GB2204608A

GB2204608A - Softener for fibers

Info

Publication number: GB2204608A
Application number: GB08809991A
Authority: GB
Inventors: Junichi Inokoshi; Kazumitsu Furuta; Tetsuo Ito; Masaki Tsumadori
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1987-05-08
Filing date: 1988-04-27
Publication date: 1988-11-16
Anticipated expiration: 2008-04-27
Also published as: MY103273A; JPS63282372A; GB8809991D0; GB2204608B

Abstract

A liquid softener composition comprises: (A) a quaternary ammonium salt having in the molecule one or two members of the group consisting of alkyl, alkenyl and ???-hydroxyalkyl groups each having 10 to 24 carbon atoms, (B) a polyamide compound having a residue of a fatty acid having 12 to 24 carbon atoms or a cationic polyamide compound prepared by neutralizing said polyamide compound with an acid, and (C) an ester derived from a fatty acid having 10 to 24 carbon atoms and glycerol. t

Description

SOFTENER FOR FIBERS The present invention relates to a softener. More particularly, the present invention relates to a liquid softener having excellent fluidity and stability and capable of softening fibers of various types.

Most domestic softeners now available on the market comprise a quaternary ammonium salt having one or two longchain alkyl groups in the molecule as the main component, since the quaternary ammonium salt exhibits an excellent softening effect on the fibers even when used in only a small amount.

Though most domestic softeners are in liquid form so that they can be handled easily, 'the quaternary ammonium salt has only a poor solubility in water and, therefore, it tends to gel in high-concentration aqueous solutions and no stable, low-viscosity composition can be obtained.

Efforts have been made to obtain a stable, low-viscosity composition by adding, for example, a nonionic surfactant, a cationic surfactant such as a mono(long-chain alkyl) quaternary ammonium salt, a solvent or an inorganic salt.

However, these processes were insufficient for achieving satisfactory shelf life at temperatures over a wide range or recovery after freezing.

Further the above-mentioned quaternary ammonium salts have an insufficient softening effect on synthetic fibers such as acrylic, polyester and polyamide fibers, though their effect on cotton fibers is remarkably good. In addition, when the above-mentioned dispersion stabilizer is added, their softening effect is often impaired.

Although the use of a combination of a quaternary ammonium salt with a glyceride is described in Japanese Patent Publication No.47384/1985 and Japanese Patent Laid-Open No.

194274/1986, it has neither a sufficient softening effect on all sorts of fibers nor excellent dispersion stability unlike the softener of the present invention.

After intensive investigations made for the purpose of overcoming the above-described defects, the inventors have completed the present invention.

According to the present invention a softener composition comprises the following components (A), (B) and (C): (A) a quaternary ammonium salt having in the molecule one or two alkyl, alkenyl or ss -hydroxy alkyl groups each having 1Q to 24 carbon atoms: (B) a polyamide compound having a residue of a fatty acid having 12 to 24 carbon atoms or a cationic polyamide compound prepared by neutralising said polyamide compound - with an acid; and (C) an ester derived from a fatty acid having 10 to 24 carbon atoms and glycerol; the weight ratio of (B) and (A) being 0.02 to 5, that of (C) to (A) being 0.01 to 3 and the sum total of (A), (B) and (C) being 3 to 25 wt. %.

- Anexcellent softening effect is attained by the synergistic effect of the three components, i.e. quaternary ammonium salt, glyceride and polyamide.

The quaternary ammonium salt (A) used in the present invention includes, for examplo, ammonium, imidazolinium and amidoammonium salts each having one or two alkyl, alkenyl and/or 6-hydroxyalkyl groups each having 10 to 24 carbon atoms and represented by the following general formulae (1) to (5). They can be used either alone or in the form of a mixture of two or more of them.

i) Ammonium salts of the following formula (1) or (2):

ii) Imidazolinium salts of the following formula (3):

iii) Amidoammonium salts of the following formula (4) or (5):

in which R1, R2, R6 and R7 each represent an alkyl, alkenyl or ss-hydroxyalkyl group each having 10 to 24 carbon atoms, R3, R4 and R5 each represent an alkyl or hydroxyalkyl group each having 1 to 3 carbon atoms, a benzyl group or a -(-C2H4-)n-H group (wherein n is 1 to 3), m represents a number of 2 or 3 and X represents a halogen or a monoalkyl sulfate group having an alkyl group having 1 to 3 carbon atoms.

