DE1444081A1 - Process for reducing the electrostatic charge on textiles - Google Patents

Description

DR - ING H F »NCKE DIPL.-ING S. STAEGER M 19 394 - ΒγλΚιι / ρ © ^EP '' ^W ICI Case No. T) / ?, 16342 description

for patent application

the rirna IMPERIAL OHSMICAL UfDUSIRIES LID., London SV I

concerning

"Electrostatic Reduction Process

of textiles o "

Priorities: 21 »September 1962 (provieional specification) 30ο August 1963 (complete specification)

British patent application Kr. 35988/62

The goal-lying explanation relates to a procedure and on finishing materials for modifying textiles, in particular for reducing the heat build-up of textiles, to charge them electrostatically.

Bs 1st well known that textiles and fabrics, particularly βοlohe that spun from synthetic "Ma ₇ are made terialien, have a marked tendency zobo fled during processing" such * B. during the

90981 2 / 09A2 I BAD ORIGINAL

H44081

Carding, spinning or weaving, electrostatic charging t>

Be was ready indicated that such a tendency can "ground decreased by Textillen or fabric · NAOB liking old together other Veredelungshilfsaitteln, bit gewlesen agents" such as "ß bit quaternary Amnoniurachloriden _v -broaiden, -Jjodiden, -aetnosulphaten uew treated will. The disadvantage of this and certain other sur modes "fell" tion of Textillen Agenslen used is that they corrosion of the metal surface of the machinery used in their processing and other methods Esch Ritten cause Since this implies a restriction on the Aawendungsbereiahes this Agen Sien "S ₉ have already been attempts undertook a cart \ m> <! «r metal surfaces a, B :. by adding a corrosion inhibitor such as E ₃ B _n Natriuanitrlt, also prevent! The existence of such corrosion inhibitors can, however, cause certain undesirable side effects "such as b" 3 an impairment of the dispersion stability if the quaternary ammonium salts are used in connection with dispersions of other finishing aids; will,.

It was found run _v that the tendency of textiles

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or textiles, the electrostatic charge is reduced and, at the same time, the corrosion during processing The machines used can be prevented if such textiles or textile fabric contain certain quaternary Anaonluanitrlten "carbonates, bicarbonates" -tetraborates, -phosphates, -ohroates, -equates, -siliostes and -hydroxides to be bandaged »

The present invention relates to a process for modifying textiles and fabrics, and in particular To reduce the curling of such textiles and textile materials, see electrostatic charging, proposed, the goods being a corrosion-prone quartttren Aanonlaverblundung the general Forael

R ₂

R ₁ - I * - R ₄ X "

Formula I.

where the anion X "can be Hltrlt, Carbonst, Bloarbonat, Tetraborat, Phosphat, Chroaat, Bensoat, Sllicat, or hydroxyl and R ₁ , R _2, R ₅ and R ₄ represent groups explained below o

9 OS a 1 2 I O 9 4 2

14 UO

In the formula, R ₁ can be an alkyl group or an alkeny group with 8 to 22 carbon atoms, Hg and B "can have lower alkyl groups of no more than 4 carbon atoms" or araIky groups, or hydroxy " substituted alkyl groups with no more than 4 carbon atoms and R * can be an alkyl or alkenyl group with 1 to 22 carbon atoms, an aralky group, or a hydrosubstituted alkyl group with no more than 4 carbon atoms, or R ₂ and R ^ together or R ₂ ,% and R ^ ssusamraen can form part of a heterocyclic ring "which is closed via the nitrogen" atom

As examples of the quaternary Aamonlumgruppen that may be anivesend In erfindungegemä8sen compounds should SoB "called" earth t

Oe% l-trimethylamiaonium "Cetyl-pyridinium" morpholiniucD _t Lauryl-diaethyl-benzylammoniumg dimethyl "(e * -hydro3tyäthyl) -ammoniuia, nium ₉ M-Oetyl-I - = (S-hydroxyätayl)" morphblinium und Ootade *? " cyl" dimethyl-ethylammonium ".

The textiles and fabrics can be used according to the procedure of the present invention a number of different "Ground work corridors" ZoB, a solution can be found

90 98 12/09 42

1U4081

the quaternary ammonium compound can be padded onto the goods, or the goods can be impregnated with such a solution, moreover. Can the solution be applied by spraying? Can other agents also be used in conjunction with the quaternary ammonium compound according to the invention? which are used in textile production and which in turn cause or cannot cause corrosion of the metal surfaces, _etc.

In applying the erfindungsgemässeiö quaternary ammonium compounds on fabrics are amounts of 0 ₅ 05 to 1.0 percent _o "#, based on the fabric" especially preferred?

The treatment can be carried out at normal or elevated temperatures and the goods treated in this way can be sent to « finally dried at any suitable temperature O

The inventive method _s can be applied to any fabric but it is especially in the treatment of hydrophobic fibers valuable zj "from such" habem consisting of Polyäthylentercphthalat9 a Polyamidρ polypropylene or PolyaerylaitriX "Such treated hydrophobic fibers have a reduced tendency verifiable electrostatically charge You can be used in the manufacture of textile fabric

and textile articles

f all types can be used _o Z ₀ B ₀ yarns with

9 0 9812/0942

-Fädest * 'the jam © <sin% m ' such 'treated propylene produced slat »b @ i the Hsretellwag won Blaelinetstoi» ropes «ÖemüeesöhutssiotaeÄp iäs © hasSoken and artificial

»Sisgpelf-a & ejms di @ from Poly» © taf ii @ s @ Art ia®d was treated ₉ . fedaaoa swr production i7®mf @ ppie & ®n ₅ Basques and Plur = ·

