AU643874B2

AU643874B2 - Fabric softener composition and ammonium salt

Info

Publication number: AU643874B2
Application number: AU11111/92A
Authority: AU
Inventors: Toru Hayase; Junichi Inokoshi; Tohru Katoh; Uichiro Nishimoto; Yoshifumi Nishimoto; Kazutaka Shiratsuchi; Kohshiro Sotoya; Osamu Tachizawa; Masaaki Yamamura
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1990-08-22
Filing date: 1992-02-19
Publication date: 1993-11-25
Anticipated expiration: 2012-02-19
Also published as: ES2074614T3; CA2061513A1; HK159995A; DE69109579D1; ATE122419T1; AU1111192A; JPH0759792B2; EP0472178B1; JPH04108174A; EP0472178A1; DE69109579T2

Abstract

An aqueous fabric softener composition is disclosed, which comprises water and, as a softener new material, a neutralization product of: (A) a di-long chain type tertiary amine compound containing one <CHEM> group in which R represents an alkyl or alkenyl group containing from 11 to 21 carbon atom, one -CONH- group and one alkyl or alkenyl group containing from 11 to 22 carbon atoms with (B) an inorganic acid or an organic acid containing from 1 to 6 carbon atoms, a quaternization product of Compound (A) or a mixture of the neutralization product of Compound (A) with Compound (B) and the quaternization product of Compound (A). The fabric softener composition of the present invention imparts the sufficient softness, the antistaticity and the resiliency (fluffy feeling) to clothes of various fibers.

Description

5438 4 '4 S F Ref: 203983

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

Name and Address of Applicant: Kao Corporation 14-10, Nihonbashi Chuo-ku Tokyo

JAPAN

Kayabacho 1-chome Actual Inventor(s): 0 0 0 0 Masaaki Yamamura, Junichi Inokoshi, Kazutaka Shiratsuchi, Toru Hayase, Ulchiro Nishimoto, Kohshiro Sotoya, Tohru Katoh, Yoshifumi Nishimoto and Osamu Tachizawa Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Fabric Softener Composition and Ammonium Salt Address for Service: Invention Title: The following statement is a full description of this invention, Including the best method of performing it known to me/us:- 5845/3 FApRIC SOFTENER COMPOSITION AND AMMONIUM SALT FIELD OF THE INVENTION The present invention relates to a novel ammonium salt and a fabric softener composition. More particularly it relates to an ammonium salt and a liquid fabric softener composition which impart an improved softness and resiliency (fluffy feeling) to clothes of various fibers.

BACKGROUND OF THE INVENTION O The large majority of home laundering agents /O available on the market today under the name of softeners are compositions based on quaternary ammonium salts containing two long-chain alkyl groups within the molecule, such as dihydrogenated tallow-alkyl dimethylammonium chloride, for instance. This is because quaternary ammonium salts produce satisfactory softening effects on'various fibers even when used in small quantities.

However, despite their remarkable softening effects Son cotton and the like, the above-mentioned quaternary ammonium salts are less effective for synthetic fibers such 9o as acrylic, polyester and polyamide fibers. Moreover, if they are used in high concentrations, the resiliency and the feel of clothes are adversely affected.

Furthermore, the above quaternary ammonium salts are so hydrophobic that when put in rinse water, they are not 6S well dispersed at low to moderate pulsator speeds and tend to S be deposited unevenly on che clothes. In addition, 1 *oSSS o• oo- particular4y when they are stored at low temperature for a prolonged time, these compositions tend to gain in viscosity and form gels or undergo phase separation. The commercial softeners contain, in addition to the quaternary ammonium salts, such additives as polyoxyethylene nonionic surfactants, electrolytes, solvents, and the like for improving the dispersibility and shelf life but the effects are not as satisfactory as desired.

O Liquid softeners containing various amines as to softener bases are also known. By way of illustration, a textile softening composition containing a long-chain alkylamine such as methyl di-hydrogenated tallow-alkylamines is described in JP-A-52-59796 (the term "JP-A" as used herein means "unexamined published Japanese Patent Application") 1, (corresponding to GB-1514276); a textile finishing composition containing an acylated alkanolamine, a watersoluble quaternary ammonium salt and a fatty acid ester for imparting smoothness and the pleasing feel is disclosed in JP-A-58-60070 (corresponding to U.S. Patent 4,446,034); a highly-dispersible softener containing a quaternary ammonium compound, a higher fatty acid-hydroxy(lower)alkylpolyamine condensate, and an alkylamine polyglycol ether is disclosed in JP-A-61-167083 (corresponding to U.S. Patent 4,776,965); a S stable aqueous dispersion for textile treatment which p contains a di(higher alkyl)cyclic amine P;i Br0nsted acid S is disclosed in JP-A-61-275474 (corresponding to U.S. Patent 2* -2o 4,724,089)i a softening composition containing a di-long chain alkylamine-anionic surfactant ion pair complex, a nonsilicone wax and a liquid vehicle is disclosed in JP-A-64- 85368 (corresponding to U.S. Patent 4,913,828); a textile conditioning composition containing an amine such as a hydroxy( lower) alkylalkylenediamine-higher fatty acid condensate and an amphoteric textile conditioner is disclosed in JP-A-2-6662 (corresponding to EP-332270); a textile O conditioning composition containing a di( .ig chain) to alkylamine-polycarboxylic acid complex for imparting flexibility and antistaticity to fabrics is disclosed in JP- A-2-14076 (corresponding to U.S. Patent 4,869,836).

