US3619278A

US3619278A - Process for treating textile materials

Info

Publication number: US3619278A
Application number: US826723A
Authority: US
Inventors: Zennosuke Ogawa
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 1968-06-04
Filing date: 1969-05-21
Publication date: 1971-11-09
Anticipated expiration: 1988-11-09
Also published as: JPS4832991B1; GB1261784A

Abstract

When textile materials are treated with a silicone rubber emulsion containing, as its principal component, organopolysiloxane, prepared by emulsion polymerization of organosilane or organosiloxane, which is represented by a unit formula:

IN WHICH R is a monovalent hydrocarbon radical containing from 1 to 18 carbon atoms and n is a mean value of from 1.9 to 2.1, the relative viscosity of which silicone rubber emulsion in a toluene solution at 25* C. is at least 1.8, the textile materials are provided with excellent flexibility and springiness, and what is more, when the silicone rubber emulsion is applied to textile materials together with known resin-finishing agents heretofore employed for the purpose of improving the properties of the textile materials, it will serve to prevent the reduction of the strength of the textile materials which is one of the disadvantages of the known textile-material treating agents.

Description

United States Patent 72] Inventor Zennosuke Ogawa Gumma-ken, Japan [21] Appl. No. 826,723 [22] Filed May 21,1969 [45] Patented Nov. 9, 1971 [73] Assignee Shinetsu Chemical Company Tokyo, Japan [32] Priority June 4, 1968 [33] Japan 131 43/38200 [54] PROCESS FOR TREATING TEXTILE MATERIALS 10 Claims, No Drawings [52] U.S. Cl ..117/l39.5 A, 117/138.8 A, 1l7/139.4,117/161ZA [51] Int. Cl 006m 15/66 [50] Field ofSearch 117/139.5 A, 139.5 CD, 161ZA,135.5, 138.8 A, 139.4; 260/292 M, 46.5 G [56] References Cited UNITED STATES PATENTS 2,635,040 4/1953 Rasmussen 38/144 Primary Examiner- William D. Martin Assistant E.\'aminerTheodore G. Davis A11orneyToren & McGeady ABSTRACT: When textile materials are treated with a silicone rubber emulsion containing, as its principal component, organopolysiloxane, prepared by emulsion polymerization of organosilane or organosiloxane, which is represented by a unit formula:

2 in which R is a monovalent hydrocarbon radical containing from 1 to 18 carbon atoms and n is a mean value of from 1.9 to 2.1, the relative viscosity of which silicone rubber emulsion in a toluene solution at 25 C. is at least 1.8, the textile materials are provided with excellent flexibility and springiness, and what is more, when the silicone rubber emulsion is applied to textile materials together with known resin-finishing agents heretofore employed for the purpose ofimproving the properties of the textile materials, it will serve to prevent the reduction of the strength of the textile materials which is one of the disadvantages ofthe known textile-material treating agents.

PROCESS FOR TREATING TEXTILE MATERIALS SUMMARY OF THE INVENTION This invention relates to a process of treating textile materials, especially for the purpose of providing them with flexibility and springiness.

Textile materials on the market are usually treated with resin so that they may be creaseand shrinkage-resistant, but such fabrics are apt to feel hard and have inferior physical properties due to their reduced strength. To overcome the difficulties, silicone oil or others are employed as a softener together with the treating agents, but a comparatively large amount of resin has to be employed under a severe condition when carrying out the permanent press which has become very popular these days. Therefore the use of the softener mentioned above often fails to maintain the desired strength and flexibility of the fabrics.

Consequently, to solve the problem, such methods as impregnating textile materials with dimethyl polysiloxane oil and a peroxide compound, such as benzene peroxide, and heating them, or treating the textile materials with solutions containing as their principal components methyl hydrogen polysiloxane, hydroxyl-group-terminated dimethyl polysiloxane and an organic tin compound, have been suggested. But the former treatment has a disadvantage in practicing in that the peroxide compound may explode when heated or subjected to impact, and when the latter method is resorted to, the treating solution has to be adjusted every time it is used, because it is unstable and cannot stand a longer storage.

