Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them

Definitions

• the present invention was therefore based on the object of developing a process based on technically easily accessible starting materials for producing such textile finishing agents which are as colorless as possible and which, at the same time, are still further improved in the entirety of their application properties.
• the solution to this problem was found in the method according to claim 2.
• the finishing agents obtainable in this way are not only colorless or almost colorless, but also have the following very important properties: storage stability of the neutral solution and bath stability in acid solution with good reactivity at the same time; high chlorine and hydrolysis resistance on the finished textile; good abrasion resistance; pleasant textile grip even without plasticizer; low soiling; low release of formaldehyde. After all, the finished textiles can be printed very well. The combination of colorlessness with all of these excellent properties, which have practically no disadvantages, makes the finishing agent obtainable according to the invention extremely valuable.
• approximately equimolar amounts are urea and polyethylene glycol III (one end of which may be etherified with methyl, ethyl, propyl or butyl alcohol; However, preference is given to the free, that is to say unetherified at both chain ends, polyethylene glycols) of degree of polymerization 9 to 100, preferably 9 to 20, expediently in an inert gas stream in order to exclude air and to remove the ammonia formed, some without catalyst, with stirring (about 2 to 7, preferably 3 to 6) Heated to 130 to 160, preferably 145 to 155 ° C.
• the reaction can be carried out under pressure or under pressure continuously or batchwise with or preferably without a solvent.
• Higher-boiling organic liquids e.g. aromatic or araliphatic hydrocarbons, for example toluene, xylene, ethylbenzene, isopropylbenzene and mixtures thereof.
• the solvent is distilled off after the reaction.
• the alkyl glycol or glycol IV, preferably methyl glycol, and optionally the catalyst are added to the reaction mixture with stirring, and heating is advantageously continued for 2 to 40, preferably 5 to 20, hours, preferably in a vacuum, while the inert gas stream is passed through or in vacuo with catalyst to 130 to 165, in particular 145 to 155 ° C, or without catalyst to 150 to 200, in particular 160 to 190 ° C, with a lower temperature of course corresponding to a longer reaction time and vice versa.
• the reaction temperature is only of importance insofar as discoloration is to be expected if the temperature is too high and the reaction time is excessively increased if the temperature is too low.
• the molar ratio of alkyl glycol or glycol IV to the urea used for the second stage should be 1: (0.5 to 1), preferably about 1: 1. At a ratio of 1: (1), the excess of IV is then distilled off.
• the molar ratio of carbamate I to carbamate II is in the range from 12: 1 to 1:20, preferably from 1: 1 to 1:15, , in particular from 1: 2.5 to 1:12, the range from 12: 1 to about 1: 1 only being considered for polyester-cotton mixed goods.
• the catalyst which is expediently used in the second stage consists of nickel ion-containing, generally acidic ion exchangers, preferably acidic synthetic resin exchangers.
• Such exchangers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 1/1, page 528, Table 3.
• Strongly and moderately strong acid exchangers for example phenolic or polystyrene sulfonic acid resins, or exchangers containing corresponding acid resins, for example bifunctional condensation resins, are preferably used. It is also possible to use styrene-phosphonic acid, styrene-phosphinic acid, resorcinol resins and aliphatic or aromatic carboxylic acid resins.
• the aforementioned cation exchangers are commercially available in numerous variants.
• the exchanger is loaded with nickel using the customary methods, expediently by treatment with solutions, advantageously aqueous solutions, of nickel salts.
• Suitable nickel salts are suitably nickel chloride, acetate, bromide, nitrate or preferably nickel sulfate.
• the nickel compounds can also be present as corresponding hydrates, for example nickel chloride hexahydrate.
• nickel phosphate, nickel carbonate, nickel bicarbonate, nickel borate, nickel oxalate, nickel propionate for example, nickel phosphate, nickel carbonate, nickel bicarbonate, nickel borate, nickel oxalate, nickel propionate.
• the exchanger is expediently activated with acid, preferably with sulfuric acid or the acid corresponding to the anion of the nickel salt, before the treatment with the nickel salt.
• the exchanger is first left under or in water at a temperature of 15 to 40 ° C. for 10 to 30 minutes, then activated with acid for 10 to 60 minutes, advantageously in the form , a 2 to 15 weight percent aqueous solution, at a temperature of 15 to 40 ° C and washes the exchanger with water to the neutral point.
