AT266032B - Process for modifying the properties of articles containing keratin fibers - Google Patents

Description

  

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  Process for modifying the properties of articles containing keratin fibers
The invention relates to a method for modifying the properties of articles containing keratin fibers, in particular for reducing the shrinkage of textile fabrics containing keratin fibers.



   The shrinkage with felting of articles containing keratin fibers has been a serious problem in the textile industry. Much effort has gone into research and development leading to several methods of inhibiting the shrinkage and entanglement of such structures. However, a method for inhibiting relaxation shrinkage has not yet been developed. The most widely used process to date comprises the breakdown of fiber flakes by chlorination. A similar effect is achieved by using acid and permanganate. However, these two methods have the disadvantage of a decrease in tear strength and abrasion resistance as a result of fiber degradation.

   Furthermore, fabrics treated according to this method must be weighted down in order to retain sufficient strength after degradation and thus to meet the requirements for their use. As a result of the degradation and weight loss during the treatment, more wool is required and therefore the product is more expensive.



   Attempts have also been made to avoid the degradative effects of chlorination and other oxidative processes. These attempts have led to the development of several methods, which are currently little used. One such method is the deposition of a polymeric material, e.g. B. a polymer of the polyamide type on the surface of the keratinous fibers. In this procedure, the tissue is passed through a solution of a diamine and then treated with a salt of a dibasic acid. The polyamide is created at the interface between the diamine and the salt of the dibasic acid and creates a coating on the fiber.



   While this adequately prevents shrinkage, the method has several disadvantages. First and foremost, the diamine causes migration of the dyes, thereby severely restricting the choice of dyes that can be used and the type thereof. A fabric produced according to this method also has a rough feel and can only be deformed poorly when stretched, so that the properties of the fabric are very poor. Furthermore, the relaxation shrinkage is not inhibited accordingly.



   Other polymers have also been developed to form a film on the keratinous fibers. Combinations of polyamides with epoxy resins and / or acrylates have been used. Polyesters made to provide high molecular weight flexibility have also been used with peroxidic curing agents. With these methods too, fabrics with a rough feel and poor stretching are obtained if such amounts of these modifying substances are used that the shrinkage is inhibited to a sufficient extent. Again the

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Relaxation shrinkage is not sufficiently inhibited.



   Another method for preventing the shrinkage of keratin fiber-containing structures uses isocyanates. When using isocyanates alone, one has to reflux for a long time to achieve a sufficient reaction and to make the fabric shrink-resistant, which is uneconomical. To achieve the desired shrinkage resistance, the
Large amounts of isocyanate compounds are added to fibers, which, however, make them rough and stiff
Fabric with a feel that is more reminiscent of horsehair than wool.



   The relaxation shrinkage and shrinkage with felting are not the only problems that occur in fabrics containing keratin fibers. These tissues also have a low
Degree of dimensional stability, especially when wet; z. B. The creases of woolen trousers practically disappear when wet. The same applies to the glossy finish on woolen fabrics during finishing.



   To overcome these difficulties, the tissues have been given permanent shapes through the use of various reducing agents. According to these known methods, the
Tissue impregnated with the reducing agent, whereupon some of the cystine disulfide bonds of the molecules in the keratin fibers were broken. The reduced fabrics obtained in this way could be ironed warm, usually in the presence of large amounts of moisture, and in doing so assumed shapes which essentially survived later becoming damp. These processes have been very successful, especially after being improved by adding certain compounds that make the use of greater
Avoid excessive amounts of moisture during ironing. The fabrics treated in this way were given advantageous properties.



   However, these processes are degradation processes and generally lead to a deterioration in the physical properties of tissues. Furthermore, regardless of the reducing agent used, the reduced keratin fibers have a characteristic unpleasant odor. While additives have been developed to remove this odor, these methods add cost.



   Although the known methods of fixing keratin fibers in permanent forms are practically useful, a method would be very desirable which imparts improved properties to these physical properties instead of impaired physical properties and which allows the unpleasant odor of the reduced keratin fibers to be avoided without the use of expensive additives. To an even greater extent, a process would be desirable that allows these problems to be solved and also results in a fabric that is pretreated on an industrial scale for later permanent fixation by the clothing manufacturer without the use of large amounts of water.



   The difficulties with the known methods mentioned are overcome by a method not belonging to the prior art. According to this method, a monomeric, polyfunctional compound in combination with a polyfunctional isocyanate is applied to articles containing keratin. This process is perfectly suitable for textile production. According to the invention, however, the hand of the fabric is improved by reacting the keratin fibers with a polyfunctional isocyanate or a compound containing at least two -N = C = X groups, where X is an oxygen or a sulfur atom, and a polymeric polyhydroxy compound. In order to fix the fibers in a certain shape, it is only necessary to keep the fibers in the desired shape during the reaction.



   The inventive method can be used to improve the properties of any keratin fiber-containing structures such. Woven, non-woven, knitted, dyed or undyed, can be used.



   The structures can consist entirely of wool fibers or of mixtures of such with synthetic, natural or other keratin fibers. Preferred synthetic fibers consist e.g. B. of polyamides, e.g. B. poly (hexamethylene adipamide) and polyamides derived from caprolactam; Polyesters, e.g. B. poly (ethylene terephthalate); and acrylic fibers, e.g. B. acrylonitrile homopolymers or copolymers with at least 85% bound acrylonitrile, z. B. acrylonitrile / methacrylate (85/15) and cellulose derivatives, e.g. B. cellulose acetate or viscose rayon. Cotton is preferred among the natural fibers to be mixed with the keratinous fibers. Other keratin fibers are e.g. B.

   Mohair, alpaca cashmere, vicuna, guanaco, camel hair, silk, llama, etc. similar



   The method according to the invention requires the use of relatively small amounts of substance to achieve the necessary stabilization and / or fixability. The method of application is simple: the keratin fibers are impregnated by any conventional method, e.g. B. by padding, dipping, spraying od. Similar. Procedure, and subsequently the components on

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 the fibers dried and hardened. These stages can be carried out in tandem systems available in textile factories.



   The modified products prepared according to the invention are not only superior in almost every respect to those treated by known processes, but also superior to the same fabrics before the treatment. No degradation of the wool fiber occurs in the process according to the invention. On the contrary, there will be improvements in strength and abrasion resistance over untreated control fabrics.
 EMI3.1
 After the reaction with the systems according to the invention, dyes appear much more easily and to a greater extent, so that less dye is required for a certain color shade.

   For example, after the inventive treatment of the keratin fibers, up to 20% less dye is required to achieve the same shade if the keratin fibers are dyed with pre-metallized and acidic milled dyes, as they are usually used for dyeing keratin fibers, especially wool.



   A particular advantage of the method according to the invention is that there is practically no relaxation shrinkage of the tissue. This is very desirable because it makes it unnecessary to let the fabric jump in before cutting into clothes, as is necessary with the known methods; this saves labor and material, since there is always a loss in the length of the fabric when the fabric is relaxed before cutting.



   The process also enables the production of clothes of lighter weight that can be washed under matting without shrinking. This was not possible with the known procedures. This saves on wool and, moreover, it is often very desirable to use lighter fabrics to make more comfortable clothing.



   Fabrics treated by the process according to the invention can be given any desired feel and / or any desired stretching, depending on the desired use. This can be achieved by matching the structure of the tissue with the amount of compounds absorbed for its treatment. Although lightweight fabrics can be made with a high degree of stretch and a soft, comfortable feel, the increased elasticity of the fabrics treated according to the invention gives them a more compact feel, while untreated lightweight fabrics of the same construction feel weak and not compact.

   According to one embodiment of the process according to the invention, a precondensate is produced from the polyfunctional isocyanate and the polymeric polyhydroxy compound, and the precondensate is applied to the counterparts containing keratin fibers.
 EMI3.2
 To understand meren polyhydroxy compound that is formed when the reaction is terminated before a gel insoluble in organic solvents, especially in chlorinated hydrocarbons, is formed.



   At least equimolar amounts of the polyfunctional isocyanate and the polymeric polyhydroxy compound are used to prepare the precondensate, but a small molar excess is preferably used. In general, a molar excess of about 1.0 to 1.1 —N = C = X groups of the polyfunctional isocyanate over the total —OH groups is present.



   A small amount of water is preferably present in the preparation of the precondensate.



   The amount of water added is less than that required to gel the precondensate. Generally, no more than about 0.5 percent water, based on the weight of the polymeric polyhydroxy compound, is required to achieve the desired effect.



   An additional amount of polyfunctional isocyanate is preferably added to the precondensate after the condensation. This additional. Isoeyanate increases the stability of the precondensate, reacts with the permissible water in the wool and thereby intensifies the reaction of the precondensate with the keratin fibers. However, it has been found that the shrinkage by the precondensates can also be prevented if an excess of active hydrogen atoms is present from water supplied from outside, water in the articles containing keratin fibers or from added reactants.



  For example, a molar ratio of "N = C = X groups to total active hydrogen atoms of about 0.6 already produces a certain inhibition of shrinkage in the case of articles containing keratin fibers or enables such fibers to be fixed. Indeed, molar ratios of ' * N = C = X '"to total active hydrogen atoms below about 1 improvements are achieved, but then significantly more precondensate is required in order to achieve sufficiently low shrinkage values or sufficient fixability. However, if this ratio exceeds 1, then

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 smaller amounts, e.g. B. only a few percent (2 to 5%, depending on the fabric), of precondensate required to achieve a low shrinkage desired by the consumer.



   In another embodiment of the process according to the invention, the polyfunctional
Isocyanate and the polymeric polyhydroxy compound, preferably together with one of the known ones
Catalysts for the reaction of active hydrogen atoms with isocyanates from their solution in a non-reactive solvent are applied directly to the structures containing keratin fibers, d. H. without first producing a precondensate. By avoiding the production of a pre-condensate, the costs and the monitoring tasks during the production of the same are saved.



   A certain improvement is already observed if the polyfunctional isocyanate, the polymeric polyhydroxy compound, optionally a further reactant and the catalyst are used in a molar ratio of = C = X groups to total active hydrogen atoms of at least about 0.4, especially higher than 0.5 is used. However, the best results will be at higher
Molar ratios of e.g. B. over higher than 1 or 1, 1 achieved. Technically, as in the case of the use of the precondensate according to the invention, an inhibition of shrinkage is also achieved here with fewer reactants if higher molar ratios of = C = X groups to the total active
Used hydrogen atoms.



   The polyfunctional isocyanate and the polymeric polyhydroxy compound, with or without a further reactant, are preferably reacted with the keratin fibers of the structure in the presence of a catalyst. Any of the known catalysts for reacting active hydrogen atoms with isocyanates can be used.



   The reaction between the isocyanate and the polymeric hydroxy compound or the precondensates thereof on the one hand and the keratin fibers on the other hand is significantly intensified if it is carried out in the presence of a reactant with at least two groups that contain at least one active hydrogen atom that can be determined by the Zerewitinoff process . (Zerewitinoff, Ber., 40, 2023 [1907]; Ber., 41, 2236, [1908J: Kohler, J. Am. Chem. Soc., 49, 3181 [1927]. These compounds contain at least two groups or combinations thereof , e.g. -OH, "NH.", - NRH -, COOH -, - SH groups, or groups which react similarly under the reaction conditions.



   In most cases, the system of isocyanate and the polymeric polyhydroxy compound, as such or in the form of a precondensate and optionally a further reactant with at least two active hydrogen atoms can be applied to the fabric or structure from a single solution. In some cases, however, when the further reactant is very reactive with the remaining - N = C = X groups, e.g. B. if certain amines are used as a further reactant, this reactant is preferably applied separately to the tissue or structure. This is achieved by padding the fibers with the amine, preferably drying them, and then allowing the system of isocyanate and polymeric hydroxyl compound to act on the fibers, or vice versa.

   When selecting an organic solvent for preparing solutions for the application of the above compounds, a non-reactive solvent should be selected.



     A solvent in which a reaction between the isocyanate and the active reactants containing hydrogen atoms is largely inhibited, even in the presence of a catalyst, is referred to as “non-reactive” here. However, small amounts of reactive solvents can be present if their amount is so small that a substantial amount of compounds with which they can react does not precipitate; This means that enough substances that are reactive with keratin fibers remain in order to ensure adequate shrinkage inhibition and / or fixability of the tissue or structure.



   Suitable organic solvents are e.g. B. chlorinated hydrocarbons, e.g. B. trichlorethylene, methylene chloride, perchlorethylene, ethylene dichloride, chloroform u. similar ; aromatic solvents, e.g. B. toluene, xylene, benzene, mixed aromatics, e.g. The solvent solvents, etc. similar ; n-butyl acetate, n-butyl ether, n-butyl phosphate, p-dioxane, ethyloxalate, methyl isobutyl ketone, pyridine, quinoline. N, N-dimethylformamide, N, N-dimethylacetamide, 2, 2, 4-trimethylpentane and the like. similar Mixtures of solvents can also be used.



   The use of a non-reactive organic solvent makes it possible to combine all the desired reactants in a single solution, since the reaction between them is largely inhibited. This significantly facilitates the uniform application of all reactants, including the catalyst, to the structures in controllable quantities. In the absence of a non-reactive solvent, the reactants and catalysts would often be quite light

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 EMI5.1
 
 EMI5.2
 wherein X has the meanings given above and R is a radical of the above compounds with terminal isocyanate groups.



   The reactant used in a preferred embodiment of the method according to the invention very likely produces a certain crosslinking of the reaction product from the above system and the keratin fibers - the mechanism of the crosslinking is, however, unclear.



   The presence of tolerated moisture in the keratin fibers consumes free isocyanate groups and thereby lowers the ratio of the -N = C = X groups to the active hydrogen atoms in the overall system, as a result of which the felt-like shrinkage remains high or the fixation low at low initial values of this ratio. This difficulty can easily be overcome by either drying the structures and keeping them dry during the treatment, or by compensating for the tolerated humidity by adding equivalent amounts of isocyanate groups for the reaction with this water.