The above-mentioned silicone oil provides cellulosic fabrics with comparatively good flexibility, but when the textile materials are of synthetic fibers such as polyester, polyamide or a mixture of polyester and cotton, no sufficient flexibility can be expected to be imparted by the silicone oil.

On the other hand, there has been proposed a method for treating textile materials with silicone rubber emulsion, which comprises polymerizing a cyclic organosiloxane in the presence of acid or alkali as catalyzer, and then dispersing it with an emulsifier. Such silicone rubber emulsion, however, has disadvantages in respect of its stability.

The present invention relates to a method of treating textile materials which is free from the above disadvantages. The primary object of the invention is to provide a process for treating textile materials which gives them excellent flexibility and springiness in order to improve their touch, and another object is to provide a process of treating textile materials in which emulsions, easy to handle and having excellent stability, are employed to give the above-mentioned effect. Still another object is to provide a process, which, even when employed in combination with known processes comprising the treatment with resin substances, gives superior touch to the textile materials, besides improving their tear resistance.

Still'further objects of the present invention shall be made clear by the detailed description of the process given below.

The present invention is characterized by treating textile materials with a silicone rubber emulsion containing, as its principal component, organopolysiloxane, prepared by emulsion-polymerization of organosilane or organosiloxane, which is represented by the unit formula:

RuSiO (in which R is a monovalent hydrocarbon radical containing from one to 18 carbon atoms and n is a mean value offrom 1.9 to 2.1 whose relative viscosity in a toluene solution (I g./100 cc.) at 25 C. is at least 1.8.

To give a more detailed explanation, the silicone rubber emulsion prepared by emulsion-polymerization of organosilane or organosiloxane, is an emulsion consisting of corpuscles smaller than I micron, so that it can stand a long storage. and when textile materials are treated with this silicone rubber emulsion, better flexibility and springiness than those provided by the heretofore employed treating agents are obtained, and especially when the emulsion is employed together with the known resin-finishing agents, not only the flexibility and springiness and other physical properties of textiles are improved but also entire or partial reduction of their strength is prevented, which is apt to be brought about by the resin-finishing agents.

The silicone rubber emulsion employed in the process of the invention is prepared by emulsion polymerization of organosilanes such as alkoxysilanes, or of cyclic or low-molecular straight-chained organosiloxanes. For example, it is prepared from octamethyl tetracyclosiloxane which is emulsified in an acid-type anionic emulsifier such as alkyl sulfonate or alkylsulfate, and is polymerized until the desired polymerization degree is obtained, and subsequently neutralized with alkali.

Organopolysiloxane contained in said emulsion, which is represented by the above-mentioned unit formula, must not be of too small polymerization degree. The relative viscosity, 177, of the polysiloxane, when measured at 25 C. in a toluene solution (1 g. of polysiloxane/100 cc. of toluene), must be 1.8 or above. If it is below 1.8, the textile materials treated with the emulsion will not acquire the desired excellent flexibility and other physical properties. The organic radical (R) contained in said organopolysiloxane is a hydrocarbon radical containing from one to 18 carbon atoms as mentioned before, and it is exemplified by saturated or unsaturated hydrocarbon groups such as methyl, ethyl, vinyl and allyl, and aromatic hydrocarbon groups such as phenyl. On the other hand, when the ratio of said organic radical to silicon atoms given by R/Si n is smaller than 1.9 the textile materials treated with the emulsion will become hard and possess no excellent flexibility, so that the value ofn is defined to be between 1.9 and 2.1.

The process of the present invention, for the treatment of textile materials, is carried out very easily in the manner in which the known resin-finishing method is practiced. 1n the first plate, the silicone rubber emulsion prepared by emulsionpolymerization of organosilane or organosiloxane is diluted with water until the solid content of the solution becomes 0.1-5 percent by weight, then a textile material is dipped in the aqueous solution thus prepared and squeezed on a mangle so that the solution content of the textile material may be 30-200 percent. The solution-impregnated textile material is then dried at -l00 C. and further heated for 30 seconds 5 minutes at l20l80 C. If necessary, the treated textile material may be subjected to soaping, washing with hot and/or cold water, and then dried. Apart from the dipping method, roller coating can be employed in order to apply the silicone rubber emulsion to the textile. The ratio of the silicone rubber component applied to the textile is generally 01-10 percent by weight of the textile.

