DE1469470A1 - Process for rendering textile materials antistatic - Google Patents

Description

Sanyo Chemical Industry Company, Ltd. 1, Ichinohashi-nomotocho 11, Higashiyama-ku, Kyoto, Japan

Method of Antistaticing Textile Materials Priority: Japan September 23, 1963, No. 51152/63

The invention relates to a method of imparting to textile materials antistatic properties and protect against yellowing _TO. In particular, the invention relates to an antistatic and anti-yellowing agent for textiles, which contains a substantially water-insoluble compound consisting of a high molecular weight part and anionic parts, to a method for textiles by treating or coating their surfaces with this compound-antistatic and To give anti-yellowing properties and on textiles with a surface film containing this compound.

I «. In the following the term »anti-aging» means the protection of the textiles from the compensation due to absorption or adsorption of a trace of iron in the water on the surface and the expression "essentially insoluble in water"

909818/0990

means insoluble in water or slightly soluble in water or partially water-soluble, i.e. "the ability to act as an aqueous, colloidal solution, aqueous dispersion or aqueous emulsion with or without an emulsifier.

Various methods are known to give to textiles antistatic properties that are in the wash and ψ of dry cleaning (dry cleaning) remain "Of these methods, obviously most useful in the American patents 2,694,688, 2,723,256, 2,725,577 and 2,741,568 and British in the Patent 819021 described. In this process, the textiles are treated with a cationic compound of high molecular weight and then or simultaneously with a specific anionic compound. However, these conventional methods have many disadvantages; For example, textiles treated in this way tend to "yellow" when they are worn and washed repeatedly, because they adsorb or absorb a trace of the iron present in the water during washing. In addition, such textiles have a too hard "handle". Such antistatic agents or methods to give textiles antistatic properties. zu .erteilen, if they cause yellowing of the fabrics on repeated washing, of course not be used for synthetic textile products with "wash-and-wear" properties and especially not for garments where a high degree of whiteness is always a main condition.

90 9818/09 90 _BAD ORIGINAL

It is therefore an object of the invention to provide permanent antistatic agents for textiles, especially for synthetic fibers such as Polyester, iiylon, 'polyacrylonitrile, acetate and polyolefine, that tend to accumulate electrostatic charge, as well as for woven and knitted fabrics made from these materials Products, with the ones obtained, uit these antistatic agents treated textiles are essentially free of the tendency to yellowing as a result of adsorption Trace of iron present in the water when worn and washed repeatedly.

Another object of the invention are methods of making textiles To give anti-static and anti-yellowing properties «

Another object of the invention are textiles with excellent Neten anti-static and anti-yellowing properties.

Further objects and features of the invention will emerge from the following detailed description.

It has been found that the Ver ilburigsneigung _b due to adsorption of Sisen in wet textiles which have been with a cationic compound of high molecular weight and then treated or simultaneously with various anionic compounds, is related to the type of anionifachen compounds used in 2usantennang. It was further found that the disadvantages of the conventional

'9 0 9 818/0990 ^BAD original

1469A70

Get lost without adversely affecting the benefits of these Procedures can be turned off, if certain, carefully selected anionic compounds, i.e. anionic Compounds each having more than 4 carbon atoms and up to 10 anionic functional groups in the molecule can be used.

The anionic compounds listed in the table are used in the processes described in the above-mentioned American and British patent publications.

Table 1
Anionic compounds that are commonly used.

SALTS VOH U ¹

Sodium and ammonium laurates
Sodium and ammonium myristates
|, Natriuiiibehenate

Tallow fatty acid soap

Sodium octyl sulfate

Hatrium-, valium- and üjümoniuiü-aodecylsulxate

Technical ^x 'atrium dodecyl sulfate

Sodium tetradecyl sulfate

liatric hexadecyl sulfate

I sodium salt geuischter ^ ₁₀ - G <* _Q Alkenyl sulfate (ülko-

get that by reducing alratoil with sodium

get vrerden)
Sodium hexadecenyl sulf a't
Sodium octadecenyl sulfate

Sodium alkyl sulfate with ^ 20 carbon atoms N-'Diethyl-cyclohex-1-ammonium dodecyl sulfate Sodium and ammonium salts of sulphates mixed Dodecyl-tetradecyl alcohols, the uit 1 Ι, ίοΐ ethylene oxide condensed,

90 9 818 / Ip "9 9 0 ^BAD original

1A69A70

MOoPMATE:

Dilithanolamine salt of latiryl phosphate (LIono- or

Diester)

The sodium salt of petroleum sulionate containing 12 to 14 carbon atoms

iJsodium salt of petroleum sulfonate with 16 Ms 18 carbon atoms

liatrium dodecylbenzene sulfonate

l ^ atrium dodecyltoluene sulfonate

J? ^ IiIT iIUx ^ lLI LG

iS:

High molecular weight copolymers of dtyrene and maleic acid Ethylene polyacrylate (degree of olysis: p

• Because organic compounds of this type, for example salts of ⁿ ettlures, sulphates, phosphates and sulphonates with only one anionic functional u group in the molecule are used, the treated textiles tend to adsorb the iron traces present in the water and consequently A similar disadvantage can be observed when organic compounds with a large number of anionic functional groups per molecule, E, B. a high molecular weight copolymer of styrene and maleic acid can be used. Us, it was found that these phenomena unerwünsdhten can be avoided if erfindunge- be used according · organic compounds containing more than 4 carbon atoms and 2 to 10 anionic functional üruppen per molecule.

- «- U69A70

The present invention thus comprises (1) an .antistatic and anti-yellowing agent for textiles, since a substantially water-insoluble compound contains, which consists of a high molecular weight part with a number of quaternary nitrogen atoms and of anionic parts each with more than 4 carbon atoms and 2 to 10 anionic functional groups, wherein the cationic part and the anionic |, sceien parts are chemically bonded together, (2) a method for textiles by Beiiandeln or "coat the surfaces with this compound untistatik- and antiwear · to give gilbungseigenschaften and. (3) Textiles with a surface film containing this compound.