Furthermore, JP-A-52-5394 (corresponding to U.S.

Patent 4,045,361) discloses a fabric conditioner comprising a /S mono- or di(long chain)alkyl-alkylenediamine antistatic agent and a quaternary ammonium softening agent.

However, these amine-containing softeners are not O sufficient in the ability to soften the substrate fabrics, although they are superior to those softening compositions eZo based on quaternary ammonium salts in dispersibility and shelf life.

SUMMARY OF THE INVENTION a The present inventors have conducted extensive studies of amine-containing softener compositions. As a result, they found that an ammonium salt obtained by neutralizing or quaternizing a specific di-long chain amine e compound ip superior in the softening effect and it imparts sufficient resiliency (fluffy feeling) to clothes. The present invention is completed on the above findings.

Accordingly, the present invention provides an aqueous fabric softener composition comprising water and, as a softener raw material, an ammonium salt obtained by neutralizing the following Compound a di-long chain tertiary amine compound o containing one R-C-O- group wherein R represents an alkyl or alkenyl group containing from 11 to 21 carbon atoms, one -CONH- group and one alkyl or alkenyl group containing from 11 to 22 carbon atoms, with an inorganic acid or an organic acid containing from 1 to 6 carbon atoms, or by quaternizing Compound or a mixture of the ammonium Ssalt obtained by neutralizing Compound with Compound (B) and the ammonium salt obtained by quaternizing Compound The present invention further provides an ammonium 20 salt obtained by neutralizing Compound with Compound (B) or quaternizing Compound BRIEF DESCRIPTION OF THE DRAWINGS a Fig. 1 is the NMR spectra of the ammonium salt synthesized in Example 1.

Fig. 2 is the IR spectra of the ammonium salt synthesized in Example 2.

DETAILED DESCRIPTION OF THE INVENTION The substituent R in the di-long chain tertiary amine compound is an alkyl or alkenyl group containing from 11 to 21 carbon atoms, preferably from 13 to 19 carbon atoms and more preferably from 15 to 17 carbon atoms. These groups may be a straight-chain or branched, though straight-chain ones O are preferred. Specific examples thereof include, for to example, n-heptadecyl, n-pentadecyl, n-heptadecenyl and npentadecenyl.

The di-long chain tertiary amine compound (A) (hereinafter referred to as "Compound which is a precursor of the softener raw material to be contained in the /1 fabric softener composition of the invention, is any of the compounds of the following formulas through

C

3

H

6

NHCOR

2 O R 1 (A-l) CmH 2 mOCOR 3

CH

2

CONHR

2

R

4 -N (A-2)

C

z H40COR 3 ft ft

CH

2

CONHR

I

R

5 -N (A-3)

C

2

H

4 0COR 3 wherein, R 1 represents an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms;

R

2

R

3 each represents an alkyl or alkenyl O group containing from 11 to 21 carbon atoms;

R

4 represents an alkyl group containing from 1 to 4 carbon atoms;

R

5 represents an alkyl or alkenyl group to containing from 12 to 22 carbon atoms; and m is an integer of from 2 to 9.

Specific and preferred examples of the group represented by R 1 include, for example, methyl group and hydroxyethyl group. As the alkyl or alkenyl group represented by R 2 those containing from 13 to 20 carbon atoms are preferred and those containing from 15 to 18 carbon atoms are more preferred. As the alkyl or alkenyl group .represented by R 3 those containing from 13 to 19 carbon atoms are preferred and those containing from 15 to 17 carbon {o atoms are more preferred. Specific and preferred example of the group represented by R 4 include, for example, methyl group. As the alkyl or alkenyl group represented by R 5 those containing from 14 to 20 carbon atoms are preferred and 00 6* 6 those containing from 16 to 18 carbon atoms are more preferred. The symbol m is preferably 2. The alkyl or alkenyl group represented by R 2 or R 3 may be straight-chain or branched, though straight-chain ones are preferred.

The compounds of formulas though can be used either alone or a mixture of two or more of them.

The compound can be synthesized by reacting: a compound of formula (AB-1):

C

3

H

6

NH

2

R

1 -N (AB-1)

CH

2 mOH wherein R 1 and m are as defined hereinbefore, which can be obtained by cyanoethylation and hydrogenation of an N-lower alkylalkanolamine, a dialkanolamine diethanolamine) or an N-alkyl- N-alkanol obtained by reacting an alkylene halohydrin iS 9-bromo-l-nonanol) with an N-lower alkylamine, with a fatty acid containing 12 to 22 carbon atoms.

The compound can be synthesized by subjecting a 0 compound of formula (AB-2): oi 5**S S 7

CH

2

C=O

R

4 N (AB-2) C2H4-0 wherein R 4 is as defined hereinbefore, which can be obtained by intramolecular dehydrative ring-formation reaction of an N-lower alkyldiethanols amine, to ring-opening amidation with an aliphatic amine such as laurylamine or stearylamine, and reacting the resulting amide with a fatty acid halide containing from 12 to 22 carbon atoms such as stearoyl chloride.

/o The compound can be synthesized by reacting: a compound of formula (AB-3): CH2--C O

R

5 -N (AB-3)

C

2 H4-O O wherein R 5 is as defined hereinbefore, which can be obtained by intramolecular dehydrative o ring-formation reaction of an N-higher alkyl or alkenyldiethanolamine with a lower alkylamine such as methylamine, ethylamine or butylamine, and further with a fatty acid halide containing from 12 to 22 carbon atoms such as stearoyl chloride.

o o* Thp fatty acid to be used in the synthesis of the compounds of formulas though are those containing from 12 to 22 carbon atoms, preferably from 14 to 20 carbon atoms, and more preferably from 16 to 18 carbon atoms.

