HK1014971A - Products of the reaction between isocyanates and hydroxyl compounds for textile finishing - Google Patents

Description

Reaction products of isocyanates with hydroxyl compounds for textile finishing

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The invention relates to products containing blocked isocyanate groups, obtained by reacting products containing isocyanate groups with hydroxyl compounds and then blocking the products obtained, and also to their use for treating fiber materials.

Blocked isocyanates prepared by reacting polyisocyanates with polyols and then blocking the NCO groups still free with blocking agents are known, for example, from EP-A196309, EP-A262069 and WO 92/00358. Blocked isocyanates prepared by reacting polyisocyanates with nitrogen-containing polyhydroxyl compounds and subsequent blocking are also known and are described in EP-A196309. The reaction of polyisocyanates with polyols and nitrogen-containing hydroxyl compounds is also known and described, for example, in EP-A262069 and EP-A537578. It is also known to use extenders in combination with perfluoroalkyl-containing polymers (i.e.builders) in the oil-and water-repellent finishing of fiber materials. The use of blocked isocyanates and blocked low molecular weight polyurethanes as extenders is also known and described, for example, in EP-A196309 and EP-A537578.

The prior art blocked isocyanates have both advantages and disadvantages. For example, they are not well suited to achieve the desired level of effect on fibrous materials made from certain fibers or certain fiber blends; the permanence of the effects achieved with the known blocked isocyanates after washing and dry cleaning and the abrasion resistance of the finished fibre materials are also not very desirable.

The object of the present invention is to provide compositions based on blocked isocyanates which are suitable for a wide variety of applications on fiber materials, preferably as extenders together with perfluoroalkyl-containing polymers, i.e.which are suitable for fiber materials made from different types of fibers and also for producing various effects.

The object of the invention is achieved by a composition obtained by the following steps:

a) reacting a diisocyanate or a mixture of diisocyanates (component I) with one or more alcohols having from 2 to 8 carbon atoms and/or one or more mono-and/or diethers of such alcohols (component II), the alcohols or their ethers having at least two alcoholic hydroxyl groups and not more than two C-O-C bonds, and the reaction being carried out such that the product formed still has free isocyanate groups,

b) reacting the reaction product obtained in step a) with an organic amine or a mixture of such amines containing two or more alcoholic hydroxyl groups, the reaction being carried out such that the product formed still has free isocyanate groups, with the proviso that at least one of the alcohols, ethers or amines used in step a) and/or b) contains three or more alcoholic hydroxyl groups,

c) blocking the free isocyanate groups of the product obtained in step b) by reaction with a blocking agent,

d) dispersing the product obtained after step c) in water and adjusting the pH if necessary.

The composition of the invention has the following advantages:

1. can be used on various fiber materials and can be used on various fiber materials,

2. they are suitable for achieving different finishing effects,

3. the finished fiber material has good effect durability after washing and dry cleaning processing.

The diisocyanates used in step a) for the preparation of the compositions according to the invention are known and are described, for example, in EP-A537578 (the integrity of which is not required). Preferred diisocyanates are aromatic diisocyanates, particularly suitable diisocyanates are diphenylmethane diisocyanates of the general formula (III),in particular diphenylmethane-4, 4-diisocyanate, or tolylene diisocyanates of the formula (IV),

in this case, it is possible to use the individual isomers or mixtures of isomeric diphenylmethane diisocyanates or tolylene diisocyanates.

The reaction with the diisocyanate is carried out with the alcohol of step a) having 2 to 8 carbon atoms or a mono-or diether of such an alcohol or a mixture of these alcohols and their mono-or diethers. These alcohols and mono-or diethers must have at least two free hydroxyl groups and not more than two C-O-C bonds.

In step a) of preparing the compositions according to the invention, suitable di-or polyhydric alcohols having from 2 to 8 carbon atoms are known. Straight-chained or branched fatty alcohols are suitable and preferred. Dihydric alcohols, such as ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol and 1, 6-hexanediol are highly suitable. Tri-and polyhydric alcohols, such as glycerol, trimethylolpropane and pentaerythritol, are highly suitable. Among the polyhydric alcohols, trihydric alcohols are preferred. 1, 2-propanediol and 1, 1, 1-trimethylolpropane are particularly suitable. The mono-or diethers which can be used in step a) are also known. They consist of two or three molecules of di-or polyhydric alcohols which are linked to one another, for example by ether bonds, and have at least two free hydroxyl groups and not more than two C-O-C bonds (ether alcohols). Monoethers (e.g., diethylene glycol or dipropylene glycol) and diethers (triethylene glycol or tripropylene glycol) are highly suitable. In step a) of reaction with the various components having hydroxyl functionality (alcohols and/or ethers), these components can be reacted with the diisocyanate component in a mixture or in stages.