Bs can be any compounds that consist of a high molecular weight Part with a number of quaternary nitrogen atoms

and consist of anionic parts each having more than 4 carbon atoms and 2 to 10 anionic functional groups, wherein the hoctimolecular part and the anionic parts are chemically bonded to each other, are used as antistatic and anti-yellowing compounds according to the invention. Typical and particularly suitable 'compounds are those which consist of a high molecular weight part with an AxizBhX of cadica of the following general formulas (I) or (II) and anionic parts each with more than 4 carbon atoms and 2 to 10 anionic functional groups such as -COO, -SO ₃ I -OSO ₅ , -OPO ₃ , -OPO ₃ M ₁ = 0 ₂ P0 _2> -PO ₃ or

M exist, where M is hydrogen, gin MetallatoiB! a .

■ ■ ■ 1 ■

90981Ϊ / 0990, _{BATHROOM 0R1GINAL} j

U69470

Aiamoniumradikal or an organically substituted amnionium radikai can be j

Rp and E., are alkyl radicals with 1 "to 12 Konlenstoffatoiaen, Alkenyl radicals with 3 "to 12 carbon atoms, hydroxyalkyl radicals with 2 to 12 carbon atoms and / or alkoxyalkyl radicals with 2 to 12 carbon atoms or R ,, and R-, are together a G- group which forms a heterocyclic ring having 5 to 6 ring members, which is the nitrogen atom contains and also contains a second heteroatom such as 0, H, or S as a ring member and alkyl side chains with 1 to 6 Can carry carbon atoms, and.R. is an alkyl radical with 1 to 18 carbon atoms, an alkenyl radical with 3 to 18 carbon atoms, an lydroyalkyl radical with 2 to 18 Carbon atoms, an alkoxyalkyl radical containing 2 to 18 carbon atoms, an aralkyl radical with 7 to 20 carbon atoms, a phenoxyalkyl radical with 7 to 20 carbon atoms or a jäpoxyalkyl radical with 3 to 18 carbon atoms »

(H)

BAD OBIGiNAt 909810/0990

U69470

R ₁ - and IL- are hydrogen or alkyl radicals with 1 to 6

P- ¹ O-

Carbon atoms, m and η integers from 1 to 2 and B ₇ , has the meaning defined above in the general formula (i) »'- ■■■

Among the high molecular parts having a number of radicals of formula (I), those are particularly preferred which consist of at least having the following general formula (III to 20 wt _o $ from a structural:

RO R ₂ - -. CH ₉ - C - GO - R ₁ - Jr - R, (III)

■ R is hydrogen or an alkyl radical with 1 to 2 carbon atoms, R. is an alkylene radical with 2 to 4 carbon atoms, Rp and R ~ are alkyl radicals with 1 to 4 carbon atoms or hydroxyalkyl radicals with 2 to 4 carbon atoms and R. is an alkyl radical with 1 to 4 carbon atoms, an alkenyl radical with 3 to 4 carbon atoms, a hydroxyalkyl radical with 2 and 4 carbon atoms, an alkoxy radical with 2 to 5 carbon atoms, an aralkyl radical with 7 to 8 carbon atoms or an epoxyalkyl radical with 3 to 8 carbon atoms.

These compounds according to the invention can be prepared in a known manner. £ .B <, the production is carried out by converting a compound (later referred to as a cationic ^ compound), which consists of a high molecular weight part with 909818/0990 ^: " ^ft ■ ■ * 'BAD ORIGINAL

a number of radicals defined by the formulas (i), (II) or (ill) given above and the usual counter anions such as 01, Br, J, OH ₅ OSO ₅ , C ₂ H ₅ OSO ₅ , CH ₅ - ^ L_ ^ -SO ₅ or 110-, with a compound (later referred to as an anionic compound), which consists of an anionisohen part with more than 4 carbon atoms and 2 to 10 anionic

-OSD ₃ .

functional groups such as -GOO, -SO ₅ Z-OPO ₅ , -OPO ₅ M, = 0 ₂ P0 ₂ , -PO ₅ or -PO ₅ M, where M is hydrogen, a metal atom, an ammonium radical, an organic ammonium radical or one the usual countercations such as H, Na, K, Ca, FH ₄ , CH ₅ IiH ₅ , NH (C ₂ H ₄ OH) ₅ , N (CH ₅ ) ₄ , N (C ₂ H ₅ ) ₄ and N (GH ₅ ), (C ₂ H.OH). Said cationic compound is by polymerization of a monomer with an ethylene-like unsaturation or a polymerizable double bond and a quaternary nitrogen atom (or by copolymerization of this compound with a suitable copolymerizable monomer) or by polymerization of a monomer with an ethylene-like unsaturation or a polymerizable double bond and a tertiary Nitrogen atom (or by copolymerization of this compound with a suitable copolymerizable ionomer) 'and subsequent quaternization of the tertiary nitrogen atoms.

The compounds according to the invention can, however, also by

Implementation of a monomer with an ethylenically unsaturated one Bond or a polymerizable double bond and

9 OS «18/0990 ^BAD0RIGINAL

H69470

a quaternary nitrogen atom with the anionic compounds and polymerizing the obtained monomer (or copolymerizing this monomer with a suitable copolymer Monomers).

In the compound according to the invention, the preferred one average molar ratio of quaternary nitrogen atom and anionic part at 1: 0.3 to 1: 1.

Some of the ones used to make the anti-static and anti-yellowing compounds Cationic compounds suitable according to the invention are listed as examples in 'fabeile 2.

Table 2

Examples of cationic compounds which are suitable for the preparation of the compounds according to the invention,

Poly-ß-acryloyl-oxyethyl-trimethylanmonium-methyl sulfate Poly-ß-acryloyl-oxyethyl-methyl-diethylammonium-ethyl sulfate Poly-ß-methacryloyl-oxyä thyl-diä thy lme thy lammonium-methyl-

sulfate poly-ß-methacryloyl-oxyethyl-trimethylamnionium chloride

Poly-ß-methacryloyl-oxyethyl-diethylallylammonium chloride

Poly-ß-methacryloyl-oxyäthyl-dime thyihydroxyäthylammonium-

chloride ■

Poly-ß-methacryloyl-oxyäthyl-diethylme thoxyme thyl-ammonium

chloride

Poly-ß-acryloyl-oxyethyl-diethylbenzylammonium chloride

Poly-ß-acryloyl-oxyethyl-dimethylglycidylammonium chloride.