• the treatment with the nickel salt solution is expediently carried out at temperatures between 10 and 50 ° C., advantageously between 20 and 30 ° C.
• the reaction can be carried out under pressure or under pressure, batchwise, for example by a stirring or batch process, or preferably continuously, for example in exchange columns, in a fixed bed, fluidized bed, in the fluidized bed, in tray columns. It is expedient to use 5 to 50 percent by weight nickel salt solutions and treatment times of 10 to 60 minutes. Subsequently, it is advantageously rinsed with water until the washing liquid emerging from the exchange column has a neutral reaction, and then washing with one of the abovementioned inert solvents or an alcohol at 15 to 40 ° C. for 10 to 60 minutes is largely anhydrous.
• a loading of 0.01 to 0.2, preferably from 0.02 to 0.1, in particular 0.02 to 0.08 parts by weight of nickel per part by weight of exchanger and an amount of 0.01 to 0.25, preferably from 0, are expedient , 02 to 0.1 parts by weight of exchanger per part by weight of urea.
• nickel salts are also suitable as catalysts instead of the ion exchangers containing nickel ions, but the ion exchangers are much easier to separate from the reaction product by filtration or sedimentation than the salts (which should be precipitated as hydroxide).
• reaction mixture can be cooled to about 70 ° C and the catalyst - advantageously L by filtration - to be separated. Excess methylglycol is then distilled off, if necessary under reduced pressure.
• the carbamate mixture obtained in the manner described is then methylolated in the customary manner for conversion into the desired textile finishing agent.
• it is treated with excess aqueous formaldehyde solution at pH 7.5 to 11, preferably 8.5 to 10 for 1 to 10, preferably 2 to 5 hours at a temperature of 10 to 80, preferably 30 to 60 ° C.
• the solution is then neutralized with any water-soluble acid, for example sulfuric acid, and if necessary diluted with water to the desired concentration. If necessary, the solution can be filtered, possibly with the addition of filter aids such as activated carbon.
• the completely or almost colorless, clear, aqueous solution thus obtained is the finished textile finishing agent. It comes in the form of concentrated (30 to 70% by weight) solutions with a pH in the range from 5 to 8, preferably 6 to 7, 5 on the market and can be diluted, acidified, mixed with catalysts and other auxiliary agents, other finishing agents, pigments, plasticizers etc. for use. It is used for shrink-proof and crease-resistant and thus easy care for textiles that contain or consist of cellulose in native or regenerated form.
• a column is filled with 1000 parts of a commercially available cation exchanger made from sulfonated crosslinked polystyrene and left to stand for 15 minutes with the addition of 1000 parts of water. 500 parts of 10 percent hydrochloric acid are then added, the column is left to stand for 20 minutes and the column is washed neutral with distilled water. 3400 parts of a 10% solution of NiSO 4 .7 H 2 0 are added to the exchanger thus activated. If there is no longer an acidic solution at the column outlet, the absorption of the nickel salt has ended. The exchanger filling is washed neutral with water and then washed water-free with methanol and dried. The exchanger is ready for use and contains 8 - 8.5 parts nickel per 100 parts exchanger.
• the mixture of 276 parts of polyethylene ethylenediol with a molecular weight of 810 (H (OCH 2 ) 18 0H) and 21 parts of urea is heated to 145 ° C. for three hours while stirring and simultaneously passing a stream of nitrogen through it. The conversion is then 65% (measured by determining the residual urea content). Then 472 parts of methyl glycol, 373 parts of urea and 31 parts of a commercially available cation exchanger treated as above under 1a) are added. The re- Action mixture is heated to reflux temperature (maximum 150 ° C) for 15 hours while stirring and passing a stream of nitrogen. The reaction solution is then cooled to 120 ° C. and the exchanger is filtered off. 936 parts of a co-carbamate are obtained. This corresponds to a yield of 91% of theory. The residual urea content is 0.4%.
• 300 parts of a polyethylene ether diol of molecular weight 600 are heated in a stirrer with 300 parts of urea to 150-155 ° C. for three hours while passing through a stream of nitrogen.
• the degree of implementation is 90%.
