CH416472A - Method for mounting part of a watch case on the body thereof and tools for implementing this method - Google Patents

Description

  

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 It is known to refine cellulose-containing fiber materials with aminoplasts. Cellulose-based textiles are often treated with such products to make the material resistant to shrinkage, to give them crease resistance or to create permanent mechanical effects such as seersucker effects or wrinkles. A disadvantage here is that the tensile strength of the treated textiles is often reduced; Another disadvantage is that the treated textiles often have a harder feel.

   These disadvantages have been overcome to some extent by incorporating plasticizers such as polyethylene emulsions or adducts of ethylene oxide with phenols or amines. For many purposes, however, these agents are insufficiently effective and impair the ability of the treated textiles to absorb water.



  It has now been found that by using special esters containing mercaptan (-SH) groups in connection with certain aminoplasts, cellulose-based materials can be obtained which have improved properties, and in particular textiles can be produced which have a fuller texture have a softer grip. The textiles treated by the process according to the invention show at most only a very slight deterioration in their water absorption.



  The present invention thus relates to a method for finishing cellulosic textile materials which do not contain keratin-containing fibers, characterized in that (1) the fiber material in any order or simultaneously with an ester which contains on average at least two mercaptan groups per molecule and by reacting at least (a) one compound having at least two carboxy groups and (b) a compound containing at least two alcoholic hydroxyl groups, at least one of the compounds (a) or (b) containing one or more mercaptan groups , and (2)

   an aminoplast precondensate or a nitrogen-containing reactant, which are free of ethylenically unsaturated bonds, treated and the aminoplast precondensate or the nitrogen-containing reactant cures on the fiber. The reaction products from a) and b) are optionally reacted with (c) a compound having not more than one carboxy group or one alcoholic hydroxyl group, at least one of the compounds (a), (b) and (c) having one or more mercapto groups exhibit.



  It is assumed that the esters containing mercaptan groups used also harden on the fiber. As previously indicated, the treatment of the fibers with the aminoplast precondensate or the nitrogenous reactant and ester can be carried out in any order. Thus, the fibers can be impregnated with a mixture of the aminoplast precondensate or the nitrogen-containing reactant and the ester and the aminoplast precondensate or the nitrogen-containing reactant can then be cured.

   On the other hand, the fibers can also be impregnated first with the ester and then with the amino plastic precondensate or the nitrogen-containing reactant or vice versa and then the amino plastic precondensate or the nitrogen-containing reactant can be cured.

   Or the fibers can first be impregnated with the aminoplast precondensate or the nitrogen-containing reactant, which is then cured, after which the fibers are treated with the ester. Cellulose-containing textile materials which can be treated by the process according to the invention include those made from cotton, regenerated cellulose (including viscose and cuprammonium rayon), jute, linen, hemp, ramie and sisal fibers;

   furthermore cellulosic fiber materials in which some, but not all of the three hydroxyl groups available per anhydroglucose unit are chemically, e.g. B. modified by acylation, etherification or cyanoethylation. This includes methyl cellulose and cellulose monoacetate, but not e.g. B. cellulose triacetate. The textile materials are z. B. as woven, non-woven and knitted materials.



  According to the process according to the invention, mixtures of two or more cellulose-based fiber products or mixtures thereof can also be treated with synthetic fibers, it being understood, however, that mixtures with keratin-containing fibers are not covered by the present invention.



  Preferred esters for use in the process according to the invention are those which contain on average no more than six mercaptan groups per molecule. In general, these esters have an average molecular weight between 400 and 10,000. If desired, however, esters can also be used which have an average molecular weight of up to 20,000 and even 40,000.



  Such esters can be those products which are obtained by reacting the following products in any desired sequence: (d) a Monomercaptomonocarboxylic acid or a monohydric Monomercaptoalcohol, (e) a compound having two, but not more than two alcoholic hydroxyl groups and (f) a compound with at least three carboxy groups.



  If desired, components (e) and (f) are allowed to react to form an ester which has terminal hydroxyl or carboxyl groups, this ester then being esterified with (d).



  The esters which can be used according to the invention can also be those products obtained by esterification (g) of a monomercaptodicarboxylic acid with (h) a compound having at least two, but not more than six alcoholic hydroxyl groups and optionally (i) a dicarboxylic acid containing no mercaptan groups or an anhydride such an acid or (j) a monocarboxylic acid, preferably a monomercaptomonocarboxylic acid or (k) a monohydric alcohol, preferably a monohydric monomercaptoalcohol.



  In a corresponding manner, those esters can also be used which are obtainable by reacting the following compounds in any sequence: (d) a Monomercaptomonocarboxylic acid or a monohydric Monomercaptoalcohol, (1) a compound with at least three alcoholic hydroxyl groups per molecule and (m) a compound with two and no more than two carboxy groups per molecule.



  As known to those skilled in the art of making polyesters. Instead of the respective carboxylic acid, the carboxylic anhydride can be used and instead of an alcohol a 1,2-epoxide can be used, one epoxide group corresponding to two alcoholic hydroxyl groups.



  The esters are prepared in a manner known per se, preferably in that the reaction components in the presence of a catalyst such as a strong

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 Acid (especially an anion exchange resin, p-toluenesulfonic acid or 50% sulfuric acid) and an inert solvent such as toluene, xylene, trichlorethylene or perchlorethylene, with which the water formed during the reaction can be separated off in the form of an azeotrope.



  Products which contain at least two carboxy groups or anhydrides thereof which can be used as reaction component (a) include succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, sebacic acid, malonic acid, citric acid, tricarballylic acid, pyromellitic acid and dimerized or trimerized fatty acids and their anhydrides (if they exist) and thio malic acid HOOCCH2CH (SH) COOH,

     which is also known as mercaptosuccinic acid.



     Monomercaptomonocarboxylic acids used as component (d) generally correspond to the formula HOOC-R-SH, where R is a divalent organic radical, the stated HOOC group is directly connected to a carbon atom of the radical R and the stated -SH- Group is directly connected to the same or a different carbon atom of the radical R. These compounds preferably also correspond to the formula HOOC-C, H "SH, where r is a positive integer from 1 and up to 18 or even 24.

   Mercaptoundecylic acid, mercaptostearic acid and, in particular, thioglycolic acid and 2- and 3-mercaptopropionic acid can be used, i.e. H. Products of the formula above wherein r is 1 or 2. It is also possible to use aromatic acids containing mercaptan groups, such as o- and p-mercaptobenzoic acid.



  Monohydric Monomercaptoalcohols, which are used as component (d), generally correspond to the formula HO-R'-SH, where R 'is a divalent organic radical and the HO group and the -SH group are directly linked to carbon atoms of the radical R' are connected. They preferably also correspond to the formula HO-C, Hzt SH, where t is a positive integer from 2 to 18 and preferably 2 or 3, such as 2-mercaptoethanol, 1-mercaptopropan-2-ol and 2-mercaptopropan-1-ol . However, compounds such as 1-chloro-3-mercapto-propan-2-ol can also be used.



  Compounds which contain at least three carboxy groups, or anhydrides thereof which can be used as component (f), include citric acid, tricarbaliic acid, pyromellitic acid and trimerized linoleic acid and their anhydrides (if they exist).