Organic amines having two or more alcoholic hydroxyl groups which can be used in the reaction in step b) are known. In preparing the compositions of the present invention, secondary or tertiary amines are preferably used in step b), although primary amines having at least two alcoholic hydroxyl groups on the organic residue bound to the nitrogen may also be used. Examples of highly suitable secondary amines are diethanolamine and dipropanolamine. Tertiary amines of the general formula (A) are preferred:

R_3-yN(R′-OH)_y (A)

(where R is an alkyl group of 1 to 18, preferably 1 to 4, carbon atoms, R' is a linear or branched alkylene group of 2 to 4 carbon atoms, and y is 2 or 3), including alkoxylated amines such as N-methyl, N-dodecyl or N-stearyl diethanolamine and triethanolamine.

In preparing the compositions of the present invention, it is important that the resulting products have some degree of branching. This is achieved by the fact that at least one of the compounds (alcohols, ethers, amines) which is reacted with isocyanate groups in step a) or b) contains at least three alcoholic hydroxyl groups. For example propylene glycol in step a) and triethanolamine in step b); or trimethylolpropane is used in step a) and N-methyldiethanolamine in step b). It is possible to avoid gelling by changing the reaction conditions (e.g. degree of branching).

Step a) is preferably carried out in such an amount that 0.1 to 0.5 equivalents of alcoholic hydroxyl groups are used per equivalent of isocyanate groups. In this case, step b) is preferably carried out so that the reaction product of step a) and the alcoholic hydroxyl group-containing amine are present in an amount of 0.05 to 0.5 equivalent of alcoholic hydroxyl groups per equivalent of isocyanate groups used in step a). The amounts of diisocyanate, alcohol and/or ether and amine used to carry out steps a) and b) are such that the reaction product obtained after step a) and after step b) still contains free isocyanate groups. The amounts of diisocyanate, alcohol and/or ether and amine are preferably chosen such that not more than 0.7 equivalents of the sum of the alcoholic hydroxyl groups used in steps a) and b) are used per equivalent of the isocyanate groups used in step a). It is particularly preferred to use from 0.3 to 0.5 equivalents per equivalent of isocyanate used in step a), and in this case from 0.05 to 0.3 equivalents of alcoholic hydroxyl groups in step b).

Preferred compositions of the invention are those in which 1, 2-propanediol or a mixture of 1, 2-propanediol and one or more mono-or diethers of 1, 2-propanediol, each ether having two hydroxyl groups, are used as component (II) in step a). Particularly preferred compositions according to the invention are those in which a diisocyanate or a mixture of diisocyanates is used as component (I) of step a) and component (II) is reacted in the presence of a reaction product containing free isocyanate groups; the reaction products containing free isocyanate groups are obtained by reacting the diisocyanates or mixtures of diisocyanates with diols or mixtures of the alcohols and their mono-and/or diethers. Particularly preferred compositions according to the invention are also compositions in which mixtures of diisocyanates or reaction products containing free isocyanate groups are used as component (I) in step a); the reaction products containing free isocyanate groups are obtained by reacting the diisocyanates with 1, 2-propanediol or mixtures of 1, 2-propanediol and one or more mono-or diethers of 1, 2-propanediol. Particularly preferred compositions of the invention are also those wherein the mixture of diisocyanate and its reaction product is obtained by reacting a mixture of diisocyanate and 1, 2-propanediol or with a mono-or diether mixture of 1, 2-propanediol and one or more 1, 2-propanediol in a ratio of 0.1 to 0.3 equivalents of alcoholic hydroxyl groups per equivalent of isocyanate groups.

Particularly preferred compositions are also those in which component (I) is first reacted in step a) with a tri-or polyhydric alcohol to give a product which still contains free isocyanate groups and the product obtained is then reacted in step B) with a compound of the formula (B):

R″N(CH₂CH₂OH)₂ (B)

(wherein R' is an alkyl group of 1 to 4 carbon atoms) to give a composition of products which still contain free isocyanate groups.

Blocking agents for blocking the free isocyanate groups present in step c) are known and are described (not necessarily required to be complete) in EP-A537,578. Highly suitable blocking agents are ketoximes, particularly butanone oxime. The amount and conditions of the blocking agent used in step c) are such that the reaction product obtained contains substantially no free isocyanate groups.

The reaction of step a), b) and/or the blocking reaction of step c) is preferably carried out in a homogeneous liquid phase, preferably in a solvent. Suitable solvents are polar aprotic organic solvents, as described, for example, in EP-A537578. Examples of highly suitable solvents are organic acid esters or ethers. Particularly suitable solvents are lower ketones which are practically insoluble in water, preferably methylisobutylketone. The organic solvent may then be removed from the composition of the invention, for example by distillation, preferably after the aqueous dispersion comprising the composition has been prepared.

The reaction of step a) is preferably carried out in the presence of a catalyst in order to achieve a suitable reaction rate. Any catalyst suitable for the reaction of an isocyanate group with an alcoholic hydroxyl group may be used. Examples of suitable catalysts are tertiary amines, including 1, 4-diazabicyclo [ 2.2.2 ] octane. Particularly suitable catalysts are organotin compounds, such as dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dilaurate or tin octoate. The reaction of step b) or c) does not require the presence of a catalyst, although it is preferred not to remove the catalyst used in the reaction of step a) from the product obtained in step a) before carrying out the reactions of steps b) and c).

