BE655507A - - Google Patents

Description

  

   <Desc / Clms Page number 1>
 



  "Amélicré process of anti-static lava resistant finish ± * hydrophobic fibrous material". @
It is already known to apply to hydrophobic fibrous material compounds containing in the molecule, in addition to groups capable of being crosslinked, residues of polyethylene oxide, by a single padding bath, in most of the applications. in an aqueous bath, optionally together with curing catalysts, and to convert them after drying and fixing into the insoluble state, usually at a temperature

 <Desc / Clms Page number 2>

 
 EMI2.1
 4.tv, é:., En1; t. the d;:!; rt'n.ut. pino.1> 1t 4 .. X4% iQulaaoa, o 8 Ee: Q; 1t1JX. allowing a tOnt.a.j, oXl Qlw i SUC 1 8!? a tu t.Sd.YJP. ^. 1 b. of; m.p4a.tes) of '4111: fQjQsQ.nt niffNlSâS.

   IV1.Y M6, $. 1 .. "'e B & GCLL1 cl1 ss1blEh or 11: \ 1q. Qn4% 15 J! 1jnt: et) qu à 1 & tfI! LP; 1 from 1% l to .. end 4u e * nacaaina-
 EMI2.2
 
 EMI2.3
 Se, d, e qnelqes h.ErUr8 'Se-1Ql1 àe tela poeooôd40 Wa 4'ob.o., <% 4a uxqsnsoment, oeéuoas pro4nioee, ouxt zm% i +> tihoeonaa <njismo.t, Q Ea at p4utie on 1. ij (¯t1 t1ua. dles, 3m, s: <eh ftUi.ta.q: Q> CQn.ataire: i, Q8, restas d 'o: qcl dQ pethy3. ayamt;

   WJ ;. .ti'Q; t; t1G; tt1qu.e. 1. "a1dEt de: pro4uà% a de p? É <x <m <'dons% ioa dsraipl: rsta or pan r4 <ti <ti'amlnoa alout ... axis; d1.e-SJ & eatt! 3! dl fi 1a: uiQ!) plyrmts or d "i8OQa: tQs pe3Ly <" vaQna Q, aMé'1 with amine8 p1: -im.a.:!:. res Qu aeo.an,; iro p 8} 1. Eln.t; e; I; tt ëlLté: 1? QlpQaù: .en.ts; on de a.ordrit, os polyvalon% 04 em zoe4xetrzre, c: 1l. Tlun. 6I.ta.1 '.; Y; $ E); Ul "alkaline we have9 amines pr1ma1rtlS cm s; Q) J; daQles' pQiywa1eaùQa au par PQêl: '1sa.tion de monoaétaa go, t .et En Qe <1.u1 aoncvnne 1 & ccmpsitio dos' biuf1 de fou ...



  .ardary crn, peizt o1te the following cases consistent with the principle of ritlle; u] .IJJ.ti.o-It. t 4) The remains of polyalkylene oxide and divera Stupas suitable for. and eleven crosslinked under active fozne are found; only in the mtma molecule. In such a case it is not necessary to add this hardening catalyst but there is the dj3! EcgeB 'that the baths are not very stable. Since part of the components themselves are difficult to access, this case
 EMI2.4
 is only of theoretical interest for many principles
 EMI2.5
 of netiouiation.
 EMI2.6
 



  B) The groups necessary for the crosslinking are present in various compounds of which at least one - or also both - contains or contain polyalkylene oxide residues. Also in this case the presence of a catalyst is not necessary, but a limited stability of the bath is also to be expected.



  C) The conditions correspond to case A) but one of the

 <Desc / Clms Page number 3>

 groups or both groups capable of being crosslinked is or are present in a preliminary stage which is initially inactive.



  In this case, a particularly hot active catalyst is required. In this case, the stability of the bath at room temperature is generally sufficient, but it is temporarily limited.



   D) The conditions correspond to case B) except that in this case also there are preliminary phases of one or both groups capable of being crosslinked and that also in this case, with sufficient but not absolute stability of the bath, a hot active catalyst must be added.



   According to the usual finishing processes, the fibrous material is soaked in padding baths prepared according to A, B, C or D, expressed with a scarf, dried beforehand in air at room temperature or by moderate heating and subjected to a curing process at room temperature or elevated temperature. It is only in the absence of substantial amounts of liquid water that crosslinking and film formation takes place. However, this procedure has the undesirable side effect that the resin layers produced by the drying and curing process cause a marked stiffness of the material treated and that on the materials is observed, primarily in places of folding and on a dark background, irritating white lines, ie a "white break".

   These disadvantages are all the more marked as the surface films are thicker and water resistant. Since in order to achieve permanent antistatic effects, especially in washing machines, relatively high resin layers are required at the start, / follow with additional washing, subsequent treatment of such primers with plasticizers or a "breaking the resins" with the aid of molding machines, without it being possible to completely eliminate the "white breaking" on fabrics of hydrophobic fibrous material. In addition, in the case of breakage

 <Desc / Clms Page number 4>

 of resins, care must always be taken that the structure of the resin is not too untangled, which would cause a remarkable reduction in the resistance to washing of the diapers.



