FI56372C - KATJONISK YTAKTIV FOERENING SOM REDUCERAS MATERIALS FOERMAOGA TILL ELEKTROSTATISK UPPLADDNING OCH / ELLER FOERBAETTRAR DERAS MJUKHET - Google Patents

Description

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Vflä W ^ un-ÄGONiiessKRiPT 56372 C (45) Patent granted 10 01 1980 Patent meddelat V 'V (51) Kv.lk. * / Lnt.CI. * c 07 C 93/04 § q | y | | p | | q ^ q (21) Pitenttlhtkamu * - Rttanuntekning 321 + 2/72 (22) HakamltpUvI - AraOknlnpdtg 17.11.72 (23) Alkupiiv! - Glltlghätsdag 17.11.72 (41) Tullut | ulklsaktl - Bllvlt offantllf 20.05.73

Patent * and National Board of Registration (44) Nihtivlkilptnon ja kuL | ulkil * un pvm. -

Patent · och registrstyrelsen 'Anaökan utltjd och utl.ikrtftan publlcerad 28.09.79 (32) (33) (31) Pyy4 «« y atuolkaui — Begird prlorltat 19. H. 71 11.10.72 Sweden-Sweden (SE) 1U793 / 71, 13069/72 Proof-Styrkt (71) MoDoKemi AB, Fack, S — UUU 01 Stenungsund, Sweden-Sverige (SE) (72) Eva Margareta Martinsson, Stenungsund, Karl Martin Edvin Hellsten, Ödsmäl, Sweden-Sverige (SE) (7) ^) Oy Kolster At (51 *) A cationic surfactant that reduces the tendency of substances to electrostatically charge and / or improve their softness -

The present invention relates to a cationic surfactant which reduces the tendency of substances to charge electrostatically and / or improves their softness, and which has the general formula RI-O- (CH 2 CHXO) n -CH 2 -CH (OH) CH 2 .R111 and R 11 -O- (CH 2 CHX O) n -CH 2 -CH (OH) CH 2 R 17 wherein R 1 and R 2 independently represent an aliphatic group having 8 to 22 carbon atoms, R 1 and R 2 independently represent methyl or an ethyl group, X represents hydrogen or a methyl or ethyl group, the average value of the numbers n1 and n2 is 0-5, and A is an anion.

In the past, treatment of a textile material with quaternary compounds of the type (R ") 2 (R ') 2N + C1, where R' is a methyl or ethyl group and R" is a cetyl or stearyl group, has attempted to give the textile material a softer feel and reduce the ability of this material to charge with static electricity. A significant disadvantage of these types of compounds is that, due to their hydrophobic nature, they severely impair the water absorption capacity of the textile material. The compounds in question are prepared by quaternizing, for example, distearylamine with methyl chloride or dimethyl sulfate. Distearylamine is obtained by heating in the presence of ammonia the corresponding fatty acid which, through its ammonium salt and amide compound, forms stearonitrile, which is converted to stearylamine by hydrogenation. This method of preparation has proven to be both cumbersome and expensive and results in relatively poor yields.

It has now surprisingly been shown that a new class of cationic quaternary compounds provides a very good emollient and antistatic effect at the same time as these new compounds are very simple and inexpensive to prepare. Furthermore, a textile material treated with these compounds has significantly better water-absorbing properties than those treated with the previously disclosed quaternary alkyl compounds.

Extensive studies of the effect of these compounds using various textile materials have shown that the compounds of the invention have clearly better antistatic properties throughout than the quaternary compounds used previously. It is very notable in this case that the presence of a glyceryl group and small amounts of alkylene glycol units, in particular ethylene glycol units, considerably improves the antistatic values in these compounds. As for the emollient properties of these compounds, they are also affected by the number of alkylene glycol units present in the compound, and it has been found that compounds in which n 1 and n 2 values are 0-2 have the best properties. In view of the above, we prefer those compounds of the above formula wherein X is hydrogen and n 1 and n 2 are on average 0-2. Highly preferred compounds of the invention are those in which R * and are independently a hydrocarbon chain having 8 to 10 carbon atoms, since they are freeze-thaw-resistant in aqueous solutions of 5 to 10, i.e. they have no or only a slight tendency to gel formation and phase separation upon repeated freezing and thawing. Furthermore, they are flowable in a concentrated form which facilitates the manufacture of consumer products.