   The mechanism of hardening is not fully understood. In the practical implementation of the method according to the invention, however,. found that very good shrinkage inhibition and / or very good fixation of the fibers as well as improved grip could be achieved with very small amounts of blocked or unblocked isocyanates.



   The curing rate on the impregnated fibers can be increased at a temperature higher than room temperature. Temperatures above about 104 to 1270C are preferred. Temperatures above about 149 C will generally be too high, but these higher temperatures can be used if the keratin fibers are only exposed to these higher temperatures for such a short time that no undesired degradation occurs.



   In many cases, better anti-shrinkage properties are achieved if an aging period is included between curing and washing. Aging is also preferably used for permanent fixation of keratin fibers, but abrasion is generally used for the clothing manufacturer

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 in this embodiment according to the invention neither feasible nor necessary. This aging, which is likely to be an extension of the hardening, can take place over a longer or shorter period of time, depending on the desired extent of the shrinkage inhibition and / or the fixation. Aging times of about 12 to about 24 hours or more or less are quite satisfactory.



   In the case of the anti-shrinkage according to the invention, it was found that the properties of the fabrics and structures treated according to the invention are improved by mechanical treatment of the fabric fibers after aging. This is most effectively accomplished by laundering, in which the fabric is repeatedly dipped in an aqueous solution containing small amounts of a wetting agent and squeezed between rollers at regular intervals. Similar effects are achieved with normal dyeing after treatment. This immersion in aqueous media could lead to hydrolysis of the reaction product of the keratin fibers with the isocyanate and the polymeric polyhydroxy compound or a precondensate thereof. Washing or equivalent treatment or other mechanical treatment of the fabric after curing is particularly preferred.



   Different amounts of the individual reactants can be used to modify the properties of structures containing keratin fibers. Even with about a number of total uptake of all added components, excellent inhibition of relaxation and shrinkage with felting and / or excellent fixability was achieved. If only an inhibition of the relaxation shrinkage or a lower fixability is to be achieved, then smaller amounts can be used. Generally no more than about 6 percent by weight of the components are required. Large quantities, e.g. B. up to about 10% or more, may optionally be used for special uses that do not require a soft hand.



   A largely neutral pH of the tissue or treatment solution gave improved results. Strongly basic solutions, e.g. B. with a pH value of about 9, damage the keratin fibers if the exposure is too long. A pH below about 3 also causes difficulties. The tissue, which is often strongly acidic as a result of carbonization using strong acids, is preferably washed or neutralized before the treatment according to the invention to increase the pH value.



   Isocyanates suitable for use in the process according to the invention are e.g. B. aryl diisocyanates, e.g. B.



   2, 4-toluene diisocyanate,
2, 6-toluene diisocyanate, 4, 4'-diphenylmethane diisocyanate, p-phenylene diisocyanate,
1,5-naphthylene diisocyanate, m -phenylene diisocyanate, diphenyl 4, 4 '- diisocyanate,
 EMI6.1
 Diphenylsulfone - 4, 4 '- diisocyanate, 1-isopropylbenzene-3, 5 - diisocyanate, 1-methylphenylene - 2, 4 - diisocyanate, naphthylin-1, 4-diisocyanate,
 EMI6.2
 diisothiocyanate and diisocyanate, xylylene-1,4-diisocyanate,
Xylylene-1,3-diisocyanate,
4,4'-diphenylene methane diisocyanate.



   4,4'-diphenylene propane diisocyanate and xylylene-1,4-diisothiocyanate and the like. similar., alicyclic diisocyanates, e.g. B. dicyclohexamethane-4,4'-diisocyanate u. similar., alkylene diisocyanates, e.g. B. tetramethylene diisocyanate, hexamethylene diisocyanate u. similar., as well as mixtures thereof and the corresponding isothiocyanates. Among these compounds, the aryl diisocyanates are preferred because of their solubility and easy accessibility.



   Other isocyanates are e.g. B. polymethylene diisocyanates and diisothiocyanates, e.g. B. Ethylenedi. - isocyanate, dimethylene diisocyanate, dodecanemethylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and the corresponding diisothiocyanates; Alkylene diisocyanates and diisothiocyanates, e.g. B. Propylene -1. 2 -diisocyanate, 2, 3 -dimethyltetramethylene diiso-

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 EMI7.1
 - diisothiocyanate, butylene -1, 2 - diisocyana t, butylene -1, 3 - diisothiocyanate and diisothiocyanate, e.g. B. 1,4-Diisocyanatocyclohexane. Cyclopentylene-1,3-diisocyanate and cyclohexylene-1,2-diisothiocyanate; aromatic polyisocyanates and polyisothiocyanates, e.g. B. aliphatic aromatic diisocyanates and diisothiocyanates, e.g.

   B. phenylethylene diisocyanate [CHCH (NCO) CH NCO]; Diisocyanates and diisothiocyanates and heteroatoms, e.g. B.SCNCHOCHNSC. AndSCNHCHOCHCH NSC
 EMI7.2
 
The preferred diisocyanates, diisothiocyanates and mixed isocyanate-isothiocyanates have the general formula ZCN-R-NCZ, where R is a divalent hydrocarbon radical, preferably an aryl radical, and Z is a chalcogen of less than 33 atomic weight. Because of its easy accessibility, toluene-2,4-diisocyanate is preferred.



   These isocyanates or precondensates with terminal isocyanate groups produced from them can be produced from the corresponding blocked compounds by customary processes.



  Blocked isocyanates and blocked precondensates with terminal isocyanate groups contain little or no free isocyanate groups due to the addition of compounds with active hydrogen atoms (which were determined by the Zerewitinoff method) to these groups. These addition products are relatively inert (storage stable) at room temperature, but have only a limited thermal stability, so that after heating above a certain temperature, called the unblocking temperature, the addition product is activated or released and thus provides a similar reaction product with the keratin fibers the unblocked connection.



   Preferred adduct-forming compounds give adducts which can be activated or blocked by heat alone. Typical compounds with active hydrogen atoms that form heat-reversible adducts are e.g. B.:
1. Tertiary alcohols, e.g. tert-butyl alcohol, tert-amyl alcohol, dimethylethinyl carbinol, dimethylphenylcarbinol, methyldiphenylcarbinol, triphenylcarbinol, l-nitro-tert-butylcarbinol, l-chloro-tert-butylcarbinol and triphenylsilinol and the like. similar ;

  
2. secondary aromatic amines that contain only one group with one hydrogen atom, the
 EMI7.3
 
B. the diaryl compounds such as diphenylamine, phenyl-2-mercaptothiazole, 2-mercapto-5-chlorobenzothiazole, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan and ethynyldimethylthiocarbinol and the like. similar ;
4. Lactams, e.g., # -caprolactam, # -valerolactam, γ-butyrolactam and ß-propiolactam;
5. Imides, e.g. B. carbimide, succinimide, phthalimide, naphthalimide, glutarimide and the like. similar ;
6. Monohydric phenols in which only the hydroxyl group contains reactive hydrogen atoms with the isocyanate group, e.g. B. the phenols.

   Cresols, xylenols, trimethylphenols, ethylphenols, propylphenols, chlorophenols, nitrophenols, thymol, carvacrol, mono-a-phenylethylphenol, di- - <x-phenylethylphenol, tri-a-phenylethylphenol and tert-butylphenol and the like. similar ;
7. Compounds with enolizable hydrogen atoms, e.g. B. acetoacetic ester, diethyl malonate, ethyl n-butyl malonate, ethyl benzyl malonate,. Acetylacetone, acetonylacetone, benzimidazole and phenyl-3-methyl-5-pyrazolone and the like. similar
 EMI7.4
 

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Succinimide, phthalimide, tert. -Butyl alcohol. tert. - Amyl -reactive hydrogen atoms containing reactants are mixed, the formation of condensation products is slowed down to the application of heat.



   To prepare the monoadducts in general, the polyisocyanate and the adduct-forming compound are usually dissolved in suitable inert solvents, e.g. B. toluene, methyl ethyl ketone or o-dichlorobenzene, dissolved. The solutions are mixed by stirring and then left to stand. The
The reaction is to be initiated at a temperature below the decomposition temperature of the desired product, preferably at a temperature of no more than about 100 OC. In most cases, a satisfactory reaction takes place even at room temperature. If the solvent used for the isocyanate compound and the blocking agent does not also dissolve the resulting adduct, this separates out of the solution and is obtained therefrom by filtration or evaporation of the solvent.

   Depending on the reactant used, the time required for the formation of the adduct is a few minutes to several hours.



   To produce a monoadduct of a polyisocyanate, an excess of polyisocyanate is usually used, so that the deposited product is largely pure monoadduct. The precipitated product may contain small amounts of unreacted reactants, which may be prepared by known methods, e.g. B. by recrystallization or extraction, can be removed.



   After heating above the deblocking temperature, e.g. B. during hardening, can
Isocyanate react with the polymeric hydroxy compound and the keratin fibers in the presence of the blocking agent. The mechanism of this reaction is no better elucidated than the reaction when using unblocked isocyanates, but the results of the reactions suggest that the reaction mechanisms are similar.



   If a blocked precondensate is used, it is also activated and released when it is heated above the deblocking temperature, so that it can deliver the same reaction product with the keratin fibers as a non-blocked precondensate.



   If a blocked compound is used, the ratio of the = C = X groups to the active hydrogen atoms can be calculated from the number of such groups theoretically present after dissociation.



   Catalysts and / or further reactants can be used in this embodiment according to the invention as well as when using unblocked isocyanate compounds.



   Since these blocked isocyanate compounds can only react with other reactants or the keratin fibers after their heat activation, they are quite stable, so that the use of a non-reactive organic solvent is not necessary. As a result, the blocked isocyanate compounds on keratin fibers can also be extracted from aqueous systems, e.g. B. in the form of an aqueous emulsion or dispersion, but you achieve a better and more uniform penetration of the blocked isocyanate compounds into the keratin fibers when using these compounds in organic solution.



   "Polymeric polyhydroxy compound" is to be understood as meaning a linear long-chain polymer with terminal hydroxyl groups, including branched-chain, polyfunctional polymeric hydroxy compounds. Suitable polymeric polyhydroxy compounds are, for. B. Polyether polyols, polyalkylene ether glycols and polyalkylene arylene arylene ethers - thioether glycols and polyalkylene ether triols, polyalkylene ether glycols and triols are preferred. Mixtures of these polyols can optionally be used.



   The polyalkylene glycols can be symbolized by the formula HO (ROH, where Pure is an alkylene radical that does not always have to be the same and n is an integer. Such glycols are, for example,
 EMI8.1
 Polyalkylene ether glycols can be used.



   Polyalkylene ether triols can be prepared by reacting one or more alkylene oxides with one or more low molecular weight aliphatic triols. The most used
 EMI8.2
    B. butane, 3, 4-epoxyhexane, l, 2-epoxy-5-hexene, I, 2-epoxy-3-butane u. similar Ethylene, propylene and butylene oxide are preferred. In addition to mixtures of such oxides, minor amounts of alkylene oxides with cyclic substituents can be present, e.g. B. styrene oxide, cyclohexene oxide, 1, 2-epoxy

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 EMI9.1
 sit molecular weights from about 92 to about 250.

   Examples of such are glycerol, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolafane, 2,4-dimethylol-2-methylol-pentanediol-1,5 and the trimethyl ether of Sorbitol.



   Representative examples of polyalkylene ether triols are polypropylene ether triol (molecular weight 700) from the reaction of 608 parts of 1,2-propylene oxide with 92 parts of glycerol, polypropylene ether triol (molecular weight 1535) from the reaction of 1,401 parts of 1,2-propylene oxide with 134 parts len trimethylpropane, polypropylene ether triol (molecular weight 2500) from the reaction of 2366 parts of 1,2-propylene oxide with 134 parts of 1,2,6-hexanetriol and polypropylene ether triol (molecular weight of 6000) from the reaction of 5866 parts of 1,2-propylene oxide with 134 Parts 1, 2, 6-hexanetriol.



   Other suitable polytriols are, for. B. polyoxypropylene triols, polyoxybutylene triols, the NIAX triols LG 56, LG 42, LG 112 u. similar from Union Carbide; the triplet G-4000 u. similar of the company
Jefferson Chemical; Actol 32-160 from Natril Aniline u. similar



   The polyalkylene arylene ether glycols are similar to the polyalkylene ether glycols, but some arylene radicals are present in these. Examples of such arylene radicals are phenylene, naphthalene and
Anthracene radicals, which are represented by various substituents, e.g. B. alkyl groups can be substituted.



   In general, at least one alkylene ether radical with a molecular weight of about 600 should be present in these glycols for each arylene radical present.



   The polyalkylene ether thioether glycols and the polyalkylene arylene ether glycols are similar to the polyether glycols described above, but some of the ether oxygen atoms have been replaced by sulfur atoms. These glycols can advantageously be obtained by condensation of various glycols, e.g. B. thiodiglycol, in the presence of a catalyst, e.g. B. p-toluenesulfonic acid.



   The stabilization of a tissue depends to a large extent on its density. For example, at lower densities, more intense treatments are usually used for best results.



   Variations of the method according to the invention can achieve greater or lesser inhibition of relaxation and shrinkage due to felting. It can e.g. B. with some fabrics, if these are not to be made washable, it may be desirable to reduce only the relaxation shrinkage. In the case of washable fabrics, on the other hand, both relaxation and shrinkage with felting must be reduced to an acceptable level.



   With the method according to the invention, permanent shapes can be imparted to keratin fibers and in particular a larger proportion of fabrics containing keratin fibers by hardening the keratin fibers treated according to the invention while at the same time keeping the fibers in the desired shape. The keratin fibers and preferably fabrics containing them are most expediently kept in the desired shape at least during the initial stage of hardening by pressing devices which are preferably heated to initiate and facilitate hardening. For example, hand irons, pleated papers, trough presses, decatizing devices, paper presses, calender rolls, Hoffmann presses and the like can be used as pressing devices. similar be used.