   However, the applicant has discovered that it is possible to produce on hydrophobic fibrous material relatively thick antistatic resinous layers, offering excellent adhesive power and very high resistance to washing, especially in washing machines, without being accompanied by modifications. Unpleasant in terms of feel and surface, if crosslinked surface films containing polyethylene oxide residues are produced in the presence of liquid water by a two-bath padding process or by a spray padding process. The only addition of amino plast formers containing polyethylene oxide groups for the formation of surface films should, however, be excluded.



  In principle, all the crosslinking principles or also the compounds already described in the case of the single-bath padding process can be applied for the production of anti-static wash-resistant finishes also in the context of the process. wet curing. In addition, all other reactions which take place in the presence of water for a short time and which are suitable for the production of insoluble resins can also be applied.



   The systems mentioned below have especially proved their worth: Polyvalent epoxides, hydrochlorides (+ alkaline catalysts) polyvalent primary or secondary amines; polyvalent epoxies, hydrochlorides (+ alkaline catalysts) or thiosulfates / sodium sulfide or poly- marcapto compounds
 EMI4.1
 vant..s; polyvalent isocyanates / polyvalent primary or secondary amines; polyvalent acid chlorides / polyvalent primary or secondary amines;

 <Desc / Clms Page number 5>

 polyvalent amines / polyvalent alkylating agents; polyvalent ethylene imides / polyvalent primary or secondary amines; Polyvalent vinyl monomers / polymerization catalysts.



  Surface films with good antistatic effect should contain at least 50% of polyethylene oxide groups (-C2H4O-) n.



  However, this value may be 10% lower if the resin contains other hydrophilic residues offering an antistatic effect, such as, for example, basic nitrogen atoms, residues of carboxylic and / or sulphonic acids or if one wants to eliminate as much as possible the antistatic effect in favor of other effects by addition or chemical incorporation of dyes, pigments (colored), plasticizers, bactericides, fungicides, antisalting additions, hydrophobilizers, optical brighteners, etc. The upper limit for the polyethylene oxide residue content of the resins still allowing wash-resistant fixing is about 96-98%. In most cases, the polyethylene oxide content of the surface films produced will vary between about 60-90%.

   It is therefore necessary that all of the resinous precondensation products which are still soluble and capable of being crosslinked contain at least approximately 50% of their total weight of solid substance in the form of polyethylene oxide residues.



   In the case of several reactants, it is irrelevant that the minimum polyalkylene oxide residue is contained only in one or more reaction partners. The hardening in the presence of liquid water can, in principle, be carried out in such a way as to impregnate the fibrous material as in the drying and curing process, to express and to subject it, if necessary, to the intermediate drying at room temperature or by short heating. Although in many cases intermediate drying has a favorable effect on the wash resistance of the antistatic effects

 <Desc / Clms Page number 6>

 after the wet hardening process, such intermediate drying is not necessary and should be omitted in cases where upon drying already hardening can take place.

   Then, the impregnated and pre-dried fibrous material is treated in a second curing bath containing water, or by spraying with a curing liquid containing water. In both cases, the crosslinking of the padded pre-condensation products can take place in the presence of liquid water.



   To prevent the water-soluble substances applied in the toularding bath from coming off, the hardening bath or coolant should contain about 5 to
30% useful substances, in most cases salts, such as, for example, sodium chloride or sodium sulphate. dium. While it is possible to prepare high concentration solutions from the substances, such solutions can also be used at a high degree of concentration.

   In most cases it is useful to bring the temperature / curing baths or liquids to be sprayed to a range between 40 and the boiling point of the individual aqueous solutions so that the curing of the resinous films can. be done in the shortest possible time. However, if there are special reasons, it is also possible to practice in suitable apparatus, for example autoclaves, pressure hardening at temperatures considerably above 100 C. In other reactions which take with lower temperatures also a sufficiently rapid course, one can also operate at the temperature of the room, or at a temperature still lower than the ambient temperature.



   The periods of time required for curing also depend to a high degree on the kind of crosslinking adopted in each case. They can vary between a few seconds and approximately 15 minutes.



   Once the hardening in the presence of liquid water is complete, it is recommended to rinse the finished fibrous material with

 <Desc / Clms Page number 7>

 water which may be heated or contain, for example, wetting agents or acid or alkaline additions, to remove adhesive substances. Then the material is dried in a known manner. her
As regards the practical reaction of the process there are many more possibilities than in the case of the dry hardening process.
 EMI7.1
 



  Garlic Bit Ait Di
The padding baths can be composed in principle in the same way as those designated in the introduction.
 EMI7.2
 by A, B, C and D. In this case, all the ingredients necessary for the crosslinking are already contained in the padding bath.



  The hardening in the presence of liquid water is carried out as already described so that after spinning on the scarf, the impregnated fibrous material is subsequently treated until the desired absorption of the bath, with or without intermediate drying (no hardening. not yet allowed) with a. curing bath or by sprinkling with aqueous curing liquids and drying after subjecting it to rinsing thoroughly.