The application of "quaternary amnsonium var" 3 of the formula 1 to hydrophobic FM @ n can ia with the "use of other textile iraredsliangas" was found _p _that a very satisfactory ap-

bucket .w8s; srig®s & Emulsion- © in ©! ¹ ! SsaserunlSslie liquid exists that. © ine on dissolved quaternary ammonium · = compound of formula 1 "contains" - as water-insoluble '.'"■■■" - 'peeling liquid is preferably a silicone sonic liquid used and in particular, one of the silicone liquids which are described in the Belgian iPatantsuhrift 618 544 and which have a viscosity of between 3,000 and 200,000 at 2 ° 0 Centistoke beeitsea »As a quaternary niuraverbindiiiigaii der - Pormel 1 wirö: -preferably '-a connection in the X" there is litritaaion and -in particular--

9098 12/0 942 ba _P OBte «NAL

It was found that the compounds according to the invention are used in the modification of textiles can be used as parboil & tofflxation agent tone value a *. If "" B ", immediately acting cotton dyes are used on celluloee, they result in" if the dyeing is treated with the compounds according to the invention, With one of the conditions there is less staining white cotton in contact with it Pall let if no such follow-up treatment is carried out »■

It was also stated that the invention Compounds are effective as a textile net suit "

They can be prepared in the present invention suitable quaternary ammonium compounds on different paths, "" ~ B. ~ _n can from other quaternary Amraoniueaalsen by ion exchange or duroh Badikalaustausch (metathesis) under suitable conditions "Zob quaternary Anmoniuahalogenide duroh treatment with silver nitrite in aqueous solution can be converted into sitrite and quaternary ammonium chloride can be converted into nitrites by treating the sodium nitrite in methanol «The ion exchange can SoB? by using a suitable ion exchange resin, especially an AalOiffi »iMHWiti4Usoh °

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harsee <3in © r start »Base (strong base anion #xchemge resin) carried out«? € Fd®n. Thus, from the production of a quaternary ammonium compound of the formula ₉ which contains an anion X, from an equivalent quaternary ammonium salt with a different anion, it becomes pus. aqueous solution containing an anion X ", and then an aqueous solution of the quaternary ammonium algae, which has a different anion, is passed over the ears, whereby a partial or complete conversion of the quaternary ammonium compound of formula 1 is effected«

In preparing the ^ invention "artäresi ammonium compounds from other quaternary AmmoMumsalsen complete conversion is unnecessary, since it was found that mixtures of quaternary ©», other qisartären Ammoniumealsen in the inventive process are effective Aimoaiunverbindungen the formula \, also with "Although quaternary ammonium halides as those are themselves corrosive, it was nevertheless found that it is only necessary to "convert a portion of the halogen anions into an anion X" in order to neutralize the corrosive inherent properties or to reduce them to such a degree that there is no resistance In the case of the production machines, in the case in which a partial conversion of a normal ammonium halide into the corresponding bitite is effected.

9098 1 2/09 42

it was found that Zttsaoimensetauiigen, which contain "about 155f ▼ on the nitrite" are suitable for the processes according to the invention, because they represent effectively antistatic agents and only insignificantly "corrosion of the machines Yeruraaohen" you discovery that "only a partial conversion into one quaternary Aaaaoniuaverbindnng the Fora el 1 needed ISTJ let of substantial "benefits, well sometimes let difficult" one rolletändlge Uawand development ~ reach su and it takes more time and materials in 4ede "case and therefore aie expensive 1st, as partial conversion, which is sufficient to obtain sufficient results _for the process according to the invention being usable "In the case of the conversion of quaternary analogous halogenates into the corresponding nitrites, a very good corrosion prevention is achieved with a 70% conversion of the nitrites," but if it is desirable for economic reasons Restricting conversion will be very satisfactory de resistance to corrosion »it compositions obtained which contain between 15 and 3% the nitrite,

3s 1st AUOH known _e quaternary Aanoniusisalze 2J, tetraborate _t fieaktlan by the tetrsboratsauren salt of a tertiary Aaina with an alkylene oxide 1J ₁ old Athylenoxyd hersustellon. So it was just surprisingly featured ₀ that

- 10 «-

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The reaction voss salpet ^ isaiirea Sal-sen tertiary anise with klteylenoxyUQn ® * B " ithylenosyd quaternary® Amraonius mitrite can be produced ₀ This was aio & t su« rwarten _s there

S3;.: ^ F} eiiie seh * mQhwp & h® w & ü . unstaMl «Acid is <äi® Bali® with tertiary ^ lülaea © smertungsgenaee - the same-» case -beMietaMl

Auefübrtmgs ^ erssas the present

a process for preparing the general formula

» _Ε w ffl ■ β» SW '»Vft

formula ΪΙ

proposed wherein R _KB ®gs> Β 'and Rg groups nsenstehend explained aind ₅ welohes is .gekennsseiobnet ₉ characterized that a Alkyienoxyd with a solution of nitrites "tertiary Aminealisem uffigesatst is _Q

In the above formula, Be is an alkyl «or AXkeny» radical with β to 22 carbon atoms Rg land B ^ are AUqpl «» - or Hydroxy-alky! Groups with not more than 4 carbon atoms, or aie can also be combined? so that they are with the

3 BAD ORIG> NAL

909812/0942

S ticks toff at obi form a heterocyclic ring, and R ₈ is a hydroxyaryl or hydroxypropyl group «,

The alkylene oxide can be ethylene "or JPropyleno ^ pl"

tertiary solution of the nitrous acid / amine salt is provided se by treating a solution of a salt of a strong mineral acid and an amine of the formula

Formula III

in a non-aqueous solvent that is miscible with water, in which sodium as the mineral acid has a very good

¹ owns

ring solubility / produced with a concentrated aqueous solution of sodium aitrite «

The strong mineral acids ₉ can be used "are z * B" s

Hydrochloric acid "sulfuric acid ₉ hydrobromic acid ₈ hydriodic acid" nitric acid and phosphoric acid "but it is preferred to use hydrochloric acid or sulfuric acid"

The Rait niohtwässrige water-miscible solvents in which the Natriumsais the mineral acid has a very low Ldsezeit t ann Z.6, Isopropancl "ethanol" methanol

- 12 -909812 / 0 942

or aaeton, but as will generally use barorira ^ isopropanol au ,,

Dia manufacture of the Quaternary. Ammonium nitrite salse vegetables the above procedure can be carried out with a series of terfabrenab changes. 23 «can be the solution to the tertiary amine in the non-aqueous with water niaohba « re "Solvent treated with a strong mineral acid" ground and the cooled solution can continue with a «External solution of sodium nitrite treats« ground »the obtained solution of the nitrous acid tertiary amineal can be "freed" from precipitated battrium salt "from the mineral acid 2oB" by filtration at will.

