DE2060114A1 - Carbamic acid esters, which are suitable as textile auxiliaries - Google Patents

Description

KCHBMmülT! "-

DS. O. DIPL-CW. WAITER BBl

AlTIID ΚΟΕΐΕΚΘ ■ "" 1 IW 1Q7ff

DR. J153. DiPL-ClSM. ».-J. WOW- k. «^ UW. 13 / .U

with JOB. HANS Ciiß. BtIl "'*. 623 FtIAHKfURT AM MA1H-UÖCBSI

Our No. 16 7 * »2

Atlas Chemical Industries, Inc. Wilmington, Del., V.St.A.

Carbamic acid esters, which are suitable as textile auxiliaries

The invention relates to carbamic acid esters which are used as textile conditioning agents are suitable. Textiles that comply with the invention ·? Carbamic acid esters in accordance with the present invention have improved physical properties. The carbamic acid esters according to the invention are suitable for treating textiles and give them anti-soiling and / or dirt-repellent properties.

In the past few years, permanent ironing has been used in the textile industry introduced by textiles. The treatment is carried out by touching the textiles with a wakery Solution or dispersion of a crosslinking agent that reacts with textiles Impregnated permanent ironing agent and the impregnated material is then heated for the purpose of hardening. This treatment stabilizes the pasern in the position that it is in the textile material during the hardening. Therefore, when a force is applied to the treated textile material and then removed v / ird, the textile material easily returns to its original

1 09825/2102

Position back. This creates a textile material with permanent ironing properties.

The crosslinking treatment, however, has to do with tear resistance, hand resistance, dirt resistance and abrasion resistance adverse effects of the textile material. Therefore, the crosslinked textile material has the favorable properties of a permanently ironed object, poor abrasion resistance, poor vulnerability, poor quality Texture and poor stain resistance. It is known to improve some of the above properties by using polyester fibers, alone or in admixture with cotton.

However, polyester fibers tend to accept oily dirt and grime and hold on. Therefore, when the garment is worn, dirt and / or oily contaminants will accumulate on the garment and settle on the fabric. If the garment becomes soiled, it will be used to remove the Dirt and / or oily deposits are subjected to a cleaning process, and only dry cleaning with solvents (drycleaning) enables the garment to be cleaned successfully.

However, the commonly used cleaning consists of a washing process that the housewife in a conventional washing machine can perform. In a washing process it is actually impossible the dirt and / or oil stains from the garment to remove, and moreover, if about the undesirable. Particles of dirt have been removed from the garment an almost clean garment is washed, the same dirt that is in the washing water, again on the garment deposited before washing is complete

BATH ORIGINAL

109825/2102

So if the garment is removed from the washing machine and then dried, it is not properly clean. Such a condition, which has hitherto been inevitable, is very unfavorable because, after the garment has been worn, never again takes on a really clean appearance, but instead because of the dirt and / or oil components, deposited on it and left behind, turns light gray and / or yellow. Further use and further washing processes of the garment increase the intensity of the gray tones to the point where the garment is discolored finally can no longer be worn.

The present invention was therefore based on the object of finding new textile treatment agents for use in textiles, in particular also those containing polyester, which give the textiles anti-soiling and / or dirt-repellent properties and which also remain on the textiles during numerous washing processes then when they come into contact with detergent solutions. Treatment with the inventive textile treatment agents must also cause the textiles, even if they contain _t not to defilement and then wash again with dirt and oil constituents of the washing water contaminated v / ground polyester fibers. According to the invention, the textiles should also be treated in such a way that they have both permanent ironing and dirt-repellent properties.

According to the invention, this object is achieved by a new class of Carbamic acid esters dissolved, the at least one thermally labile carbamic acid ester group and at least one thermally stable carbamic acid ester group derived from a polyoxyethylene ether of the type described below

10 9 8 2 5/2102 »AD .ORKStNAL

The new carbamic acid esters of the present invention can be prepared by simultaneously or sequentially in any order an aromatic polyisocyanate; a Polyoxyethylene ether and a thermally reversible blocking agent, e.g. phenol, methylphenol, dimethylphenol, trimethylphenol, Ethylphenol, Carprolactam or mixtures of these compounds, reacts with one another. The polyisocyanate can with the blocking agent are reacted in such a ratio that an NCO group remains, and can then be reacted with the polyoxyethylene ether. On the other hand, it is possible to carry out the reaction in reverse so that the Polyisocyanate is first reacted with the polyoxyethylene ether and then with the blocking agent. It is also possible, to carry out the reaction so that all reactants are mixed in an appropriate ratio so that the reactions going on at the same time.

The amounts of polyoxyethylene ether, polyisocyanate and blocking agent are selected to ensure that the obtained carbamate at least one thermally stable carbamate group, which is derived from the polyoxyethylene ether, at least one thermally labile carbamate group which is derived from the blocking agent and does not contain a free isocyanate group. This can be achieved by reacting polyisocyanate, blocking agent and polyoxyethylene ether in such amounts that the ratio of moles of blocking agent to NCO groups is less is than one and the number of NCO groups is equal to or less than the sum of the hydroxyl groups and the moles of blocking agent is. One mole of a polyoxyethylene ether with two hydroxyl groups and two moles of a diisocyanate can therefore with two moles Blocking agents are reacted while one mole of the polyoxyethylene ether and zv / ei mole of a triisocyanate with four moles a blocking agent can be implemented.