The compatibility of the silicone rubber emulsion with inorganic salts can be improved by the addition of nonionic, anionic or cationic emulsifier or high molecular materials, such as polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, or block copolymer of polyoxyethylene and polyoxypropylene, and said silicone rubber emulsion can be employed in conjunction with resin-finishing agents such as methylol melamine, methylol urea or methylol melamine urea, the amount of the resin-finishing agent added to the emulsion being preferably less than 300 g./l. of the emulsion so as not to impair the purpose of the invention; in such a case, to the emulsion may be added 50 percent solution of a hardening agent selected from the group consisting of zinc nitrate, magnesium chloride and an organic amine salt, in an amount of 5-30 percent of the resin contained in the emulsion. On the other hand, in practicing the method of the invention, various finishing agents containing as a principal component, polyethylene, silicone oil, polyacrylic ester, polyvinyl alcohol, polyvinyl acetate or fluorine-containing resin may be used together with the silicone rubber emulsion.

The process of the invention may be applicable to every kind of textile made of natural, semisynthetic or synthetic fibers, as well as to mixed or blended fabrics, giving an excellent effect.

The invention will now be described by several exampies, in which the parts and percent are parts and percent by weight,

4. Resilience-recovery rate:

A test piece was subjected to 50 percent elongation either lengthwise or breadthwise for 1 minute, and 5 seconds after its length (1,) was measured, and the resilience recovery rate was and the value of the relative viscosity, 17r, is the viscosity mea- 5 calculated by the following equation: sured at 25 C. of the toluene solution of poiysiloxane prepared by dissolving l g. of polysiloxane in 100 cc. of 2l l 100 toluene. The values of the physical properties of the textile l materials given by the treatment of the present invention were obtained as follows:

1, Te i t where 1,, is the original length of the test piece. 5 test pieces, 63.5 mm. X 100 mm. in size, were cut 5 i i y Ofthe r a ing Solution. lengthwise, and another 5 of the same size, breadthwise, from The "eating solution was P in a Vessel and Was allowed 10 the textile material subjected to the process of the invention, Stand h 5 hours- The degree Ofthe Stability wasludged y the and each test piece was placed on an Elmendorf Tester, with a following Standard 20.5 mm. cut made with a sharp knife in the center of the test 5th degree: NO Separation IS obserfed piece at a right angle to its longer side, and the tear resistance 4th degree: some Spots scums of 011 are Observed values (g.), both lengthwise and breadthwise, represented by the surfacethe average of 5 values given by the test piece before the 3rd degree: Spots or scums ofoll are observed all over the remaining 43 mm, was torn, were adopted. Surface- 2 Crease-recovery rate; 2nd degree: A thick layer of oil or ofscums is observed on 5 test pieces, l5 mm. X 40 mm. in size, were cut lengthwise, the top Ofthe emulsionanother 5 of the same size, breadthwise, from the textile 151 degree: The emulsion decomposed and completely material subjected to the process of the invention, and each separatedwas folded into two so that the longer side might be halved. it was then put between two flat boards, and was allowed to PREPARATION OF THE TREATING SOLUTIONS stand for 5 minutes with a load of 500 g. on it. After this, the

. Emulsions E-O, whose composmons are given in table l-h opening angle of the test piece was measured with a Monsanto were prepared by the method of emulsion-polymerization, crease-recovery tester, and the crease-recovery rate was cal- WM] 1 A D d f Culated by the following equation: e emu sions were prepare or compara Ive purposes by adding an emuls1fier.a diluent and water in the ratios given a. in table l-a to various or anosiloxanes, and to these emulsions g were added a 50 percent aqueous solution of dimethylol hydroxyethylene urea(resin-finishing agent). a 50 percent 3. Measurement with Handle-O-Meter: aqueous solution of zinc nitrate (hardening agent), and water, A test piece of the size of 20 cm. X 20 cm. was subjected to in the ratio given in table 2, obtaining the treating solutions a test in which a Handle-O-Meter was employed, and the re- Nos. l-30. sistance which the test piece showed was measured with an 40 The stability of each treating solution as tested is also given electric load cell. The measurement was made on the test in table 2. The results proved that the organopolysiloxanepiece lengthwise and breadthwise, both on the right side and containing treating solutions employed in practicing the on the wrong side, and the result was shown by the total ofthe method of the invention are more stable than the others used values obtained. for comparative purposes.