Specific examples thereof include, for example, palmitic acid, stearic acid, oleic acid and elaidic acid.

The acid to be used to neutralize Compound (A) which is used as the softener raw material of the fabric D softener composition of the invention includes inorganic /o acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and so on; and organic acids containing from 1 to 6 carbon atoms, such as acetic acid, lactic acid, glycolic acid, citric acid, maleic acid and so on, although hydrochloric acid is preferred in that it is most inexpensive 1 and effective.

Regarding the neutralization process of Compound it is optional to neutralize Compound beforehand and g disperse it in water, or to pour Compound whether in liquid form or in solid form, into an aqueous solution of the g0 acid. Of course, Compound and the acid may be simultaneously added to water.

The quaternization of Compound can be S accomplished through known method, for example, using a lower alkyl halide or a di-lower alkyl sulfate.

Examples of the lower alkyl halide include those containing a halogen atom chlorine atom,, bromine atom) S9 and having, 1 or 2 carbon atoms such as methyl clI oride while examples of the di-lower alkyl sulfate include those having 1 or 2 carbon atoms such as dimethyl sulfate and diethyl sulfate.

The lower alkyl halide or the di-lower alkyl sulfate (hereinafter referred to as a "quaternizing agent") is reacted with Compound in a molar ratio of the quaternizing agent to Compound of 1/1 to 3/1. When an O amount of the quaternizing agent is smaller than the range, eo the reaction yield tends to lower. On the other hand, when an amount of the quaternizing agent is larger than the range, the quaternizing agent may remain in the reaction product.

The quaternization is preferably conducted at a temperature of from 30 to 120 0 C, more preferably at a ls temperature of from 50 to 90 0 C. The quaternization can be carried out either without solvents or in the presence of an alcoholic solvent such as ethanol, isopropanol, and the like.

The quaternization can be carried out without using a catalyst.

Zo As the ammonium salt obtained by neutralizing Compound with Compound or by quaternizing Compound with a quaternizing agent iiccording to the present Sinvention, ammonium salts represented by the following formulas through are preferred: .1 0•

S.

0* R' C 3

H

6 NHC OR 2 N+X (C-1) R 6 C H 2 .OC OR 3 R4 CH 2

CONHR

2 N+ X- (C-2) R 6

C

2

H

4

OCOR'

R

5

CH

2

UONHR'

N+ X" (C-3) R 6

C

2 Ii4OCOR 3 wherein RI, R 2 R 3 R 4 R 5 and m are as defined above; R 6 represents a hydrogen atom, a hydroxy group, or an alkyl group containing 1 or 2 carbon atoms; and X- represents an anion selected from the group consisting of residues of an inorganic acid and an organic acid, a halogen atom and a lower alkyl IP sulfate.

Specific examples of the alkyl group represented by

~R

6 include methyl and ethyl groups.

a6 Among the group represented by R a hydrogen atom and an alkyl group containing I. or 2 cnarbon atoms are 1 preferred.

.*to* a.

Examples of the residue of an inorganic acid and an organic acid represented by X -include residues of the inorganic acid and the organic acid listed above for Compound Specific examples the residues of the inorganic acid include groups represented by Cl', NO 3

H

2 P0 4 1/2 HP0 4 1/3

PO

4 3 HS04O and 1/2 S0 4 2 and specific examples of the residues of. the organic acid include acetyl, lactoyl, glycoloyl, oxalyl and maleoyl groups. Specific examples of the halogen atom include chlorine atom and bromine atom, and specific /0 examples of the lower alkyl sulfate include methyl sulfate and ethyl sulfate.

Among the anions for the group represented by 1/2 SO4-, a halogen atom and a lower alkyl sulfate re preferred.

Specific and preferred examples of the ammonium salt of the present inveintion are mentioned below.

CH, CHzCH 2

CH

2

NHCOC

17

H

3 N Cl-

CH

3

CH

2 CH20COC 1 7

H

3

CH

3

CH

2

CH

2

CH

2 NHCOCnH 2 3 N Cl-

CH

3

CH

2 CHzOCOC 21

H

43 4**S*1 *4 S

S

G H 3

CE

2

CH

2

CH

2 NIICO CE 2 pCH (CE 2 qCH3 N+ LCk 3 C1

CE

3

CH

2

CH

2 OCO (CH 2 pCH CE 2 qCH 3

CE

3 wherein p and q each represents a value of f rom 0 to 16, provided that the sum of p and q is f rom 10 to 16.

SCE

3 CH2CH 2

CH

2

NHCOC

17

H

3 N+ C1- H CH 2

CH

2 0COC 17

H

3

CE

3

CH

2

CH

2

CE

2

NHCOC

17

H

3 N' CH 3 S0 4

CE

3

CH

2

(CE

2 7

CH

2 0C0DC 17

H

3

CE

3

/CH

2

CONHC

17

H

3 H CH 2

CH

2

OCOC

1

-,E

3

C

18

H

37

CH

2

CONHC

4 Hq 0 CE 3

CH

2

.CH

2 0OC0C 17

H

3 *o

CE

3

CH

2

CH

2

CH

2

NECOC

17

H

3 N+ Br-

CE

3

CE

2

(CE

2 7

CH

2 0C0C 17

E

3 'a 13a

CH

3

CH

2

CONHC

15

H

31 N 1/2 S0 4 2- H CH 2 CH20COC 15

H

31 For the preparation of a fabric softener composition containing the ammonium salt obtained by neutralizing or quaternizing Compound of the invention as an essential ingredient, it is preferable that the total amount of the ammonium salt obtained by neutralizing Compound and the ammonium salt obtained by quaternizing Compound in the fabric softener composition of the invention ranges from 4 to by weight, preferably 6 to 30 by weight, and moLe to preferably from 10 to 30 by weight, based on the total weight of the composition, in view of the viscosity of the final product and ease of handling. The balance of the composition can be water.