Under normal conditions the reactions of steps a) and b) are carried out at a temperature of 0-150 ℃ and the blocking of step c) is carried out at a temperature of 0-100 ℃. The reaction of steps a), b) and c) is preferably carried out at a temperature of from 20 to 90 ℃ and particularly preferably from 40 to 80 ℃. It is advantageous to prepare and use the compositions of the present invention as aqueous dispersions, especially when handling and environmental concerns are taken into account. For this purpose, the reaction product obtained in step c) is dispersed in water. Since the reaction product obtained in step c) does not normally form a stable dispersion with water, the concentration of dispersant familiar to the person skilled in the art is used for this purpose. Suitable dispersing agents are nonionic surfactants such as alkoxylated fatty alcohols, fatty acids and sorbitan esters as well as ethylene oxide-propylene oxide block copolymers and amine oxides. Cationic surfactants are also suitable dispersants, for example tetraalkylammonium salts or ethoxylated alkylamines and their salts, and alkoxylated and quaternized alkylamines. Particularly suitable dispersants are in many cases ethoxylated castor oils having an average of from 10 to 50, particularly preferably from 25 to 40, ethylene oxide units. Suitable dispersants may be used alone or in a mixture of two or more dispersants. Examples of highly suitable dispersants are mixtures of ethoxylated castor oil with fatty alcohols or fatty acid alkoxylates. The pH of the dispersion can be adjusted to the optimum range for stability and intended use of the dispersion as or after it is prepared. The pH of the dispersion is adjusted to a value of from 1.5 to 9, preferably from 2.5 to 4, under normal conditions. The pH can be adjusted using reagents known to those skilled in the art, such as organic or inorganic acids.

The dispersion is normally prepared as follows: homogenizing water, dispersant or dispersant mixture and, if desired, further components, and finely distributing the reaction product obtained in step c) and, if desired, an acid for adjusting the pH in this mixture by means of a high-speed mechanical stirrer. The acid may also be added to the water/dispersant mixture prior to addition of the reaction product. The mixture may be prepared with water, dispersant, reaction product, acid and other components in any reasonable order. The resulting mixture can be converted into a stable finely divided dispersion by means of a high-pressure homogenizer at a pressure of from 100 to 500 bar, preferably from 200 to 300 bar. Mixing or high-pressure homogenization can be carried out at conventional temperatures or at elevated temperatures. At too low a temperature there is a risk of precipitation of the product from the dispersion, while the maximum temperature is determined by the boiling point of the water/solvent mixture. Step d) is preferably carried out at 20 to 40 ℃. High pressure homogenization with additional cooling is advantageous. After the dispersion has been obtained, it is advantageous to remove any solvent still present, for example by distillation, if desired under reduced pressure. In addition to the advantages of environmental suitability and flash point increase, solvent-free dispersion systems also have the advantage of increased stability.

The novel compositions obtained in step c) or d) are very suitable for treating fibrous materials, in particular for treating textile fabrics of a woven or knitted sheet-like structure. Suitable fibre materials are fibre materials made from natural or regenerated cellulose and fibres of animal origin, preferably wool; it may also be made of synthetic organic fibers (e.g. polyester fibers) and mixtures thereof. Other products suitable for textile finishing, such as cellulose crosslinkers, fabric softeners, silicone elastomers or flame retardants, may also be used if desired, and are preferably added to the dispersion of the composition of the invention. Suitable products which can also be used for this purpose are known to the person skilled in the art. Examples include hexylidene urea derivatives as cellulose crosslinkers, silicones as fabric softeners and/or dispersions comprising modified polyethylene, phosphorous containing products for flame retardant finishing. The compositions of the present invention are preferably used in combination with fluoropolymers for oil-, water-and soil-repellent finishing of fibrous materials. The mixing ratio of fluoropolymer to the composition according to the invention can be from 1: 0.03 to 1: 1.5, preferably from 1: 0.3 to 1: 0.75, in each case based on anhydrous, solvent-free and additive-free active substance. Fluoropolymers suitable for water-, oil-and dirt-repellent finishing are known to the person skilled in the art, and mention may be made, for example, of perfluoroalkyl-containing acrylic polymers and perfluoroalkyl-containing polyurethanes. The fiber materials finished by the composition have good effect durability after washing or dry cleaning processing. These effects are often maintained after water-, oil-, dirt-repellent finishing even after cleaning (using a process called "post-wash air-drying" or "post-wash tumble-drying") without ironing.

The use of the composition of the invention in the form of an aqueous dispersion of ethoxylated castor oil as dispersant results in a lotion with excellent stability and fluidity. Many of the compositions of the present invention are also suitable for low-stick and low-shrink finishing of wool, which when used with fluoropolymers enables both oil-and water-repellent finishing (one operation).

The compositions of the invention are preferably applied to the fibrous material in the form of an aqueous dispersion. In addition to the reaction product of step c), dispersant and water, other components already indicated above may be included. The compositions according to the invention can be applied to the fibre materials by customary methods known to the person skilled in the art, for example padding, sizing, spraying, exhaust methods, etc., particularly preferably by application using a pad-mangle. The concentration to be set advantageously can be determined simply by the person skilled in the art. The fibre material obtained is finished in a customary manner, for example by drying.

