulose ethers act both as an emulsifying agent and as a protective colloid or stabilizer. Very often, however, and particularly when a low level of hydrocarbon is desired or when it is necessary to further increase the intensity of the color or provide better penetration, the addition of surfactants is useful.

Preferably 0.16 - 2.1 parts surfactant is used per 100 parts water and in special cases up to 4.2 parts. Sodium lauryl sulphate is an example of such an agent and tends to improve the washability of prints in the case of filled printing pastes containing methylcellulose, which is contrary to what was expected. .

Sulf oxylates It is possible to incorporate formaldehyde sulfoxylates into the filler pastes according to the invention so as to obtain landfill printing pastes. Sodium carboxymethylcellulose is a satisfactory ingredient of these pastes. Antifoaming Agents Methylcellulose produces abundant foam, as does carboxymethylcellulose. It is advantageous to use antifoaming agents in proportions comprised between 0.01 and 0.21%, in some cases up to 2.1%, based on the water content. Emulsions without resinous emulsions acting <I>as</I> reinforcing Example <I>1</I> <I>High viscosity emulsion</I> 0n dissolves 0.75 parts of high viscosity methylcellulose (4000cps) at 20° C. in a 2% aqueous solution in 49.25 parts of water and incorporates in portions and with stirring 50 parts of mineral spirits having a specific gravity of 0.791, a flash point of 380° C. and a Kauri butanol value of 44-46, designated under the trade name of Amsco Mineral Spirits N 46 . Ort thus obtains a paste of very viscous Charge.

Emulsion composition based on water content: 101.5% hydrocarbon, 1.5% cellulose ether.

Example <I>2</I> Emulsions <I>of</I> medium viscosity 0n procedure as in example 1, but with the following modification: instead of methylcellulose at 4000 eps an uses methylcellulose at 1500 cps . The emulsion thus obtained is of a more fluid consistency.

The color intensity obtained by means of color concentrates containing a resinous emulsion of the oil-in-water type and a hydrocarbon emulsion according to this example is only one shade lower than the intensity obtained by means of the product described in example 1.

It is advantageous to employ these medium viscosity emulsions in cases where greater penetrating power or lower viscosity is required, such as in cases of surface etching or stencil printing.

Composition of the emulsion: identical to that of example 1.

Example <I>3</I> <I>Emulsion</I> contains a solution of a surfactant <I>f</I> a) Ort mixes 90 parts of the emulsion described in Example 1 with 10 parts of a 10% aqueous solution of sodium lauryl sulphate brand name product (Duponol ME). Normal dilution of the emulsion with water will decrease the intensity of the Color. This drawback is avoided by incorporating a surfactant which increases the viscosity of methylcellulose solutions when added in small amounts. In this example and despite the fact that water is added at the same time as the Duponol ME, the viscosity of the aqueous phase is increased, because of the action exerted by the Duponol ME in the presence of methylcellulose on the viscosity. The paste obtained is denser with the addition of a solution of Duponol ME than without this addition. This viscosity-increasing action decreases the tendency of the methylcellulose to redissolve and results in prints having greater washability.

Emulsion composition relative to RTI ID="0003.0273" WI="10" HE="4" LX="1806" LY="264"> water content: 84.4% hydrocarbon, 1.27 .% cellulose ether, 1.88% Duponol ME.

b) If a 5% sodium lauryl sulfate solution is used instead of the 10% solution, a somewhat lower viscosity product is obtained.

Emulsion composition based on water content: 83.6% hydrocarbon, 1.25% cellulose ether, 0.93% Duponol ME.

Example <I>4</I> <I>Emulsion</I> having an <I>medium</I> hydrocarbon content Ort dissolves 0.784 parts of methylcellulose at 4000 cps in 51.456 parts of water. Ort adds to this solution slowly, in portions and with stirring, 47.76 parts of mineral spirits. Ort uses a high-speed turbomixer rotating at approximately 3600 rpm, the turbine of which rotates in a cylindrical housing with a very small clearance. The mixer is equipped with an adjustable baffle and can be immersed in the vessel where the emulsion is made.

Emulsion composition based on water content: 92.8% hydrocarbon, 1.5% cellulose ether.

Methylcellulose can also be replaced by high viscosity sodium carboxymethylcellulose which, in 1% aqueous solution, has a viscosity of about 2000 cps (determined by the falling ball method according to Hercules) and which is abbreviated as CMC H.V. .

Example <I>5</I> <I>Emulsion</I> having a <I>low</I> methylcellulose content Ort dissolves 0.375 parts of methylcellulose at 4000 cps in 49.625 parts of water, yielding an aqueous phase containing 0.75% methylcellulose. 50 parts of the mineral spirit mentioned in Example 1 are incorporated into this aqueous phase, with stirring and in portions, which gives a paste of viscous and fluid filler.