  The monomercaptodicarboxylic acids (g) generally correspond to the formula
 EMI2.58
 where R ″ represents a trivalent aliphatic or alicyclic radical, the specified carboxy and mercapto groups being connected directly to a carbon atom or carbon atoms of the radical R ″. A preferred compound is thio malic acid.



  The compounds that have at least two alcoholic hydroxyl groups (b, e, h, 1) include ethylene glycol. Propylene glycol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, polyoxyethylene glycols, polyoxypropylene glycols, polyoxybutylene glycols, poly (oxy- l, l-dimethylethylene ) -glycols, polyepichlorohydrins, glycerine, 1,1,1-trimethylolethane, 1,1,1-trimethytolpropane, hexane-1,2,5-triol, hexane-1,2,6-triol,

        3-hydroxymethylpentane-2,4-diol, pentaerythritol, mannitol, sorbitol and adducts of ethylene oxide or propylene oxide with such alcohols, including mixed polyhydric polyethers. obtained by treating an active hydrogen-containing product such as ethylene glycol with e.g. B. propylene oxide and subsequent reaction of the adduct with a second alkylene oxide, e.g. B. ethylene oxide can be obtained.



     Mono-1,2-epoxides, which can be used instead of a dihydric alcohol, include: ethylene oxide, propylene oxide, butylene oxide, 1,1-dimethylethylene oxide, epichlorohydrin, glycidyl ethers of alcohols (such as n-butyl and iso-octyl glycidyl ethers) or of phenols (such as phenyl and p-tolylglycidyl ethers), N-glycidyl compounds (such as N-Gl_v- cidyl-N-methylaniline or N-glycidyl-n-butylamine)

     and glycidyl esters of carboxylic acids (such as glycidyl acetate).



  Instead of trihydric and higher-valent alcohols, monohydric monoepoxy alcohols such as glycidol or a diepoxide such as a diglycidyl ether of an alcohol or a phenol can also be used.



  The dicarboxylic acids (i) which do not have any mercapto groups generally correspond to the formula HOOC-R @ -COOH, in which R2 is a divalent aliphatic, aromatic or alicyclic radical; such acids are e.g. B. succinic acid, adipic acid, phthalic acid, hexahydro- phthalic acid, sebacic acid and malic acid and dimerized fatty acids and anhydrides of these acids. Although ethylenically unsaturated dicarboxylic acids can be used, they are not preferred acids.



  The dicarboxylic acids (m) and their anhydrides can be selected from the group of compounds which are mentioned above for (i); they can also be dicarboxylic acids (g) containing mercaptan groups and their anhydrides.



  In the production of a polymercaptan ester for use according to the invention, it is often desirable to use a monofunctional compound such as a monocarboxylic acid (j) or a monohydric alcohol (k) as the chain end link.

   Examples are aliphatic alcohols such as methanol. Ethanol. 2-Ethylhexanol, 2-Methoxy ethanol and monomethyl ether of polyoxyethylene glycols and polyoxy propylene glycols; cycloaliphatic alcohols such as cyclohexanol; aliphatic carboxylic acid such as acetic acid, 2-ethylhexanoic acid, stearic acid and oleic acid; and aromatic acids such as benzoic acid. As already indicated, it is particularly advantageous to use a compound which contains a mercapto group as the chain end link.

   Examples of these are monomercaptomonocarboxylic acids and monohydric monomercapto alcohols and in particular thioglycolic acid, 2-mercapto propionic acid, 3-mercaptopropionic acid, 2-mercaptoethanol and 2-mercaptopropan-I-ol.



  The polymercaptan esters are generally known products (see, e.g., U.S. Patents 2,456,314, 2,461,920, 2,914,585 and 3,138,573, French Patent 1,503,633 and British Patent 941,829). The mercaptan esters preferably used in the process according to the invention contain, bonded directly to carbon atoms, on average n groups of the formula 1 - [(CO) b. (O) a, X (O) .ICO (O) b, Z (O) b # CO (O) a,] - YSH 1 wherein a 'and b' are each 0 or I and are not the same, n is an integer of at least 1 and at most 6, Y and Z both represent a divalent organic radical and X a divalent one means organic radical which must contain an —SH group when n is 1.



  In detail, the average structure of the preferred esters can be represented by one of the following formulas:
 EMI2.187
 

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 EMI3.1
 and in particular by one of the formulas
 EMI3.2
 where R \ is the residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid after removal of the -COOH groups, R 'is the residue of an aliphatic, araliphatic or cycloaliphatic diol after removal of the two hydroxyl groups, R is an organic residue,

   which has at least two carbon atoms and is connected directly via carbon atoms of this radical to the specified ester chains having terminal mercaptan groups, RS is the radical of an aliphatic, cycloaliphatic or aromatic carboxylic acid containing a mercaptan group after removal of the -COOH groups, m 'is an integer of at least 1, p is an integer of at least 2 and R, R', r and t have the meanings given above.



  It goes without saying that formulas 11 to XVII represent the average structure of the esters. Other products may also be present because of incomplete esterification. Furthermore, as already indicated,

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 not all of the radicals R, R ', R2, R', R "and RS are identical to one another.



  Many of the esters described above are insoluble in water, but can be used in the form of aqueous dispersions or emulsions. However, they can also be used in organic solvents, e.g. B. lower alcohols (such as ethyl alcohol), lower ketones (such as ethyl methyl ketone), benzene or halogenated, in particular chlorinated and / or fluorinated hydrocarbons, such as the solvents used in dry cleaning carbon tetrachloride, trichlorethylene and perchlorethylene.



  The amount of ester used depends on the desired effect. For most purposes, amounts in the range 0.1 to 5 percent based on the weight of the material to be treated are suitable. In general, woven fabrics require 0.2 to 3 percent by weight of ester, while lesser amounts of 0.1 to 1.5 percent by weight are necessary for treating knitted fabrics. The feel of the treated material naturally depends on the amount of ester used. The optimal amount necessary to achieve the desired effect can be determined by simple experiments. Furthermore, the composition and structure of the fabric composed of the fibers also have an influence on the amount of ester required.



  The amino plastic precondensates or nitrogen-containing reactants used according to the invention contain at least two groups of the formula -CHZOR6 per molecule directly linked to an amide nitrogen atom, where R6 represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an acetyl group.

   Examples of such nitrogen-containing reactants are the N-hydroxymethyl, N-alkoxymethyl and N-acetoxymethyl derivatives of the following amides and amidic compounds:

   1. Cyclic ureas of the formula
 EMI4.33
 wherein Q is oxygen or sulfur and Y 'is either a group of the formula
 EMI4.34
 or represents a divalent group with 2 to 4 carbon atoms in the chain, which can be substituted with methyl, methoxy and hydroxyl groups and can be interrupted by -CO-, -O- or -NR ', where R' is a Represents alkyl or hydroxyalkyl group of up to 4 carbon atoms.