The invention will now be described in the following with reference to working examples

Example 1

Step a): 450 g of component (I) (2.5 equivalents based on free isocyanate groups) and 33.5 g of 1, 1, 1-trimethylolpropane (0.75 equivalents based on hydroxyl groups) are dissolved in 720 g of methylisobutylketone at 40 ℃ with stirring in a four-necked flask equipped with a reflux condenser, while passing nitrogen through the entire course of steps a) to c). Component (I) is the reaction product of an isomeric mixture of diphenylmethane diisocyanates with a mixture of 1, 2-propanediol, dipropylene glycol and tripropylene glycol, the reaction product still comprising about 65% by weight of unreacted diphenylmethane diisocyanate and being substantially free of compounds having free hydroxyl groups. The diisocyanate isomer mixture is an isomeric diphenylmethane diisocyanate mixture wherein the largest isomer by weight is 4, 4' -diphenylmethane diisocyanate, which is commercially available, for example, from Dow Chemical or Bayer, and the alcohol mixture is a mixture of about 5% by weight of 1, 2-propanediol, 15% by weight of dipropylene glycol and 80% by weight of tripropylene glycol. To the solution obtained 0.6 g of dibutyltin dilaurate dissolved in 5.4 g of methylisobutylketone are added with stirring. The temperature was raised to 54 ℃ over 3 minutes and the solution was then stirred on a water bath at 42 ℃ for a further 30 minutes.

Step b): to the solution was then added 14.9 g of N-methyldiethanolamine (0.25 equivalents based on hydroxyl groups) dissolved in 90 g of methylisobutylketone. The temperature was increased from 40 ℃ to 45 ℃ over 5 minutes and the solution was stirred on a water bath at 42 ℃ for another 30 minutes.

Step c): to the solution was added 130.7 g of butanone oxime (1.5 equivalents) dissolved in 125 g of methyl isobutyl ketone. The temperature rose to 61 ℃ in 1 minute. The solution was then stirred on a water bath at 42 ℃ for another 30 minutes to give a slightly viscous, slightly turbid product which was free of NCO groups by testing with an infrared spectrometer. The product was added methylisobutylketone to 1573 g, corresponding to an active substance content of 40% by weight.

Step d): 500 g of the solution obtained in step c), containing 200 g of active substance, are added to a solution prepared at room temperature comprising

20 grams of EMULSOGEN EL,

30g of 1, 2-propanediol, and

500 g tap water

The solution of (4) was stirred at 20 ℃ with a high speed stirrer (Ultra-Turrax). EMULSOGEN EL is an ethoxylated castor oil containing an average of 36 to 38 ethylene oxide units, available from Hoechst corporation. The pH of the resulting mixture was 6.9, and adjusted to pH2.8 by dropwise addition of about 30% hydrochloric acid. The mixture was stirred for a further 3 minutes and then homogenized in a high-pressure homogenizer (manufacturer-Manton-Gaulin) four times at an operating pressure of about 250 bar. The initial temperature of the mixture was 20 ℃ and the final temperature of the dispersion obtained after the fourth pass was 35 ℃.

The methyl isobutyl ketone solvent and a portion of the water were distilled off in a rotary evaporator at a bath temperature of 70 ℃ and under reduced pressure. A dry matter determination was then carried out and the amount of water calculated to be required was added in order to obtain a dispersion with a solids content of 30% by weight. The resulting dispersion has good stability under the influence of both mechanical and thermal influences.

Example 2

Step a): 70g of 2, 4-tolylene diisocyanate (0.8 equivalents based on free isocyanate groups) and 8 g of 1, 1, 1-trimethylolpropane (0.18 equivalents based on hydroxyl groups) containing approximately 5% of the 2, 6-isomer were dissolved in 175 g of methylisobutylketone at 60 ℃ with vigorous stirring in a four-necked flask equipped with a reflux condenser, and passed under nitrogen over the entire course of steps a) to c). The resulting solution was cooled to 25 ℃. To the solution was added under stirring 0.2 g of dibutyltin dilaurate dissolved in 1.8 g of methylisobutylketone. The temperature rose from 25 ℃ to 38 ℃. The solution was then stirred for another 30 minutes during which time the temperature was reduced to 28 ℃.

Step b): to the solution was added 3.5 grams of triethanolamine (0.06 equivalents based on hydroxyl groups) dissolved in 30 grams of methyl isobutyl ketone. The temperature rose to 34 ℃. The solution was then stirred for another 30 minutes during which time the temperature was reduced to 27 ℃.

Step c): to the solution was added 48.8 g of butanone oxime (0.56 eq) dissolved in 40g of methyl isobutyl ketone. The temperature was raised to 57 ℃ and the solution was then stirred for a further 30 minutes during which the temperature was reduced to 32 ℃ to give a slightly viscous, slightly turbid product which was tested by infrared spectroscopy for the absence of NCO groups. The active substance in the resulting solution was about 129 grams or 33%.