  E1
As in case C, the padding bath is provided only with a compound a) which contains polyethylene oxide residues in a satisfactory amount and various groups necessary for the crosslinking, at least one of which is still in a stage. preliminary inactive. The catalysts still required are added to the curing bath or the quench liquid.
 EMI7.3
 



  Fi, Gl $ H11 Jl, K1t Liq Ml $ 01
These conditions apply if for the crosslinking two different compounds (b or c) and, in addition, catalysts
 EMI7.4
 are still necessary (H il el, Xi Mi $ 01) or not (F1, 01),

 <Desc / Clms Page number 8>

 N1
There is only one compound (a) which is, however, in the curing bath while the catalyst required for retioulation is applied from the toularding bath.



  According to this process, it is possible to obtain, for example, antistatic surface films by impregnation of fibrous material with polymerization catalysts and subsequent treatment with vinyl monomers containing polyfunctional polyethylene oxide residues. A particularly interesting variant of this method consists in producing, by preliminary treatment with ozone on the fibrous material, radical polymerization catalysts. In this case, the ozone current fulfills the functions of the toularding bath.



   The following table shows the most important possibilities A1 to O1 in which the wet hardening process can be carried out. Their number naturally increases dramatically when more than two compounds are present, which can react with each other while forming resins containing polyethylene oxide groups.

 <Desc / Clms Page number 9>

 
 EMI9.1
 



  These Coaposés Composta Catalysts Oatalysts The bath of required duration in the are required are oont- cisa- tion or the for the bath of naked in the 11qu1d 'erro- rticula- padding bath of whipping or lardage nentlsn fluid of salt
 EMI9.2
 
<tb> A1 <SEP> a <SEP> a
<tb>
 
 EMI9.3
 31 b, b, Cl a a +]) 1 b t 0 b, o + El a a + - oatalysts i b, O b - - o Gi b, o o - - b b, b + .. 0 + catalysts! Jl b, 0 0 + - b + oetalyers
 EMI9.4
 
<tb> K1 <SEP> b, <SEP> c <SEP> b <SEP> + <SEP> +
<tb> L1 <SEP> b, <SEP> o <SEP> o <SEP> + <SEP> b
<tb>
 
 EMI9.5
 fi b, o b. 0 .... catalysts 1 a + a 1 b, 0 .. + + b.

   0
 EMI9.6
 Per "vatalyseura" are also understood in this case substances which react with the hidden reducing groups of the film-forming compounds and thus transform them into / really reactive groups, without being incorporated into the polymer which forms; for example alkalis.
 EMI9.7
 



  . 8 tt is a compound containing more than about 50 polyethylene oxide groups and in the same molecule all of the groups necessary for crosslinking or their preliminary stages; b and o are two different compounds which, not each by itself but together, with or without catalysts, are capable of forming insoluble resins. They should together contain about 50% of their total weight in polyethylene oxide groups.
 EMI9.8
 



  It is unimportant that the necessary quantity of 3 grol, y pes of polyethylene oxide is present only in b or only in o or in both reaction partners., /

 <Desc / Clms Page number 10>

 
In cases E1 to O1, the padding bath does not contain all the ingredients necessary for the formation of resins, so the bath stabilities are absolute. This represents a further advantage compared to the dry fixing process, in which there is always the danger of growth of the molecule in the padding bath, even if it is not observed at the same time. exterior, since the crosslinking reactions also terminate at room temperature.



   Cases E1, M1 and F1 to L1 have been found to be particularly favorable, if the substances b or o are easy to mix with salts or catalysts in the curing baths or in the coolants.



     On the other hand, it may, however, be advantageous in special cases that a reagent can be released into the curing bath. This opens up the possibility that small amounts of b or c will suffice in the curing solution, since due to the release effect they are precipitated in high concentration on the fibrous material.



   Another advantage of the process object of the present invention consists in the fact that there is practically no yellowing which cannot always be avoided in the case of resins containing amino groups after drying, at cause of the action of atmospheric oxygen, in most of these at a high temperature. To improve the curing conditions or the properties of the resins, it is possible to add to the padding bath or to the curing bath or to the solution to be sprayed with retioulation agents, dyes, pigments (colored), bactericides, fungicides, anti-sizing agents, hydrophilic additions, plasticizers, optical brighteners, and the like.

   Preferred are additions which can be incorporated through the reactive groups so that they are resistant to washing. The main advantage by oom-

 <Desc / Clms Page number 11>

   parison with the dry hardening process, i.e. the pleasant feel and the absence of blanking even in the case of relatively thick antistatic surface films, makes it possible to considerably increase the permanence of the primers even when screwed. - with respect to washing in washing machines, by increasing the layers of resin.

   While with the dry curing process one can already observe with a resin layer of about 3% based on the weight of the fibrous material, a marked stiffness of the touch and, especially in the case of fabrics, a white breakage, the surface films produced by the wet process do not show any disadvantages even if they are high; wind at 10-20% based on the weight of the fibrous material.