The reaction between the solution of the nitrous acid tertiary amine salt and the alkylene oxide can be carried out at room temperature or at any temperature below the boiling point of the solvent or the decomposition temperature.

below door de · hitsalses ύο », depending on« hurry / the lower fempe-

«Earth _o

The quaternary ammonium nitrite * may require the person dislocates ion β product e "H _e duroh evaporation of üOsungsmittels isolated wardenο

The invention is illustrated by the following examples

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14U081

but in no way * All parts UNAE are printed in Gewloht "

example 1

There were typical compounds of the invention, brought to Stüoke of JSylon- and Polyäthylenterephthalatpolyesterstapelfaserware by padding from an aqueous solution on "You" Kalanderauspreeeung and Lösungakonzentratlon were adjusted so that 0.1 1> of. Agenees was deposited on the Easer "Goods 1 hour at 60" 70 ⁰ C in a stream of warm air dried "They were left thereon for 24 hours at 20 ⁰ C in an atmosphere of 52 j6 relative humidity oondltionieren. The antistatic effect achieved by the treatment was then determined with an apparatus similar to that of Hayek and Chrome? (American Dyestuff Reporter 1951 »£ 0 164)» The antistatic effect produced by these treatments is explained in the following table. Yes, untreated goods and goods treated with cetyltrimethylammonium bromide were also included as old controls.

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Upset

C etyl "tr ine tbyl" aesonium bromide

0 etyl «tria« tbyl ~ araonissainitrite

Iaury! -Dimethyl » hensyl ° -as "oniuiii <~ nitrite

LauryIdittethy1- (ß-hydroraäthyl) aBBDoniuaoi tri%

Sftearyldinethyl- (g-hydroxyethyl> ammonium nitrite

(e ^ hydroxyäthy1) awnonium borate

Table 1 Antistatic Wirkui 1 / 2T 1 / 2Ϊ 2o. aasa 69 0-1 0-1 740 0-Ϊ 1800 0-1 .24. 36 1 . . 19th 6th 30th 42 0-1 180 0-1 62 0-1 92 2 38 78 50 116

Mk is the charge that is generated after heating for 2 minutes. arbitrarily expressed in microamperes

1/2 $ is the time in seconds »it takes for the charge> * Ä to move to fall to half its value »

Example 2 Weiohstablatreifan were partially dissolved in aqueous Lusungai

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ORIGINAL BATHROOM

of the antistatic Agenaea of Example 1. After 3 days, the appearance of the strips was examined, using the values given in the table?.! summarized results were obtained "water and Getyltrimethylaramoniumbroraid were _r taken as control examples on,

Table 2 Antistatic agent Strips look like

3 Tawan>

Water alone koiroaion Cetyltrimethylammoniuabromide severe corrosion Cetyltrinethylammonium nitrite none " Lauryl-diethyl-beneyl-amraoniuni-

nitrite. 'η «

Lauryl ~ di »ethyl ~ (ß-hydroethyl)

-ammoniuamitrite ■ * «

Stearyl-dimethyl- (ß-hydro3cyäthyl)

-ammoniunnitrite ""

31 earyl-dimethyl- (ß-hydroaqrathyl)

• -ainmoniuoborat saving a *

Example 3

_O A solution of 117 parts Dioethyllaurylaain in 157 parts Isopropancl wur3e stirred at room temperature and concentrated 25 parts? Ahwefelsäura during the tent space of a half hour ^ added the solution if allowed to room temperature abkühlenρ and a solution of 35 parts sodium "nitrite in 60 parts of water were added »after a 2 hour *

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the permanent stirring nurde DA® precipitated sodium sulfate was filtered off, "3) ea filtrate" urde turn gerttbrt at Zimiaarteiaperatttir and ethylene oxide initiated until the Lorning by 23 "3 Ctewo-feil® zugenoraaen" Bas RufeI had ¹¹ Qn was "urther 18 Stun the continued UIB eiehargustellen, the reaction is complete dasa "ar" that was Zaoprop ^ nol then under reduced pressure boi a bath temperature below 35 ⁰ C ahdestil- "lines," obei a EÜoketaad 183.4 parts lauryl dimetbyl "(S-hyaroaiyathyD-aasioniuamitrit «Urüokbllsbo Bas product was easily soluble in water» whereby eö sohäumendes Löswag resulted in »

. Belapi81 ₁ 4,. .

