FI63974B - FOERFARANDE FOER BEHANDLING AV TEXTILER MED EN HAERDANDE POLYOXIPROPYLENPOLYMER - Google Patents

Description

RSR [B] (1l) K ^ CONSUMPTION tXQHA

l J 'V UTLÄGGN f NGSSKMFT O ^ 7 (^ ^ (S1) Kv.ik? /int.ci.3 D 06 M 15/68; FINLAND — FINLAND pi) Ρκ «Βΐω ^ -Ν« ιηιβω «ι 782389 ( 22) Htk «mltpilvl - AiNehnlnf« d »g 02.08.78) (23) AlkupUvt — Glttl (h« t * dif 02.08.78 78 (41) Tulhit lulkMul - Mivtt offwMdg 05.02.79 ^ tantti ·] · (44) NlhUvtlulpanon j · kmilJullulMn date—

Patanth och ragisterttyreltwi Antttkin utlifd och utl. * Krifc * n pubUcarad 31.05.83 I

(32) (33) (31) Requested «cuoikM * —B« gird prloriMt 04.08.77

Ol.O2.78 Great Britain-StorhritannieniGB) 32803/77, 1 + 097/78 r (71) I.W.S. Nominee Company Limited, Wool House, Carlton Gardens,

London SW1Y 5AE, England-England (GB) (72) David Malcolm Levis, Otley, Yorkshire, Keith Robert Fraser Cockett,

Keighley, West Yorkshire, David Allenach, Headingly, Leeds,

England-England (GB) (7 * 0 Oy Borenius & Co. Ab (5 * 0 Method for treating textiles with a curable polyoxypropylene polymer - Förfarande för behandling av textileiler med en härdande polyoxypropylenpolymer

The invention relates to a method for treating textiles, in particular with water-soluble polymeric materials. Polymeric materials such as the "Bunte" salt compounds described in GB Patent No. 1,423,342 or the poly (carbamoyl sulfonates) described in GB Patent No. 1,419,306 are particularly well suited as textile finishes, especially for keratin-containing textile materials, e.g. wool, to improve shrinkage resistance.

These resins have hitherto been added to textile piece products mainly by means of pillow dumplings. However, pillow mangoes are relatively expensive, and not all textile winemakers have such a mangle at their disposal. Accordingly, the invention seeks to provide a method for treating textiles with either concentrated or dilute broths using commonly available wet processing equipment and using a simple processing method and using inexpensive additional chemicals.

According to the invention, there is provided a process for treating textiles which is characterized in that an aqueous solution containing a curable polymeric material of the following general formula is added to the textile material.

CH 3 I J

CH2-0-CH2-CH-0-R

CLL3

CH - O - CH2 - CH - O - R

ch3

CH2 - O - CH2 - CH - O - R

n wherein R is

OH O

1. 1 'CH2-CH-CH2-SSO3 Na +, C-CH2-SSO5 Ka + or 0 11 C-NH- (CH2) 6-NH-CO-SO3 Na + and n is 5 to 25, and an inorganic acid salt of a divalent metal and possibly alkali, causing the polymer to completely migrate into the textile and curing the polymer. The phrase "curing" also includes causing it to cure.

The structural formulas of the preferred polymeric material are

CH3 Ί OH

1 1, CH2 - O - CH2 - CH - O - CH2 - CH - CH2 - SSO3 Na +

CH3 OH

CH - O - CH2 - CH - O - CH2 - CH - CH2 - SSO3 Na +

CH3 OH

1 1.

CH2 - O - CH2 - CH - O - CH2 - CH - CH2 - SS03 Na + - _ n and 3 63974 CH3 o CH2-O-CH2-CH -o- C-NH- (CH2) g-NH-CO-SO3 Na + CHq 0 • d »+ B. CH-O-CH2-CH-O-C-NH- (CH2) g-NH-CO-SO3 Na CH3 O CH2-O-CH2-CH-O-C-NH- (CH2) g-NH-CO-SOg Na + n where n in each formula is about 13.

The amount of polymeric material added will generally be 1/2 to 10% by weight, especially 2 to 4% by weight of the weight of the fibers.