  Examples of such cyclic ureas are ethylene urea (imidazolidin-2-one), dihydroxyethylene urea (4,5-dihydroxyimidazolidin-2-one), hydantoin, urone (tetrahydrooxadiazin-4-one), 1,2-propylene urea (4-methyl) - imidazolidin-2-one), 1,3-propyleneurea (hexahydro-2H-pyrimid-2-one), hydroxypropyleneurea (5-hydroxy-hexahydro-2H-pyrimid-2-one), dimethylpropyleneurea (5,5Dimethyl- hexahydro-2H-pyrimid-2-one),

      Dimethylhydroxypropylene urea and dimethyl methoxypropylene urea (4-hydroxy- and 4-methoxy-5,5-dimethyl-hexahydro-2H-pyrimid-2-one), 5-ethyltriazin-2-one and 5- (2-hydroxyethyl) triazine 2-on.



     1I. Carbamates and dicarbamates of monohydric and dihydric aliphatic alcohols with up to 4 carbon atoms, e.g. B. methyl, ethyl, isopropyl, 2-hydroxyethyl, 2-methoxy ethyl, 2-hydroxy-n-propyl and 3-hydroxy-n-propyl carbamate and ethylene and 1,4-butylene -dicarbamate.



  111. Aminoplast precondensates are e.g. B. the corresponding compounds of urea, thiourea, melamine and other polyamino-1,3,5-triazines.



  If desired, aminoplast precondensates can be used which contain both N-hydroxymethyl and N-alkoxymethyl groups or both N-hydroxymethyl and N-acetoxymethyl groups (e.g. a hexamethylolmelamine in which 1 to 5 of the methylol groups are etherified or esterified).



  The aminoplast precondensate or the nitrogen-containing reactant is generally used as such. However, if a urea-formaldehyde or melamine-formaldehyde product is used, it can, if desired, be prepared in situ in the customary manner from a urea-formaldehyde concentrate or melamine-formaldehyde concentrate and the necessary additional amount of urea or melamine are formed.



  The aminoplast precondensates or nitrogen-containing reactants used are generally soluble in water and can be applied from aqueous solution. They can also be applied from aqueous emulsions, from solutions in dry cleaning solvents, or from solutions in mixtures of water with a suitable miscible solvent such as methanol.



  The quantitative ratio between ester and aminoplast can vary within wide limits. Thus, per mercapto (thiol) group equivalents, 2 to 50 and up to 75, but generally and preferably 5 to 40 N-methylol, N-alkoxymethyl or N-acetoxymethyl groups can be used. Equivalents of the aminoplast are used.



  It can happen that the desired effects only occur to their full extent when essentially all of the ester has hardened. At room temperatures (e.g. 20 C) this can take five to ten days or even longer. If the ester was applied before or together with the aminoplast precondensate or nitrogen-containing reactant and heat is used to accelerate the curing of the aminoplast precondensate or nitrogen-containing reactant, the ester will cure rapidly. The hardening reaction can largely be accelerated by using a catalyst.

   It is therefore generally preferred to add the catalyst to the material to be treated at the same time as the ester is applied, although it can be applied beforehand or afterwards as desired. The curing time can be controlled by selecting a suitable catalyst and the selected curing time depends on the specific application of the method according to the invention.

   The catalysts can be bases, siccatives. oxidative hardening agents. Sulfur, sulfur-containing organic compounds, salts and chelates of heavy metals or catalysts which form free radicals such as azodiisobutyronitrile, peroxides and hydroperoxides or a combination of such products. Primary or secondary amines can be used as organic bases

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 such as di-lower alkanolamines, e.g. B. mono- and diethanolamine, and polyamines, e.g.

   B. ethylene diamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine and hexamethylene diamine can be used. As inorganic bases, the water-soluble oxides and hydroxides, z. For example, use sodium hydroxide, water-soluble and strongly basic salts such as tri-sodium phosphate and ammonia.

   Suitable sulfur-containing organic compounds are compounds in which the sulfur atoms are not exclusively in the form of mercaptan groups and represent the mercaptobenzothiazoles and their derivatives, dithiocarbamates, thiuram sulfides, thioureas, disulfides, alkylxanthogen sulfides or alkylxanthates.

   Examples of siccativa are calcium, copper, iron, lead, cerium and cobalt naphthenate. Examples of usable peroxides and hydroperoxides are cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate and chlorobenzoyl peroxide.



  Further suitable products are salts of a heavy metal and an acid with an acid strength (-log pK) of less than 5 and chelates of heavy metals, including chelates, which are also salts. Heavy metal is to be understood as a metal that is described in Lange, Handbook of Chemistry, 10.

   Edition, McGraw-Hill Book Co, on pages 60-61 as heavy, i.e. H. a metal of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII, a metal of group IIIA with an atomic number of at least 13, a metal of group IVA with an atomic number of at least 32 or a metal of group VA with an atomic number of at least 51.

      This preferably means a metal from groups IB, IIB, IVB, VB, VIB, VIIB and VIII, in particular from the first row of these metals, i.e. H. Titanium, vanadium, chromium, manganese. Nickel and especially iron, cobalt and copper. Suitable salt-forming, non-drying acids are mineral acids, especially hydrochloric, hydrobromic, nitric, sulfuric, phosphoric and phosphorous acids and organic acids such as chloroacetic acid, fumaric acid, maleic acid, oxalic acid, salicylic acid and very especially citric acid.

   Suitable chelating products include compounds in which the chelating atoms are oxygen and / or sulfur, e.g. B. 1,2- and 1,3-diketones such as acetylacetone, alkylenediamines such as ethylenediamine and especially ethylenediaminetetraacetic acid.



  The amount of catalyst can vary within wide limits. In general, 0.1 to 20, preferably 1 to 10 weight percent based on the weight of the ester used is necessary, although much larger amounts can be used.



  The hardening of the ester is also facilitated by using elevated temperatures. If particularly fast results are to be achieved, temperatures in the range from 30 to 180 C are used. High humidity also accelerates the curing process in the presence of catalysts.



  The aminoplast precondensates or nitrogen-containing reactants can be cured at room temperature or, as already indicated, at elevated temperatures. The mechanism by which the ester exerts its activity in conjunction with the aminoplast precondensate or the nitrogenous reactant is not known. It is assumed that either the -SH groups of the ester react with the N-methylol groups (present as such or in situ from esterified or etherified N-methylol groups) or the -SH groups are oxidized, with molecules of the ester being oxidized by means of disulfide- Bridges are coupled.

   However, the utility of the present invention does not depend on this assumption being correct. In many cases it is desirable to include a catalyst for curing the aminoplast precondensate or the nitrogenous reactant. Useful catalysts include latently acidic components (which can be metal salts) or mixtures thereof, or certain basic substances. Ammonium salts, which are latent acids and develop their acidity in the mixture when heated, are e.g.

   B. ammonium chloride, ammonium dihydrogen phosphate, ammonium sulfate and ammonium thiocyanate. Such ammonium salts can be used in a mixture with metal salts, which bring about a similar catalytic effect.



  Amine salts can also be used, e.g. B. 2-Amino-2-methylpropanol hydrochloride. Suitable, latently acidic metal salts include zinc nitrate, zinc fluoroborate, zinc chloride, zirconium oxychloride, magnesium chloride, magnesium fluoroborate and magnesium dihydrogen orthophosphate. These catalysts are generally employed in concentrations of 0.3 to 5 percent by weight based on the weight of the resinous material of the aminoplast precondensate or the nitrogenous reactant.

