DE2236273A1 - AMPHOTIC TOOLS FOR THE FINISHING OF NATURAL OR SYNTHETIC FIBERS CONTAINING TEXTILES, LEATHER OR PAPER - Google Patents

Description

D ₁ . P. '//..!..!.oL ", Lr. D. Gudd
6 Frankfurt / M., Gr. Eschenheimer Sir. 32

SANDOZ Α.β. Case 150-3308

ΟΗ-4002 Basel / Switzerland Ι ?? "ί« ϊΓ <972 ■ -

Amphoteric auxiliaries for the finishing of textiles, leather or paper containing natural or synthetic fibers

The present invention describes new amphoteric compounds, The particularly valuable auxiliaries are for the refinement of natural or synthetic fibers containing Textiles, leather or paper. These compounds are particularly suitable for use in a wide pH range. she have a high substantivity to natural and synthetic textile materials, as well as leather and paper these very good plasticizing and antistatic properties

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shafts and increase their absorbency. Also own the compounds also have a bactericidal effect, reduce the dry soiling of synthetic fiber materials, such as Polyamide carpets, so that they are antistatic, dirt-repellent and bactericidal in one step with the new compounds can be equipped.

The present invention relates in particular to the use of compounds of the formula

¹ 1 ' ^a eß (i)

RIX (CH JI N (CH ₀ ) H N-

L 2 nja J_ ^v 2'n m

or their quaternized derivatives

wherein R is an optionally substituted hydrocarbon radical with 5 to 22 carbon atoms

R and R _? each independently hydrogen

or an optionally substituted low molecular weight Alkyl radical,

where at least one of the substituents R ₁ or R _{2 is} a hydroxyalkyl or carboxyalkyl radical with 1-4 carbon atoms or a radical of the formula -CH ₂ SO- ^ η -CH ₂ CH ₂ -CN, -CH ₂ CH ₂ CONH ₂ , {CH ₂ -CH ₂ -0) _p H or (CH ₃ ) O) H, where ρ is 1 to 10

X -CONH-, -COO, -0-, or -S-

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^: '"""' ■ '■■ 2238273

η 1 to 8

m Zero or an integer from 1 to 6 a zero or 1,

M each hydrogen or ammonium or a charge "

equivalent of a metal ion "mean * as an aid., for finishing textiles, leather or paper containing natural or synthetic fibers _.;

The invention also relates to amphoteric compounds of Formula (i) and their quaternized derivatives »The invention further relates to a process for the preparation of compounds of the formula (i) by adding compounds of the formula ·. ·

I I-A * IU. · - Ü

-NH m

where R, R_, R, X, a, η and m have the above meaning with formaldehyde and a bisulfite of the general formula M (HSO ₁ ,) where M has the above meaning, sulfomethylated, optionally the hydrogen atoms still bonded to the nitrogen in converts other substituents R and optionally quaternized the compounds obtained. The quaternizing agent used is preferably a low molecular weight alkyl halogen or alkenyl halogen compound or dialkyl sulfuric acid ester. Another object of the invention are the refined textiles containing natural or synthetic fibers, and the refined leather or

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Papers. Finishing is primarily understood to mean softening, antistatic, bactericidal and dirt-repellent Equip. Textiles containing natural or synthetic fibers include, for example, those which are wholly or partially made of natural cellulose fibers such as cotton, animal fibers such as full or Silk as well as regenerated cellulose fibers exist. In addition, those fall under it, the whole or partly consist of polymerization, polyaddition or polycondensation compounds. To the polymers are for example polyethylene and polyisobutylene as well as polyvinyl bonds such as polyvinyl acetate, To include polyvinyl alcohol, polyvinyl ether, or polyacrylic polymers such as polyacrylonitrile. To the Polyaddition compounds include, for example, the polyurethanes and, in addition to the polycondensates, the polyamides. As an optionally substituted, hydrocarbon radical R is preferably a linear or branched or alicyclic hydrocarbon radical with 5 to 22 carbon atoms are used. These preferably include alkyl radicals such as pentyl, hexyl, heptyl, octyl, nonyl, Decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, Nonadecyl, eicosyl, or docosyl. Alkenyl radicals include, for example, tetradecenyl, Hexadecenyl or octadecenyl. Examples of aryl or aralkyl radicals that fall under R are phenyl, pheny] - ■ methyl, phenylethyl, pheny] propyl, phony] butyl etc.