- The quaternary ammonium salt (A) includes, for ~example, dodecyltrimethylammonium chloride, hexadecyldimethylethylammonium bromide, octadecyl trimethylammonium chloride, didodecyldimethylammonium chloride, dihexadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, di(hydrogenated beef tallow alkyl)dimethylammonium chloride, di(hardened palm oil alkyl)dimethylammonium chloride, bis(B- hydroxystearyl)diethylammonium chloride, 2-heptadecyl l-methyl-l- [ (2-octadecanoylamino) ethyl) imidazolinium methyl sulfate, di[(2-dodecanoylamino)ethyl]dimethylammonium methyl sulfate and di[(2-octadecanoylamino)ethyl]methylethylammonium ethyl sulfate. They may be used either alone or in the form of a mixture of two or more of them.

Among them, quaternary ammonium compounds of the formula (1) or (2) are preferred. Particularly those of the formula (1) are preferred.

The polyamide compound (B) used in the present invention includes, for example, a mixture of compounds prepared by the following process.

1 mol of diethylenetriamine or dipropylenetriamine is reacted with about 2 mol of a fatty acid having 12 to 24 carbon atoms at a reaction temperature in the range of 100 to 1600C until the condensate having an acid value of 10 or less is obtained. Then about 1 to 2 mol of epichlorohydrin is added dropwise thereto while the condensate is kept at 100 to 1600C to form an adduct practically in a moment. The adduct is cooled to about 60 to 1000C and 0.05 to 1 mol of an alkali is added thereto to conduct ring-opening polymerization.

The fatty acids having 12 to 24 carbon atoms prepared by this reaction include lauric, myristic, palmitic, stearic, arachidic, behenic and lignoceric acids as well as those drived from non-hardened or hardened beef tallow, palm oil, rape oil and fish oil. Although the alkali used in the ring-opening polymerization of the epichlorohydrin adduct is not particularly limited, it is preferably an aqueous solution of sodium hydroxide or potassium hydroxide.

The ring-opening polymerization product of the polyamide compound may be neutralized with a suitable acid.

In the neutralization, 0.3 to 1.5 mol of an acid is ,used per mol of the amine. The acids include, for example, mineral acids such as hydrochloric and nitric acids, and monobasic acids having 2 or 3 carbon atoms such as acetic, propionic and glycolic acids.

The petails ofthe process for the preparation of the polyamide compounds used in the present invention will be understood from Referential 'Examples described below.

The glyceride (C) used in the present invention is a monoester or diester derived from a straight chain or branched, saturated or unsaturated fatty acid having 10 to 24 carbon atoms and glycerol or from an oil or a fat comprising the above fatty acid as the constituent, or a mixture of a monoester and a diester or a mixture thereof with a triester. When the mixture is used, preferably it has a monoester content of at least 85 wt. %. When the monoester content is below 85 wt. %, no softener composition having sufficient softening effect and dispersion stability can be obtained. The glyceride of the present invention includes, for example, esters of glycerol with capric, lauric, myristic, palmitic, oleic, stearic, isostearic, arachidic, behenic or lignoceric acid as well as those obtained by fractionation from non-hardened or hardened beef tallow, lard, palm oil, rape oil and fish oil. They are used either singly or in the form of a mixture of them. Particularly preferred are those obtained by fractionation from natural oils or fats such as hardened lard oil, hardened palm oil, hardened rape oil and hardened beef tallow.

The quaternary ammonium salt (A), polyamide compound (B) and glyceride (C) are used as the indispensable components in the present invention.

The weight ratio of the component (B) to the component (A) [(B)/(A)] is 0.02 to 5, preferably 0.05 to 1 and that of the component (C) to the component (A) [(C)/(A) is 0.01 to 3, preferably 0.05 to 1.

When the ratios of the components are outside these ranges, no excellent dispersion stability can be obtained and the softening effect is insufficient.

In due consideration of the current conditions of domestic use of the softener, the sum total of the components (A), (B) and (C) in the softener of the present invention in liquid form is at least 3 wt. % from the viewpoint of the softening and antistatic effects and at most 25 ,wt. % from the viewpoints of the viscosity of the liquid composition, storage stability and economy.

When the softener component (A), (B) or (C) is used singly, or a mixture of the components (A) and (B), (B) and (C) or (A) and (C) is used in amounts described above, it is difficult to obtain a softener composition having excellent shelf stability and viscosity stability. On the contrary, the softener of the present invention comprising the components (A), (B) and (C) in 'amounts within the above-described ranges have excellent shelf'stability and viscosity stability and is capable of exerting excellent softening and antistatic effects on all of cotton fibers, blended fibers and synthetic fibers.

