DE2239592B2 - PROCESS FOR THE ANTISTATIC, DIRT-REPELLENT AND WATER-ABSORBING EQUIPMENT OF SYNTHETIC FIBERS - Google Patents

Description

RO

I!)

CH ₂ = CC- (OC ₂ H ₁ L- (OC ₃ H ₆ I _n -R '

where R is hydrogen or CH ₃ and R 'is chlorine, bromine. Iodine. OCH ₃ . OC ₂ H ₅ . SCH ₃ or SC _{2 means} H ₅ . η is equal to or greater than O and at most 10 and Wi is at least 10. with b) a polymerizable monomer and / or a divinyi compound or

(C) a mixture of a compound having a polymerizable vinyl group at one end or as a side chain of a polyalkylene glycol. whose polyalkylene oxide unit has a molecular weight from 400 to 10,000, with a vinyl monomer having at least two vinyl groups on the fibers and subsequent heating, characterized in that that the impregnated fibers are heated in the presence of moisture.

2. The method according to claim 1, characterized in that that the impregnated fisers are heated in the presence of steam.

3. The method according to claim 1 and 2, characterized in that on the fibers before In addition, heat a cationic anti-icing agent, an alkylethylene urea of the formula

(J

CH, | CH ₂ ) _n NHC N

CH,

CH,

45

wherein / 1 denotes 5 to 30, or applies a derivative of the oil.

From DT-PS 10 28 524 a method is .tür anti-Itatic Finishing of textiles from hydrophobic LOlymcrisatcn known, which is called anti-static Medium Polyäthylcnglykolacrylale or -methacrylate Used and after the application on the synthetic fiber cams heated. According to the I) T-OS I4M453 . .Used to use anti-static textile equipment Copolymers from polymerizable monomers and methylalkylene glycol esters generally more unsaturated Siii. en. Here, too, the antistatic agent .iiif dei synthetic fibers is heated dry. With these V -rfahren / ur antistatic textile finish remains d.i · - Finishing material in disjointed Layer in patches on the fiber and result in only one relatively poor endurance of the finish, particularly poor washability The Germans' announced internals Patent application C 6081 IVc / 8k relate to a method of using fibers made from native cellulose against the attack to protect by microorganisms by exposing these cellulose fibers with an aqueous solution or Emulsion of curable aminoplasts can be impregnated and heated without intermediate drying. The DTOS 17 69 665 relates to a method of crease-proofing completely or partially made of cellulosic fibers by impregnation of the fibers with a solution or dispersion of a resin precondensate which reacts under acidic conditions and of a catalyst, the impregnated textile fiber being exposed to hot water exposure to hot steam. Both publications thus relate to technical areas that have nothing to do with the problem underlying the invention.

The object on which the invention is based is to address the disadvantages of known antistatic Avoid textile finishes and antistatic, dirt-repellent and water-absorbing finishes of synthetic fibers with increased durability, in particular increased wash resistance receive.

The inventive method for antistatic. dirt-repellent and water-absorbing equipment of synthetic fibers by application

(A) one of quaternary nitrogen compounds. free product, which mainly consists of a PoK alkylene oxide unit and at least two acrylic groups and / or methacrylic groups on both Ends, one end or as a side chain of the main chain has, or

(B) a mixed polymer of a) a compound the general formula

R O

CH ₂ = C --C- (OC ₂ FU ₁ - (OCHJ ₁₁ -R-

where R is hydrogen or CH, and R 'is chlorine. Bromine. Iodine. OCH ₃ . OC ₂ H ₅ . SCH ₃ or SC _{2 means} H ₅ . η is equal to or greater than 0 and at most 10 and »1 at least 10. with b) a polymerizable monomer and / or a divinyl bond or

(C) a mixture of a compound having a polymerizable vinyl group at one end or as a side chain of a polyalkylene glycol. whose polyalkylene oxide unit has a molecular weight of 400 to Has 10,000. with a vinyl monomer having at least two vinyl groups on the fibers and then Heating is characterized in that the impregnated fibers are in the presence of moisture heated.

The impregnated fibers are preferably heated in the presence of steam.

Furthermore it is \ orieilhafl. .ml the fibers \ ur dem Heating in addition to the equipment mentioned above a cationic antistatic agent, an alkali metal urea of the formula

II.

[CIfI ₁₁ NlH

(H,

(H,

where / denotes 1 ^ to 3d, or a derivative of the latter to raise

In the case of the synthetic fibers equipped according to the invention, such as a polyamide, polyester. Polyacrylonitrile or polyolefins, the surface of the synthetic fiber is made up of a continuous polymer film of the treatment agent in a thickness of 0.01 to 10 μ. preferably 0.1 to 3 μ covered. Such antistatic Synthetic fiber structures according to the invention have surprisingly durable antistatic properties "-

R ₁ O

shafts and at the same time dirt-repellent and water-absorbent properties.

The treatment agent (A) is a vinyl monomer of a polyalkylene glycol with at least two acrylic and / or methacrylic groups in a molecule, according to, for example, the following general formulas:

OR ₂

O R,

Ii r

κ> PO CH, -Ο-CC-CH ₂

I II:;

CH ₂ -CC- (OCH ₄ I _n , - Ο -C-CH

(Here R ₁ and R _{2 can be the} same or different and mean H or CH, O ni mm = 5 - 5Ou ι. Examples of the treatment agents (Al are Pol \ - Sthyleiiiilykoldimethacrylat, Polyäthyleneglykoldiacrylat. Pokäthyleneglykoltriacrylat, Di- or Trimeth-

H
CH ₂ = CCO-CH ₂

/
CH, -C-CO-CH ₂

CH, O

CH _: - O - CC = CH ₂

OR ₁

acrylal from block polyalkylene glycol from polyethylene oxide and polypropylene oxide as well as acrylate and methacrylate derivatives of polyalkylene oxides. according to the following general formulas:

O H

HC-C (OCH, CH, hr-O -C-C -C -CH ₃
OCH-CH-

-O - C — CH-CH,

O CH,
OR ₂
R ₁ OOR 0, CH, - 0-C - C-CH, O

Il "" ü

CH; - CC ■ - (OC ₂ H ₄ J _1n - O - C - CH - O —C -CH - CH - (OC ₁ H ₄ L ~ O - C-CH ----- CH,

ι H

I I!

CH ₂ -O CC CH- (OC ₂ H ₄ LOC-CH-CH; O R. CH, O - C - C-CH ₂

(Here R.,. R,. m and κ have the above meanings.) The treatment agents (B) are copolymers of components a) and b). Examples of component ai are methoxypolyethylene glycol acrylate, ethoxypropylene glycol acrylate, ethoxypolyethylene glycol acrylate. chlorinated polyethylene glycol methacrylate. chlorinated poly (ethyl glycolate). Methyl sulfide polyethylene glycol methacrylate. Methox \ poh propylcnglykolpolyäthylcnglykolacrylat and Mcihox \ polypropyleneglykolpolyäthylengl \ kolmethact \ lat Such compounds have an excellent antistatic effect if m in the general formula at least H). is preferably at least 20th. If in is below IO, the antistatic effect will not be sufficient, and if m is above hi !! pm, then A \ c. Svnthese of the connection difficult.

O CH ₃

Examples of component b) which are necessary to obtain the mixed polymer (B) are acrylonitrile. Acrylic acid. Methyl acrylate, ethyl acrylate. Methacrylic acid. Methyl methacrylate. Ethyl methyl acrylate. Acnlamid. Sodium allyl sulfonate and sodium styrene milfonate as polymerizable monomer, and example e for the divinyl compound ^ ind AthslengKkoldi.tcrylat. Ethylene glycol dimethacrylate and polyethylene glycol diacrylal.

The treatment agent (Bi is a binary or 'eniäres polymer, which one after ^ h known methods “Longer redox polymerisation by Nti ^ chpoly-ηκ-nMcrunu of the components al and bi, Fm contains a mixed polymer consisting of IO to 40 dew.- ".. acrylonitrile was obtained as component b) is particularly put with regard to its antistatic properties. if

the degree of interpolymerization is below 10%, the effect obtained is insufficient. If he is 40% exceeds, the particle size of the interpolymer becomes large, and the antistatic property becomes large and their durability then becomes bad.

When applied, the mixed polymer (B) is used as a dispersion or solution in water or a organic solvents are used.