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and the radicals derived therefrom and substituted on the aromatic nucleus by hydroxyl or cyanide groups. Possible FL or Rp, independently of one another, are in each case hydrogen or an optionally substituted, low molecular weight alkyl radical. Alkyl radicals with 1 to 4 carbon atoms are preferably used, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, hydroxyethyl, hydroxypropyl, carboxymethyl, carboxyethyl, carboxypropyl, or a radical of the formula -CH ₂ SO®M®, -CH ₂ CH ₂ CN, -CHgCHgCONHg, {GHg-CH ₂ -O) H or - (CH ₂ -CH (CH) -0) H, where ρ is 1 to 10, preferably a radical of the formula

M in each case represents hydrogen or ammonium or Charge equivalent of a metal ion, with alkali and earth al kai hones such as sodium, potassium, magnesium, Calcium and barium ions come into question and the ammonium group itself or the ammonium group from ethanolamine, diethanolamine and triethanolamine dissipating ammonium groups.

As quaternizing agents, optionally substituted, low molecular weight alkyl or alkenyl halides, preferably with 1 to 12 carbon atoms, can be used. Particularly suitable are, for example, the halides of methyl, ethyl, propyl, chloromethyl, 2-chloroethyl, 2-hydroxyethyl, Benzyl or benzyl substituted with halogen or cyanide.

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X stands for the groups- CONFI-, -COO-, - 0- or -S-, preferably for -CONH-. η is 1 to 8, preferably 2 or jj. m is 0 or an integer from 1 to 6, preferably 0 or an integer 1 to 4.

It is also possible to produce the suIfoäthylderivat by using acetaldehyde instead of formaldehyde. Compounds of the formula (II) are, for example, compounds of the formula RNH ₉ *, preferably fatty amines, condensation products of a fatty amine with a polyalkylene polyamine or condensation products of a compound RCOOH, preferably a fatty acid with polyalkylene polyamine. Instead of the fatty acids, their enteric, anhydrides or acid chlorides can also be used. The compound (II) are employed with formaldehyde and bisulfite at 10-110 ⁰ C, vorzugsv / else at 60-95 ° C to. The hydrogen atoms that can be replaced on the basic nitrogen atom are partially or completely substituted by the methylsulfonic acid groups. Unless all of the hydrogen atoms bonded to the basic nitrogen are substituted by sulfonomethyl groups, before or after the sulfomethylation there is also an alkylation with, for example, alkyl halides or a

Addition of acrylamide, acrylonitrile, ethylene oxide or propylene oxide possible. The sulfomethylation product, corresponding to formula (I), can then be quaternized, e.g.

with alkyl halides such as methyl iodide, methyl chloride, 2-chloroethanol, Benzyl chloride or dialkyl sulfuric acid esters, e.g.

Dimethyl sulfate.

The novel compounds according to the invention are in one wide pH range of about 2 to 12, preferably 4 to 11

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applied. The combinability of the compounds according to the invention is also advantageous Compounds with anionic detergents, for example alkylarylsulfonates, and textile auxiliaries anionic nature, such as plasticizers or optical brighteners. So can plasticizer preparations with a certain amount of Anionic optical brighteners are produced which are added to the detergent or the final rinse bath after washing without the brightening effect being impaired by the presence of the compounds according to the invention. Except in the fields mentioned, the compounds according to the invention can also as a dyeing aid or as a fatliquoring agent in of leather and as plasticizers and antistatic agents in paper and industry.