Poly-ß-acryloyl-oxyäthyl-dimethyl-phenoxyäthylammonium-

chloride poly-ß-vinyloxyethyl diethylmethylammonium methyl sulfate Poly-ß-vinyloxyätliyl-troaietliylamnioniumchlorid Poly-β-vinyloxyethyl-dimethylmethoxymethylammonium chloride

909818/0990 _BAD original

U69470

Poly-ß-acrylamidoethyl diethylmethylammonium methyl sulfate Poly-ß-acrylamidoethyl diethylglyeidylaimoniuiiichlorid Poly-acrylamidopropyl-dimethylallylammonium chloride poly-acrylamidopropyl-diethylbutoxymethylajmoniumchlorid

Polymer obtained by quaternizing acrylamidoethyl diethylanine with methylol-chloroacetamide poly-acrylamidopropyl-methylmorpholinium chloride Poly-acrylamidoethyl-hatoxymethylmorpholinium chloride Poly-ß-methacrylamidoethyl-methylpiperidinium-methyl-

- '■ ■ ■ sulfate

Poly-ß-vinyloxyethyl-allylpiperidinium chloride Poly-β-vinyloxyethyl-kethylpiperidinium chloride Poly-H-methyl-2-vinylpyridinium ~ methyl sulfate poly ^ N-ethyl ~ 4-vinyl-pyridinium chloride Poly-III-methyl-4-methyl-2-vinyl-pyridinium-methyl sulfate

Oleopolymer from ß-Iaethacryloyl-öxyäthyl-diethylmethylaromoniummethylsulfat and vinyl acetate

Oleopolymer from ß-Acrylamidoäthyi-diethylmethoxymethylammoniumchlorid and acrylamide

Oopolymer made from ß-vinyloxyethyl diethylmethylammonium chloride and methyl methacrylate.

Some of the anionic turns that are used to manufacture of the antistatic and anti-yellowing compounds according to the invention Suitable are those that each have more than 4 carbon atoms and 2 "to 10 anionic functional groups such as

-SO3
-000, / - OSO ₅ , -OPO ₃ , -OPO ₃ M, «0 ₂ P0 ₂ , -PO ₃ or -PO ₃ M,

where .M is hydrogen, a metal atom ,. an ammonium radical or is an organic ammonium radical. From these connections are those with a molecular weight between 100 and and with "2 to 6 anionic functional groups in the Molecule are particularly suitable and in many cases give very satisfactory results.

909810/0990

Typical and preferred representatives of these anionic compounds are listed in Table 3 .

Table 3

Examples of anionic compounds that can be used to manufacture of the compounds according to the invention are suitable (they find usually in the form of their oalt application),

Pimelic acid

ouberic acid

Azelaic acid

Sebacic acid

Itaconic acid

J: \ ionylsuccinic acid nonenylsuccinic acid Dodecyl succinic acid dodeaenyl succinic acid octadecenylsuccinic acid, cyclohexane, carboxylic acid Isophthalic acid terephthalic acid tetrahydrophthalic acid Tricarbaryl acid trimellitic acid Pyromellitic acid

Benzene disulfonic acid butylnaphthalene disulfonic acid Methylnaphthalene disulphonic acid, nonyldiphenyl ether tisulphonic acid Dodecyldiphenylether disulfonic acid Diphenylether disulfonic acid Phenylphenolsulfonic acid

_C3 Formalin condensate of iaphthalenesulfonic acid

J ₀ ! «Orraalin condensate of phenylphenolsulfonic acid

0>. iOrmaline condensate of phenolsulfonic acid

^ ₁ POLTSUIFATE

to pentaerythritol ethylene oxide and propylene oxide adduct

* ° ·. Poiysudfat (sour) -

O ethylene glycol propylene oxide adduct disulfate (acidic)

Polybutylene glycol disulfate (acidic)

BATH ORIGINAL

1469A70.

• POLiPHOSPHATE

Glyoerin propylene oxide adduct triphosphate (acidic) Ethylene glycol propylene oxide adduct diphosphate (acidic)

POLYPHuSPHONSAUmSH
■ Diphenyl ether diphosphonic acid

atf KIΐ CARBOXYL AND ANIMtu ^ diiURb ¹ GKUPPM

Oleic acid sulphate (acidic)

Dioxydtearic acid sulphate (acidic)

BuIfonat of monoesterified calinic acid (acidic)

tfU-sulfonated fatty acid (acidic)

Hicinoleic acid phosphate (acidic)

The following compounds may be cited as characteristic examples of monomers with an unsaturated ethylene bond or a polymerizable double bond and a quaternary nitrogen atom: methacryloyl-oxyalkyl-trialkylarionium compounds such as methaeryloyl-oxyethyl-trimethylammonium chloride and methacryloyloxyethyl-methdiethylammonium-methylsulfatylammonium; Acryloyl-oxyalkyl-trialkylammonium precursors such as aoryloyl-oxyethyl-trimethylammonium chloride; Hetiiacrylamidoalkyl-trialkylammonium compounds such Methacrylamidoäthyl-diäthylmethylamiiionium-fflethylsulfat j vinyloxyalkyl-trialkylammonium compounds such Vinyloxyäthyl-trimethylammonium j N-vinyloxyalkyl-H ^ alkyl- piperidinium compounds such as H-Vinyloxyäthyl-H-metliyl-O ^ ₀ iperidiniumciiloridf N-vinyl -W-alkyl-imidazolinium-Verbin-

o>, fertilize like l-Yinyl-K-metiiyi-imidazoliniummetiiylsulfatj

° 'H-alkyl-vinyl-pyridinium compounds such as N-methyl-2-vinyl _o pyridinium methyl sulfate and a mixture of two or more of these monomers.

BATH ORIGINAL

Typical examples of ionomers with an ethylene-like unsaturation or a polymerizable double bond and a tertiary nitrogen atom may be mentioned; Dialkylaminoalkyl acrylates such as ß ~ diethylaminoethyl acrylate; Dialkylaminoalkyl alkacrylate such as ß-diethylaminoethyl methacrylate and beta-dimethylaminoethyl methacrylate and vinyl pyridines such as 4-vinylpyridine, 2-methyl-5-vinylpyridine and 2,4-diethyl-5-vinylpyridine _o

As copolymerizable monomeric compounds with at least an ethylene-like unsaturated bond or polymerizable Double bonds can be used, for example: olefins such as ethylene, propylene and butylene; Acrylic compounds such as acrylonitrile, acrylic acid and luethylacryate; ^ Acrylic compounds such as methacrylamide and diethyl methacrylate; Vinylidene compounds such as vinylidene chloride; Vinyl compounds such as vinyl halides, vinyl acetate, styrene, methyl vinyl ketones, Vinyl pyridines and vinyl isobutyl ethers and dienes such as butadiene and 2-chlorobutadiene.

