US2937155A - Composition containing alkyl silane triol and aminoplast resin and article coated therewith - Google Patents

Description

2,937,155 United States Patent ice May 2,937,155 By a durable or permanent nature, with respect to COMPOSITION CONTAINING ALKYL SILANE TRI- OL AND AMINOPLAST RESIN AND ARTICLE COATED THEREWITH John W. Eastes, Ridley Park, Pm, and Richard D. Var- 9 Claims. (Cl. 260-294) This invention relates to a composition comprising water-insoluble hydrocarbon silane triols and aminoplast resins, and further to the treatment of fibrous materials and to the materials so treated.

Various so-called silicone derivatives have been used in the past to impregnate textile materials for purposes of imparting water repellent characteristics thereto. Thus, water-soluble salts of substituted silane triols have been applied to textile materials for such purposes, but these require prolonged drying in air, and thus, for the most part, are commercially not feasible in that few, if any, textile finishing plants operate at such low production rates, or have sufficient storage areas available for long air drying operations. When a fabric so treated is dried rapidly by heating on conventional equipment, such as tenter frames, followed by a usual process wash, the finished fabric loses its water repellency.

Silicone derivatives, such as methyl hydrogen siloxane,

have been employed widely in the textile finishing industry for purposes of adding water repellency to textile materials, either alone or in combination with other finish.-

ing materials.

The emulsion of methyl hydrogen siloxane evolves hydrogen and, as a result, the hazards of fire or explosion tend to restrict its use.

Still further, many of the new water repellent finishes employing silicone materials impart to the treated fabric a thin hand and other characteristics which, in certain instances, are undesirable.

It is an object of the present invention to provide improved compositions for imparting water repellent characteristics 'to textile materials.

Another object is to provide a process for imparting a water repellent finish to textile materials.

It is a still further object of this invention to provide a water repellent composition from which hydrogen is not evolved, and thus the hazard resulting from the evolution of hydrogen in more conventional siliconetype water repellent compositions is eliminated.

It is still a further object to provide a water repellent composition which may be applied to textile materials and which may be dried and cured in reasonable periods of time, i.e. times closely related to the drying and ouring times employed in usual resin finishing operations.

It is still another object of the present invention to provide a textile treating composition which, when applied to textile materials, will provide, in addition to durable water repellency, a full hand to fabric so treated, and excellent draping characteristics, as well as other valuable attributes.

These and other objects and advantages of the. present invention will become more fully apparent upon cona water repellent finish, it is meant one which is durable to' both prolonged laundering and repeated dry cleaning operations, depending upon the nature of the textile material.

The invention accordingly comprises a composition containing a water-insoluble hydrocarbon alkyl silane triol in which the hydrocarbon alkyl group contains at least 10 carbon atoms, and up to as many as 20, and preferably contains from between 12 and 18 carbon atoms. Used in conjunction with said long-chain alkyl silane triol is a substantially monomeric thermosetting aminoplast material that preferably has been alcohol reacted, which may be either water soluble or water insoluble, which characteristic may be controlled by the size of the alkoxy substituent(s) thereon. Thereafter, the treated material is dried and the thermosetting resin cured to a substantially water-insoluble state, employing temperatures in excess of F.

The alkyl silane triols or hydrolyzed alkyl trichloro silanes of the present invention may be prepared by hydrolyzing an alkyl trichloro silane, in which the alkyl group contains from between 10 and 20, and preferably from between 12 and 18 carbon atoms, in accordance with the general procedure described in US. Patent No. 2,507,200.

Illustratively, these long-chain alkyl trichloro silanes can be hydrolyzed to solid silane triol products in water in a variety of ways. Thus, the hydrolysis may be carried out by first dissolving sodium hydroxide in water, cooling by adding ice, and then gradually adding the alkyl chloro silane with vigorous agitation. The resulting prodnot is then filtered off, washed with water, and filtered with suction. The filter cake may weigh several times the original alkyl chloro silane, due to the water held by the hydrolyzed product.

A typical hydrolyzed material may be used without drying by forming an aqueous dispersion, using either an anionic or a nonionic surface active agent for emulsification purposes. Or, the hydrolyzed product may be dried at room temperature or in vacuo, in which case a solid, wax-like product results. This solid is soluble in aromatic hydrocarbons such as benzene, toluene, xylene or their chloro substituted derivatives and the like, and are believed to have low order molecular weights within the range or about 3300 to about 3900, as measured by the depression of the freezing point of the benzene solutions.