   It is also possible according to the invention to crimp the keratin fibers either in the fabrics or before weaving, e.g. B. in roving, slivers, yarns and. similar



   Prior to weaving, the fibers can be held in place by curing while holding the fibers in a curled or otherwise deformed shape.



   The impregnation according to the invention can be carried out before the deformation of the fibers or, if necessary, after the same, but for the purpose of better control it is generally preferred to impregnate the fibers with the substances used according to the invention before they are deformed.



   A permanently crimped yarn can also be obtained by knitting the yarn into a knitted fabric and fixing the fabric by impregnation with the preparations used according to the invention and subsequent hardening. After hardening and fixing, the knitted fabric is separated into the yarn. The yarn obtained is permanently fixed in the form in which it was fixed as a knitted fabric.



     The fixing of a crimp in keratin fibers in the form of a fabric has its greatest area of application in "stretch" fabrics. In the manufacture of stretch fabrics from pure wool or fabrics with at least a larger proportion of wool fibers, a base fabric is made to shrink by dipping it in a solution, with or without reducing agents, in order to increase the amplitude of the crimp in the warp and protective yarns or both. After the tissue has been stretched, a large

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 going back to this increased ripple amplitude. If such a fabric is treated according to the invention and cured in the shrunk state, then the speed of return from a stretched shape, i.e. H. the speed of elastic recovery of the tissue, greatly increased.



   Here, too, the inventive impregnation of the fabric can be carried out before or after the shrinkage, but in this embodiment it is generally preferred to treat the fabric with one of the preparations after the shrinkage in order to avoid effects of the shrink bath on the preparations that can be used according to the invention . The impregnated fabric is then dried and cured in order to fix the fabric in the shrunk state.



   A crimping of the chamois of a fabric can also be brought about by mechanical measures, e.g. B. by compaction, whereby a tissue in a certain direction mechanically to
Is brought to shrink, e.g. B. in the direction of the chain. For this purpose, the fabric can be impregnated, dried, compacted and hardened according to the invention in order to permanently fix the fabric in its compacted form. This procedure is particularly useful. to get fabrics with "stretch" in the direction of the warp.



   Fabrics with increased "stretch" in the weft direction can be obtained if the fabric is impregnated according to the invention and tensile forces are applied to it during drying and / or curing
Warming and possibly aging in the direction of the chain can act. This procedure increases the crimp amplitude of the weft yarns.



   Fabrics treated according to the invention can be made permanent forms in the textile mill, e.g. B. by
Presses, to give a permanent glossy finish, or are pretreated there for later permanent fixation by the clothing manufacturer.



   A blocked polyfunctional isocyanate or a blocked precondensate is preferably used for the pretreatment, since the blocked compounds are more stable during shipping and storage than the corresponding unblocked compounds. The storage times of pretreated fabrics vary considerably and the blocked connections offer greater security with the same
Effect.



   In this embodiment of the method according to the invention, the blocked compounds on the tissue for the reaction with the keratin fibers and other compounds with active hydrogen atoms occurring in the tissue are activated by fixing in heat, the hardening at least being initiated. Cure can then be completed during an aging period. To achieve the best results, the tissue is kept in the desired shape during aging or at least until hardening is largely complete.



   A further advantage of this embodiment of the method according to the invention is that the preparations to be used with blocked compounds can be applied to the tissue from an aqueous system. Emulsions of such preparations are normally produced from solutions of the blocked isocyanate compounds in organic solvents by adding water and known emulsifiers. This approach is less expensive than using organic solutions alone, but better penetration and grip are achieved when the blocked compounds are applied to the keratinous fibers from organic solution.



   The method according to the invention is explained in more detail using the examples below. In these examples, unless otherwise stated. Parts given on a dry weight basis, as percent absorption on the treated wool. In many of the following examples, especially with a shrinkage of more than about 5%, the shrinkage values can be further reduced if the uptake of the components is increased. In the examples, the effect of varying certain constituents is shown by lowering the absorption on the wool, so that the different effects became more apparent.



     Example 1: Production of a precondensate.



   102 kg of polypropylene glycol (molecular weight about 2000) were placed in an unjacketed reaction vessel made of corrosion-resistant steel. The reaction vessel was then closed and the pressure in the same was reduced to about 10 mm Hg column and the reaction vessel was flushed with dry nitrogen. The pressure setting and flushing were repeated three times and 104 kg of dry toluene were then poured into the reactor. During the reaction, the reaction vessel was filled with nitrogen as a protective gas. The pressure was reduced again to a 10 mm Hg column and the reaction vessel was heated to 1400 ° C. in order to distill off the toluene, whereupon the jacket was cooled to room temperature by adding cold water.

   External pressure was set and 20.5 kg of silicone resin L45

 <Desc / Clms Page number 11>

 
 EMI11.1
 

 <Desc / Clms Page number 12>

 



  Table 1
 EMI12.1
 
<tb>
<tb> tissue <SEP> recording <SEP> (alto) <SEP> dry weight <SEP>: <SEP> area shrinkage <SEP>% <SEP>: <SEP>
<tb> Precondensate <SEP> Silicon <SEP> Quadrol <SEP> Relaxation <SEP>: <SEP> felt-like
<tb> Control <SEP> X --- 16, <SEP> 1 <SEP> 46, <SEP> 3 <SEP>
<tb> Control <SEP> X <SEP> 3, <SEP> 15 <SEP> 0, <SEP> 34 <SEP> 0, <SEP> 23 <SEP> 0, <SEP> 9 <SEP> 2, < SEP> 7 <SEP>
<tb> Control <SEP> X <SEP> 3, <SEP> 49 <SEP> 0, <SEP> 38 <SEP> 0, <SEP> 26 <SEP> 0, <SEP> 9 <SEP> 3, < SEP> 0
<tb> Control <SEP> X <SEP> 3, <SEP> 49 <SEP> 0, <SEP> 94 <SEP> 0, <SEP> 26 <SEP> 0, <SEP> 6 <SEP> 4, < SEP> 1 <SEP>
<tb> Control <SEP> X <SEP> 3, <SEP> 84 <SEP> 0, <SEP> 41 <SEP> 0, <SEP> 28 <SEP> 0, <SEP> 8 <SEP> 3, < SEP> 4 <SEP>
<tb> Control <SEP> Y <SEP> 3,15 <SEP> 0, <SEP> 34 <SEP> 0, <SEP> 23 <SEP> 1, <SEP> 2 <SEP> 2,

   <SEP> 3 <SEP>
<tb> Control <SEP> Y <SEP> 3, <SEP> 49 <SEP> 0, <SEP> 38 <SEP> 0, <SEP> 26 <SEP> 0, <SEP> 4 <SEP> 1, < SEP> 8 <SEP>
<tb> Control <SEP> Y <SEP> 3, <SEP> 49 <SEP> 0, <SEP> 94 <SEP> 0, <SEP> 26 <SEP> 0, <SEP> 7 <SEP> 2, < SEP> 1 <SEP>
<tb> Control <SEP> Y <SEP> 3, <SEP> 84 <SEP> 0, <SEP> 41 <SEP> 0, <SEP> 28 <SEP> 0, <SEP> 6 <SEP> 1, < SEP> 6 <SEP>
<tb> Control <SEP> Z <SEP> 3, <SEP> 15 <SEP> 0, <SEP> 34 <SEP> 0, <SEP> 23 <SEP> 0, <SEP> 1 <SEP> 2, < SEP> 4 <SEP>
<tb> Control <SEP> Z <SEP> 3, <SEP> 49 <SEP> 0, <SEP> 38 <SEP> 0, <SEP> 26 <SEP> 0, <SEP> 9 <SEP> 1, < SEP> 0 <SEP>
<tb> Control <SEP> Z <SEP> 3, <SEP> 49 <SEP> 0, <SEP> 94 <SEP> 0, <SEP> 26 <SEP> 0, <SEP> 4 <SEP> 2, < SEP> 0 <SEP>
<tb> Control <SEP> Z <SEP> 3, <SEP> 84 <SEP> 0, <SEP> 41 <SEP> 0, <SEP> 28 <SEP> 0, <SEP> 9 <SEP> 1, < SEP> 9 <SEP>
<tb>
 
Example 2:

   A solution of the precondensate from Example 1 in trichlorethylene was padded onto a cloth swatch of a pure wool fabric from Example 1 until 3, 00/0 precondensate was absorbed. The thoroughly impregnated fabric was then dried at 60 ° C. and aged for 48 h at room temperature without heat treatment. The cloth was then tested for relaxation and felt-like shrinkage as in Example 1, and found to be 0.9 and 2.7%, respectively.



     Example 3: Cloth samples of the pure wool fabric from Example 1 were thoroughly impregnated with trichlorethylene solutions which contained the amounts of precondensate from Example 1 and from Quadrol indicated in Table 2. The table also shows the percentage uptake (dry weight) of the various compounds. These swatches were then dried, cured and tested according to Example 1.



   Table 2
 EMI12.2
 
<tb>
<tb> recording <SEP> area shrinkage
<tb> precondensate <SEP> Quadrol <SEP> relaxation felt-like
<tb> 16, <SEP> 1 <SEP> 46, <SEP> 3 <SEP> (control)
<tb> 2, <SEP> 0 <SEP> "<SEP> 0, <SEP> 35 <SEP> 5, <SEP> 9 <SEP> 5, <SEP> 9 <SEP>
<tb> 2, <SEP> 0 <SEP> 0, <SEP> 25 <SEP> 4, <SEP> 7 <SEP> 5, <SEP> 5 <SEP>
<tb> 2, <SEP> 0 <SEP> 0, <SEP> 10 <SEP> 5, <SEP> 1 <SEP> 3, <SEP> 7 <SEP>
<tb> 2, <SEP> 0 <SEP> 0, <SEP> 06 <SEP> 5, <SEP> 8 <SEP> 2, <SEP> 8 <SEP>
<tb> 2, <SEP> 0 <SEP> 0, <SEP> 03 <SEP> 5, <SEP> 9 <SEP> 3, <SEP> 6 <SEP>
<tb> 2, <SEP> 0 <SEP> 0, <SEP> 01 <SEP> 9, <SEP> 0 <SEP> 2, <SEP> 5 <SEP>
<tb>
 The absorption of the connections can be increased.

   if lower area shrinkage

 <Desc / Clms Page number 13>

 
 EMI13.1
 
 EMI13.2
 
<tb>
<tb> Description <SEP> Reaction recording <SEP>% <SEP> Area shrinkage <SEP>
<tb> partner <SEP> dry weight <SEP>
<tb> precon reaction relaxation felt-like
<tb> densat <SEP> partner
<tb> Control --- 16, <SEP> 1 <SEP> 46, <SEP> 3 <SEP>
<tb> A <SEP> l, <SEP> 4-butane <SEP>
<tb> diol <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 09 <SEP> 9, <SEP> 5 <SEP> 5, <SEP> 3 <SEP>
<tb> B <SEP> 1, <SEP> 4-butanediol <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 09 <SEP> 5, <SEP> 5 <SEP> 4, <SEP> 0 <SEP>
<tb>
 

 <Desc / Clms Page number 14>

 Table 3 (continued):

   
 EMI14.1
 
<tb>
<tb> Description <SEP> Reaction recording <SEP>% <SEP> Area shrinkage
<tb> partner <SEP> dry weight
<tb> precon reaction relaxation felt-like
<tb> densat <SEP> partner
<tb> A <SEP> methyl diethanolamine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 1 <SEP> 7, <SEP> 8 <SEP> 2, <SEP> 8 <SEP>
<tb> B <SEP> methyl diethanolamine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 1 <SEP> 4,5 <SEP> 2, <SEP> 7 <SEP>
<tb> A <SEP> Trimethylolpropane <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 09 <SEP> 9, <SEP> 2 <SEP> 4, <SEP> 6 <SEP>
<tb> B <SEP> Trimethylolpropane <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 09 <SEP> 5, <SEP> 2 <SEP> 5, <SEP> 2 <SEP>
<tb> A <SEP> Triethanolamine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 10 <SEP> 7, <SEP> 7 <SEP> 0, <SEP> 8 <SEP>
<tb> B <SEP> triethanolamine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 10 <SEP> 4,1 <SEP> 3, <SEP> 3 <SEP>
<tb> A <SEP> Azelaic acid <SEP> 2, <SEP> 0 <SEP> 0,

   <SEP> 19 <SEP> 9, <SEP> 2 <SEP> 1, <SEP> 2 <SEP>
<tb> B <SEP> Azelaic acid <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 19 <SEP> 5, <SEP> 4 <SEP> 2, <SEP> 1 <SEP>
<tb> A <SEP> pimelic acid <SEP> 8, <SEP> 0 <SEP> 0, <SEP> 16 <SEP> 0, <SEP> 3 <SEP> 7, <SEP> 8 <SEP>
<tb> B <SEP> pimelic acid <SEP> 8, <SEP> 0 <SEP> 0, <SEP> 16 <SEP> 6,5 <SEP> 8, <SEP> 6 <SEP>
<tb> A <SEP> citric acid <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 10 <SEP> 7, <SEP> 0 <SEP> 10, <SEP> 8 <SEP>
<tb> B <SEP> citric acid <SEP> 2, <SEP> 0 <SEP> 0.10 <SEP> 6, <SEP> 5 <SEP> 21, <SEP> 7 <SEP>
<tb> A <SEP> MOCA <SEP> + <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 27 <SEP> 7, <SEP> 3 <SEP> 3, <SEP> 2 <SEP >
<tb> B <SEP> MOCA <SEP> + <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 27 <SEP> 4, <SEP> 7 <SEP> 3.5
<tb> A <SEP> 1, <SEP> 6-Hexa- <SEP>
<tb> methylenediamine <SEP> 2, <SEP> 0 <SEP> 0.12 <SEP> 6, <SEP> 2 <SEP> 2, <SEP> 0 <SEP>
<tb> B <SEP> 1,