The amount of copolymerizable monomer is between 0 to 80% by weight, based on the monomers used, variable, The amount chosen depends on economic considerations and the desired physical properties of the polymer if a copolymerizable ionomer is used, so the preferred amount is 1 to 50 grains.

909818/0990

BATH ORIGINAL

H69A70

The degree of polymerization of the cationic compound in the The above-mentioned process is greater than 10 (with a content of at least 20% by weight of monomers with a polymerizable Double bond and a quaternary nitrogen atom) , but the degree of polymerization is not directly related to the desired anti-static and anti-yellowing properties. Within the range of degree of polymerisation that can be achieved with conventional processes, the compound obtained shows satisfactory properties and can be easily applied to textiles; Poly-ßmethacryloyl-oxyäthyl-diethylmethylammonium-methylsulfat with a viscosity of 2,000-100,000 cP delivers, for example in the form of a 30 # aqueous solution at room temperature good results*

The process by which textiles have anti-static and anti-yellowing properties can be granted according to the invention, can be in the following two main processes organize:

(1) The textiles are treated with an emulsion or a solution containing the compound according to the invention.

(2) The textiles are treated with the cationic and anionic compounds in order to obtain the To form a connection with the anti-static and anti-yellowing properties on the textiles.

9818/0990 ^{BAD OR1GINAL}

In the method (1) the compound of the invention is emulsified or with the antistatic and anti-yellowing properties in water in mixtures of water with organic solvents or in organic solvents ge ^ - solves · used mineral oils, alcohols, polyhydric alcohols, Äthylenglykoläther, polyoxyalkylene polyols, ketones, esters, ethers, dioxane, halogenated hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons or any mixtures of two or more of these substances which are suitable for the production of an antistatic and anti-yellowing agent according to the invention.

As required, emulsifiers, etc. can be added _o -The obtained .Lösung _v or emulsion can be applied to the textiles by means of suitable methods such as brushing, padding, dipping and spraying, such as nonionic surface- 'active agents Textilweiehmacher, optical brighteners, equipment resins ,.

The second method can turn into the following two to be subdivided »

(a) The textiles are first treated with the cationic Compound and then with the anionic compound (or also vice versa) in order to produce the compound according to the invention in situ on the textiles

909818/0990

-> BADORiGlNAL

(b) The textiles are bathed in the cationic Compound immersed and then the anionic compound is added to the bath (or vice versa) to achieve the invention Connection to be made in situ on the textiles

Uach the method 2a, the textiles are first with a solution or emulsion containing the cationic compound, treated for example by dipping, padding or spraying and then treatment is carried out with a solution containing the anionic compound. The antistatic compound according to the invention is produced on the textiles. Just like the first method, different ones can be used Additives can be added to the bath.

The method 2b consists in that the textiles in a bath be immersed with the cationic compound and that with constant stirring of the bath a solution with the anionic Compound is added to the compound according to the invention with the antistatic and anti-yellowing properties to produce on the textiles. This method is characterized in that the textiles contain the active ingredients can absorb in the bath in a more economical manner and that textiles such as knitwear, blankets and threads are granted anti-static and anti-yellowing properties without that they are pressed too hard. As with the aforementioned Process, various additives can be added to the bathroom

909818/0990

U69A70

Even if in processes 2a and 2b the ratio of kafcionic and anionic compound is not very critical, it turns out to be useful, about the equivalent ; Amount or more of anionic compounds to be used ©

In all the processes mentioned, the concentration of the solution is variable within a wide range, but 0.1 to 5 weight solutions are particularly preferred. The treatment temperature is not critical, because no significant difference can be observed with regard to the effect. when the treatment is carried out at high or low temperature. Textiles are usually treated in an aqueous bath at a temperature between room temperature and about 50 ^{0 O.}

The antistatic and anti-yellowing agent of the invention can be used with advantage on textiles such as fibers, threads, yarns, knitting and woven goods etc. are applied which are wholly or partly made of ϊϊν ± αη, polyacrylonitriles, polyesters, polyolefins, Wool etc. are made that can become electrically charged and tend to be adsorbed by repeated washing of the iron traces contained in the water to yellow.

The amount of anti-static and anti-yellowing compound of the The present invention, which is to be deposited on the textiles, is variable within a wide range. In general, 0.1 to 5 levels provide? 6 of the invention

909818/0990

U69470

Compound "based on the textiles satisfactory results.

The antistatic and anti-yellowing agent of the present invention gives textiles good, permanent anti-static properties and much better anti-yellowing properties than conventional ones Means o

The effects of the anti-static and anti-yellowing compounds of the present invention on smooth-woven nylon cloths in Serglei eh. with those of conventional antistatic agents are in the Tables 4, b, 6 and 7 compiled

Table 4

Results of a test in which plain-woven nylon cloths with poly-ß-methacryloyl-oxyethyl-diethylmethyI compounds have been treated with a change in their anionic components »

Antistatic properties (electrical resistance in ohms)

White (reflection in <&)

Anionic parts

Methyl sulfate
Sebum fatty acid
Octyl sulfate

lung immediately after nimbly

3xT (f 3x10 ^ 7x1 0 ¹

after washing 5 times

6x10-6x1 ü ^fc

öx1Ö

after 5 times
Dry cleaning

4x10
5x1 0 ¹

öxio '