A volume of 76 bisiethyl @ tearyla @ in in ISO ¹ tallen leopropaaol was stirred at a diameteisperetur and 12.2% silo conB @ nt? I®Fter sulfuric acid during the process of a 1/2 volume ₉ sugigeno Bie erbaltem® solution left @@ s one cools down to Zionierteaperatur before a solution of 17.2 parts iatritis nitrite in 30 file Saaeer was sugsg · Hash of a 2 hour lasting stirring mirda the precipitated 8atriuasulfai: Filtrierto The filtrate is ο diluted with further 45 parts water and with stirring ethylene oxide at 2iss ~ raertesaperatur initiated bia the 3a $ aung urn 11.2 Sew »-feila 8Ugenomiaen hattQo Bas stirring only the« reiter® e®tstststst »whereupon a T @ &% e @ igtt, thata part of the & Saung heia Dilute with water and, in the case of Alkalisobsaohea, with Hatriuashy «- droxyä telü? remained »which indicated that the reaction was complete o The xsopropanol was then reduced under reduced

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Pressure is not distilled off at a bath temperature about 35 ⁰ C to give a residue VOA "106.5 parts stearyl dimethyl ^ CSS-hydroxyethyl) = aaimonium-aitrit remained ₀

Example 5

ll _e 85 ropes Silfcer »± trit were weighed 50 mlο Distillation * tea water was added and the mixture to 60 ⁰ C erwärmtοEine solution of 28 g Oetyltrimethylammonlumbromid in 200 ml ο de» stilliertee water was slowly added with stirring, keeping the temperature at 60 ⁰ C was kept "The reaction *" mixture was left to stand and the liquid above it was filtered and evaporated to dryness. The product thus obtained was dried over phosphorus pentoxide, giving 21 ₉ 5 g of cetyltrimethylammonium nitrite. Part of it was made twice from acetone recrystallized »whereby a white powdery solid similar to cetyltrimethylammonium bromide was obtained? which melted at 242 ⁰ C o When it was dispersed in water, its properties were similar to the cetyltrimetbylammonium bromide ,, _o Bo the specific conductivity / concentration ratio was almost identical. The corrosive properties of both Connections are illustrated by the following examples ο

a) it was »20 ^ aqueous dispersions of cetyltrime-

- 10 -BAD

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H UO 81

tbylamoniumbroeid and Oetyltrinethylamoiiiumnitrii berge «· and a few drops of each were applied to strips of brightly polished white steel. The drops were allowed to dry, leaving a thin spot of Festatoffea on the steel surface. relative humidity was kept ", the steel began rusting very soon under the cetyltrimethylammonium and it was already very pronounced after 16 hours , but the surface below the stain remained unaffected, "which showed that the cetyltrimethylammonium ni""acted as a corrosion inhibitor *

b) Brightly polished stainless steel strelfts were partially cut into two pounds Aqueous Mspei-ulons of GetyltrlmetbylammoniuabDBid and Cetyl t rime thy lammoniuimi trit immersed in who are locked in Found bores, which were periodically shaken »The Strip that comes into contact with all of the cetyltrimethylamiaonium » Bromide dispersion found “soon began to corrode and naoh one On the day, considerable amounts of corrosion products had formed ο the strip, which came into contact with the cetyltrimethyl.

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lonlunnitrltdlsperelon remained bare and and even after a few months no corrosion could be observed «

Example 6

An acid was built up, which an Aaberllte IHA 400 (01) -Rare (an ion exchangers of a strong base) contained » 300 al of a 1 solar irrigation fluid flow through the Acid passed, which was then washed with about 1800 al of carbon dioxide-free distilled water a dispersion of 18.2 g of Cetyltrlaetbylanraonitmhroaid in. 500 al distilled water slowly passed through the acid and the resulting liquid was poured on a water bath Evaporated to dryness «The solid residue was dried over Phoephorpentoxjd * with 17.5 g of a product old the same Corrosion-preventing properties, as described in Example 5 "was obtained" Bine analysis on residual Sroaid added, dafi sine 81? had taken place o

In this case, the antistatic effectiveness was determined by padding a solution onto test pieces of a polyethylene terephthalate textile material. They were ^{dried at 80 0} O and the electrical resistance of a strip ron 127 ζ 19 aa measured at 65 $ relative humidity and 25 ⁰ C · The below

909812/0942

specified kort «Beslehen aicfe» off O ₉ I ft Agea «,!» sucked · »on the weight of the textile

a) Textile fabric + 0.1 $ Oetyltrlrati ^ latfsoniinnltrit, produced by ion exchange

Resistance 6 χ 10 ^ Ohs (7 ζ 10 ^ üim naon «Int« 6 MIn. Duration »the Htlßflxieren at 110 ⁰ C),

b) Sextile fabric + 0.1 £ CetyltriaethylaaBottiiabZOBid (control) ffidereta & d 4 10 ^& (B x 10 ^ 0ha naoJi a 6 min

e ^: - ■

Heat setting at ⁰

Sin untreated leztiletoff of the glelohen dimensions fcat under the same conditional a mideretand of aehr al «10 ■■?

These results show that is even a stronger antistatic agent than Oet ^ ltriiietlQrlaaaoniumbroeid (a low resistance corresponds to an ionen Örad antietatisolic effect), and swar especially before the

Example 7

The procedure of Example 6 was repeated, but with one-molar Hatrlunsarbonat instead of the one-molar Hatrlu «- · nitrite was used (in this case there was no'-Sotwaik

- 21 -

.909812 / 0942

digkelt to ensure "that the distilled water used to wash the column was free of carbon monoxide" was Ea Cefcyltrimethy! Ammonium carbonate obtained »with the conversion 76 # scam.

They described in Example 5 fixed to investigate the corrosive character were carried out with this substance, whereby the same Epgebniaae were obtained »d« ho it became found * .that it was the same previous corrosion inhibiting properties such as cetyltrimethylammonium nitrite owned o

The antistatic effect was as in Example 6 investigated <> A fabric that with 0 ₉ 1 $> Cetyltrimethy! Ammonium was provided had a resistance of 9x10 'ohms, which according to

^{As a result of heat setting for} 6 minutes at 110 ° C. to 4 χ 10% of an increase in cetyltrimethylammonium nitritol, this compound on polythylene terephthalate is a somewhat more effective antistatic agent than cetyltrimethylammonium bromide.