109825/2102

20601H

The reaction is carried out under such conditions that moisture and preferably also practically oxygen is excluded in order to minimize discoloration of the carbamic acid ester obtained. Temperatures of up to 200 ^° C. can be used. The reaction is preferably carried out at 35 to 100.degree. C. when carprolactam is used as the blocking agent, and at 50 to 160.degree. C. when a phenol is used as the blocking agent. The reaction can be carried out in the absence or in the presence of a solvent which is inert towards isocyanate groups. Examples of such solvents are Cellosolve acetate, acetone, methyl ethyl ketone, cyclohexanone, chloroform, benzene, perchlorethylene, chlorobenzene and trifluoroethane «Optionally, catalysts such as aliphatic tert. Amines, alkali or alkaline earth metal oxides, carbonates, alcoholates, and phenates and metal salts of carboxylic acids can be used to facilitate the reaction. If a catalyst is used, it should be neutralized after the reaction is complete.

The polyisocyanates which can be used to prepare the carbamic acid esters according to the invention are aromatic polyisocyanates, ie isocyanates with at least two NCO groups which are bonded directly to carbon atoms of an aromatic ring. Examples of such aromatic polyisocyanates which can be used to prepare the carbamic acid esters according to the invention are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, phenylene diisocyanate, methoxyphenylene-2,4-diisocyanate, diphenylmethane ^ jV-diisocyanate, 3-methyldiphenylmethane - ¹ I, V-diisocyanate Diphenylether-2, JJ, 4 '- triisocyanate and mixtures of these compounds. The preferred isocyanate is 2,4-toluene diisocyanate.

109825/210 2

20601U

The water-soluble or easily dispersible polyoxyethylene ethers with a molecular weight of at least 6,000 and preferably at least 10,000, which contain at least one aliphatic hydroxyl group and preferably at least two aliphatic hydroxyl groups and a content of at least 90 % by weight, can be used as polyoxyethylene ethers for the preparation of the carbamic acid esters according to the invention. of oxyethylene groups, which are present as polyoxyethylene chains with a content of at least 60 oxyethylene groups. A preferred class of these polyoxyethylene ethers has a molecular weight of no more than about 100 ». 000 and has two aliphatic primary hydroxyl groups, each directly bonded to a polyoxyethylene chain with at least 60 oxyethylene groups. These polyoxyethylene ethers are known compounds and many of them are commercially available. A particularly preferred class of polyoxyethylene ethers consists of polyoxyethylene glycols with a molecular weight of at least 6,000 and the reaction products of a molar excess of a polyoxyethylene glycol with a molecular weight of at least 3,000 with an organic diisocyanate, a dicarboxylic acid, a dicarboxylic acid

ep
anhydride or an organic dioxy compound with two oxirane epoxy groups, the oxirane oxygen of which is bonded to adjacent carbon atoms and preferably to adjacent carbon atoms of a cycloaliphatic ring

The reaction of the polyoxyethylene glycol with the organic diisocyanate can be carried out under those reaction conditions which are customary for the reaction of a diisocyanate with a glycol. The reaction can be carried out, for example, by heating a mixture of the reactants to a temperature of 100 to 200 ^° C. in the presence or absence of an amine as a catalyst. The organic diisocyanate can

109825/2102

20601U

be an aromatic or an aliphatic diisocyanate. Examples such diisocyanates are hexamethylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate and methoxyphenylene diisocyanates. .

The implementation of polyoxyethylene glycol with the dicarboxylic acid or the dicaric anhydride can be carried out under customary esterification conditions. For example, a mixture from three hol glycol and two moles of acid or anhydride to one Temperature of 150 to 200 ° C can be heated until the esterification is practically complete. The reaction can be carried out in the absence or presence of an acid catalyst, e.g. Toluenesulfonic acid, or a basic catalyst, e.g. Sodium hydroxide. Examples of dicarboxylic acids and dicarboxylic anhydrides are succinic acid., Ilaleic acid, Terephthalic acid, diglycolic acid, adipic acid and their anhydrides.

The reaction of a polyoxyethylene glycol with an organic The polyoxyethylene ethers produced by the epoxy compound are described in U.S. Patents 2,990,396 and 3,182,099.

109825/2102

BATH

20601U

The following examples serve to illustrate the present invention without restricting it. if unless otherwise indicated, all parts and percentages are by weight.

example 1

188 grams of phenol was dissolved in approximately 350 ml of distilled toluene from which all of the water had been azeotropically removed. This solution was mixed with 348 g of 2,4-toluene diisocyanate, which was washed with about 114 ml of toluene in the flask

e was moved. Then the mixture was grührt and heated for 2 hours under nitrogen at reflux (100-110 ⁰ C), wherein a solution of monophenol-blocked 2,4-toluene diisocyanate was obtained in toluene. 250 grams of toluene was added to 374 grams of Carbowax 600O (polyoxyethylene glycol having a molecular weight of about 600O; from Union Carbide) and the mixture was refluxed for about 2 hours to azeotropically remove about 1 ml of water. 50 g (0.1 mol of reactants) of the above-mentioned solution of phenol-blocked 2,4-toluene diisocyanate in toluene and 100 g of dried toluene were admixed with 1.0 g of hydrogenated tallow dimethylamine in 5 g of toluene. The mixture was then heated to about 8O ⁰ C and the Carbowax and described above toluene solution was added over about 10 minutes is added through a heated funnel with Dempf. The stirred mixture was heated at about 80-82 ° C for 2 hours. The heat was then removed. The mixture was neutralized with 3 g of glacial acetic acid, diluted with 4.5 g of toluene and the toluene was distilled in vacuo, whereby 397 g of a viscous, cloudy liquid Carbowax 6000 - 2,4-toluene diisocyanate-phenolcarbamic acid ester product (1: 2: 2), the - ■ hardened after cooling to a wax-like plague, were obtained. The product is dispersible in water

109825/2102

20601U

and soluble in dioxane.

Example 2

374 g Carbowax 6OOO were added to 250 g of toluene and the mixture was heated and I ₁ S hours under reflux, 0.5 ml of water azeotropically to remove, whereby a turbid (hazy), viscous product was obtained.