Emulsion composition based on water content: 100.80% hydrocarbon, 0.76% cellulose ether.

Example <I>6</I> Emulsion with added <I>de</I> water-soluble melamine-formaldehyde resin Aerotex brand M-3 (aqueous solution of the trimethyl Aher of trimethylolm61amine having a non-volatile content of 80%). Ort obtains a Filler paste which gives prints with excellent washfastness, if hardening is done carefully. By addition of amino aldehyde resin, the cellulose ether becomes more quickly insoluble during heat curing. To accelerate hardening, catalysts such as diammonium hydrogen phosphate, ammonium sulphate or benzoic acid can be added to the emulsion.

Emulsion composition based on water content: 83.3% hydrocarbon, 1.25% cellulose ether, 0.93% Duponol ME, 1.5% Aerotex M -3 sec.

b) If 97 parts of the filler paste described in example 3b are mixed with 3 parts of the resinous solution of Aerotex M-3, a similar filler paste is obtained which nevertheless comprises a higher content of methylamine resin.

Emulsion composition based on water content: 82.7% hydrocarbon, 1.24. 0/0 cellulose ether, 0.92% Duponol ME, 4.55% Aerotex M-3 sec.

<I>Emulsions</I> containing <I>melamine-formaldehyde</I> resins, <I>and</I> usable <I>as</I> reinforcing agents - cement <I>of</I> the present filler pastes, can be prepared as follows A) 37.93 Parts of Polyester resin E (product of the esterification of a fatty acid of 1 dehydrated castor oil with an alcohol resulting from the condensation of bis-phenol with epichlorohydrin) described in example 2 of Swiss patent NO 328397, in solution in xylol and at 50% non-toxic materials. volatiles, 4.22 parts of a butylated m61amine-formaldehyde resin in a 50% non-volatile solution and, as solvents, 20% xylol and 30% butyl alcohol, 0.31 part of a drying agent in the form of a mixture of naphthenates, 12.2 parts of a 10% aqueous solution of sodium lauryl sulphate, 20.65 parts of a 20% aqueous solution of casein containing anticryptogamics and ammonia, 5 .5 parts of an ammonium hydroxide solution comprising 1 part concentrated ammonium hydroxide and 1 part water, 10.54 parts of a 20% aqueous solution of methyl cellulose having a viscosity of 15 cps ( at 200° C., in 2% aqueous solution), 3.58 parts of a 30 volume % hydrogen peroxide solution and 5.07 parts of water are emulsified in the following manner to resin solutions, an add two-thirds of the sodium lauryl sulfate solution, mix the remaining one-third with the water and casein solution in a separate container, and add this mixture slowly and in portions to the mixture containing the residues. nes. Then add the solution of ammonium hydroxide and, finally, the solution of oxygenated water in portions and with slow stirring, each time waiting for the disappearance of the foam before introducing a new portion, which requires about 2 to 12 hours. Finally, add the methylcellulose solution and homogenize the emulsion. You can also add the methylcellulose before the hydrogen peroxide solution.

B) The Polyester E resin can be replaced by a minor quantity of linseed oil modified with about 5% maleic anhydride which, in addition to condensation, has undergone esterification with pentaerythrite. Such an oil is commercially available under the trade name Esskol. The latter is also used in solution in xylol and with a non-volatile matter content of 50%.

The E-polyester resin mentioned can also be replaced by other resins mentioned above, for example, alkyd resins modified with styrene, oils modified with styrene, etc. From meine year can replace the resin m & - mine by other aminoaldehyde resins, such as urea-formaldehyde resins, urea-formaldehyde resins substituted, more particularly alkylated, or melamine-formaldehyde resins.

Contaminant emulsions, <I>as</I> agent <I>for</I> strengthening a resinous emulsion Example <I>7</I> <I>Emulsion</I> reinforced a) 0n mixture 5.9 Parts of the resinous emulsion described under A, 47.0 Parts of a 3% aqueous solution of methylcellulose having a viscosity of 4000 cps and 47.05 Parts of water. 0n homogenize. 100 parts of the same mineral essence as in Example 1 are added to this emulsion, with stirring using a suitable mixer and in portions.

Emulsion composition based on water content: 106.3% hydrocarbon, 1.6% cellulose ether, 1.34% resin.

You can replace methyleellulose with CMC H.V.

b) If mineral spirits are replaced by xylol, an emulsion of somewhat lower viscosity is obtained.

The methylcellulose can be replaced by CMC H.V. and, instead of the resin emulsion described under A, an equal amount of the resin emulsion described under B may be used.