Example 8

The procedure of Example 6 was repeated, but using one molar sodium hydroxide in place of the one molar sodium nitrite. It was Oetyltrimethylammpniumhydroxyd he hold ~, the conversion was 90 i »»

-22

909812 miii ^

1U408r

The tests described in Example 5 for examining the corrosive characters were carried out with this substance Agent successfully prevented the corrosion of soft »tabl» but its 2 'aqueous dispersion caused a small one Corrosion, especially below the waterline o The material is therefore far less corrosive than getyltrimethylammonium bromide, although eβ is not as good a corrosion inhibitor as cetyltrimethylammonium nitrite or cetyltrimethylammonium carbonate »

The antistatic effectiveness was examined as in Example 6 <A. Textile fabric with 0 _p 1 # from this fabric »

' 8th

had a resistance of 2.4 χ 10 ohms, doho to expect that was that the fabric would act as an effective antistatic agent »

Example 9 <. ■

Ea was prepared using the procedure of Example 6 (by replacing the one molar sodium nitrite with one molar sodium tetraborate) with a conversion of 99 _P 5 $> . .-

The application of tests to study the corrosion ,, _the:; described in Example 5, showed that this substance is the

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HU081

Corrosion of the soft table was effectively prevented o the aqueous dispersion caused slight corrosion * above the waterline, although to a much lesser extent as DetyItrimethylaumoniumbromld *

0.1 # of this agent as described in Example 6 to a! Extilstoffprobestück "showed a resistance of 1.1 ohms χ 10, which is a 6 Kin" permanent heat set at 11O ⁰ C for 4 χ * 10 ohms rose, d .fcu the agent acts as an effective antistatic agent »

10

It was prepared by a similar method Oetyltrimethy! Ammonium »silicate, the conversion 74 $> cheating This product was compared eu cetyltrimethylammonium a certain · effectiveness in suppressing corrosion caused by an aqueous dispersion, but it was less wirkeam as the products described in the previous examples "In the form", it satisfactorily prevented the corrosion of white steel

WiQ

The antistatic effectiveness was determined in Example 6 o

24

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1 081

24 -. ■ ■; ^: ■■■■■;

A textile cloth, which was provided with 0.1 ^ of this material had a resistance of 0.1 Ohm 10 ac, _o h _e d that was expected eu "that the fabric -würde act as an effective antistatic agent ο ... . · .-

Example 11

It became cetyltritaethylamaoniuffibeneoat from cetyltrimetbyJLaiaso ~ niuabroBid by the ion exchange process and also from Cetyltriraethylamsaoniuahydroxyd (prepared as in Example 8) The application of the two aqueous dispersion corrosion states produced by reaction with the necessary amount of benzoic acid nor showed slight corrosion «No corrosion, became duron the pure product caused as determined by the test described in Example 5 «

The antistatic activity was "equipped as in Example 6" medium * A fabric that i 0.1> of this material ..

had a resistance of 3.3 χ 10 ohms, i.e. «h <> that It would be beneficial for the substance to be an effective antistatic Acting agent; would ο

Example 12 It was OetyLtrimethylarnmoniumohromat from Cetyltrlmethylammo-

- 25th

^J ' ' ^ "--- ■ - ·> - * §AÖ ORIGINAL

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niuBbromide produced by the ion exchange process »Xo In contrast to the previous balances, this was a colored one Compound, la Jiatrlumohromato! The aqueous dispersion / corrosion tea showed only very little corrosion. No corrosion was caused by the pure product, never by the Seat described in Example 5 was found.

1%

Sb would cetyltrimethylammonium nitrate by reacting iron cetyltrimethylammonium bromide with silver nitrate. The product caused severe corrosion similar to cetyltrimethylammonium chromide, as determined by the standard tests. This example of a corrosive salt is given for comparison week

Example U

Ma WIiMd Cetyltrimethylammoniumorthophosphat produced by the ion exchange process (actually 100 £ -lge conversion from Getyltx'lmethylaramoniumbromid) n

Application d) :: · Corrosion steate described in Example $ showed that the aqueous solution of this substance caused slight corrosion. The pure product also caused corrosion

26th

1ΛΑ4081

causes some corrosion, so it could be claimed will that its mode of action be bad? be as that of Links; which are described in Examples 1 to 12 » although it was better than that of cetyltrimethylammonium bromido

The antistatic effectiveness was determined as in Example 6 _o

A textile fabric with 0.1 # of the material,

ο ·

had a resistance of 3 χ 1Cr Ohm, so the material was expected to be antistatic8. Agent would work _ö

Belspi «! 15th

Ea was ^ C '; yl-H ^ äthylmorpholiJiiuinnitrit prepared by the method of Böiepiel <>, wherein a solution of 23 _t 25 gr H-Cetyl ^ S ^ athylmorpholiniumäthos "lfat in distilled water instead of the were öetyltrimethylammoniusnbromids used Analysis for oil JTitritgehalt tends * that only a 55 # conversion had been found, "but this was enough to show a complete freedom? u, as was determined by the tß

a largely complete wall in oil . % eil «ei © e imwamflJung can f® & « inen

BAD ABOVE »NAL

27 -,. 'U44081

The Köirgil ^ teSi'fce'lProdufct was applied to a textile material as in ^ 0 »1 ^c / <> the product gave a wi-

4 χίθ ⁸ ohms, in comparison * su 9 x 10 ⁸ ohms at 100 5 $ H-cetyl N-ethylmorpholinitfBäthoBiAlfat, doho the product acts as' a somewhat more effective stereo antielatic A ^ ene than the original N-cetyl ~ N-ethy1- morpholinium ethosulfate »

16

was CetyTpyridiniumnitrite from the corresponding firomid produced by the ion exchange process »where in 60 # Conversion was achieved »The pure product thus obtained successfully prevented the corrosion of mild steel «his The aqueous solution was incomplete in this respect effective, but noticeably better than 100 # bromide

The antistatic activity was determined as in Example 6 « Am Textile toi C, which was marked with 0 "1 - $ J of this fabric,

8 8

had a W :! ! arose from 2 _P 2 χ 10 Ohm compared to 1.8 y 10 ■ _: Ohm of the original bromide, doh "both have similar antistatic JSig; . create «,. . "-'-'-- ■ : '.;·.> ■■ ,.. ·