This product was gradually added to a heated solution (about 8O ⁰ C) of 17.5 g of 2,4-toluene diisocyanate in 100 g of dried toluene. This mixture was heated for 2 hours at 10O ⁰ G and mixed with 11.3 g of caprolactam in 100 g of dried toluene. The mixture was stirred ^{at about 80 ° C. over power.} The toluene was added to a bath temperature (pot temperature) of 84 ⁰ C under vacuum stripped to 360 g of a turbid (hazy), viscous condensation product of Carbowax 6000 to 2.4-toluene diisocyanate - caprolactam (1: 2: 2) to obtain. The product is dispersible in water and soluble in dioxane.

Example 3

225 g Carbowax 2OM (a polyoxyethylene ether with a Molecular weight from 15,000 to 20,000 synthesized by reacting about 3 moles of Carbowax 6000 with about 2 moles of diepoxide sold by Union Carbide), 17.5 g 2,4-toluene diisocyanate and 11.3 g Ca ^ prolactam were reacted according to the method of Example 2 to to obtain an addition product of the three reactants (1: 2: 2) · Make addition of water to one Dioxane solution of the product gave a cloudy solution. A sample of the product in toluene solution, which was diluted with dioxane gave a faintly yellow, opaque (hazy) solution containing 10.5 # solids ^

109825/2102

- ίο -

12.2 ?? Toluene and 77.35? Contained dioxane.

Example 4

250 g of toluene were added to 748 g of Carbowax 6000. The mixture was ^{heated under reflux at about 120 °} C. for 2 hours in order to azeotropically remove 1 ml of water. This solution was then slowly added to 26.2 g of 2,4-toluene diisocyanate in 100 g of dried toluene over a period of 10 minutes with stirring. The temperature rose from 58 ⁰ C to 8l ° C. 1 g of hydrogenated tallow dimethylamine in 5 ml of toluene was then added. The mixture was heated for about 2 hours at about 80 ° C (under a nitrogen atmosphere). 9.4 g of ^p henol and 50 ml of dried toluene was added. The mixture was stirred at about 80 ° C. overnight. 3 g of glacial acetic acid were then added and the toluene was stripped from the mixture under reduced pressure in order to obtain about 750 g of 2: 3: 2 addition products of Carbowax 6000, toluene diisocyanate and phenol. The product is soluble in dioxane and dispersible in water.

Example "5

100 ml of toluene were admixed with 225 g of Carbowax 20M and the water present (about 0.5 ml) was removed azeotropically within one hour. The toluene was then stripped off in vacuo. 200 ml A'thylacetat were slowly added at 50 ⁰ C. Then 0.5 g of dimethyloctadecylamine and 8.93 g of the condensation product of 2,4-toluene diisocyanate and phenol (1: 1, prepared by reacting phenol with toluene diisocyanate within 2 hours at 150 ^° C.) were added. The mixture was stirred and heated at 45 ° C for about 2 hours.

10 9 8 2 5/2102

20601U

Then the catalyst was neutralized with acetic acid. The product of the plague was poured into warm water to get a slightly viscous, milky, almost white 10% solution of the 1: 2: 2 condensate product of Carbowax 2OM toluene diisocyanate - obtain phenol.

Example 6

Example 5 was repeated with the exception that three times as much of the 1: 1 - toluene diisocyanate - phenol condensation product was used. The reaction product is the 1: 6: 6 condensation product of Carbovrax 2OM - toluene diisoeyanate - phenol.

Example 7

A mixture of 200 ml. Toluene and 225 g Carbowax 20M was azeotroped to remove approximately 0.5 ml of water. The toluene distilled under vacuum ". 200 ml / ithylacetat, 17.5 g 2.1-toluene diisocyanate and 0.5 l dimethyloctadecylamine were added and the mixture was heated with stirring at about 75 ° C. for about 2 hours 3 g of caprolactam were added, the temperature was increased to 75 ^° C. and kept at this temperature for 12 hours with stirring. The product was then cooled, neutralized with glacial acetic acid and divided into three parts, which were dissolved in dioxane, isopropanol or Ganser The product is a 1: 6: 6 condensation product of Carbowax 2OM, toluene diisoeyanate and caprolactam.

Example 8

A 1: 6: 6 condensation product of Carbowax 20M, toluene diisocyanate and caprolactam was made according to the procedure of Example 7 prepared. The product was available in three equal portions divided into carbitol acetate ^

109825/2102

BADORlGlNAi.

20601H

Propylene glycol or Ansul 1m were dissolved in order to make them to use on textiles.

Example 9

A 1: 6: 6 - condensation product of Carbowax 2OM, 2, 4-toluene diisocyanate and Canrolactam was prepared according to the procedure of Example 7, except that, instead of Xthylacetat used as a reaction solvent was Cellusolveacetftt. The product was divided into three portions which were dissolved in carbitol acetate, dimethylformamide and propylene glycol.

Example 10

22? g of Carbowax 20M and 50 ml of 1,1,2-trichloroethane were azeotropically distilled to remove any water present. The trichloroethane was distilled off. l85 ml Cellusolve acetate (grade urethane) suitable for dissolving urethane and 10.4 g of caprolactam was added. The mixture was cooled to 45 ° C. with 16.1 g of 2,4-fluoro-diisocyanate added and the mixture heated at 45-48 ° C for 1 hour while stirring. The condensation product of Carbowax 2OM, toluene diisocyanate and Caprolactam was then cooled, divided into three separate portions and divided into cellulose solve acetate, dioxane and Propylene glycol dissolved.

Example 11

1125 g Carbowax 2OM, 914.8 g suitable for dissolving urethane® (urethane grade) Cellusolve acetate and 230 ml 1,1,1-Trichlorftthan were azeotropically distilled for 45 minutes collecting 250 ml of the distillate, to obtain an anhydrous solution of the product.