In the fabric softener composition of the invention, a silicone compound such as dimethylpolysiloxane or a partially amino- or polyoxyalkylene-modified dimethylpolysiloxane, particularly a partially polyoxyalkylene-modified S dimethylpolysiloxane can be added in addition to the ammonium salt obtained by neutralizing Compound and/or the sO ammonium salt obtained by quaternizing Compound and water. In this case, the feel of the clothes finished by S such a fabric softener composition can be improved without detracting the water-absorbing property of the clothes. Such 14 44 a siliccne.compound is preferably used in the fabric softener composition of the invention in a proportion of from 0.3 to by weight based the total weight of the ammonium salt obtained by neutralizing Compound and the ammonium salt obtained by quaternizing Compound of the present invention.

The fabric softener composition of the invention imparts to clothes of various fibers a softness with bouncy 0Q while giving the softening effect equivalent to that of di- /0 hydrogenated tallow-alkyl dimethylammonium chloride, which has been widely used in the art.

In an aqueous liquid fabric softener composition of the invention, it is preferable to control the viscosity of the final product by adding an inorganic electrolyte, such as sodium chloride, calcium chloride, magnesium chloride or the like, in a proportion of from 0.05 to 0.4 by weight based on the total weight of the composition.

Although the fabric softener composition of the invention has a long shelf life, it can be further stabilized 2o for assurance of the quality of the composition under severe storage conditions by incorporating additives including nonionic surfactants such as polyoxyethylene (5-50 moles)alkyl or alkenyl(C 12 -2 4 ethers, polyoxyethylene (5-50 moles)s alkyl or alkenylamines; solvents such as ethanol, isopropyl Z alcohol, propylene glycol and ethylene glycol; and/or urea.

o s* o 15 Moreover, esters, nonionic or cationic compounds, long-chain alcohols, and the like, which are known as a softener raw material, may be incorporated in the fabric softener composition of the invention.

Furthermore, there may be further incorporated in the fabric softener composition of the invention a pigment or a dye for improving appearance of the product, a fluorescent whitener for improving finished whiteness, and a perfume for improving a sensory value during use and after finishing.

/0 The fabric softener composition of the invention can be prepared in the form of a solution, a suspension, an emulsion or the like in a conventional manner.

The fabric softener composition of the present invention imparts the sufficient softness, the antistaticity and the resiliency (fluffy feeling) to clothes of various fabrics.

The present invention is illustrated by the following b examples in further detail. However, the present invention is not restricted thereby.

EXAMPLE 1 Synthesis of N-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethyl]-N,N-dimethylammonium chloride: 248 g of stearic acid and 66 g of N-(2-hydroxyethyl)- N-methyl-l,3-propylenediamine were introduced to a four-neck *.0.00 flask equipped with a stirrer, a thermometer and a dehydration tube and heated to 180 0 C. At the temperature, heating 0 16 C was continued for 10 hours while removing water formed course of reaction. After completion of the heating, 300 g of the reaction mixture was dissolved to 60 g of isopropyl alcohol and the resulting solution was introduced to an autoclave S equipped with a stirrer, a thermometer and a pressure meter.

Then, 28 g of methyl chloride was forcedly introduced to the autoclave and reaction was allowed to proceed at 100°C for 8 hours. After completion of the reaction, isopropyl alcohol was removed under a reduced pressure, thereby 320 g of the /o aimed compound was obtained. Based on an NMR spectra and an IR spectra, it was confirmed that the resulting compound had the following structure.

0

CH

3 CH2CH 2 0CC 17 N Cl-

CH

3

CH

2 CH2CHzNHCC 17

H

3

II

0 NMR Spectra (CDC1 3 Internal Standard TMS): 2.1 ppm 2H, 2.3 ppm (t, S0 II II 2.35 ppm 2H, (OC-CHA-, NHC-CH--)), 3.3 ppm 6H, ((CH3) 2 3.35 ppm 2H, 3.9 ppm 4H, 1 17 0

II

4.55 ppm 2H, 8.1 ppm 1H, 0 IR Spectra (KBr pellet): 1734 cm- 1 1642 c:m 1 1466 cm- 1 1188 cm- 1 EXAMPLE 2 Synthesis of N-[3-(lauroylamino)propyl]-N-[2-(behenoyloxy)s ethyl]-N,N-diemthylammonium chloride: 100 g of lauric acid and 66 a of N-(2-hydroxyethyl)- N-methyl-1,3-propylenediamine were introduced to a four-neck flask equipped with a stirrer, a thermometer and a dehydration tube and heated to 180 0 C. At the temperature, heating I/ was continued for 3 hours while removing water formed course of reaction. Next, 170 g of behenic acid was added to the reaction mixture and the reaction was further proceeded at 180 0 C for 8 hours. After completion of reaction, 280 g of the reaction mixture was dissolved to 55 g of isopropyl St alcohol and the resulting solution was introduced to an autoclave equipped with a stirrer, a thermometer and a pressure meter. Then, 28 g of methyl chloride was forcedly introduced to the autoclave and reaction was allowed to ~proceed at 100 0 C for 8 hours. After completion of the 40 reaction, isopropyl alcohol was removed under a reduced pressure, thereby 300 g of the aimed compound was obtained.