The treating agent (C) is obtained by mixing a polyalkylene glycol monovinyl compound with a vinyl series monomer. that has at least two vinyl groups, i.e. one polyfunctional one Vinyl compound is. The polyalkylene glycol monovinyl compound contains a polyalkylene oxide unit with a molecular weight of 400 to 10,000. preferably from 800 to 4000. Examples of these are polyethylene glycol methacrylate, methoxypolyethylene glycol acrylate, Methoxy polyethylene glycol methacrylate. Ethoxy polyethylene glycol acrylate, ethoxy polyethylene glycol Kol methacrylate, chlorinated polyethylene glycol methacrylate, Polypropylene glycol acrylate, polypropylene glycol methacrylate, Methoxypolypropylene Glycol Acry-Fat. Methyl sulfide polyethylene glycol methaervlate and Compounds with a vinyl group as a side chain according to the following formula:

OOR ₂

, -F OCH ₂ Ci-I ₂ J _n - O- C-CH-CH ₂ -OC-CH-Ch-IOCH ₂ CH ₂ L-OR ₁

CH ₂ OH

CH ₂ - 0-CC-CH ₂ OR,

(here R ₁ and R _{2 have} the meaning of water- R

material. Methyl or ethyl, and m is an integer from 5 to 500).

The reason for limiting the molecular weight of the polyalkylene oxide segment is dar- ^ in. that with a molecular weight lower than 400 the effect aimed at by the invention is not sufficient can be obtained, and when it exceeds 10,000, the synthesis of the compound becomes difficult.

The vinyl monomer with at least two vinyl " groups in the mixture (C) is, for example, a diacrylate or triacrylate compound.

The treating agent (C) is obtained by adding the above-mentioned monovinyl compound with the polyfunctional vinyl compound mixed, the j ° resulting mixture in the form of a dispersion or solution in water or an organic solvent applies to the synthetic fiber. As for the mixing ratio of these compounds, thus the effect of the invention becomes remarkable. VK en η the vinyl compound with at least two vinyl groups in an amount from 3.0 to 50.0% by weight. preferably 5.0 to 40.0% by weight. Based on the fixed portion of the monovinyl compound. is present.

The preferably additionally used cationic antistatic agent consists, for example, of a compound with a poly - /? - methaerylo \ yäthyI-diethylmcthylammonium methoxysulfate as the main component and a compound of the quaternary ammonium salt series, such as an acryltrimethylammonium salt /. Dialkyldimethylammonium salt. AlkyUrirnitylammoniumalz and Alkyldimethylbenzylammoniumalz. Alkyl pyridinium salt. A Ik ν I morpholiniumsal /. Alkylimidazoliniumsal / and compounds (lic (.lurch aih'cmcmcn the following formulas ^(l ° uetiehen are again:

ICIFCH, OL H.

NH H-CH ₂ O) ,,

Cl

CH, (CH ₂ CH ₂ O) _n H.

O R '

j R- C- NHCH ₂ CH ₂ CH ₂ --N- R i X | 3i

R "'

(Here R. R '. R "and R'" can be identical or different and have the meaning of H or a lower alkyl group, X stands for a halogen. m and »can be identical or different and at least 5 and at most 30) .

Octadecylethylene urea is one of the additional alkylene ureas that may be used most effective.

The additional cationic antistatic agent. the alkylene urea or its derivative mixed with the treating agents (A) to (C), respectively, and this mixture is used as a dispersion or Solution in water or organic solvent applied to the synthetic fiber. It is useful to that the adhering amount of a mixture of such compounds is 0.03 to 10% by weight, preferably 0.03 to 7% by weight, calculated as solids and based on the weight of the fibers.

Apparatus previously used in a dye works can be used for treatment with steam. In the case of moist heating one uses / wake-up an atmosphere that is about 80 to KX) ".. steam contains. The treatment time for steam treatment is preferably 60 to 'HX) seconds and the temperature 80 to 150'C. You can also use Heat in the presence of vapor of an organic solvent if this is the polyalkylene glycol monovinyl compound does not solve.

When moist heating according to the invention, a Polymcrisicrinitiator, such as ammonium sulfate can be used at the same time. Potassium sulphate. Benzovene oxide and A / o-

bisisobutyl nitrile, can be used. In particular when using a redox polymerization initiator it is possible to obtain a finishing film at a lower temperature. About an equipment film to form on a hydrophobic fabric, it is necessary to to use a hydrophobic polymerization initiator.

Furthermore, it is possible to obtain permanent usability of the treatment pad by forcibly introducing oxygen or air into a treatment liquid containing treatment agent (A) or (C). The synthetic fiber is treated continuously while oxygen is supplied at a flow rate of at least 2.1 cm ³ / l · min, e.g. B. at 20 "C, expediently at least 10 cm ³ / min into the treatment liquid. On this occasion, the temperature of the treatment liquid can be raised accordingly, and with regard to the decomposition of the polymerization initiator and the formation of a polymer film, is a temperature in the range from 0 to 60 ° C. is expedient.

The application of the finishing agent to the synthetic fiber can be done with any immersion method, block method. Coating method or spray method.

According to the invention, synthetic fibers made of polyamide, polyester, polyacrylonitrile. Polyolefin. Polyurethane and cellulose derivatives as well as mixed fibers and mixed staple fibers made therefrom and those fibers whose properties have been modified, but also knitted and woven fabrics, nonwovens. Threads. Yarns, staple fibers and films made from these synthetic fibers. Knitwear or woven goods expediently have a density equal to or less than 0.5gern ³ . The volume is calculated by multiplying the thickness of the fabric under a load of 3 g / cm ³ by the area of the fabric. Examples of such synthetic fibers that can be equipped according to the invention are more specifically about the following:

Polyester fibers made by combining an aliphatic dicarboxylic acid. such as sebacic acid and adipic acid, and an aromatic dicarboxylic acid. like terephthalic acid. Isophthalic acid. 2,6-naphthalenedicarboxylic acid and diphenic acid with ethylene glycol or butylene glycol and condensation of the mixture obtained gives:
Polyamide fibers obtained by condensation polymerization of an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, an aromatic dicarboxylic acid such as phthalic acid. Isophthalic acid, terephthalic acid. 2,6-naphthalenedicarboxylic acid and diphenic acid, and a dicarboxylic acid with an aliphatic ring or heterocyclic ring such as 1,2-cyclobutanedicarboxylic acid or 2,6-dicarboxypyridine with an aliphatic diamine such as hexamethylenediamine, an aromatic diamine such as p-xylylenediamine and m - Xylylenediamine, lactams such as -OC- (CH ₂ J _n -NH- (n = 3.4, 6. 8. 10. 11) and aminocarboxylic acid;
Polyacrylonitrile fibers, the homopolymers or copolymers of acrylonitrile and optionally methyl methacrylate, vinyl chloride. Vinylidene chloride, vinyl acetate, styrene, sodium styrene sulfonate and sodium allyl sulfonate;
Polyolefin fibers made from ethylene and propylene:
modified polyester fibers such as

a polyester obtained by blending with a synthetic high polymer of the polyester series has been received. and the following general formulas individually or in a suitable combination owns:

R-Ar-X

R-Ar-W-X

wherein R is an alkyl group having 2 to 18 carbon atoms. Ar is an aromatic hydrocarbon residue or phenolic nucleus. X is an adipic acid group or its salt and W is the group

or

(»= 2 to 16) means, or the formula

R-0 - ^ - CHCH ₂ O-Jv-H

wherein R 'represents a hydrogen atom or an alkyl group. R "denotes a hydrogen atom. CH, or C ₂ H ₅ and η 2 to 500 denotes.

After the finish according to the invention, such fibers have such antistatic properties as Cotton on. The fiber is extremely dirt-repellent and water-absorbent.

Polyamide fibers that have been modified and that are in the form of block copolymers.

contain 15 to 85% by weight of polyether units. Such Block polyether amides are prepared by adding a monomer to form a polyamide, e.g. B. Lactams. ω-amino acids or a diamine and a dicarboxylic acid in the presence of a polyether with a terminal amino group or an organic salt thereof in solution or molten Polycondensed state, the polyether having an amino group, a carboxyl group or a Has amino group and a carboxyl group at its end and the polyamide has a carboxyl group, has an amino group or a carboxyl group and an amino group at its terminal. These polyamides have z. B. a final content of polyether unit of 0.1 to 20 wt .-%, preferably 0.3 to 10 wt .-%.