Example <I>8</I> Emztlsiou reinforced <I>and</I> diluted with <I>de</I> Water 0n dilutes 300 Parts of the Filler paste described in Example 7b using 100 Parts of water. A similar dilute emulsion can be prepared from the emulsion described in Example 7a. These diluted emulsions in combination with the RTI ID="0004.0549" WI="12" HE="3" LX="1842" LY="2251"> colored concentrates containing resin emulsions of the oil type in water gives lower color intensity and less shine than the emulsions described in example 7, but they are still suitable for many uses, for example for stencil printing where more penetrating power is required. .

Composition of the emulsion based on its water content: 62.85% hydrocarbon, 0.9% cellulose ether, 0.78% resin. The methylcellulose can be replaced by CMC H.V.

Example <I>9</I> Boosted <I>Emulsion</I> a) Ort mixes 23.65 parts of a 3.% aqueous solution of methylcellulose prepared from water and 2.88 parts of the concentrated mineral emulsion described under A and an incorporates into this mixture, in portions and with stirring in a suitable mixer, 47.710 parts of the mineral spirits mentioned in 1 Example 1. The emulsion obtained in this way has a viscosity similar to that of the emulsion described in Example 7b.

Composition of the emulsion based on its water content: 96.9% hydrocarbon, 1.6% cellulose ether, 1.28% resin.

Methylcellulose can be replaced by CMC H.V.

b) Instead of the resinous emulsion according to A, an identical quantity of the resinous emulsion according to B is used. The emulsion thus obtained has similar properties and the same composition as that which is described in 9a.

Example <I>10</I> <I>Emulsion with low content <I>in</I> methylcellulose Ort Bissout 0.353 parts of m & hylcellulose at 4000 cps in 46.777 parts of water to form a solution to 0.75% methylcellulose and by mixing this solution with 2.87 parts of the concentrated oil-in-water resinous emulsion described under A. Ort adds to the product thus obtained, under good stirring and in portions, 50 parts of the mineral spirit mentioned in Example 1. The filler paste obtained is similar to that of Example 7a, but the aqueous phase and consequently the entire emulsion, has a lower viscosity, in methylcellulose content reduced by 50%. The product is viscous and fluid, the printing qualities are good.

Composition of the emulsion based on its water content: 105.0% hydrocarbon, 0.85% cellulose ether, 1.27% resin.

Example <I>11</I> <I>Emulsion with average content <I>en</I> methylcellulose 0n Bissout 0.53 Part of methylcellulose at 4000 cps in 46.6 Parts of water and year add 2.87 parts of the emulsion described under A. The mixture is well homogenized. Pulse and add, in portions and with good stirring, 50 parts of mineral spirits. The consistency of the paste thus obtained is thicker than that of the filler paste of example 10, less thick than that of example 7a. The product is well suited for printing.

Composition of the emulsion with respect to its water content: 105.6% hydrocarbon, 1.23% cellulose ether, 1.27% resin. Example <I>12</I> <I>Emulsion</I> with low RTI ID="0005.0273" WI="10" HE="4" LX="1513" LY="241"> content <I >in</I> resinous emulsion <I>ä</I> as strengthening agent: 0n Bissout 0.707 part of methylcellulose at 4000 cps in 47.853 parts of water, mixing the solution obtained with 1.44 parts of the emulsion described under A. Into this mixture, with good stirring, 50 parts of the mineral spirits mentioned in Example 1 are incorporated. example from 23.563 parts of a 3.% solution of high viscosity methyl cellulose, to which 25 parts of water are added. The product obtained is in the form of a viscous paste. Pigmented prints produced using this Emulsion have somewhat inferior rubbing stability and washability properties to prints produced from thinner emulsions high in Resin Emulsion.

Composition of the emulsion with respect to its water content: 103.75% hydrocarbon, 1.52% cellulose ether, 0.63% resin.

Example <I>13</I> <I>Emulsion with low</I> content <I>of</I> methylcellulose <I>and</I> resin emulsion reinforcing agent A mixture is prepared with 11.782 parts of a 3% aqueous solution of high viscosity methylcellulose (4000 cps) and 36.781 parts of water. This mixture contains 0.353 parts methyl cellulose and 48.21 parts water. Ort adds to it 1437 parts of the resinous emulsion & written under A and an homogenized. 0n incorporates into this mixture, in portions and with good agitation, 50 parts of mineral spirits. The emulsion thus obtained has a certain fluidity and is particularly suitable for pasta. low viscosity print.

Composition of the emulsion with respect to its water content: 103.0% hydrocarbon, 0.78% cellulose ether, 0.63% resin.

Example <I>14</I> <I>Emulsion</I> containing <I>du </I> VM <I> & P Naphtha </I> <I>as</I> 0n hydrocarbon added to 54 .55 parts of the aqueous phase of Example 7a which contains the resinous emulsion described under A, 45.45 Parts of VM & P Naphtha having a flash point of 50° C. and a specific gravity of 0.731. The product obtained contains, relative to its water content, 89.75% hydrocarbon, 1.48% cellulose ether, 1.3% resin. It has a viscosity similar to that of the emulsion of Example 9a and is in the form of a fluid and mobile paste which is particularly suitable for stencil printing with color concentrates containing resinous emulsions of the type oil in water and makes soaping or spraying of prints unnecessary. As VM & P. Naphtha evaporates from the emulsion faster than water, high color values and high gloss are immediately obtained.