• 68.4 parts of methyl glycol, 54 parts of urea and 35 parts of a nickel-containing exchanger obtained according to Example 1a) are then added.
• the reaction mixture is heated to reflux temperature (maximum 155 ° C.) with stirring for 18 hours.
• the exchanger is filtered off.
• There are 401 parts of the co-carbamate a residual urea content of 0.3%. This corresponds to a yield of 94%.
• the catalyst After cooling to 90 ° C., the catalyst is separated off by filtration. At about 100 ° C, the excess methyl glycol is distilled off under reduced pressure. There are 2700 parts of a co-carbamate obtained from 30% Polyäthylen2011herdiolmonocarbamat and 70% methoxyäthylcarbamat. This corresponds to a yield of 92% of theory The residual urea content is 0.2%.
• the two carbamates are heated together with 4800 parts of a 40% formaldehyde solution with the addition of 55 parts of 50% sodium hydroxide solution at 50 to 55 ° C. for 3 hours. After neutralization with dilute sulfuric acid, 5700 parts of water are added. 17330 parts of a 50% solution of the methylolation mixture containing 1.9% free formaldehyde are obtained.
• a stirring apparatus 590 parts of a polyethylene ether diol with a molecular weight of 590 (H (OCH 2 CH 2 ) 13 0H) and 60 parts of urea are heated at 150 ° C. for 4 hours while passing a stream of nitrogen through them. A degree of implementation of 91% is achieved. Then 1140 parts of methyl glycol, 900 parts of urea and 90 parts of the nickel-containing catalyst prepared according to Example la) are added. The reaction mixture is heated to the reflux temperature which is reached at about 134 to 135 ° C. The mixture is heated for 15 hours, the temperature should not exceed 155 ° C.
• a cocarbamate mixture consisting of 25% polyetherdiol monocarbamate H (OCH 2 CH 2 ) 13 OCONH 2 and 75% methoxyethyl carbamate are obtained.
• This mixture is with 2160 parts of a 40% formaldehyde solution with the addition of 35 parts of a 50% sodium hydroxide solution at 50 to 60 ° C hydroxymethylated and then neutralized with dilute sulfuric acid. 4550 parts of an approximately 65% solution of the methylolation mixture with a content of 2.6% free formaldehyde are obtained.
• a stirred apparatus 810 are parts of a Polyäthy- l enjuherdiols (H (OCH 2 CH 2) 18 OH) and 60 parts of urea heated by the molecular weight of 810 for 5 hours at 150 ° C while passing a stream of nitrogen. After this time, the degree of implementation is 92%. Then 2680 parts of dipropylene glycol, 1200 parts of urea and 100 parts of the nickel-containing exchanger prepared according to Example 1a) are added. The reaction mixture is heated to 155 ° C. for 16 hours while passing a stream of nitrogen through it. After cooling to about 100 ° C, the catalyst is separated off by filtration. 4350 parts of the cocarbamate mixture are obtained, consisting of 24% of a polyethylene ether diol monocarbamate H (OCH 2 CH 2 ) 18 OCONH 2 and 76% dipropylene glycol monocarbamate.
• the mixture of these cocarbamates is hydroxymethylated with 2800 parts of a 40% formaldehyde solution with the addition of 40 parts of a 50% sodium hydroxide solution at 50 ° C. and a reaction time of 3 hours and then neutralized with dilute sulfuric acid. 7250 parts of a 75% solution of the methylolated cocarbamates are obtained.
• An aqueous solution is prepared which contains 7.5% of the dimethylolcocarbamate (100%) according to Example 4 and 0.18% basic aluminum chloride.
• a sample of a polyester / cotton blend (50:50; sheets) that has only been bleached is padded with this solution, with the liquor absorption being 65%. The samples are then heated to 205 ° C for 20 seconds.
• Methylolated polyethylene oxide monocarbamates alone i.e. not in the form of the mixture according to the invention, are not used at all for comparison, since, as is well known, they give an insufficient finishing effect (due to their high molecular weight) because the crosslinking possibilities with the cellulosic hydroxyl groups are too low (durable press rating too low and shrinkage too high).
• the formaldehyde odor of the finished fabric is determined in a sealed vessel according to test method 112 - 1975 from the Association of Textile Chemists an Colorists. With this method, the amount of formaldehyde released under conditions similar to those of practical storage can be determined analytically. The experiment is carried out twice; the average values are given below.