,8th

before the

after this

Iron-iron

te st

-ü

test

78, b 7ö, 4 78.1

909818/0990

4th 8th 9 Ootadecenyl
sulfate 5x10 ⁷ 2x10 ⁷ 5x10 ^b 6x10 ⁷ 87.0 77.3 VJI 10 laury! phosphate 2x10 ⁷ 3x10 ⁷ = 6x10 ⁹ 1x10 ^ö 86.4 7ί> .3 6th 11 Poiyaorylate
(Polymerization ₇
degree 3000) 2x10 ' 6x10 ⁷ öx10 ⁸ 2x10 ⁸ 87.0 77.2 7th 12th Nonyisuocinate 3x10 ⁷ 4x10 ^b 3x10 ⁷ 87.0 85.4 13th
Λ Ä Dodecyl succinate 2x10 ⁷ 4x10 ⁸ 4x10 ⁷ 87.0 86.0 Pyromellitate 2x10 ⁷ 5x10 ^ö 4x10 ⁷ 87.0 85.4 Nonyldiphe nyl-
ether disulfonate 3x10 ⁷
Λ _4 «1 1 2x10 ⁸ 3x10 ⁷ 87.0 86.U Di phe nylathe r-
diphosphate. 3x1 O ^ö γ
5x1 υ ob. ^ «5.4 Sorbitol propylene
oxide adduct
phosphate 7x10 ⁸ 3x10 ⁷ 87.0 85.2 Polybutylene
glycol disulfate 7x10 ⁸ 5x10 ⁷
1x10 ¹¹ 87.0
. 87.0 85.3
80.3

Notes:

treatment

Each test piece was eingetauoht in a bathroom with the compound at 40 ⁰ O & I5 aqueous solution, up to 50 # of the recording expressed and dried.

! Pest on anti-static properties

Each test piece was konditioniertβ to 20 ⁰ C and 65 / relative humidity & Then, the electric resistance was measured in 'Ohm between the two sides of the cloth with a Supermegaohmmesser.

9 09818/0990

- · 21 -

1 A69A70

Washing test

Each test piece was washed with a 0.2% aqueous solution of a household synthetic detergent at 40 ⁰ O for 10 minutes at a 50-fold liquor ratio with a Launder-O-meter, rinsed and dried.

Dry cleaning test

Each test piece was washed with a petroleum-based dry cleaning agent at room temperature (25 ⁰ G) for 10 minutes at a tjüfachen liquid ratio with a Launder-O-meter, rinsed with fresh solvent and dried «

iron adsorption steat

A solution of iron (III) hydroxide (pH 7) ppm 240 Bisen was made of iron alum and sodium hydroxide "Each test piece was 60 minutes treated with this solution at 4O ⁰ C at a 100-fold lUüssigkeitsverhältnis, then rinsed with water and dried · The reflection of each test piece in $> before and after the above treatment was measured at a wavelength of 450 μl. measured with the aid of a photoelectric colorimeter in comparison to the reflection of MgO = 100 $.

These values, from which conclusions can be drawn about the white, were compared with one another.

909818/0990

H69470

Table 5

Results of a series of tests in which plain-woven nylon cloths with polyacrylamidopropyl trimethyl ammonium compounds with changing their anionic components. (The treatment procedures and the measurement methods are the same as in Table 4).

Anionic parts Antistatic properties
(electrical resistance
in ohms) after 5ma]
To wash after 5maJ
Dry
cleaning White
(Reflection
in %) after
to the
Bisen
test No. ühlorid immediately
after
Treat
lung 7x10 ⁹ 1x10 ⁹ I.
. before
to the
• iron
test 77.2 1 Sebum fatty acid 5x10 ^ö 6x10 ^b 5x10 ⁷ 87 oO 78.2 2 Octadecenyl
sulfate 3x10 ⁷ 6x10 ⁸ 2x10 ⁷ 87.0 76.4 3 Laurylpho sphat 2x10 ⁷ 6x10 ⁸ 8x10 ⁷ 87.0 76.7 4th Polyacrylate
(Polymerization
degree 3000) 1x10 ⁷ 9x10 ⁸ 2x10 ⁷ 86.9 77.2 VJl Nonyisuocinate 4x10 ⁷ 7x10 ⁸ 5x10 ⁷ 87.0 84.7 6th Dodecenyl
look for it 4x10 ⁷ 4x10 ⁸ 4x10 ⁷ 87.0 86.5 7th Nonyldiphe nyi-
ather-disu-ifonat 3x10 ⁷ 5x10 ⁸ i? x1ü ⁷ 87.0 8> .8 8th Diphenyl ether
disulfonate 2x10 ⁷ 6x10 ⁸ 4x10 ⁷ 86.ö B6.0 9 control 1x10 ⁷ - 1K ₁ O ¹¹ 87.0 BO. 3 10 IXiO ¹¹ 87.0

909818/0990

Table 6

Results of a series of tests in which plain-woven nylon cloths with poly-N-methyl-if-vinyl-pyridinium compounds under Changes in their anionic components were treated. (The treatment procedures and the measurement methods are the same as in Table 4).

Anionic parts Antistatic properties
(electrical resistance
in ohms) after 5 times
To wash after 5 times
Dry
cleaning White
(Reflection
in *) laugh
learn
-Jüisai
test CTr Methyl sulfate immediately
after
Treat
lung 4X1O ¹⁰ 4x10 ⁹ before
to the
iron
test 71.5 1 Sebum acid 8x10 ⁸ 3x1O ⁹ 7x10 ⁸ 86.4 72.1 2 Octadecenyl
sulfate i> x10 ⁸ 4x10 ⁹ 7x10 ⁸ 86.4 70.3 3 jauryiphosphate 5x10 ⁸ 4x10 ⁹ 7x10 ⁹ 86.4 70.8 4th Dodecylbenzene
suifonat 2x10 ⁸ 3x10 ⁹ 6x1 U ^Ö 86.4 70.8 5 Nonyl succinate 4x10 ⁸ 4x10 ⁹ 6 * 10 ^d 86.3 84.5 6th Dodeoenyl
succinate 5x1 ü ^ö 3x10 ⁹ 4x10 ⁸ 86.3 86.0 7th Diphe nyiathe r-
diphosphate 2x10 ⁸ 3x10 ⁹ 5x10 ^ö 86.4 84.4 8th ionyidiphe nyiather-
disulfonate 2x10 ⁸ 4x10 ⁹ 6x10 ⁸ 86.4 83.4 9 control 4x10 ⁸ - 1x10 ¹¹ 86.3 80.3 10 1x10 ¹¹ 87.0

909818/0990

Table 7

.Results of a series of tests in which plain-woven nylon fabrics with copolymers of ß-methacryloyl-oxyethyl-diethylmethylammonium compounds and vinyl acetate were treated while changing their anionic components »(The treatment processes and the measurement methods are the same as in Table 4).