They are used in the manner customary for textile finishes, such as by dipping, pulling out and spraying, the Products from their aqueous solutions or from organic ones

Solvents can be applied. For example, the textile material is treated with the aqueous solutions of the compound in concentrations of 0.05 to 3 % based on the fiber material from a long liquor or 0.1 to 60 g per liter from a short liquor (on a padder), preferably in the pH range from about 4 to 11 is being worked on. After being spun off or squeezed off, the treated material is then normally dried at JO up to 140 ° C.

The following examples are intended to explain the invention better but without limiting it. The parts mentioned in the examples are parts by weight, the percentages are percentages by weight and the degrees Celsius degrees. · '· ■ · ._.

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At. game 1

510 parts of stearic acid are put together in a suIfier flask heated to l6o ° with 292 parts of triethylenetetramine until 37 parts of water have distilled off and the condensation product is a Has reached an acid number of 2.7.

At 90 °, for the time being, parts of the product thus obtained are added to 97 parts of 37 # formaldehyde solution and after 30 minutes 312 parts 40/1 aqueous sodium bisulfite solution was added dropwise and that The reaction mixture is then kept at 89-90 ° for a further 4 hours with stirring. The result is a slightly yellowish-brown color Paste that is dispersible in water with a weakly alkaline reaction and has very good softening and antistatic properties having.

Example2

V in a SuIfierkolben / ground 224 parts of lauric acid I3O heated ⁰ 131 parts of dipropylene added dropwise to the melt and. The reaction mixture is then heated to 190 ° under nitrogen and left at this temperature until 20 parts of v / water have distilled off. The excess amine is then evaporated with evacuation to 40 mm Hg and the pale yellowish condensation product is allowed to cool to 82 °.

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Then 2 ^ 3 parts of yj ^ olQe aqueous formaldehyde solution and 780 parts of 40 ^ ige aqueous sodium disulfite solution are allowed to flow in and the mixture is allowed to react for a further 2 1/2 hours at 80 °. After cooling to room temperature, the product is obtained as a pale yellowish thick paste which is finely dispersible in water.

Applied to cotton using the exhaust process, the product gives a very soft and pleasant feel while on Nylon and polyester fiber material applied also greatly reduces the tendency to static charging and dry soiling is reduced. With simultaneous application of the product, together with an anionic optical brightener, its lightening effect is not impaired in any way by the plasticizer product.

Similar effects are obtained with products that are quaternized of 27I parts of the above sulfomethylation product with 50 parts of dimethyl sulfate or 25 parts of benzyl chloride were manufactured.

Example3

According to the information in Example 2, II7 parts of a 1? A. Parts of Oe.l acid and ¹ Il part of diethylenetrianiine available condensation product with

BAD ORlGhMAL 209886/1370 '-τ-—'

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Parts 5? 'Of formaldehyde solution and 2 ^ 4 parts of 40% sodium bisulf it solution brought to reaction. 424 parts of a yellow paste are obtained, which can be finely distributed in water.

The fabrics finished with this product stand out particularly due to good rewettability and strong reduction of static charge.

Similar effects are obtained with a product, for the production of which instead of the 117 parts of the mentioned in Example 5 condensation obtainable from oleic acid and diethylenetriamine product 67 parts of one from 42.6 parts of caprylic acid and 30.9 Parts of diethylenetriamine produced urasetzungproducts used and the rest of the procedure is the same as described in Example 3. The product presents a clear, yellowish color Liquid has a practically neutral reaction.

Example 4

I08 parts of techn. Stearic acid melted at 90 ° and then mixed with 52.4 parts of dipropylenetriamine. The reaction mixture is then under Abdostillieren of the water formed during the condensation at 185 - ⁰ I9O heated, v / obei Atnin the excess is removed at the end of the reaction by evacuation.