   Depending on the applied retioulation principle, the permeations achieved by the wet curing process will also vary with equal layers of resin. Where the influence of the substrate can also be important. In particularly favorable conditions it is possible to achieve, in particular with resin layers of 10-20, a permanence of antistatic effects resistant to 100 washes and more at 60 C in the washing machine, without unpleasant changes in the feel. or the surface are observed. According to the dry curing process applied heretofore exclusively, such resistance to washing was not possible without adversely affecting the other properties of the finished fibrous material.



   The method which is the subject of the present invention is suitable for all (mixed) fibrous materials, where appropriate dyed beforehand such as, for example, filaments in the stretched state or not, yarns, fabrics, knits, or skein materials. and beads consisting of less than 50 hydrophobic fibrous material, either by modification of natural substances with a high degree of polymerization (for example cellulose esters) or by complete synthesis using polymerization of vinyl monomers, for example polypropylene, polyaoryloni-

 <Desc / Clms Page number 12>

 trile, polyvinyl chloride, polyvinylidene cyanide and vinyl aoetate, polyvinyl alcohol, ando,

   or with the aid of (oo) -polyoondensation or (co) -polyadditon (for example polyamides, polyurethanes, polyesters).



   Preparation of compounds I, II, III mentioned in the following examples: Polyamide I
535 g of a 40% solution of the polyamine II still containing Ó.ss-chlorohydrin groups are mixed with 720 ml of 24% aqueous ammonia. At room temperature, 24 g of caustic soda are dissolved in 60 milliliters of water, or added dropwise over 30 minutes and the mixture is stirred for 60 minutes at 60 C. The mixture is distilled by pressure distillation. reduce water and excess ammonia, until you no longer smell ammonia. From this amine solutions of about 24 to 40% of a polyfonational high molecular weight amino-polyethylene-glyool are obtained.



  Polyamine II still containing Ó-ss-chlorohydrin residues.



   From 600 gr of polyethylene glycol with a molecular weight of 600 aveo 5 gr of boron tritluoride etherate as catalyst and by the action of 223 gr of epichlorohydrin, a bis ether is prepared at 70-80 C. chlorohydrin which is converted at 25-30 C with 284 g of 24% aqueous ammonia and with the addition of 276 g of 33% sodium hydroxide solution and removal of excess ammonite, in a 40% solution of NH2-CH2-CHOH-CH2- O- (C2H4O) 13-CH2-CHOH-CH2NH2 (for the most part).

   840 g of a 40% diamine thus prepared are mixed with 320 g of 100% bis-chlorohydrin ether as mentioned above, and at 25-30 C the 35 g solution is introduced slowly and dropwise. of caustic soda in 50 milliliters of water. Stirring is continued at 25-30 C until the contents of the container begin to become viscous and begin to rise up the stirrer. By immediate addition of about 18% hydrochloric acid, the pH is adjusted to 6.0 by means of a solid electrode.

 <Desc / Clms Page number 13>

 Soil, diluted with water until concentrations of 30-40% are reached.

   Practically colorless aqueous and viscous solutions are obtained.
 EMI13.1
 



  3thor de ,, 01yohlqrnydr1ne III Are mixed in a nitrogen atmosphere 1500 g of
 EMI13.2
 1500 mol oxethylated triethanolemine and 15 g of boron trifluoride ethrate. After heating to about W C, 4 g of epichlorohydrin are introduced for about 40 minutes with stirring. The temperature of the reaction mixture is maintained at 120-UO-O until the contents of the vessel begin to rise up the stirrer. 10 milliliters of concentrated hydrochloric acid dissolved in 2930 milliliters of water are immediately added and the mixture is cooled to room temperature to give a slightly yellow viscous 40% solution.



   The following examples illustrate the invention without, however, limiting its scope.



    EXAMPLE 1
At room temperature, we treat a tiassu in a row
 EMI13.3
 of polyethylene terephthalate with a solution containing per liter 400 g of a reaction product at 27 obtained from 240 parts by weight of a solution of polyamine I at 30% and 3 g of acrylic acid chloride at a pH 8.0-8.5.



  After wringing on a scarf, to a bath absorption of 50%, the still wet material is treated for another 2 minutes at 100 ° C with an aqueous solution which contains 250 g / l of sodium chloride. After rinsing with water and drying at looal temperature, a fabric is obtained which offers excellent antistatic effects, a very soft feel and no breakage.
 EMI13.4
 White.

   After 5 washes in a mechanical washing machine at 60'0 with 4 g / 1 of an alkaline commercial detergent enti-mousset the specific surface resistance measured under normal conditions (20 C and 65% relative humidity of the air) was increases

 <Desc / Clms Page number 14>

 only about 100,000 M # .cm. (untreated 800,000 M #. cm / cm). cm
A fabric in the same way is subjected, after drying at room temperature for 2 minutes at 120 ° C. to a drying and curing process.

   With about the same wash resistance, a distinct stiffness to the touch and white breakage was observed, properties which were still to be observed after rinsing with water * EXAMPLE 2
A) As described in Example 1) a fila fabric of polyethylene terephthalate is impregnated with a solution containing 300 g of a 40% aqueous solution of the polyamine (IIà and 30 g of compound I- (C2H4O ) 13C2H4I.