   However, it is also possible to use strong acids such as hydrochloric acid and sulfuric acid, which can be used in the form of aqueous solutions (e.g. 4 to 8 N) or are dissolved in a mixture of water and a solvent which is immiscible or only partially miscible with water . Acid gases can also be used. Useful basic salts are e.g. B. sodium bicarbonate and sodium carbonate.



  Are strongly acidic catalysts used in liquid or gaseous form. it may be that heating is not necessary. In other cases it may be necessary that the treated material e.g. B. is heated to a temperature of 80 to 200 C for 30 seconds to 10 minutes and preferably to 120 to 180 C for 2 to 7 minutes.



  To impregnate the fibers, it is particularly advantageous to use an aqueous emulsion which contains (1) an ester mentioned above, (2) an emulsifier of preferably nonionic or anionic nature (e.g. a product containing polyoxyethylene chains) and ( 3) contains a protective colloid (e.g. sodium carboxymethyl cellulose, hydroxyethyl cellulose, methoxyethyl cellulose or a methyl vinyl ether-maleic anhydride copolymer in the form of an alkali or ammonium salt).



  The ester, the aminoplast precondensate or the nitrogen-containing reactant and any catalyst used are applied to the material by conventional methods. Are z. B. To treat fabrics or yarns, the products can be impregnated by allowing them to migrate through a bath or by immersing them therein. If articles of clothing or parts of articles of clothing are to be treated, it is advantageous to spray them with a solution, dispersion or suspension containing the ester, the aminoplast precondensate or the nitrogen-containing reactants and optionally the catalyst. It is even more beneficial to circulate the garments in such a solution, emulsion or suspension.



  A crease-resistant finish can be applied to cellulose-based textiles by impregnating them with the ester, an aminoplast precondensate or a nitrogen-containing reactant and a catalyst for the aminoplast precondensate or the nitrogen-containing reactant and then drying the fabric in the flat State is cured at a high temperature.

   Compared to the fabrics treated only with aminoplast, the fabrics treated by the process according to the invention are considerably softer and either have significantly improved crease resistance in the dry

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 Condition without reduction in tear strength or significantly improved tear strength without reduction in crease resistance in the dry state.



  On the other hand, cellulose-based textile fabrics with good crease resistance in the moist state can be obtained by treating the cellulose material with an aqueous solution of an aminoplast precondensate or a nitrogen-containing reactant (e.g. methylolated dihydroxyethylene urea) and with a strongly acidic catalyst (e.g.

   B. hydrochloric acid) is impregnated and then the moist fabric is kept in the flat state generally for 16 to 24 hours, then washed with water, neutralized and dried, the fabric is then with the ester (generally in an aqueous emulsion, preferably a Contains catalyst) is treated.



  The material aftertreated with the ester in this way has a much better crease resistance in the moist state and the same tear resistance compared to a fabric that has only been treated with the aminoplast.



  A permanently ironed cellulose-based garment can be produced by treating the fabric in bar form with the ester (preferably in the form of an aqueous emulsion), an aminopoast precondensate or a nitrogen-containing reactant and a catalyst for the aminoplast precondensate or the nitrogen-containing reactant the impregnated fabric is dried, the fabric treated in this way is processed into an item of clothing, folds or pleats are applied and the aminoplast precondensate or the nitrogen-containing reactant is preferably cured at an elevated temperature.

   In comparison to items of clothing that have only been treated with the aminoplast, the items of clothing treated according to the method according to the invention have a much softer feel and show a far better balance between crease resistance and tear resistance.



  Unlike other plasticizers currently used, the esters used in the process according to the invention do not adversely affect the water absorption of the treated cellulosic materials.



  The products used in the process according to the invention can be used in conjunction with dirt-repellent agents, antistatic agents; Bacteriostatics, products to prevent rotting, products to promote fire resistance and surface-active substances are used. They can also contain water repellants such as paraffin wax and optical brighteners.



  The present invention is further illustrated by the following examples. Unless otherwise stated, parts and percentages are based on weight. The esters used were prepared in the following manner. Thiol A A mixture of 26.8 g 1,1,1-trimethylolpropane, 170 g polyoxypropylene glycol with an average molecular weight of 425, 48.4 g adipic acid, 55.2 g thioglycolic acid, 3 g p-toluenesulfonic acid and 350 ml perchlorethylene was heated to boiling under reflux and nitrogen.



  25 ml of water formed during the reaction were separated off in the form of its azeotrope with perchlorethylene. The mixture was then cooled and washed with water. The organic layer was separated and the solvent evaporated, leaving 278.9 g of thiol A with a thiol content of 1.88 equiv / kg.



  Other esters listed in Table 1 below were prepared in a similar manner. except that in the production of thiol U the p-toluenesulfonic acid was replaced by 1 ml of 50% aqueous sulfuric acid.
 EMI6.51
 
<tb> Table <SEP> 1
<tb> Thiol <SEP> Components <SEP> Thiol content
<tb> starting product <SEP> molar ratio <SEP> (equiv. / kg)
<tb> B <SEP> Glycerin <SEP> 1 <SEP> 2.35
<tb> adipic acid <SEP> 4
<tb> butane-1,4-diol <SEP> 4
<tb> Thioglycolic acid <SEP> 3
<tb> C <SEP> Trimers <SEP> Acid <SEP> Empol <SEP> 1043 <SEP> 1 <SEP> 1.09
<tb> polyoxypropylene glycol,
<tb> average <SEP> mol. wt. <SEP> 425 <SEP> 3
<tb> Thioglycolic acid <SEP> 3
<tb> D <SEP> polyoxypropylenetriol,
<tb> average <SEP> mol-wt.

   <SEP> 3000 <SEP> 1 <SEP> 0.83
<tb> mercaptosuccinic acid <SEP> 3
<tb> n-pentanol <SEP> 3
<tb> E <SEP> polyoxypropylenetriol,
<tb> average <SEP> mol. wt. <SEP> 3000 <SEP> 1 <SEP> 0.62
<tb> adipic acid <SEP> 3
<tb> 2-mercaptoethanol <SEP> 3
<tb> F <SEP> polyoxypropylene glycol,
<tb> average <SEP> mol. wt.

   <SEP> 1000 <SEP> 3 <SEP> 1.15
<tb> mercaptosuccinic acid
<tb> Thiolglycolic acid <SEP> 2
<tb> G <SEP> hexane-1,2,6-triol <SEP> 1 <SEP> 0.94
<tb> Dimers <SEP> Acid <SEP> Empol <SEP> 1022 <SEP> 5
<tb> hexane-1,6-diol <SEP> 4
<tb> Thioglycolic acid <SEP> 2.5
 

 <Desc / Clms Page number 7>

 
 EMI7.1
 
<tb> Table <SEP> 1 <SEP> (continued)
<tb> Thiol <SEP> Components <SEP> Thiol content
<tb> starting product <SEP> molar ratio <SEP> (equiv. / kg)
<tb> H <SEP> Trimers <SEP> Acid <SEP> Empol <SEP> 1043 <SEP> 1 <SEP> 1.64
<tb> butane-1,4-diol <SEP> 3
<tb> Thioglycolic acid <SEP> 3
<tb> 1 <SEP> polyoxypropylenetriol,
<tb> average <SEP> mol. wt.