BAD ORIGfNAL

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The amidation product obtained in this way is calcined to 86-90 ° and by adding 97 parts of aqueous formaldehyde solution and 512 parts of 40% aqueous sodium bisulfite solution sulphonated. The product is obtained as a thick, pale yellowish paste which can be finely distributed in water. That The product can be used together with anionic detergents and optical brighteners without impairing the degree of whiteness and in addition to a good plasticizing effect, it also has a very good antistatic effect. The one equipped with this product Synthetic fiber material, such as polyamide, is also significantly less prone to staining than a non- ' armored pattern. The product is also suitable for the simultaneous dyeing and finishing of textile material with anionic ™ or cationic dyes.

Similar results are obtained when instead of the above described condensation product of 108 parts of stearic acid and 52.4 parts of dipropylenetriamine a thermal Condensation product from Il8.8 parts of techn. Stearic acid and 41.2 parts of diethylenetriamine or such from 14o parts Behenic acid and 4l, 2 parts of diethylenetriamine are used and the rest of the procedure is the same as described above.

Example '

8o parts of lauric acid and 52.4 parts are put in a sulphonation flask

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Parts of dipropylenetriamine are thermally condensed at 190 ° and the condensation product obtained is reacted at 80 ° with 64.8 parts of 1% formula dehyde solution and 208 parts of 40% stored bisulfite solution. A pale yellowish soft paste is obtained which forms fine dispersions in water and is particularly suitable for the antistatic treatment of synthetic fiber material. The product also has a dirt-releasing effect and can be used as a wash bath detergent. Similar results are also obtained when the abovementioned condensation product of lauric acid and dipropylenetriamine is initially reacted with 2.5.2 parts of propylene oxide at 82-84 ° and the procedure is otherwise the same as described above.

Example 6

126 parts of behenylaminopropylamine are placed in a reaction vessel Melted at 78 ° and melted 73 parts of 37% formaldehyde solution and 2j4 parts of 40% sodium bisulfite solution were added dropwise. After a reaction time of about three hours at 80 °, a soft paste is obtained after cooling to room temperature, which with Dilutes water, forms opalescent solutions. The product is also suitable in the presence of anionic dyes and textile auxiliaries excellent for finishing textile fibers.

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Products and their manufacture have similar properties • Instead of 126 parts of behenylaminopropylamine, 111 parts of stearylaminopropylamine are used and the rest of the procedure is the same as described above.

Example?

Parts of what is available according to the above example, paragraph 1 The condensation product is quaternized at 60 ° with 30.8 parts of diethyl sulfate in the presence of sodium hydroxide solution at pH 7-8. The product is obtained in the form of a slightly yellowish, soft paste which can be finely distributed in water. On fiber material when applied, a pronounced antistatic effect is achieved in addition to a good softening effect.

Examples

I39 parts of the according to Example 6 from stearylaminopropylamine and Formaldohyd / bisulfite available condensation product are at 92 ° for 5 hours with 22 parts of monochlorohydrin in Presence of sodium hydroxide alkylated at pH between 7-8. A viscous, yellowish product is obtained which is in V / ater is finely distributed and can be combined with ahionic Textile auxiliaries are very good for the finishing of textile material suitable.

¹ ■ BATHROOM

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A product with similar properties is obtained if, instead of 22 parts of monochlorohydrin, 11.7 parts of monochloroacetic acid - Sodium salt used for alkylation v / ground.

Example"?

70.5 parts of the technical according to Example 4 from 108 parts. Stearic acid and 52.4 parts dipropylene condensation product produced are alkylated at I30 ⁰ for 4 1/2 hours with 46.5 parts Mono chloroacetic acid sodium salt, and then at 90 ° with 37 parts l6,2; & strength, aqueous formaldehyde solution and 52 parts of sodium 4o ^ aqueous sodium bisulfite solution condensed. The sulfomethylation product is obtained as a yellowish, thick paste that can be finely dispersed in water and is particularly suitable for the antistatic, dirt-repellent and antibacterial finishing of fiber material. A product with similar properties is obtained if 5 parts of monochloropropionic acid are used for the alkylation instead of monochloroacetic acid, the alkylation being carried out at 95-100 ° in the presence of sodium hydroxide and otherwise the same procedure as described above.