Example 17

Ss was partisan groups! Ürimethylammoniumbicarbonat through the ion-'toff ^ h "<rerfnhi ^rt i hergestellt-, Application of Example 5

909812 / 09Λ2-

bösohrieb © ne> ien Korrosionsieete * se-iges that the pure product successfully prevented the corrosion of mild steel, and ea became only a light one. Corrosion in the case of aqueous difepersion

The same effect as in Example 6 was examined

Am fextiiötöff 'fit * toit O ₉ I. $ provided by oiissm material "ar> had a resistance of i" § ιε ICr Ohm "that is, we expect that the material will be an effective anti-static agent

work »

18th

Ber fixed sur BeBtiteiaung the antistBtisohen Wirkeapikeit was repeated "where a & er a from eine® AorärlpoXymer feergeBtellter fabric ⁽ⁿ AkriliaD," ₉ eingetr "g3nc8 v / aren & eiehe & K the MS divides dtJB i'Giyäthj'-lent ere |.) Ht.halB-TG3 was used ο

fiin AQ.fyitextilaitoff "who was with Ö» 1 j4 Cetyltrlmethylacimonium "ttitrit 1rers0iieis, had a resistance of 2.8 ohms χ loT la comparison tsu 1.4 x 10® olim at OetyltrlüiethylainmoniuabrolBld and 10 ⁵ 0hm unbehaiidelten with a textile fabric, is why iet the first ** niet aätietatiBohee agent door a Aoryltextiletoff vtrkeämer ale let & terev

^"<- ^ ^v::: - ^ϊ; .. ■ - · '■■■■' - ^-; ■ - ■■. '' ■ ■ - 29 - ■■■■■■■ - ■ ■ -

»09812/0942

-J9-. . Τ4Λ40.81

Example 19

One piece of cotton limbrla was dyed on a 1 year old Parbfcontlefe with Durazol brilliant red B 150 ο (C ₀ Ι «No. 3!) 78O, where CoI ₀ extends to the“ Color Index ¹ ? A * Edition refers to _s jointly published by the Society of Dyers and Colourist and 'the Araerioan! Textile Chemist & Colourist Association) ο

O _s 1 gr Cetyltrimethylammoniumnitrit was dissolved in 150 ml water, the solution was cooled to 20 ⁰ O and a 5 g piece dey above colored Textiletoffee described hineingegebenα The temperature of the solution was raised to 60 to 70 ⁰ C and there for 20 Hin "long At the end of this period the fabric was taken out _P rinsed in water and dried

example 20th

Example 19 was repeated with the difference that that as a dye Durazn ·! Violet 2B was used (CoIo Direct Violet

Example 21 '-.

Up to Example 19 was repeated with the difference that DurassoI ~ B! Au R was used as the dye (CoXo No. _0. 27 925) ο

9Ö9812 / 0942

The color fastness to water of the strips of example 19p2Q and 21 together with other colored but otherwise unb © - handsLten control tax fabrics was investigated in accordance with IoS ₀ Oo Recoraandation R 105 Part 22 (BoSb 2681/1956), described in "Standard Methods for the Determination of ths Color Pastaesa of Textiles * ¹ (second edition®) (Society of Dy®rs and Colouriats) o In comparison with the untreated control pieces a, the treated Textilstoff® showed a considerably lower staining of the neighboring white cotton and the® wool became® not practical: · dyed ₀ The treated textile exhibits less loss of color depth than the control piece

Example 23

The wetting effect of Getyltrmethylammoniumnitrite was determined with the help of the Jlerbigapparatee * (JoSoCoDyers and Colourists, 5K No. ₀ I _{July 9} , 1963, Seit® 233) - The principle of this method consists in putting a weighed skein of raw cotton yarn into a solution for a certain time dea wetting agent «, The yarn is then taken out, centrifuged and recovered. The increase in weight resulting from the absorption of moisture is taken as a measure of the wetting effect.

The results obtained are shown in Table 3,

BAD ORIG'NAL 90981 2 /: 09: 4 ^:,; .- ■■ ·

- 51

U44081

color 3

ta »ecessiw ta aas β st» a ts sse ts

Concentration on Oetyl-trlnttUjrl * nitrite

Or4

O ₉ Z

Proeente absorbed humidity

64

909812/094

52-- U4 40

Yarn ,, on the olmt the stigab · a®! © tsualtt®! ® only ia .dipped in water and .under the same 8 @ äissgüKg @ 2i g®tuet @ t was »' absorbed · ^: 30 £ V« nolitlgtatt <><'

lishee antistatiscäies Ageias «ux ^ &# for you application on an off -! foS ^ rapgtieiiflidttt btetelmdee ®men betitliot * 2) 1® method-BdB'tifBsung% @@ tand therein _s the developed Xadting on the & ± n®T i @ oli @ rt @ »Gartipeökyiig on ^ i & ei · Spindel * u> nmhavm es nurturing de @ B? eübla & i & l®re & -on a spindle wos € en

I'm from Folyjpp ^ l ^ st geeposmense @asi (rön 2 Denisi * 3200 with threads of 40 J ^ nier per Bides) "from © in and & ®a © @ lbe»

f? urd @ in sfrei skins divided _Q A Appretlerungs "from a Î strength Jistil @ IOEN in water of what" illko.sfisökiiälsflUßüi ^ ktit was "" A Äppr tirde the bargain A aufgebfaoht «« ti®raag®alttel ₉ because ® from the above

stocks ftbi? S ^ geilSstes Ost ^ ltrisae ^ ssrl «- '

uf f # il B au% @ br @ 6! it < > The 4ee Jkppretierimgsmättels on

the §mm'm & Sf for feil k iiad Seil B.gl@ieli

^: 909ti2 / 0942

Bio-spun yarns from part A and part B were then drawn off at a speed of 152 m / min, under the same conditions * (geometrically identical packings were obtained on the bobbins). Draw-off was interrupted when 1.36 kg of the drawn yarn was wound onto each spindle. Me spindle with the venal A was isolated and placed on an electric meter, the distance from the aar "Slektrometersonde to the surface of

Coil was 13 cm, measured at the center of the axis the coil. The measured charge was 2200 volts. Me ! Charge on the bobbin with the yarn from Part B was in exactly determined in the same way, the measured charge was 120 volts / ra.