The softener of the present invention comprising the quaternary ammonium salt (A), polyamide compound (B) and glyceride (C) as indispensable components can further contain, when it is in liquid form, nonionic surfactants such as polyethylene glycol, water-soluble salts such as common salt or ammonium chloride, solvents such as propylene glycol or ethylene glycol and urea in order to improve the shelf stability and to adjust the viscosity.

Further, a pigment or a dye can be incorporated in the softener in order to improve the appearance thereof, a fluorescent brightener can be incorporated therein to whiten the fibers and a flavor can be incorporated therein to enjoy the smell in the course of and after the softening treatment.

[Effect of the invention] The softener of the present invention imparts sufficient softness and antistatic property to various fibers and has excellent shelf stability at various temperatures and recovery after freezing.

[Examples) The following Examples will further illustrate the present invention, which by no means limit the invention.

The following Referential Examples will illustrate the processes for preparing the polyamide compounds used in the present invention.

Referential Example 1 52 g of diethylenetriamine was added to 280 g of stearic acid and the mixture was heated at 120 to 140"C for 4 h. During this step, about 15 g of water distilled. The mixture was further heated at 140 to 1500C for 6 h to obtain a condensate having an acid value of 5.9. 69 g of epichlorohydrin was added dropwise thereto at that temperature. The mixture was cooled to 80eC. 165 g of isopropyl alcohol and 13 g of a 30 % aqueous sodium hydroxide solution were added thereto and the reaction was conducted for 6 h to obtain a polyamide compound.

Then 70 % aqueous glycolic acid was added thereto in such an amount that the molar ratio thereof to diethylenetriamine would be 1:1 to obtain a neutralized product. The physical properties of the non-neutralized product and the neutralized one are shown in Table 1.

Table 1

Melting point Acid value Amine value ( C) Non-neutralized product 38 # 45 3 48 Neutralized product 40 # 46 61 40 Referential Example 2 The reaction was conducted in the same manner as that of Referential Example 1 except that stearic acid was roplaced with 350 g of behenic acid and glycolic acid was replaced with hydroxyacetic acid to obtain non-neutralized and neutralized polyamide compounds.

The molar ratio of the starting materials were: diethylenetriamne/fatty acid/epichlorohydrin/sodium hydroxide/hydroxyacetic acid = 1/2/1.5/0.2/1.2.

Referential Examples 3 to 6 The same procedure as that of Referential Example 1 was repeated except t-hat various starting materials were used and the molar ratio of them was altered to obtain non-neutralized and neutralized products.

The starting materials and the molar ratio of them are shown in Table 2.

Table 2

Ref. Ex. Amine Fatty acid Epihalohydrin Alkali Acid Molar ratio 3 dipropylenetriamine lauric acid epichlorohydrin potassium propionic 1/2/1.5/0.2/1.2 hydroxide acid 4 ditto hydrogenated beef ditto ditto glycolic 1/2/1.5/0.2/1.2 tallow acid acid 5 diethylenetriamine hydrogenated rapa ditto sodium hydro- 1/2/1.5/0.2/1.2 oil acids hydroxide chloric acid 6 ditto hydrogenated palm ditto ditto nitric 1/2/1.5/0.2/1.5 oil acids acid Example 1 Composition:: distearyldimethylammonium chloride (A) polyamide compound (non-neutralized one prepared in Referential Example 1) (B) glycerol monostearate (monoester content: 98 wt. %) (C) water The sum total of (A), (B) and (C) was 5 wt. %, the amount of water was the balance, the ratio of (B) to (A) was 0 to 10 (see Table 3) and the ratio of (C) to (A) was 0 to 10 (see Table 3).

The viscosity of the above-mentioned composition immediately after the preparation, that of the composition after freezing at -200C followed by thawing, and softening effect thereof on various fibers were examined to obtain the results shown in Tables 3 and 4, respectively.

The viscosity was determined with a BM viscometer at 300C and the recovery after freezing was determined by repeating freezing at -200C followed by leaving to stand at 300C td effect thawing five times. The recovery after freezing was not examined when the composition had a high viscosity immediately after the preparation thereof or when the composition was a gel or phase separation was observed therein.

The softening effect was evaluated as follows: (1) softening method: Commercially available cotton towels and acrylic jersey clothes were washed with a commercially available detergent tabu" (registered trademark of Kao Corporation) repeatedly five times to remove treatments from them. They were then stirred in a 0.067 % solution of the above-mentioned composition in hard water (3.50DH) at a bath ratio of 1/30 at 250C for 5 min.