   <SEP> 6-hexa- <SEP>
<tb> methylenediamine <SEP> 2, <SEP> 0 <SEP> 0.12 <SEP> 3, <SEP> 9 <SEP> 2, <SEP> 5 <SEP>
<tb> A <SEP> 2, <SEP> 6-Diami- <SEP>
<tb> nopyridine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 11 <SEP> 8, <SEP> 3 <SEP> 2, <SEP> 8 <SEP>
<tb> B <SEP> 2, <SEP> 6-Diami- <SEP>
<tb> nopyridine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 11 <SEP> 4, <SEP> 7 <SEP> 3, <SEP> 2 <SEP>
<tb>
 

 <Desc / Clms Page number 15>

   Table 3 (continued):

   
 EMI15.1
 
<tb>
<tb> Description <SEP> Reaction recording <SEP>% <SEP> Area shrinkage
<tb> partner <SEP> dry weight
<tb> precon reaction relaxation felt-like
<tb> densat <SEP> partner
<tb> A <SEP> 3, <SEP> 3'-diaminodipropylamine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 09 <SEP> 3, <SEP> 2 <SEP> 2, <SEP > 4 <SEP>
<tb> B <SEP> 3, <SEP> 3'-diaminodipropylamine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 09 <SEP> 3, <SEP> 4 <SEP> 1, <SEP > 9 <SEP>
<tb> A <SEP> Triethylenetetramine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 07 <SEP> 7, <SEP> 7 <SEP> 0, <SEP> 4 <SEP>
<tb> B <SEP> triethylenetetramine <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 07 <SEP> 2, <SEP> 6 <SEP> 2, <SEP> 0 <SEP>
<tb>
 + MOCA is the trade name for 4,4'-methylene-bis- (2-chloroaniline)
Precondensates were produced from propylene glycols with molecular weights of around 1200, 3000 and 4000.

   The condensation procedure was the same as in Example 1 in all cases, but the amounts of ingredients added were changed to compensate for differences in the hydroxyl numbers of these glycols.
 EMI15.2
 
<tb>
<tb>



  Approach <SEP> with <SEP> polypropylene glycol <SEP> (PPG) <SEP> 1200 <SEP>: <SEP>
<tb> parts by weight
<tb> PPG <SEP> 1200 <SEP> 386, <SEP> 00 <SEP>
<tb> L45 <SEP> Silicon <SEP> 0, <SEP> 15 <SEP>
<tb> water <SEP> 1.30
<tb> (I. <SEP> addition) <SEP> toluene-2, <SEP> 4-diisocyanate <SEP> 81.30
<tb> (2nd <SEP> addition) <SEP> toluene-2, <SEP> 4-diisocyanate <SEP> 117.00
<tb> Approach <SEP> with <SEP> polypropylene glycol <SEP> 3 <SEP> 000 <SEP>: <SEP>
<tb> PPG <SEP> 3 <SEP> 000 <SEP> 492.50
<tb> L45 <SEP> Silicon <SEP> 0, <SEP> 07 <SEP>
<tb> water <SEP> 1, <SEP> 31
<tb> (I. <SEP> addition) <SEP> toluene-2,4-diisocyanate <SEP> 47.00
<tb> (2nd <SEP> addition) <SEP> toluylene-2,4-diisocyanate <SEP> 89.50
<tb> approach <SEP> with <SEP> polypropylene glycol <SEP> 4000 <SEP> A:

   <SEP>
<tb> PPG <SEP> 4000 <SEP> 527, <SEP> 00
<tb> L45 <SEP> silicone <SEP> 0.05
<tb> water <SEP> 1, <SEP> 05
<tb> (1st <SEP> addition) <SEP> toluene-2, <SEP> 4-diisocyanate <SEP> 37.60
<tb> (2nd <SEP> addition) <SEP> toluylene-2,4-diisocyanate <SEP> 71.00
<tb>
 

 <Desc / Clms Page number 16>

 
 EMI16.1
 
<tb>
<tb> Approach <SEP> with <SEP> polypropylene glycol <SEP> 4000 <SEP> B <SEP>: <SEP>
<tb> PPG4000 <SEP> 527, <SEP> 00 <SEP>
<tb> L45 <SEP> Silicon <SEP> 0, <SEP> 05 <SEP>
<tb> water <SEP> 1, <SEP> 05 <SEP>
<tb> (l. <SEP> addition) <SEP> toluene-2, <SEP> 4-diisocyanate <SEP> 37, <SEP> 60 <SEP>
<tb> (2nd addition) toluene-2,4-diisocyanate <SEP> 35.50
<tb>
 
The viscosities of the above precondensation products in the form of 7figer solutions in trichlorethylene were about 5250, 400, 1200 and 1050 cP (Brockfield viscometer spindle No. 2).



     Example 9: The 70% proprietary solutions of the precondensates prepared with glycols of the various molecular weights were diluted and mixed according to the method of Example 1. Samples of the pure wool fabric from Example 1 were treated with these solutions up to the absorption indicated in Table 4. The fabric samples were then dried for 5 minutes at 71 ° C., cured for 5 minutes at 1210 ° C., aged for 48 hours and then tested according to Example 1.



   Table 4
 EMI16.2
 
<tb>
<tb> Glycol <SEP> for <SEP> closer <SEP> approaching <SEP> recording <SEP>% <SEP> area shrinkage
<tb> Position <SEP> of the <SEP> Pre <SEP> Molecular <SEP> Quadrol <SEP> Pre <SEP>
<tb> condensate <SEP> weight <SEP> condensate <SEP> Relaxa-felting-like
<tb> control, <SEP> none --- 16, <SEP> 1 <SEP> 46, <SEP> 3 <SEP>
<tb> Polypropylene glycol <SEP> (1200) <SEP> 1200 <SEP> 0.204 <SEP> 2.75 <SEP> 5.8 <SEP> 4.9
<tb> 1200 <SEP> 0.256 <SEP> 3.5 <SEP> 4.1 <SEP> 3.3
<tb> 1200 <SEP> 0, <SEP> 31 <SEP> 4, <SEP> 25 <SEP> 4, <SEP> 2 <SEP> 3, <SEP> 0 <SEP>
<tb> Polypropylene glycol <SEP> (3 <SEP> 000) <SEP> 3000 <SEP> 0.204 <SEP> 2.75 <SEP> 4.7 <SEP> 8.4
<tb> 3000 <SEP> 0, <SEP> 256 <SEP> 3, <SEP> 5 <SEP> 4, <SEP> 6 <SEP> 5, <SEP> 4 <SEP>
<tb> 3000 <SEP> 0, <SEP> 31 <SEP> 4, <SEP> 25 <SEP> 4, <SEP> 9 <SEP> 4,

   <SEP> 3 <SEP>
<tb> Polypropylene glycol <SEP> (4 <SEP> 000 <SEP> A) <SEP> 4000 <SEP> 0.204 <SEP> 2.75 <SEP> 5.1 <SEP> 6.2
<tb> 4000 <SEP> 0, <SEP> 256 <SEP> 2, <SEP> 5 <SEP> 4, <SEP> 2 <SEP> 3, <SEP> 7 <SEP>
<tb> 4000 <SEP> 0, <SEP> 31 <SEP> 4, <SEP> 25 <SEP> 4, <SEP> 4 <SEP> 3, <SEP> 8 <SEP>
<tb>
 
Example 10: The precondensate designated 4000B was mixed in the presence or absence of excess toluene-2,4-diisocyanate and with or without Quadrol, as indicated in Table 5. Samples of the pure wool fabric from Example 1 were treated with the solutions up to the recordings given in Table 5. The fabric samples were dried for 5 minutes at 71 ° C., cured for 5 minutes at 1210 ° C., aged for 48 hours, and the shrinkage values were then determined.



   Table 5
 EMI16.3
 
<tb>
<tb> absorption <SEP>% <SEP> dry weight <SEP> area shrinkage <SEP>% <SEP>
<tb> precondensate <SEP> added <SEP> Quadrol <SEP> relaxation felt-like
<tb> 4000 <SEP> B <SEP> excess <SEP> on
<tb> diisocyanate
<tb> 16, <SEP> 1 <SEP> 46, <SEP> 3Contr. <SEP>
<tb>



  3, <SEP> 4 <SEP> 0, <SEP> 20-9, <SEP> 9 <SEP> 42, <SEP> 8 <SEP>
<tb> 2.0 <SEP> - <SEP> - <SEP> 7.8 <SEP> 45.2
<tb>
 

 <Desc / Clms Page number 17>

   Table 5 (continued):
 EMI17.1
 
<tb>
<tb> absorption <SEP>% <SEP> dry weight <SEP> area shrinkage <SEP>% <SEP>
<tb> Precondensate <SEP> Added <SEP> Quadrol <SEP> Relaxations <SEP> - <SEP> felt-like <SEP>
<tb> 4000 <SEP> B <SEP> excess <SEP> on
<tb> diisocyanate
<tb> 3, <SEP> 4 <SEP> 0, <SEP> 20 <SEP> 0, <SEP> 15 <SEP> 3, <SEP> 2 <SEP> 7, <SEP> 3 <SEP>
<tb> 2, <SEP> 0-0, <SEP> 10 <SEP> 5, <SEP> 1 <SEP> 24.5
<tb>
   Example 11: This example shows the effect of varying the ratio of the -NCO groups to the -OH groups in the compounds.

   The various amounts of Quadrol indicated in Table 6 were added to the precondensate from Example 1. Swatches of the fabric from Example 1 were treated with dilute solutions up to the absorption shown in Table 6. Dried for 5 min at 71 ° C and cured for 5 min at 1210C. This was followed by aging for 18 hours and testing of the fabric samples according to Example 1 for their shrinkage values.



   Fabrics treated in a predried state are designated by the letter “A” and fabrics treated with tolerated water are designated by the letter “B”.



   Table 6
 EMI17.2
 
<tb>
<tb> Description <SEP> recording <SEP> (0/0) <SEP> area shrinkage <SEP> (lo)
<tb> Vorkon-Quadrol <SEP> NCO / OH <SEP> Relaxation felt-like <SEP>
<tb> densat <SEP> ratio
<tb> Control --- 16, <SEP> 1 <SEP> 46, <SEP> 3 <SEP>
<tb> A <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 51 <SEP> 1, <SEP> 0 <SEP> 5, <SEP> 9 <SEP> 10, <SEP> 2 < SEP>
<tb> B <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 51 <SEP> 1, <SEP> 0 <SEP> 4, <SEP> 5 <SEP> 9, <SEP> 2 < SEP>
<tb> A <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 72 <SEP> 0, <SEP> 70 <SEP> 5, <SEP> 5 <SEP> 11, <SEP> 0 < SEP>
<tb> B <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 72 <SEP> 0, <SEP> 70 <SEP> 4, <SEP> 9 <SEP> 9, <SEP> 5 < SEP>
<tb> A <SEP> 3, <SEP> 0 <SEP> 1, <SEP> 27 <SEP> 0, <SEP> 40 <SEP> 9, <SEP> 1 <SEP> 48, <SEP> 7 < SEP>
<tb> B <SEP> 3, <SEP> 0 <SEP> 1, <SEP> 27 <SEP> 0, <SEP> 40 <SEP> 10, <SEP> 3 <SEP> 48, <SEP> 5 < SEP>
<tb> A <SEP> 3,

   <SEP> 0 <SEP> 0, <SEP> 39 <SEP> 1, <SEP> 30 <SEP> 5, <SEP> 4 <SEP> 8, <SEP> 3 <SEP>
<tb> B <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 39 <SEP> 1, <SEP> 30 <SEP> 3, <SEP> 8 <SEP> 8, <SEP> 7 < SEP>
<tb> A <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 3 <SEP> 1, <SEP> 7 <SEP> 6, <SEP> 2 <SEP> 6, <SEP> 9 < SEP>
<tb> B <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 3 <SEP> 1, <SEP> 7 <SEP> 5, <SEP> 0 <SEP> 7, <SEP> 9 < SEP>
<tb> A <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 25 <SEP> 2, <SEP> 0 <SEP> 6, <SEP> 0 <SEP> 6, <SEP> 9 < SEP>
<tb> B <SEP> 3, <SEP> 0 <SEP> 0, <SEP> 25 <SEP> 2, <SEP> 0 <SEP> 5, <SEP> 1 <SEP> 7.

   <SEP> 1 <SEP>
<tb> B <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 15 <SEP> 2, <SEP> 3 <SEP> 3, <SEP> 9 <SEP> 4, <SEP> 6 < SEP>
<tb> B <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 10 <SEP> 3, <SEP> 4 <SEP> 5, <SEP> 1 <SEP> 3, <SEP> 7 < SEP>
<tb> B <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 06 <SEP> 6, <SEP> 1 <SEP> 5, <SEP> 8 <SEP> 2, <SEP> 8 < SEP>
<tb> B <SEP> 2, <SEP> 0 <SEP> 0, <SEP> 01 <SEP> 33, <SEP> 0 <SEP> 9, <SEP> 0 <SEP> 2, <SEP> 5 < SEP>
<tb>
 
In the examples below, the various reactants were mixed with a common solvent without prior heating or otherwise promoting precondensation of the components from their application to the tissues.



   In the preparation of these solutions, the polymeric polyhydroxy compound was first diluted to a content of less than about 20% in trichlorethylene. The polyfunctional isocyanate was also
 EMI17.3
 ratio of the various reactants received. The solution obtained in this way was further diluted with trichlorethylene, depending on the absorption achieved in the moist state and the desired dryness

 <Desc / Clms Page number 18>

 content of tissue.