BATH

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Example. 10

Nylon fabric is treated on the padder at 20 ° with an aqueous dispersion of a product prepared according to Example 2 or 8, so that after squeezing off and drying, a fabric coverage of 0.2 # results. After conditioning (20 ⁰ C, 65 # rd. Humidity, 24h) of the treated fabrics antistatic effect by means of a static voltmeter wurde'dle determined. The measured half-life of the voltage drop from 100 to 50 volts was less than 0.2 seconds. Compared to goods that have not been treated for more than 3 minutes. The finish also has antimicrobial properties.

Example 11

One by washing several times with a commercially available heavy-duty detergent rough and brittle cotton terry fabric wire with a liquor which is 2 g / l of that available according to Example 3 or 4 Contains products, 5 minutes in a drum washing machine flushed. Then it is spun and dried. The fabric treated in this way is characterized by its softness and smoothness as well as very good absorbency.

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Example 12

Cotton-terry cloth fabric is changed at a liquor ratio of 1:30 in a bath which, based on the fabric, contains 0.1% of the active substance of the product shown in Example 1, for 20 minutes at h & ° . Then it is spun and dried at 110 °. The fabric treated in this way has a soft feel and very good absorbency.

Example 13

Cotton poplin is treated with an aqueous bath on the foulard, the 10 g per liter of the product prepared according to Example 9 and 1 g of a commercially available anionic optical Contains brighteners. The goods treated in this way are characterized by a soft, pleasant feel and the The degree of whiteness is just as good as with treatment only with the optical brightener.

Example 14

Nylon carpet material is treated with a bath on a padder, so that a fabric covering of 0.4 % of the product produced according to Example 6 results. Through this treatment becomes

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The dry soiling of the carpet, which was determined by the dust test using vacuum cleaner dirt, is greatly reduced.

20988B / 1370

Main products of the singly e n with S plele,

1. General formula

• H

N-CHgSO ^ M

Case 150-3308

Examples R. ^R l R ₂ a η m M. 1 C ₁₇ H ₃₅ CHgSO Na CH ₂ SO ₃ Na 1 2 2 N / A 2 ^C 11 ^H 23 CH _o S0., Na
2 3 CHgSO Na 1 3 1 N / A 3 CH
17 23
° 7 ^H 15 do
do do
do 1
1 2
2 1
1 N / A
N / A 4th ^C 17 ^H i5
^C 17 ^H ? 5
^C 21 ^H 43 do
do
do do
do
do 1
1
1 3
2
2 1
1
1 N / A
N / A
N / A 5 ^C 11 ^H 23
^C 11 ^H 2J CHgSO Na
CIIgSO Na H
CH ₂ CHCHj 1
1 KN KN 1
1 N / A
N / A 6th ^c l8 ^H 57 CHgSO Na
CHgSO Na cd cd
2 2
KN KN
O O
CQ CO
OJ CU
K K 0
0 3
3 1 N / A
N / A 9 ^C 17 ^H 35
C ₁₇ Hj ₅ CHgCOONa
CHgCHgCOONa CHgCOONa
CHgCHgCOONa 1
1 KN KN 1
1 N / A
N / A 2 Product from Example 2, quaternized with dimethyl
sulfate or benzyl chloride. 7th Product from Example 6, quaternized with diethyl
sulfate. 8th Product from Example 6, quaternized with monochlorine
hydrin or monochloroacetic acid.