The polymers can be cured, e.g., by removing the treated products from the treatment bath after it has been consumed, and curing at a high temperature (e.g., 120-160 ° C) suitably in a stretching frame, or by removing the products from the bath, drying them, e.g.

At 50 ° C and then by evaporation to effect curing.

The bases promote the crosslinking or curing of the polymeric material. It is often advantageous to premix the base with the polymeric material for a certain reaction period so as to obtain a partially crosslinked or activated polymer before it is added to the textile product. This is particularly advantageous when using concentrated treatment broths. Typical reaction times suitable for use are 10 to 60 minutes. When using dilute treatment broths, it may be advantageous to increase the pH of the treatment bath by adding base at the end of the fixation period or shortly thereafter to promote curing, although this is not necessary. Curing can also be accomplished by other methods, e.g., heat curing. Any suitable base can be used, e.g. alkali metal carbonates or hydroxides, but particularly good results are obtained using ammonium hydroxide or dilute treatment broths using trisodium phosphate.

63974 it

When a base is used, this base must suitably be present in such an amount that the treatment broth becomes basic, suitably to a pH of 8 to 10. When using dilute treatment broths, it must be ensured that the amount of basic compound present or added is sufficient to effect a basic reaction in a textile which may contain residual acid from a pre-treatment, e.g. a carbon treatment.

Particularly preferred inorganic salts are neutral salts, especially salts of strong acids, e.g. MgSO 4, CaCl 2, ZnSO 2 and especially MgCl 2. The amounts required vary depending on the nature of the compound, but in general 1 ... 100 g / l, especially 5 .. .10 g / l.

The process of the invention can be applied using either diluted or concentrated treatment broths. When using concentrated broths, usually in a ratio of 1: 1 to 3: 1, the broth is almost completely absorbed into the textile product. The processing steps are: 1) Mixing the polymer compound and the base, and allowing them to react.

2) The broth obtained in accordance with the preceding paragraph is added to the products in a washing machine or batting machine.

3) Mix the products until the broth is evenly distributed.

4) The products are sprayed with an inorganic salt solution and stirring is continued until the salt is evenly distributed, and 5) the products are rinsed, drained and dried.

In order to avoid a slight discolouration of the products to be treated, a weak bleach is suitably added at a late stage in the treatment. Suitable bleaching agents include oxidizing agents, e.g. hydrogen peroxide, and reducing agents, e.g. bisulphite.

A separate curing step is not required because the polymer is fully cured after step 4). The treatment can also be performed at room temperature, so energy costs are kept to a minimum.

In order to check that the broth is evenly distributed after steps 3) and 4), indicator colors can be used. When a pink indicator color is added to the original broth, the products will have a uniform pink color when step 3) is completed. When a blue indicator color is added with the saline solution, the end of step 4) can be seen as indicating that the products have a uniform purple color. Both of these colors are completely removed during the rinsing step.

s 63974

The process based on the use of a concentrated treatment broth can be carried out in any suitable treatment device suitable for the use of a concentrated broth, in which the products become well mixed, suitably in a drum machine. Washing machines are particularly well suited for this purpose. When handling woven products, e.g., Shetland sweaters, which are usually quilted, the processing can be performed on a quilting machine.

In the case where the treatment is carried out using dilute treatment broths, the dilution ratios being suitably 10: 1 to 100: 1, in particular 20: 1 to 30: 1, the treatment can advantageously be carried out in side-wing machines, reel machines, support machines and rope washing machines. . The various steps of the treatment are suitably carried out using dilute treatment broths as follows: 1) adding the polymer to the bath in which the products to be treated are located and having a pH of 5 to 8, 2) adding an inorganic salt solution and raising the temperature to 50 ° C, 3 ) after complete migration (usually in 30 to 60 minutes) the base is added to give a pH of 9..10, and 4) after a further 15 to 30 minutes the products are drained and dried.

In steps 3) and 4), the products can be dyed in the same bath without drying, thus saving one processing step.

Thus, the invention can be applied to both concentrated and dilute treatment broths simply by using commonly available and inexpensive chemicals, in commonly used equipment, and by a short and simple set of treatment steps.

