WO2003027057A1

WO2003027057A1 - Method for preparing of cationic surfactants and fabric softener composition using the same

Info

Publication number: WO2003027057A1
Application number: PCT/KR2002/001826
Authority: WO
Inventors: Gug-In Jeong; Jeong-Wook Ha; Yeo-Kyeong Yoon; Tae-Seong Kim; Eun-Joo Lee
Original assignee: Lg Household & Health Care Ltd.
Priority date: 2001-09-28
Filing date: 2002-09-27
Publication date: 2003-04-03
Also published as: JP2005503431A; CN1589255A; CN1301961C

Abstract

The present invention relates to a process for the preparation of a cationic surfactant and a fiber softening composition comprising it and more particularly to a process for preparing a cationic surfactant comprising reacting a fatty acid and an amine, tertiarizing it and quaterizing with neutralization and a fiber softening composition using it. Also, the invention provides a process for preparing a cationic surfactant comprising the steps of reacting a fatty acid and an amine, tertiarizing it and quaternarizing it with dimethylsulfate or alkylhalide, and a fiber softening composition comprising it. The cationic surfactants prepared according to the methods of the present invention are excellent in solubility in water by possessing an amine group or hydroxyl group, which is hydrophilic, within molecules and have highly excellent physicochemical performances such as softening properties, anti-electrostratic properties, dispersion properties, etc, and accordingly they can provide a fiber softening composition having good softening effects to clothes and anti-electrostatic effects as well as having excellent dispersion in water and bio-degradable effects.

Description

METHOD FOR PREPARING OF CATIONIC SURFACTANTS AND FABRIC

SOFTENER COMPOSITION USING THE SAME

BACKGROUND OF THE INVENTION

(a) Field of the invention

The present invention relates to a process for the preparation of a

cationic surfactants and a fiber softening composition comprising the same and

more particularly, to a process for the preparation of a cationic surfactant having

excellent solubility in water by possessing an amide group or hydroxyl group,

which is hydrophilic, within molecules and showing highly excellent softening

properties, anti-electrostatic properties and dispersion, and a fiber softening

composition comprising the same.

(B) Description of the Related Art

Cationic surfactants provide their hydrophilic portion as a cation when

dissolved in water. Such cationic surfactants show normal surface active effects

such as cleaning, emulsification, solubility, etc. and at the same time, they exhibit

softening effects or anti-electrostatic effects, they are classified into quaternary

ammonium salts and amine derivatives according to their structural

characteristics.

In prior arts, DDAC (dimethyl dialkyl ammonium chloride) was widely

used as a typical cationic surfactant (JAOCS 61 , 367(1984), and 65(10),

1682(1988)), but recently, its usage amounts are being reduced slowly because

of its low bio-degradability. Hence, studies on introducing a group having degradable functional groups such as an ester or amide within an alkyl group into

a molecule are in active progress.

As such cationic surfactants, quaternary ammonium salts of amidoamine,

quaternary ammonium salts of amidoesteramine, cationic surfactants of

imidazoline and imidazoline esters, etc. are conventionally widely used and they

are mostly used as a major component of fiber softeners.

For example, Japanese Patent Pyung No. 6-345704 describes an

amidoamine compound, a process for preparing cationic surfactants using it, and

a method of using it as a softener, and Japanese Patent Pyung No. 6-336466

describes an amidoesteramine compound, a process for preparing cationic

surfactants using it, and a method of using it as a softener. Also, Japanese

Patent Pyung No. 4-257372 discloses a process for preparing imidazoline ester

and a softening composition, and Japanese Patent Pyung No. 2-1479 discloses a

process for preparing an imidazoline and a conditioning compound comprising it.

Above imidazoline and imidazoline ester are prepared by reacting a

diethyltriamine and aminoethylaminoethanole with two equivalents of fatty acids

and quaternalizing the reactant with dimethylsulfate. However, these cationic

surfactants show an improved bio-degradability as compared with cationic

dialkyldimethylammonium salts, but they are still unsatisfactory.

Recently, it has been reported that when an alkyl group, which is a

lipophilic portion of cationic surfactants includes easily-degradable functional

groups such as an ester group, their bio-degradability becomes highly excellent

as compared with the above-mentioned prior dimethyldialkyl ammonium chloride, amide type quaternary ammonium salts, and imidazoline type cationic surfactants

(Tenside Surfactant Detergent, 1993, 30, 186-191).

Hence, various derivatives of quaternary ammonium salts having an

ester group within molecules are being widely studied, and as a commercialized

typical example, International Laid-Open Patent No. 94/07928 describes a

method of preparing a softener and haircare products using quaternalized

cationic surfactants induced from a triethanole amine. International Laid-Open

Patent No. 93/23510 discloses a method of preparing a condensed fiber softener

and bio-degradable fiber softening composition using cationic surfactants having

an ester bond between two hydrophobic groups, and International Laid-Open

Patent No. 92/15745 discloses a method of preparing a condensed fiber

softening composition using a linear fatty alcohol ethoxylate, polydialkylsiloxane,

etc in an imidazoline or imidazoline ester. Also, International Laid-Open Patent

No. 94/14935 describes a method of preparing a condensed fiber softening

dispersion comprising quaternary ammonium compounds prepared from

triethanole amines and fatty acids and International Laid-Open Patent No.

94/13772 describes a method of preparing a highly-condensed fiber softener

using a quaternary ammonium compound having an ester group within molecules

and a non-ionic dispersion in a small amount.

However, in case of imidazoline type quaternary ammonium salts, their

structure is unstable and thus imidazoline ring is broken in water. Also, in case

of quaternary ammonium salts containing an ester group within molecules, their

solubility to water is quite poor, and thus, in order to maintain product stability for an extended time period, they have to use compounds such as glycerines, lower

alcohols, non-ionic dispersions, etc. in a large amount, which causes the

deterioration of the inherent, basic performances of ammonium salts.

Accordingly, in order to increase hydrophilic properties, an oleyl group is

introduced into an alkyl group, which is a hydrophobic portion, but this causes

severe discoloration and foul odors during process.

Recently, in order to make quaternalization easy, cationic surfactants

wherein tertiary amines are neutralized with acids are being studied for example,

in Japanese Laid-Open Patent Pyung No. 5-195433, Pyung No. 5-195432, Pyung

No. 6-57632, Pyung No. 5-132860, Pyung No. 5-230763, etc., but as several

by-products are produced when cured fatty acids are reacted with amines in the

above methods, expensive amines that are not generally used for an industrial

purpose had to be used and thus they were not desirable.

Also, in Japanese Laid-Open Patent Pyung No. 3-295855, Pyung No.

4-208964, Pyung No. 4-267468, Pyung No. 4-28023, and Pyung No.4-6984,

there are disclosed fiber softeners having amidoester type tertiary amines and

quaternary salts with an excellent dispersion in water as a major component, but

these fiber softeners have a problem that their storage stability falls down at a

high temperature.

SUMMARY OF THE INVENTION

The present invention is made in consideration of the problems of the

prior art, and it is an object of the invention to provide a process for the

preparation of a cationic surfactant having excellent solubility in water by possessing an amide group or hydroxyl group, which is hydrophilic, within

molecules and showing highly excellent softening properties, anti-electrostatic

properties and dispersion.