Step d): adding the whole solution obtained in step c) to a solution prepared at 35 deg.C comprising

10 grams of MARLIPALL O13/500,

3 grams of DEHYQUART AU56,

22 g of monoethylene glycol and

350 g tap water

The solution of (4) was stirred at 35 ℃ with a high-speed stirrer (Ultra-Turrax). MALALO 13/500 is an ethoxylated oxo alcohol available from Huls corporation. DEHYQUART AU56 is a quaternary ammonium methyl sulfate salt available from Henkel corporation. The pH of the resulting mixture was 6.1, and adjusted to pH3.2 by dropwise addition of about 30% hydrochloric acid. The mixture was stirred for a further 3 minutes and then homogenized in a high-pressure homogenizer (Manton-Gaulin, manufacturer) four times at an operating pressure of about 250 bar. The initial temperature of the mixture was 20 ℃ and the final temperature of the dispersion obtained after the fourth pass was 35 ℃.

The methylisobutylketone solvent and some water were distilled off in a rotary evaporator at a bath temperature of 70 ℃ and under reduced pressure, and the dry matter was then determined and the amount of water required to be added was calculated therefrom in order to obtain a dispersion with a dry matter content of 30% by weight, which dispersion had good stability under the influence of mechanical and heat.

Example 3

Step a): 75 g of component (I) (0.416 equivalent, based on free isocyanate groups) used in example 1 and 5.6 g of 1, 1, 1-trimethylolpropane (0.126 equivalent, based on hydroxyl groups) were dissolved in 110 g of methylisobutylketone at 40 ℃ with stirring in a four-necked flask equipped with a reflux condenser, while passing nitrogen through the entire course of steps a) to c). To the resulting solution was added under stirring 0.1 g of dibutyltin dilaurate dissolved in 0.9 g of methylisobutylketone. The temperature was raised to 55 ℃ in 1 minute, and the solution was stirred on a water bath at 41 ℃ for another 30 minutes.

Step b): to the solution was added 2.38 g of N-methyldiethanolamine (0.04 eq. based on hydroxy) dissolved in 40g of methylisobutylketone. The temperature rose from 40 ℃ to 45 ℃ in 1 minute. The solution was then stirred on a water bath at 41 ℃ for another 30 minutes.

Step c): to the solution was added 21.75 g of butanone oxime (0.25 eq) dissolved in 20 g of methyl isobutyl ketone. The temperature rose to 59 ℃ in 1 minute. The solution was then stirred on a water bath at 41 ℃ for another 30 minutes. This gave a slightly sticky, whitish, turbid product which, as determined by infrared spectroscopy, contained no NCO groups and had an active substance content of about 104 g.

Step d): blending the solution obtained in step c) at 20 ℃ with a high-speed stirrer (Ultra-Turrax) comprising

5.5 grams of EMULSOGEN EL,

5.5G of IMBENTIN T/400G,

16 g of 1, 2-propanediol and

290 g tap water

In the solution of (1). IMBENTIN T/400G is an ethoxylated tridecanol containing 40 ethylene oxide units, available from Dr.W.Kolb company (Hedingen, Switzerland), the resulting mixture having a pH of 5.7, was adjusted to 2.8 by adding about 30% hydrochloric acid dropwise. The mixture was stirred for a further 3 minutes and then homogenized in a high-pressure homogenizer (manufacturer Manton-Gaulin) four times at an operating pressure of about 250 bar without cooling. The initial temperature of the mixture was 20 ℃ and the final temperature of the dispersion obtained after the fourth pass was 35 ℃.

Methylisobutylketone and some water were distilled off in a rotary evaporator at a bath temperature of 70 ℃ and under reduced pressure, and then a dry matter determination was carried out and the amount of water required was calculated therefrom in order to obtain a dispersion with a dry matter content of 30% by weight. The resulting dispersion has good stability to mechanical and thermal influences.

The invention will now be illustrated by the following application examples, the results of which are assessed by the test method described below, in which a finished fabric sample is left for 24 hours at 20 ℃/65% relative humidity before the test is carried out.

The oil-repellent effect was determined according to AATCC 118-. The wettability with 8 different liquid hydrocarbons was tested. The method is rated on a scale of 1-8, with 8 being the best (the most oil-repellent effect).

The water-repellent effect was tested according to AATCC 22-1980 (spray test) and DIN 53888(Bundesmann rain test). The latter is a visual assessment of the "water-repellent effect" (3 times per fabric, after 1, 5 and 10 minutes of rainfall), rated on a scale from 1 (worst) to 5 (best, water is excluded, no wetting phenomena) and then the water absorption (in% by weight) is determined. In the spray test, the wetting is also visually classified on a scale of 0-100 (100 being the most optimal, i.e., the least wetting), and the AATCC test method described above is from "AATCC Technical Manual (American Association of textile Chemists and Colorists Technical Manual) Vol.58, 1983, ps, 248, 270, 271.

Application example 1 (inventive example)

A finishing liquor having the following composition was prepared

10g/l of the dispersion from example 1

40g/l fluoropolymer

5g/l surfactant preparation

1g/l 60% by weight of acetic acid

The balance being water.

The fluoropolymer used is an aqueous dispersion comprising 15% by weight of a perfluoroalkyl acrylic copolymer and the surfactant used is an aqueous solution of an ethoxylated fatty alcohol and an araliphatic ether alcohol.