The method according to the invention can be generally applied to the finishing of textiles, but the method is particularly well suited for the treatment of textile products made of keratin-containing fibers, such as wool. When wool is treated, an even better ability to withstand the shrinkage caused by regional felting during subsequent washes is achieved.

The method according to the invention can be applied to textile products in various forms, from loose fibrous material, fluff, cups and yarns to finished piece products and garments. The invention has been found to be particularly advantageous in the treatment of woven pieces and trimmings, in particular products knitted from Shetland or lamb's wool.

When using dilute treatment broths, it is observed that as the temperature approaches 50 ° C, the solution of polymer and salt changes to a milky appearance, but becomes clearer again as the temperature is raised.

The best results are obtained by applying the method at or near a temperature representative of the maximum turbidity.

The products to be treated must suitably be free of dirt, grease and spinning oil, so it is advisable to carry out a prewash in a washing solution, suitably a non-ionic solution. A non-ionic or anionic detergent may also be added to the treatment broth to completely moisten the products during processing.

The following examples illustrate the invention.

The various polymeric materials used in the examples under their trademarks have the following structure: "Synthappret LKF" is an 80% solids isocyanate-terminated polyoxypropylene resin with three nominal functionalities, manufactured by Bayer AG. Its bisulfite addition product (BAP) was prepared using known methods, as described, e.g., in GB Patent 1,419,306.

"Lankrolan SHR3" (Lankro Chemicals Ltd) is a Bunte salt of a polyether having 0-C-CH2SS0 'Na + end groups and otherwise according to the general formula above.

7,63974 "Impranil DLH" (registered trademark) is an anionic aliphatic urethane dispersion free of organic solvents and emulsifiers, supplied by Bayer AG as a 40% aqueous dispersion. "Impranil DLN" and "Impranil 4693" are similar in structure.

The amount of polymer used is expressed as a percentage by weight of wool (oww).

The amount of polymer added is expressed as a percentage by weight of the wool. washing tests

In the following examples, tissue samples were probed in a "Cubex" type washing machine with 15 liters of phosphate buffer solution, pH = 7, temperature 40 ° C and wash load weight 1 kg, using additional weights if necessary. The shrinkage results due to regional felting are presented as the percentage change in area after 1 hour or 3 hours of washing.

Example 1

The Shetland wool fabric (2/8 worsted yarn, knitted to a coverage factor of 0.85) was washed, pre-washed and padded in "Lissapol NX" (registered trademark) using 2 g / l and containing 2 g / l of anhydrous sodium sulfate. The tissue was then rinsed.

To a fresh bath at 20 ° C with a liquid ratio of 30: 1 was added 1.5 g / l of 0.0880 ammonia and then 5 minutes later 3.5% by weight of "Lankrolan SHR3", dry weight. calculated. Then 10 g / l magnesium sulfate was added, Treatment bath pH = 9.5.

The temperature was raised to 50 ° C over 10 minutes and then maintained at 50 ° C for 5 minutes, after which 2% by weight of sodium betabisulfite, based on the weight of the tissue, was added and the bath was used for a further 15 minutes at the same temperature.

The samples were then dried and the following washing test results 8,63974 were obtained with samples dried in air or tumble.

Area shrinkage 1 h wash 2 h wash 3 h wash Air dried 12 3

Dried in a drum 00 1

Examples 2, 3 and 4

Unbleached plain wool flannel weighing 185 g / m 2 was tested. The fabric was pre-washed using 1 g / l non-ionic detergent (Lissapol M, ICI) and 2 g / l Na 2 CO 3 at 40 ° C for 10 min, followed by rinsing.

The tissue sample was treated in a broth bath with a dilution ratio of 40: 1, the temperature decreased to 50 ° C and the pH = 7. The bath contained 2.0% by weight "BAP", based on the weight of wool, and 10 g / l of one of the following salts: MgCl 2, CaCl 2, ZnSO 4. The temperature was maintained at 50 ° C until the transition was complete. The tissue was then either 1) rinsed and dried at 140 ° C for 15 min (heat curing), 2) dried at 50 ° C for 15 min and steamed for 5 min (steam curing), 3) cured in a treatment bath by adjusting the pH to 9. and holding the product in a bath for 30 min and then drying at 50 ° C for 15 min (bath curing).