It is an another object of the invention to provide a process for the

preparation of a cationic surfactant with a high efficiency by a simple method

while minimizing by-products.

It is still another object of the invention to provide a fiber softening

composition having uniform adhesion effects onto clothes and thereby having

excellent softening properties, anti-electrostatic effects, and absorption.

It is still another object of the invention to provide a fiber softening

composition with a remarkably-improved storage stability, dispersion in water and

bio-degradable effects.

To achieve the foregoing objects, the present invention provides a

process for preparing a cationic surfactant represented by the following formula

1 :

wherein Ri is a linear or branched alkyl group, alkenyl group, or a mixed

group comprising one or more kinds of C₇-C₂ι; X is CH₃, (CH₂)_mOH,

(CH₂)_mOCOR₂, (CH₂)mNH₂, or (CH₂)_mNHCOR₂, wherein R₂ is a linear or branched

alkyl group, alkenyl group, or a mixed group comprising one or more kinds of

C₇-C₂ι, and m is an integer of 2 to 6; Y is a hydrogen atom, CH₂CHOHCH₂OH,

CHaCHOHCHaCI, CH₂CH₂CN, CH₂CH₂COOCH₃, CH₂CH₂COOH, or CH₂CH₂OH ; Z is a hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glyconic acid,

apple acid, tin acid, tartaric acid; and n is an integer of 2 to 6;

comprising the steps of:

a) reacting an amine and a higher fatty acid;

b) tertiarizing the reactant obtained from step a); and

c) quaternarizing the tertiary amine obtained from step b) by neutralizing

it with an acid.

Further, the invention provides a fiber softening composition comprising

the compound represented by the above formula 1.

Also, the present invention provides a process for preparing a cationic

surfactant represented by the following formula 2:

wherein R³ is a linear or branched alkyl group, alkenyl group, or a mixed

group comprising one or more kinds of C₇-C₂₁;

R⁴is a linear or branched alkyl group, alkenyl group, or a mixed group comprising

one or more kinds of C C₂₁;

X is CH₃, (CH₂)_mOH, (CH₂)_mOCOR⁵, (CH₂)_mNH₂, or (CH₂)_mNHCOR⁵,

wherein R⁵ is a linear or branched alkyl group, alkenyl group, or a mixed group

comprising one or more kinds of C -C₂₁, m is an integer of 2 to 6;

Y is a hydrogen atom, CH₂CHOHCH₂OH, CH₂CHOHCH₂CI, CH₂CH₂CN,

CH₂CH₂COOCH₃, CH₂CH₂COOH, or CH₂CH₂OH; M is a sulfate or halogen atom; and

n is an integer of 2 to 6;

comprising the steps of:

a) reacting a fatty acid of the following formula 6:

O i l R³COH

wherein R³ is as defined above;

and an amine of the following formula 7:

H₂N(CH₂)_nNH-X

wherein n and X are as defined above;

to prepare an amido amine of the following formula 5:

O il R CNH(CH₂)nNH-X

wherein R³, n and X are as defined above;

b) tertiarizing the amido amine of the above formula 5 with a tertiarizing

agent (Y) to prepare a compound of the following formula 4:

wherein R³, n, X and Y are as defined above;

c) quaternarizing the compound of above formula 4 with a compound of

the following formula 3:

R⁴-M

wherein R⁴ and M are as defined above. Further, the invention provides a fiber softening composition comprising

the amido ammonium salt represented by the above formula 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is hereafter described in detail.

The present invention is characterized by a process for preparing a cationic

surfactant of formula 1 as defined above by reaction of using a fatty acid, an

amine and a tertiarizing agent and then quaternarization reaction by neutralizing

with an acid, and a fiber softening composition comprising it.

Also, the present invention is characterized by a process for preparing a cationic

surfactant of formula 2 as defined above by reacting a fatty acid and an amine,

tertiarizing it and quaternarizing it with a dimethylsulfate or alkylhalide, and a fiber

softening composition comprising it.

The present invention can improve solubility in water by introducing an

amide or hydroxyl group, which is hydrophilic, within molecules and minimize

by-products while maintaining softening power, anti-electrostatic power, etc.,

which are the intrinsic performances of quaternary ammonium salts, to same or

high extent as the prior quaternary ammonium salts.

The following description is directed to a process for preparing of the

cationic surfactant of formula 1 of the present invention. Preparation of

quaternarized ester derivative of formula 1 as defined above is shown in the

following scheme 1 :

[Scheme 1] O O

R¹COH + H₂N(CH₂)_nNH-X → R¹ CNH(CH₂)nNH-X + Y

ft

— r CNh CHj Z

^Nγ

In the scheme 1 above, Ri is a linear or branched alkyl group, alkenyl

group, or a mixed group comprising one or more kinds of C7-C₂₁; X is CH₃,

(CH₂)_mOH, (CH₂)_mOCOR₂, (CH₂)_mNH₂, or (CH₂)_mNHCOR₂, wherein R₂is a linear

or branched alkyl group, alkenyl group, or a mixed group comprising one or more

kinds of C₇-C₂₁, and m is an integer of 2 to 6; Y is a hydrogen atom,

CH₂CHOHCH₂OH, CH₂CHOHCH₂CI, CH₂CH₂CN, CH₂CH₂COOCH₃,

CH₂CH₂COOH, or CH₂CH₂OH ; Z is a hydrochloric acid, sulfuric acid, nitric acid,

phosphoric acid, glyconic acid, apple acid, tin acid, tartaric acid; and n is an

integer of 2 to 6;

As shown in scheme 1 , the present invention is proceeded by the

reactions of three steps.

First, in a first step, a higher fatty acid and an amine are reacted to

produce an amido amine.

As the amine used in the first reaction, there can be used quaternary

ammonium salts of amidoamine, quaternary ammonium salts of amidoesteramine,

imidazolines, imidazoline esters, etc., and it is preferred to use

aminoethylaminoethanole or diethylenetriamine. The amine is used in an

amount of 0.5 to 1.0 equivalent with regard to 1 equivalent of the higher fatty acid,

and if the amount of the amine is less than 0.5 equivalent, unreacted fatty acids remain or the amount of amines, which can become quaternary salts, is

decreased, thereby causing the deterioration of physicochemical properties, and

if it exceeds 1.0 equivalent, the amount of unreacted amines is increased and

thus toxicity increases and the productivity is low.

As the higher fatty acid, it is preferable to use a mixture of one or more

kinds having a linear or branched alkyl group or alkenyl group of C₈-C₂₂.

For example, there are stearic acid, octanoic acid, decanoic acid, dodecanoic

acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid,

docosanoic acid, etc.

In the first reaction, the amine and the higher fatty acid are reacted

without solvents, and it is preferred that reaction temperature is 100 — 180 ^°C

and reaction time is 1 — 20 hours.

In a second step, a tertiarizing agent is added to the produced amido

amine to tertiary it.

It is preferred to use the tertiarizing agent used in the second reaction in

an amount of less than 1.0 equivalent with regard to 1 equivalent of the amido

amine, which is the reactant prepared from the first reaction. If the amount of

the tertiarizing agent exceeds 1 equivalent, unreacted tertizaring agent remains

and thus discoloration and foul odor occur and physicochemical properties are

deteriorated.