S *18 e -18- Based on an NMR spectra and an IR spectra, it was conf irmed -that the resulting compound had the following structure.

0

CE

3

CH

2 CHr 2 0CCL 21 ±i 43

CH

3

CH

2

CH

2

CH

2 NH-CCjj1123 NMR Spectra (CDCl,, Internal Standard TMS): 2.1 ppm (in, 2H, 2.3 ppm (t, 0 0 2H1), 2.35 ppm. 211, (OC-CH-, NHC-CTH-)), 3.3 ppm 611, ((C-1 3 2 .3.35 ppm 2H1, 1+ (-Cfl 2 3.9 ppm (mn, 4H, (-CH2-N-CH2-)), 0 4.55 ppm. 2H1 8.0 ppm 111, IR Spectra (I(Br pellet): 1733 cm-1, 1642 cur', 1466 cm'1, 1188 cm- *EXAMPLE 3 Synthesis of 3- (stearoylamino)propyl]-N-[9- (stearoyloxy)nionyl N-diinethyl amnmonium methylsulfate: 400 g a 40 aqueous solution of iethylamine and 180 g of 9-chlorononano. were introduced into an autoclave 5 19 equipped with a stirrer, a thermometer and a pressure pump and heated to 100 0 C. At the temperature, 93 g of a 48 aqueou solution of sodium hydroxide was forcedly introduced to the autoclave over 6 hours and the resulting mixture was aged for 1 hours. After cooling, the content was taken out from the autoclave and unreacted methylamine and water were removed therefrom under reduced pressure. Then, ethanol was added thereto and sodium chloride thus precipitated was O filtered off. Ethanol was distilled off from the filtrate lo and the resulting solution was further subjected to distillation to give 125 g of 9-(N-methylamino)nonanol.

120 g of 9-(N-methylamino)nonanol was introduced to an autoclave equipped with a stirrer, a thermometer, a pressure meter and a drop funnel, 36.8 g of acrylonitrile was /s added thereto dropwise at 70 0 C and the resulting mixture was aged for 1 hour. Then, 7.8 g of Raney nickel was added to the mixture and hydrogen gas was introduced to the autoclave till the inner pressure reached to 20 kg/cm 2 -G to thereby allow hydration reaction to proceed at 600C for 8 hours.

2o After cooling, the content was taken out from the autoclave and subjected to distillation to give 122 g of N-(9-hydroxynonyl) -N-methyl-1,3-propylenediamine.

284 g of stearic acid and 115 g of N-(9-hydroxynonyl) -sthyl-1,3-propylenediamine were introduced to a r6 four-n-ck jlask equipped with a stirrer, a thermometer and a dehydration tube and heated to 180°C. At the temperature, heating was continued for 10 hours while removing water formed course of reaction. After cooling the reaction mixture, 70 g of isopropyl alcohol was added to the mixture and the resulting mLi.cure was heated to 601C. At the Stemperature, 62 g of dimethyl sulfate was dropwise added to the mixture iover 2 hours. After aging for 5 hours, isopropyl alcohol was distil~led off from the reaction mixture, thereby 420 g of the aimed compound was obtained. Based on an NMR spectra and an IR spectra, it was confirmed that the j'o resulting compound had the following structure.

0 C11 3

CH-

2

(UCH

2 7-,CH 2 0CC 1 ,H3 N+ CH 3 S0 4

CH

3 C11 2 C11 2 C1 2 NHCClIH 23 0 N~MR Spectra (CDCl 3 internal standard TMS): 2.1 ppm (mn, 2H, 2.3 ppm (t, 0 0 2H1), 2.35 ppm 211, (aC-CF12-, sloe.:3.3 ppm 611, 2 3-4 ppm 211, (-CH2-NI1CO-)), 3.8 ppm, 3H1, (CH3SO4()), 3.9 ppm (mn, 411, (-CH2-N-CH2-)), 0 4.4 ppm, 2H1, 8.0 ppm 1H1, 21 0 (-1C) IR S~ectra (RBr pellet): 1731 cur', 1640 cur', 1466 1188 cur' EXAMPLE 4 Synthesis of N-[3-(isostearoylamino)propyl)-N-[2-(isostearoyloxy ethyl] N-dimethylammonium chloride: The procedure of Example 1 was rep~ated except that s280 g Emersol 87 (trade name, manufactured by EMERY) was used in place of stearic acid, thereby the aimed compound having the following formula was obtained.

CH3 CH 2

CH

2

CH

2 NHCO CM 2 CH CU 2 qCH 3

N+CH

3 C1_

CM

3

CH

2

CII

2 OCO (CM 2 ,CH CH 2 qCH 3 I wherein p and q each represents a value of from 0 to 16, provided that the sum of p and q is from 10 to 16.

EXAMPLE Synthesis of Hydrochloric acid salt N-[3-(stearoylamino)propyl stearoyloxy) ethoxy) ethyl -N-methylamine: Stearic acid and N-(hydroxyethyl )-N-methyl-i, 3- -oropylenediainine were reacted as in the manner of Example 1 and 300 g the resulting product was dropwise added to a f ourneck flask containing 1500 g of water and 49 g a hydrochloric acid. Water was removed from the resulting -22 mixture by.freeze-drying, thereby the aimed compound was obtained. Based on an NMR spectra and an IR spectra, it was confirmed that the resulting compound had the following structure.