   Example 12: Various trichlorethylene solutions of toluene-2,4-diisocyanate of the various polymeric polyols, of Quadrol and the catalyst were prepared and padded onto a sample of the pure wool fabric from Example 1 in such quantities that the absorption (dry content) given in Table 7 was achieved. Half of the swatches were cured for 5 minutes at 1210C (designated by the letter “C”) and the remainder were cured for 15 minutes at 1210C (designated by the letter “D”). The shrinkage values were then determined according to Example 1.



   The amount of diisocyanate was kept low in this example in order to show more clearly the differences in the effect of the various polymeric polyols. The high shrinkage values shown here can easily be reduced by increasing the amount of diisocyanate to about 2 to 40/0. However, even at very low levels of diisocyanate, this was unnecessary when triols were used, thus providing excellent anti-shrinkage properties even at these low levels.

 <Desc / Clms Page number 19>

 



  Table 7
 EMI19.1
 
<tb>
<tb> Description <SEP>: <SEP> solution <SEP> absorption <SEP> (0/0) <SEP> dryness <SEP> area shrinkage <SEP> (il) <SEP>: <SEP>
<tb> polymer
<tb> Polyol <SEP> x) <SEP> Diiso-Polyol <SEP>: <SEP> Kataly-Quadrol <SEP>: <SEP> Relaxation <SEP>: <SEP> Felt-like <SEP>: <SEP>
<tb> approximately <SEP> cyanate <SEP>: <SEP> sator
<tb> Molecular <SEP> x) <SEP>
<tb> weight <SEP>:

   <SEP>
<tb> a) <SEP> b) <SEP> c) <SEP> d) <SEP> e) <SEP> f) <SEP> g) <SEP> h)
<tb> Control ---- 16, <SEP> 1 <SEP> 46, <SEP> 3 <SEP>
<tb> C <SEP> (PEG) <SEP> poly-
<tb> ether glycol-200 <SEP> 1, <SEP> 65 <SEP> 0, <SEP> 85 <SEP> 0, <SEP> 147-NMM <SEP> 0, <SEP> 18 <SEP> 3, < SEP> 6 <SEP> 12, <SEP> 2 <SEP>
<tb> 0, <SEP> 0445-TMBDA
<tb> 0, <SEP> 029 <SEP> SO
<tb> D <SEP> PEG-200 <SEP> 1, <SEP> 65 <SEP> 0, <SEP> 85 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 0 <SEP> 14, <SEP> 0 <SEP>
<tb> C <SEP> PEG-450 <SEP> 1, <SEP> 27 <SEP> 1, <SEP> 23 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 4 <SEP> 24, <SEP> 9 <SEP>
<tb> D <SEP> PEG-450 <SEP> 1, <SEP> 27 <SEP> 1, <SEP> 23 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 3, <SEP> 9 <SEP> 30, <SEP> 5 <SEP>
<tb> C <SEP> PEG-1000 <SEP> 0, <SEP> 94 <SEP> 1, <SEP> 56 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0,

   <SEP> 18 <SEP> 4, <SEP> 3 <SEP> 13, <SEP> 0 <SEP>
<tb> D <SEP> PEG-1000 <SEP> 0, <SEP> 94 <SEP> 1, <SEP> 56 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 5 <SEP> 17, <SEP> 4 <SEP>
<tb> C <SEP> PEG-1150 <SEP> 0, <SEP> 98 <SEP> 1, <SEP> 52 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 4 <SEP> 15, <SEP> 6 <SEP>
<tb> D <SEP> PEG-1150 <SEP> 0, <SEP> 98 <SEP> 1, <SEP> 52 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 4 <SEP> 18, <SEP> 6 <SEP>
<tb> C <SEP> PEG-1450 <SEP> 0, <SEP> 82 <SEP> 1, <SEP> 68 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 2 <SEP> 12, <SEP> 00 <SEP>
<tb> D <SEP> PEG-1450 <SEP> 0, <SEP> 82 <SEP> 1, <SEP> 68 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 0 <SEP> 21, <SEP> 4 <SEP>
<tb> C <SEP> PEG-20000 <SEP> 0.53 <SEP> 1.97 <SEP> 0.029 <SEP> SO <SEP> 0.

   <SEP> 18 <SEP> 6, <SEP> 5 <SEP> 17, <SEP> 7 <SEP>
<tb>
 

 <Desc / Clms Page number 20>

   Table 7 (continued):
 EMI20.1
 
<tb>
<tb> Description <SEP>: <SEP> Solution <SEP> Absorption <SEP> (glu) <SEP> Dry content <SEP> Area shrinkage <SEP> (lu) <SEP>: <SEP>
<tb> polymer
<tb> Polyol <SEP> x) <SEP> Diiso- <SEP> Polyol: <SEP> Kataly- <SEP> Quadrol: <SEP> Relazation: <SEP> felt-like:
<tb> approximately <SEP> cyanate <SEP>: <SEP> sator
<tb> molecular-x)
<tb> weight <SEP>:

   <SEP>
<tb> a) <SEP> b) <SEP> c) <SEP> d) <SEP> e) <SEP> f) <SEP> g) <SEP> h) <SEP>
<tb> D <SEP> PEG-20000 <SEP> 0.53 <SEP> 1.97 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 4.8 <SEP> 21.7
<tb> C <SEP> PBG-500 <SEP> 1, <SEP> 22 <SEP> 1, <SEP> 28 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 0 <SEP> 9, <SEP> 4 <SEP>
<tb> D <SEP> PBG-500 <SEP> 1, <SEP> 22 <SEP> 1, <SEP> 28 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 5, <SEP> 7 <SEP> 9, <SEP> 1 <SEP>
<tb> C <SEP> PBG-1000 <SEP> 0.94 <SEP> 1.56 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 5.3 <SEP> 3.3
<tb> D <SEP> PBG-1000 <SEP> 0, <SEP> 94 <SEP> 1, <SEP> 56 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 6 <SEP> 3, <SEP> 5 <SEP>
<tb> C <SEP> PBG-1500 <SEP> 0, <SEP> 81 <SEP> 1, <SEP> 69 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 5, <SEP> 3 <SEP> 4, <SEP> 0 <SEP>
<tb> D <SEP> PBG-1500 <SEP> 0,

   <SEP> 81 <SEP> 1, <SEP> 69 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 4 <SEP> 6, < SEP> 9 <SEP>
<tb> C <SEP> PBG-2000 <SEP> 0.75 <SEP> 1.75 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 4.6 <SEP> 11.4
<tb> D <SEP> PBG-2000 <SEP> 0.75 <SEP> 1.75 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 4.2 <SEP> 4.6
<tb> C <SEP> PPG-400 <SEP> 1.32 <SEP> 1.18 <SEP> 0.147-NMM <SEP> 0.18 <SEP> 3.8 <SEP> 29.9
<tb> 0, <SEP> 0445-TMBDA <SEP>
<tb> 0, <SEP> 029 <SEP> SO
<tb> D <SEP> PPG-400 <SEP> 1, <SEP> 32 <SEP> 1, <SEP> 18 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 9 <SEP> 18, <SEP> 0 <SEP>
<tb> C <SEP> PPG-1200 <SEP> 0.88 <SEP> 1.62 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 5.1 <SEP> 3.4
<tb> D <SEP> PPG-1200 <SEP> 0, <SEP> 88 <SEP> 1, <SEP> 62 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 6 <SEP> 4, <SEP> 1 <SEP>
<tb> C <SEP> PPG-3000 <SEP> 0.67 <SEP> 1,

  83 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 4.0 <SEP> 4.1
<tb>
 

 <Desc / Clms Page number 21>

   Table 7 (continued):
 EMI21.1
 
<tb>
<tb> Designation <SEP>: <SEP> Solution <SEP> Recording <SEP> ('10) <SEP> Dry content <SEP> Area shrinkage <SEP> (left) <SEP>: <SEP>
<tb> polymer
<tb> Polyol <SEP> x) <SEP> Diiso-Polyol <SEP>: <SEP> Kataly-Quadrol <SEP>: <SEP> Relaxation <SEP>: <SEP> Felt-like <SEP>: <SEP>
<tb> approximately <SEP> cyanate <SEP>: <SEP> sator <SEP>: <SEP>
<tb> molecular-x)
<tb> weight <SEP>:

   <SEP>
<tb> a) <SEP> b) <SEP> c) <SEP> d) <SEP> e) <SEP> f) <SEP> g) <SEP> h)
<tb> D <SEP> PPG-3000 <SEP> 0. <SEP> 67 <SEP> 1, <SEP> 83 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 9 <SEP> 4, <SEP> 8 <SEP>
<tb> C <SEP> PPG-4000 <SEP> 0, <SEP> 63 <SEP> 1, <SEP> 87 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 8, <SEP> 2 <SEP> 36, <SEP> 5 <SEP>
<tb> D <SEP> PPG-4000 <SEP> 0, <SEP> 63 <SEP> 1, <SEP> 87 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 6, <SEP> 9 <SEP> 35, <SEP> 8 <SEP>
<tb> C <SEP> PPG-2000 <SEP> 0, <SEP> 75 <SEP> 1, <SEP> 75 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 6, <SEP> 2 <SEP> 9, <SEP> 3 <SEP>
<tb> D <SEP> PPG-2000 <SEP> 0, <SEP> 75 <SEP> 1, <SEP> 75 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 6 <SEP> 8, <SEP> 8 <SEP>
<tb> C <SEP> Niax <SEP> LG
<tb> 56 <SEP> -3 <SEP> 000 <SEP> 0, <SEP> 74 <SEP> 1,

   <SEP> 76 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 2 <SEP> 24, <SEP> 8 <SEP>
<tb> D <SEP> Niax <SEP> LG
<tb> 56-3000 <SEP> 0, <SEP> 74 <SEP> 1, <SEP> 76 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4 , <SEP> 8 <SEP> 3, <SEP> 2 <SEP>
<tb> C <SEP> Niax <SEP> triol
<tb> LHT <SEP> 42-4400 <SEP> 0, <SEP> 84 <SEP> 1, <SEP> 66 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 4 <SEP> 3, <SEP> 5 <SEP>
<tb> D <SEP> Niax <SEP> triol
<tb> LHT <SEP> 42-4400 <SEP> 0, <SEP> 84 <SEP> 1, <SEP> 66 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 4 <SEP> 3, <SEP> 7 <SEP>
<tb>
 

 <Desc / Clms Page number 22>

   Table 7 (continued):

   
 EMI22.1
 
<tb>
<tb> Description <SEP> Solution <SEP> Absorption <SEP> (0/0) <SEP> Dry content <SEP> Area shrinkage <SEP> (0/0) <SEP>:
<tb> polymer
<tb> Polyol <SEP> x) <SEP> Diiso-Polyol <SEP>: <SEP> Kataly-Quadrol <SEP>: <SEP> Relaxation <SEP>: <SEP> Felt-like <SEP>: <SEP>
<tb> approximately <SEP> cyanate <SEP>: <SEP> sator <SEP>: <SEP>
<tb> Molecular <SEP> x)
<tb> weight <SEP>:

   <SEP>
<tb> a) <SEP> b) <SEP> c) <SEP> d) <SEP> e) <SEP> f) <SEP> g) <SEP> h)
<tb> C <SEP> Triol <SEP> G-4000 <SEP> 0.69 <SEP> 1.81 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 4.6 <SEP> 4 ,1
<tb> D <SEP> Triol <SEP> G-4000 <SEP> 0.69 <SEP> 1.81 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 3.6 <SEP> 4 , 3
<tb> C <SEP> Actol <SEP> 32-1000 <SEP> 1.34 <SEP> 1.16 <SEP> 0.029 <SEP> SO <SEP> 0.18 <SEP> 3.6 <SEP> 3 , 4
<tb> D <SEP> Actol32-1000 <SEP> 1, <SEP> 34 <SEP> 1,16 <SEP> 0, <SEP> 029 <SEP> SO <SEP> 0, <SEP> 18 <SEP> 4, <SEP> 1 <SEP> 4, <SEP> 4 <SEP>
<tb>
 
 EMI22.2
 
<tb>
<tb> x)

   <SEP> NMM <SEP> = <SEP> N-methylmorpholine <SEP> PBG <SEP> = <SEP> polybutylene glycol
<tb> TMBDA <SEP> = <SEP> trimethylbutanediamine <SEP> PPG <SEP> = <SEP> polypropylene glycol
<tb> SO <SEP> = <SEP> Stanno-octoat <SEP> Niax <SEP> = <SEP> Trade name <SEP> for <SEP> polymer <SEP> triols
<tb> PEG <SEP> = <SEP> Polyethylene glycol <SEP> Actol <SEP> = <SEP> Trade name <SEP> for <SEP> polymer <SEP> triols
<tb>
 

 <Desc / Clms Page number 23>

   Example 13 Various trichlorethylene solutions of 2,4-toluene-2,4-diisocyanate, various amounts of Quadrol, various polymeric polyols and catalyst were padded onto the fabric samples of the fabric from Example 1. The uptake of the various compounds is shown in Table 8.

   The specimens marked with the letter “C” were cured for 5 minutes at 121 ° C., aged for 24 hours and then tested for shrinkage. The fabric swatches designated with the letter “D” were cured for 15 minutes and aged for 18 hours before testing for their shrinkage. The swatches labeled "D" were also washed prior to testing.