One notable advantage of these new cationic compounds is that they are easy to prepare on an industrial scale. Thus, they can be obtained by reacting an alcohol having 8 to 22 carbon atoms, optionally attached with 0.5 moles of ethylene, propylene or butylene oxide in a manner known per se, with epichlorohydrin to give the corresponding chlorine glycerol ether, which in turn, is reacted with a secondary amine of the general formula in which R and R 1 independently represent a methyl or ethyl group to form a quaternary compound in the form of its chloride salt. If deemed suitable, this anion can be exchanged for other anions in a manner known per se, e.g. by adding a sodium salt having a higher dissolution constant than with sodium chloride or by using ion exchange with an anion exchanger. As the anions - in addition to chloride ions, mention may be made of hydroxyl, bromide, methyl sulphate, acetate, sulphate, carbonate, citrate and tartrate ions, of which monovalent ions are most preferred.

The preparation method described herein can be combined into the following two reaction steps.

1) R (CH 2 CHXO) H + CH 2 -CHO 10 Cl 2 -> n 2 n 2 n 2/2 -> R 10 (CH 2 CH 2 O) n CH 2 CH (OH) CH 2 Cl

T TTT TV

2) 2R 0 (CH2CHXO) n CH2CH (OH) CH2C1 + RR NH -> Γ I / \ / \ TO m IV 0 --- ^ R ^ CH CIIXO) OH_CH (OH) CH NRR Cl v 2 Λ ^ 2 2t, g

III IV

In the wedding reaction formulas, R, R / R, X and n 2 have the same meaning as above.

The reaction between the alcohol, alternatively its alkylene oxide adduct and epichlorohydrin, is carried out at a temperature of about 100-150 ° C in the presence of a catalyst. In particular, SnCl 2, BF 2 and HCl 2 proved to be excellent catalysts and provide a rapid and easily controlled reaction, but other acid catalysts such as toluenesulfonic acid and sulfuric acid can also be used. In order to obtain a complete reaction of the alcohol compound, epichlorohydrin is usually added in excess. Quaternization of the secondary amine with chloroglyceryl ether is performed with an alkali. sodium hydroxide, in the presence of a temperature of about 100-150 ° C. The reaction is usually carried out in the presence of an organic solvent having a boiling point of at least 60 ° C, the solvent being, for example, methanol, ethanol or diethylene glycol monoethyl ether.

The compounds of the invention may also be prepared using various modifications of the method described above. Thus, chloroglyceryl ether S6372 can be reacted with ammonia or a primary amine having a methyl or ethyl substituent, followed by quaternization using e.g. methyl or ethyl chloride or dimethyl or diethyl sulfate. However, this process is more complex than previously described and involves several reaction steps while providing a higher amount of by-products and a lower overall yield.

The alcohols having from 8 to 22 carbon atoms used in the preparation of the compounds of the invention may be both synthetic and derived from natural products. "Naturally occurring" alcohols, so-called fatty alcohols, are usually prepared by reduction of fatty acids or fatty acid esters obtained from vegetable oils, soybean oil, linseed oil, corn oil or castor oil, animal oils or fats such as fish oil, whale oil or whale oil. Examples of suitable alcohols include octyl alcohol, desyl alcohol, dodecyl alcohol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol, icosyl alcohol, oleyl alcohol and icocenyl alcohol. Synthetic alcohols are preferably prepared by the Ziegler method or the oxidation method. Most alcohols prepared by the oxidation process have a more or less branched carbon chain, as a result of which a large amount of isomer is possible in this case. The physical and chemical properties of these alcohols are very similar to those of straight-chain primary alcohols.