C11 3

CH

2

CH

2

CH

2

NHCOC

17

H

3 N+ C1- H CH 2

CH

2

OCOC

17

H

3 NI4R Spectra (CDCl.

3 Internal Standard VMS): 2.05 ppm (in, 2H1, 2.2 ppm. (t, 0 0 211), 2.35 ppm 211, (0C-C-F1-, NrHC-C-H-)), 2.75 ppm 3H1, (Cfl2-N-), 3.05 ppm 2H1, (N-0fl 2 3.2 ppm 2H1, (N-CH2-C-0O-C0)) 3.4 ppm 2H1, ff-NHC0--)) 0 ppm 2H1, 7.1 ppm 1H1, 0 k-N1HC-))r 12.0 ppm (br, 1H1, IR Spectra (KBr pellet): 1740 cm- 1 1647 cm-1 1470 cm'1, 1167 cm- 1 555523 EXAMPLE 6 Hydrochloric acid salt of N-[3-(stearoylamino)methyl (stearoyloxy) ethyl] -N-methylamine: N-Methylmorpholone was synthesized in the manner of Example 2 of Japanese Pc tent Application Hei-3-20709.

s- Namely, dehydrative ring-formation reaction of Nmethyldiethanolamine was carried out in the presence of a catalyst having the composition of Cu/Ni/Pd =5/1/0.01, S -thereby N-methylmorpholone was obtained.

115 g of N-methylmorpholone and 269 g of stearylamine to were introduced into a four-neck flask equipped with a stirrer and a thermometer and heated to 100 0 C. At the temperature, reaction was proceeded for 2 hours. 350 g of acetone was added to the resulting mixture and 303.5 g of stearoyl chloride was dropwise added thereto with stirring.

As a result, the aimed compound was precipitated as a while precipitate. The white precipitate was separated from acetone by filtration and then dried to thereby 560 g of the O aimed compound was obtained. Based on an NMR spectra and an IR spectra, it was confirmed that the resulting compound had R the following structure.

CH

3 CHzCONHC 1

H

3 s N Cl1 H CHzCHOCOCC 7 IHj S24* a NM4j Spectra (CDCl 3 Internal Standard TMS): 2.4 ppm. (mn, 2H, 3.05 ppm, 3H, 3.2 ppm. 2H, (CONH.-CH2-)), 3.55 ppm (br, 1H), 3.75 ppm. (br, 1H, 4.1 ppm 2H, (N-CH-CNH ppma 2H, (-N-C-Cfl2CO-) 8.6 ppm (br, 1H, 11.6 ppm (br, 1Hi, IR Spectra (K~r pellet): 1745 cm-1, 1675 cm-1 1475 1158 cm-1 EXAMPLE 7 Synthesis of (N'-butylainindo)methyl) 2-(stearoyloxy)ethyl] -N-stearyl-N-methylamnionium chloride: N-Stearylmorpholone was obtained in a similar manner as in the aforementioned Example 6 using Nstearyldiethanolamine.

353 g of N-stearylmorpholone and 73 g of butylamine were introduced to an autoclave equipped with a stirrer, a 'o thermometer and a pressuze meter and heated ,o 100 0 C. At the temperature, the reaction was proceeded for 2 hours. Then, 400 g of the reaction kroduct and 800 g of acetone as a solvent were introduced to a four-neck flask equipped with a stirrer, a thermometer and a cooling tube. The content of the flask was heated to 501C and 285 g of stearoy. chloride and 78 g of a 48% aqueous solution of sodium hydroxide were p dropwise added thereto simultaneously. The resulting mixture' was aged for 3 hours at the temperature and NaCi formed was removed therefrom by filtration. The filtrate was introduced to an autoclave and 57 g of methyl chloride was forcedly 57 introduced tJareto. After reacting at 100 0 C for about 8 hours, the reaction mixture was taken out from the autoclave.

A white precipitate was removed from the reaction mixture by..

filtration and dried to thereby obtain 605 g of the aimed compound. Based on an NNR spectra and an IR spectra, it was (confirmed that the resulting compound had the following structure.

C

18

H

37

CH

2 CON11C 4

H

9 N+ C1-

CH

3

CH

2

CH

2 OCOC17 3 NMR Spectra (CDCl 3 Internal Standard TM4S): 2.4 ppm 2H1, (O-CO-CH2-)), 3.2 ppm 2H1, (CONH-CH2-)), 3.35 ppm 311, 3.6 ppm 2M1, 3.9 ppm 211, (-N-CH2-C-OCO-)), ppm 211, (-CH2OCO-)), 4.6 ppm 2H1, (N-CH2CONH-)) 9. 4 ppm 1Hi, (-CONHi-)) IR Spectra (KBr pellet): 1735 cm-1, 1673 cnf', 61473 1160 cnf' 0 EXA1~tPLES 8 TO 23 AND COMPARATIVE EXAXPLES 1 TO 4 The compounds used in the following Examples and Comparative Examples are set forth in Table 1 below.

a a

P.CR*

a a a a. a a a.

a fl-a a.

a a a.

a. a.

a a a -27a. a a.

a.

a S a a at-a..