Cetyltrimethylammonium applied to polypropylene threads. nitrite thus sets the during the pulling off of the threads developed static electricity and acts as a antistatic agent. Chemical analysis showed that the yarn of part B 0.05 wt .- ^ CetyItrimethy! ammonium nitrite, based on the weight of the threads.

Example g>

Me effectiveness of cetyltrimethylammonium bromide as a water-soluble antistatic. Means was determined when applied according to the procedures of Example 24, on a yarn made of polypropylene thread «indent

- 34 ^; 909812/0942 '

H44081

this substance instead of cetyltrimethylaiiifeöniuiiraltit was used in part B, Bine visual appraisal of the developed static charges ssesgte »that Cetyltriiflethylammoniumbroraiö and 'Getyltrimethy! Ammonium' - nitrite had no distinguishable antistatic leiguag »

-Example- 26 -

The corrosive properties of Sohmälsemulsionen (10 wt # 5 ₉ contained the quaternary ammonium compounds were as indicated follows Weiehstahlstrsifen were partially immersed in emulsion untersehiedliohe amounts quaytHren Ammoniuronitrits and -. "Bromide contained They were examined after 20 hours," the in. Table 4 clearly shows the anti-corrosive effect of the nitrite-containing emulsions.

Table 4, Quaternary compound added to 15fi emulelon

»Jhts

Op 15g Cetyltrimethylammoiiiuntnitrite

0.075 g of cetyltrimethylammonium bromide and Of075 g of cetyltriraethyl ammonium nitrite

Oo105 g of cetyltrimethylammonium bromide and Of045 g of cetyl-triethylammonium-binittitol

O ₉ 12 g of cetyl ^ trimethylaamonium bromide and

0.03 g of Oetyltrimethylammonium Nitrite

Op15 g Oetyltrimethylammeniumbromid

corrosion

some none none

no

somewhat strong BAD ORIG »NAL

9 09812/09

27

H-A.4081

^r '"KiHi Mieejfimg auö ^ etylÖiiPiöthflbfcnsylamraönittJinitrlt and

^ broaifl mti 87 ¥> quart fir era nitrite "was on a

-t * -

- ■; '? olypropylene yarn aue hand in hand 0 _t § ^ -ilgon solution in Aseton on-

·! I,. \ ^ If> raoht «Baa I / Beung ^ l- ^ eI was öu'roh Trookncsn in a«

! . Pfiöluftetroia eliminates m & Äit »ntiet & titöhe

β as follows Hufgegeigt »$ ia ProbestÜfcfl ^ e

d | i has been asserted in the above way «r« r # under ^ enffting in an itöfttiöüierliohe Over three nylon rollers and "gteogen" in metalliBohöö drive wheel. JDAB (iarn was driven at a constant Oeeohwindiökeit unfl the geeeiate "rseugte etatiächi Mektrisltlt was & fit erf of an electrometer, FLAE la represents KHht one of Nylonrjllen mounted m & t _f wherein" a bonus. "A distance of 2 cm from the Oara tiea & a * Me taken ledung was after a _{Xaufon for 5 kin s} at a speed of 60.9 m / min >> +0.33 volt / ee.

.gB

The static charge was applied to a PJPobeetilök the polypropylene yarn wl * in Example 27 /? Em «i8in ₉ However, without the use of the quaternary terblend» you conditions dta testes were: .u as described in Example 27, afcör in the «*» case; the charge generated is more than 50,000 volts / oa.

909812/09 * 2

1.4-U081

Example 29 I.

A Polypjfü] *; ienfaa / orgarn was treated as in Baiapiel 27, with the Un *; *.-.- uchled that the compound used consisted of a mixture of doaeoylflimethyltienisylaissmoniuianltrit and -bromid with a content of 75%. The Öarn areeugte etatleohe charge treated on the derrrt was® / Rftoh ϋϋΆ method by BsiapiarX 27 ^ aaeeeen and tu 10 Voit / o »

Am PolirproiSflanfasergajra tsrurds wi® in 3β1 «ρ1 · 1 2? treated, tnit üea tlät ^ rHOhled, the & Ϊ9 used quarttw connection

»Bromia with a fair trade of 8? £ ftitrlt. The on dör. G ^ jcn treated in this way was found to be the same charge θ · ιβ method of Example 87 measured and iu 10 volts / oo

of the transverse variety, which was used in c.üü examples 27, 29, and 50 for the addition of IPoifparopjlenfftdengarn, irurfi ^ n in 1 £ -lger Sonzentrütton in a £ 10 fier lh BeIeXΊ24 veif ^ eten sons * urd 'n hitrauf gemttjl u * n * in apiel S5 used VerfÄhren naoh corrosive Bigeneohaften examined · Ba was after 20 hours of any of the Mix ine gen! "Corrosion be feet found

- 37 ~ ι '009812 / ΟΘ42

Claims (1)