   The fabric is treated for a further 2 minutes at 100 ° C with a solution of 250 g / l of sodium chloride * After 5 washes in a mechanical washing machine at 60 C, the specific surface resistance is only 30,000 M # .cm (untreated 800,000 M # .cm) cm cm
The touch and the condition of the surface do not show any unfavorable changes.



   B) As described in Example 1), a fabric of polyethylene terephthalate yarns is impregnated with a bath containing 400 g / l of a 30% solution of polyamine I and 60 g / l of a about 80% solution of phosphorous acid tris-ethylene imide.

   After filtering, the still wet material is treated for 2 minutes at 100 ° C. with a solution containing per liter 250 grams of sodium chloride. With satisfactory properties of the touch and the surface, the specific surface resistance after 5 washes in a washing machine. mechanical washer at 60 C still amounts to 4000 M #. cm. cm
With the corresponding primer according to the dry hardening process, a stiffness of the touoher and a white breakage are clearly observed.

 <Desc / Clms Page number 15>

 



   C) A padding bath is prepared containing 50 g / l of an 80% solution of tris-ethylene-imide phosphoric acid and 450 g / l of a 31% solution of polycarboxylic acid obtained from polychlorohydrin III by reacting all the reactive residues of Ó.ss-chlorohydrin with the sodium salt of thio-glyoolic acid at a pH of 8.5-9. The hardening takes place at 100 ° C. by a treatment for 5 minutes with a bath containing 250 gr of sodium chloride per liter.

   After 5 washes in a mechanical washing machine at 60 ° C., a further 29,000 M # .cm is measured. EXAMPLE 3 A fabric of polyoaprolaotam yarns is treated with a bath containing per liter 400 g of a 32% solution of polyamine (II) containing groups of hydrochloride and 50 g of anhydrous sodium arbonate.



   After expressing at 50% bath absorption, the still wet fibrous material is suspended at 100 ° C. in a solution of 250 g / 1 of sodium chloride * A fabric impregnated in the same manner is subjected for 2 minutes to 120 ° C. C to hardening to its. In both cases, after 25 washes in a mechanical washer, about 30,000 M # .cm is still measured (untreated 500,000 M # .cm). It turns out, however, that the feel and surface properties achieved by the wet process are much more favorable than those achieved by the dry fixing process.



  EXAMPLE 4
A fabric of polyethylene terephthalate yarns is treated with a toularding bath containing per liter 300 g of a 40-dose solution of polychlorohydrin (III) ether, 50 g of thiourea and 16 g of hydroxide. sodium. After expressing at 50% absorption bath, the material is treated for a further 2 minutes at 100 ° C in a curing bath containing 250 g / l sodium chloride.

   The feel of the fabric provided with an antistatic primer, obtained after rinsing and drying, is excellent;

 <Desc / Clms Page number 16>

 the fabric does not show white breaking. After 80 washes in a mechanical washing machine at 60 ° C. with 4 g / l of a commercial alkaline anti-foam washing agent, a further 30,000 M # .cm is measured. cm
A material treated by the dry curing process (2 minutes at 120 ° C) offers a very hard feel and strong white stop, even after rinsing.

   b) In a padding bath containing per liter 240 g of the 40% solution of polychlorohydrin III ether, 160 g of the 40% solution of the compound corresponding to the formula NH2-CHOH-CH2-O- (C2H4O) 13-CH2-CHOH-CH2NH2 and 24 g of sodium hydroxide, a fabric is impregnated with polyoaprolaotam and after dewatering a 50% bath absorption, it is further treated in the wet state for 2 minutes at 100 C with a solution containing 250 gr of sodium chloride per liter. The treated material offers a pleasant touch.

   After 30 washes in a mechanical washing machine at 60 C with 40 g / l of a commercial washing agent! alkaline defoamer, a further 28,000 M # .cm is measured (in the untreated cm state 500,000 M # .cm). cm
A material treated analogously by the dry fixing process exhibits less favorable touch and surface properties with about the same washout resistance of the antistatic effect.



     EXAMPLE 5 a) A strand fabric of polyethylene terephthalate at room temperature is impregnated with 500 g / l of a 32% solution of a polyamine (II) containing groups of hydrochloride.