The aminoplast resin of this invention must be substantially monomeric, and preferably alcohol reacted with lower alkyl alcohols containing from 1 to 4 carbon atoms.

, Examples of suitable aminoplast resins, including their alcohol reaction products, are melamine-formaldehyde condensates, guana-mine-formaldehyde condensates, ureaformaldehyde condensates, including cyclic ureas, such as, for example, ethylene urea, 1,2- and 1,3-propylene urea, and the like are given. In addition, the alcohol reaction products of succinamide-formaldehyde condensates, adipamide, alkyl thio-bis propionamides, as well as other well-known thermosetting aminoplast materials, are intended to be included.

These thermosetting materials may be used either alone or in combination with one another.

Of the above exemplary aminoplast materials, the alkylated melamine-formaldehyde condensates and, in particular, alkylated polymethylol melamine condensates, are greatly preferred. These materials may contain from 1 to 6 moles of combined formaldehyde and from 1 to 6 moles of combined alcohol. The number of carbon atoms in the alkyl groups afiect the solubility characteristics of the alkylated methylol melamine. Thus, for example, the methyl, ethyl, propyl methylol melamines, when substantially monomeric, are substantially water soluble, while the butylated and higher alkyl materials tend to be water insoluble or somewhat hydrophobic.

Depending on whether water, a hydrocarbon solvent, or a mixture of the two is employed as the liquid medium of the present composition, the basic nature of the composition is determined. If the medium is water, and the aminoplast is water soluble, the composition may be generally classified as an aqueous dispersion. If a hydrocarbon solvent such as benzene is employed as the sole liquid medium, the composition will be a solution, in that both of the eseential components are soluble therein. If

a hydrocarbon solvent and water in substantial amountboth constitute the liquid medium, both the essential components may then be principally in the oil phase or internal phase of the composition or emulsion. This would be true when both the silane triol and aminoplast were water insoluble. While such a composition is somewhat more difiicult to employ, from a point of view of a practical finishing operation, it has been found that the combina tion of the water-insoluble alkylated methylol melamine resin with the longchain alkyl silane triols renders a fibrous material so treated more durably water repellent than the other proposed combinations.

The mixture of the silane triol and the aminoplast resin is employed in conjunction with a catalyst, which functions to assist in the polymerization of the aminoplast during a curing heat treatment.

Suitable catalysts within the meaning of the present invention include ammonium salts, such as ammonium chloride and ammonium sulfate, amine salts, such as triethanolamine hydrochloride and dilute acids, such as acetic, tartaric, lactic, and the like, and organic or inorganic salts which form acids and acid salts when heated at elevated temperatures as, for example, magnesium chloride, zinc nitrate, and the like.

These curing catalysts may be employed in amounts of from between about 1 to 60% and preferably from about 2 to 25%, based on the weight of the curable resin solids of the treating composition employed, which in this case is the amount of aminoplast resin employed in the composition.

In a preferred embodiment of the present invention, a compatible surface active agent is included in the composition, which assists and functions in a composition, in which the liquid medium is in part aqueous, to maintain a stable dispersion, particularly with respect to the silane triol content, which would be dispersed in the form of finely divided solid particles. In addition, surface active agents enable the composition of the silane triol and the aminoplast resin to more readily wet the textile material to which it is applied.

These surface active agents must be non-ionic or anionic in character. Examples of suitable non-ionic surface active agents include the condensate of stearyl amine with moles of ethylene oxide, which product is known commercially as Ethomeen-18-20; the condensate of hydrogenated tallow amide with moles of ethylene oxide, commercially known as Ethomide HT-25; the condensate of coco fatty acids with 15 moles of ethylene oxide, commercially known as Ethofat C-25; polyethylene glycol monolaurates, and many others. Examples of suitable anionic types of surface active agents which may be used in the present invention are ispropyl naphthalene sodium sulfonate, commercially available as Aerosol OS; the dihexyl ester of sodium sulfosuccinic acid, commercially available as Aerosol MA; various sulfated fatty acid esters, and the like.