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Claims (1)

Claims or their quaternized derivatives wherein R is an optionally substituted hydrocarbon radical having 5 to 22 carbon atoms R and Rp each independently of one another are hydrogen or an optionally substituted low molecular weight alkyl radical, where at least one of the substituents R or Rp is a hydroxyalkyl or carboxyalkyl radical with 1-4 carbon atoms or a radical of the formula -CHpSO-Mtf ^, -CH ₂ CH ₂ -CN, -CH ₂ CH ₂ CONH ₂ , - (CHg -CHg-O) H or - (CH ₂ -CH (CH ^) O) H, where ρ 1 to 10 X -CONH -, - -COO, -0-, or -S-
η 1 to 8 m zero or an integer, number from 1 to 6 a zero or 1, M each represent hydrogen or ammonium or a charge equivalent of a metal ion, as auxiliary tel for the finishing of textiles, leather or paper containing natural or synthetic fibers. 209886/1370 - 20 - Case 150-3308 . Process for the preparation of compounds of the formula (I), characterized in that one compounds of the formula Al (CH, N - (CH ₀ ) - where R, R, R ₂ , X, a, η and m have the meaning according to claim 1, with formaldehyde and a bisulfite of the general formula M (HSO.) where M has the meaning according to claim I, sulfomethylated, optionally the hydrogen atoms still bonded to the nitrogen are converted into other substituents R 1 and the compounds obtained are optionally quaternized. J> · Ve! 'Go to Patent No. 2, characterized in that quaternizing is carried out with a compound of the formula R ^ -HaI, in which R _{7 is} an optionally substituted, low molecular weight alkyl or alkenyl radical and Hal' is halogen, or with dialkylsulfuric acid esters. H. Amphoteric compounds of the formula ⁿ L ^{x (011} E -N- (CH ₂ ) ^ rN-CH ₀ SO, ^ tP (I) and their quaternized derivatives wherein R, R, R, X, n, m, a and M have the meaning according to the patent claim 1 have. 209886/137 0 - 21 - Case 150-3508 5. Compounds according to claim 4, wherein. R is a linear or branched, saturated 'or unsaturated alkyl radical having 5 to 22 carbon atoms or a, ge ~ ^v optionally substituted benzyl radical, R are each independently hydrogen or a methyl, 1- Aethy, propyl, isopropyl or Butyl radical, a hydroxyalkyl or carboxyalkyl radical with 1-4 carbon atoms or a radical of the formula -CH _? SO ^> P, -CHp ₂ -CH ₀ Ch ₀ CONH ₀₁ - (CH ₀ -CH ₀ -O) H or - (CH ₀ -CH (CHjO) H, wherein • cL ei d. ' c. ei p d. _? P ρ 1 to 10, Hydroxyalkyl or carboxyalkyl radical with 1-4 carbon atoms or a radical of the formula -CHgSO, ® IXP, -CHgCHg-CN, -CHpCHpCONHp, - (CH-CHp-O) H or - (CHp-CH (CH.JO) H, wherein ρ 1 to 10, η 2 or 5
'm zero or 1 to 4 X -CONH- mean. 6. Compounds according to claim 5, wherein RV / hydrogen, methyl or -CHpSO-, Μ and R ₂ -CH ₂ SO ₇ M mean. 7 · Use of compounds of the formula (T) or their quaternized derivatives according to claim 1, characterized in that R, R ,, R ₀ , η, m and X have the meaning according to 1 d 2 0 9 8 8 6/1370 - 22 - Case 150-3308 Claim 5. 8. Use according to claim 7, characterized in that R, R .. j R ₀ , η, m and X have the meaning according to claim 6. 9. The method according to claim 2, characterized in that that one uses a compound M (HSO-,) where M is hydrogen, an alkali or alkaline earth metal ion. 10. Use of compounds of the formula (I) or their quaternized Derivatives according to claim 1 for softening, for antistatic, bactericidal or dirt-repellent finishing. 11. The treated according to claim 1, natural. or synthetic Textiles, leather or paper containing fibers The patent attorney 2Ü9886 / 1 37Ü