   <SEP> 700 <SEP> 1 <SEP> 1.78
<tb> adipic acid <SEP> 3
<tb> butane-1,4-diol <SEP> 3
<tb> Thioglycolic acid <SEP> 3
<tb> J <SEP> hexane-1,2,6-triol <SEP> 1 <SEP> 0.99
<tb> Dimers <SEP> Acid <SEP> Empol <SEP> 1022 <SEP> 2
<tb> polyoxypropylene glycol,
<tb> average <SEP> mol. wt. <SEP> 425 <SEP> 2
<tb> Thioglycolic acid <SEP> 3
<tb> K <SEP> Glycerin <SEP> 1 <SEP> 2.07
<tb> adipic acid <SEP> 2
<tb> polyoxyethylene glycol,
<tb> average <SEP> mol. wt.

   <SEP> 400 <SEP> 2
<tb> Thioglycolic acid <SEP> 3
<tb> L <SEP> 1,1,1-trimethylolpropane <SEP> 1 <SEP> 0.82
<tb> succinic acid <SEP> 4
<tb> Comerginol <SEP> 65 <SEP> 4
<tb> Thioglycolic acid <SEP> 3
<tb> M <SEP> Trimers <SEP> Acid <SEP> Emol <SEP> 1043 <SEP> 1 <SEP> 2.11
<tb> butane-1,4-diol <SEP> 3
<tb> 3-mercaptopropionic acid <SEP> 3
<tb> N <SEP> 1,1,1-trimethylolpropane <SEP> 1 <SEP> 1.95
<tb> adipic acid <SEP> 2
<tb> polyoxypropylene glycol,
<tb> average <SEP> mol. wt. <SEP> 425 <SEP> 2
<tb> 3-mercaptopropionic acid <SEP> 3
<tb> O <SEP> 1,1,1-trimethyl <SEP> olpropane <SEP> 1 <SEP> 1.63
<tb> adipic acid <SEP> 2
<tb> 2,2-Bis- (p- (2-hydroxypropoxy) -phenyl) -propane <SEP> 2
<tb> Thioglycolic acid <SEP> 3
<tb> P <SEP> Glycerin <SEP> 1 <SEP> 1.10
<tb> adipic acid <SEP> 4
<tb> polyoxypropylene glycol,
<tb> average <SEP> mol. wt.

   <SEP> 425 <SEP> 4
<tb> Thioglycolic acid <SEP> 3
<tb> Q <SEP> polyoxypropylenetriol,
<tb> average <SEP> mol. wt. <SEP> 700 <SEP> 1 <SEP> 1.36
<tb> adipic acid <SEP> 3
<tb> 2,2-Bis- (p- (2-hydroxypropoxy) -phenyl) -propane <SEP> 3
<tb> Thiolglycolic acid <SEP> 3
<tb> R <SEP> Trimers <SEP> Acid <SEP> Empol <SEP> 1043 <SEP> 1 <SEP> 0.85
<tb> polyoxyethylene glycol,
<tb> average <SEP> mol. wt. <SEP> 300 <SEP> 3
<tb> Thioglycolic acid <SEP> 3
 

 <Desc / Clms Page number 8>

 
 EMI8.1
 
<tb> Table <SEP> 1 <SEP> (continued)
<tb> Thiol <SEP> Components <SEP> Thiol content
<tb> starting product <SEP> molar ratio <SEP> (equiv. / kg)
<tb> S <SEP> polyoxypropylenetriol,
<tb> average <SEP> mol. wt.

   <SEP> 3000 <SEP> l <SEP> 0.48
<tb> succinic anhydride <SEP> 3
<tb> 2-mercaptoeth <SEP> anol <SEP> 3
<tb> T <SEP> pentaerythritol propylene oxide tetrol adduct,
<tb> average <SEP> mol. wt. <SEP> 650 <SEP> 1
<tb> Dimers <SEP> Acid <SEP> Empol <SEP> 1022 <SEP> <SEP> 4
<tb> 2-mercaptoethanol <SEP> 4
<tb> U <SEP> Glycerin <SEP> 1
<tb> Phthalic anhydride <SEP> 4
<tb> butane-1,4-diol <SEP> 4
<tb> Thioglycolic acid <SEP> 3
<tb> V <SEP> polyoxypropylene glycol,
<tb> average <SEP> mol. wt. <SEP> 1000 <SEP> 6 <SEP> 0.68
<tb> mercaptosuccinic acid <SEP> 5
<tb> W <SEP> polyoxypropylene glycol,
<tb> average <SEP> mol. wt. <SEP> 2000 <SEP> 11 <SEP> 0.40
<tb> mercaptosuccinic acid <SEP> 10
<tb> X <SEP> polyoxypropylene glycol,
<tb> average <SEP> mol. wt.

   <SEP> 425 <SEP> 1 <SEP> 1 <SEP> 1.65
<tb> mercaptosuccinic acid <SEP> 10
<tb> Y <SEP> butane-1,4-diol <SEP> 6 <SEP> 3.98
<tb> mercaptosuccinic acid <SEP> 5
<tb> Z <SEP> Comerginol65 <SEP> 2 <SEP> 1.79
<tb> mercaptosuccinic acid <SEP> 1
<tb> Thioglycolic acid <SEP> 2
<tb> A '<SEP> polyoxypropylene glycol,
<tb> average <SEP> mol. wt. <SEP> 425 <SEP> 11 <SEP> 0.93
<tb> mercaptosuccinic acid <SEP> 6
<tb> adipic acid <SEP> 4
<tb> acetic acid <SEP> 2
     Trimeric acid Empol 1043 is available from Unilever-Emery N.V., Gouda, Holland.

   It is a trimerized, unsaturated C, 8 fatty acid with an average molecular weight of about 800 and a carboxy group content of about 3.4 equiv / kg. Dimer acid Empol 1022 was obtained from the same company. It is a dimerized C, 8 unsaturated fatty acid with an average molecular weight of about 570 and a carboxy group content of about 3.4 equiv / kg.



      Comerginol 65 was obtained from the English company Bibby Chemicals Ltd-Liverpool. The product has an average molecular weight of about 700 and a hydroxyl number of 155-165. It consists essentially of diprimary alcohols which were produced by catalytic hydrogenation of the methyl ester of long-chain aromatic-aliphatic fatty acids together with small amounts of monohydric and trihydric alcohols formed as by-products.



  Emulsions of the polythiols were prepared by mixing the following ingredients at room temperature in a Silverson mixer until a uniform emulsion was obtained:
 EMI8.33
 
<tb> Thiol <SEP> 500 <SEP> g
<tb> Emulsifier <SEP> 1 <SEP> 50 <SEP> g
<tb> Sodium arboxymethyl cellulose <SEP> 5 <SEP> g
<tb> water <SEP> 445 <SEP> g.
    Emulsifier 1 is an adduct of a mixture of 1 mol of C, 6- and C, 8-aliphatic primary amines and 70 mol of ethylene oxide.