Any of the above illustrative surface active agents and equivalent functioning surface active agents may be employed singly or in combination with one another. When employed in the composition of the present invention, they may be used in amounts of from between 10% up to 50% by weight of the silane triol present in the co position.

The aminoplast resinous component of the present composition is employed in an amount of from about 25 to about 1000% by weight of the long-chain alkyl silane triol in the composition, and between about 50 and about 500% of the aminoplast with respect to the silane tn'ol resin is recommended.

If desired, a wide variety of textile-treating additives may be incorporated into the treating compositions of the present invention. For example, softening agents may be added to produce varying hand effects in the finished material. Odor preventatives may be mixed into the present composition, as exemplified by small amounts of urea or dicyandiamide, which functions to take up any formaldehyde released in the pad bath or in the curing operation.

While the composition of the present invention is extremely well adapted to the treatment of cellulosic fabric, as exemplified by cotton and rayon fabrics, the treatment described herein is applicable to any woven, knitted or felted textile material. This includes fabrics made up in whole or in part of fibers of cotton, viscose rayon, cuprammonium rayon, cellulose acetate, wool, silk, flax, nylon, of both' the adipamide and caprolactam types, homo and copolymers of acrylonitrile, polyesters such as polyethylene glycol, terraphthalate, etc.

In treating the textile material, a pad bath is the most convenient means of uniformly impregnating a textile material. However, sprays and other suitable means such as immersion may be used to apply the compositions.

Considerable latitude may be exercised in selecting the particular concentration of solids in the pad bath. For most purposes, a bath containing between about 2% and about 40% of solids is recommended. The adjustment of the squeeze rolls is correlated with the pad bath concentration in the usual manner, to provide the desired add-on. With the novel compositions, these factors should be adjusted to provide an add-on to the textile material of at least 1% and a practical maximum of 25% of the silane triol and aminoplast combined, based on the weight of the dry fibrous material. Preferably, the treated material should contain between 0.5 to 5% of the silane triol and 0.5 to 10% of the aminoplast resin.

It is not known for certain whether the treating composition penetrates into the interior of the fabric or individual fibers, or remains on their surface. Thus, the expression contacted, as used herein, is intended to include either deposits of the agents in the interior of the fibers, or on the surface, or a mixture of both.

The treated fabric may be dried and cured in two separate operations, or may be dried and cured simultaneously. If the former, the material is dried in equipment operating at temperatures of at least F. It is usually preferred to dry and cure in a single operation, in order to simplify the process. The drying and curing is performed in equipment operating at temperatures ranging from between F. and the point at which deterioration of the fibrous material commences. In general, this operation may be conducted at temperatures between about 200 and 500 F. for periods ranging from between 10 seconds and 30 minutes, with the time for cure decreasing as the temperature is increased. For most fibrous materials, the optimum drying and curing is obtained by exposure to temperatures between 250 and 400 F. for a period of between 30 seconds and 15 minutes.

In order that the present invention may be more fully understood, the following examples are given primarily by way of illustration. No details therein should be construed'as limitations on the present invention, except as they appear in the appended claims. All parts and percentages are by weight unless otherwise indicated.

In the following examples, reference is made to the following wash and dry cleaning procedures: (1) Sanforized wash test; (2) dry cleaning; (3) process wash; (4) Bendix wash; and (5) rayon wash.

The Sanforized wash test is made according to the procedure outlined in the test entitled "Dimensional Changes in Textile Fabrics, Cotton and Rayon, Standard Test Method 14-52, found on page 132 of the 1952 edition of the Technical Manual and Yearbook of the A.A.T.C.C.

Dry cleaning tests are run in a tumble jar rotating at 55 r.p.m. and of a 6-liter capacity. Varsol No. H is used as the solvent and 2 liters are used in each test. The samples are rotated for 20 minutes in clean solvent with this 20-minute period being one dry cleaning cycle. The solvent is then removed and replaced by 2 liters of fresh, clean solvent. This procedure is repeated until a total of three cycles have been run. The test swatches are then extracted in a centrifugal extractor, and laid on a flat bed press until dry. They are then thoroughly steamed to remove any last trace of solvent and pressed lightly to remove wrinkles.

The words process'wash indicate a wash that is given a fabric following a resin treatment. The sample is passed in open width through a padder, two ends through a solution of 0.1% polymerized ethylene oxide alkyl phenol condensation product and 0.1% sodium carbonate, after which it receives 5 ends through clear water. It is then dried.