 <Desc / Clms Page number 24>

 



  Table 8
 EMI24.1
 
<tb>
<tb> Name <SEP>: <SEP> Polymer <SEP> Polyol <SEP>: <SEP> Absorption <SEP> (0/0) <SEP> Dry weight <SEP> Area shrinkage <SEP> (%):
<tb> Diiso- <SEP> Polyol <SEP>: <SEP> Kataly- <SEP> Quadrol: <SEP> Relaxation: <SEP> felt-like:
<tb> cyanate <SEP>: <SEP> sator <SEP>:

   <SEP>
<tb> Control ---- 16, <SEP> 1 <SEP> 46, <SEP> 3
<tb> C <SEP> PBG-1000 <SEP> 1.14 <SEP> 1.89 <SEP> 0, <SEP> 147 <SEP> NMM <SEP> 0.22 <SEP> 0.6 <SEP> 2.9
<tb> 0.0145 <SEP> TMBDA
<tb> 0, <SEP> 03 <SEP> SO <SEP>
<tb> D <SEP> PBG-1000 <SEP> 1.14 <SEP> 1.89 <SEP> 0.03 <SEP> SO <SEP> 0.22 <SEP> 1, <SEP> 1 <SEP> 5.0
<tb> C <SEP> PPG-3000 <SEP> 0, <SEP> 81 <SEP> 2.21 <SEP> 0.03 <SEP> SO <SEP> 0.22 <SEP> 1, <SEP> 4 <SEP> 3, <SEP> 1 <SEP>
<tb> D <SEP> PPG-3000 <SEP> 0.81 <SEP> 2.21 <SEP> 0.03 <SEP> SO <SEP> 0.22 <SEP> 1, <SEP> 1 <SEP> 11.5
<tb> C <SEP> Actol <SEP> 32-160 <SEP> 1.62 <SEP> 1.40 <SEP> 0.03 <SEP> SO <SEP> 0.22 <SEP> 1.4 <SEP > 5.2
<tb> D <SEP> Actol <SEP> 32-160 <SEP> 1.62 <SEP> 1.40 <SEP> 0.03 <SEP> SO <SEP> 0.22 <SEP> 1.2 <SEP > 17.3
<tb> C <SEP> Actol <SEP> 32-160 <SEP> 1.32 <SEP> 1.71 <SEP> 0.03 <SEP> SO <SEP> 0.22 <SEP> 1.0 <SEP > 4.7
<tb> D <SEP> Actol32-160 <SEP> 1,

  32 <SEP> 1.71 <SEP> 0.03 <SEP> SO <SEP> 0.22 <SEP> 0.4 <SEP> 14.8
<tb>
 

 <Desc / Clms Page number 25>

 
 EMI25.1
 Preparations were added and the solutions were then padded onto a sample of the pure wool fabric from Example 1. The absorption of diisocyanate on the fabric was 1.06%, that of Quadrol 0.22% and that of glycol 1.97%. Each fabric was dried for 5 minutes at 710C and then cured at 1210C for the times shown in Table 9 and aged for 24 hours. The shrinkage values were then determined. Again the letters "C" and "D" are used to denote 5 min and w. Display 15 min curing time at 1210C. The swatches labeled "D" were washed prior to testing.



   Table 9
 EMI25.2
 
<tb>
<tb> Name <SEP> catalyst <SEP> hardening <SEP> area shrinkage <SEP> (%)
<tb> time <SEP> (min)
<tb> relaxation felt-like
<tb> Control-16, <SEP> 1 <SEP> 46, <SEP> 3 <SEP>
<tb> C <SEP> none <SEP> 5 <SEP> 2, <SEP> 1 <SEP> 19. <SEP> 2 <SEP>
<tb> D <SEP> none <SEP> 15 <SEP> 0, <SEP> 8 <SEP> 33, <SEP> 8 <SEP>
<tb> C <SEP> stannous octoate
<tb> 0, <SEP> 96 <SEP> parts,
<tb> trimethylbutanediamine
<tb> 0, <SEP> 48 <SEP> parts <SEP> 5 <SEP> 1, <SEP> 2 <SEP> 4, <SEP> 3 <SEP>
<tb> D <SEP> stannous octoate
<tb> 0, <SEP> 96 <SEP> parts,
<tb> trimethylbutanediamine
<tb> 0, <SEP> 48 <SEP> parts <SEP> 15 <SEP> 1, <SEP> 2 <SEP> 15, <SEP> 3 <SEP>
<tb> C <SEP> stannous octoate
<tb> 0, <SEP> 96 <SEP> 5 <SEP> 1, <SEP> 4 <SEP> 4, <SEP> 0 <SEP>
<tb> D <SEP> stannous octoate
<tb> 0, <SEP> 96 <SEP> 15 <SEP> 1, <SEP> 5 <SEP> 22,

   <SEP> 7 <SEP>
<tb> C <SEP> N-methylmorpholine
<tb> 4, <SEP> 83 <SEP> parts,
<tb> stannous octoate
<tb> 0, <SEP> 96 <SEP> parts, <SEP>
<tb> trimethylbutanediamine
<tb> 0, <SEP> 48 <SEP> parts <SEP> 5 <SEP> 1, <SEP> 5 <SEP> 4, <SEP> 2 <SEP>
<tb> D <SEP> N-methylmorpholine
<tb> 4, <SEP> 83 <SEP> parts,
<tb> stannous octoate
<tb> 0, <SEP> 96 <SEP> parts,
<tb> trimethylbutanediamine
<tb> 0, <SEP> 48 <SEP> parts <SEP> 15 <SEP> 1, <SEP> 5 <SEP> 16, <SEP> 0 <SEP>
<tb>
 

 <Desc / Clms Page number 26>

 Table 9 (continued):

   
 EMI26.1
 
<tb>
<tb> Description <SEP> catalyst <SEP> hardening area shrinkage
<tb> time <SEP> (min)
<tb> relaxation felt-like
<tb> C <SEP> N-methylmorpholine <SEP> 4, <SEP> 83 <SEP> parts
<tb> trimethylbutanediamine
<tb> 0, <SEP> 48 <SEP> parts <SEP> 5 <SEP> 2, <SEP> 1 <SEP> 16, <SEP> 5 <SEP>
<tb> D <SEP> N-methylmorpholine <SEP> 4, <SEP> 83 <SEP> parts
<tb> trimethylbutanediamine
<tb> 0, <SEP> 48 <SEP> parts <SEP> 15 <SEP> 1,9 <SEP> 31, <SEP> 0 <SEP>
<tb> C <SEP> N-methylmorpholine <SEP> 4, <SEP> 83 <SEP> parts of <SEP>
<tb> stannous octoate
<tb> 0, <SEP> 96 <SEP> parts <SEP> 5 <SEP> 1, <SEP> 2 <SEP> 3, <SEP> 6 <SEP>
<tb> D <SEP> N-methylmorpholine <SEP> 4, <SEP> 83 <SEP> parts of <SEP>
<tb> stannous octoate
<tb> 0, <SEP> 96 <SEP> parts <SEP> 15 <SEP> 1, <SEP> 2 <SEP> 12, <SEP> 0 <SEP>
<tb>
 
The values for the felt-like shrinkage of the samples that contained tolerated water,

   could be reduced by adding additional diisocyanate. These results are worse than with the anhydrous samples, since the ratio of the NCO groups to the total OH groups (including the -OH groups from the water in the fabric) was lower than with the anhydrous samples
Inspect.



   Example 15 Trichlorethylene solutions with a content of 100 parts of toluene-2,4-diisocyanate and 186 parts of polypropylene glycol (molecular weight about 1200) were added to various reactants. These solutions also contained the catalyst preparations according to Example 12. The solutions were diluted with trichlorethylene to a fat content of about 3% and applied to a sample of the pure wool fabric from Example 1 up to an absorption of 1.060/0 diisocyanate, 1.97%
Polypropylene glycol, the same amounts of catalyst as in Example 12 and the amounts of the further reactant shown in Table 10. The impregnated fabrics were then applied
Dried 5 min at 710C, cured at 1210C for the times listed in Table 10 and
Aged for 24 hours. They were then tested for their shrinkage values.

   This drying at lower
A temperature of 710C and hardening at a higher temperature served to simplify the recovery of the solvent.



   If 1,6-hexanediamine was used, this reaction partner was padded onto the fabric, dried on it and the preparation of toluylene-2,4-diisocyanate, polypropylene glycol and catalyst was padded onto the fabric. This two-step process was used because if all the components were mixed, the preparation would have a short pot life. The letters "C" and "D" are used as in the previous examples.

 <Desc / Clms Page number 27>

 



  Table 10
 EMI27.1
 
<tb>
<tb> Designation <SEP> Another <SEP> recording <SEP> hardening area shrinkage
<tb> reaction of the <SEP> white-time <SEP>
<tb> partner <SEP> teren <SEP> Rea- <SEP> (min)
<tb> tion partner <SEP>%
<tb> Relaxation <SEP> felt-like
<tb> control - 16. <SEP> 1 <SEP> 46, <SEP> 3 <SEP>
<tb> C <SEP> 1, <SEP> 6-hexane <SEP>
<tb> diamine <SEP> 0, <SEP> 18 <SEP> 5 <SEP> 2,1 <SEP> 4, <SEP> 7 <SEP>
<tb> D <SEP> 1, <SEP> 6-hexane <SEP>
<tb> diamine <SEP> 0, <SEP> 18 <SEP> 15 <SEP> 1, <SEP> 9 <SEP> 5, <SEP> 3 <SEP>
<tb> C <SEP> Azelaic acid <SEP> 0, <SEP> 29 <SEP> 5 <SEP> 5, <SEP> 0 <SEP> 41, <SEP> 8 <SEP>
<tb> D <SEP> Azelaic acid <SEP> 0, <SEP> 29 <SEP> 15 <SEP> 1, <SEP> 2 <SEP> 43, <SEP> 1 <SEP>
<tb> C <SEP> methyldi-
<tb> Ethanolamine <SEP> 0, <SEP> 18 <SEP> 5 <SEP> 3, <SEP> 8 <SEP> 39, <SEP> 2 <SEP>
<tb> D <SEP> methyldi-
<tb> ethanolamine <SEP> 0,

   <SEP> 18 <SEP> 15 <SEP> 3.1 <SEP> 44.1
<tb> C <SEP> triethanolamine <SEP> 0, <SEP> 15 <SEP> 5 <SEP> 1, <SEP> 1 <SEP> 8, <SEP> 3 <SEP>
<tb> D <SEP> Triethanolamine <SEP> 0. <SEP> 15 <SEP> 15 <SEP> 1, <SEP> 0 <SEP> 7, <SEP> 5 <SEP>
<tb>
   Example 16: There were various trichlorethylene solutions containing 100 parts of toluene-2, 4-diisocyanate and 130 parts of the triol Actol 32 to 160, in the presence or absence of a further reactant, as indicated in Table 11 and with the same content Catalyst as in Example 12, padded onto a sample of the pure wool fabric from Example 1. When using 1,6-hexanediamine, the diisocyanate-actol solution was padded separately and, after drying, the 1,6-hexanediamine was padded onto the fabric and dried.

   In the other tests in this example, the reactant was added directly to the solution. The tests designated with the letter "C" were dried for 5 minutes at 710C, cured for 5 minutes at 1210C and aged for 24 hours before they were tested for their shrinkage values. The samples labeled with the letter "D" were dried in the same manner and cured for 15 minutes at 1210C, aged for 24 hours and then washed before being tested for their shrinkage values. During its impregnation, 1.32% diisocyanate, 1.71% Actol and the various amounts of the reactant listed in Table 11 were absorbed on the fabric.



   Table 11
 EMI27.2
 
<tb>
<tb> Designation <SEP> Another <SEP> recording <SEP> at <SEP> area shrinkage
<tb> reaction <SEP> further <SEP> repartner <SEP> action partners
<tb> relaxation <SEP> felt-like
<tb> Control <SEP> 16.1 <SEP> 46.3
<tb> C <SEP> Quadrol <SEP> 0, <SEP> 22 <SEP> 1, <SEP> 3 <SEP> 6, <SEP> 2 <SEP>
<tb>
 

 <Desc / Clms Page number 28>

 Table 11 (continued):

     
 EMI28.1
 
<tb>
<tb> Designation <SEP> Another <SEP> recording <SEP> at <SEP> area shrinkage
<tb> Reaction-further <SEP> Re- <SEP>
<tb> partner <SEP> action partners
<tb> relaxation felt-like
<tb> D <SEP> Quadrol <SEP> 0, <SEP> 22 <SEP> 2, <SEP> 0 <SEP> 13, <SEP> 9 <SEP>
<tb> C <SEP> I, <SEP> 6-hexanedi- <SEP>
<tb> amine <SEP> 0.18 <SEP> 1, <SEP> 4 <SEP> 3, <SEP> 4 <SEP>
<tb> D <SEP> 1, <SEP> 6-hexanedi- <SEP>
<tb> amin <SEP> 0, <SEP> 18 <SEP> 1, <SEP> 0 <SEP> 3, <SEP> 0 <SEP>
<tb> C <SEP> Azelaic acid <SEP> 0, <SEP> 29 <SEP> 1, <SEP> 5 <SEP> 4, <SEP> 3 <SEP>
<tb> D <SEP> Azelaic acid <SEP> 0, <SEP> 29 <SEP> 1, <SEP> 9 <SEP> 7, <SEP> 1 <SEP>
<tb> C <SEP> methyl diethanolamine <SEP> 0, <SEP> 18 <SEP> 1, <SEP> 9 <SEP> 3, <SEP> 9
<tb> D <SEP> methyl diethanolamine <SEP> 0, <SEP> 18 <SEP> 1, <SEP> 3 <SEP> 6, <SEP> 5 <SEP>
<tb>
 
 EMI28.2
 :

   Eine'Trichloräthylenlösunglen N-methylmorpholine, 0.96 parts of stannous octoate and 0.48 parts of trimethylbutanediamine were padded to various samples of the pure wool fabric from Example 1, up to an absorption of 1.22% diisocyanate, 2.50% polyethylene glycol, 0.27% Quadrol, 0.147% N-methylmorpholine, 0.03% stannous octoate, and 0.0145% trimethylbutanediamine on the fabric. These fabrics were then dried and cured under the conditions given in Table 12, whereupon they were aged in the same manner as in the previous examples for 24 hours at room temperature. They were then tested for their shrinkage values.