As the tertiarizing agent, there are glycidol, ephichlorohydrine,

acrylonitrile, methyl acrylate, acrylic acid, vinyl alcohol, etc.

Also, the above tertiarizing reaction may be carried out with or without solvents. In case of using the solvents, as reaction solvents, there are used one

or more primary, secondary, tertiary or polyvalent alcohols selected from the

group consisting of water, methanole, ethanole, propylalcohol, hexyleneglycol,

butylalcohol, isopropylalcohol, ethyleneglycol, glycerine, propyleneglycol,

polyethyleneglycol and it is preferable to use 1 to 99% by weight of the total

weight of the reactants.

It is preferred that the above tertiarizaing reaction is carried out at reaction

temperature of 30 ~ 100 ^°C and for reaction time of 0.1 ~ 5 hours.

In a third step, the tertiarized amine compound is neutralized with an acid

to quaternarize it, thereby producing a quaternary salt.

Especially, the present invention is characterized in that in the

quaternarizing step, the neutralization is performed only by acid to prepare a

quaternary salt, instead of quaternarizing by addition of an additional

quaternarizing reagent as used before. According to such process, quaternary

salts of quaternarized amido amine, quaternary salts of amido ester amine or

quaternary salts of diamido amine can be prepared with high efficiency.

As the acid used in the above neutralization in the present invention, it is

preferable to use hydrochloric acid, sulfuric acid, phosphoric acid, glyconic acid,

apple acid, tin acid or tartaric acid.

As above described, according the present invention, the cationic

surfactant represented by formula as defined can be prepared with high efficiency

which is excellent in solubility in water by possessing an amide group or hydroxyl

group, which is hydrophilic, within molecules and is highly excellent in physicochemical characteristics such as softening properties, anti-electrostatic

properties and dispersion properties.

Further, the present invention provides a fiber softening composition

comprising the compound of formula 1 prepared from the methods as described

above.

The inventors continued to apply compounds suitable for use of fiber

softeners as a major component and as a result, they found that the fiber

softening composition comprising the quaternary salt of amidoamine of formula 1

as defined above as a major component is excellent uniform adhesion effects

onto clothes and thus has excellent softening properties, anti-electrostatic effects,

and absorption at the same time as well as excellent dispersion in water and

bio-degradability, thereby completing the present invention.

In the formula 1 , R₂ is linear or branched alkyl group, alkenyl group or

alkylalkenyl group of C₇ to C₂ι, and if the number of carbon atoms is less than 7,

the adhesion effects onto clothes are not maintained, thereby causing the

deterioration of softening effects and anti-electrostatic effects and if the number

of carbon atoms exceeds 22, slipping or excessive softening effects occur,

thereby causing poor touch.

In the fiber softening composition of the present invention, the fiber

softening composition comprises the quaternary salt of amidoamine of formula 1

as defined above as a major component. In addition to the quaternary salt of

amidoamine of formula 1 , quaternary salts of amidoesteramine, or quaternary

salts of diamidoamine may be comprised, and especially, it is preferable to comprise the quaternary salts of amidoamine. The quaternary salt of

amidoamine of formula 1 may be used alone or in a mixture and it is preferred to

use the quaternary salt of amidoamine of formula 1 in an amount of 1 to 30 parts

by weight in the fiber softening composition. When the quaternary salt of

amidoamine of formula 1 is used alone or by mixture in the fiber softening

composition, if it is used in an amount of less than 1 part by weight, softening

effects or anti-electrostatic effects onto all kinds of clothes are unsatisfactory and

if it is used exceeding 30 parts by weight, softening stability and freezing stability

may become poor.

The fiber softening composition according to the present invention may

use, if necessary, a non-ionic surfactant as a softening agent in addition to the

compound of formula 1 , which is a cationic softening component.

The examples of the non-ionic surfactant used as a suitable softening

agent of the cationic softening component in the present invention include

polyoxyethylene (2 to 50 mol) alkyl-alkenylether or polyoxyethylne (2 to

50 mol) -alkyl phenyl ether (2 to 50 mol) of C₁₀-C₂₀; polyoxyethylene (2 to 50 mol)

alkyl-alkenylester or polyoxyethylene (2 to 50 mol) alkyl-hydroxy fatty acid ester

of Ci₀-C₂₀; sorbitane fatty acid alkyl ester or its ethylene oxide (15 to 40 mol)

additives, polyoxyethylene (1 to 30 mol) alkyl-alkenylamide; polyoxyethylene (1 to

50 mol) alkyl-alkenylamine, glyceryl monoalkyl-alkenyl ester; ethylene oxide

additives (2 to 50 mol) of cured castor oil; alkylamineoxide; and

amidopropylamineoxide, and these surfactants can be used alone or in a mixture

of two more kinds. It is preferred to use the non-ionic surfactant in an amount of 0.1 to 30 parts by weight with regard to 100 parts by weight of the compound of

formula 1. If the content of the non-ionic surfactant exceeds 30 parts by weight,

the stability of products is deteriorated and it prevents the cationic softening

component of the quaternary salt of amidoamine represented by formula 1 from

being adhered to clothes, thereby causing the deterioration of softening effects.

Also, if necessary, the fiber softening composition of present invention

may further comprise a dispersion stabilizer. As the dispersion stabilizer, there

can be used lower alcohol or glycols of Ci to C₈, higher alcohols of C₁₂ to C₂₀,

iodide, magnesium, sodium chloride, calcium chloride, sodium nitrate, or a

mixture thereof. More preferably, there can be used ethanole, isopropyl alcohol,

ethyleneglycol, propyleneglycol, hexyleneglycol, trimethylpentanediol,

setylalcohol, stearylalcohol, magnesium chloride, sodium chloride, calcium

chloride, sodium nitrate, a mixture of thereof. It is preferred to use the

dispersion stabilizer in an amount of 0.1 to 30 parts by weight with regard to 100

parts by weight of the compound of formula 1. If the content of the dispersion

stabilizer exceeds 30 parts by weight, the softening effects of the fiber softening

composition may be deteriorated and cause unnecessary increase in cost.

Furthermore, the fiber softening composition of the present invention

may further comprise fragrants, antiseptic agents.disinfectants, fluorescent

whitening agents, colorants, anti-oxidants, anti-foaming agents, etc., which are

generally used as an additive of fiber softeners, within the range of not affecting

product stability, and their content may be 0.1 to 3% by weight.

The following decription is directed to a process for preparing of the cationic surfactant of formula 2 of the present invention. Preparation of

quaternarized ester derivative of formula 2 as defined above is shown in the

following scheme 2:

[Scheme 2]

O O

R³COH + H₂N(CH₂)_nNH-X → R³CNH(CH₂)nNH-X + Y

^Y

In the scheme 2 above, R³ is a linear or branched alkyl group, alkenyl

group, or a mixed group comprising one or more kinds of C₇-C₂₁;

R⁴ is a linear or branched alkyl group, alkenyl group, or a mixed group comprising

one or more kinds of C C₂ι;

X is CH₃, (CH₂)_mOH, (CH₂)_mOCOR⁵, (CH₂)_mNH₂, or (CH₂)_mNHCOR^{5 ύ}l ^ ,

comprising one or more kinds of C₇-C₂ι, m is an integer of 2 to 6;

Y is a hydrogen atom, CH₂CHOHCH₂OH, CH₂CHOHCH₂CI, CH₂CH₂CN,

CH₂CH₂COOCH₃, CH₂CH₂COOH, or CH₂CH₂OH;

M is a sulfate or halogen atom; and

n is an integer of 2 to 6

As shown in scheme 2, the present invention is proceeded by the reactions of three steps.