The Bendix wash involves washing in an automatic Bendix home washer. The wash runs for 12 minutes at about 160 F. using 20 liters of water, containing 2 grams Lux soap and 40 grams of sodium carbonate. This is followed by three rinses and a final spin-dry.

In the rayon wash, samples are placed in a cylindricaltype reverse wash wheel with sample+load to make 3 lbs. Water at 100 F. with soap to make running suds (approximately 1.2% soap solution) is used. This is run 15 minutes, after which it is stopped, drained, then refilled with water at 100 F. and run an additional 5 minutes. Thereafter, the wheel is stopped, drained, refilled, and run minutes. Samples are then extracted and pressed dry. Details of this test appear in the 1950 Technical Manual and Yearbook of the A.A.T.C.C., page 133, Test Method 40-52.

These tests are run generally in accordance with the standard tests set forth, which correspond to these designations in the 1952 Technical Manual and Yearbook of the American Association of Technical Chemists and Colorists.

EXAMPLE 1 6.2 parts of sodium hydroxide was dissolved in 370 parts of ice water. The resulting solution was stirred rapidly while 25 parts of octadecyl trichloro silane was added. A white precipitate resulted, which was filtered ofi, washed with water, and drained on a suction filter.

12 parts of the hydrolyzed octadecyl trichloro silane, 40 parts of an 80% solution of essentially monomeric trimethoxy trimethylol melamine, and 4 parts of a 25% Aerosol OT were intimately mixed. The Aerosol OT is an anionic surface active agent, identified as sodium dioctyl sulfosuccinate. 28 parts of this mix were diluted with 170 parts of water and 2 parts of ammonium sulfate catalyst was added.

This emulsion was applied to 80" x 80" cotton, so as to add on 3% silane triol and 8% melamine resin to obtain a water repellent finish durable to both dry clean- EXAMPLE 2 12.4 parts of sodium hydroxide was dissolved in 1200 parts of ice water. The solution was agitated while 48 parts of octadecyl trichloro silane was gradually added. Upon completion of the addition, a resulting white precipitate was filtered oif, washed with water, and drained on a suction filter for 5 hours. The product weighed 482 parts and contained a substantial portion of the order of 10% of octadecyl silane triol- 90 parts of this product and 90 parts of trimethoxy triing and laundering.

methylol melamine (80% resin solids) and 3.6 parts of a 25 solution of Aerosol OT were mixed together and agitated for a one-hour period. This mixture was then diluted with water and various catalysts, as given in Table I hereinbelow, were added thereto, in the proportions so indicated. Applications of these dispersions to cotton cloth by padding to a 100% wet pick-up were made on 9 samples of cloth, as indicated in Table I hereinbelow. This resulted in 8% melamine resin and 1% of the octadecyl silane triol, based on the dry fabric weight. The treated cloths were dried for 10 minutes at 175 F. and cured for 5 minutes at 300 F. to provide the indicated durable water repellency. In addition to these properties of water repellency, the treated cloths had excellent dimensional stability and good wrinkle resistance.

Table I A B O Hydrolyzed silsne+melamine resin emulsion parts.. 40. 8 40. 8 40. 8 (NHOrSO ...do---- 2.0 1.0

Triethanolamine H01 (30% solution) .-.parts-- 4. 0 Water ..--...d0---- 157.2 158 2 155.2

Total --do-.-- 200 200 200 Cloth Sample No 1 2 3 1 2 3 1 2 3 Spray ratings:

Initial 100 100 90 100 90 90 90 80 90 After one Bendix was 80 80 80 After one Santorize was 80 90 80 Aiter3Dry cleanings. 80 80 EXAMPLE 3 Simultaneous hydrolysis and dispersion of long-chain alkyl trichloro silanes were carried out by first dissolving triethanolamine and a suitable long-chain alkyl acid, such as stearic or oleic acid, in hot water, and then cooling the resulting solution to room temperature. This soap solution was agitated while the chloro silane was gradually added. The resulting dispersions were mixed with trimethoxy trimethylol melamine as given in Table II hereinbelow in the proportions so indicated. The dispersions were applied to cotton cloth by padding to a 100% wet pick-up. This resulted in the application of 2% of the silane triols and 8% of the melamine resin, based on the dry weight of the cloth. The treated fabrics were dried for 10 minutes at 190 F. and. cured for 5 minutes at 300 F. to give a water repellent finish durable to both dry cleaning and laundering.