Suitable secondary amines in the process of the invention include dimethylamine and diethylamine, which are commonly marketed. Useful primary amines include methylamine and ethylamine.

The compounds of the invention have proven to be very suitable for use in imparting a soft feel to a textile material and in reducing the static tendency of certain materials to charge. Thus, these compounds can be advantageously added when rinsing the textile material, and since they have a good affinity for textile fibers, the addition can in principle take place during any rinsing, although the best effect is obtained when the addition takes place in the last rinse water. The amount of these quaternary compounds added when rinsing the textile material varies depending on the textile material, the washing conditions and the desired effect, but in general it can be said that the addition should be 0.01 to 0.50 g, preferably 0.05 to 0.15 g per liter of rinse water. , or 0.1-5.0 g, preferably 0.5 ~ 1.5 g, per kilogram of textile material. The compounds can also be added during the prewash or the main wash, but in this case the effect obtained is somewhat worse. The textile material may be woven or non-woven and may comprise both synthetic and natural fibers such as cotton linen, wool, rayon, polyvinyl chloride fibers, polyethylene fibers, polypropylene fibers, polyamine fibers, polyester fibers and polyamide fibers. In the manufacture of paper-based products such as sheets, paper garments, napkins, hand towels, caps, sanitary napkins and adsorption pads, the compounds of the invention can be added to an aqueous pulp slurry of 0.02-2% by weight of cellulose to impart good softness and water absorption to the finished product. Furthermore, it has proved suitable to add solutions of the compounds according to the invention, e.g. by spraying or brushing, to a material which is prone to undesired electrostatic charging. This technique is very useful for handling a material or object that is usually washed very infrequently or not at all. Examples of such products are carpets and upholstered furniture, furs of polyacrylonitrile or rayon wool, hides and skins, paper and paper products, glass and other mineral wool, gramophone sheets, audio and video tapes, paint and varnish surfaces, metal foils, electronic foils and For articles of a fibrous or textile nature, such as carpets, cellulose fiber-based products, leathers and mineral wool, these compounds also have a significant emollient effect.

The compounds according to the invention are usually used in the form of a 5-10% aqueous solution which, in addition to the active substance, also contains, for example, solubility-promoting additives, such as ethyl diglycol, to reduce the viscosity of the solution. In a known manner, it is also possible to add nonionic surfactants, such as adducts between ethylene oxide or propylene oxide and aliphatic alcohols or alkylphenols, and to increase the rewettability of the textile material thus treated.

For certain uses, it may be desirable for a compound of the invention to be dissolved in a fluid solvent so that it can evaporate rapidly. In such cases, for example, acetone, methanol, ethanol, isopropanol or mixtures thereof can be used as solvents.

The following examples further illustrate the invention.

Example 1

A vessel equipped with heating and stirring equipment and a reflux condenser was charged with 300 g (1 mole) of tallow fatty alcohol melt (a mixture of cetyl, stearyl and icicyl alcohols) to which 0.5 moles of ethylene oxide per 1 mole of alcohol had been added, using sodium hydroxide 6 56372 as an alkaline catalyst. The melt was maintained at 75 ° C with stirring, after which 3 g of SnCl 3 and 101 g (1.1 moles) of epichlorohydrin were passed in over 1 hour. The temperature was raised to 125 ° C and maintained at this temperature for a further 2 hours. The remaining epichlorohydrin was removed by vacuum treatment and the resulting reaction product was 390 g of a pale golden, thick-flowing liquid.