If you want to finish a hydrophobic fiber according to the invention, this is difficult because the treatment agent are hydrophilic. As a result, a method has been developed according to the invention that works to polymerize the surface of a hydrophobic fiber in a solution allowed, especially when treating a hydrophobic fiber with a treatment liquid, the main contains the treatment agent (A). The tem perature of the treatment bath is as far as required The polymerization initiator used is special that's important. A practically water-insoluble hydrophobic polymerization initiator, e.g. B. fine particles a water-insoluble polymerization initiator such as benzoyl

f> 5 peroxide. Acetyl peroxide. t-butyl hydroperoxide. Perox) carbamate, 2,2'-azobisisobutyronitrile and tetramethylthiuram disulfide, optionally in stabilized form Form mixed with, for example, magnesium sulfa

709 523/4

Is used. Particles of a hydrophobic initiator are deposited on the surface of a hydrophobic fiber adsorbed in water, and the vinyl monomer dissolved in water is polymerized on the fiber. Even it is possible to carry out polymerization at low temperature by introducing a Redo.x type polymer to be carried out as initiator.

Below are methods of measuring the antistatic properties, water-absorbing properties Properties and adhering amounts explained. as given in the examples.

A sample treated according to the invention is kept for 5 hours in a controlled chamber of 21) C and relative humidity of 65%. The amount adhered is then measured. In addition, the sample is kept at 20 C and more for 15 hours Humidity of 40% left. The level of static electricity is then measured.

1. Static electricity measure (V)

Measuring machine:

Static rotation tester.
End fabric of friction:

Cotton fabric with 50 yarn count in width.
Measurement conditions:

20 ± I C. Humidity 40 ± 1%.

The degree of static electricity ιV) is called Average of five measurements given.

2. Durability

Washing machine:

Electric washing machine.
Laundry detergent:

A detergent.
Concentration used:

() .2% by weight.
Washing conditions:

40 C and 10 minutes.

After a sample has undergone such a wash. is it dried as follows:

Dryer:

Household dryers.
Drying conditions:

70 and 10 minutes.

The above information relates to a single wash. Ten such washes subjected sample is referred to as "sample after washing". It goes without saying that the one such Prooe subjected to treatment in the control chamber at the specified temperature and humidity is left standing and measured on it. A sample washed with a time 0 is such before the above washing treatment.

3. Adherent amount

This results from the percentage difference between the weight of a sample before and after the treatment, based on the weight of the sample before treatment

Relationship of attachment

Is in here

H _n - weight of the sample before treatment.
U ■ = weight of the sample after treatment

The term "loss ratio" is used in the following examples. This is measured by the adhesion ratio measurement method. The loss ratio is the percentage of material that falls off or is removed after washing based on the amount of adhesion of the sample before washing or washed at time zero.

4. Water absorption property

A drop of water (0.04 cm ³ drops) is dropped onto a sample from a position 5 cm high and the time taken for the drop to be completely absorbed is measured. The shorter the time, the better the water-absorbing quality.

Various aspects of the invention are set out below, particularly with reference to aul Examples explained.

example 1

A pile terephthalate yarn of 250 denier and 84 threads is wrongly twisted into a fabric woven and the fabric subjected to delayed wetting or cleaning according to conventional methods.

Then it is dried and such treatments

subjected according to the invention, as indicated with ml to m 5. The adherent crowd and that

Static electricity levels for these substances are given in Table 1.

The composition of the treatment liquid

and the treatment conditions of the polymerizable compound are as follows:

Sample m 1

An aqueous solution with 3 wt .-% polyethylene

ülvkoldimethacrvlat. its Polyoxväthvlensegmenl

has a molecular weight of 500. is with 0.3 wt .-% ammonium persulfate (APS) as a polymerization initiator offset.

An aqueous one
methacnlal of

(Mense in percent) =

IV- H _n

100.

Sample m2

Solution of polyethylene glycol di-3% by weight. its polyoxyethylene segment Has a molecular weight of 1000, 0.3 wt .-% APS is used as a polymerization initiator offset.

Sample m3

An aqueous solution of 3 wt .-% polyethylene

glycol dimethacrylate, its polyoxyethylene segment

has a molecular weight of 2000, to which 0.3% by weight of APSaIs polymerization initiator has been added.

Sample m4

An aqueous solution of 3 wt .-% polyethylene

glycol trimethacrylate. whose polyoxyethylene segment has a molecular weight of 1000 is with 0.3% by weight of APS added as a polymerization initiator.

Sample m5

An aqueous solution of 3 wt .-% polyethylene glycol monomethacrylate, whose polyoxyethylene segment has a molecular weight of 1,000. 0.3% by weight of APS is added as a polymerization initiator. Any of the foregoing five solutions that

vary in molecular weight and structure of the l'oUäthslenglvkols will differ evenly squeezed by means of a scoring device, and the adhering amount is adjusted to 8Xwt%. Then the fabric is in the presence for 3 minutes at 105 ° C treated by heated steam and then the unreacted substance in water with 0.05 wt% ordinary soap saponified at 50 to remove this substance; on it is with water washed and dried.

Table 1

Sample m M *

Affiliations

IP ".ι

Mali the sun lichen I lcklri / itat (Vi

2.42
2.3?
2.3N
2.65
1.10

after

2.19
2.11
2.12
2.2X
0.41

Loss before
relationship

9.50
9.44

10.92
6.94

62.75

522

259

248

251

1205

5380

II.IL'h

826

310

292

283

3252

5460

Measured.
Washed.

From Table 1 it can be seen that with increasing molecular weight of the polyethylene glycol, the generated static electricity decreases. Compared to mono- \ im! Compounds are divinyl and trivinyl compounds excellent in durability and adhesive property. It can also be seen that the molecular weight of the polyoxyethylene segment of at least 1000 gives excellent antistatic properties. The film thicknesses of m 1 to m4 at this time are based on observation under an electron microscope about 0.8μ.

Example 2

A tricolor fabric is obtained by knitting a polyamide yarn consisting of f-caprolactam of 40 denier and 10 threads, which has been subjected to preheating and wetting. As in Example 1, this substance is treated with a 5% strength aqueous solution of polyethylene glycol diacrylate, the polyoxyethylene segment of which has a molecular weight of 1000. treated, this solution having been treated with 0.5% potassium persulfate as a polymerization initiator. In this case, the adhering amount is set to 79% by weight. Then, a part of the sample obtained is treated for five minutes at 105 ⁰ C with heated water vapor while the other part of the trockenbehandelle sample is treated for 45 seconds at 160 C at 110 C and dried thereon. The coated sample treated in this way is saponified, washed with water and dried, as in Example 1. The test values to be measured and the measured values. method are the same as in Example 1, the results obtained are shown below

Table 2

lichamHunusniclhodc

M

Λ η hiifl men j;

in ".1

Dry
Heat treatment

Dampluaini treatment
Empty

w *

before

0.6

after

Mall de 1
static
Hectri / iliit (Vl

\ oi after

Loss ratio

0.41 31.1 3250 4360

11.4

238 326

8820 9050

Measured.
C! L ^- See

Table 2 shows that the polymerizable compound difficult to polymerize in the presence of air, as in dry heat treatment is to be brought. but in the presence of steam, namely with a moist heat treatment, completely can pohmerize. With dry heat treatment however, some effects are observed. Table 2 also shows that polymerization in one Solvent vapor is possible, as it has been used for the fire bath. In a star, in where there is no large amount of air. occurs the response in the same way. as in a so-called general vinyl polymerization.

Example 3

A single yarn with the yarn number count consisting of 48 Pol \ acrylonitrile, is used Zweifacheiiksu> lT bin is gebeucht in the usual manner and dipped in a padding bath, by adding the merisationsinitiator 0.5GeU.- ¹ O APS as Poh added to a 3% aqueous solution of polyethylene glycol diacrylate with a molecular weight of the polyoxyethylene segment of 1000 has been obtained. The fabric is squeezed evenly to adjust the adhered amount to 125% by weight, and then heated with steam at 105 ° C. for 5 minutes. On the other hand, the fabric is dipped in a padding bath, the strength by the addition of 0.3 wt .-% APS as Pohmerisationinttiator to a l% aqueous solution, as has been mentioned above, obtain a "polymer of the same kind, and heated to 100 ⁰ C. . The two substances are then treated and tested in the same way as in Example 1. The results can be found in the following table.

Table 3

Treatment method

Quantity
in "'"

before after

Loss ratio

Measure of
static
i-.le.klri / itiit | Vi

\ or after

Inlay treatment *!

0.60 0.50 17.0 2650 2400

continuation

Treatment method c

Hips
in "A

W *
before

ι-ημο

after

MaH del
static
I lckln / il.ii

IVI

Loss obsolescence

after

Steam treatment
Empty

3.52 3.0X 12.5

S20

7350 7M0

M * = measured.
W * -.- Washed.