First, in a first step, a fatty acid of formula 6 as defined above and an

amine of formula 7 as defined above are reacted to produce an amido amine of

formula 5 as defined above.

As the amine used in the first reaction, there can be used quaternary

ammonium salts of amidoamine, quaternary ammonium salts of amidoesteramine,

imidazolines, imidazoline esters, etc., and it is preferred to use

aminoethylaminoethanole or diethylenetriamine. The amine is used in an

and if the amount of the amine is less than 0.5 equivalent, unreacted fatty acids

remain or the amount of amines, which can become quaternary salts, is

decreased, thereby causing the deterioration of physicochemical properties, and

if it exceeds 1.0 equivalent, the amount of unreacted amines is increased and

thus toxicity increases and the productivity is low.

As the fatty acid, it is preferable to use a higher fatty acid of one or more

kinds having a linear or branched alkyl group or alkenyl group of C₈-C₂₂. For

example, there are stearic acid, octanoic acid, decanoic acid, dodecanoic acid,

tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid,

docosanoic acid, etc.

In the first reaction, the amine and the higher fatty acid are reacted

without solvents, and it is preferred that reaction temperature is 100 — 180 °C

and reaction time is 1 — 20 hours. If the reaction temperature is less than

100 ^°C , the reaction is proceeded very slow and thus reaction time becomes very extended, and if exceeding 180 ^°C , reaction is proceeded fast but in

consideration of efficiency and time altogether, much energy is consumed as

compared to time to be reduced and the content of tertiary amine is increased.

Also, if the reaction time is less than 1 hour, a reaction yield is very low and if

exceeding 20 hours, a yield is not increased any more.

In a second step, a tertiarizing agent (Y) is added to the produced amido

amine of formula 5 to tertiary it.

It is preferred to use the tertiarizing agent used in the second reaction in

an amount of less than 1.0 equivalent, and more preferably 0.5 to 1.0 equivalent,

with regard to 1 equivalent of the amido amine, which is the reactant prepared

from the first reaction, If the amount of the tertiarizing agent exceeds 1 equivalent,

unreacted tertizaring agent remains and thus discoloration and foul odor occur

and physicochemical properties are deteriorated

As the tertiarizing agent, there are glycidol, ephichlorohydrine,

acrylonitrile, methyl acrylate, acrylic acid, vinyl alcohol, etc.

Also, the above tertiarizing reaction may be carried out with or without

solvents. In case of using the solvents, as reaction solvents, there are used one

or more primary, secondary, tertiary or polyvalent alcohols selected from the

group consisting of water, methanole, ethanole, propylalcohol, hexyleneglycol,

butylalcohol, isopropylalcohol, ethyleneglycol, glycerine, propyleneglycol,

polyethyleneglycol and it is preferable to use 1 to 99% by weight of the total

weight of the reactants.

It is preferred that the above tertiarizaing reaction is carried out at reaction temperature of 30 — 100 ^°C and for reaction time of 0.1 ~ 5 hours. If the

reaction temperature is less than 30 ^°C, a reaction rate is very slow and thus

reaction time becomes very extended, and if exceeding 100 ^°C, undesired

by-products may be produced in a large amount. Also, if the reaction time is

less than 0.1 hour, reaction is hardly proceeded, and if exceeding 5 hours, a

by-reaction occurs and thus the amount of the by-products is increased.

In a third step, the tertiarized amine compound is neutralized with a

compound of formula 3 to quaternarize it, thereby producing a quaternary salt of

formula 2.

As the compound of formula 3 used as a quaternarizing agent in the

present invention, it is preferable to use a dimethylsulfate or an alkylhalide having

an alkyl group of C C₂ι.

It is preferred to use the compound of formula 3 used as quaternarizing

agent within a range of not exceeding the equivalent of the total amine after the

tertiarizing reaction is completed. It is preferred that the reaction temperature 30

to 100 ^°C and the reaction time is 1.0 to 8.0 hours.

Also, in the present invention, after the first reaction, the quaternarizing

reaction can be proceeded directly, omitting the tertiarizing reaction, which is the

second step.

Further, the present invention provides a fiber softening composition

comprising the amidoammonium salt having an amide group and hydroxyl group

within molecules represented by formula 2 prepared from the methods as

described above. The inventors continued to apply compounds suitable for use of fiber

softeners as a major component and as a result, they found that the fiber

softening composition using the amido ammonium salt having an amide group

and a hydroxyl group within molecules, which is prepared by reacting a fatty acid

and an amine, tertiarizing it, and quaternarizing it with a dimethylsulfate or

alkylhalide, is excellent uniform adhesion effects onto clothes and thus has

excellent softening properties, anti-electrostatic effects, and absorption at the

same time as well as excellent dispersion in water and bio-degradability, thereby

completing the present invention.

In the amido ammonium salt represented by formula 2 in the present

invention, R² is a linear or branched alkyl group, alkenyl group or alkylalkenyl

group of Cι to C₂ι, and if the number of carbon atoms is less than 1 , the adhesion

effects onto clothes are not maintained, thereby causing the deterioration of

softening effects and anti-electrostatic effects and if the number of carbon atoms

exceeds 21 , slipping or excessive softening effects occur, thereby causing poor

touch.

It is preferred to use the amido ammonium salt represented by formula 2

in an amount of 1 to 30 parts by weight with regard to 100 parts by weight of the

fiber softening composition. If the content is less than 1 part by weight,

softening effects or anti-electrostatic effects onto all kinds of clothes are

unsatisfactory and if it exceeds 30 parts by weight, softening stability and freezing

stability may become poor.

The fiber softening composition according to the present invention may use, if necessary, a non-ionic surfactant as a softening agent in addition to the

amido ammonium salt represented by formula 2, which is a cationic softening

component.

As the above non-ionic surfactant, there can be used polyoxyethylene (2

to 50 mol) alkyl-alkenylether or polyoxyethylne (2 to 50 mol)-alkyl phenyl ether (2

to 50 mol) of C₁₀-C₂₀; polyoxyethylene (2 to 50 mol) alkyl-alkenylester or

polyoxyethylene (2 to 50 mol) alkyl-hydroxy fatty acid ester of Cι₀-C₂₀; sorbitane

fatty acid alkyl ester or its ethylene oxide (15 to 40 mol) additives,

polyoxyethylene (1 to 30 mol) alkyl-alkenylamide; polyoxyethylene (1 to 50 mol)

alkyl-alkenylamine, glyceryl monoalkyl-alkenyl ester; ethylene oxide additives (2

to 50 mol) of cured castor oil; alkylamineoxide; and amidopropylamineoxide.

The non-ionic surfactant can be used alone or in a mixture of two more kinds. It

is preferred to use the non-ionic surfactant in an amount of 0.1 to 30 parts by

weight with regard to 100 parts by weight of the amido ammonium salt. If the

content of the non-ionic surfactant exceeds 30 parts by weight, the stability of

products is deteriorated and it prevents the amido ammonium salt, which is a

cationic softening component, from being adhered to clothes, thereby causing the

deterioration of softening effects.