Table II Hydrolysis Emulsion A B O D Total ..do--..- 861. 1 873.7 889. 3 874. 2

Pad Beth Composition:

Above Emulsion .-parts.. 138 144. 6 142. 4 144. 6 solution of trimethoxy trimethylol melamine- ..parts. 20 20 20 20 Water --do.--- 42 35. 4 37. 6 35. 4

Total .a... zoo zoo zoo zoo Spray Ratings:

Initial 100 100 100 100 After one Bendix wash 90 90 80 Aiter two Bendix washes... 80 90 90 80 After three Bendix washes- 80 80 80 70 After one Santorized wash-- 80 80 so 70 Aiter three dry cleanings 70 70 70 50 Octadecyl trichloro silane was hydrolyzed and the resultant product was filtered and the filter cake dried at between 40 and 50 C. Four parts of this product was dissolved in 16 parts of xylene and the solution emulsified by adding to it, using high speed stirring, an aqueous solution consisting of parts of Aerosol ND-273, a nonionic emulsifier described more fully in US. Patent No. 2,606,199, and 15 parts of water. This gave a water-inoil system that was inverted to an oil-in-water system, by stirring in 60 parts more wtaer. To this was added 20 parts of an 80% solution of trimethoxy methylol melamine, 8.2 parts of a 30% solution of triethanolamine hydrochloride and 71.8 parts of water, and the resulting dispersion was applied to cotton by padding, dried at minutes at 190 F. and cured 5 minutes at 300 F. to add 2% silane and 8% melamine resin, based on the weight of the fabric.

The treatment imparted a water repellent finish that was durable to both laundering and dry cleaning.

The present combination of the hydrolyzed product of long-chain alkyl trichloro silanes in conjunction with thermosetting aminoplast resins has been found to be particularly effective when a third component is added to this combination, namely, an alkyd resin. The addition of the alkyd resin (whether oil-free or oil-modified, including short, medium, and long oil-modified resins) provides greater durability to both laundering and dry cleamng to fabrics which have been treated therewith. The following example is to illustrate this feature of the present invention.

EXAMPLE 5 Octadecyl trichloro silane was hydrolyzed by the general procedure set forth hereinabove. This product after drying had a molecular weight of 3940, as determined by the depression of the freezing point of a benzene solution. It was used to prepare a finishing composition as follows:

' Percent Octadecyl trichloro silane hydrolysis product"--- Xylene 60% butylated trimethylol melamine (solution in The 7.5 parts of alkyd resin consists of 3.75 parts real resin and 3.75 parts of mineral spirits.

The above composition was prepared by melting the chloro silane hydrolysis product and dissolving it in the xylene. This solution was then incorporated in a solution of the butylated trimethylol melamine and alkyd resins. In a separate container, 4 parts of the polyethylene tertdodecyl thioether were dissolved in part of the water, after which the solvent solution was incorporated into the aqueous non-ionic solution, using high speed stirring. This oil-in-water emulsion was finally diluted with the balance of the water to make up 100 parts total.

The above product was then made into pad liquors by the following processes: In the first, the pad bath solution consists of parts of the hydrolyzed silane emulsion prepared as hereinabove and 75 parts of water. In the second, the pad bath solution consists of 16.6% of the hydrolyzed silane emulsion and 83.4% of water.

Cotton and rayon gabardine were then passed through the above two pad bath liquors, giving two dips and two nips, whereupon a wet pick-up of about 80% was obtained. This caused the material to have deposited on the fabric 3% silane triol and 2% silane triol, respectively. The treated fabrics were then dried 3 minutes at 225 F. and the cotton was cured for 6 minutes at 300 F. The treated fabric was then process washed.

The treated materials were then tested for spray ratings after the indicated processing, with the following results:

Table III Cotton Rayon Process Washed 37 29 3 7 27 Benin; Benin souiis sou'iis Initial 100 160 100 100 One Sanforlzed wash 100 100 3 additional rayon washos.. S0

3 dry cleanings 9O 80 80 12 dry cleanings 80 80 80 80 3 rayon w h 100 6 rayon washes 90 80 In the composition of the present invention and in the process for its application to various fibrous and textile materials, other additives not inconsistent with the performance of the silane triol or the aminoplast resin and/ or necessary additives such as non-ionic surface active agents, and/or alkyd resins may be employed. As examples, suitable emulsifiers, softeners, lubricants, pigments, dyes, and the like may be used therewith.