* l l.mleiibehandlunii: The toilet / bath is on HK) (. erhii / i. and the sample is immersed in it for a predetermined time

As can be seen from Table 3, it is that of the immersion treatment subjected sample poor in adherence amount and antistatic property. If during the inlay treatment the warming; as homopolymerization progresses, so too continued, and when the temperature reaches 100 "C, results gelation occurs almost immediately (within 10 minutes). As a result, the formation of a film is on the fiber surface difficult. The Einlegmethodc is not completely unsatisfactory, but certain Improvements are brought about.

Alien glycol trimethylacrylal with a pole \ ox \ athvlensegmcnt of a molecular weight of HKK. The adhering amount will be 43 ", set, the substance is treated for 3 minutes at 120 C ii saturated tetrachlorethylene vapor. 20 Wed The grooves are placed in acetone at 50 ° C. to remove homopolymers and then at 160 ° C. for 1 minute dry warm treated. The fabric is then treated in the same way as in Example 1 to obtain the au; the following table results zi obtained.

Table 4

Hchandlunsismclhodc M * Ver Measure dei t ιVi Adhesion mcngc desire static in ".ι \ cr- I -leklh / iUi ■ eh W * h.illnis Follow me \ or n.

solvent
treatment
Empty

I »7 1.76 10.6

730

10,000

iL'nicsscn.
icu a ^ chcn.

Example 4

A crepon fabric. that by weaving a bottle of yarn of 50 denier and 24 threads. is buckled as in example 1 and in a Inserted padding bath, which is obtained by adding 0.5% by weight of benzoyl peroxide as a polymerization initiator to a 5% tetrachlorethylene solution from PoU-Wie as can be seen from the table, the goal is dei Invention achieved in a satisfactory manner if one carries out a solvent treatment.

Example 5

The same polyester fabric as in Example 1 is inserted and padded in a 3% aqueous solution a union! the formula

HOOO CH ₁ ο

CH ₂ = C -C - (OC ₂ Ht) ₁₀ - O - C _{- CH - CH 2} - O - C - CH - CH - (OC ₃ H ₆ J ₁₀ - O - C - CH = CH ₂

CH ₂ -OCC-CH ₂ CH ₂ -OCC = CH ₂
O CH ₃ O CH,

mixed with 0.5% potassium persulfate, then the 25% is obtained. When the frictional stresses before

Fabric so squeezed that 90% adhere, and then washing and after washing ten times at ^ m

Treated in steam for 5 minutes. Then the substance of this example will have been measured to be the

saponified in the same way as in Example 1 and 60 results 550 V. or 280 V at 20 "C and 40%

• Finally measured on the amount adhered to relative humidity.

Se pi le 6

The samples used in this example are listed in the table below. The one used here Polyester is a normal polyester fiber, consisting of ethylene glycol and terephthalic acid for clothing, and the polyamide used is obtained by polymerizing caprolactam.

Table 5

No. material Denier of threads Name of the knitted or thickness density woven fabric (mm) (g cm ³ 1 polyester 75-24 Taffeta 0.095 0.84 2 polyester 50-24 twill 0.085 0.70 3 polyester 75-24 twill 0.14 1.03 4th polyester 250-S4 Matt worsted *) 0.55 0.23 5 polyester 75-24 Tropical *) 0.19 0.43 6th Polyester 65% A **) poplin 0.31 0.15 Rayon 35% 7th polyamide 30-6 shirt 0.11 0.56 8th polyester 50-24 Taffeta 0.080 0.73 9 polyamide 50-24 Jersey*) 0.58 0.21

• | l'nicr use of an edited ciarn.
Λ ** Ι S-Ί λ is 40 S 2. S IZl 30 S 2.

Before the samples are subjected to the antistatic treatment, the following treatments are carried out:

Ordinary substances are heated for 30 seconds at 180 C for 30 minutes in an aqueous Solution of 2 g / liter soda and 1 g / liter of a nonionic surfactant.

A tricot knit has been treated similarly.

Knitted and woven fabrics using pretreated yarns are treated in a relaxed state for 30 seconds at 30 C in water, then in a similar manner, and then heated to 180 C for 30 seconds.

Table 6 shows the results of the measurements Properties of these substances after the treatments.

D.TS used herein, treatment means X is an aqueous solution of 25% copolymer, holding egg by copolymerizing a mixed monomer having a gel point of 25, obtained by mixing Methoxypolyäthylenglykolmethacrylat having a molecular weight of 1000, and PoI _-, -äthylenglykoldimethacrylat having a molecular weight of 1100 and acrylonitrile in a ratio of 75%: 25%.

The treatment agent Y used here is a water-soluble emulsion of 50% of a mixed polymer, obtained by copolymerization of 30% dimethyl terephthalate, 20% ethylene glycol and 50% Polyethylene glycol with a molecular weight of 2000.

The treatment agent Z used here is a liquid water dispersion containing 30% p-ß-Methacryloxyäthyldiäthylmethylammonium - methoxysulphate. "

The treatment method consists in padding the active substance or fabric in the treatment agent Concentrations given in Table 6, followed by drying of the fabric for 3 minutes at 120 C and finally heating the fabric for 40 seconds at 160 C.

In the case of a polyester-rayon blend fabric, i.e. No. 6 in Table 5, the anti-crease and the Hand-improving agent for rayon the following resin treatment agent in a mixture with the treatment agent of Table 6 intended for pad treatment.

Resin treating agent

Methylated dimethylolurea ... 6%

Highly condensed urea resin ... 1%

Dimethylpolysiloxane 1%

Zn (NO ₂ ) ₂ 0.2%

The treated active ingredients and websloffs obtained are bagged in the usual manner and carefully placed on top washed with water. The results obtained can be found in the following table:

Table 6

No. sample loading con / .cn- frictional stress

number- hand- tration would take (V) mer-

from Ta-mittel orig- in

bark 5! icher ~ Wa-

Fabric schung

(g liter) ("")

♦ 5 1 (lO 14th 1 -—- - 38 4300 5200 1 15th 2 41 4200 5600 3 16 3 - - 42 5600 8100 4th 17th 4th 94 5300 5400 50 5 ^bS 18 5 X 50 62 5200 6300 6th 19th 6th X 50 85 3600 5400 7th 20th 7th X 50 80 4200 4600 8th 8th X 26th 41 39 (X) 4300 55 ⁹ 9 X 35 90 6100 6300 10 I. X 25th 40 600 4200 11th 2 X 25th 45 360 4500 12th 3 X 50 390 5100 4th X 25th 120 1100 5 Y 50 260 1600 6th Y 50 240 1900 7th 380 2800 X 520 3900 9 420 1800 1 560 4500 3 410 4300

continuation

Sample ·· User manual luriL's-ÜUS Ta- millL'l
bright 5

Con / dennion

recording

Rcihunüsspannupt:

4th
6th
S.
9

4th
6th
S.
<■)
i

4th
6th
S.
<■)

4th
(P

4th
H

Y
Y
Y
Y
Z
Z
Z
Z
Z
Z
X
X
X
X
X
X

Y
Y

li! Lilerl Γ

25th
25th
50

25th
50
50

25th
60

IOD

KKI

100

50
50

96 88

44 94

37 42 91 83 43 SS 42 45 9N

9f> KK) 93

^l > 5 90

dear Sloff

230 320 450 560 340 260 120 230 190 370 280 150 80 120 31 (1 230

120 90

110 160

ne- to wha- ^ in ·

4800 4200 4100 5200 5800 5900 6300 5500 3900 6800 3700 3200 900 1400 S 700 I 100 4200 3X00

5900 5260 on their frictional tension at 20 C and 40% relative Measured humidity. The results of the following table are obtained:

Table 7

Sample recording frictional stress; (V)

number of

Table 5 Origin after

licher fabric washing ("oil

From the results in Table 6 it can be seen that that when using treatment agent X (see numbers 14. 13. 15 and IS) samples with low Densities below n. \ Suir 'excellent antistatic Properties have been granted. On the other hand, an ordinary antistatic agent, how Y and Z do not achieve good durability, see if the prchcn have low densities ι>. iinimern 1 " Sin 301.