  Example 1 Samples of bleached cotton poplin (108 g / m 2) were padded in liquids 1 to 7 in such a way that 70% of the liquid was absorbed. The samples were dried in their original size in a tenter at 70 ° C. for 10 minutes and then cured by heating to 150 ° C. for 5 minutes.

   The wrinkle angle and tensile strength of the treated cloth were measured and are shown in Table 11.

 <Desc / Clms Page number 9>

 Liquid 1
 EMI9.1
 
<tb> Aminoplast precondensate <SEP> A <SEP> 60 <SEP> g
<tb> M9C12 <SEP> - <SEP> 6H20 <SEP> 18 <SEP> g.
<tb> per <SEP> liter of <SEP> water.
 Liquids 2 to 7 Liquids 2 to 7 had the same composition as liquid 1, but additionally contained 20 g of the thiols A, B, C, D, E or F in emulsion form per liter of water.



     Aminoplast precondensate A is a cocondensate of a methylated hexamethylotmelamine containing 4.5 methoxymethyl groups per molecule with N, N'-dimethylol etherealurea.



     In this and the following examples, the dry wrinkle angle of the treated samples was measured by the Monsanto method. Six samples (six folded parallel to the warp and six parallel to the weft) were used in each test and the samples were folded under a load of 2 kg for 3 minutes, after which they were left hanging on a wire for 3 minutes before the crease angle was measured. The values given in the tables are obtained by taking the average of the six values obtained by folding along the weft thread on the one hand and along the warp thread on the other hand, adding the two average values and dividing them by two.

   The tear strength was measured by the Elmendorf method in accordance with TAPPI standard T 414n-49. Three samples, each measuring 63 x 63 mm, were used and the tensile strength measured in the direction of the warp thread.

   All measurements of the crease angle and the tear strength were carried out on cloths which had been conditioned in an atmosphere with a relative humidity of 66% and a temperature of 25 ° C. for at least 8 hours.
 EMI9.26
 
<tb> Table <SEP> 11
<tb> liquid <SEP> crease angle <SEP> tensile strength <SEP> (g)
<tb> 1 <SEP> (control) <SEP> 911 <SEP> 336
<tb> 2 <SEP> 98 <SEP> 320
<tb> 3 <SEP> 99 <SEP> 352
<tb> 4 <SEP> 112 <SEP> 368
<tb> 5 <SEP> 104 <SEP> 368
<tb> 6 <SEP> 107 <SEP> 320
<tb> 7 <SEP> 104 <SEP> 400
<tb> untreated <SEP> 45 <SEP> 1040
 The addition of the thiol had no negative impact on the chlorine resistance of the tissue treated with the above fluids.



  Equivalent results were found when replacing polythiols A through F with any of polythiols G through Z and A '. Example 2 Example 1 was repeated using the following liquids: Liquid 8
 EMI9.31
 
<tb> Aminoplast precondensate <SEP> B <SEP> 100 <SEP> g
<tb> M9C12 <SEP> - <SEP> 6H20 <SEP> 18 <SEP> g
<tb> per <SEP> liter of <SEP> water.
 Liquids 9 to 12 Liquids 9 to 12 were identical to liquid 8, but contained an additional 20 g of thiols C, D, E or

   F per liter of water in emulsion form. Aminoplast precondensate B is a 75% aqueous solution of a methylated methylolmelamine which contains an average of 3 N-methoxymethyl and 2 N-hydroxymethyl groups per molecule.



  The results of these tests are shown in Table III.
 EMI9.41
 
<tb> Table <SEP> IIl
<tb> liquid <SEP> crease angle <SEP> tensile strength <SEP> (g)
<tb> 8 <SEP> (control) <SEP> 981 <SEP> 416
<tb> 9 <SEP> 110 <SEP> 384
<tb> 10 <SEP> 113 <SEP> 400
<tb> 11 <SEP> 110 <SEP> 400
<tb> 12 <SEP> 109 <SEP> 368
<tb> untreated <SEP> 45 <SEP> 1040
 The sample treated with liquid 11 had a particularly soft hand. Example 3 Samples of the cotton poplin used in Example 1 were padded with liquids 1 to 8 in such a way that the absorption was 70%. The samples were then dried for 10 minutes at 70 ° C. in a tenter, maintaining their original dimensions, and then heated at 150 ° C. for 5 minutes to harden the resin.

   Some of the cloth samples treated in this way were then padded with a solution of a thiol in perchlorethylene in such a way that 150% of the solution and 2% of the thiol were absorbed. The st) treated cloth samples were dried as described above. The resin was then allowed to cure by storing the cloth samples for one day at room temperature.

   The crease angles and tear strengths determined are shown in Table IV.
 EMI9.54
 
<tb> Table <SEP> IV
<tb> Treated <SEP> with <SEP> crease- <SEP> tear resistance
<tb> wave) <SEP> (g)
<tb> Untreated <SEP> 43 <SEP> 1016
<tb> liquid <SEP> 1 <SEP> alone <SEP> 911 <SEP> 336
<tb> liquid <SEP> 1 <SEP> + thiol <SEP> C <SEP> 1111 <SEP> 400
<tb> liquid <SEP> 1 <SEP> + thiol <SEP> D <SEP> 113 <SEP> 384
<tb> liquid <SEP> 1 <SEP> + thiol <SEP> E <SEP> 105 <SEP> 416
<tb> liquid <SEP> 1 <SEP> + thiol <SEP> F <SEP> 110 <SEP> 400
<tb> liquid <SEP> 8 <SEP> alone <SEP> 98 <SEP> 416
<tb> liquid <SEP> 8 <SEP> + thiol <SEP> D <SEP> 1111 <SEP> 448
<tb> liquid <SEP> 8 <SEP> + thiol <SEP> F <SEP> 106 <SEP> 400
 Example 4 Cotton poplin was made with a solution of a

  Thiols padded in perchlorethylene in such a way that the uptake of the solution was 150% and the uptake of thiol was 2%. The samples were then dried for 10 minutes at 70 ° C. in a tenter while retaining their original mass and then kept at room temperature for 24 hours. They were then treated with either liquid 1 or liquid 8, dried as stated above and finally cured at 150 ° C. for 5 minutes.

   The results obtained are shown in Table V.

 <Desc / Clms Page number 10>

 
 EMI10.1
 
<tb> Table <SEP> V
<tb> Treated <SEP> with <SEP> crease- <SEP> tear resistance
<tb> wave) <SEP> (g)
<tb> Untreated <SEP> 43 '<SEP> 1016
<tb> liquid <SEP> 1 <SEP> alone <SEP> 910 <SEP> 336
<tb> Thiol <SEP> A + <SEP> liquid <SEP> 1 <SEP> 106 <SEP> 384
<tb> Thiol <SEP> B + liquid <SEP> 1 <SEP> 112 <SEP> 384
<tb> Thiol <SEP> C + liquid <SEP> 1 <SEP> 108 <SEP> 368
<tb> Thiol <SEP> D <SEP> + <SEP> Liquid <SEP> 1 <SEP> 1150 <SEP> 400
<tb> Thiol <SEP> E + liquid <SEP> 1 <SEP> 112 <SEP> 368
<tb> Thiol <SEP> F + <SEP> liquid <SEP> 1 <SEP> 116 <SEP> 416
<tb> liquid <SEP> 8 <SEP> alone <SEP> 98 <SEP> 416
<tb> Thiol <SEP> A <SEP> + liquid <SEP> 8 <SEP> 112 <SEP> 352
<tb> Thiol <SEP> B <SEP> + <SEP> liquid <SEP> 8 <SEP>

  1260 <SEP> 384
<tb> Thiol <SEP> C + liquid <SEP> 8 <SEP> 1I6 <SEP> 320
<tb> Thiol <SEP> D + liquid <SEP> 8 <SEP> 116 <SEP> 384
<tb> Thiol <SEP> E <SEP> + <SEP> liquid <SEP> 8 <SEP> 114 '<SEP> 384
<tb> Thiol <SEP> F + liquid <SEP> 8 <SEP> 117 <SEP> 352
 The sample treated with thiol E and liquid 1 had a particularly soft hand.