Also, if necessary, the fiber softening composition of present invention

may further comprise a dispersion stabilizer.

As the dispersion stabilizer, there can be used lower alcohol or glycols of

Cι to C₈, higher alcohols of C₁₂ to C₂₀, iodide, magnesium, sodium chloride,

calcium chloride, sodium nitrate, or a mixture thereof. More preferably, there can be used ethanole, isopropyl alcohol, ethyleneglycol, propyleneglycol,

hexyleneglycol, trimethylpentanediol, setylalcohol, stearylalcohol, magnesium

chloride, sodium chloride, calcium chloride, sodium nitrate, a mixture of thereof.

It is preferred to use the dispersion stabilizer in an amount of 0.1 to 30

parts by weight with regard to 100 parts by weight of the compound of formula 1.

If the content of the dispersion stabilizer exceeds 30 parts by weight, the

softening effects of the fiber softening composition may be deteriorated and

cause unnecessary increase in cost.

Furthermore, the fiber softening composition of the present invention

may further comprise fragrants, antiseptic agents, disinfectants, fluorescent

product stability, and their content may be 0.1 to 3% by weight.

The present invention will be explained in more detail with reference to

the following Examples. However, these are to illustrate the present invention,

and the present invention is not limited to them.

[Example 1]

104 g (1.0 mol) of 2-(2-aminoethylamino)ethanol and 408 g (1.5 mol) of

stearic acid were amidified in four-sphere flask with a mechanical stirrer,

thermometer, condenser and evaporating equipment at a temperature of 120 —

130 °C for 2 hours while refluxing water produced during reaction, and then the

temperature was raised to 160 - 170 ^°C to proceed an esterification reaction for

3 hours while removing water. After the reaction was complete, the total amine value was 90%, tertiary amine value was 10%, secondary amine value was 80%,

and acid value was 2%. The analysis of the reactants regarding an amine value

and acid value was conducted using A.O.C.S. Analysis (Official Method Te 2a-64,

1987), and 60 g of ethanole was added to the amidoesteramine thus prepared, to

which 74 g of ephichlorohydrine was slowed dropped to allow the reaction to

proceed for 1 hour, and then the reactant was neutralized with 97 g of

hydrochloric acid (35%) to terminate the reaction.

[Example 2]

103 g (1.0 mol) of diethylenetriamine and 544 g (2.0 mol) of stearic acid

were amidified in the apparatus identical to that used in Example 1 at a

temperature of 120 ~ 130 ^°C for 10 hours while refluxing water produced during

reaction. After the reaction was complete, the total amine value was 95%,

tertiary amine value was 3%, secondary amine value was 90%, and acid value

was 2%. The analysis of the reactants regarding an amine value and acid value

was conducted using A.O.C.S. Analysis (Official Method Te 2a-64, 1987), and 80

g of ethanole was added to the diamidoamine thus prepared, to which 87 g of

ephichlorohydrine was slowed dropped to allow the reaction to proceed for 1 hour,

and then the reactant was neutralized with 103 g of hydrochloric acid (35%) to

terminate the reaction.

[Example 3]

104 g (1.0 mol) of 2-(2-aminoethylamino)ethanole and 408 g (1.5 mol) of

stearic acid were amidified in the apparatus identical to that used in Example 1 at

a temperature of 120 — 130 °C for 2 hours while refluxing water produced during reaction. After the reaction was complete, the primary amine value was 1%,

tertiary amine value was 3%, and 1 equivalent of fatty acid was consumed. The

analysis of the reactants regarding an amine value and acid value was conducted

using A.O.C.S. Analysis (Official Method Te 2a-64, 1987). 53 g of acrylonitrile

was slowly added to the amidoesteramine thus prepared at a temperature of 70

— 90 ^°C for 1 hour. Afterthe tertiarizing reaction was complete, the temperature

was raised to 160 — 170 ^°C to proceed an esterification reaction for 3 hours while

removing water. After the reaction was complete, 70 g of ethanole was added,

and the reactant was neutralized with 103 g of hydrochloric acid (35%) to

terminate the reaction.

[Comparative Example 1]

104 g (1.0 mol) of 2-(2-aminoethylamino)ethanole and 272 g (1.0 mol) of

a temperature of 120 — 130 °C for 15 hours while refluxing water produced

during reaction. After the reaction was complete, the total amine value was 95%,

tertiary amine value was 4%, and acid value was 4%. The analysis of the

reactants regarding an amine value and acid value was conducted using A.O.C.S.

Analysis (Official Method Te 2a-64, 1987). 50 g of ethanole was added to the

amido amine thus prepared, and the reactant was neutralized with 103 g of

hydrochloric acid (35%) at a temperature of 50 — 60 °C to terminate the reaction.

[Example 4]

The procedures were carried out in the same manner as Example 1 ,

except changing the kind of alkyl groups as shown in Table 1 below, to prepare cationic surfactants of formula 1a to formula M

Table 1

[Example 5]

A fiber softening composition comprising 6% by weight of compound of

formula 1 a, 0.5% by weight of a mixture of cured castor oil and polyoxyethylene

(POE) whose molecular weight is 40, 0.5% by weight of ethyleneglycol, 0.03% by

weight of calcium chloride and 0.1 % by weight of fragrance was prepared.

[Example 6]

A fiber softening composition was prepared in the same manner as

Example 5 except comprising 6% by weight of a compound represented by

formula 1 b instead of the compound of formula 1 a.

[Example 7]

A fiber softening composition was prepared in the same manner as

Example 5 except comprising 6% by weight of a compound represented by

formula 1 c instead of the compound of formula 1a.

[Example 8]

A fiber softening composition was prepared in the same manner as Example 5 except comprising 6% by weight of a compound represented by

formula 1d instead of the compound of formula 1a.

[Example 9]

A fiber softening composition was prepared in the same manner as

Example 5 except comprising 6% by weight of a compound represented by

formula 1 e instead of the compound of formula 1a.

[Example 10]

A fiber softening composition was prepared in the same manner as

Example 5 except comprising 6% by weight of a compound represented by

formula 1 f instead of the compound of formula 1 a.

[Example 11]

A fiber softening composition comprising 4% by weight of a compound

represented by formula 1d, 2% by weight of dialkylester type quaternary

ammonium salt, 0.5% by weight of a mixture of cured castor oil and

polyoxyethylene whose molecular weight is 40, 0.5% by weight of ethyleneglycol,

0.03% by weight of calcium chloride and 0.1% by weight of fragrance was

prepared.

[Example 12]

A fiber softening composition was prepared in the same manner as

Example 11 except comprising 2% by weight of oleylimidazoliniummethylsulfate,

instead of dialkylester type quaternary ammonium salt.

[Example 13]

A fiber softening composition comprising 6% by weight of a compound represented by formula 1d and 0.5% by weight of a mixture of cured castor oil

and polyoxyethylene whose molecular weight is 40 was prepared.

[Example 14]

A fiber softening composition was prepared in the same manner as

Example 13 except comprising 12% by weight of the compound represented by

formula 1d.