On the other hand it corresponds to the expectation that with Increasing the concentration rute results are obtained even when the samples are high densities to have. llierzti pasture Ni 31 to 40 carried out. But even if you use the treatment agent X are used, no results are obtained from the samples with high densities. As for Y and /, so there are also no leaks in helium: the concentration to recognize

From the result in No. IS / u it can be seen that a similar result is obtained if the sample • ■ is in active substance Vis den I M.iebniwn of Ni) 6. ] "\! - 3.S ii-h! Vi ι ·. ' zn. d-iH similar Eüekl · · I ¹ I '■■ :)' ■■ u-uien λ-: u. the PmIvi! ..: ■ *! '> i \ .; mid '■ ■ -te

M e ι ■. ρ ι e: "

line aqueous I iisun: .. 'from Micw.- ",, l'nKiii h> len j | - I -Idinielhai \ > lal. ran Po I \ iillu Iciu-h kol.mieil. • in' l · ilekulai uew κ hl \ '<n | ooc. h; ii and <). V ¹ ,,. \ ηιηιο- ■ mimpciMilfai is aiii the sample "dci [' abelle ^. Example 6. clipped. the samples weuk-n ^ minutes int steam heated to ins (. D.iraul wi, len the 3
4th
6th
S.
9

40
41
92
S3
40
90

450 320 1 (V)

200 610 360

3100

29 (X)

^ 20

630

3250

It can be seen from Table 7 that Sample Nos. 3. 4 and 6 show excellent antistatic properties at low densities. Compared to the Values of table '■> it can be seen that Damp! treatment to obtain better static properties will.

Example p

A polyester yarn made from polyethyleneterephthala! of 75 denier and 24 threads is wrongly twisted in order to to produce a substance of amunce tinting, which is desized and buckled according to the usual methods, on it! Washed with water and dried is then the Stell in treatment agent !! the in Approaches indicated in Table 8 inserted and evenly squeezed out by a padding machine The uptake ratio is Sl%. Then the substances are wv in a warm, humid steam atmosphere at 100 C and treated warm for 5 minutes with Marseille soap (0.05% by weight) I Mmut. treated at 50 C ', washed sufficiently with water and dried.

The obtained samples are washed for a predetermined time under the above washing conditions, and the rubbing environment is adjusted to predetermined temperatures and humidity. The generated levels of static electricity are then measured by the above-mentioned method. The directives specified in the table * ■) are obtained

!! ■ iii ■

A-l'l < -Γ |
Α-Γ'Ι (-Γ |

\ Γι (ii

\ ι hall IV ■ - .. η bright.

20 Ί

20 H ί>

"continuation ratio of ⁵ VC-I ³ )
) CI ³ ) = 100/10
= 100/27
= 100/33 relationship Remarks rn M * 0
0
0
5 65% RH . ·, Ufipkcil 30th 20 C. 40% RH 30th 5 DI ⁴ ) = = 50/0 of treatment
remedies. 10 1000
230
240
370 3600
1350
1400
1950 5 Dl ⁴ i = - 50 / 1.7 calculated as to 600 0 10 2580 η DI ⁴ ) = = 50 / 2.2 Solid
• ng / g 0 550
210
210
330 630
320
370
400 2600
1100
1050
1800 ? DI ⁴ ) = = 50 / 4.5 20/3
20/8
20 / 9.9 0 540 600 590 2500 1200 mixed up
Machining tools ¹ ) S. DI ⁴ ) = = 50 5.5 10/0 Frictional stress (V) 0 140 420 in si 10 / 1.5 ίο 7
8th
9
H) C. 0 280 110 300 800 300 4th
5
6th I C-I = 100/0 10/2 ·> 11 20 C. 0 i00 KX) 190 400 220 7th AI ²
AI ² ) C-I = 100/2 10/4 W * 0 80 170 200 270 360 A-I ) C-I = 100/5 10/5 12th 0 75 330 150 190 760 9 A-I I C-I = 100/10 13th 10 130 230 370 IO A-I ) C-1 = 100/27 20/0 14th
2} 0 280 780 250 750 2 (XXl η A-I I C-I = 100/33 20 / 0.6 15th 0 190 670 A-I DI =
DI = 50/0
50 / 1.7 20 / 1.5 as 16 S.
5
2300 430 200 530 1500 640 12th D-I = 50 / 2.2 20/3 catalyst 17th 170 290
450
2500 260 5 (Xl 830
15S0
6900 13th B- D-I = 504.5 20/8 will be a 180 280 500 14th B- D-I = 50 / 5.5 20 / 9.9 Solution of
N η I it (> r 25 ^ltf 240
400
2550 330
470
7 (KK) 720
14 (X)
71 (X) 15th B- 10/0
10 / 1.5 -> g Ll le I
ammonium
persulfate
added. 19th B- 10/2 20th 17th B- 10/4 21
11th
U nbe- Measured who Λη / ahl I IS
19th B- 10/5 acts Measurement conditions 20th B-
B- W.ischh 21 B- M * = -> ■> B- -.s <- * B- \ V =

¹ I cie weight ratio of a processing agent in I Liier eirer

set processing agent solution.
^: 10% by weight aqueous solution of a mixed polymer.

obtained by (! »polymerizing a mixture of 70: 30Cic» .- «» methoxy polyalhylene glycol methacrylate and acrylonitrile

has been.
Ί 30 "ige aqueous solution of poly- / i-mcthacrylcmmelh \ IJi-

ethyl methyl ammonium methyl oxysulfate.
^J | >) 0 ° nige aqueous liquid dispersion of Ocladecylälh \ li: n-

urea.
■ | ÜO% igc aqueous solution of Polyäthylcnglykoldimeihacrslat.

whose l'olyoxya'thylenscgmcnt a molecular weight mn lOOC has

Tabel

Kcihnniissspannung (Vl

ir. rl

Be at A-I alone or B-I alone (m 1 urul m 12) also excellent antistatic L properties

: j is enough. According to the invention, however, they become much better antistatic properties with a smaller temperature gradient achieved. The antistatic properties do not decrease after 30 washings / u strongly from. compared to m I and m 12. from what

■ t> it is found that the samples also have an excellent Shelf life is granted.

Incidentally, each sample is made using one Oil-soluble dye, Sudan black B (.Ihr. 26 150) colored, and the influence of the antistatic agent

λο the polyoxyethylene series is determined. It results that untreated samples do not color at all but each of the treated samples is well stained. From the fact that samples stain after washing 30 times, it turns out that

The film formed according to the invention is excellent Has durability.

Me ι s ρ ι e I

410 8 (K) 4 (X) 2000 3450 S. 2 (K) 230 280 IKKl 1 250 0 150 190 240 S (K) KKK) 0 190 2 (X) 160 550 7X0 0 160 190 220 KKK) IKM) ■ * ko 450 3 (K) 15 (K) 1691 ■

In the IVKesierstoff of Amimzentönung. like him in Example N has been used. will be in the light 10 . '. given treatment agent and immersed in it treated according to the method of Example S. Then the levels of static electricity that graze aiii these treated fabrics produced is measured. 3 (K) 15 (K) 1691 The results of the following table are obtained:

Table 10

ratio of
mixed up
Treatment agents')

23 A-2 ² ! CI = 100/0

24 A-3 ³ ) CI = 100/0

25 A-4 ⁴ ) CI = 100/0

26 A-5 ⁵ ) CI = 100/0

27 B-2 ⁶ ) C-1 = 50/5

28 B-3 ⁷ ) CI = 50/5

29 B-4 ^S ) CI = 50/5

Relationship remarks

of treatment

lungsrntteln.

calculated as

Solid

lü g)

20/3

20/3
20/3
20/3

10 / 1.5
101.5
ΙΟΊ, 5

as

catalyst

will

5 g liter

Ammonium-

persulfate

solution

added

¹ I weight ratio of treatment agent in! Liier an adjusted treatment agent solution.

^: 1 20% by weight aqueous solution of a mixed polymer, obtained by copolymerizing a mixture of 70/30% by weight of a mixed monomer with a gelation point of 25. Obtained by mixing methyl oxyethylene glycol methacrylate with a molecular weight of 15 (K) mil polyhylene glycol dimethacrylate of a Molefcub 1 KM) with acrylonitrile.

) 20 "οige aqueous solution of a copolymer, erhallen Copolymcrisiercn by a mixture of 60 to 40 (ie," .- "" .HIS one shown in Figure ²⁾ Mischmonomcr mil Acnlniinl obtained

^J l 2o 'strength aqueous solution of a copolymer, erhallen C'opoljnierisicrcn by a mixture of 7 (30: 1 by weight ",, a Monomergemischcs. Erhallen RNII as above in ¹ I Ailnlenglvkoldiacrylat.

Ί 2o 'oii: e I aqueous ösune a mixed polymer obtained by Vorpolymerisicren a mixture of 70: 30 by weight ⁿ "from Methoxypolya'thylcnglykolmclhacrylat a molecular weight of 6500 with acrylonitrile.