TABLE 1-a Diomete; l l 0 Organopo ysl oxanes water corpusclo Member of the series Viscosity Parts Emulsifler. parts parts Other additives, parts t) A Dimethyl silicone oil 1.01 30 Polyloxygthylene lauryl 67 t 1 l-5 et er, B ..do 1.24 30 v.,do e. 67 Toluene, 10; perchloroethylene. 9.. l-fi ggg methylpoly' 28 Polyoxyethylene lauryl 47 Undo h v H Methyl hydrogen polysiloxane. 1.00 3 ether D... Silicone rubber having a unit 2.14 15 Poiyoxyethylene cetyi 35 Toluene, 20; perchloroethylene, 9,. 10-50 formula (CHa):SiO. ether, 5.

TABLE 1-b E- v 31 00116 rubber having a unit 1. 53 30 Polyoxyethylene oleyl 67 1 1 0- 1-0- 5 formula (CH SiO. ether, 3. F do ,1 1. 62 5 do 1.73 licone rubber having a unit 1. 96 0 formula (CH3)1.7SiO ,15. I Silicone rubber having a unit 0 formula Ha)1.5 i 1.|s- J Silicone rubber having a unit 1.81

formula (0119 810. d0 2.03 ilicone tubber having a unit 1. 96 formula (CH;)1, SiO M. Silicone rubber having a unit 1.94 30 iolyoxyethylene l-tluryl 65 0.3-0. 5

80131111111 (611 (CHQ=CII)0 I other, 5.

l I\' Silicone rubber having a unit 1.87 lolyoxyethylene nonyl 47 l fsoinulu (CH )1 ,-(C H phenyl other, 31

l 1.05- O. Silicone rubber having a, unit 1. J8 30 Polyoxyethylene t-etyl t t s t 0. 8-!

other, 5.

1 Insoluble in toluene.

TABLE 2 60% aqueous solution of 50% dimethylol aqueous hydroxy solution of Treating Emulsion ethylene zinc solution urea, nitrate, Water, Stability, number Kind Parts parts parts per degree 1 O 7 1 92 2 A 2 7 1 90 4 3 B 2 7 1 90 3 *4 C 2 7 1 90 2 5 D 4 7 1 88 1 6 E 2 7 1 90 5 7 F 2 7 1 90 5 8 G 2 7 1 90 5 9 H 2 7 1 90 5 10 I 2 7 1 90 5 11 .T 2 7 1 90 5 12 K 2 7 1 90 5 13 L 2 7 1 90 5 14 M 2 7 1 90 5 15 N 3 7 1 89 5 16 O 3 7 1 89 5 l7 0 6 1 93 5 18 A 1 6 1 92 4 19 A 2 6 1 91 4 20 A 3 6 1 90 4 21 J 1 6 1 92 5 22 J 2 6 1 91 5 23 J' 3 6 1 90 5 24 0 15 2.3 82.7 5 25 A 1 15 2.3 81.7 3-4 26 A 2 15 2.3 80.7 3-4 27 A 3 15 2.3 79.7 3-4 28 J l 15 2.3 81.7 5 29 .T 2 15 2.3 80.7 5 30 J 3 15 2.3 79.7 5

TABLE 3 Tear resist- Crease- Value obtained Treating ance, lengthrecovery by means of solution wise+breadthrate, II-andle-O-Meter Number wise, g. percent (Slit: 10 mm.), g. Touch 1 483 64. 0 64. 0 Hard. 2 609 66. 2 60. 0 Ha sh. 3 733 66. 4 58. 0 Slippery sol't, limp. 4 710 67.3 60.0 D0. 5 781 73.5 50. 0 Slippery soft, spriugy. 6 695 65.8 50. 5 Slippery soft, limp. 7 760 67.1 57.5 D0. 8 762 67. 4 50. 5 D0. 9 645 09. 7 69. 0 Hard, stifi. 10 596 68.6 72.3 D0. 11 750 73.0 58. 5 Slippery soft, springy. 12 770 73. 2 5R. 7 D0. 13 765 73. 8 60. 1 Slightly hard; springy. 14 705 88. 1 62.2 Extremely springy. 15 685 68.9 01.0 llarslnsprlngy. 16 845 59. 1 57. 8 Slippery soft.