[Example 15]

A fiber softening composition comprising 18% by weight of a compound

represented by formula 1 d, 0.5% by weight of a mixture of cured castor oil and

polyoxyethylene whose molecular weight is 40, 0.2% by weight of a mixture of

stearyl alcohol and polyoxyethylene whose molecular weight is 30, 0.5% by

weight of ethyleneglycol, 0.03% by weight of calcium chloride and 0.1% by weight

of fragrance was prepared.

[Example 16]

A fiber softening composition was prepared in the same manner as

Example 15 except comprising 0.8% by weight of a mixture of cured castor oil

and polyoxyethylene whose molecular weight is 40 instead of 0.5% by weight,

and 0.2% by weight of a mixture of laurinic amide and polyoxyethylene whose

molecular weight is 15 instead of 0.2% by weight of a mixture of stearyl alcohol

and polyoxyethylene whose molecular weight is 30.

[Example 17]

A fiber softening composition comprising 6% by weight of a compound

represented by formula 1g, 0.5% by weight of a mixture of cured castor oil and polyoxyethylene whose molecular weight is 40, 0.5% by weight of ethyleneglycol,

0.03% by weight of calcium chloride and 0.1% by weight of fragrance was

prepared.

[Example 18]

A fiber softening composition was prepared in the same manner as

Example 17 except comprising 6% by weight of a compound represented by

formula 1 h instead of the compound of formula 1g.

[Example 19]

A fiber softening composition was prepared in the same manner as

Example 17 except comprising 6% by weight of a compound represented by

formula 1 i instead of the compound of formula 1 g.

[Example 20]

A fiber softening composition was prepared in the same manner as

Example 17 except comprising 6% by weight of a compound represented by

formula 1j instead of the compound of formula 1 g.

[Example 21]

A fiber softening composition was prepared in the same manner as

Example 17 except comprising 6% by weight of a compound represented by

formula 1 k instead of the compound of formula 1 g.

[Example 22]

A fiber softening composition was prepared in the same manner as

Example 17 except comprising 6% by weight of a compound represented by

formula 11 instead of the compound of formula 1 g. [Example 23]

A fiber softening composition comprising 4% by weight of a compound

represented by formula 1 d, 2% by weight of dialkylester type quaternary

ammonium salt, 0.5% by weight of a mixture of cured castor oil and

polyoxyethylene whose molecular weight is 40, 0.5% by weight of ethyleneglycol,

0.03% by weight of calcium chloride and 0.1% by weight of fragrance was

prepared.

[Example 24]

A fiber softening composition was prepared in the same manner as

Example 23 except comprising 2% by weight of oleylimidazoliniumsulfate instead

of dialkylester type quaternary ammonium.

[Example 25]

A fiber softening composition comprising 6% by weight of a compound

represented by formula 1 d and 0.5% by weight of a mixture of cured castor oil

and polyoxyethylene whose molecular weight is 40 was prepared.

[Example 26]

A fiber softening composition was prepared in the same manner as

Example 25 except comprising 12% by weight of the compound represented by

formula 1d.

[Example 27]

A fiber softening composition comprising 18% by weight of a compound

represented by formula 1d, 0.5% by weight of a mixture of cured castor oil and

polyoxyethylene whose molecular weight is 40, 0.2% by weight of a mixture of stearyl alcohol and polyoxyethylene whose molecular weight is 30, 0.5% by

of fragrance was prepared.

[Example 28]

A fiber softening composition was prepared in the same manner as

Example 27 except comprising 0.8% by weight of a mixture of cured castor oil

and polyoxyethylene whose molecular weight is 40 instead of 0.5% by weight,

and 0.2% by weight of a mixture of laurinic amide and polyoxyethylene whose

and polyoxyethylene whose molecular weight is 30.

[Comparative Example 2]

A fiber softening composition comprising 6% by weight of

distearyldimethyl quaternary ammonium salt as a cationic surfactant, 0.5% by

weight of a mixture of steraryl alcohol and polyoxyethylene whose molecular

weight is 30, 0.5% by weight of ethyleneglycol, 0.03% by weight of calcium

chloride and 0.1 % by weight of fragrance was prepared.

[Comparative Examples 3 to 6]

Fiber softening compositions of Comparative Examples 3 to 6 were

prepared in the same manner as Comparative Example 2 except comprising 6%

by weight of esteramide type quaternary salt, amidoesteramine quaternary

ammonium salt, dialkylester type quaternary ammonium salt, and

olelimidazoliummethylsulfate, respectively as a cationic surfactant.

[Experimental Example 1] As for the fiber softening compositions of Examples 5 to 28 according to

the present invention and Comparative Examples 2 to 6, their performance tests

on normal products or condensed products were conducted as shown in Table 2

to 6, while being classified according to the standard content of pure materials,

similarly to conventionally available products. In general, in normal products,

the standard content of the pure material of fiber softener is 3 to 12% by weight,

and in condensed products, it is almost 10 to 30% by weight, but when they are

converted into a usage concentration in softening process at the stage of rinsing

stage after washing, in both normal products and condensed products, 0.7 mi of

pure material of the fiber softener per I of washing water, i.e., same concentration,

is used.

The performance tests of the fiber softeners of the present invention

were conducted according to softening effect test, anti-electrostatic property test,

dispersion-in-water test, bio-degradability test, and storage stability test and the

results are shown in Table 2 to 6 below.

(Softening Effect Test)

Towels made of 100% of cotton that are commercially available were

washed five times using the standard usage of a normal detergent in washer and

spun. The spun cotton towels were subjected to softening process in each

rinsing water (bath ratio 1 :30, 25 °C) in which the fiber softening compositions

prepared from above Examples 5 to 28 are dissolved according to the standard

of normal usage (6.7 ιπ-ft/10 I washing water or 2.2 mU/I O I washing water), then

spun, and conditioninged for 2 hours under conditions of 20 ^°C and 65% of comparative humidity. Next, functional evaluations on the fiber softening

composition of Examples 1 to 24 and Comparative Examples 2 to 6 were

performed by experienced persons. The degree of touch is designated from

minimum 1 point to 5 point as a softening score and the evaluations were

repeated more than three times, and then softening effects are determined using

their average value. Softening effects were evaluated as follows: highly

excellent (®) if the softening effect score is 4.5 or more, excellent(O) if it is 3.5 to

4.5, average (Δ) if it is 2.5 to 3.5, and poor (x) if it is less than 2.5.

(Anti-electrostatic Property Test (Half-life Determination))

As for the samples, which were subjected to softening treatment in the

same manner as the above softening effects test, and then conditioninged for 24

hours under conditions of 20 ^°C, 40% of comparative humidity, their leaking rates

were measured by applying KS K-0555A test method using an electrostatic

voltage (Satic Voltmeter) which is the product of Swiss Rothschild Company, to

time during the period when the voltage falls down the half value after applying

initial voltage 150 V, and the same procedures were repeated more than three

times. Anti-electrostatic effects are evaluated as follows: highly excellent (©) if

the leaking rate is 10 seconds or less, excellent(O) if it is 10 to 10⁴, average (Δ)

if it is 10⁴ to 10⁵, and poor (x) if it is more than 10⁵.