Antistatic properties (electrical resistance

White (reflection

in ohms) immediately
after
Treat
lung after 5ma
Laundry after 5ma!
Dry
cleaning before
to the
Up to
test in %) .. Anionic parts 4x10 ⁹ 3x10 ¹⁰ 6x10 ⁹ 87.3 after
pem
nj-Eisea
test , Methyl sulfate 7x10 ⁸ 5x10 ⁹ 7x10 ⁸ 87.4 [79.4 Sebum fatty acid 6x10 ⁸ 5x10 ⁹ 7x10 ⁸ 87.3 Γ79.6 Octadecenyl
sulfate 3x10 ⁸ 6x10 ⁹ 5x10 ⁸ 87.3 78.2 Lauryl phosphate 7x10 ⁸ 5x10 ⁹ 7x10 ⁸ 87.2 77.6 Dodecylbenzoi-
sulfonate 5x10 ⁸ 7x10 ⁹ 6x10 ⁸ 87.3 I.
79.4 Jonyl succinate 4x10 ⁸ 5x10 ⁹ 5x1O ⁸ 87.3 85.2 Dodecenyl
succinate 6x10 ⁸ 5x10 ⁹ 7x10 ⁸ 87.3 86.8 Dodecyldiphenyl
ether disulfonate 4x10 ⁸ 5x10 ⁹ 6x10 ⁸ 87.3 86 ·· 4 Diphenyl ether- ■
diphosphonate 5x10 ⁹ 7x10 ⁹ 7x10 ^ö 87.2 86.0 Sorbitol propylene
oxide adduct
phosphate 1X10 ¹¹ - 1x1O ¹¹ 87 * 0 85 ο 1 control 80.3

909818/0990

Tables 4 to 7 show that, with the high molecular weight part of the molecule unchanged, there are no significant differences between the cloths treated with the conventional antistatic compounds and the cloths treated with the antistatic and anti-yellowing compounds according to the invention with regard to the antistatic properties and the washing properties. and dry cleaning resistance can be determined. If, however, comparisons are made with regard to the tendency of textiles to yellow due to the adsorption of Bisen, then noticeable differences in the degree of yellowing can be observed. The cloths treated with the compounds according to the invention, for example No. ₀ 7-13 of Table 4, No. 6-9 of Table 5, No. 6-y of Table 6 and No. 6-10 of Table 7 adsorb much less of the im Iron present in water than the cloths treated with the conventional antistatic compounds, e.g. No. 1-6 of Table 4, No. 1 - 5 of Table 5, No. 1 - 5 of Table 6 and No. 1 -5 of Table 7 .

In other words, it was found that the treatment resulted in reduced iron adsorption can be achieved when the high molecular weight part is combined with anionic parts each having more than 4 carbon have atoms and 2 to 10 anionic functional groups, while no such effect is to be expected if anionic parts each have only one anionic functional

909818/0990

len group to be used · Conversely, it is more similar Way not possible to achieve a satisfactory result if the anionic part is an extraordinarily large number Has anionisoher functional groups, such as that in sodium polyacrylate the case is (degree of polymerisation 3000, see No. b in table 4 and No.!? in table 5) ο

Those with the antistatic and anti-yellowing compounds according to the invention treated textiles even show a lower level in comparison with the untreated controls It has a tendency to adsorb iron and is less prone to yellowing.

The following examples are intended to provide a better understanding of the invention. "All parts are parts by weight.

example 1

To 50 parts of a 30 ^ igen aqueous solution of Poiy-ümethacryloyl-oxyäthyl-diethylmethylammonium-Methyisulfat a solution was gradually added with stirring at room temperature, which by mixing ü7.3 parts of disodium nonylsuccinate, 7 parts of polypropylene glycol (molecular weight 300) and 1b , 7 parts of water and heating of the mixture obtained to about 50 ⁰ C had been prepared. A white paste (1) was obtained which easily dispersed in water. Textiles were made at room temperature

909818/0990

U69A70

for 5 to 1U minutes in a 3-6 aqueous emulsion of (I) placed, then squeezed out and dried.

The test results are compiled in Tables 8 and 9 It can be seen from the tables that the textiles treated with (I) have excellent, permanent antistatic properties and have better anti-yellowing properties than the corresponding control and also than those with Samples treated with the usual agent (II), where (II) contains the same components as (I), but nonyl succinate by a common anionic group such as octadecenyl sulfate is replaced "

Table 8

Results of a test for antistatic properties (The aiest method is the same as in Table 4)

plain woven

plain woven polyester o-tree

middle

after
invention

(II):
conventional

control
(without)

Nylon bag Century Polyester cloth 5 times
ge
wa
ting wolle-Iuch 5 times
Gewa
ting immediately
after
Treat
lung 5 max
ge
wa
ting immediately
after
Hand-held
lung immediately
after
Treat
lung -n_ ■ "· 2x10 ⁸ ~ n_ 5x10 ⁷ 2x10 ⁷ 4x10 ⁸ 3x10 ⁷ 7x10 ⁸ 1x10 ⁶ 5x1O ⁷ 3x10 ⁷ 5x10 ⁸ 5x10 ⁷ - 1x10 ⁶ - 1X10 ¹¹ - 1x10 ¹¹ 3x10 ^ö

909818/0990

U69470

Table 9

Results of a test for anti-yellowing properties. (The test procedure is the same as in Table 4.)

.smooth
Nylon u srebtes
h (tf) plain woven
Polyester ^ r-Tuoh (#) after this
Iron-
teet Polyesters
Cotton.
Cloth {%> sr-
-e- middle before the
iron
test naok dem
iron
test before the
iron
test 83.7 before the
Üi se ri
te st after
to the
iron
test (I) I.
well that
invention 87.0 85.4 84.6 75.3 88.3 84.0 (II):
conventional 87.0 77.3 84.6 81.5 88.2 62.4 control
(without) 87.0 80.3 84.5 88.5 77.8

Example 2

A white paste (III), which could easily be dispersed in water, was made according to Example 1 from the following compounds manufactured and used for the treatment of textiles according to the procedure of example 1

aqueous solution of poly-ü-methaoryloyloxyethyl diethylmethyl ammonium methyl sulfate 50 parts

70 ^ ige aqueous solution of monosodium dodecenyl succinate 33 "

liquid hydrocarbon 2-methyl-2,4-pentanediol isopropanol
water

15 μ 6 « 1 ', 5 ¹ V

14.5 "Tables 10 and 11 compare the effects

909818/0990

-29- U69A70

compiled obtained with (III), the corresponding control and the conventional agent (IV), wherein (IV) prepared in the same way as (III), but instead of a common anionic group such as ootyl sulfate of dodecenyl succinate was used.