109825/2102

- 13 -.

Then, in a separate reaction vessel, 22.6 g of caprolactam, 52.2 g of 2,4-toluene diisocyanate and 74.8 g of Cellusolve acetate were heated for 4 hours at about 70 ° C. and the solution was cooled. 360.7 g of the above solution of Carbowax 2OM and 24.3 g of the solution of the product of toluene diisocyanate and caprolactam were mixed and heated for 3 hours with stirring under nitrogen at about 70 ⁰ C. 89 g propylene? glycol was added while heating and stirring continued. At the end of the reaction, the carbamic acid ester product was diluted with water to a concentration of 28 ?? Solids diluted.

Example 12

The method of Example 11 was modified in such a way that the final reaction solution was only ^{heated at 70 ° C. for 1 hour, then the temperature was increased to 90 °} C. for a further two-hour reaction and about 50 $ more of the toluene diisocyanate - caprolactam (1: 1) - Reaction product used to obtain a Carbowax 20M - toluene diisocyanate - caprolactam carbamic acid ester. The product contained 28% pesticides in a mixture of Collusolve acetate, propylene glycol and water.

Example 13

600 g of a polyoxyethylene glycol with an average molecular weight of about 6000 were mixed with 600 g of anhydrous toluene and 2 g of boron trifluoride-ether complex (Hj% boron trifluoride). The mixture was stirred and heated to about 60 ° C under a nitrogen atmosphere, and 20 g of 3, M-epoxy-δ-methylcyclohexylmethyl-3, ^ -epoxy-δ-methylcyclohexanecarboxylate were added. Stirring was continued at about 100 ° C for 3 hours. There were 27 g of a 1: 1 condensation product

109825/2102

20601H

of 2,4-toluene diisocyanate and phenol were added and the mixture was ^{stirred at about 100 °} C. for a further 2 hours.

Example 14

600 g (0.15 mol) of a polyoxyethylene glycol having a molecular weight of about 4,000 was refluxed with 600 ml of toluene to azeotropically remove about 1 ml of water. The anhydrous solution was admixed with 17.4 g (0.10 mol) of toluene diisocyanate and 1.0 g of dimethyloctadecylamine and the mixture was ^{heated at about 100 °} C. for 2 hours with stirring and under nitrogen. Then 27 g (0.10 mol) of a 1: 1 condensation product of 2,4-toluene diisocyanate and phenol were added and the mixture was heated at 100 ° C. for a further 2 hours.

Example 15

750 g (about 0.1 mol) of Carbowax 6000 and 6.7 g (0.067 mol) of succinic anhydride and 0.2 g of antimony trioxide were stirred under nitrogen and gradually heated to about 200.degree. The temperature was maintained until the end of the esterification at 200 ⁰ C to 210 ° C (the acid number dropped to near 0). The polyester was cooled to 100 ⁰ C and diluted with 700 ml of cellosolve acetate. Then 9.0 g (0.033 mol) of a 1: 1 2,4-toluene diisocyanate-phenol condensation product were added and the mixture was heated at about 100 ° C. for 2 hours.

According to the invention, the above-described Carbamic acid ester used to treat textiles to give them improved physical properties such as anti-pollution properties. It

109825/2102

it was found that when the carbamic acid ester up Textiles were applied and then heated the textiles have been cured to an elevated temperature, the carbamic acid esters are bound to the textiles so that the textile material bestowed, improved properties by the following Washing cannot be removed. Although the present one Invention should not be limited by theoretical considerations, it is believed that the thermal labile carbamate group of the carbamic acid ester elevated temperature decomposes to form an aromatic NCO group and form free phenol or free caprolactam 2u, and that the aromatic NGO group then with the Permanent ironing agent, the textile material and / or other NCO groups reacts to form thermally stable groups form.

The inventive carbamic acid esters can advantageously alone or in combination with a wide variety of chemical treatment agents for application can be used on textiles. The chemical treatment agents can ζ Β. Permanent ironing agents, softeners, antistatic Compounds, emulsifying agents, wetting agents and numerous other compounds that affect the physical Increase the properties of the textile material. The textiles can with the carbamic acid esters of the present Invention together with any of the aforementioned chemical treatment agents either used simultaneously or separately in each order will. A preferred application of the carbamic acid esters of the present invention is use the ester together with a permanent ironing agent. ' According to the invention, Demp-emMss is also a textile treatment mixture, which contains a permanent ironing resin and a carbamic acid ester.

109825/2102

$ AD

20601H

The amounts of permanent ironing agent and carbamic acid ester present in the textile treatment mixtures according to the invention can vary within a fairly wide range and depend mainly on the particular permanent ironing agent and the carbamic acid ester selected and on the particular textile to be treated with it. In general, the inventive textile treatment mixtures contain from about $ 50 to $ 95, preferably from about $ 55 to $ 80 (wt .- #) of the permanent ironing agent and from about 50 to about 5 wt .- ^, preferably from about 5 to 20 wt. - $ of the carbamate, based on the total weight of permanent ironing agent and carbamate.

Temporary ironing means that are used in the production of the inventive Textile treatment mixtures can be used, including both monomers and polymers, which, when they are applied to textiles and cured under the conditions customary in the art enter into a reaction with the textile material and the permanent ironing and / or crease resistance properties give the textile material.