The resulting finish was applied to a green wool fabric (calculated on the weight of the fabric) using a pad-mangle at room temperature with a pick-up of about 90% by weight. The fabric was then dried in a drying oven at 110 ℃ for 10 minutes and condensed at 150 ℃ for 5 minutes. The fabric is ironed after each washing or dry cleaning process.

Application example 2 (inventive example)

Application example 1 was repeated, but the finishing liquor used was 10g/l of the dispersion from example 2 instead of the dispersion from example 1.

Application example 3 (inventive example)

Application example 1 was repeated, but the finishing liquor used was 10g/l of the dispersion from example 3 instead of the dispersion from example 1.

Application example 4 (non-inventive example)

Application example 1 was repeated, but the finish used was 10g/l of a dispersion comprising 30% by weight of the reaction product of tolylene diisocyanate and trimethylolpropane, whose free NCO groups had been blocked with butanone oxime, i.e.the product whose preparation had not undergone step b).

Application example 5 (non-inventive example)

Application example 1 was repeated, but the finishing liquor used was 10g/l of a dispersion comprising about 30% by weight of diphenylmethane diisocyanate product having NCO groups blocked with butanone oxime (i.e.the product was prepared without steps a) and b)).

The test results of the wool fabrics finished in application examples 1 to 5 are shown in Table 1.

TABLE 1

	Application examples
						No.1	No.2	No.3	No.4	No.5
	Rain test waterproof effect of original value oil resistance spray test	610012％5/5/5	610012％5/5/5	610015％5/4/4	610043％5/2/2						610024％5/4/3
Waterproof effect of rainwater test of oil resistance spray test at 30 ℃ after 5 times of washing						610031％5/2/2	610035％5/2/2	610028％3/3/3	510054％2/1/0	610042％3/2/1
	Waterproof effect of oil-resistant spray test rainwater test after 1 dry-cleaning treatment with cleaning accelerant	610037％3/2/2	610034％5/3/2	610023％5/4/3	69049％2/1/0						610040％3/2/1

Using example 6 (inventive example) a finishing liquor of the following composition was prepared: 30g/l dispersion from example 1 70g/l fluoropolymer 5g/l surfactant preparation 1g/l 60% by weight acetic acid 15g/l alkyl modified melamine-formaldehyde derivative 5g/l acid donor balance water based on magnesium salt

The fluoropolymer used was an aqueous dispersion comprising 12.5% by weight of a perfluoroalkyl acrylic copolymer and the surfactant formulation was an aqueous solution of ethoxylated fatty alcohol and aralkyl ether alcohol.

The resulting finish was applied to a polyester/cotton (65%: 35%) mixed fabric having a wet pick-up of about 62% by weight (based on the weight of the fabric) at room temperature using a padding machine, and the fabric was dried in a drying oven at 110 ℃ for 10 minutes and then condensed at 150 ℃ for 5 minutes. The fabric is ironed after each washing or dry cleaning process.

Application example 7 (inventive example)

Application example 6 was repeated, but the finishing liquor used was 30g/l of the dispersion from example 2 instead of the dispersion from example 1.

Application example 8 (inventive example)

Example 6 was used as a green body, but the finish used was 30g/l of the dispersion from example 3 instead of the dispersion from example 1.

Application example 9 (non-inventive example)

Application example 6 was repeated, but the finish used was a dispersion comprising 30g/l of the reaction product of tolylene diisocyanate with free NCO groups blocked with butanone oxime and trimethylolpropane (i.e.the reaction product not prepared according to step b) instead of the dispersion from example 1.

Application example 10 (not an embodiment of the invention)

Application example 6 was repeated, but the finish used was a dispersion comprising about 30% by weight of the dispersion obtained from diphenylmethane diisocyanate product having NCO groups blocked with butanone oxime (i.e.the product was prepared without steps a) and b)) instead of the dispersion from example 1 at 30 g/l.

The test results of the cotton/polyester fabrics finished in application examples 6 to 10 are shown in Table 2.

TABLE 2

	Application examples
						No.6	No.7	No.8	No.9	No.10
	Rain test anti-oil of original value oil-resistant spray testWater effect	61004％5/5/5	61006％5/5/5	61007％5/5/5	610019％4/4/4						610022％4/4/4
Waterproof effect of 10-time washing/60 ℃ oil resistance spray test rainwater test						61007％4/3/3	61008％4/3/3	610012％4/4/3	57021％1/0/0	68022％1/0/0
	Waterproof effect of oil-resistant spray test rainwater test after dry-cleaning treatment for 3 times by using cleaning accelerant	61005％5/5/5	61006％5/5/5	61006％5/5/5	610021％3/3/3						510028％2/1/0

Application example 11 (inventive example)

A finishing liquor having the following composition was prepared:

6g/l of the dispersion from example 1

30g/l fluoropolymer

2g/l of 60% strength by weight acetic acid

The balance of water

The fluoropolymer used is an aqueous dispersion comprising 15% by weight of a perfluoroalkyl acrylic copolymer.