Table 10

Results of a test for anti-static üiigensohaften _e (The test procedure is the same as in Table 4.)

plain woven 5 times plain woven 5 times plain woven poly 5 times Nylon cloth ge Polyester cloth ge propylene cloth Gewa middle immediately wa immediately wa immediately ting after ting after ting well that Treat . · Ί ■ Treat _n- Treat lung 4x10 ⁸ lung 3x10 ⁸ lung 2x10 ⁸ (III) ι .. .. 8x10 ⁸ 6x10 ⁸ - ^ 3x10 ⁸ after
invention 3x10 ⁷ 2x10 ⁷ 2x10 ⁷ (IV):
conventional 7x10 ⁷ - 4x10 ⁷ - 2x10 ⁷ - control 1 1 11 (without) 1x10 ¹¹ 1x10 ^M. 1x10

Table 11

Results of a test for anti-yellowing properties «, (The test procedure is the same as in Table 4.)

909818/0990

middle

(III): after, the invention

()
conventional

Control (without)

plain woven
Nyiontuoh ($) after this
iron
test plain weave! plain weave
Polyester cloth ipolypropylene
(/) iTuoh (5δ) after the
iron
test before the
iron
test after,
to the
iron
test before the
iron
test 86 · U before the
iron
test 84.1 78.3 76.2 87.0 78.1 84.6 74.5 78.2 ^: 68.1 87.0 80 · 3 84.5 81.5 78.4 I. 72.3 87.0 84.5

Example 3

A white paste (V) that can easily disperse in water left, became according to Example 1 from the following compounds Uyion plain woven cloths were treated according to the procedure of Example 1 with this agent.

30 # aqueous solution of polyacrylamidopropyltrimethylammonium chloride

aqueous solution of disodium butylnaphthalene disulfonet

liquid hydrocarbon 2-methyl-2,4-pentanediol water

SO parts

38.2 "

5 "

5 »

1.8 »

These treated cloths showed satisfactory anti-static properties and better anti-yellowing properties than the control and as the same, with the conventional

909818/0590

U6947Q

Agent (VI) treated. Cloth, where (Vl) the same components as (V) contained butylnaphthalene disulfonate but with a common anionic group such as petroleum sulf onat was replaced »

Example 4

In a 3 # strength aqueous solution of poly-N-methyl- <i- * vinylpyridinium methyl sulfate plain woven nylon duos were immersed at room temperature for 10 minutes, squeezed out and dried. The cloth was then immersed in an aqueous solution of urodium pyromellitate at 40 ° C. for 10 minutes immersed to the anti-static and anti-yellowing compound of the invention on the cloth, then the cloth was rinsed and dried. Compared to the untreated Control and the usual procedure using poly-N-methyl-2-vinyi-pyridinium methyl sulfate and a common anionic compound such as sodium ootadecenyl sulfate instead of sodium pyromellitate treated cloth showed this according to the method according to the invention treated cloth much better anti-yellowing properties

Example 5

If polyester cloths were made by following the procedure of Example 4 using polyacrylamidopropyl butoxymethylmorphoiiniumchxorid and the sodium salt of sorbitol propylene oxide (12 mol) adduct phosphate were treated at

909818/0990

U69470

Similar to the anti-static and anti-yellowing test, good results obtained as in example 4 «

Example 6.

When cloths made of polyester-wool blends according to the procedure of Example 4 using Poly-N-vinyl-N ~ methylimidazolinium methyl sulfate and the sodium salt of χ-sulfonated stearic acid were the results similarly good in the anti-static and anti-yellowing test as in Example 4.

Example 7.

A polyester cloth was made by following the procedure of Example 4

using a polymer of 70 wt. _o ? £ ß-Methacryloyl oxyäthyl-diethylmethylammonium-Methylsulfat and 30 wt.

Example 8 *

A cloth of a cotton Poiyester mixture was prepared according to the procedure of Example 4 using a copolymer of 75 wt. ^ N-methyl-2-methyl-5-vinyl-pyridinium bromide and 25 wt. F> acrylamide and disodium butyinaphthalin -disulf'onate treated. The anti-static and anti-yellowing properties of the cloth were significantly improved.

909818/0990

H69470

Example 9

A polypropylene cloth was made following the procedure of the example

4 using poly-ß-vinyloxyethyl diethylmethylammonium methyl sulfate and disodium dodecyl succinate ". The anti-static and anti-yellowing properties of the Tuches were vastly improved

Example 10

5 parts of a 30 $ aqueous solution of poly-ß-methacryloyioxyäthyl diethylmethylammonium methyl sulfate and 5 parts of a cationic plasticizer (Safanol NTQ, manufactured from Sanyo Chemical Industry Company, Kyoto, Japan) were dissolved in and into water to 2000 parts Solution, 100 parts each of the various knitted fabrics made of synthetic fibers were immersed at 40.degree. Then 500 parts of a 1.5% aqueous solution of Disodium dodeceny succinate gradually added to the bath » After the addition of the disodium dodecenyl suocinate, the knitwear was left to stand for 30 minutes, rinsed and dried.

The test results are summarized in Tables 12 and 13 * It can be seen from the tables that the knitwear treated in this way (A) is good and is washable Antistatic properties, a satisfactory, soft handle and better anti-yellowing properties.

90 98 18/0 9 90 ^{8AD 0RfG} 'NAL

indicate as the control goods, a ± s those using the anionic compound of a known type such as sodium octyl sulfate instead of disodium dodecenyl succinate (B) Goods and those with an I ^ igen aqueous solution of Poiy-öme thacryloyl-oxyethyl-diethylmethylammonium-methylsulfate (C) treated goods alone.