Of the permanent ironing agents, the aminoplast resins are preferred according to the invention. These nitrogen-containing resins react, when they are applied to ^{the textile material and are heated in the presence of a catalyst at temperatures of 130 °} C. to 200 ° C., with the textile material and are chemically bonded to it. Examples of aminoplast resins which can be used according to the invention are the ethylene ureas, for example dimethylol dihydroxyethylene urea, dimethylol ethylene urea, ethylene urea of f-formaldehyde and hydroxyethylene urea formaldehyde, urea formaldehyde, for example propylene urea formaldehyde

109825/2102

20601H

and dimethylol urea formaldehyde, melamine formaldehyde e.g. tetramethylol-melamine and pentamethylol-melamine, carbamate, e.g. Alkyl carbamate formaldehydes, formaldehyde aerolein condensation products, Alkylolamides, e.g., methylolformamide and methylolcetamide, acrylamides, e.g. n-methylolacrylamide, n-methylolmethy! acrylamide and n-methylol-n-methacrylamide, Di-ureas, e.g. trimethylol-acetylene-diurea and tetramethylol acetylenic urea, Triazenes, e.g. dimethylol-n-ethyl-triazon, Urons. e.g., dimethyloluron and dihydroxydimethyloluron. Mixtures of the amino plasma resins can also be used will.

Further examples of permanent ironing agents which are useful in the preparation of textile treatment compositions according to the invention include aldehydes, e.g. Formaldehyde and α-hydroxyadipaldehyde, epoxides, for example, ethylene glycol diglycidyl ether and vinylcyclohexene dioxide, xthyleneimine derivatives, for example bis-aziridinylcarbonyl and tris (l-aziridinyl) phosphine oxide, chlorohydrin, sulfone derivatives, for example divinyl sulfone and dihydroxyethyl sulfone, e.g. -tris (betasulfatoethyl) sulfonium salt.

The following examples illustrate the toxicity treatment mixtures according to the invention which contain a permanent ironing agent and a carbamic acid ester. Of course, further textile treatment mixtures according to the invention can be prepared in which other permanent gel agents and carbamic acid esters of the type described above are used in the following examples. The following examples serve to illustrate the invention without restricting it. Each item relating to the weight,

109825/2102

Example l6

Carbamate of Example 3
Dimethylol dihydroxyethylene urea

Example 17

Carbamate of the example

Dime thy lol - dihydroxy-äthyl'enharnst off

Example l8

Carbamate of the example

i, 3-Di: methylol-hexahydro-pyrimidinone-2

Example 19

Carbamate of the example

Dirnethylol methoxy ethyl caramate

Example 20

Carbamate of Example 3
Carbamate of Example 4
Diethylol-5-hydroxypropylene urea

Doiopiol 21

Part 36

20 80

50 50

5 95

90

Carbamate of Example 6 25

Dinatriun-trisfbetasulfatoathyl) sulfonium- ",. sal ?, (inner salt)

Example 22

Carbamates of the example ld.methyl-hexahydropyrimidinone-2

Β :; j game 23

(Io3 example] ο

109825/2102

60 "50

BATH ORIGINAL

Parts

Dimethylol dihydroxyethylene urea 35 Dimethylol -5,5-dimethy! -Propylene urea 35

. According to the present invention, the above described, a permanent iron and a carbamic acid ester containing textile treatment mixtures for the treatment of textiles used to make them physical properties, such as permanent ironing properties, Crinkle resistance, tear and tensile strength, vulnerability (hr.nd), abrasion resistance, dirt-repellent Eiron3ehole and anti-redeposition properties r: ur, borrow. It has been found that when ^ he

Toxic Treatment Mixtures on the

en
Textile material is applied / and the treated text !! material is heated to an elevated temperature. the ironing agents and the carbamic acid ester Tw: -r><Tir; ren, so that the improved properties that have been given to the textile material are not removed by subsequent washing.

⁷ Vr- Toxtilharzkatalysator for the permanent ironing agent can be .icder of the acid or latently acidic catalysts, -! • rich: in the technology usually used to facilitate the reaction of the permanent ironing agent with the textiles. The expression "latently acidic catalyst" is understood to mean a substance which develops acidity during the hardening stage. Particularly r-eeir.nete catalysts include metal salts of strong acids, for example magnesium chloride, magnesium sulfate, zinc nitrate and / \ luminiurasulfat, ammonium salts, for example ammonium chloride, ammonium dihydrogen phosphate and ammonium thiocyanate, amine salts, for example triethylamine hydrochloride and triethanolamine hydrochloride.

109825/2102

BATH

The amount of curing catalyst used for the permanent ironing agent depends on the nature of the permanent ironing agent, the catalyst, and the curing temperature and curing time. In general, when using about 1 to 50 wt .- ¹ ? , preferably from about 10 to about 35 weight percent of the catalyst based on the weight of the permanent ironing agent, will give adequate results. The amount of catalyst to be used is that which is commonly used to activate the reaction between permanent ironing resins and active hydrogen atoms present in the textiles to be treated with them. The textile treatment mixtures according to the invention can be applied to the textiles from an aqueous medium, an organic solvent or an emulsion of water and organic solvent. Examples of organic solvents that can be used include isopropanol, 1,1,1-trichloroethane, 1,1,2-trichloroethane, perchlorethylene, carbon tetrachloride, chloroform, pentachloroethane and a dichlorobenzene. Examples of surfactants that can be used to emulsify the carbamic acid ester in organic solvents include polyoxyethylene (25) castor-51, isopropylamine dodecylbenzenesulfonate, quaternary diethyl sulfate of polyoxyethylene (20) hydrogenated tallowamine, and polyoxyethylene (10) nonyphenol.

The textile materials can with the bath containing the textile treatment agents of the present invention, treated by any suitable method, e.g. immersion or spraying. at the dipping method, the textiles can either run through a padding machine, whereby the textiles are immersed in the bath first

109825/2102

20601H

and then be squeezed or the textiles can immersed in the bath and the excess liquid centrifuged off. When using the spray method the textiles simply sprayed with the bath liquid and dried using a suitable method. Of the Carbamic acid ester j the permanent ironing agent and the textile resin catalyst can be applied simultaneously or from separate baths.