-a a

V

4 *9 fl *9 59 5 9 4 9 4 5 9 4 C *9 '4 99 4 9 9 4 4 9 a 4 4 994 *9* TABLE 1 Compound Formula Rto R 5 and m in f ormula

R

1 I M eth yl

R

2 CO I R 3 CO: Hydrogenated tallow f atty acid residue m: 2 Neutralizing Quaterniz ing agrent acren~t A-1i A-i Hydrochloric acid A-12 RI: Hydroxyethyl

R

2 CO, R 3 CO: Oleoyl m: 2 Glycolic acid A-13 A-1 A- 21 A-22 A-31 A-2

R

1 Hydroxyethyl

R

2 CO, R 3 CO: Lauroyl/stearoyl (1:1) m: 2

R

2 Stearyl

R

3 CO: Lauroyl

R

4 Methyl

R

2 Hydrogenated tallow alkyl

R

3 CO: Stearoyl

R

4 Methyl

R

1 Methyl

R

3 CO: Stearoyl

R

5 Stearyl

CH

3 Cl Glycolic acid A-2 A-3 Hydrochloric acid Hydrochloric acid 0 0 .00 OflO 0.0. .0 00 00 0 0 0 000 0 0 0 00 SO *000 0 0S *0 00 0* 0 0 0 0 0 S 5 0 055 505 5.0 555 TABLE 1 (cont'd) Compound Fotmula A-32 B-1 B-2 A-3 R' to R 5 and m in f ormula

R

1 Methyl

R

3 CO: Unhydrogenated tallow fatty acid residue Oleyl Di-hydrogenated tallow alkyl-dimethylammoniun chloride Neutralizing Quaternizing acent, gn Acetic acid Stearyl R"COi; Stearoyl Hydrochloric acid I Note: 1) Formula

IN-CH

2 R'-C 1

C;

2

H

4

NHCOR"

The compositions indicated in Table 2 were evaluated for the softness and the resiliency by the following test.

Evaluation of softness and resiliency Method: Using a 30 1 laundering machine, 2 kg of commercial cotton towels and 1 kg of acrylic jersey fabrics were laundered in 3.50 DH hard water with a commercial detergent (Attack, trade name, a product of Kao Corporation) 5 times to remove the textile finishes from the respective fibers.

/0 Then, 1.5 g of one of the compositions indicated in Table 2 was added and the wash load was treated under pulsation at 0 C for 1 minute.

In each of the test compositions, a polyoxyethylenemodified dimethylpolysiloxane was incorporated in the amount /i of 1 by weight based on the total amount of the compound according to the invention. The balance was water.

Evaluation method: The fabrics treated as above were dried in the interior atmosphere and, then, allowed to stand in a constant W temperature-humidity chamber controlled at 25°C and 65% RH.

The fabrics were then evaluated for the softness and

S

the resiliency.

The evaluation of the softness and the resiliency was performed by five expert panelists by the method of paired S Z comparison using a fabric treated with 10 cc of a softening agent containing 15 by weight of di-hydrogenated tallow- 30

S

alkyl dimethylammonium chloride as a reference control. The scoring schema was as follows.

Definitely superior to control in the softness or the resiliency Slightly superior to control in the softness or the resiliency 0: Equivalent to control Slightly inferior to control in the softness or the resiliency Definitely inferior to control in the softness or the resiliency The results are indicated by the mean values of the evaluation results of the five panelists.

S

31 TABLE 2 (Softness and resiliency) Formulation by weight) Compound according Other to the invention incredient Performance Softness Resiliency Example 8 Example 9 Example 11 Example 13 Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 A-11 (18) A-11 (15) A-12 A-13 (18) A-21 (18) A-21 (15) A-22 (18) A-22 (15) A-22 13) A-31 (18) A-31 (15) A-32 B-I (3) B-2 (3) B-l (3) B-2 B-1 (3) B-1 B-2 Comparative Example 1 Comparative Example 2 a 9 a a *r a a so a

S

sa It is apparent from Table 2 that the use of the compound of the invention leads to satisfactory results in both terms of the softness and resiliency.

32 EXAMPLES 20 to 22 and COMPARATIVE EXAMPLES 3 and 4 Using the compositions indicated in Table 3, the stacking height of cotton towels was measured for evaluation of the resiliency.

Evaluation of resiliency: Three Lu,'ton towels, treated as in the manner of Examples 8 through 19 and each folded in 8, were stacked up and compressed under a pressure load of 5 g/cm 2 for minutes. The pressing load was then removed and the height /0 of the stack was measured. The higher height of the stack indicates the higher resiliency of the towels.

TABLE 3 Evaluation of resiliency (stacking height of towels) Resiliency Formulation (height of stack) (cm) Example 20 Same as Example 11 9.2 Example 21 Same as Example 15 9.4 Example 22 Same as Example 18 9.4 Comparative Same as O Example 3 Comparative Example 1 8.9 Comparative Same as Example 4 Comparative Example 2 8.8 a SEXAMPLE 19 An aqueous fabric softener composition of the following formulation was prepared.

33 a a« a (Formulation) Component Amount (by weight) The neutralization product of di-long chain tertiary amine compound 18 Polyoxyethylene (average added moles: lauryl ether 1 Calcium chloride 0.1 Perfume 0.4 Dye 20 ppm Defoaming agent 100 ppm Water balance This aqueous fabric softener composition imparted to clothes o: softness with good resiliency. Also, this aqueous fabric softener composition showed good dispersion stability at storage for a long period of time.

While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the /o spirit and scope thereof.

3 a i a a.