• a padding liquor is made from the following substances:
• This liquor is padded onto polyester / cotton fabric (65:35; sheets), the liquor absorption being 50-55%. After drying, the fabric is heated in a stenter to 205 ° C for 20 seconds.
• the wettability or the absorbency of the tissue is determined according to the AATCC test method 79-1975. The shorter the average wetting time, the more absorbent the textile material is. A time of less than 10 seconds corresponds to a good pumping speed for textile printing.
• the cocarbamate formulation (a) gave a hydrophilic finish, as can be seen from the following table:
• A, B and C are printed with various patterns using the film printing process, using the following printing paste:
• the tendency of the samples to redeposition of oily substances and contaminants which are dissolved or dispersed in the washing liquid is determined.
• the padding liquors described in Examples 10a, b and c are padded onto polyester-cotton fabric (50:50; sheets); the tissues are then heated to 205 ° C for 20 seconds.
• the samples obtained are designated A (recipe 10a), B (recipe 10b) and C (recipe 10c) and subjected to the Celanese re-soiling test explained at the end of the description.
• the soiling of the fabrics in the Launder-Ometer is determined using a Hunter reflectometer, type D-40, manufactured by Hunter Associates Laboratory, Inc., 5421 Briar Ridge Road, Fairfax, Va., U.S.A.
• the dimethylolcocarbamate prepared according to Example 4 and prepared according to Example 9 is applied to polyester-cotton fabric (bedding) and fixed as in Example 9. Comparative samples of the same tissue will do in the same manner with a corresponding prepara- g of a 45% N-methylol-2-methoxyethyl-carbamate solution and b with the preparation described in Example 10 and treated c, in which dimethylol-4,5- dihydroxy-ethylene urine is used.
• the samples are heated to 205 ° C for 20 seconds.
• dimethylolcocarbamate of the invention has a relatively low tendency to form dust (important because of dust generation in sewing and fabric packaging plants).
• a block fleet is padded onto polyester-cotton fabric (65/35) with a weight of 120 g / m 2, the liquor absorption is 70%. After drying, the fabric is heated in a stenter to 205 ° C for 20 seconds.
• the fabric is dried and heated as described above (20 seconds at 205 ° C).
• the table shows the superiority of the equipment according to the invention over that of the closest prior art. Despite using an expensive plasticizer, Sample B's grip is less than that of Sample A, which did not use a plasticizer. Shrink and crease resistance properties and whiteness are approximately the same. These and various other results are therefore not listed in this table.
• the equipment according to the invention does not appear to be inferior to the known one.
• the comparative tests of Examples 9 and 13 illustrate the superiority of the mixtures according to the invention, inter alia. compared to a single component.
• the other component polyethylene oxide monocarbamate
• the comparative tests of Examples 9 to 14 show the superiority of the mixture according to the invention even over some of the best finishing agents currently customary.
• Samples of a bleached polyester-cotton fabric (50:50; sheets, 108 g / m 2 ) are padded with an aqueous solution containing the following substances:
• the fleet intake is 65%.
• the fabric is heated to 205 ° C in a stenter for 20 seconds.
• Finishing agent A consists of a 50% aqueous solution of a mixture of 9 parts of dimethylol-diethylene glycol monocarbamate and 1 part of dimethylol-polyethylene glycol (800) -monocarbamate (N, N-dimethylolmonocarbamate of a polyethylene glycol of molecular weight 800).
• Finishing agent B consists of a 50% aqueous solution of the same components in a weight ratio of 19: 1 (95% dimethylol-diethylene glycol monocarbamate and 5% dimethylol-polyethylene glycol (800) monocarbamate, based on the weight of the carbamate mixture).
• Samples 2 samples measuring 15 x 15 cm.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1979
  • 1979-01-04 US US06/000,815 patent/US4207073A/en not_active Expired - Lifetime
  • 1979-12-18 EP EP79105252A patent/EP0013388A3/fr not_active Withdrawn
  • 1979-12-28 JP JP17056579A patent/JPS5593877A/ja active Pending
• 1980
  • 1980-01-02 CA CA342,918A patent/CA1131413A/fr not_active Expired

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