- 37 *
Claims ι 1. Process for modifying textiles and textile materials and in particular for reducing the tendency of such textiles and textile materials to become electrostatically charged, characterized in that the goods are treated with a corrosion-preventing quaternary ammonium compound of the general formula " ^R 3
is treated, in which the anion X "* represents the nitrite, carbonate, bicarbonate, traborate, phosphate, chromate, benzoate, silicate or hydroxyl anion, R _{1 is} an alkyl or alkenyl group with 8 to 22 Carbon atoms, R «and R, independently of one another, denote a lower alkyl group with not more than 4 carbon atoms, an aralkyl group or a hydroxy-substituted alkyl group with not more than 4 carbon atoms and R. denotes an alkyl or alkenyl group with 1 to 22 carbon atoms, an aralkyl group or denotes a hydroxy-substituted alkyl group with no more than carbon atoms, or in which Rg and R, together or R ₂ , R * and R ^ together, form the part of a heterocyclic ring which is closed by the nitrogen atom - 38 909812/0942 HU081 3 « 2. The method according to Ananruch 1 _r, characterized in that the quaternary ammonium compound has the Cetyltrimethylammoniuiükation as a cation. 5. '/ experience according to claim 1, characterized in that it is worthwhile because the quaternary ammonium compound ale cation the cetylpyri— possesses dinium cation, 4. The method according to claim 1, characterized in that the quaternary aminonlura compound has as cation daa lf-cetyl ~ N «~ äthylraorpholiniurakation _o 5. The method according to any one of claims 1 to 4, characterized in that that the quaternary ammonium compound with the Αηϊοη X "" from a corresponding quaternary ammonium salt is made with a different anion by ion exchange or by radical oil exchange (metatheay) » 6. The method according to claim 5 _f, characterized in that the ion exchange is carried out with the aid of an anion exchange resin of a strong base, 7 * procedure nash one of claims 1 to 6, characterized in that the y quaternary ammonium compound with the anion X "with a corresponding quaternary ammonium salt with einetr. Arsion different g- = jnLcoiifc int, .. 39 909812/0 9 / * 2 UU081 β · method according to Anepruoh 7 »daduroh known that the Quaternary ammonium compound bit the anion X "is paired with a quaternary ammonium halide. 9 · Method according to Anepruoh 8, daduroh marked that the qua ^ rtire ammonium halide is a quartarea ammonium bromide " 10 · The method according to Anepruoh I ₁ daduroh known that the '"are treated with a clot of a quaternary ammonium nitrite and a quaternary ammonium halide became· 11. Procedure naoh Anepruoh 10, daduroh marked: without _f that the quaternary ammonium cation, let the oetyltrimethylamaonium cation. 12 · Procedure according to one of the test 10 or 11, because of that knowledgeable that the quarturic aomonlum halide is included quartHree ammonium bromide iet. 13. The method naoh one of claims 1 to 12, daduroh marked that the goods are colored goods. - 40 - 9098 1 2/0942 1U4081 14. The method according to claim 13 »thereby marked, that the goods are old cellulose fabrics dyed with a directly acting cotton dye, 15 · The method according to any one of claims 1 to 13, characterized marked that the product is a hydrophobic product » 16, method according to claim 15 »characterized in that that the goods are made from polyethylene terephthalate is. 17. The method of claim 15 »gekenneeiohnet characterized in that the _t ^ ere a polyamide goods let. . _R nnch method of claim 15 »gekennseichnet in that the hydrophobic product is made of polypropylene" 19 · The method of claim 15 »daduroh gekennselohnet _t that the hydrophobic product is a 1st Polyaorylnitrilware · 20. 'experience according to one of claims 1 to 19 »daduroh characterized in that the goods are treated with the quaternary ammonium compound in an aqueous solution. - 41 - 909812/0942 - * ¹ - HU081 21 »Method according to one of claims 1 to 20, characterized It is noted that the amount of quartz ammonium compound which is applied to the goods is 0.05 to 1.0% the "fare amounts to 22. Method according to one of claims 1 to 21, thereby grtreimsei paves the way for others to change textile finishing «Angenslen together with quaternary ammonium» connection to be applied 23. TerfahTfm according to claim 22, daduroh gikennseiehnet, dme «im padengarn spun from polypropylene with a wterlgea L * auleion of a water-insoluble Sohmftlif lüssig cold, dii? the quarters Ammoniunnrerbindung dissolved corresponds WQt ₉ is beliandelt. 34 · Terfahren according to claim 23, daduroh marked, the waeserunluslichen narrow liquid a is" 25m Terfah-en according to claim 24, characterized in that the sill consume liquid is a silicone consume »liquid with a viscosity between 1000 and 200 Cestistoke« - 42 - 909812/0942 HU081 26, Process for the preparation of quaternary ammonium nitrites of the general formula wherein R ₅ denotes an alkyl or alkenyl group having 8 to 22 carbon atoms, Rg and R ₇ independently of one another denote a lower alkyl group or hydroxyalkyl group having not more than 4 carbon atoms, or which together form the part of a heterocyclic ring which is closed by the nitrogen atom is, and Rg denotes a Hydrocyäthyl or a hydroxyl group, which is characterized in that Äthylen- or Propylenoxycl with a nitrous acid; Salt of a tertiary amine of the formula I ⁶ R ₅ -NR _{7 is} implemented. 27. The method according to Annnruch 26, characterized by that the reaction between the ethylene oxide or propylene oxide and the nitrous acid base of the tertiary amine in one non-aqueous water-miscible solvent is carried out. - 43 - BATH ORIGINAL 909812/0942 HU081 28. Method neon claim 27 »characterized in that the solutions) ittel is Ieopropanol, £ ethanol ₍ methanol or acetone. 29 · traversing *; λ according to one of claims 27 or 28, dadaroh Kekennzeichnafc that the nitrous acid salt of the tertiary Amines by replacing a solution of a salt of a strong one Mineral acid dea tertiary amine in a non-aqueous solvent miscible with Wapser with a concentrated aqueous solution of sodium nitrite is carried out b one of the 3Oo procedure ν ι according to / requests 26 to 29 »daduroh gekenn · draws »that the reaction between ethylene or Propyl-noxy * in the ealpetrigeal part of the tertiary Amine is carried out at injection temperature BATH £ Λ P Q \ ■ "■ Γ κ?; 9 O 9 8 1 2 / O 9 A 2