(2) Evaluation -method: The towels and clothes treated as described above were air-dried in a room and then left to stand in an air-conditioned room at 250C and 65 % RH for 24 h.

The softness of them was evaluated by a paired comparison with a cloth treated with a softener comprising 5 wt. % of a di(hydrogenated beef tallow alkyl)dimethylammonium chloride as the control. The criteria were as follows: +2: The sample was softer than the control.

+1: The sample was a little softer than the control 0: The sample was as soft as the control -1: The control was a little softer than the sample.

-2: The control was softer than the sample.

Table 3

Item Initial dispersibility Viscosity recovery after freezing C/A 0 0.01 | 0.1 t 0.5 | 1 | 3 | 10 | 0 | 0.01 | 0.1 t 0.5 | 1 1 3 10 B/A o ' A A A A A x X, - - - - - - 0.02 O ≈ &commat; &commat; &commat; zt x x A &commat; &commat; O A 0.1 0 O O O O O x &commat; x x x A &commat; &commat; O L ~ 0.5 0 O O O &commat; &commat; &commat; 0 x x A O O O A ~ x O O O e E X ~ A A O O A ~ S x 0 O O AAx /\ A A AA 10 v x x x x x x x - - - - - - # 50 # 200cP 0 200 # 500cP # 500 # 800cP X gel having a viscosity of at least 800cP was obtained or phase separation was observed.

Table 4

i ccucucucucucucu ~1 llllrl Cloth Cotton towel Acrylic jersey cloth '00000CU 1 I I 00000U) 0 0.01 0.1 0.5 1 . &commat; I IIOCU l control 0 -0.5 -0.5 -1.0 -1.0 -* controL + X + I fa Q 0 > +0.5 o 0.5 o 0.5 o o - 2 0 + un + 1.0 .1-1.0 1.1.0 0 - 2 > t O 1.0 +1.5 O 1.5 + 0.5 N 4 + 1.0 +1.5 +2.0 o 2.0 + 1.0 0 - 2 ol o ? 9999Y9 ç +0.5 +0.5 +0.5 +0.5 +0.5 o o +0.5 e4 ex + 1.0 o 1.0 +1.0 ~ -2 < ~ ~ ~ 0 ~ -2 +0.5 +0.5 +0.5 +0.5 .10.5 I -2 < I o I -1.5 -1.5 -2 o 2 In -0.5 -0.5 - 1.0 - 1.5 -2 -2 -2 l O . ' T H c o n LD o e4 4 e4 ew e4 ~ l l l l l l l ~ O O O O O ev O e D Y: ~ o o o o o eq z u.o Y7 LD LD i 3 o o o ~ ~ o o ~ 4J | I T + T | z O O ~ O O ~ CJ | ~ T ~ UZ O O UZ . O O ~ O O ~ O ~ ~ &commat; H O a O O O O ~ ~ It is apparent from Table 3 that when 5 wt. % of distearyldimethylammonium chloride is used alone, no stable product can be obtained. Even when distearyldimethylammonium chloride is used in combination with the glyceride, no stable liquid product can be obtained, since it has too high a viscosity or eventually gels, or otherwise it causes phase separation.When the polyamide compound is incorporated therein, a liquid product of a lower viscosity can be obtained and it has an excellent viscosity recovery after freezing.

Even when the products having an excellent initial dispersibility was left to stand in a constanttemperature bath at 50eC for 4 weeks, neither phase separation nor viscosity change was observed.

Table 4 indicates that when distearyldimethylammonium chloride is used in combination with the polyamide compound and glyceride, a synergistic softening effect on both cotton and synthetic fibers can be exhibited.

Example 2 The same procedure as that of Example 1 was repeated except that the amounts of the components and the ratio of them were altered as shown below to examine the initial dispersibility and recovery after freezing.

Composition: di(hardened beef tallow) dimethylammonium methyl sulfate (A) polyamide compound (neutralized one prepared in Referential Example 1) (B) hardened beef tallow glyceride (C) (monoester content: 95 wt. %) water The ratios of (B) to (A) and (C) to (A) were both in the range of 0 to 0.5 and the sum total of (A), (B) and (C) was 5 to 30 wt. % with the balance being water.