"ι 20% aqueous solution of Polyäthylcnglykoldimcthacrylat. whose l'ohoxyäthylensegmcnt a molecular weight of IfKK).

"j" OVniee aqueous solution of polyethylene glycol dimethacrylate. whose polyoxyethyl segment has a molecular weight! around

5000 has.

") 20% ice aqueous solution of Polyälhyleneglykollnmethac.-ylat. whose Polyoityäthylenscgmenl a molecular weight of 1000 has.

Table 11

M *

Frictional stress (Vl

C *

20 C. 65 ",. Rl-

\ V ·

0 OK

0
0
0

190
190

170
200

160
140
170

220
210
190
210

200
190
210

20 C. 40 ",, rl
0 10

150
140
150
150

230
210
200

520
490

3X0

4M)

750
690
680

M *
C "W *

Measured value.
Measured conditions.
Washing frequency wedge lAn

Vcrclcichsbcispicl 1

The same polyester fabric as used in example S is placed in 1 liter of an aqueous solution adjusted in such a way that the solids ratio of the treatment agent A-2 C-I = 8.20 (g / g) where 1 liter of an aqueous solution with 20 g of only C-I as a solid, the same treatment as in Example S is subjected. The frictional stresses are then measured and the results of the following Get table:

Table 12

M *
Keihungsspannune ιVi

A-2 CI = 8 20
A-2 CI = 0 20

20 C. 65 ",, RH in 30th 20 C. 40 ",, RlI 10 in W * 1000 2050 6300 7000 0 IHK) 19X0 Il 6450 7000 10 X 30 15th 790

M * measured value.

<* Measured conditions.

W * WMsehnngshiiufigkcil (Λη / ahlt

S * I * Mi, | herh; iltnis der Hehar.dl

By processing in a star, in which (-I If there is an excess amount, because no soldi Excellent antistatic properties and durability, as can be seen from Examples S and 9. Br'nalten. Also, when the temperature is high, the int! static properties are very different from Those when the temperature is low! and Ί · ι Temperattiriiradient is high.

Example K)

The same polyester fabric as in example X is used with Reagents / mixtures according to the approaches in Table 13 under the same treatment conditions as in Example X subjected: the series stresses are then measured and the results are shown in Table 14 obtain.

Table 1 3

Mixing ratio of the treatment agents

in pg

Solids ratio of the treatment agents in g, g

A-2C-2 ¹ ) =
A-2 C-3 ² ) =
A-2 C-4 ') =

A-2 D- :: ⁴ ) =

A-2 D-3 ⁵ ) =

10010 20/3

100 10 20'3

10010 20/3

100 3.x 20/3

100 3.3 20/3 Ί 3d "ι, iuc wüUrigc emulsion, mainly consisting of

CH,

CH,

CH ₁

Cl

^:) 30 ″ aqueous emulsion, consisting mainly of I cn.

CH, N HC11 _; CH, O I., H
(H ₁

Cl

¹ I 30 "igc aqueous solution, consisting mainly of butyl

trimethylammonium salt.
^Δ ) Something like a paste-like emulsion of alkylethyl urine

of the general HormeME). where π = 4. ') 90gcw .- "strength paste-like emulsion of the general AlkyläthylenharnstofT Eormcl (E). Wherein μ = 9".

Table 14 M *
Frame voltage ι V i RH St. Tl C *
20 C. 4 (1 ",, 690 0 720 160 650 30th 140 660 M. 140 740 32 140 33 170 34

In this example, too, satisfactory antistatic properties and durability are achieved. When a film formed as in Example 8 is colored for confirmation, the samples are found stained as good after washing 3 times.

Example 11

A treatment liquid consisting of 1 liter of aqueous solution with a solids ratio of

Treatment agent Λ-2 C-I from 20/8 is being prepared and therein the same polyester fabric as in Example 8 is inserted and uniformly squeezed out with a padding machine. The uptake ratio at this point is 85%. Then the fabric is under various sorts Heat treated conditions and the frictional stresses of the obtained samples are measured in the same Way as in example! 8 measured. The results can be found in the following table.

Table 15

m heat treatment conditions M *

Frictional stress (V)

C *

20 C. 40 ",, rl-

W *

0 10

450 1800 2510 490 2200 2900

35 moist warm 240 1000

(95 C 15 min)

36 moist and warm 220 980

(100 C 10 min)

37 moist and warm 250 950

(120 C 5 min)

38 moist warm 240 HHK)

(135 C 2 min)

39 dry and warm

(100 C 5 min)

40 dry warm

(150 C 1 min)

When the heating temperatures are low, the film formation reaction proceeds slowly, and accordingly the heating period becomes longer. If you have a shelf life peeling of the film due to if its coloring is carried out as in Example 8, those are subjected to the moist heat treatment Samples better than those obtained by dry heat treatment. If, moreover, the educated Films are viewed under a microscope, the samples are after the wet heat treatment more even and smoother than the samples after the dry heat treatment.

Example 12

A polyester tricot knitted fabric made from yarn of 75 denier and 24 threads, a polyamide tricot knitted fabric made from thread yarn of 40 denier and 10 threads, a polyacrylic fiber double knitted fabric made from a single thread with a number of yarns of 48, and a polypropylene crepon knitted fabric made from a single thread with 50 denier and 24 threads (all after padding and drying ) are as in Example 9 with the same treatment agent as m 2 '. of Table 10. The measured results

of the samples can be found in the following table.

Table 16 material M *
Frictional stress
C *
20 C. 40% RH
W *
0 (V)
• 10 30th untreated m polyester
polyamide
Polyacrylic
Polypropylene 1000
750
350
1200 25,000
4100
4000
3,500 2900
4800
4700
4200 above 10,000
above 10,000
above 10000
above 10,000
709 523 / ' 41
42
43
44

hs is fesl / ustelleii. that according to the belief everyone the various lasers are given excellent antistatic ligament switching and the detection a particularly noticeable effect with Polvesler fibers developed.

Be ι s ρ ι e I 13

75 denier and 24 thread polyester yarn, made of polyethylene terephthalate has been twisted incorrectly to make a tropicaltone warp / u manufacture. This fabric is buckled and washed well with water using known methods dried. The treatment liquids listed in the table below are separated from each other.

Table 1 7

Treatment mixing ratio of the
liquid'i treatment tools (g.gl * l

Hcliandluiigs · Mixing ratio of the
llüs, igki-it * l Hchandlungsniiltcl Ig g | * |

Ci Mclliowpolviithvlenglykol-

melhacrylal **) Trimelhylolailian-tiimethnmlal

7 the same.

S the same.

1 ! S Methoxy polyethylene glycol = 2 (1 0 treatment methacrylate **) trimethylol ethane trimethacrylate the same = 20 0.2 3 the same = 20 0.6 ' 4th the same = 20 1 5 the same = 20 Tabel L * in 1 ·. ·

- 20 p

= 20 10

= 20 11

* l Mixing ratio in 1 liter aqueous solution.
** l Molecular weight of the l '(il> oxyalhylene content was IIXK).

What the trimethylolethane trimelhiicrylate in table 17 is concerned, it will be after collecting a predetermined Amount dissolved in a small amount of toluene and mixed with a solution of a nonionic added surfactant as a dispersant to prepare an emulsion. On it will washed in water and used. Each of the prepared liquids is combined with ammonium persulfate Concentration of 2 g, 1 as a polymerization catalyst offset.

The tropical fabric is immersed in the treatment liquids prepared in this way and then passed through a pad device squeezed evenly. The uptake ratio at this point is 64%. Danr the fabric is treated warm in a steam atmosphere for 5 minutes at 110 ° C. Furthermore wire the fabric treated with soap (Marseille soap, 0.05 wt .-%, 50 C 1 minute) and carefully washed with water see and dried. The results can be found in the following table:

Friction tension IVI

llar / anhafuhaltnis

1 7 (X) 5H00 61 (X) 1.2 0 I) 650 33 (K) 5700 1.2 0.04 0 3 420 2100 2900 1.2 1.0 1.0 4th 300 670 1500 1.4 1.4 1.3 5 340 450 1100 1.9 1.9 1.7 6th 1100 1500 2100 2.2 2.1 2.1 7th 2100 2300 2500 2.4 2.4 2.0 8th 2400 2650 3800 2.4 2.4 2.1 Untreated 6500 6200 6300

I ♦ = Means the protected value W * = means washing frequency ΙΛη / uhll. L * - means liquid

From the above results, it can be seen that when the amount of trimethylol ethane trimethyl acrylate is less than 3 wt .-%, based on the weight of the methoxypolyethylene glycol methacrylate, a Effect similar to that of a crosslinking agent and the amount of resin adhered is not changed by washing. At the same time the frictional tension increases, while the durability is good. On the other hand, when the amount becomes less than 50% by weight, becomes the ratio of adhering resin is large and the degree of decrease of this ratio in washing small. However, the frictional tension becomes bad.