<I>Bulking pastes containing surfactants</I> <I>Example 15</I> <I>E</I> emulsion <I>containing </I> Duponol <I>ME </I> 90 parts of different emulsions are mixed with each time 10 parts of an aqueous solution of Duponol ME. The type of emulsion used, the solution content of Duponol ME and the composition of the diluent emulsions thus obtained are described below.

<I>Example 16</I> Emulsion containing <I>emulsifying agents</I> To 100 parts of the emulsion described in Example 7a, 1 part of one of the following surfactants in the form of brand products a) Ethofat 142-20: ester of a monofatty acid with, as acid, technical oleic acid (Red Oil) and, per molecule of fatty acid, 10 molecules of ethylene oxide; specific gravity 1.028, non-ionic.

b) Tween 85: polyoxyethylene sorbitan trioleate.

c) Emulphor AG: condensation product of ethylene oxide and fatty acids (polyglycolic ester of a long chain fatty acid of the oleic acid type); non-ionic.

d) Tergitol 7: branched chain sodium heptadecylsulfate; non-ionic.

e) Aerosol OT: dioctyl ester of sodium sulfosuccinate; anionic type.

f) Sterox SK: polyoxyethylene thioether; non-ionic.

g) Avcolube 100: mixture of 50% sorbitan monopalmitate and 50 d/o polyoxyethylene sorbitan monopalmitate; non-ionic.

h) Atlas G-2859: polyoxyethylene sorbit 4,5-oleate; non-ionic. (g) Victawet 12: phosphoric ester in which one of the hydrogen atoms of phosphoric acid has been replaced by a medium-chain alkyl group and the other two hydrogen atoms by water-soluble alcohol residues medium chain (for example a residue of polyethylene glycol); non-ionic.

K) Victamul 89: organic ester of phosphoric acid; non-ionic.

By decreasing viscosity of filler pastes containing these emulsifiers, we have: Victawet 12, Tergitol 7, Atlas G-2859, Emulphor AG, Avcolube 100, Victamul 89, Ethofat 142-20, Tween 85, Aerosol OT, Sterox SK. The best results are obtained with Emulphor AG and Atlas G-2859, if the reduction of haze due to a surface precipitate on pigmented prints is desired. By means of Victawet 12, vivid colors are obtained and Emulphor AG most effectively reduces the tendency to foam formation.

Emulsions containing <I>resinous emulsions</I> <I>with cationic reinforcing agents</I> <I>Example 17</I> A cationic emulsion can be prepared according to the process described in Example 7b, by replacing the casein acting as a protective colloid with methylcellulose at 400 cps and the anionic emulsifying agent with an emulsifying agent chosen from the following examples lauryl-pyridinium chloride, cetyl-dimethyl-benzyl-ammonium chloride (commercial product brand Triton K-60) or methyl-dodecyl-benzyl-trimethyl-ammonium chloride (commercial product brand Hyamine 2389).

The cationic emulsions thus obtained present some advantages over anionic emulsions in many fields of application.

Claims (6)

1. Stable aqueous emulsion of the oil-in-water type usable for the preparation of compositions intended for the printing of textiles, and containing a water-soluble cellulose ether and a hydrocarbon or mixture of hydrocarbons immiscible with water, characterized by a hydrocarbon content of 62.5 to 108 parts by weight and a cellulose ether content of 0.5 to 1.7 parts by weight, per 100 parts of water, cellulose ether in aqueous solution at 2 fl/o having at 20° C. a viscosity of at least 1200 cps. II. Process for preparing the emulsion according to Claim I, characterized in that the cellulose ether is dissolved in water and the hydrocarbon or hydrocarbons are emulsified in this solution. SUB-CLAIMS 1. Emulsion according to claim I, characterized by a content of at least 80 parts by weight of hydrocarbons per 100 parts of water. 2. Emulsion according to claim I, containing as hydrocarbons, an aliphatic fraction of petroleum having a flash point between 5 and 650 and a Kauri butanol index between 33 and 46. 3. Emulsion according to claim I, containing as hydrocarbon fraction, one or more aromatic hydrocarbons. 4. Emulsion according to claim 1, wherein the cellulose ether is methylcellulose. 5. An emulsion according to claim 1, wherein the cellulose ether is a water-soluble salt of carboxymethyl cellulose. 6. Emulsion according to claim I, further characterized by the presence of resins capable of insolu biliser cellulose ether.