The amount of carbamic acid ester applied to the textiles can vary from about 0.1 to about 10% by weight , preferably from about 0.5 to about 5% by weight, based on the dry weight of the textiles.

It is necessary to subject the textiles containing the carbamic acid ester to an elevated temperature in order to initiate the curing reaction between the carbamic acid ester and the textile. The special, used. The temperature and the duration of the heating stage will depend on the nature of the textiles used and the particular carbamic acid ester used. In any case, however, such a temperature and heating time is necessary that causes a sufficient reaction of the carbamic acid ester with the textiles, generally the heat curing is carried out at temperatures of about 37.8 C to 177 0, and at a low temperature for periods of time from about ΊΟ to about 60 minutes, and at the higher temperature in periods of from about 0.5 to 10 minutes. the preferred temperature is from about 1'I9 to 1.7 7 ⁰ C. '

The textiles made with the textile treatment mixtures according to the invention can be treated, include all textiles that are usually used in technology with permanent and / or anti-pollution agents

109825/2102

20601U

e.g. textiles made of cellulose or modified cellulose, such as cotton, rayon, linen and their mixtures, are composed, textiles that contain non-cellulosic substances such as polyester, nylon, Acrylic fibers and their mixtures, textiles made from a mixture of cellulosic and non-cellulosic substances Substances are composed. The textiles can be in the form of threads, fibers, and yarns In the form of threads or as woven, non-woven, knitted or otherwise manufactured fabrics, Sheets or fabrics are present. The preferred textiles are polyester fabrics and cotton / polyester blends. The following examples explain the application of the textile treatment agents according to the invention to textiles, without thereby limiting the invention. Unless otherwise stated, all parts and percentages are based on weight.

The following procedures and abbreviations are used in the examples below; The redeposition of dirt is determined against untreated fabric. About 16 ml of a standard dirt mix, the 38% moss, 17 ?! Corson's Home -

a
Crete (sand mixture) , 11% Kolin clay (Peerless clay No. 2), 11% silica (20n mesh), 1.7595 Molacco lamp soot, 0.5 ?! containing red iron oxide M-1860 and 8.75 ^ nujol, were diluted to one liter with hot tap water. 1 ^, 24 χ 115.24 cm wide test samples of the above treated fabrics were immersed in 2Π0 ml of the soil solution, "moves the tissue in the soil solution at about 6O ⁰ C 5Π minutes along with control samples (duplicate) in l- $ icer Detcrgonslösung, the samples removed, rinsed vigorously in cold tap water, dried at about 71 ° C in or automatic standard tissue drying device and the contaminated samples against the

109825/2102

8AD LOCAL

20601U

Control samples assessed. After washing in tide and The samples were assessed with hot water:

ROS - Excessive * retained oil and solid dirt

S - retained solid dirt. SS - little retained solid dirt NR- no retention of oil or dirt.

never removed ?; the soil on the treated fabrics was determined by the Deerin® Milliken Research Corporation stain removal method. Four drops of the Gulf transmission liquid are dropped onto a glass surface. After 15 seconds, a sample of the test fabric was placed on the oil. A sheet of polyethylene was placed over the test fabric, a standard weight of 3j63 kg was placed on the polyethylene over the oil drop, the weight, the polyethylene, and the fabric were removed after 30 seconds, the test fabric was placed between two paper towels, the weight applied for 30 seconds, the test fabric washed once and visually assessed for soil removal against a photographic standard. Soil removal ratings range from 5 ₃ ^ "no soil retained" to 1 °, "no soil removed". The following laboratory wash procedure was used for all washes. The samples and at least 1.36 kg of 226.8 g heavy fabric in pieces measuring -91.4 x 91 »^ cm in size were placed in a standard automatic washing machine, mixed with about 46 g of the Tide detergent, about ^ 9 Run in C hot water and wash the samples in a 12-minute wash cycle.

109825/2102

BATH

After the required number of wash cycles, the samples and fabric were about 45 minutes at about 71 ° C and dried with a Iron (hand'.iron) ironed. Ironing has been omitted if the samples are treated with a durable press finish in addition to the carbamate xvurden.

In Examples 24 to 27, textile treatment baths which had the specified compositions were applied to 100% polyester fabric with a moisture absorption of SCi% according to Butterworth. The treated fabrics were ^{dried at 100 °} C. for 3 minutes. Samples of each treated fabrics were cured for 3 minutes at 121 ⁰ C, 12 minutes at 163 ° C and 10 minutes at 204 ⁰ C and conditioniert before testing at room temperature overnight. The results are shown in Table I.

109825/2102

206011

Tabel 163 ° EOS I. Assessment of the dirt Dirt removal EOS rejection storage EOS S. 121 ° C 163 ° C 20iJ ⁰ C Example bathroom 121 ° C SS S. No. S. S. 4 3 3 Inconvenient
trade-
te
Gexiebe - EOS SS 5 5 ^ 24 (1) SS SS 4 5 4 25 (2) SS 5 5 4 26 (3) SS i, n i, 27 (4) SS

(1) 1.35 parts of the carbamate from Example 1 and 98.65 parts

Water.

(2) 1.35 parts of the carbainate from Example 2, 0.07 part of dimethyl stearylamine acetate and 98.58 parts of water.

(3) 12.86 parts of the carbamate solution of Example 3, 0.07 part Dimethyl stearylamine acetate, 3.21 parts isopropanol and 83.86 Part V / ater.

.1.35 parts of the carbainate of Example 1 and 98.65 parts Water.

109825/2102

20601U

In Examples 28 and 29, textile treatment baths with the specified compositions are applied to fabrics made from 65 parts of polyester and 35 parts of cotton, with a moisture absorption of 80 % according to Butterworth (80 % wet pickup on the Butterwovth pad) being achieved. The treated fabrics are ^{dried at 100 °} C. for three minutes and cured at 163 ^° C. for 10 minutes. The test results are shown in Table II.

bath Table II Dirt repellent P; 3isp. Schmut two-way storage Con (1) 2 trolls (2) EOS 1" 23 (3) S. 3 29 S.