Example 14

Apart from a polyester fabric from Tropicalton, as used in Example 13, there is a doubt polyacrylic fiber from a single yarn, a number 48 yarn and a polypropylene crepon fabric made of a thread yarn of 50 denier and 24 threads (each after buckling and drying) used.

1 etramethylolmethantetramethacrylai is taken so that 2 g, 1 to 29 g / 1 of a compound I orrnel

O

II ((KH ₂ CH ₂ ) ,,, OC (H ClI; OC (H _: CH UXH ₂ UI ₂ ) ,,, (H.

CH ₂ C

ClI, OCC (H ₂ O Hl,

be, and an emulsion is made according to the method of Example 13 prepared. A similar aqueous one Dispersing liquid with 2 g / l ammonium persulphate is prepared in which the aforementioned substances are immersed and padded, whereupon they treated with steam. Then the fabrics are measured for frictional tension. The results can be found in Tables 19 and 20.

Tabel

l'rohe

1 * = Gcschal / κτ value.
W '* = washing frequency (number).

Table 20

Frictional stress (V)

W *

0 1 10

Treated goods
Untreated goods

680
9400

720
9000

1700
9000

Example 15

(a) Methoxypolyäthylcnglykolmethacrylat. its polyoxyethylene content has a molecular weight of 400 Has. and 2 g of trimethylolethane trimethacrylate are dissolved and followed by the procedure of Example 13 mixed. The mixture is mixed with water in such an amount that 1 liter of a treatment liquid v-r-it is prepared.

| b | 1 ine completely identical treatment liquid wedge as a). however, the molecular weight of the polyoxyethylene content 2000 is prepared. In each of the above two treatment liquids

: o the same substance is immersed as in Example 13, evenly squeezed out with a padding device, treated in a similar manner warm and on rubbing tensions (V) and adhering resin ratio were measured. The results can be found in the following

: s table.

Ta be

Rcibunizsspannuni: 520 I. 550 ι Vi 30th K-h.imlch IO ,, a 40 W * nor b 0 460 600 Ablution! 6 51) 0 16 (H) 1050 1300 10 (M) O < ΐ p PoUester- 21 (H) tropical fabric Polvacrvl- 10 (HX) < Double 2900 w irk w are Polypropylene creponware

e 21
I- ibuivjsspannun.i: (Vt Ratio d e * Rc adherent ll.ir/ * W.

13 (H) 1520 28 (X) 1.9 i.7 1.7

2S0 470 13 (Hi 1.4 1.4 1.2

As can be seen from this table, the molecular weight of the polyoxyalkylene portion has / was none great influence, but that with a treatment fl uid: - speed. the polyoxyalkylene portion of which has a relatively high molecular weight shows a preferable one Result.

However, as can be seen from other examples, let us see from the point of view of synthesis technology and of the effect say that the cheapest treatment liquid wedge has a polyoxyalkylene moiety having a molecular weight has from about 1000 to 5000.

Example 16

A taffeta fabric, consisting of polyethylene terephtha latgarn of 50 denier and 24 threads, obtained durcl Mixed spinning of 1.5% sodium dodecylbenzene sulfonate as an ion component and 1.5% polyethylene

ho glycol with a molecular weight of 20,000 al electrical conductivity component with polyethylene terephthalate is added in an aqueous solution which contains ig liters of sodium carbonate and 2 g / liter of a nonionic surfactant

The fabric is dyed in 2% CJ Fluorescent Brightener 22 for 120 minutes at 120 ^° C. and dried. Using this example, the following antistatic treatments are carried out.

BclumillimiismiHcl

Polyilhylene glycol (Mol .- <each \\ leht 6001-dimethacrylate

Polyethylene glycol (Moi .- (ieuicht W) Olmklhacrylat

Polyethylene glycol (1000 mole weight) trimethacrylate

none

A polyester fiber that has not been mixed with antistatic agents. is processed into a similar Taflstoff, as mentioned above . The fabric is buckled and dyed with a fluorescent dye. The dyed fabric is treated as indicated for m 1 to rn4 and designated with rn 5. 6. 7 and 8.

After the treatment , the samples are

1 part 22

KIMI / CU-11.1IhMl

l.i.I iU-l,

treated with a 2 g I current
Ammonium persulfate solution for 5 minutes
105 C

the same

the same

the same

same way before dyeing to remove a polymer which is a homopolymer and is in a state that it easily falls off. After drying , the samples are checked for their weight gain. Frictional tension and water-absorbing properties were measured. The results can be found in the following table.

l'mh.

ι pcukIus- Kuhiinjisspannun !: IVl W.issci.iIimm
relationship- I. lycnsc hall

/ unahnic

I. \\; * ♦ modified polyester Diesicr n.7 240 490 O.S. 3s.li Λ the same Vlonoese n.l ! 050 2600 o.s 600 the same funnel o.s 210 520 0.6 35.0 4th the same untreated 0.0 2W) O 3100 250 600 5 and he modified the pole Diester 0.7 650 1500 0.9 510 (1 the same Monoester 0.1 15W) 5300 2.1 600 < 7th the same Trieste 0.7 590 1400 O.S. 630 8th the same untreated 0.0 56 (X) 68 (X) 240 600 Not washed. - washed twice

From the results for the samples m 1 and m3 it is possible to determine after the buckling of the fabric in a relaxed manner that when using diester or state dried and then treated with treatment tester on a modified polyester the anti-liquids, their compositions

in the following table under numbers 1.

2. Find 3.4 and 5. Behold the adherent menaen

y t

Static properties are particularly improved. The wash resistance is excellent.

Example 17

A salt consisting of equimolar amounts i mixture) of polyethylene oxide with an average molecular weight of about 4300, the ends of which are converted to D5% in amino groups, and adipic acid and f-caprolactam are used to obtain a block polyether amide, the polyethylene segment of which is a Has a weight ratio of 40%. This block polyether amide, 0.2% titanium dioxide and polyamide, are mixed-spun into a yarn of 30 denier and 6 threads made of modified polyamide, the proportion of which is 1.5% by weight of polyethylene oxide segment. This yarn becomes a 28 gauge, 2 strip. 88 inch active ingredient knitted with 74 meshes / inch. at this point in time about 80%.

Table 23 Sales of the treatment agent

No. 1, a treatment liquid obtained by dissolving 3% by weight of polyethylene glycol dimethacrylate having a molecular weight of the polyoxyethylene segment of 500 in water with the addition of 0.3% by weight of ammonium persulfate as a polymerization initiator the water smell "

32

continuation

Sales of the treatment agent

No. 2, a treatment liquid obtained by dissolving 3% by weight of polyethylene glycol dimethacrylate with a molecular weight of the polyoxyethylene segment of TOOO in water and the addition of 0.3% by weight ammonium persulfate as a polymerization initiator for the aqueous solution

No. 3 treatment liquid obtained by dissolving 3% by weight of polyethylene glycol dimethacrylate with a molecular weight of the polyoxyethylene segment of 2000 in water and the addition of 0.3% by weight ammonium persulfate as polymer initiators to the aqueous solution

No. 4 processing liquid, obtained by dissolving 3% by weight of polyethylene glycol trimacrylate with a molecular weight of the polyoxyethylene segment of 1000 in water and adding 0.3% by weight of ammonium persulfate as a polymerization initiator to the aqueous solution

No. 5 processing fluid. obtained by dissolving 3% by weight of polyethylene glycol monomethacrylate with a molecular weight of the polyoxyethylene segment of 1000 in water and adding 0.3% by weight of ammonium persulfate as a polymerization initiator to the aqueous solution

p * = regulation or approach.

N * = number of the processing liquid.

Hand- ratio of the water friction tension

l- weight gain sorption- (V)

number dtuer

(Seconds)

five times washing 2 times

washed time

see punkl0

5 0.2 600 700 1900 6th untreated 600 2200 1800 blank

From Table 24 it can be seen that in the case of Nos. 1 to 4, the ratio of weight gain large and durability of water absorption property and the antistatic property are excellent, "in case No. 5 when processed with with the monovinyl monomer, there was almost no weight gain and no effect was observed.