  Example 5 Samples of a bleached viscose fabric (177 g / m2) were padded with liquids 13 to 19 in such a way that 80% of the liquid was absorbed. The samples were dried for 10 minutes at 70 ° C. in a tenter while maintaining their original dimensions and then heated to 150 ° C. for 5 minutes to harden. Table VI gives the crease angles and tear strengths of the treated samples: again.



  Liquid 13
 EMI10.9
 
<tb> aminopiast precondensate <SEP> C <SEP> 200 <SEP> g
<tb> NHQH2P04 <SEP> 12 <SEP> g
<tb> per <SEP> liter of <SEP> water.
    Aminoplast precondensate C is a 50% strength aqueous solution of a methylated urea-formaldehyde resin in which the urea: formaldehyde molar ratio was 1: 1.8. Liquids 14 to 19 Liquids 14 to 19 were identical to liquid 13 and additionally contained 20 g of thiols A, B, C. D, E or

   F per liter of water in emulsion form.
 EMI10.17
 
<tb> Table <SEP> V1
<tb> liquid <SEP> crease angle <SEP> tensile strength <SEP> (g)
<tb> Untreated <SEP> 1U1 '<SEP> 2256
<tb> 13 <SEP> 108 <SEP> 1456
<tb> 14 <SEP> 127 <SEP> 2096
<tb> 15 <SEP> 124 <SEP> 2128
<tb> 16 <SEP> 131 <SEP> 1904
<tb> 17 <SEP> 134 <SEP> 2176
<tb> 18 <SEP> 127 <SEP> 2432
<tb> 19 <SEP> 1l4 <SEP> 2224
 Example 6 Samples of the viscose cloth used in Example 5 were padded with the liquid 13 in such a way that the absorption was 80%. The samples were then dried for 10 minutes at 70.degree. C. on the stenter while maintaining their original mass, and then heated at 150.degree. C. for 5 minutes to harden the aminoplast.

   Some of the samples were then padded with a solution of the respective thiol in perchlorethylene in such a way that the thiol uptake was 2%. The samples were dried as described above. They were then left to store for 24 hours at room temperature before the crease angle and tear strength of the treated samples were determined.

   
 EMI10.29
 
<tb> Table <SEP> VII
<tb> Treated <SEP> with <SEP> crease- <SEP> tear resistance
<tb> wave) <SEP> (g)
<tb> Untreated <SEP> 1011 <SEP> 2256
<tb> liquid <SEP> 13 <SEP> 108 <SEP> 145 (,
<tb> liquid <SEP> 13 + ThiolA <SEP> 115 <SEP> 1968
<tb> liquid <SEP> 13 + Thio1B <SEP> 112 <SEP> 2576
<tb> liquid <SEP> 13 <SEP> + thiol <SEP> C <SEP> 115 <SEP> 225 (,
<tb> liquid <SEP> 13 + Thio1 <SEP> D <SEP> 116 <SEP> 2160
<tb> liquid <SEP> 13 + thiol <SEP> E <SEP> 115 <SEP> 2400
<tb> liquid <SEP> 13 + thiol <SEP> F <SEP> 1l4 <SEP> 2368
 Example 7 The viscose fabric used in Example 5 was padded with a solution of the respective thiol in perchlorethylene in such a way that 2% thiol was absorbed.

   The cloth samples were dried for 10 minutes at 70 ° C. on a tenter frame while maintaining their original dimensions and stored at room temperature for 24 hours. Some of the samples were then padded with the liquid 13 in such a way that 80% liquid was absorbed. The cloth samples treated in this way were dried as described above and the aminoplast resin was cured by heating the cloth samples to 150 ° C. for 5 minutes.

   The crease angles and the tear strengths of the fabrics are given in Table VIlI.
 EMI10.40
 
<tb> Table <SEP> VIII
<tb> Treated <SEP> with <SEP> crease- <SEP> tear resistance
<tb> angle <SEP> (g)
<tb> Untreated <SEP> IM, <SEP> 2256
<tb> liquid <SEP> 13 <SEP> alone <SEP> 108 <SEP> 145 (,

  
<tb> Thiol <SEP> A + liquid <SEP> 13 <SEP> 119 <SEP> 1984
<tb> Thiol <SEP> B <SEP> + <SEP> liquid <SEP> 13 <SEP> 122 '<SEP> 2128
<tb> Thiol <SEP> C + liquid <SEP> 13 <SEP> 12-t '<SEP> 2032
<tb> Thiol <SEP> D + liquid <SEP> 13 <SEP> 125 <SEP> 2304
<tb> Thiol <SEP> E <SEP> + <SEP> liquid <SEP> 13 <SEP> 1141 <SEP> 2384
<tb> Thiol <SEP> F + <SEP> liquid <SEP> 13 <SEP> 116 <SEP> 2192
 Example 8 Samples of the cotton poplin used in Example 1 were padded with liquids 20 to 28 in this way. that the receptacle 701 7, (, The cloth samples were then dried for 10 minutes at 60 ° C. on the tenter while maintaining their original dimensions. They were then cured by being heated at 155 ° C. for 5 minutes.

   The crease angles and the tear strengths of the cloth samples treated in this way were measured. The handle of the treated cloth was determined by a committee and the absorption properties were determined according to test method 39-1952 of the American Association of Textile Chemists and Colorists. The results are given in Table IX.

   The treated materials were washed in a solution containing 2 g / 1 soap and 0.8 g / 1 anhydrous sodium carbonate in an English Electric Reversomatic washing machine on program 5, 10 minutes in a Parnall Tumble Dier -dry-

 <Desc / Clms Page number 11>

    drum dried at full heat and then the crease angles and tear strengths measured.



  Liquid 20
 EMI11.3
 
<tb> Nitrogen-containing <SEP> reactant <SEP> D <SEP> 120 <SEP> g
<tb> M9C12 <SEP> - <SEP> 6H20 <SEP> 20 <SEP> g
<tb> per <SEP> liter of <SEP> water.
 Liquids 21 to 26 The liquids 21 to 26 corresponded to the liquid 20, except that they additionally contained 20 g of the thiol A, B, C, D, E or F per liter of water in emulsion form. Liquids 27 and 28 Liquids 27 and 28 corresponded to liquid 20, but additionally contained 20 g of a polyethylene glycol with a molecular weight of 1500 and 20 g of a commercially available cationic softener with 25% solids content per liter of water.