   Table 12
 EMI28.3
 
<tb>
<tb> Curing conditions <SEP> Area shrinkage <SEP>%
<tb> relaxation <SEP> felt-like
<tb> Control <SEP> 16,1 <SEP> 46, <SEP> 3 <SEP>
<tb> no <SEP> heat treatment <SEP> - <SEP> 24 <SEP> h
<tb> Aging <SEP> 2, <SEP> 7 <SEP> 25, <SEP> 2 <SEP>
<tb> 2 <SEP> min <SEP> at <SEP> 1210C <SEP> - <SEP> 24 <SEP> h
<tb> Aging <SEP> 2, <SEP> 5 <SEP> 11, <SEP> 9 <SEP>
<tb> 5 <SEP> min <SEP> at <SEP> 121 C-24 <SEP> h
<tb> Aging <SEP> 2, <SEP> 1 <SEP> 11, <SEP> 2 <SEP>
<tb> 5 <SEP> min <SEP> at <SEP> 104 C-24 <SEP> h
<tb> Aging <SEP> 2, <SEP> 7 <SEP> 14, <SEP> 3 <SEP>
<tb> 5 <SEP> min <SEP> at <SEP> 880C <SEP> - <SEP> 24 <SEP> h
<tb> Aging <SEP> 4, <SEP> 1 <SEP> 16, <SEP> 9 <SEP>
<tb>
 
The uptake was kept low in this example to clearly show the effect of different curing conditions.

   

 <Desc / Clms Page number 29>

 



   Example 18: A trichlorethylene solution containing 100 parts of toluene- - 2,4-diisocyanate, 130 parts of the triol Actol 32 to 160, 16.5 parts of Quadrol, 4.83 parts of N-methylmorpholine, 0.48 parts of trimethylbutanediamine was used , and 0.96 parts of cobalt naphthenate. This solution was further diluted with trichlorethylene and then applied to a sample of the pure wool fabric from Example 1 up to an absorption of 1.320/0 diisocyanate, 1.71% Actol, 0.22% Quadrol and the same amounts of catalyst as in Example 12, padded. The fabric was then divided into 2 specimens, one cured for 5 minutes at 1210C and the other for 15 minutes at 1210C. Both were then aged for 24 hours and tested for their shrinkage values.

   The sample cured for 5 minutes had a relaxation shrinkage of 2.5% and the sample cured for 15 minutes had a relaxation shrinkage of 2.7%.



   Example 19: A trichlorethylene solution containing 100 parts of hexamethylene diisocyanate, 135 parts of the triol Actol 32 to 160, 17.4 parts of Quadrol, 4.83 parts of N-methylmorpholine, 0.48 parts of trimethylbutanediamine and 0.96 parts was produced Stannous octoate produced. This solution was further diluted with trichlorethylene and applied to a fabric swatch of the pure wool fabric
 EMI29.1
 Both fabrics were left to age for 48 hours and the shrinkage values were determined. The fabric cured for 5 minutes had a relaxation shrinkage of 1.70/0 and a felt-like shrinkage of 2.5% while the fabric cured for 15 minutes had a relaxation shrinkage of 1.70/0 and a felt-like shrinkage of 10.9%.

   An untreated control had a relaxation shrinkage of 16.1% and a matting shrinkage of 46.3%.



   Example 20: A pure wool fabric similar to that used in Example 1 but with two warp threads and two weft threads more than 2.54 cm each was treated with a trichlorethylene solution of the precondensate from Example 1 and from Quadrol up to an absorption of 2.87% precondensate and 0 , 23% Quadrol impregnated. The impregnated fabric was dried at 71 ° C. for 5 minutes and then cured at 2120 ° C. for 10 minutes. For comparison purposes, a sample of the same fabric was not treated according to the invention, but rather subjected to a typical chlorine treatment to prevent shrinkage. The surface shrinkage and various properties of these fabrics were measured and are shown in Table 13.

 <Desc / Clms Page number 30>

 



  Table 13
 EMI30.1
 
<tb>
<tb> fabric <SEP>: <SEP> absorption <SEP>% <SEP> surface shrinkage- <SEP> tensile strength- <SEP> elongation <SEP>%: <SEP> tear resistance- <SEP> bending resistance- <SEP> level
<tb> Dry weight <SEP>: <SEP> action <SEP> (%): <SEP> speed: <SEP> rigidity: <SEP> ring: <SEP> abrasion:
<tb> Precon- <SEP> Quadrol: <SEP> Relax .: <SEP> felt- <SEP> warp: <SEP> weft: <SEP> warp: <SEP> weft: <SEP> warp: <SEP> weft : <SEP> (Cyclen) <SEP> (Cyclen)
<tb> densat <SEP>: <SEP> like <SEP>: <SEP> kg <SEP> (In- <SEP> (In- <SEP> g <SEP> (In- <SEP> chain: <SEP> Shot:
<tb> stron) <SEP> stron) <SEP>: <SEP> stron) <SEP>:

   <SEP>
<tb> Untreated
<tb> Control <SEP> 16, <SEP> 0 <SEP> 36.7 <SEP> 15.2 <SEP> 21.3 <SEP> 34.0 <SEP> 29.3 <SEP> 1274 <SEP> 1007 <SEP> 234 <SEP> 111 <SEP> 596
<tb> Chlorinated <SEP> control <SEP> 9, <SEP> 3 <SEP> 2.5 <SEP> 12.2 <SEP> 15.5 <SEP> 26.0 <SEP> 27.3 <SEP> 1243 <SEP> 866 <SEP> 128 <SEP> 63 <SEP> 408
<tb> Treated
<tb> tissue <SEP> 2.87 <SEP> 0.23 <SEP> 4.2 <SEP> 1.4 <SEP> 18.3 <SEP> 26.0 <SEP> 35.6 <SEP> 30 , <SEP> 6 <SEP> 1302 <SEP> 1001 <SEP> 510 <SEP> 272 <SEP> 826
<tb>
 

 <Desc / Clms Page number 31>

 
Example 21: The pure wool fabric from example 20 was impregnated with a precondensate solution according to example 1 up to an absorption of 3.0% precondensate, 0.22% Quadrol and 0.3% silicone finish.

   The fabric was then dried for 5 minutes at 710 ° C., folded over one another and pressed under steam in a Hoffman press for 30 seconds, left without steam for another 30 seconds and kept under vacuum for a further 10 seconds. The folded fabric was then cured for 10 minutes at 1210C while still being held in the folded state.



   After aging for 18 hours, the folded fabric was immersed in water containing 0.1% Surfonic N-95, a nonionic wetting agent, for 30 minutes at 770 ° C., dried in the unfolded state and the folding was subjectively assessed. In an appraisal system for the folding. according to which the best fold received a grade of 5.0 and a flat fabric received a grade of 1.0, the fabric folded according to the above procedure received a grade of 5.0.



   A swatch of the same fabric was impregnated up to the same uptake, dried as before, cured for 10 min at 1210C and folded and tested as above. The fabric treated in this way received a grade of 1.0.



   In another experiment, a sample of the same fabric was folded in a Hoffman press in the same way as before, and then impregnated and cured as above. The fabric treated in this way received a rating of 5.0.



     Example 22: A single yarn was removed from a treated fabric according to Example 20, embedded in the epoxy resin known under the trade name Araldite and this was then
 EMI31.1
 
So often considered. Photographs produced at this magnification were enlarged to 5.3 times the diameter, but again no coating was observed on the individual fibers. Photomicrographs with a magnification of 50,000 times the diameter also showed no visible coating.



     Example 23: Examples of the pure wool fabric from Example 1 were padded with an aqueous emulsion of a blocked precondensate with terminal isocyanate groups, which is sold by Thiokol Company under the trade name “JL-2 Emulsion”. The uptake of the precondensate on the fabric was 5%.



   The impregnated fabric was dried for 20 minutes at 1210 ° C. and then cured for 3 minutes at 154 ° C. in order to cause the precondensate to dissociate.



   The fabric treated in this way had a relaxation shrinkage of 1.00/0 and a felt-like shrinkage of 1.000. The latter was washed three times for 30 minutes in an automatic
Washer detected.



   If this process was repeated, but with 3% uptake of the blocked precondensate, the relaxation and felt-like shrinkages were 1, 8 and 4, 6%, respectively.



   The corresponding values in an untreated control experiment were 10, 6 and 14, 1%, respectively.



     Example 24: The process of Example 23 was repeated, but instead of the emulsion from Example 23, the "Emulsion D-95407-JL" from Thiokol was used. The values for the relaxation and felt-like shrinkage with 5% absorption were 0.5 and 10/0, respectively, and with 3% absorption 0, 2 and 1.8%, respectively.



   Example 25: The precondensates from Examples 23 and 24 were separated from the emulsions and dissolved in ethyl acetate. Fabric swatches were treated as in Example 23 with these solutions. With slightly lower recordings, slightly improved results were achieved in this way. The hand of these fabrics was better than that of the fabrics that had been treated with aqueous systems.



   Example 26: A mixture of diisocyanate isomers with a content of 800/0 toluene- - 2,4-diisocyanate and 20% toluene-2,6-diisocyanate were obtained by adding stoichiometric amounts of different compounds with active hydrogen atoms, which are in different solvents were dissolved, which again contained various catalysts, blocked, as shown in Table 14.



   After the exothermic reaction had ended, the solutions obtained were heated to 80 ° C. for 3 h.



  The warm solutions were diluted with the solvent heated to the same temperature to a solids content of 10% and then 10% trichlorethylene solutions of polypropylene glycol (molecular weight about 2,000), containing quadrol, trimethylbutanediamine and tin octoate

 <Desc / Clms Page number 32>

 added.

   The preparations thus obtained were diluted with a mixture of trichlorethylene and the solvent used during the blocking in a ratio of 1: 1, so that the following dry weights of the various compounds were used with a 135% moisture increase when padding the fabric from Example 1; 2.46% polypropylene glycol, 0.28% Quadrol, 0.0445% trimethylbutanediamine, 0.029% tin octoate, and blocked isocyanate in such an amount that 1.30% active isocyanate compound was present.



   The impregnated fabric was then dried and cured at the temperature given in Table 14.



   In each case the relaxation and entangling shrinkage of the fabric samples was significantly inhibited.



   Table 14
 EMI32.1
 
<tb>
<tb> blocking <SEP> agent <SEP> solvent <SEP> catalyst <SEP> curing <SEP>
<tb> temperature
<tb> (OC)
<tb> Ethanol <SEP> Ethanol <SEP> none <SEP> 160
<tb> 2-methyl-2-propanol <SEP> toluene <SEP> triethylamine <SEP> 150
<tb> m-cresol <SEP> benzene <SEP> triethylamine <SEP> 95
<tb> o-nitrophenol <SEP> toluene <SEP> triethylenediamine <SEP> 85
<tb> 0 <SEP> - <SEP> chlorophenol <SEP> chloroform <SEP> triethylenediamine <SEP> 65
<tb> Guaiacol <SEP> Chloroform <SEP> Triethylamine <SEP> 100
<tb> Resorcinol <SEP> Dioxane <SEP> Triethylamine <SEP> 90
<tb> Phloroglucine <SEP> Dioxane <SEP> Triethylamine <SEP> 120
<tb> 1-dodecanethiol <SEP> toluene <SEP> triethylamine <SEP> 120
<tb> Thiophenol <SEP> (Benzene-Chloroform <SEP> Triethylenethiol)

   <SEP> diamine <SEP> 100
<tb> Acetoacetic acid ethyl-toluene <SEP> sodium <SEP>
<tb> ester <SEP> methylate <SEP> 100
<tb> Malonic acid diethyl toluene <SEP> Sodium <SEP>
<tb> ester <SEP> methylate <SEP> 95
<tb> c- <SEP> caprolactam <SEP> toluene <SEP> triethylenediamine <SEP> 150
<tb> carbamic acid <SEP> tetrachloro <SEP> triethyl
<tb> ethyl ester <SEP> carbon <SEP> amine <SEP> 135
<tb> boric acid <SEP> tetrahydro- <SEP>
<tb> furan <SEP> none <SEP> 85
<tb>
 
Largely similar results were obtained when these compounds with active hydrogen atoms were used to block the precondensate from Example 1 and this blocked precondensate was applied to the fabric and cured under the same conditions.

 <Desc / Clms Page number 33>

 



   Example 27: The preparations from Example 26 lead to largely similar results when used in an aqueous emulsion, but the fabrics treated in this way have a somewhat harder feel.



   The dry folding was tested in the following examples on pretreated fabrics. The samples had the following dimensions: 11.43 cm in the direction of the weft and 15.24 cm in the direction of the warp. These samples were folded in half, with the fold being parallel to the weft threads. The samples were then placed in a Hoffman press, the lid closed and blocked, and the samples pressed for various lengths of time, as indicated in the example, generally with 30 sec baking and 10 sec vacuum treatment.
 EMI33.1
 Drying, the wrinkles still present in the samples were subjectively assessed by at least 3 observers, with grades from 1 (no significant wrinkle) to 5 (very sharp wrinkle) being found.



   Example 28: A trichlorethylene solution with a content of 8.8 g of the precondensate from Example 1, 0.9 g of Quadrol and 0.62 g of silicone resin 1172 was applied to a sample of a woolen fabric "Style No. 477" from Deering Milliken up to 145 % Moisture absorption padded. After a drying time of 5 min at 71 ° C., the fabric was folded and pressed on a Hoffman press using press cycles of 30 sec steaming, 30 sec baking and 10 sec vacuum application. The folded web was then removed from the press and condensed for 5 minutes at 120 ° C. while held in the folded state. It was then left to age overnight and the fabric tested as indicated above.

   The fold of this fabric was rated 5.0, i.e. H. the highest possible.