ί!) 10.8 parts of dihydroxydimethylol ethylene urea, 1.35 "Tjüc zinc nitrate hexahydrate and 87.85 parts of water.

(2) 9.53 parts of the product of Example 3 (1 part carbamate), 5 parts zinc nitrate xahydrate and 85.47 parts Wp.soer.

(3) 1 part of the carbamate from Example 4, 10.8 parts of dihydroxy climethjiol-ethyleneurea, 1 * 35 parts zinc nitrate hexahydrate and 86.85 parts of water.

109825/2102

20601H

In Examples 30, 31, 32 and 33, textile treatment baths with a content of 20 parts of a ¹ 15 $ aqueous solution of dihydroxy-dimethylol-ethylene urea, 1.5 parts of a 65 * aqueous solution of magnesium dichloride hexahydrate, the specified collected amounts of carbamate, and the balance water and applied to tissue of 65 parts polyester and 35 parts of cotton, wherein "is obtained Peuchtaufnahme of 70% by Butterworth. The treated fabric for 3 minutes at 107 ° C to be dried and for 10 minutes at 163 ⁰ C. Half of the treated fabrics are washed 5 times in hot water with a detergent. Before the test, all fabrics are conditioned overnight at a relative humidity of 6-5 % and a temperature of 22.2 ° C. In each case before After the washing processes and after the 5 washing processes, the fabrics are immersed in the soil solution, and the soil-repellent effect is assessed after each immersion in the soil solution Search results are shown in Table III ".

Table III
Dirt recovery Dirt repellent

Ex.
Mr. Carb amat O washes 5 washes 0 washes 5 washes Contr. (D EOS EOS 1 1 Contr. (2) EOS EOS 1 1 30th (3) NO SS 3 3.5 31 W. NO S. 2.5 3 32 (5) NO SS 3 3 33 (6) NO NO U

109825/2102

20601U

(1) Untreated fabric.

(2) Tissue treated with a bath containing 9 parts of dihydroxydimethylol ethylene urea, 1 part magnesium dichloride hexahydrate and contains 90 parts of water.

(3) 50 parts of a 10 # aqueous solution of the carbamate of Example 5.

™ (i |) 18 parts of a 28% solution of the carbamate from example 6 in dioxane and ethyl acetate.

(5) 18 parts of a 28 # solution of the carbamate from Example

6 in water and ethyl acetate.

(6) 14 parts of a 32.7% solution of the carbamate of Example

7 in ethyl acetate and isopropanol.

In Examples 34 and 35, textile treatment baths of the specified compositions are applied to fabric made of 100 % polyester, with an 80% moisture absorption according to Butterworth being achieved. The treated fabric samples are cured dried for 3 minutes at 107 ⁰ C and 30 seconds at 19O ⁰ C. Half of the samples are washed 10 times in hot water with tide. All samples are conditioned overnight prior to the experiments. The test results are compiled in table tV.

109825/2102

20601H

Table IV

Dirt redeposition Dirt repellency

E.g. bath O washes 5-10 washes 0 washes 10 washes

Untreated

deites

Fabric - EOS EOS

3 * f (D NR NR
35 (2) NO NO

(1) 5 parts of a 28 # solution of the carbamate from Example 9 in ceilosolve acetate and propylene glycol + 95 parts of water.

(2) 5 parts of a 28 I solution of the carbamate from Example 8 in ethyl acetate and propylene glycol + 95 parts of water.

In Examples 3 ^ and 37 textile treatment baths with a content of 20 parts of an aqueous solution of dihydroxydimethylol-ethylene urea, 5 parts of a 65-5 aqueous solution of magnesium chloride ^ · hexahydrate, 18 parts of the specified carbamate solution and 57 parts of water are used on fabric from 65 Parts of polyester and 35 parts of cotton applied »whereby a moisture absorption of 70 % according to Butterworth is achieved. The treated fabrics are ^{dried at 107 °} C. for 3 minutes and cured at 163 ^° C. for 10 minutes. Half of the treated fabrics are washed 10 times in hot water with detergent. All tissues are kept at a relative overnight before the experiments

109826/2102

20601H

Humidity of 65% and a temperature of 22.2 ° C conditioned Tissues are respectively before washing and after 10 washing Vorgangen in a soil releasing _s immersed and after each immersion, the soil-repellent effect will be evaluated. The test results are summarized in Table V.

Carbamate
solution Tabel V 10 washes Dirt deflection 10 washes (D Schmut zitf iederab lage
tion SS 0 washes 2 Ex.
No. (2) 0 washes EOS 3 2 Contr. (3) SS SS 2 3 Contr. EOS SS i », η 36 NO Ί. 37 NO , 5 , 5

(1) Untreated fabric.

50 tfis

(2) Tissue treated with a bath containing 20 parts of a ^ aqueous

Solution of dihydroxydimethylol ethylene urea, 5 parts of a 65) iigen aqueous solution of magnesium chloride hexahydrate and Contains parts of water.

(3) 28 # solution of the carbamate from Example 9 dissolved in Cellosolve acetate and propylene glycol.

( ² J) 28 liquid solution of the carbamate from Example 8 dissolved in ethyl acetate and propylene glycol.

109825/2 102

■■■ ■ ■ ·; ■ ---- - BS

- 31 -

η Eeispiel 38 is made a textile treatment bath, the parts Λ5 _s contains the carbamates of Example 10, 1.05 parts Cellosolvecotat 2.5 parts of propylene glycol and 95 parts water.