  Nitrogen-containing reactant D is a 45% aqueous solution of N, N'-dimethylol-4,5-dihydroxyethylene urea.
 EMI11.13
 
<tb> Table <SEP> IX
<tb> liquid <SEP> wrinkle angle <SEP> tear resistance <SEP> handle <SEP> water
<tb> C) <SEP> (g) <SEP> absorption
<tb> unwashed <SEP> washed <SEP> unwashed <SEP> washed <SEP> (sec.)
<tb> 20 <SEP> 107 <SEP> 105 <SEP> 156 <SEP> 156 <SEP> hard <SEP> 3.9
<tb> 21 <SEP> 111 <SEP> 102 <SEP> 164 <SEP> 156 <SEP> fairly <SEP> soft <SEP> 4.0
<tb> 22 <SEP> 114 <SEP> 103 <SEP> 172 <SEP> 160 <SEP> fairly <SEP> hard <SEP> 4.7
<tb> 23 <SEP> 127 <SEP> 117 <SEP> 172 <SEP> 240 <SEP> fairly <SEP> soft <SEP> 8.7
<tb> 24 <SEP> 122 <SEP> 112 <SEP> 220 <SEP> 200 <SEP> soft <SEP> 6.2
<tb> 25 <SEP> 12 (07 <SEP> 196 <SEP> 180 <SEP> fairly <SEP> soft <SEP> 3,

  8th
<tb> 26 <SEP> 121 <SEP> 108 <SEP> 204 <SEP> 180 <SEP> soft <SEP> 7.0
<tb> 27 <SEP> 113 <SEP> 104 <SEP> 208 <SEP> 192 <SEP> fairly <SEP> hard <SEP> 7.2
<tb> 28 <SEP> 117 <SEP> 99 <SEP> 276 <SEP> 232 <SEP> soft <SEP> 1700
<tb> untreated <SEP> 42 <SEP> 45 <SEP> 52 (1 <SEP> 364 <SEP> soft <SEP> 5,2
 Example 9 Samples of the cotton poplin used in Example 1 were padded in such a way that 70% of a solution was taken up which contained 300 g of aminoplast D and 100 ml of concentrated hydrochloric acid per liter of water. The cloth samples were placed on a roller, coated with a polyethylene film, and then kept wet for 18 hours while the roller was slowly rotating.



  The cloth samples were then rinsed with water, a solution of 5 g sodium carbonate per liter and again with water and finally dried on a tenter frame while maintaining their original dimensions.



  Some of these cloth samples were then padded with liquids 29 to 33 in such a way that 7 (1% o was absorbed. They were then dried for 10 minutes at 70 ° C., after which they were stored for 5 days at room temperature to harden. The wet and dry wrinkle angles and the tensile strength of the cotton samples treated in this way were measured and are shown in Table X.



  Liquids 29-33 Liquids 29-33 contained 20 grams of Thiol C per liter of water; Liquids 30 to 33 also contained 2 g of monoethanolamine and 2 g of sodium dimethyldithiocarbamate. 0.1 g copper sulfate or 10 g 100 vol hydrogen peroxide per liter of water.
 EMI11.29
 
<tb> Table <SEP> X
<tb> liquid <SEP> crease angle <SEP> (') <SEP> tensile strength
<tb> moist <SEP> dry <SEP> (g)
<tb> more nitrogenous
<tb> Reactant <SEP> D <SEP> (alone) <SEP> 112 <SEP> 61 <SEP> 272
<tb> 29 <SEP> 127 <SEP> 70 <SEP> 320
<tb> 30 <SEP> 126 <SEP> 70 <SEP> 312
<tb> 31 <SEP> 118 <SEP> 68 <SEP> 3 (l8
<tb> 32 <SEP> 136 <SEP> 66 <SEP> 312
<tb> 33 <SEP> 128 <SEP> 70 <SEP> 328
<tb> untreated <SEP> 59 <SEP> 48 <SEP> 560


 

Claims (1)

PATENT CLAIM A process for finishing cellulosic textile materials which do not contain any keratin-containing fibers, characterized in that (1) the fiber material in any order or at the same time with an ester which contains on average at least two mercaptan groups per molecule and by reacting at least ( a) a compound having at least two carboxy groups and (b) a compound containing at least two alcoholic hydroxyl groups, at least one of the compounds (a) or (b) containing one or more mercaptan groups, and (2) one Aminoplast precondensate or a nitrogenous reactant, which are free of ethylenically unsaturated bonds, treated and the aminopolastic precondensate or the nitrogen-containing reactants on the fiber harden. SUBClaims 1. Process according to claim, characterized in that the ester is obtained from (a), (b) and (c) a compound having not more than one carboxy group or one alcoholic hydroxyl group, at least one of the compounds a), b) or c) has one or more mercapto groups. 2. Process according to patent claim, characterized in that the ester has an average molecular weight between 400 and 10,000. 3. Process according to dependent claim 1, characterized in that the ester is obtained in that in any order (d) a Monomercaptomonocarboxylic acid or a monohydric Monomercaptoalcohol, (e) a compound with two and not more than two alcoholic hydroxyl groups per molecule and <Desc / Clms Page number 12> (f) a compound which has at least three carboxy groups per molecule is converted. 4th Process according to dependent claim 1, characterized in that the ester can be obtained by adding, in any order (g) a monomercaptodicarboxylic acid, (h) a compound with at least two and not more than six alcoholic hydroxyl groups per molecule and one of the following compounds (i) a dicarboxylic acid which does not contain a mercapto group or an anhydride of this acid or (j) a Monomercaptomonocarboxylic acid or (k) a monohydric Monomercapto alcohol. 5. Process according to dependent claim 1, characterized in that the ester can be obtained by adding, in any order (d) a monomercaptocarboxylic acid or a monohydric monomercapto alcohol, (1) a compound with at least three alcoholic hydroxyl groups per molecule and (m) a compound with two and no more than two carboxy groups per molecule are converted. 6. The method according to claim, characterized in that 0.1 to 5 wt.% Of the ester, based on the weight of the treated cellulose-based fiber material are used. 7th Process according to claim, characterized in that an aminoplast precondensate or a nitrogen-containing reactant is used which contains at least two groups of the formula -CH20R6, where R6 is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or the acetyl group and the group directly with the amide Nitrogen atom or the amide nitrogen atoms of urea, thiourea or a cyclic urea of the formula EMI12.29 where Q is oxygen or sulfur and Y 'is either a group of the formula EMI12.30 or a bivalent, 2 to 4 carbon atoms in the chain containing group, wherein the chain can be substituted by methyl, methoxy and hydroxy groups and can be interrupted by -CO-, -O- or -NR ', where R' is an alkyl or a hydroxyalkyl group with up to 4 carbon atoms, or with an amide nitrogen atom or amide nitrogen atoms of a carbamate or di-carbamate of a mono- or dihydric aliphatic alcohol with up to 4 carbon atoms or of a polyamino-1,3,5-triazine. B. The method according to claim, characterized in that 5 to 40 N-methylol, N-alkoxymethyl or N-acetoxymethyl group equivalents aminoplast precondensate per thiol group equivalent ester is used.