   After expressing at 50% absorption of bath, the still wet tissue is treated for 2 minutes at 100 ° C. in a curing bath containing per liter 16 g of sodium hydroxide and 250 g of sodium chloride * After rinsing with water and drying at local temperature, a material is obtained whose feel does not show any modification compared to the material of

 <Desc / Clms Page number 17>

 starting and which is free from white breakage * After 15 washes in a mechanical washing machine at 60 C with 4 g / 1 of a
 EMI17.1
 commercial alkaline wash and the specific surface resistance is still around 35,000 M # .cm in oon- cm
 EMI17.2
 ditiona normal (in the untreated state we measure about 800,000, M #). b)

   In the manner indicated under a), a
 EMI17.3
 woven fabric of poly---oaprolecteme yarns with 400 g / l of a 30 solution of a polyvalent acrylemide obtained from 480 g of polyamine I and 12 g of acrylic acid chloride at a pH of 8 -8.5. After drying at room temperature, the fabric is further treated with a bath containing 3 g / 1 of ammonium persulfate and 250 g / 1 of sodium chloride; we rinse it and dry it as usual. After 10 lifts in a washing machine
 EMI17.4
 m6oeniqu6 to 6000 with 4 g / 1 of a commercial washing agent al- celin anti-mousso, the specific surface resistance is
 EMI17.5
 still at about 50,000 GJl..am. cm
The feel and the surface properties are not adversely affected.



  EXAMPLE 6
 EMI17.6
 a) In an impregnation bath containing 50 g / 1 of divinyloulroce (in this present: b) in a mixture of aoetone and water (1: 1) in dissolved form, a fabric is impregnated with polyoaprolaotam and after draining to a bath absorption of 50% it is treated while still wet in a bath containing
 EMI17.7
 nant 400 gr of a 32% solution of polyamine 1 (in this case: o), 50 gr of sodium chloride and 50 gr of carbonate
 EMI17.8
 of sodium per liter.

   After rinsing thoroughly, a material is obtained which offers a good touoher and after 10 washes in a mechanical washing machine at 60 ° C., a specific surface resistance of 50,000 M # cm. cm b) Similar results are obtained if one uses
 EMI17.9
 as a toularding bath instead of 50 gr of divinyleultonot

 <Desc / Clms Page number 18>

 80 gr of trio-ethylene-imide of phosphric acid (in the present case;

   b) dissolved in water. c) With 50 g / l of cyanide chloride, dissolved in anhydrous carbon tetrachloride, similar results are also obtained. d) We also arrive at similar results with a
 EMI18.1
 toularding bath containing 50 g / l of trls-ao1'Oyl-hexa-hydro-a-triazine dissolved in a mixture of acetone and water (1: 1) 6 e) A tissue of polyethylene terephtelate is imoreginated. ne with a padding bath containing per liter 800 g of a 20% solution of polyvalent thioaulturic acid ester obtained from polyohlorohydrin III ether by reaction with, theoretical quantities of sodium thiosulphate at 80 * C and at pH 9.

   After dewatering at 50% bath absorption and after drying in air, the material is treated for 1 minute at 100 ° C. in a curing bath containing sodium sulfide containing 250 g / l of sodium chloride and 50 g / 1 of crystalline water. After rinsing with water and drying, a material is obtained with an excellent feel, not revealing white breakage and which, after 90 washes in a mechanical washing machine at 60 ° C with 4 g / 1 d 'a commercial full-foam aloaline washing agent, still offers a specific surface resistance of 40,000 M # .cm cm
 EMI18.2
 only.

   (untreated 600,000 Mit4er) cm
 EMI18.3
 f) A polyethylene terephthalate fabric is impregnated for 5 minutes at 70 ° 0 with padding baths containing 50 g / l of i, 30OYanatO of hexamethylene and 0.5 g / l of dilaurate: of dibutyl tin, dissolved in carbon tetrachloride,
 EMI18.4
 or 10 g / l of 8.6-naphthalene diaulfochloride or 50 g / l of 4.4-diphenyl diphenyl disulfoelm, dissolved in ohlorobenzene, or 50 g / l of a polyglyoid ether of glycerol or 50 g / l of d chloride oxalyl, dissolved in carbon tetrachloride. After drying at looal temperature. (in air), we treat the tissues

 <Desc / Clms Page number 19>

 thus pretreated for 2 minutes at 60. with a 25% solution of polyamine I.

   After rinsing thoroughly to remove the residue from the hardening bath, a very good feel of the textile material and antistatic finishes are achieved which can withstand repeated washing at 60 C.



  EXAMPLE 7
In an aqueous padding bath oontaining 500 g1 / of a 32% solution of polyamine 1 (in the present case: o), a fabric is impregnated with polyca prolactam yarns and, after spinning, a bath absorption of 50%, we still treat it as it is! still wet for 2 minutes at 100 C in a curing bath, containing 250 g / l of sodium chloride and 240 g / l of phosphoric acid tris-ethylene-imide (in this case: b) at l 'dissolved state. After rinsing and drying and after 15 washes in a mechanical washing machine, a specific surface resistance of 20,000 M # cm is still measured. cm The material obtained offers a very good touch.



  EXAMPLE 8 a) A fabric of polyethylene terephthalete yarns is impregnated with a toularding bath containing per liter 500 g of a 40% solution of polychlorohydrin (III) (in this case: b).



  After dewatering at 50% bath absorption, the fabric is treated for 1 minute at 100 ° C. in a curing bath containing dissolved sodium sulphide containing 50 g / l of crystalline water (which in this case has the effect of a reagent and an alkaline catalyst) and 250 g / l of sodium ohloride.



  After rinsing with water and drying, despite a 10% resin layer, a material of excellent antistatic finish is obtained which shows no stiffness to the touch and no dryness.