■ he bath is applied to a fabric made of 100 % polyester up to an absorption of 80 % . The treated Gewebeprober, dried 3 minutes at 107 ⁰ C and cured for 30 seconds ooi 190 ⁰ C. The adherence of the samples is washed 5 times in hot water with tide. All samples x * are conditioned overnight before the experiments. The test results are shown in Table VI.

Table VI Dirt repellent 1.5 Dirt redeposition 0 washes 5 washes 3.5 Bor.sp. 0 washes 5 vials Untreated 1; c it tissue EOS EOS H. ?8th NO NO , 7 , 0

In Example 39, a textile treatment is ethyleneurea-Dihydroxydimethylol with a content of 9 parts, 3.2 parts liiCneRiumchloridThexahydrat, 5.8 parts of the carbamates of Beirpiel 10, 4.2 parts of cellosolve acetate, 10 parts of propylene glycol ■ cn * 67.8 parts water to a fabric made of 65 parts polyester and 35 parts cotton applied to a moisture absorption of 75%. The treated fabrics are dried cured 3 minutes at 107 ° C and 10 minutes at 163 ⁰ C. Half of the loading

109825/2102

20601H

Treated fabric is washed 5 times in hot water with detergent. All the treated tissue are conditioned overnight at a relative humidity of 65% and a temperature of 22.2 ⁰ C, before being subjected to the tests. In each case before the washing and after the 5 washing processes, the fabrics are immersed in dirt solutions, and the dirt repellency is assessed after each immersion. The test results are compiled in Table VII.

Table VII

Dirt _{redeposition dirt repellency}

Ex.
No. (D 0 washes 5 washes 0 washes 5 washing Contr. (2) EOS EOS 2.0 1.5 Contr. EOS EOS 1.5 1.3 39 SS NO 3.5 3.3

(1) Untreated fabric.

(2) Tissue treated with a bath containing 9 parts of dihydroxydimethylol-ethylene urea, 3.2 parts magnesium chloride hexahydrate, 4.2 parts cellosolve acetate, 10 parts propylene glycol and 73.6 parts Contains parts of water.

In Examples 40 and 4l testil treatment baths are used

109825/2102

20601 H.

a content of 20 parts of a 45 # aqueous solution of dihydroxydimethylol ethylene urea, 3.3 parts of magnesium chloride hexahydrate, 20 parts of the specified carbamate solution and the remainder water on fabric made of 50 parts polyester and 50 parts cotton up to a moisture absorption of 70 % applied. The treated fabrics are dried cured 3 minutes at 107 ⁰ C and 10 minutes at l63 ° C. Half of the treated fabrics are washed 5 times with hot water and detergent. Before the tests, all fabrics are conditioned overnight at a relative humidity of 65 % and a temperature of 22.2 ° C. Before each wash and after the 5 washing processes, the fabrics are immersed in soil solutions, and the soil repellency is assessed after each immersion. The test results are shown in Table VIII.

Carbainate
solution Tabel VIII 5 washes Dirt repellent 5 washes (D Dirt repositioning
tion NO 0 washes 2.3 Ex.
No. (2) 0 washes EOS • 2.0 2.3 Contr. (3) S. SS 1.0 3.5 Control (4) EOS SS 3.5 1.8 40 SS 3.0 41 SS

(1) Untreated a fabric.

109825/2102

20601U

- 31 »-

(2) Tissue treated with a bath containing 20 parts of a 45 # aqueous solution * dihydroxydimethylol-ethylene urea, 3.3 parts Magnesium chloride hexahydrate and the remainder to 100 parts v / water contains.

(3) Carbamate solution from Example 11.
(H) Carbamate solution from Example 12.

109825/2102

Claims (1)

20601U Patent claims: \ l) Carbamic acid esters which are suitable as textile auxiliaries, characterized in that they contain a thermally labile carbamate group and a thermally stable carbamate group and are made from the reaction product of a) an organic aromatic polyisocyanate, b) caprolactan, a phenol or a mixture of these both compounds as a thermally reversible blocking agent, and c) a polyoxyethylene ether with a molecular weight of at least 6,000, at least one aliphatic hydroxyl group and a content of at least 90 percent by weight of oxyethylene groups, which are present as polyoxy, ethylene chains with a content of at least βθ oxyethylene groups. 2. carbamic acid ester according to claim 1, characterized in that that the polyoxyethylene ether (c) at least Contains 2 aliphatic hydroxyl groups. 3 · Carbamic acid ester according to one of claims 1 or 2, characterized characterized in that the polyoxyethylene ether (c) is a polyoxyethylene glycol having a molecular weight of at least C,000. k. Carbamic acid ester according to one of Claims 1 to 3, characterized in that the polyoxyethylene ether (c) is obtained from the reaction product of a diisocyanate with a molar excess of a polyoxyethylene glycol with a molecular weight of n.indc at least 3,000 exists. 109825/2102 20601H 5. carbamic acid ester according to any one of claims 1 to 3, characterized characterized j that the polyoxyethylene ether (c) from the Reaction product of a dicarboxylic acid or a dicarboxylic acid anhydride with a molar excess of a polyethylene glycol with a molecular weight of at least 3,000. 6. carbamic acid ester according to any one of claims 1 to 3 »characterized characterized in that the polyoxyethylene ether (c) from the iteaction product of an organic diepoxy compound with two O:; iran-epoxy groups whose oxirane-oxygen is attached to neighboring Carbon atoms is bonded with a molar excess > ines polyethylene glycol with a molecular weight of mindüdbons 3,000 exists. 7. Carbamic acid ester according to one of claims 1 to 6, characterized in that the proportions of organic polyisocyanate, blocking agent and aliphatic polyether r, o are set, that the ratio of the moles of blocking agent zv. NCO groups is less than 1 and the number of NCO groups is not greater than the sum of the hydroxyl groups and the blocking agent. For: Atlas Chemical Industries, Inc. Lawyer 109825/210 2