An autoclave equipped with equipment for heating and stirring was charged with 350 g (0.9 moles) of the above reaction product, 125 g of ethanol in which 20 g (0.5 moles) of dimethylamine were dissolved, and 23 g (0.56 moles) of ) sodium hydroxide and 15 g of water. The mixture was autoclaved at 125 ° C for 3 hours, after which time residual dimethylamine was removed by purging with nitrogen gas. The reaction product consisted of a slightly yellow substance, m.p. was 37-1 + 0oC and was found to contain 57% quaternary amine, 10% tertiary amine, 23% ethanol, 6% HaCl and U% water. This product is hereinafter referred to as A.

Examples 2-7

In the same manner as in Example 1, further products according to the invention were prepared. The remaining products, designated B-G, were as follows: B. Reaction product obtained from 2 moles of cetyl alcohol, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

C. Reaction product obtained from 2 moles of tallow fatty alcohol, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

D. Reaction product obtained from 2 moles of tallow fatty alcohol, 1 mole of butylene oxide, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

E. Reaction product obtained from 2 moles of tallow fatty alcohol, k moles of ethylene oxide, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

F. Reaction product obtained from 2 moles of tallow fatty alcohol, 8 moles of ethylene oxide, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

G. Reaction product obtained from a 2 mole mixture of fatty alcohols with 8 m 2 of C 20 and C 22 alcohols * 8 moles of ethylene oxide, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

Example 8 This example compared a commercial product consisting of 75% distearyldimethylammonium chloride in a series of washing experiments in a cylinder washer, in which cotton terry specimens were first washed with a commercially available high detergent at 90 ° C. To the last rinse water was added an amount of compound A-E corresponding to 0.5 g per kg of product to be washed. This washing and post-treatment was repeated five times. After each completed wash, the softness of the terry cloth was subjectively determined by six individuals. The following results were obtained.

7 56372 _Number of persons. who looked

Compound Wash Commercially Compounds Equal to the best of the invention A 1 O 1 5 2 0 1 5 3 1 0 5 4, 0 O 6 5 0 O 6 B 1 2 2 2 2 1 3 2 3 2 13 k 1 2 3 5 0 3 3 ci 1 1 h 2 11 h 3 o 2 h U o 1 5 5 0 15 D 1 O 0 6 2 0 0 6 3 0 0 6 k O 0 6 5 0 0 6 E 1 2 3 1 2 2 3 1.

3 2 2 2 k 2 2 2 5 1.3 2 8 56372

The results show that products A and D had the best textile softening properties and were clearly better than the comparative test, and that products B and C had good softening properties without ethylene glycol units and were also clearly better in the comparative tests. As the number of alkylene glycol units increases by more than about 1 unit per alcohol chain, the emollient effect decreases again, and at an amount of about 2 units per alcohol chain, a emollient effect comparable to the control experiment is obtained.

Example 9 In this example, the antistatic properties of Compounds A-E and, for comparison, the commercial product described in Example 8 were tested using a series of washing experiments in a cylinder-washing machine, whereby the nylon specimens were first washed with a commercially available detergent at 22 ° C. To the last rinsing water was added 0.5 g of the product according to the invention per 1 kg of detergents. At the end of the treatment was determined as the time required for the amount of flow for electrical-discharge side, which was added to the nylon when the device Rothschild Static Voltmeter R 1020. The following results were obtained.

Product Half-life, sec.

Commercial product 12 A 6 B 10 C 10 D 6 E 5 F 6 G 6

The results show that those compounds B and C of the invention which do not contain any alkylene glycol units had better antistatic properties than the commercial product. The presence of alkyl glycol units further enhances the anti-static effect so that the half-life of nylon treated with compounds A, D, E, F, G is approximately half or less compared to the half-life of commercial products.

It can be seen from these Comparative Examples 8 and 9 that the compounds according to the invention have a better antistatic effect and / or a better emollient effect than the previously used compounds resembling them in structure. It further appears that compounds in which n1 and ng in the structural formula previously shown are 0-2 have better properties in both of these ratios.