   After 130 washes in a mechanical washing machine at 60 0 with 4 g / l of a commercial alkaline full-foam leavening agent, the specific surface resistance is still at 50,000 M #. cm. cm

 <Desc / Clms Page number 20>

 b) By analogously using undiluted 40% poly (III) polycyclohydrin ether (- 20% resin layer), also very satisfactory fabric properties are obtained. mechanical
After 70 washes in a washing machine at 60, it can be measured under normal conditions (20 C;

   65% relative humidity of air), in the case of polyester fabrics and polyester knits, still 13,000 M # .cm (untreated 300,000 cm M #. Cm / cm ). cI;) By the analogous use of 400 g / l of compound III, a very good permanence of the antistatic effects is also achieved without harming the properties of touch and surface,;

        on polypropylene yarn fabrics. polyaorylonitrile, on curtain fabrics made of polyethylene terephthalate yarns, on mixed fabrics of ooton / polyester (1: 2) and on acetate rayon c2) c2) Similar effects are observed on fabrics of polyaorylonitrile. polyethylene terephthalate, working in the same way but using instead of sodium sulphide in the curing bath 30 g / 1 of diethylen-triamine (which in this case also plays the role of reagent o and aloalin oatalyst) and by heating the tissue for 1 minute at 130 ° C. in an autoclave.

      c3) Using in the hardening bath, instead of sodium sulphide, 400 g / 1 of 4.4'-dioxy-diphenyl-propane (in this case - o), 17 g / 1 of oaustic soda and 250 g / 1 of anhydrous sodium sulphate, it is still possible to measure after 40 washes in a mechanical washing machine at 60 C a specific surface resistance of 50,000 M # .cm. The material reveals a good touoher. d) If we add to the padding bath according to cl) a further 50 g / 1 of a blue dye corresponding to the formula
CuPo (SO2NH-C2H4-S2O3Na) 3 (CuPc- residue of drunken phthalcoyanine)

   the dye molecules are inoorpoes in the anti- resin

 <Desc / Clms Page number 21>

 state and dark blue antistatic layers are obtained which are water resistant and wander a pleasant touch. e) By reaction of the fourth part of the reaction groups
 EMI21.1
 tifs ,, P-ohlorhydrlne contained in the ether of polychlorhydrin III with molar quantities of a) atearylamine) of the compound CO-NH-C2H4-1ti-02H4-NHa (polyethylene residue 348 of about 2000)) of bisulfite of sodium) of the sodium salt of thioglyoolic acid, certain functions are introduced at pH 8.5-9.5 in the polychlorohydrin III ether which modify the properties of the resin.
 EMI21.2
 



  When impregnating polyethylene terephthalate or polyoeproleotam fabrics with these modified a.polyob.lorhydrinea, in accordance with (cl), a good feel and antistatic finishes are obtained which in part offer a reduced tendency to sag.
 EMI21.3
 dirt.

   The resistance to washing ooiresponà as indicated under cl). f) If one operates as indicated under cl), and if one adds to the toulardage bath, in addition to 400 g / 1 / of a 40% solution of polychlorohydrin III ether, a further 2 g / 1 of a commercial optical brightener soluble in water or 200 g / 1 of a 24% solution of an oopolymer adjusted to pH 6 from 1 mole of the oompo-
 EMI21.4
 SE CHa-CH-CO-NH-02H ,, - s203Na and 3 moles of acrylic acid or 400 g / 1 of a 25% solution of polyaorylic acid or 12 g / 1 of a suspension of 40 % of phthalooyanine of or drunk, one obtains - excluding the optical brightener which is not resistant to washing - special effects of good resistance to washing in addition to good antistatic properties and good feel.
 EMI21.5
 



  EXAMPLE E9 A fabric is impregnated with polyethylene terephthalate a-
 EMI21.6
 velo a padding bath containing 100 g / 1 of 4 * 41-dioxy-diphiayl. propane (in this case * c) and 70 g / 1 of caustic soda.



   After spinning at a bath absorption of 50% on

 <Desc / Clms Page number 22>

 the scarf, the still wet material is treated for 8 minutes at 100 ° 0 in a bath containing 200 g / l of the 40% solution of polychlorohydrin III ether (in this case - b), 250 g / 1 of sodium chloride and 30 g / 1 of oaustic soda.



   A material is obtained which offers a very good feel and which after 30 washes in a mechanical washing machine at 60 ° C. still reveals a specific surface resistance of only 50,000 M # .cm (in the untreated state 80,000 M # .cm). cm cm EXAMPLE 10
In an impregnation bath containing 240 g of a 40% solution of polychlorohydrin III ether (in this case * b) and 25 g of caustic soda per liter, a fabric is impregnated with polyethylene terephthalate.

   After draining at a 50% bath absorption, the resin formation is promoted by treatment at 100 ° C. for 1 minute in a bath containing 200 g / 1 of a 25% solution of polyamine 1 (in this case - o) and 250 g / 1 of sodium chloride.