(Diameter of Dispersion Particles)

In 0.1% aqueous solution of the fiber, the size of emulsifying particles

was measured by diameter analysis device (MALVERN Company, mastersizer)

using light scattering to determine dispersion in water. (Bio-degradability Test)

Bio-degradability was measure by OECD 301 D Closed bottle test. This

test is to judge bio-degradability within 14 days from the date specimen is

degraded, and if degradation values more than 60% come out, the specimen are

regarded as being easily biodegradable.

The fiber softeners were tested at a concentration of 2 to 10 mg/ϋ in

aerobic aqueous media to measure their bio-degradability. In order to activity,

as a comparison material, aniline, sodium acetate or sodium benzoate were used.

The bio-degradability was evaluated as follows: easily degradable (O) if the

bio-degradability is 60% or more, average (Δ) if it is 30% or more, and poor (x) if

it is 30% or less.

(Stability Test)

The storage stability was evaluated under temperature conditions of

40 ^°C (A) and -10 °C (B). At -10 ^°C , freezing and thawing were conducted two

times. The stability was evaluated as follows: excellent (0) if the stability

maintenance period is 2 months or longer, average (Δ) if it is 1 month or longer,

and poor (x) if it is 1 month or shorter.

The physicochemical experiment results regarding the fiber softening

compositions of Examples 5 to 28 and Comparative Examples 2 to 6 are shown

in Table 2 to 6 below. Table 2

Table 3

Table 4

Table 5

Table 6

As shown in Table 1 to 6 above, it is seen that the fiber softening

compositions of the present invention according to Examples 5 to 28 were

excellent in all five evaluation items as compared with the fiber softening

composition according to Comparative Examples 2 to 6. Especially, in case of

softening properties, as shown in Table 2, they were excellent when two or more

non-ionic surfactants were used altogether.

[Example 29]

156 g (1.5 mol) of 2-(2-aminoethylamino)ethanol and 400 g (1.5 mol,

average molecular weight 267) of stearic acid were amidified in four-sphere flask

with a mechanical stirrer, thermometer, condenser and evaporating equipment at

high temperature to a temperature of 165 ^°C for 5 hours while refluxing water

produced during reaction. After the reaction was complete, the total amine value was 104%, tertiary amine value was 8%, and acid value was 4%. The

analysis of the reactants regarding an amine value and acid value was conducted

using A.O.C.S. Analysis (Official Method Te 2a-64, 1987), and 265 g of ethanole

was added to the amidoesteramine thus prepared, to which 133 g of

ephichlorohydrine was slowed dropped to allow the reaction to proceed for 2

hours. The total amine value was 72%, and then 140 g of dimethylsulfate

corresponding to the amount of the total amine value was added to allow the

reaction to proceed at a temperature of 65 ^°C for 3 hours, and then the reaction

was terminated by quaternarizing it.

[Example 30]

156 g (1.5 mol) of 2-(2-aminoethylamino)ethanole, 246 g (0.9 mol

average molecular weight 267) of stearic acid and 164 g (0.6 mol, average

molecular weight 282) of oleic acid were charged into in the apparatus identical to

that used in Example 29 and were subjected to amidation at high temperature to

a temperature of 165 °C for 5 hours while refluxing water produced during

reaction. After the reaction was complete, the total amine value was 105.8%,

tertiary amine value was 4.8%, and acid value was 3.4%. The analysis of the

reactants regarding an amine value and acid value was conducted using A.O.C.S.

Analysis (Official Method Te 2a-64, 1987), and 150 g of ethanole was added to

the amidoesteramine thus prepared, to which 140 g of ephichlorohydrine was

slowed dropped to allow the reaction to proceed at a temperature of 65~70^°C for

2 hour. The total amine value was 74.7%, and 150 g of dimethylsulfate

corresponding to the amount of the total amine value was added to allow the reaction to proceed at a temperature of 65 ^°C for 3 hours, and then the reaction

was terminated by quaternarizing it.

[Example 31]

A fiber softener was prepared according to conventional methods using

the cationic surfactant prepared from Example 29.

[Experimental Example 2]

The physicochemical properties of the fiber softeners (Example 31)

prepared by using the cationic surfactant of the present invention and a prior fiber

softening product (Comparative Example 7, Comparative Example 8) were

compared and the results are shown in Table 7 below.

Table 7

[Example 32]

156 g (1.5 mol) of 2-(2-aminoethylamino)ethanol and 400 g (1.5 mol,

average molecular weight 267) of stearic acid were added into four-sphere flask

with a mechanical stirrer, thermometer, condenser and evaporating equipment

and were subjected to amidation at high temperature to a temperature of 165 ^°C

for 5 hours while refluxing water produced during reaction. After the reaction

was complete, the total amine value was 104%, tertiary amine value was 8%, and acid value was 4%. The analysis of the reactants regarding an amine value and

acid value was conducted using A.O.C.S. Analysis (Official Method Te 2a-64,

1987), and 265 g of ethanole was added to the amidoesteramine thus prepared,

to which 133 g of ephichlorohydrine was slowed dropped to allow the reaction to

proceed for 2 hour. The total amine value was 72%, and 140 g of

dimethylsulfate corresponding to the amount of the total amine value was added

to allow the reaction to proceed at a temperature of 65 ^°C for 3 hours, and then

the reaction was terminated by quaternarizing it to thereby prepare an amido

ammonium salt of formula 2a as shown in Table 8 below. Thereafter, the same

procedures were performed except changing alkyl groups, to prepare the

compounds of formulae 2b to 2.1 as shown in Table 8 below.

Table 8

[Example 33]

A fiber softening composition was prepared by mixing 6 parts by weight

of amido ammonium salt represented by formula 2a, 0.5 parts by weight of a

mixture of cured castor oil and ethylene oxide additive (molecular weight 40), 0.5

parts by weight of ethyleneglycol, and 0.5 parts by weight of fragrance.

[Example 34]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2b, instead of the amido ammonium salt represented by formula 2a.

[Example 35]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2c, instead of the amido ammonium salt represented by formula 2a. [Example 36]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2d, instead of the amido ammonium salt represented by formula 2a.

[Example 37]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2e, instead of the amido ammonium salt represented by formula 2a.

[Example 38]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2f, instead of the amido ammonium salt represented by formula 2a.

[Example 39]

A fiber softening composition was prepared by mixing 4 parts by weight

of amido ammonium salt represented by formula 2d, 2 parts by weight of

dialkylester type quaternary ammonium salt, 0.5 parts by weight of a mixture of

cured castor oil and ethylene oxide additive (molecular weight 40), 0.5 parts by

weight of ethyleneglycol, and 0.1 parts by weight of fragrance.

[Example 40]

A fiber softening composition was prepared in the same manner as

Example 39 except using 2 parts by weight of oleylimidazoliniummethylsulfate

instead of dialkylester type quaternary ammonium salt used in Example 39. [Example 41]

A fiber softening composition was prepared by mixing 6 parts by weight

of the compound represented by formula 2d, and 0.5 parts by weight of a mixture

of cured castor oil and ethylene oxide additive (molecular weight 40).

[Example 42]

A fiber softening composition was prepared in the same manner as

Example 41 except comprising 12 parts by weight of the compound represented

by formula 2d.