Transition- Shrinkage%

Eg Metal salt mixing time, min Thermal curing Steam curing Bath curing ~ ΓΤι 3 "h T" h 3Th 1h Th 2 MgCl2 35 3 11.5 2 83 5 3 CaCl2 20 9.5 25 8 19 4 12 4 ZnSO ^ 180 4 19 3.5 15 4 11 Untreated fabric 1 h wash 32%, 3 h 45%

Examples 5, 6, 7

The prewashed flannel samples were treated in a broth bath with a dilution ratio of 40: 1, temperature 50 ° C and pH = 7. This bath contained 1% by weight (solids) of the product "BAP", 1% by weight of the product "Impranil I! 9 63974 DLH" and 10 g / l of one of the following salts: MgCl 2, CaCl 2, ZnSO 4.

The temperature was maintained at 50 ° C until the transition was complete. The polymers were then cured as described in Examples 8-10.

Area shrinkage%

Metal Transition- Thermal Curing Steam Curing Bath Curing

Eg salt_time, min_1h_3h_1 h_3 h 1 h_3 h 5 MgCl2 25 4.5 1 8 4 10 1.5 5 6 CaCl2 12 10 25 4 13 4 15 7 ZnSO4 90 4 175 6 20 7 24

Examples 8 ... 13

To determine the effect of the metal salt concentration, Example 5 was repeated using different concentrations of MgCl 2. In any case, the tissue was dried and cured at 140 ° C for 15 minutes.

Eg MgCl2 conc. transition- Shrinkage% g / 1 time min 1 h 3 h 84 60 00 95 40 00 10 6 30 00 11 7 20 1 3,4 12 8 15 1,4 5,5 13 10 12 0,4 6.4 See that the rate of transition depends on the concentration of MgCl2. Fast transition times are generally not desired because the washability and processability of treated products may not meet the standards that can be achieved using a more closely controlled transition.

Examples 14 ... 18

Examples 8 to 13 were repeated using 7 g / l MgCl 2 and varying the bath temperature. Curing was done as above. The results are shown below.

1 o 63974

Bath Shift - Area Shrinkage%

Eg temperature time, min. 1 h 3 h 14 30 ° 50 05 15 40 ° 35 O 5.3 16 50 ° 20 0.5 3.5 17 60 ° 16 1 2.5 18 70 ° 12 1 6.4

Examples 19 ... 23

Examples 8 to 13 were repeated using different ratios of BAP to "Impranil DLH" in the range of 2.0% BAP / 0% DLH to 0% BAP / 2% DLH, with a total of 2% solids added. The transition time was kept constant (45 min) by varying the MgCl 2 concentration with respect to the polymers. Cured to dryness at 140 ° C for 15 minutes. The results of the washing experiments were as follows:

Area to sit%

Eg BAP% DLH% MgCl2con. 1 h 3 h 19 2.0 0 9.0 0 1 20 1.5 0.5 7.0 1.5 0.5 21 1.0 1.0 6.0 1 1 22 0.5 1.5 3 .0 0.5 1 23 0 2.0 3.5 9.8 30.3

Examples 24 ... 27

Examples 8 to 13 were repeated using a knitted fabric of a simple Jersey wool fabric knitted from 2/24 comb wool yarn to a coverage factor of 1.1. Washed with 1 g / l nonionic detergent (Lissapol N) and 2 g / l Na9SOu for 10 minutes at 40 ° C, then rinsed.

Tissue samples were treated in a bath of 1.5% BAP, 1.5% DLH (fiber weight) and 4 to 10 g / L MgCl 2> Temperature 50 ° C, pH = 7, and these values were maintained until the transition was perfect.

The tissue samples were then cured at 140 ° C for 15 minutes.

li „63974 11

MgCl2 conc. Transition- Shrinkage%

Eg g / 1 time, min 1h 3 h 2i + 4 i + 4 14 25 6 22 0 6 26 8 11 13 27 1 0 7.5 0 5

Examples 28 ... 30

Example 25 was repeated using 2 wt% BAP and 1 wt% DLH (wool weight) at a temperature of 50 ° C and a pH = 7 until the transition was complete. The samples were then either 1) removed from a bath of pH = 7 and dried in a drum, 2) cured in a bath by raising the pH to 810 minutes, then dried in a drum, or 3) cured in a bath by raising the pH to 9 for ten minutes, then dried in a drum .