34 a

Claims

1. An aqueous fabric softener composition comprising water and an ammonium salt obtained by neutralizing the following Compound a di-long chain tertiary amine compound 0 containing one R-C-0- group wherein R represents an alkyl or alkenyl group containing from 11 to 21 i carbon atcn, one -CONH- group and one alkyl or alkenyl group containing from 11 to 22 carbon atoms with an inorganic acid or an organic acid containing trom 1 to 6 carbon atoms, or by quaternizing said Compound or a mixture of said ammonium salt obtained by neutralizing said Compound with said Compound and said ammonium salt obtained by quaternizing said Compound

2. An aqueous fabric softener composition of claim S 1, wherein said Compound is at least one compound selected from the compounds represented by formulas (A-l) through C 3 H 6 NHCOR 2 SR-N (A-l) CmH 2 mOCOR 3 4 e a a CHf 2 C ONHR 2 R'-N (A-2) C 2 H 4 OCOR" Ch7ONHR' R5-N(A-3) C 2 H 4 OCOR 3 wherein, RI represents an alkyl or hydroxya7-.j'l group containing from 1 to 4 carbon atoms; R 2 R 3 each represents an alkyl or atkenyl group containing from 11 to 21 carbon atoms; R 4 represents an alkyl group containing from 1 to 4 carbon atoms; R 5 represents an alkyl or alkenyl group containing from 12 to 22 carbon atoms; and m is an integer of from 2 to 9.

3. An aque(, fabric softener composition of claim 1, wherein said Compouna is <,uaternized with methyl chloride or a dialkyl sulfatG.

4. An aqueous fabric softener composition of claim 1, wherein a total amount of said ammonium salt ranges from 4 to 40 by weight.

An ammonium salt obtained by neutralizing the following Compound a di-long chain tertiary amine compound 41 36 0 containing one group wherein R represents an alkyl or alkenyl group containing from 11 to 21 carbon atom, one -CONH- group and one alkyl or alkenyl group containing from 11 to 22 carbon atoms with an inorga.;iic acid or an organic acid containing from 1 to 6 carbon atoms, or guaternizing said Compound

6. An ammonium salt of claim 5, wherein said Compournd is at least one compound selected from the comrpounds represented by formulas through C 3 H 6 NHCQR 2 R 1 -N (A-1) C.1i 2 m0C0R 3 CH1 2 CONHR 2 RI-N C 2 H 4 OCOR 3 CH 2 CONHR' *R 5 -N (A-3) C 2 H- 4 0C0R 3 wherein, R' represents an alkyl or hydroxyalky. group containing from 1 to 4 carbon atoms :01.110 37 0 -1 R 2 R 3 each represents an alkyl or alkenyl group containing from 11 to 21 carbon atoms; R 4 represents an alkyl group containing from 1 to 4 carbon atoms; R 5 represents an alkyl or alkenyl group containing from 12 to 22 carbon atoms; and m is an integer of from 2 to 9.

7. An ammonium salt of claim. 5, wherein said Compound is quaternized with methyl chloride or a di- lower alkyl sulfat(-.

8. An ammonium salt of claim 5, wherein said aznmoniuiA salt is represented by the following formula or R1 C 3 H 6 NHCORI N+ X (C-I) SC,.,H 2 OCOR' RI CH 2 CONHR 2 N+ X (C-2) R' 6 CA 2 OCOR 3 R' CH 2 CONHR' N+ X (C-3) *R 6 C2H 4 OCOR 3 0 Ca..38 wherein, R 1 represents an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms; R 2 K 3 each represents an alkyl or alkenyl group containing from 11 to 21 carbon atoms; R 4 represents an alkyl group containing from 1 to 4 carbon atoms; represents an -ikyl or alkenyl group d containing from 12 to 22 carbon atoms; R 6 represents a hydrogen atom, a hydroxy group, or an alkyl group containing 1 or 2 carbon atom.; X" represents an anion selected from the group consisting of residues of an inorganic acid and an organic acid, a halogen atom and a lowe alkyl sulfate; and m is an integer of from 2 to 9.

9. An ammonium salt of claim 8, wherein R 6 represents a hydrogen atom or an alkyl group containing 1 or 2 carbon atoms and X- represents a halogen atom, a lower alkyl sulfate or a group represented by 1/2 SO 4 2

10. An aqueous fabric softener composition substantially as hereinbefore described with reference to any one of the Examples excluding the comparative examples.

11. An ammonium Salt substantially as hereinbefore described o with reference to any one of the Examples excluding the comparative examples. DATED this NINETEENTH day of FEBRUARY 1992 S" Kao Corporation Patent Attorneys for the Applicant SFRLSON FERGUSON 39 _i~i -I H' S y ABSTRACT OF THE DCLOSURE An aqueous fabric softener composition is disclosed, which comprises water and, as a softener new material, an ammonium salt obtained by neutralizing the following Compound a di-long chain type tertiary amine 0 C compound containing one R-C-O- group in which R represents an alkyl or alkenyl group containing from 11 to 21 carbon atom, one -CONH- group and one alkyl or alkenyl group containing from 11 to 22 carbon atoms o*oo** with the following Compound an inorganic acid or an organic acid containing from 1 to 6 carbon atoms, O*e or quaternizing Compound or a mixture of the ammonium 0 salt obtained by neutralizing Compound with Compound (B) and the ammonium salt obtained by quaternizing Compound An anuionium salt obtained by neutralizing or quaternizing o* Compound is also disclosed. The fabric softener composition of the present invention imparts the sufficient softness, the antistaticity and the resiliency (fluffy feeling) to clothes of various fibers.