Table 5

Initial i Recovery after dispersibility I freezing I \4 O | O | 0.3 031 0.31 0.3 0;: 0.31 0.5 oil O.Sj (A)*(B).tC)\| O 0.3 f) | 0.3 1 0.5 1 0.3 1 0.5 1 0.S | O.E | 0.3 1 0.5 wt. x x x X O &commat; I ≈ z 15 wt. x x x O 0 0 0 O O 0 0 0 25 wt. Z x X X O 0 A A A A 30 wt. % X X X X X X X X X < X X It is apparent from Table 5 that the softeners of the present invention comprising the components in various amounts and various ratios within the scope of the invention have excellent dispersibility and recovery after freezing.

Example 3 Softener compositions shown in Table 6were prepared and the softening effect and viscosity recovery thereof after freezing were examined in the same manner as that of Example 1 to obtain the results shown in Table 7.

Composition: quaternary ammonium (A) 4 wt. % polyamide compound (B) 0.5 wt.

glyceride (C) 1.0 wt. % water the balance Table 6

Monoester content No. Quaternary ammonium salt (A) Polyamide (B) Glyceride (C) of esters 1 di(hardened beef tallow)- Referential Example 2 hardened lard 95 wt. % dimethylammonium chloride (non-neutralized) glyceride 2 ditto Referential Example 2 ditto 95 wt. % (neutralized) 3 ditto Referential Example 1 ditto 90 wt. % (non-neutralized) 4 dipalmitoyldimethylammonium ditto hardened beef tallow 95 wt. % chloride glyceride 5 bis(ss-hydroxystearyl)diethyl- ditto ditto 95 wt. % ammonium chloride 6 di(hardened palm oil)- ditto hardened palm oil 95 wt. % dimethylammonium chloride glyceride 7 ditto ditto hardened rape oil 95 wt. % glyceride 8 ditto ditto glycerol monooleate 99 wt. % 9 distearyldimethylammonium Referential Example 3 glycerol monostearate 99 wt. % chloride (non-neutralized) 10 ditto Referential Example 4 ditto 99 wt. % (ditto) 11 ditto Referential Example 5 ditto 99 wt. % (ditto) 12 ditto Referential Example 6 ditto 99 wt. % (ditto) Table 7

Viscosity recovery Cotton towel Acrylic jersey freezing 1 # + 1.0 + 2.0 2 # + 1.0 + 2.0 3 # o1.0 +2.0 4 # + 0.5 + 1.0 5 # + 0.5 + 0.5 6 # + 1.0 + 2.0 7 # + 1.0 + 2.0 8 # + 0.5 + 1.0 Q Qo - +0.5 | +1.0 10 # + 0.5 + 2.0 11 +1.0 +2.0 12 # + 1.0 + 2.0 It is apparent from Table 7 that the softeners of the present invention has good recovery after freezing and an excellent softening effect. When the amide compounds in composition Nos. 3 to 12 were replaced with the corresponding neutralized compounds, the resulting softener having a similar composition exhibited good recovery and softening effect.

Claims

CLAIMS:

1. A liquid softener composition which comprises (A) a quaternary ammonium salt having in the molecule one or two groups which are alkyl, alkenyl, and for P -hydroxyalkyl groups each having 10 to 24 carbon atoms, (B) a polyamide compound having a residue of a fatty acid having 12 to 24 carbon atoms or a cationic polyamide compound prepared by neutralizing said polyamide compound with an acid, and (C) an ester derived from a fatty acid having 10 to 24 carbon atoms and glycerol, the weight ratio of (B) to (A) being 0.02 to 5, that of (C) to (A) being 0.01 to 3 and the sum total of (A), (B) and (C) being 3 to 25 wt. %.

2. A composition as claimed in Claim 1, in which the quaternary ammonium salt (A) is a compound of the following general formula (1) or (2):

in which each of R1 and R2 independently represent an alkyl, alkenyl or 8-hydroxyalkyl group having 10 to 24 carbon atoms, each of R3. R4 and R5 independently represent an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group or a -(-C2H4O-)n-H group (wherein n is 1 to 3) and X represents a halogen or a monoalkyl sulfate group having an alkyl group having 1 to 3 carbon atoms.

3. A composition as claimed in Claim 1, in which the polyamide compound (B) is either one prepared by reacting 1 mol of diethylenetriamine or dipropylene-triamine with 2 mol of a fatty acid having 12 to 24 carbon atoms to obtain a condensate having an acid value of 10 or below, adding about 1 to 2 mol of epichlorohydrin to the condensate and subjecting the mixture to ring-opening polymerization in the presence of an alkali, or a cationic polyamide obtained by neutralizing the ring-opening polymerization product with an acid.

4. A composition as claimed in Claim 1, in which the monoester content of the ester (C) is at least 85 wt.%.

5. A composition as claimed in Claim 1, which further includes water to 100%.