Table 12

Results of a test on anti-static properties _e (The test procedure is the same as in Table 4. < »)

Treatment
procedure polyester 5 times
ge
wa
ting ? olyester-
PolyacrylnitriJ
(75/25) 5 times
ge
wa
ting Polyacrylic
nitrile 5 times
ge
to wash after
invention
(A) immediately
after
Treat
lung 6x1 ü ^ö immediately
after
Treat
lung 1x10 ⁸ immediately
after
Treat
lung 5x10 ⁸ according to the usual
chen procedure
under use
by sodium octj
sulfate
(B) -TU
4x10 ⁷ 8x10 ⁸ 3x10 ⁷ 9x10 ^{1 above} bxiO ⁷ 2x10 ⁹ according to the usual
chen procedure
without anionic «
link
(C) G
1x10 ⁸ 1x10 ⁹ 1x10 ⁸ 2x1O ⁹ 1x10 ⁸ 2x10 ⁹ control 2x10 ⁸ - 3x10 ⁸ - 2x10 ⁸ - 3x1 over ¹⁰ 2x10 ¹⁰ . 2xlO ^1ü

909818/0990

Table 13

Results of a test for anti-yellowing properties. (The test procedure is the same as in Table 4.)

.Treatment"
procedure Polyester bottom]
_ W Po j
Γ after this
iron
gest Lyester
Lyacryln:
5/25) j Polyacrylonitrile
Ltril (#)
#) before the
jsisen-
test after this
iron
test after
invention
(A) before the
Kisen-
test ö7.ü before the
jfiisen-
tes' well that
JKi sen-
test 79c4 77.7 after the üt
xich ver
drive below
use
of sodium
ethyl sulfate
(B) 87.3 75.6 84 * 1 82.4 79.3 68.4 after the üt
.Lend Ver
drive without
anionic
link
(C) -
t
r
Ö7.3
L- 7.5 84c 1 75.2 79 · 3 68.8 control 87.3 * .3 84.2 76.3 79.4 71.6 ö7.4 84.3 78.5

Example 11 '

5 parts of a 3ü ^ igen aqueous solution of poly-u-methacryioyl-oxyethyl-diethylmethyiammonium-methyl sulfate were dissolved in water to 2000 parts, then 100 parts of a polyester cloth were placed at 40 ⁰ C in this bath. While stirring the solution, 300 parts of a 2% strength aqueous solution of disodium dodecyl sulfosuccinate were then gradually added. After adding the disodium dodecyl sulfosuccinate 909818/0990

the cloth was left standing for 30 minutes, rinsed and dried.

t _t

The cloth treated as above showed much better anti-divergence. yellowing properties than the control, than that with a anionic compound of a known type such as sodium lauryl suirate instead of disodium dodecyl sulfosuccinate treated cloth and as that with a 15% solution of poly-Io-methacryioyloxyethyl-dietymethylammonium-methyl sulfate cloth treated alone at room temperature. It also had good antistatic properties.

909818/0990

Claims (1)

Expectations 1. Procedure for protecting textiles from static electricity and yellowing, by treatment with anionic compounds, characterized in that one essentially water-insoluble compound of a high molecular weight part with a number, quaternary Nitrogen atoms and anionic parts each with more than 4 carbon atoms and 2 to 1ü anionic funk- ' partial groups is used « Process according to Claim 1, characterized by the use of compounds having a portion of high molecular weight with a number of radicals from the group of radicals with the following general formula (I) or (II), where R ₂ and R _{3 are} alkyl radicals with 1 to 12 carbon atoms, alkylene radicals with 3 to 12 carbon atoms, hydroxyalkyl radicals with 2 to 12 carbon atoms or alkoxyalkyl radicals with 2 to 12 carbon atoms also form a single group consisting of a heterocyclic ring with 5 to 6 ring members which contains a nitrogen atom and also contain a second heteroatom such as 0, N or S as a ring member and alkyl 909818/0990 can carry side chains with 1 to 6 carbon atoms and where R. is an alkyl radical with 1 to 18 carbon atoms, an alkenyl radical of 3 to 18 carbon atoms A hydroxyalkyl radical having 2 to 18 carbon atoms, an alkoxyalkyl radical having 2 to 18 carbon atoms Aralkyl radical with 7 to 20 carbon atoms, a phenoxyalky! Radical with 7 Ms 20 carbon atoms or is an epoxyalkyl radical having 3 to 18 carbon atoms, (II) where R ₁ - and Rg are hydrogen atoms or alkyl radicals 1 to 6 carbon atoms, m and η integers from 1 to 2 and R. has the meaning given above in general formula (I) ₀ 3. The method according to claim 1 or 2, characterized by the use of compounds with a part of high molecular weight, which _{consists of at least 20 wt o} $ of radicals of the following general formula, RO R ₉ - - do - R ₁ - N- R ₃ (III) ■ 2-? where R is hydrogen or an alkyl radical with 1 to 2 Carbon atoms, R- an alkylene radical with 2 to 4 9 0 9 818/0990 ¹ BATHROOM ORiQfNAL U69A70 Carbon atoms, R ₂ and R, alkyl radicals with 1 "to 4 carbon atoms. Or hydroxyalkyl radicals with 2 to 4 carbon atoms and R. are an alkyl radical with 1 to carbon atoms, an alkenyl radical with 3 to 4 carbon atoms, a hydroxyalkyl radical with 2 to 4 carbon atoms Alkoxyalkyl radical having 2 to 5 carbon atoms, an aralkyl radical having 7 to 8 carbon atoms or an epoxyalkyl radical having 3 to 8 carbon atoms. 4. The method according to claim 2 or 3 »characterized by the use of compounds with anionisohen parts of the molecule of 2 to 10 anionic functional groups such as -COO, -SO ₅ , -OSO ,, -OPO ₃ M, = 0 ₂ P0 ₂ , -OPO ,, -PO, or -ΡΟ, Μ, where M is a hydrogen atom, a metal atom, an ammonium radical or an organically substituted ammonium radical. 5. The method according to claim 1, 2, 3 or 4, characterized by the use of compounds with anionic parts, those of alkylsuccinic acid residues with 9 to 18 carbon atoms in the alkyl radical, alkenylsuccinic acid residues with 9 to 18 carbon atoms in the alkenyl radical, alkyl diphenyl ether disulfonic acid residues with 3 to 18 carbon atoms in the alkyl radical, alkylnaphthalene disulfonic acid residues with 3 to 6 carbon atoms in the alkyl radical, 909818/0990 U69470 Polyalkylnaphthalene disulfonic acid residues with 3 to 6 Carbon atoms in the alkyl radical or alkyl sulfosuccinic acid residues with 8 to 18 carbon atoms in the alkyl radical. 9818/09 90