We claim:

1. A stable composition for imparting water repellency to textiles which comprises a waterlinsoluble alkyl silane triol in which all the alkyl groups contain from 10 to 20 carbon atoms, a lower alkyl alcohol-reacted thermo setting aminoplast resin in an amount within the range of from 25% to 1000% by weight of the amount of the silane triol, and from 1 to 60% based on the weight of the aminoplast resin of a curing catalyst for said aminoplast resin.

2. A composition according to claim 1 which is an aqueous dispersion containing from 10% to 50% based on the weight of the alkyl silane triol of an emulsifying agent selected from the group consisting of anionic and nonionic emulsifying agents.

3. A composition according to claim 1 which is an oil-in-water emulsion containing from 10% to 50% based on the weight of the alkyl silane triol of an emulsifying agent selected from the group consisting of anionic and nonionic emulsifying agents.

4. An article which comprises a textile material having a durable water repellent finish comprising the heatcured reaction product of a composition according to claim 1.

5. A stable oil-in-water emulsion for imparting water repellency to textiles which comprises a water-insoluble alkyl silane triol in which all of the alkyl groups contain from 12 to 18 carbon atoms, from between 10 and 50% based on the weight of the alkyl silane tn'ol, of a member selected from the group consisting of anionic and nonionic emulsifying agents, a lower alkyl alcohol-reacted melamine-formaldehyde resin in an amount within the range of from 50% to 500% by weight of the amount of the silane triol, and from 1 to 60% based on the weight of the melamine-formaldehyde resin of a curing catalyst for said melamine-formaldehyde resin.

6. An emulsion according to claim 5 in which both the silane triol and the melamine-formaldehyde components are present in the oil phase.

7. A process for imparting water repellency to textiles which comprises contacting a textile material with a composition according to claim 1 and then heating the textile material so treated above F. to dry and cure said composition to a substantially water-insoluble state, whereby a durable water repellent finish is imparted to the textile material.

8. A process of imparting water repellency to textiles which comprises applying to a textile material at least 0.5% by weight of a water-insoluble low molecular weight alkyl silane triol in which all the alkyl groups contain from 12 to 18 carbon atoms and at least 0.5% by weight of a lower alkyl alcohol-reacted melamine-formaldehyde resin together with a curing catalyst for said resin by contacting said textiles with a composition according to claim 5 and then heating the textile material so treated above 175 F. to dry and cure said composition to a substantially water-insoluble state, whereby a durable water repellent finish is imparted to the textile material.

9. A stable composition for imparting water repellency to textiles which comprises water-insoluble octadecyl silane triol, lower alkyl alcohol-reacted thermosetting aminoplast resin in an amount within the range 10 of from 25% to 1000% by weight of the amount of the silane triol, and from 1 to 60% based on the weight of the aminoplast resin of a curing catalyst for said aminoplast resin.

References Cited in the file of this patent UNITED STATES PATENTS 2,507,200 Elliott et al. May 9, 1950 2,757,152 Solomon July 31, 1956 2,758,946 Spalding et al Aug. 14, 1956 2,781,332 Swann et al. Feb. 12, 1957 2,785,145 Cooke et al. Mar. 12, 1957

Claims (1)

1. A STABLE COMPOSITION FOR IMPARTING WATER REPELLENCY TO TEXTILES WHICH COMPRISES A WATER LINSOLUBLE ALKYL SILANE TRIOL IN WHICH ALL THE ALKYL GROUPS CONTAIN FROM 10 TO 20 CARBON ATOMS, A LOWER ALKYL ALCOHOL-REACTED THERMOSETTING AMINOPLAST RESIN IN AN AMOUNT WITHIN THE RANGE OF FROM 25% TO 1000% BY WEIGHT OF THE AMOUNT OF THE SILANE TRIOL, AND FROM 1 TO 60% BASED ON THE WEIGHT OF THE AMINOPLAST RESIN OF A CURING CATALYST FOR SAID AMINOPLAST RESIN.