     Example 29: A fabric sample according to Example 28 was, as described in Example 28, folded on a Hoffman press. While it was still folded, the fabric was padded with the solution from Example 28 until it was slightly absorbed in moisture, dried for 5 minutes at 710C and condensed for 5 minutes at 1210C. All of these operations were performed while the fabric was kept folded.



   It was then left to age overnight and tested as above. The score for the crease was 5.0, i.e. H. the highest possible.



     Example 30: Various samples of a pure wool flannel fabric were padded with trichlorethylene solutions containing the precondensate from Example 1, Quadrol and the silicone resin from Example 28, the images given in Table 15 being obtained. The fabric was then dried by drying at 71 ° C for 5 minutes and then folded and pressed with my Hoffman press. The times for steaming and baking are shown in Table 15. The fabric was then left to age for the times indicated in Table 15 and checked for folding, with or without additional heating to 121 ° C., as indicated in Table 15.

 <Desc / Clms Page number 34>

 



  Table 15
 EMI34.1
 
<tb>
<tb> Recording <SEP> (0/0) <SEP>: <SEP> Press <SEP> tour <SEP> additional <SEP> aging time <SEP> grade <SEP> for <SEP> the
<tb> (seconds) <SEP> Condensation <SEP> Before <SEP> the <SEP> test <SEP> fold:
<tb> precondensate: <SEP> Quadrol; <SEP> silicone: <SEP> in <SEP> function
<tb> Damp- <SEP> Bak- <SEP> minutes <SEP>: <SEP> (hours):
<tb> fen <SEP>: <SEP> ken <SEP>:

   <SEP>
<tb> 30 <SEP> 30-1 / 3 <SEP> 1, <SEP> 0 <SEP>
<tb> 30 <SEP> 30 <SEP> - <SEP> 18 <SEP> 1.0
<tb> 2, <SEP> 0 <SEP> 0.15 <SEP> 0.20 <SEP> 30 <SEP> 30 <SEP> - <SEP> 1/4 <SEP> 2.6
<tb> 2, <SEP> 0 <SEP> 0, <SEP> 15 <SEP> 0, <SEP> 20 <SEP> 30 <SEP> 30-18 <SEP> 3, <SEP> 4 <SEP>
<tb> 3, <SEP> 0 <SEP> 0, <SEP> 22 <SEP> 0, <SEP> 30 <SEP> 30 <SEP> 30-1 / 4 <SEP> 3, <SEP> 3 <SEP >
<tb> 3, <SEP> 0 <SEP> 0, <SEP> 22 <SEP> 0, <SEP> 30 <SEP> 30 <SEP> 30 <SEP> - <SEP> 18 <SEP> 3.8
<tb> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 30 <SEP> 30 <SEP> - <SEP> 1/4 <SEP> 3, 5
<tb> 4, <SEP> 0 <SEP> 0.29 <SEP> 0.35 <SEP> 30 <SEP> 30 <SEP> - <SEP> 18 <SEP> 3.9
<tb> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 30 <SEP> 90 <SEP> - <SEP> 18 <SEP> 3.9
<tb> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 30 <SEP> 180-1 / 4 <SEP> 4, <SEP> 0 <SEP >
<tb> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0,

   <SEP> 35 <SEP> 30 <SEP> 90 <SEP> 15 <SEP> 1/4 <SEP> 4, <SEP> 5 <SEP>
<tb> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 30 <SEP> 180 <SEP> 15 <SEP> 1/4 <SEP> 4, <SEP> 8 <SEP>
<tb> 4, <SEP> 0 <SEP> 0 <SEP> 0, <SEP> 35 <SEP> 30 <SEP> 180 <SEP> 15 <SEP> 1/4 <SEP> 1, <SEP> 5 < SEP>
<tb>
 

 <Desc / Clms Page number 35>

 
 EMI35.1
 (Dry pickup) received. These fabrics were dried at 710C for 5 minutes and heated at 1210C for 10 minutes. The fabrics were then folded according to Example 28, after a time interval as indicated in the table.

   The fact that permanent wrinkles could be fixed in the tissue during aging suggests that the condensing heating initiates the reaction between various reactants and the keratin fibers to a considerable extent, but that the condensation actually lasts for a longer time after the heating, d. H. the condensation takes a long time.



   The fabrics labeled "A" in Table 16 were pure wool combed yarn fabrics, while the fabrics labeled "B" in Table 16 consisted of blends of 85% wool and 15% nylon with 5.5 runs.



   Table 16
 EMI35.2
 
<tb>
<tb> tissue <SEP> precondensate <SEP> intake <SEP>% <SEP> silicone <SEP> time interval <SEP> before <SEP> note <SEP> for
<tb> Quadrol <SEP> the <SEP> fold <SEP> (h) <SEP> the <SEP> fold
<tb> A <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 1, <SEP> 3
<tb> C ---- 1, <SEP> 0 <SEP>
<tb> A <SEP> 3, <SEP> 25 <SEP> 0, <SEP> 24 <SEP> 0, <SEP> 35 <SEP> before <SEP> 10 <SEP> min <SEP> long
<tb> Warm up <SEP>
<tb> 1210C <SEP> folded <SEP> 3, <SEP> 9 <SEP>
<tb> B <SEP> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> before <SEP> 10 <SEP> min <SEP> long
<tb> Warm up <SEP>
<tb> 1210C <SEP> folded <SEP> 4, <SEP> 8 <SEP>
<tb> A <SEP> 3, <SEP> 25 <SEP> 0, <SEP> 24 <SEP> 0, <SEP> 35 <SEP> 1/4 <SEP> 3, <SEP> 5 <SEP>
<tb> B <SEP> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 1/4 <SEP> 3, <SEP> 6 <SEP>
<tb> A <SEP> 3, <SEP> 25 <SEP> 0,

   <SEP> 24 <SEP> 0. <SEP> 35 <SEP> 1 <SEP> 3, <SEP> 0 <SEP>
<tb> B <SEP> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 1 <SEP> 3, <SEP> 5 <SEP>
<tb> A <SEP> 3, <SEP> 25 <SEP> 0, <SEP> 24 <SEP> 0, <SEP> 35 <SEP> 3 <SEP> 3, <SEP> 1 <SEP>
<tb> B <SEP> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 3 <SEP> 3, <SEP> 2 <SEP>
<tb> A <SEP> 3, <SEP> 25 <SEP> 0, <SEP> 24 <SEP> 0, <SEP> 35 <SEP> 6 <SEP> 2, <SEP> 9 <SEP>
<tb> B <SEP> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 6 <SEP> 3, <SEP> 2 <SEP>
<tb> A <SEP> 3, <SEP> 25 <SEP> 0, <SEP> 24 <SEP> 0, <SEP> 35 <SEP> 18 <SEP> 1, <SEP> 0 <SEP>
<tb> B <SEP> 4, <SEP> 0 <SEP> 0, <SEP> 29 <SEP> 0, <SEP> 35 <SEP> 18 <SEP> 1, <SEP> 0 <SEP>
<tb>
   Example 32:

     Largely permanent folds were obtained when pure wool fabrics were treated according to Examples 1 to 28 but were folded and condensed according to Example 28. The best results in terms of permanent folding were obtained with the fabric samples in which both the relaxation and the felt-like shrinkage were low. In the method according to Example 26, the folds produced in the fabric were largely permanent, after folding in the Hoffman press, if m-cresol, o-nitrophenol, o-chlorophenol, thiophenol, acetoacetic acid ethyl ester, guaiacol, resorcinol, Boric acid or diethyl malonate were used.

   However, better results were obtained when the tissue was heated to 1210C for 5 minutes, since this temperature exceeds the unblocking temperature for these compounds and ensures the release of active isocyanate groups. For the blocked compounds activated at higher temperatures, i. H. Compounds in which the blocking agent is ethanol, 2-methyl-2-propanol, phlorglucinol, 1-dodecanethiol, thiphenol, ethyl acetoacetate, e-caprolactam or ethyl carbamic acid

 <Desc / Clms Page number 36>

 was heated to the unblocking temperatures listed in Table 14 for the individual compounds.



     Example 33: A pure wool fabric was treated with the solution from Example 28 up to the same absorption. After drying at 71 ° C, the fabric was pressed by passing it through a three-roll calender with a fiber-filled roll between two steel rolls in a vertical position. The fiber-filled roller was a 55/45 corn hull fiber filled roller. Temperatures of about 1770C and pressures of about 80 t, corresponding to 5800 kg / dm at the point of contact, were used. The fabric was then completely decorated by forcing steam through the fabric at 422 atmospheres and holding it under this steam pressure for 10 minutes after the breakthrough. The fabric treated in this way had a high gloss, which proved to be permanent when steamed and moistened.



   The reactive compounds, as mentioned above, can all be applied to the tissue from a single solution, e.g. B. by padding, spraying od. Similar., U. between a continuous process with high output. For example, product speeds of 54 m / min or more are completely possible with a conventional padding system, since the fabric only needs to be in contact with the solution until it is impregnated and this occurs very quickly with woolen fabrics in organic solutions.



   The method according to the invention can be used to inhibit relaxation shrinkage in any woolen fabric, even in stretched fabrics and fabrics that have been dried in stretched form to achieve greater mass. Normally, the larger mass obtained in this way is lost again when it later becomes wet, e.g. B. in the treatment for anti-shrinkage treatment according to known methods or during the decatization, which is required in tissues after the treatment for inhibition of relaxation shrinkage according to conventional methods. However, the higher mass obtained by stretching and drying in stretched form is retained after the treatment of the fabric according to the invention, since essentially no relaxation shrinkage occurs during the treatment, in contrast to the earlier methods with immersion in water.

   The fabric treated according to the invention also remains resistant to relaxation shrinkage when it is used later, so that it can be dyed, washed or otherwise treated without significant loss of size and unlike stretched fabrics from known processes with similar post-treatment. Furthermore, fabrics treated according to the invention can be supplied to the consumer in a form suitable for cutting without having to be decated to stabilize the mass.



   PATENT CLAIMS:
1. A method for modifying the properties of keratin fiber-containing articles, in particular for reducing the shrinkage of keratin fiber-containing textile fabrics, characterized in that these fibers with a polyfunctional isocyanate or a compound which contains at least two -N = C = X groups, wherein X is a Is oxygen or a sulfur atom, and a polymeric polyhydroxy compound.

 

Claims (1)

2. The method according to claim 1, characterized in that the polyfunctional isocyanate and the polymeric polyhydroxy compound are used as such. 3. The method according to claim l, characterized in that a blocked polyfunctional isocyanate is used. 4. The method according to claim l, characterized in that the reaction product of a polyfunctional isocyanate and a polymeric polyhydroxy compound is applied to the fibers. 5. Process according to Claims 1 and 4, characterized in that a blocked reaction product is used. 6. The method according to any one of claims 1 to 5, characterized in that the reaction is carried out in the presence of a further reactant with at least two groups which contain at least one active hydrogen atom, such as in particular an acid, an amine or a polyol. 7. The method according to claim 6, characterized in that the fibers are impregnated with a polyfunctional isocyanate and a polymeric polyhydroxy compound and the polyfunctional isocyanate and the polymeric polyhydroxy compound are cured on the fiber. <Desc / Clms Page number 37> EMI37.1 hydroxy compound applied dissolved in an organic solvent. 9. The method according to claims 1 and 2, characterized in that a ratio between isocyanate groups and hydroxyl groups of the polyfunctional isocyanate or polyhydroxy compounds is established which is higher than 0.5, preferably higher than 1.0 or 1.1. 10. The method according to claim 8, characterized in that an organic solution is used in which a reactant with at least two groups which contain at least one active hydrogen atom is also present. 11. The method according to any one of claims 1 to 10, characterized in that to reduce the shrinkage of a fabric containing keratin fibers, the fabric is impregnated with an organic, isocyanate-nonreactive solvent which has a compound with at least two -N = C = 0 groups , a polymeric hydroxy compound and a reactant with at least two groups which contain at least one active hydrogen atom, in particular an acid or a monomeric polyol, and the impregnated fabric dries and hardens to cause a reaction between the keratin fibers and the compounds contained in the organic solvent . 12. The method according to claim 1, characterized in that the reaction is carried out in the presence of a catalyst. 13. The method according to claim 11, characterized in that a water-containing fabric is impregnated with the organic solvent. 14. The method according to any one of claims 11 to 13, characterized in that the isocyanate used is an aryl diisocyanate, in particular toluene-2,4-diisocyanate. 15. The method according to claim 14, characterized in that a polyether glycol is used as the polymeric polyhydroxy compound. 16. The method according to claim 13, characterized in that the pH of the solution is kept at about 7 while it is in contact with the tissue. EMI37.2 the reaction of the fibers with the reaction product of a polyfunctional isocyanate and a polymeric polyhydroxy compound in the presence of a material having at least two groups which contain at least one active hydrogen atom is carried out. EMI37.3 according to claim 17, characterized in that cyanate carries out. 19. The method according to any one of claims 1 to 18, characterized in that a solution is used in particular for the treatment of predominantly wool fiber-containing fabric for impregnation, which is the reaction product of an excess of a polyfunctional isocyanate with a polymeric polyhydroxy compound, another reactant with at least two groups , which contain at least one active hydrogen atom, and a polyfunctional isocyanate with a ratio of the total isocyanate groups to the total hydrogen atoms added to the system from the beginning of the preparation of the reaction product of more than about 0.5, the impregnated fabric dries and hardens, whereupon this is mechanically processed in an aqueous medium. 20. The method according to claim 3 or 6, characterized in that the fibers are impregnated with a blocked polyfunctional isocyanate and a polymeric polyhydroxy compound and the impregnated fibers are heated to a temperature sufficient to activate the blocked polyfunctional isocyanate. EMI37.4 with an aqueous system or with a system contained in organic solution. 22. The method according to claim 20, characterized in that the reaction is carried out in the presence of a catalyst for the reaction of active hydrogen atoms with isocyanates.