Eg Curing conditions Area shrinkage% 1 h 3 h 28 Removed at pH 7 1 15 29 Bath to pH 8, 10 min 1 1 30 Bath to pH 9, 10 min. 1 1

Examples 31 ... 33

According to Examples 28-30, the cured tissue samples were stained with chromium, Eriochrome Black PV 200%, without drying. The color bath contained 4% Eriochrome Black PV 200% 3% Acetic acid (oww).

Dye and acid were added to the bath at 30 ° C, and the tissue was treated for 10 minutes. The temperature was then raised to boiling point within 45 minutes and maintained at boiling point for 30 minutes.

1.5% formic acid was then added and cooking was continued for another 30 minutes. The bath was then cooled to 80 ° C and 1.5% potassium dichromate was added. The bath was again heated to boiling point and cooking was continued for 45 minutes, after which it was rinsed in the cold and dried in a tumble dryer. An untreated control was also placed in the color bath. Washing results were 63974 1 2

Aluekutistuma

Eg Curing conditions during staining Area shrinkage 1 h 3 h 31 Bath to pH 7, 10 min 0 3.0 14.0 32 Bath to pH 8, 10 min 0 8.6 12 33 Removed at pH 7 6.0 70 Unprocessed wool 7.4 72

Examples 34 ... 36

Example 25 was repeated using Shetland tissue. The fabric was knitted to a coverage factor of 0.9 2/8-Shetland yarn. The tissue was washed with 1 g / l non-ionic detergent (Lissapol N) and 2 g / l Na 2 SO 4 for 10 minutes at 40 ° C, followed by rinsing.

The samples were heated in a treatment bath with a dilution ratio of 40: 1, pH = 7 and a temperature of 50 ° C and containing 6'g / 1 mg / Cl 2 and either 2.5; 2.0 or 1.5 wt% BAP / DLH in a 1: 1 ratio. The temperature and pH were kept constant until cured at 140 ° C for 15 minutes.

BAP / DLH Transition- Area Shrinkage%

Eg weight% time, min 1 h 3 h 34 2.5 45 00 35 2.0 40 1.8 2.3 36 1.5 45 1.4 6.25 Unprocessed wool 35 61

Examples 37 ... 39

Example 34 was repeated using different curing conditions. The complete transition occurred in 60 minutes. The tissues were then cured as follows: 1) removed at pH 7 and dried in a drum for 20 minutes at 100 ° C, 2) the pH of the bath was raised to 8 and maintained at this value for 15 minutes, dried in a drum for 20 minutes at 100 ° C, 3) the pH of the bath was raised to 9 and maintained at this value for 15 minutes, tumble dried for 20 minutes at 100 ° C.

Il 13 63974

Eg Curing conditions Area shrinkage% 1 h 3 h 37 Removed at pH 7 4.5 10.5 38 Bath to pH 8, 15 min 0.8 2 39 Bath to pH 9, 15 min 3 1.9

Example 40

500 g of 4/8 glove knitting yarn were prewashed in a laboratory winding-dyeing machine for 10 minutes at 40 ° C. The dilution ratio of the treatment broth was 30: 1 and it contained 1 g / l of nonionic detergent (Lissapol N) and 2 g / l of Na 2 SO 4. It was then rinsed. The treatment broth was then prepared at a dilution ratio of 30: 1, pH = 9, 50 ° C, 3.0 wt% BAP / Impranil DLH in a ratio of 1: 1 and 4 g / l MgCl 2. The pH and temperature were kept constant until the transition was complete.