   After good rinsing, a material is obtained which offers a good feel which, after 10 washes in a mechanical washing machine at 60 ° C., reveals only 2800 M # .cm. Cm EXAMPLE 11
The procedure is as described in Example 10, but the padding bath contains 280 g of an approximately 25% solution of polyamine I (in this case - c) in addition to 25 g / 1 of caustic soda and the hardening bath contains 200 g / l of the 40% solution of the polychlorohydrin III ether (in these - b) in addition to 250 g / l of sodium ohloride.



  After 5 washes in a mechanical washing machine at 60 ° C., the specific surface resistance in this case amounts to 16,000 M #. cm./cm EXAMPLE 12 a) Treating a fabric of a) polyethylene terephthalate or b) polyaorylonitrile yarns with a swelling bath containing 240 g / l of the 40% ether solution of poly-

 <Desc / Clms Page number 23>

 chlorohydrin III and 160 g / 1 of the 40% solution of the compound corresponding to the formula H2NCH2-CHOH-CH2-O- (C2H4O) 13-CH2-CHOH-CH2NH2 and after wringing on the scarf at 50% of bath absorption,

   the goods are suspended in the still wet state for 2 minutes at lo0 C in a curing bath containing 20 g / 1 of caustic soda and 250 g / 1 of sodium chloride. The material offers a good touch * After 20 washes in a mechanical washing machine at 60 C, in both cases still approximately 20,000 M # .cm cm (in the untreated state a) 800,000 M # .cm and b ) 200,000 M # .cm cm respectively), at a relative air humidity of 65% and a temperature of 20 C. b) In a toularding bath composed of 30 g / 1 of tris * scroyl-herahdro- s-triazine, 50 g of glacial acetic acid, 300 g of the 40% solution of polyamine I, 450 g of acetone and 170 g of water, a fabric is impregnated with polyethylene terephthalate.

   After draining at a bath absorption of 50%, the still wet material is treated for 2 minutes at 100 ° C. with a hardening bath containing 17 g of caustic soda and 250 g of sodium chloride per liter. After 15 washes in a mechanical washing machine at 60 ° C., a specific surface resistance of only 4500 M # cm is still measured. The touoher cm is practically the same as that of untreated material.



  EXMPLE 13 a) A polymerization catalyst is applied to a fabric of threads of polethyl terephthalate, by impregnation with a solution of 30 g / l of ammonium persulfate. After draining at a bath absorption of 50%, the still wet fabric is treated with a bath containing 400 g / 1 of a 30% solution of the reaction product obtained at pH 8-8.5 from 480 gr 'of 'a 30% solution of polyamine I and 12 g ofcroyl chloride and 50 g / 1 of sodium chloride.

   After 5 washes in a mechanical washing machine at 60 C, 110,000 M # .cm is still measured (in the untreated state 800,000 M # .cm), the touohe: of the cm om

 <Desc / Clms Page number 24>

 textile material being very good. b) Bead material of vinylidene cyanide / vinyl acetate copolymer (1: 1) is exposed to room temperature for 10 minutes to about 5% ozone flow. This ozone stream, which in this case functions as the toularding bath, causes the formation of radical polymerization catalysts on the fibrous material.

   The material thus treated beforehand is left for 30 minutes at 60 ° C. in a bath containing a 20% solution of the reaction product formed at pH 8-8.5 from 90 g, 40% solution of polyamine II and 3. gr of acroyle chloride. The textile material offers a very good feel and after 7 washes in a mechanical washing machine at 60 ° C. with 4 g / 1 of an anti-foaming alkaline commercial washing agent, it still exhibits resistance; specific surface area of 45,000 M # .cm (untreated cm! 300,000 M # .cm) under normal conditions. The material has a very good feel.



  EXAMPLE 14
A fabric of polyc aprolactam yarns is impregnated with 3.3% sodium hydroxide solution. 'it is filtered off at a bath absorption of 50% and it is treated in the still wet state for 8 minutes at 100 ° C. in a bath containing 240 g / l of a 40% solution of polychlorohydrin ether III and 160 g of a 40% solution of the compounds NH2CH2-CHOH-CH2-O- (C2H4O) 13-CH2-CHOH-CH2NH2.

** ATTENTION ** end of DESC field can contain start of CLMS **.

 

Claims (1)

After rinsing with water and drying, a material is obtained with a very pleasant feel, which does not exhibit any blank oassage. After 25 lifts in a mechanical washing machine at 60 ° C. with 4 g / l of a commercial anti-foaming agent aloalin, the material still has a surface resistance of 25,000 M #. cm, measured in normal climate (untreated cm 800,000 M # .cm). cm CLAIMS 1. Anti-static wash-resistant primer process <Desc / Clms Page number 25> of hydrophobic fibrous material, characterized in that it consists in producing, following a padding process in 2 baths or t of a spraying process by spraying, where appropriate following an intermediate drying, Crosslinked surface films containing polyethylene oxide groups in the presence of liquid water, the isolated use of aminoplast formers containing polyethylene groups for the formation of surface films, however, is excluded. 2. An antistatic primer obtained by the process according to claim 1.