Example 18

A polyester filament yarn of 250 denier and filaments made of polyethylene terephthalate is wrongly twisted and then woven into a fabric which has been buckled in a relaxed state. to obtain a sample having a unit weight of 300 gm ² . Using this sample, the treatments shown in the following table are carried out to obtain the results shown in Table 26.

Table 25

Tabel 24 Water drainage
sorption
permanently
(Seconds) Frictional stress
(V) i 2 times
Gewa
ting Bchand-
lung
nummcr Ratio of
Weight gain five times
washed Waschuni
Time
point 0 650 ( ⁰ O) 3.8 320 520 1 1.5 4.0 210 680 2 1.6 5.0 360 580 3 1.4 6.1 380 4th 1.3

No.

Immediately after each of the foregoing processing fluids Table 23 is prepared as a pad bath. the fabric is immersed in it and evenly squeezed out by a padding device. Then the substances obtained are at 3 minutes C treated in the presence of heated steam. Thereupon the unreacted substance by means of soap (Marseilles soap, 0.05% by weight, 5 minutes at 50 ° C.), and the substances are washed with water well washed and dried. The measured weight gain, the water absorption time and the The frictional stress of the sample obtained can be found in the following table.

Treatment agents

Methoxy polyethylene glycol
(600 molecular weight) methacrylate

the same

concentration

(n liters)

Polyethylene glycol (molecular weight
600) dimethacrylate
the same

Polymerization initiator

2 g 1 ammonium sulfate

0.5 g of benzoyl persulfate was dissolved in acetone, then the resulting solution was dispersed in a treatment bath

2g 1 ammonium persulfate

0.5 g of 1 benzoyl persulfal was dissolved in acetone and then dispersing the resulting solution in a treatment bath

709 523/473

continuation

Treatment agents

't

concentration

(gLiterl

Polymerization initiator

m the

Table 25

Ratio of
Weight gain

Frictional stress uni: (Vi

before the
To wash

after

lO times

To wash

Polyethylene glycol (molecular weight

methylacryloxy

methyl) acetate

acrvlat

Polyethylene glycol (molecular weight
1000) diacrylate

0.5 g of 1 benzoyl persulfal was dissolved in acetone and the obtained Solution then dispersed in a treatment had

0.5 g of 1 acetyl peroxide was dissolved in a treatment bath

Table 26 Ratio of
Weight
increase
I "..I Frictional tension! (Vi
uir after that
Wash once again
To wash 5800 m ikr
"labellc 25 0.0 6HK) 6200 1 0.2 36 (X)

IO

5 6

Treatment conditions:

The sample is treated by immersion at 100 ° C. for 30 minutes at a bath ratio of 1:50 and then for 30 minutes Soap at 80 C with an aqueous solution. the 2 g I of a nonionic surfactant and 1 gl sodium carbonate, contains.

0.1
12.1
11.6
10.2

3100
450
180
170

6500
640
480

5200

From the results in Table 26 it can be seen that in the case of methacrylate with a vinyl group, weight gain and improvement in antistatic Property can not be achieved indifferently whether a hydrophilic or hydrophobic polymerization initiator is used (ml and m2). at Methacrylate with 2 to 3 vinyl groups (m3 to in6) however, a remarkable increase in weight occurs when a hydrophobic polymerization initiator is used becomes, and the antistatic property becomes excellent (m4, 5 and 6). If a hydrophilic polymerization initiator. namely ammonium peroxide, used as with m3. that's how she is The weight gain is small even if the number of vinyl groups is two.

Example 19

The sample from Example 18 is treated for 30 minutes at 98 ° C. in an aqueous dispersion which 5g I polyethylene glycol diacrylate with quaternary nitrogen represented by the following formula and contains 0.5 g of 1 benzoyl peroxide. It is then dried and the ratio of weight gain measured. However, no weight gain is observed. The formula is:

CH, CH CH ₂ COONa

COO (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ N- C ₁₂ H ₂₅ HC CH ₂

CH ₂ CH ₂ (OCH, CH ₂ ) _{1 (} , OOC

Cl

Example 20

A polyester tow, the thread of which is one denier of 2 and whose total denier is 4 (M) OOO. is immersed in a liquid that is dispersed \ nn lOg I Polyälhyleneglykoldimethacrylal mit a molecular weight of the Polyäthylenghkolanicils \ >> n SOD and I μ I ben / oyl peroxide in water a bath ratio of I: 30 has been obtained. The Bella '.llung lasts 60 minutes at 90 C. After After this treatment the tow is washed well with water and dried. Then the ratio becomes 111 the weight / increase was measured and an increase of I 1.1 ".1 was observed

Example 21

In a 500 ml Beclier illOnil will be one; mixture vcn 20 t! I wäßriuei I ösimsi from l'olväthv lenglykoldimethacrylat with a molecular weight of the polyethylene glycol segment of 1000 and 0.5 g of I aqueous Entered ammonium persulfate solution. Two parts of the so composed solution become prepared. One portion is left to stand at 20 C room temperature. In the other will continuously introduced through a glass tube IuIt at a rate of 120 ml min, and the aqueous solution is left to stand so that it gels within 4.4 hours. The mixed aqueous solution However. 111 the waters were introduced is. polymerizes flour and is resistant after 50 hours if the introduction of air is then interrupted, the mixed aqueous solution gels within 2 hours. The results of the tests with regard to durability of the vinyl monomer in the aqueous solution when the concentration of Polyäthylcnglykoldimethaci changes ν IaIs and ammonium feeds linde 1 See Table 27. At this moment, none occurs

'f

Discoloration of the treatment liquid. Furthermore, a liquid No. 4 of Table 27 is used for 50 hours. left standing and padded on polyester taffeta, wor-

Table 27

on the affected taffeta for 5 minutes with steam at 105 ° C is treated to have a weight gain ratio of 1.3%.

• Jr. Monomer
focus
tralion Iniliator
focus
tralion conditions Vulture / hurry
(Polymeri
sation (g Liier) (g / liter) Ihi 1 20th 5 ditched 4.4 -> 20th 5 treated with air *) 50 3 40 5 ditched 4.6 4th 40 5 treated with air *) 50 5 20th 10 ditched 4.5 6th 20th 10 treated with air *) 50 7th 40 10 ditched . 2.4 S. 40 10 nimble! ' with air *) 50 9 40 20th ditched i.3 10 40 20th treated with air * l 50

miscellaneous

gelled within 2 hours after the air treatment was switched off

gelled within 2 hours after the air treatment was switched off

gelled within 2 hours after switching off the air treatment

gelled within 2 hours after the air treatment was switched off

gelled within 2 hours after the air treatment was switched off

Liquid permeability 25 C ".

* l - / ugeliihrlc t uft amount 120 ml min ll'liisMgkeil JtKImIl.

Example 22

l: in Klotzgerät is set up in such a way that a share of 10 cm of a 100 cm long and 15 cm wide matt polyester worsted yarn fabric in the longitudinal direction in a mixture of an aqueous solution of 20 g of 1 polyethylene glycol dimethyl acrylate with molecular weight of the Polyäthylenglykolantcils from KK) O and 5 g I ammonium sulfate is inserted. If the Substance is rotated by a motor to put it in the aqueous 1 solution mixture at room temperature of 20 ° C., this aqueous solution is still there even after a period of 50 hours resistant without gelation. On the other hand, if the same mixed aqueous solution is left to stand, it gels within 4.5 hours. If the above yer-

4 ° is repeated, but the circling material is replaced by a thin polyester body with a healing weight of 70 °, it can be determined that no gelation occurs. When this mixed aqueous solution placed in a 1-liter beaker, and oxygen is introduced in an amount \ on 4.2 ml / min, the solution gels niclv. Furthermore, when a similar experiment is carried out by reducing the air flow rate to 2.1 ml min, it is observed that no gelation occurs. If a similar experiment is then carried out, in which the LultdurehfUitur is reduced to 1.05 ml min, with

so oxygen is introduced into 1 liter of the mixed aqueous solution shows up after a period of 30 hours for the viscosity to rise and polymerization to begin.

Claims (1)

'f patent application: 1. Process for the antistatic, dirt-repellent and water-absorbing finishing of Synthetic fibers by application (A) a product free of quaternary nitrogen compounds, consisting mainly of a Polyalkylene oxide unit and at least two acrylic groups and / or methacrylic groups at both ends, one end or as ι ο side chain of the main chain, or (B) a mixed polymer of a) a compound of the general formula