The yarn was then rinsed and dried at 140 ° C for 15 minutes. Tissue samples were knitted to a coverage factor of 0.9. Washing experiments were performed on a Cubex machine with the following results:

Area shrinkage% 1 h 3 h Treated 3% BAP / DLH 6.5 12 Untreated 58

Claims (22)

63974 14 1. H CH2-CH-CH2-SSO3 Na +, C-CH2-SSO3 Na + or O 11. C-NH- (CH2) 5-NH-CO-SO3 Na + and n is 5 to 25, and the inorganic acid salt of the divalent metal and possibly alkali, the polymer is completely transferred to the textile and the polymer is cured. A method for treating collectible textiles with a curable polyoxypropylene-based polymer, characterized in that an aqueous solution containing a curable polymer of the following general formula CH3 CH2-O-CH2-CH-O-R CH3 i CH-O-CH2 is added to the textile material. - CH - O - R ch3 ch2 - o - ch2 - CH - o - r - * n where R is OH 0 Process according to Claim 1, characterized in that the polymer has the formula: CH 3 '1 OH 1 1 - CH 2 - O - CH 2 --CH - O - CH 2 --CH - CH 2 - SSO 3 Na + CH 3 OH II - CH - O - CH 2 - CH - O - CH2 - CH - CH2 - SSO3 Na + CH3 OH CH2 - 0 - CH2 - CH - O - CH2 - CH - CH2 - SSO3 Na + - - * n li 15 63974 in which the mean of n is about 13. Process according to Claim 1, characterized in that the structure of the polymer formula is' CH 3 Ί o IJ II CH 2 - O - CH 2 -CH-OC-NH- (CH 2) 6 - NH - CO - SO 3 Na + CH-j OIJ li CH - O - CH2 -CH-OC-NH- (CH2) 6 - NH - CO - SO3 Na + CH3 OI -3 II CH2 - O - CH2 -CH-OC-NH- (CH2) 6 - NH - CO - SO3 Na + n wherein the nsn mean is about 13. Process according to one of Claims 1 to 3, characterized in that the amount of polymer added is 0.5 to 10% by weight, based on the weight of the fibers. Process according to Claim 4, characterized in that the amount of polymer added is 2 to 4% by weight, based on the weight of the fibers. Process according to one of Claims 1 to 5, characterized in that the polymer is cured by means of an alkali. Process according to Claim 6, characterized in that the alkali is present in the aqueous medium containing the polymer from the beginning of the treatment. A method according to claim 7, characterized in that the alkali is premixed in the polymer for an aging period before being placed in the textile. Method according to Claim 8, characterized in that the aging period is 10 to 60 minutes. 16 63974 A method according to claim 6, characterized in that the alkali is added after the polymer has completely transferred to the textile from the aqueous medium. Process according to one of Claims 6 to 10, characterized in that the alkali is ammonium hydroxide or trisodium phosphate. Process according to one of Claims 6 to 11, characterized in that a sufficient amount of alkali is used to adjust the pH to 8 to 10. Process according to one of Claims 1, 12 to 12, characterized in that the inorganic salt is a neutral salt. Process according to Claim 13, characterized in that the inorganic salt is a salt of a strong acid. Process according to Claim 14, characterized in that the inorganic salt is magnesium sulphate, calcium chloride or zinc sulphate. Process according to Claim 14, characterized in that the inorganic salt is magnesium chloride. Process according to one of Claims 1 to 16, characterized in that the amount of inorganic salt used is 1 to 10 g / l of treatment bath. Process according to Claim 17, characterized in that the amount of inorganic salt used is from 5 to 10 g / l of treatment bath. A method for treating textile materials using a concentrated bath according to claim 1, characterized in that 17 63974 a) the aqueous solution of polymer and alkali is allowed to stand during the aging period, b) the bath according to a) is placed in the textile the bath is evenly distributed, d) the inorganic salt solution is sprayed onto the textile material and mixing is continued until the salt is evenly distributed, and e) the textile material is rinsed, drained and dried. A method for treating a textile material according to claim 1, using a dilute bath, characterized in that a) the polymer is added to a water bath containing the textile material, the pH of which is adjusted to 5 to 8, b) an inorganic salt solution is added and the temperature is raised to 50 ° C: e), c) after complete migration of the polymer, alkali is added to adjust the pH to 9-10 and d) after a further 15-30 minutes the textile material is drained and dried. Method according to one of Claims 1 to 20, characterized in that the textile material is wool. Method according to one of Claims 1 to 21, characterized in that the textile material is a knitted piece or garment.