1 Untreated cloth.

* 0.5 part of an emulsion prepared by emulsifying 10 parts of dibutyl tin dioctoate, 10 parts of toluene, 1 part of polyoxyethylene lauryl alcohol, and 79 arts of water was added, as a hardening catalyst for organosiloxane, to the treating solution.

EXAMPLE 1 Test pieces of cotton poplin (408') were each dipped into the treating solutions Nos. 1-16, mangled to the state containing percent of the solution in relation to the weight of the cloth (weight of silicone component/weight of cloth: 0.36 percent), subjected to the preliminary heating at 100 C. for 3 minutes, then to the heat treatment at 160 C. for 3 minutes, followed by soaping, hot-water washing, cold-water washing and drying. The tear resistance, the crease recovery rate, the value obtained by means of the Handle-O-Meter, and the touch of the test pieces thus treated are given in table 3.

EXAMPLE 2 Just as in example 1, test pieces of cotton poplin (408) were treated with treating solutions Nos. H 23, and the tear resistance, the crease-recovery rate, the value obtained by means of the Handle-O-Meter and the touch of the test pieces thus treated proved to be as given in table 4. It is clear from the table that the test pieces treated with emulsion J of the invention gave better softness. springiness and recovery of crease than those treated with hitherto employed emulsion A consisting of silicone oil.

EXAMPLE 3 Just as in example 1, test pieces of broadcloth (8OS' blend spun yarn) of 65 percent polyester fiber and 35 percent cotton were treated with treating solutions Nos. 24-30; and the tear resistance, the crease-recovery rate, the value obtained by means of Handle-O-Meter and the touch of the test pieces thus treated proved to be as given in table 5. It was found, as in example 2, that the treating solution, emulsion J, of the invention served to improve the physical properties of the textile materials better than emulsion A consisting ofsilicone oil.

EXAMPLE 4 4 parts of emulsion A and emulsion J were each diluted with 96 parts of water, obtaining treating solution Nos. 31 and 32. Test pieces of tricot l00 percent polyester fiber) were dipped into either of the treating solutions, mangled and dried at 100? C. for 4 minutes. The test pieces thus treated proved to have l.2 percent by weight of silicone per 100 percent by weight of the textile material. The values obtained the Handle-O-Meter and the resilience recovery rates of the test pieces were as given in table 6.

TABLE 4 Tear resist- Crease- Value obtained Treating ance, lengthrecovery by means of solution wise+breadthrate, Handle-O-Meter number wise, g. percent (slit: lmm.),g. Touch 620 51.1 82. 2 515 64. o 04.0 Hard. 640 64.7 62.0 663 66. 8 61.5 }Harsh. 671 68. 0 60. 0 as ea t. .0 ippery soft, springy. is? 75.1 56.0

TABLE Tear resist- Crease- Value obtained Treating ance, lengthrecovery by means of solution wise-i-breadthrate, Handle-O-Meter number wise, g. percent (slit: 10 mm.), g. Touch 1,201 67.3 137 1,184 83.3 121 Hard. 1,233 83.4 122 Lackinr. in flexibility, 1, 283 83. 5 122 rather hard in the 1,367 84.7 120 core. 1,650 84.8 109 1, 661 86.9 109 Slippery soit, springy. 1,683 87.5 107 BLE 6 32. Test ieces of 'erse of 100 ercent acr lonitrile fiber TA P l y P Y Resilience recovery 2 5 were dipped into either of them, mangled, and dried at 100 C. value obtained rate, percent for 5 minutes. The test pieces thus treated proved to have 1.8 Treatin b means of Solutions HandiyOWIeter Length Breadth percent by weight of silicone per 100 percent by weight of the wise wise Remarks textile material. Tests described in exam le 4 were conducted Number (Slit. mm.), g P

on them, giving the results shown in table 8. Untr f e 2810 91 90 Cmltml- The test pieces treated with treating solution No. 36 proved 31? 281. 5 92 93 Do. to possess excellent touch, being very pliable, flexible and slip- 32 261. 5 95 95 Tfiizliligtg gslgfiinn pery sofL invention. We claim:

1. A process of treating textile materials which is charac- TABLE 7 35 terized by treating them with a silicone rubber emulsion, containing, as its principal component, organopolysiloxane, value obtained igiz g ggggz prepared by emulsion polymerization of organosilicone com- Treating by means of pounds selected from organosilane and organosiloxane. which ae.- ..m... isbyaumormue 40 Untreated 205 90 83 Control.

cloth. 4-n 33 196 94 93 D0. T 34 148 98 97 Treating solution at thet resent van where R is a monvalent hydrocarbon radical containing from one to 18 carbon atoms and n is a mean value of from 1.9 to TABLE 8 2.1, whose relative viscosity in a toluene solution at 25C. is at Resilience recovery least 1.8. applying to said textiles said organopolysiloxane at Treating $532? rate Percent the ratio of 0.1 to 10 percent by weight ofthe textile materials, solution Hondle-O-Meter Length Breadthand then drying at 80 to 100 C. Num i 15 m W1Se W159 Remarks 2. The process of claim 1 which is characterized by treating Untreated 195 90 90 Control. textile materials with the said silicone rubber emulsion. con- 186 90 91 Do. taining organopolysiloxane in the amount ranging between 0.1 36:21:: 143 95 95 Treating solution and 5 ercent b wei ht ofthe silicone rubber emulsion.

P y g $2,253? 3. The process of claim 1 which is characterized by treating textile materials with the said silicone rubber emulsion to which has been mixed an emulsifier. where R is a monvalent The test pieces treated with treating solution No. 32 proved h dr arbon radical containing from 1 to 18 carbon atoms to possess excellent touch, being very pliable and flexible. and n is a mean value of from 1.9 to 2.1, whose relative s u O viscosity in a toluene solution at 25 EXAMPLE 5 4. The process of claim 1 which is characterized by treating 10 parts f emulsion A and emulsion J were each diluted textile materials with the said silicone rubber emulsion to with 90 parts ofwater, obtaining treating solution Nos. 33 and whlch has beenflded a resm'fimshmg g Selected from 34. Test pieces ofjersey of 100 percent polyamide resin fiber the g'oup conshsmlg of methyl?! melamm? methylol urea' methylol melamine urea and dimethylol dihydroxyethylene were dipped into either of them, mangled anddned at 100 C. urea in the amount ofless than 300 A ofsaid emulsion for 5 minutes. The test pieces thus treated proved to have 3.1

5. The process of claim 4 which is characterized by treating percent by weight of silicone per 100 percent by weight of the textile material Tests described in exam I 4 w e d t d textile materials with said silicone rubber emulsion to which p e er con e has been added said resin finishing agent, selected from the on them gwmg the results Show m table grou consistin of meth lol melamine urea meth lol The test pieces treated with treating solution No. 34 proved p g y y to possess excellent touch, being very pliable and elastic.

EXAMPLE 6 5 parts of emulsion A and emulsion F were each diluted melamine urea and dimethylol dihydroxyethylene urea, in the amount of less than 300 g./l. of said emulsion, in the presence ofa 50 weight percent solution ofa hardening agent selected from the group consisting of zinc nitrate, magnesium chloride and organic amine salt, in an amount of 5-30 percent by weight ofthe resin contained in the emulsion.

6. A process of treating textile materials which is characterized by dipping them in a silicone rubber emulsion, containing as its principal component, organopolysiloxane, prepared by emulsionpolymerization of organosilicone compounds selected from organosilane and organosiloxane, which is represented by a unit formula:

where R is a monovalent hydrocarbon radical, containing from I to 18 carbon atoms and n is a mean value of from 1.9 to 2.1, whose relative viscosity in a toluene solution at 25 C. is at least 1.8, then mangling them to the state of containing from 30 to 200 percent of the solution in relation to the weight of the textile materials, drying them at 80-l00 C. and further heating them for 30 seconds5 minutes at l-l 80 C.

7. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion, containing organopolysiloxane in the amount ranging between 0.1 and 5 percent by weight of the silicone rubber emulsion.

8. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion to which has been added a resin-finishing agent, selected from the group consisting of methylol melamine, methylol urea, methylol melamine urea and dimethylol dihydroxyethylene urea, in the amount ofless than 300 g./l. of said emulsion.

9. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion to which has been added a resin-finishing agent, selected from the group consisting of methylol melamine, methylol urea, methylol melamine urea and dimethylol dihydroxyethylene urea, in the amount of less than 300 g./l. of said emulsion, in the presence of 50 weight percent solution of a hardening agent, selected from the group consisting of zinc nitrate, magnesium chloride and organic amine salt, in an amount of 5 to 30 percent by weight of the resin contained in the emulsion.

10. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion to which has been mixed an emulsifier.

Claims

2. The process of claim 1 which is characterized by treating textile materials with the said silicone rubber emulsion, containing organopolysiloxane in the amount ranging between 0.1 and 5 percent by weight of the silicone rubber emulsion.
3. The process of claim 1 which is characterized by treating textile materials with the said silicone rubber emulsion to which has been mixed an emulsifier. where R is a moNvalent hydrocarbon radical containing from 1 to 18 carbon atoms and n is a mean value of from 1.9 to 2.1, whose relative viscosity in a toluene solution at 25* is at least 1.8, applying to said textiles said organopolysiloxane at the ratio of 0.1 to 10 percent by weight of the textile materials, and then drying at 80 to 100* C.
4. The process of claim 1 which is characterized by treating textile materials with the said silicone rubber emulsion to which has been added a resin-finishing agent, selected from the group consisting of methylol melamine methylol urea, methylol melamine urea and dimethylol dihydroxyethylene urea, in the amount of less than 300g./l. of said emulsion.
5. The process of claim 4 which is characterized by treating textile materials with said silicone rubber emulsion to which has been added said resin finishing agent, selected from the group consisting of methylol melamine urea, methylol melamine urea and dimethylol dihydroxyethylene urea, in the amount of less than 300 g./l. of said emulsion, in the presence of a 50 weight percent solution of a hardening agent selected from the group consisting of zinc nitrate, magnesium chloride and organic amine salt, in an amount of 5-30 percent by weight of the resin contained in the emulsion.
6. A process of treating textile materials which is characterized by dipping them in a silicone rubber emulsion, containing as its principal component, organopolysiloxane, prepared by emulsion-polymerization of organosilicone compounds selected from organosilane and organosiloxane, which is represented by a unit formula: where R is a monovalent hydrocarbon radical, containing from 1 to 18 carbon atoms and n is a mean value of from 1.9 to 2.1, whose relative viscosity in a toluene solution at 25* C. is at least 1.8, then mangling them to the state of containing from 30 to 200 percent of the solution in relation to the weight of the textile materials, drying them at 80*-100* C. and further heating them for 30 seconds-5 minutes at 120*-180* C.
7. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion, containing organopolysiloxane in the amount ranging between 0.1 and 5 percent by weight of the silicone rubber emulsion.
8. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion to which has been added a resin-finishing agent, selected from the group consisting of methylol melamine, methylol urea, methylol melamine urea and dimethylol dihydroxyethylene urea, in the amount of less than 300 g./l. of said emulsion.
9. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion to which has been added a resin-finishing agent, selected from the group consisting of methylol melamine, methylol urea, methylol melamine urea and dimethylol dihydroxyethylene urea, in the amount of less than 300 g./l. of said emulsion, in the presence of 50 weight percent solution of a hardening agent, selected from the group consisting of zinc nitrate, magnesium chloride and organic amine salt, in an amount of 5 to 30 percent by weight of the resin contained in the emulsion.
10. The process of claim 6 which is characterized by treating textile materials with said silicone rubber emulsion to which has been mixed an emulsifier.