The resulting finish was applied to polyester taffeta having a pick-up of about 45% by weight (based on the weight of the fabric) using a pad-mangle at room temperature. The fabric was then dried in a drying oven at 110 ℃ for 10 minutes and condensed at 150 ℃ for 5 minutes. The finished fabrics were all dried in air after washing or in a tumble dryer at 65 ℃ for 20-25 minutes to determine the LAD and LTD properties (LAD stands for "air-drying after washing", LTD stands for "tumble-drying after washing")

Application example 12 (inventive example)

Application example 11 was repeated, but the finishing liquor used was 30g/l of the dispersion from example 2 instead of the dispersion from example 1.

Application example 13 (not an embodiment of the invention)

Application example 11 was repeated, but the finishing liquor used was a dispersion comprising 30g/l of the reaction product of tolylene diisocyanate and trimethylolpropane whose free NCO groups had been blocked with butanone oxime (i.e.the product was prepared without step b)) instead of the dispersion from example 1.

Application example 14 (inventive example)

Application example 11 was repeated, but the finishing liquor used was a dispersion comprising 30g/l of about 30% by weight of the product from diphenylmethane diisocyanate whose NCO groups had been blocked with butanone oxime (i.e.the product was prepared without steps a) and b)).

The results of the tests using the fabrics made of polyester taffeta finished in examples 11 to 14 are shown in table 3.

TABLE 3

	Application examples
					No.11	No.12	No.13	No.14
	Rain test waterproof effect of original value oil resistance spray test	61000％4/4/4	61000％4/4/4	61001％4/4/4					61000％5/5/5
Waterproof effect of rainwater test in air drying oil resistance spray test at 40 ℃ after 1 time of washing					41001％4/4/4	31001％4/4/3	28010％2/2/2	21003％4/4/3
	Waterproof effect of rainwater test in air drying oil resistance spray test after 5 times of washing at 40 DEG C	2909％2/2/2	2906％2/2/2	07021％1/0/0					19015％1/0/0
Rain test waterproof effect of drying oil resistance spray test in rotating cage at 40 ℃ after 5 times of washing					31003％3/3/3	31001％4/4/4	29014％2/2/2	31004％3/3/3

It is clear from the application examples 1 to 14 that the compositions according to the invention impart excellent oil-and water-repellent properties to a wide variety of fibrous materials, maintaining better properties even after several washing or cleaning operations than the compositions not according to the invention, even after washing without ironing.

Application example 15 (inventive example)

Two finishing liquors were prepared having the following composition:

a)50g/l of the dispersion from example 1, the remainder being water.

b)100g/l of the dispersion from example 1, the remainder being water.

The resulting finishes were applied to green wool fabrics with a wet pick-up of about 90% by weight (based on the weight of the fabric) using a pad-mangle at room temperature. The fabric was then dried in a drying oven at 110 ℃ for 10 minutes followed by condensation at 150 ℃ for 5 minutes.

The surface shrinkage of the fabric 5A treated in this way after washing (according to ISO 6330-1984) was determined.

Application example 16 (inventive example)

Application example 15 was repeated, but the finishing liquor used was 50g/l and 100g/l of the dispersion from example 2 instead of the dispersion from example 1.

Application example 17 (not an embodiment of the invention)

Application example 15 was repeated, but the finishing liquor used was a dispersion comprising, in each case 50g/l and 100g/l, 30% by weight of the reaction product of tolylene diisocyanate and trimethylolpropane whose free NCO groups have been blocked with butanone oxime, instead of the dispersion from example 1.

Application example 18 (not an embodiment of the invention)

Application example 15 was repeated, but the finishing liquor used was a dispersion comprising about 30% by weight of the product obtained from diphenylmethane diisocyanate having its NCO groups blocked with butanone oxime in an amount of 50g/l and 100g/l, respectively, instead of the dispersion from example 1.

Application example 19 (not an embodiment of the invention)

The surface shrinkage of the untreated wool fabric 5A after washing (according to ISO 6330-1984) was determined.

The shrinkage (%) of the washes (according to ISO 6330-1984) using the finished wool fabrics of examples 15-18 and untreated wool fabric 5A is given in Table 4.

TABLE 4

		Application examples
							No.15	No.16	No.17	No.18	No.19
		Finishing liquor a)	Width/weft length/weft	35	56.5	78						7.88	1414
Finishing liquor b)	Width/weft						2	4	4	7.5

Length/weft

2.5

5

5

7.5

As can be seen from application examples 15-19, the compositions of the present invention reduced, and in some cases were significant, surface shrinkage of the wool after washing.

Claims (21)

1. A composition resulting from the process steps of:

a) reacting a diisocyanate or a mixture of diisocyanates (component I) with one or more alcohols having from 2 to 8 carbon atoms and/or one or more mono-and/or diethers of such alcohols (component II), the alcohols or their ethers having at least two alcoholic hydroxyl groups and not more than two C-O-C bonds, and the reaction being carried out such that the product formed still has free isocyanate groups,

b) reacting the reaction product obtained in step a) with an organic amine or a mixture of such amines containing two or more alcoholic hydroxyl groups, the reaction being carried out such that the product formed still has free isocyanate groups, with the proviso that at least one of the alcohols, ethers or amines used in step a) and/or b) contains three or more alcoholic hydroxyl groups,

c) reaction with a blocking agent to block the free isocyanate groups of the product obtained in step b),

d) dispersing the product obtained after step c) in water and adjusting the pH if necessary.