563/2

Example 10

In the same manner as in Example 1, a fatty alcohol mixture (1 mole) was reacted with epichlorohydrin (1.1 moles) and dimethylamine (0.5 moles) using ethyl diglycol as a solvent. The fatty alcohol mixture consisted of 15% desyl alcohol, U7% dodecyl alcohol and 38% tetradecyl alcohol a. . The residue consisted of water, sodium chloride and unreacted starting materials. The product had a flow point of 12 ° C, a solidification point of 10 ° C and a brightness point of 33 ° C.

From this product mixture, 12 parts by weight of the solvent mixture was dissolved in 88 parts by weight of water. The resulting solution was fluid at room temperature and had a pour point of 0 ° C. When the aqueous solution was frozen and then allowed to thaw, it had no tendency to form any gel.

The cotton terry pieces were first washed with a commercially available high detergent at 90 ° C in a cylinder washer. To the last rinse water was added the obtained product mixture or distearyldimethylammonium chloride as a fabric softener in an amount of 1.2 g of dry matter per kg of textile product. This treatment was repeated five times. After each completed wash, the softness of the terry pieces was subjectively determined by six individuals, with three individuals finding the terry pieces post-treated with the product of the invention to be softer, while the other three found no difference.

The water absorption capacity of terry cloth pieces was determined by pressing an annular specimen against the top surface of a fiberglass sheet whose bottom surface was in full contact with a given volume of water. The decrease in the volume of the finding model water as a function of time could be determined by the suction rate. The following results were obtained.

ml water / g dry textile for 50 seconds, after Untreated terry 3.1

Terrycloth treated with 1.2 g / kg distearyldimethylammonium chloride 1.1 Terrycloth treated with 1.2 g / kg cationic surfactant according to the invention

The nylon fabric, which was washed at 22 ° C, was subjected to the same wash treatment as the terry cloth. After conditioning for 1 day at 65% relative humidity and 20 ° C, the conductivity was determined with a Rotschild Static Voltmeter R 1020, whereby a fabric strip was tensioned between two metal presses to provide a voltage difference of 100 volts.

The time taken to halve the potential was determined. The following results were obtained.

Half-life sec * Untreated nylon fabric 7 ^

Nylon fabric treated with 1,2 g / kg distearyldimethylammonium chloride 31 *

Nylon fabric treated with 1.2 g / kg of the cationic surfactant of the invention 10 * due to other experimental conditions, no direct comparison can be made with the result obtained in Example 9.

The above results show that the compound is flowable at room temperature and is resistant to freezing and thawing as an aqueous solution. Compared to distearyldimethylammonium chloride, which is a commonly used fabric softener, the compound of the invention also gives textile products better properties in terms of softness, antistatic effect and absorption capacity.

Claims (6)

11 56372 A cationic surfactant which reduces the tendency of substances to charge electrostatically and / or improves their softness, characterized in that it has the general formula 1-O- (CH 2 CHXO) -CH 2 -CH (OH) CH 2 R 111 αθ RII- O- (CH 2 CHXO) q -CH 2 -ch (oh) c 1 R 17 in which R 1 and R 2 independently represent an aliphatic group, III IV having 8 to 22 carbon atoms, R and R independently represent a methyl or ethyl group, X represents hydrogen or a methyl or ethyl group, the average value of the numbers n1 and n2 is 0-5, and A is an anion. Compound according to Claim 1, characterized in that the average value of n 1 and n 2 is 0 to 2. Compound according to Claim 1 or 2, characterized in that R 1 and independently represent a hydrocarbon chain having 8 to 11 + carbon atoms. 1+. Compound according to Claims 1 to 3, characterized in that R111 and denote a methyl group and A is a monovalent acid anion. Compound according to Claims 1 to 1, characterized in that R 1 and R 2 are derived from a fatty alcohol. Compound according to Claims 1 to 1, characterized in that R 1 and R 2 are derived from a synthetic alcohol.