2. The composition of claim 1, wherein the reaction of step a), b) and/or the blocking of step c) is carried out in a homogeneous liquid phase, preferably in a solvent, and the solvent is removed if necessary, preferably after dispersion in step d).

3. A composition according to claim 2, wherein the solvent used is a ketone, preferably methylisobutylketone.

4. The composition as claimed in one or more of claims 1 to 3, wherein the reaction of step a), b) and/or the blocking of step c) is carried out in the presence of a catalyst, preferably an organotin compound.

5. The composition of one or more of claims 1 to 4, wherein in step a) 0.1 to 0.5, preferably 0.3 to 0.5 equivalents of alcoholic hydroxyl groups are used per equivalent of isocyanate groups; in step b) from 0.05 to 0.5, preferably from 0.05 to 0.3 equivalents of alcoholic hydroxyl groups are used per equivalent of isocyanate groups used in step a), in which case the sum of the equivalents of alcoholic hydroxyl groups used in steps a) and b) preferably does not exceed 0.7 per equivalent of isocyanate groups used in step a).

6. The composition of one or more of claims 1 to 5, wherein in step a) an aromatic diisocyanate, preferably diphenylmethane 4, 4' -diisocyanate or tolylene diisocyanate or a mixture of such isocyanates is used.

7. The composition as claimed in one or more of claims 1 to 6, wherein the organic amine used in step b) is a compound of the general formula (A)

R_3-yN(R′-OH)_y (A)

Wherein R is an alkyl group of 1 to 18, preferably 1 to 4 carbon atoms, R' is a linear or branched alkylene group of 2 to 4 carbon atoms and y is 2 or 3.

8. A composition as claimed in claim 7, wherein the amine used is N-methyldiethanolamine or triethanolamine.

9. The composition according to one or more of claims 1 to 8, wherein component (II) used in step a) is 1, 1, 1-trimethylolpropane or a mixture of 1, 2-propanediol and one or more mono-or diethers of 1, 2-propanediol.

10. The composition as claimed in one or more of claims 1 to 9, wherein the diisocyanate or diisocyanate mixture as component (I) of step a) is used in the presence of a reaction product containing free isocyanate groups, which is obtained by reacting this diisocyanate or diisocyanate mixture with a dihydric alcohol or a mixture of this alcohol and its mono-or diether.

11. The composition as claimed in one or more of claims 1 to 10, wherein component (I) used in step a) is a mixture of a diisocyanate and a reaction product containing free isocyanate groups, which reaction product containing free isocyanate groups is obtained by reacting this diisocyanate with 1, 2-propanediol or a mixture of 1, 2-propanediol and one or more mono-or diethers of 1, 2-propanediol.

12. The composition of claim 11 wherein the mixture of diisocyanates and reaction products thereof is obtained by reacting a mixture of diisocyanates with 1, 2-propanediol or 1, 2-propanediol and one or more mono-or diethers of 1, 2-propanediol in an equivalent ratio of isocyanate groups to alcoholic hydroxyl groups of 1: 0.1 to 0.3.

13. The composition of one or more of claims 1 to 12, wherein the reaction of steps a) and b) is carried out at a temperature in the range of 0 to 150 ℃, preferably 20 to 90 ℃, particularly preferably 40 to 80 ℃.

14. The composition according to one or more of claims 1 to 13, wherein the blocking of step c) is carried out at a temperature in the range of 0 to 100 ℃, preferably 20 to 90 ℃, particularly preferably 40 to 80 ℃.

15. The composition of one or more of claims 1 to 14, wherein the blocking agent used in step c) is a ketoxime, preferably butanone oxime.

16. The composition as claimed in one or more of claims 1 to 15, wherein in step a) component (I) is reacted with a tri-or polyhydric alcohol to give a product which still contains free isocyanate groups and the product obtained is then reacted in step B) with formula (B)

R″N(CH₂CH₂OH)₂ (B)

(wherein R' is an alkyl group of 1 to 4 carbon atoms) to give a product still containing isocyanate groups.

17. The composition as claimed in one or more of claims 1 to 16, wherein the product obtained in step c) is dispersed in water with one or more dispersants, preferably the dispersant used is an ethoxylated castor oil having an average of from 10 to 50, particularly preferably from 25 to 40, ethylene oxide units.

18. Use of the composition according to one or more of claims 1 to 17 for the treatment of fibrous materials, preferably woven or knitted textile sheet structures.

19. Use according to claim 18, wherein the fibrous material comprises natural or regenerated cellulose, fibres of animal origin (preferably wool), synthetic organic fibres or mixtures thereof.

20. Use according to claim 18 or 19, wherein the composition is used in combination with a perfluoroalkyl-containing polymer, and optionally with the addition of other products.

21. Use according to one or more of claims 18 to 20, wherein the composition is applied to the fibrous material in the form of an aqueous dispersion.