[Example 43]

A fiber softening composition was prepared by mixing 18 parts by weight

of the compound represented by formula 2d, 0.5 parts by weight of a mixture of

cured castor oil and ethylene oxide additive (molecular weight 40), 0.2 parts by

weight of a mixture of stearyl alcohol and polyoxyethylene whose molecular

weight is 30, 0.5 parts by weight of ethylene glycol, and 0.5 parts by weight of

fragrance.

[Example 44]

A fiber softening composition was prepared in the same manner as

Example 43 except comprising 0.8 part by weight of a mixture of cured castor oil

and ethylene oxide additive (molecular weight 40) instead of 0.5 parts by weight,

and 0.2 parts by weight of a mixture of laurinic acid amide of ethylene oxide

additive (additive mol 15) instead of 0.2 parts by weight of a mixture of stearyl

alcohol and polyoxyethylene whose molecular weight is 30. [Example 45]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2g, instead of the amido ammonium salt represented by formula 2a.

[Example 46]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2h, instead of the amido ammonium salt represented by formula 2a.

[Example 47]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2i, instead of the amido ammonium salt represented by formula 2a.

[Example 48]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2j, instead of the amido ammonium salt represented by formula 2a.

[Example 49]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by

formula 2k, instead of the amido ammonium salt represented by formula 2a.

[Example 50]

A fiber softening composition was prepared in the same manner as

Example 33 except comprising 6 parts by weight of compound represented by formula 21, instead of the amido ammonium salt represented by formula 2a.

[Example 51]

A fiber softening composition was prepared by mixing 4 parts by weight

of amido ammonium salt represented by formula 2d, 2 parts by weight of

dialkylester type quaternary ammonium salt, 0.5 parts by weight of a mixture of

weight of ethyleneglycol, and 0.1 parts by weight of fragrance.

[Example 52]

A fiber softening composition was prepared in the same manner as

Example 51 except using 2 parts by weight of oleylimidazoliniummethylsulfate

instead of dialkylester type quaternary ammonium salt used in Example 51.

[Example 53]

A fiber softening composition was prepared by mixing 6 parts by weight

of the compound represented by formula 2d, and 0.5 parts by weight of a mixture

of cured castor oil and ethylene oxide additive (molecular weight 40).

[Example 54]

A fiber softening composition was prepared in the same manner as

Example 53 except comprising 12 parts by weight of the compound represented

by formula 2d.

[Example 55]

A fiber softening composition was prepared by mixing 18 parts by weight

of the compound represented by formula 2d, 0.5 parts by weight of a mixture of

cured castor oil and ethylene oxide additive (molecular weight 40), 0.2 parts by weight of a mixture of stearyl alcohol and polyoxyethylene whose molecular

weight is 30, 0.5 parts by weight of ethylene glycol, and 0.1 parts by weight of

fragrance.

[Example 56]

A fiber softening composition was prepared in the same manner as

Example 55 except comprising 0.8 part by weight of a mixture of cured castor oil

and 0.2 parts by weight of a mixture of laurinic acid amide of ethylene oxide

alcohol and polyoxyethylene whose molecular weight is 30.

[Comparative Example 9]

A fiber softening composition was prepared by mixing 6 parts by weight

of distearyldimethyl quaternary ammonium salt, a mixture of stearyl alcohol and

ethylene oxide additive (additive mol 30 mol), 0.5 parts by weight of ethylene

glycol, and 0.5 parts by weight of fragrance.

[Comparative Example 10]

A fiber softening composition was prepared in the same manner as

Comparative Example 9 except using esteramide type quaternary salt instead of

distearyldimethyl quaternary ammonium salt used in Comparative Example 9.

[Comparative Example 11]

A fiber softening composition was prepared in the same manner as

Comparative Example 9 except using amidoesteramine quaternary salt instead of

distearyldimethyl quaternary ammonium salt used in Comparative Example 9. [Comparative Example 12]

A fiber softening composition was prepared in the same manner as

Comparative Example 9 except using dialkylester type quaternary salt instead of

distearyldimethyl quaternary ammonium salt used in Comparative Example 9.

[Comparative Example 13]

A fiber softening composition was prepared in the same manner as

Comparative Example 9 except using oleylimidazoliniummethylsulfate instead of

distearyldimethyl quaternary ammonium salt used in Comparative Example 9.

[Experimental Example 3]

Softening effects, anti-electrostatic ability, diameter of dispersion

particles, bio-degradability, and stability were measured using the fiber softening

compositions prepared from Examples 33 to 56 and Comparative Examples 9 to

13 as follows:

(Softening Effects)

(Softening Effect Test)

Towels made of 100% of cotton that are commercially available were

washed five times using the standard usage of a normal detergent in washer and

spun. The spun cotton towels were subjected to softening process in each

prepared from above Examples 33 to 56 and Comparative Examples 9 to 13 are

dissolved according to the standard of normal usage (6.7 m£/10 I washing water

or 2.2 m^β/10 I washing water), then spun, and conditioninged for 2 hours under

conditions of 20 ^°C and 65% of comparative humidity. Next, functional evaluations on the fiber softening composition of Examples 33 to 56 and

Comparative Examples 9 to 13 were performed by experienced persons. The

degree of touch is designated from minimum 1 point to 5 point as a softening

score and the evaluations were repeated more than three times, and then

softening effects are determined using their average value. As the standard of

evaluating softening properties, pure towel softening-treated with the fiber

softening composition of Comparative Example 9 was used. Softening effects

were evaluated according to Table 9 below.

Table 9

(Anti-electrostatic Property Test (Half-life Determination))

As for the samples, which were subjected to softening treatment in the

same manner as the above softening effects test, and then conditioninged for 24

hours under conditions of 20 ^°C , 40% of comparative humidity, their leaking rates

were measured by applying KS K-0555A test method using an electrostatic

voltage (Satic Voltmeter) which is the product of Swiss Rothschild Company, to

initial voltage 150 V, and the same procedures were repeated more than three

times. Anti-electrostatic effects are evaluated according to Table 10 below. Table 10

(Diameter of Dispersion Particles)

In 0.1 % aqueous solution of the fiber softener of Examples 33 to 56 and

Comparative Example 9-13, the size of emulsifying particles was measured by

diameter analysis device (MALVERN Company, mastersizer) using light

scattering to determine dispersion in water.

(Bio-degradability Test)

Bio-degradability was measure by OECD 301 D Closed bottle test. This

test is to judge bio-degradability within 14 days from the date specimen is

degraded, and if degradation values more than 60% come out, the specimen are

regarded as being easily biodegradable.

The fiber softeners of Examples 33 to 56 and Comparative Examples

9-13 were tested at a concentration of 2 to 10 mg/ϋ in aerobic aqueous media to

measure their bio-degradability. In order to activity, as a comparison material,

aniline, sodium acetate or sodium benzoate were used. The bio-degradability

was evaluated according to Table 11 below. Table 11

(Stability Test)

The storage stability was evaluated using the fiber softener of Examples

33 to 56 and Comparative Examples 9-13 under temperature conditions of 40 ^°C

(A) and -10 ^°C (B). At -10 ^°C, freezing and thawing were conducted two times.

The stability was evaluated according to Table 12 below.

Table 12

The physicochemical experiment results regarding the fiber softening

compositions of Examples 33 to 56 and Comparative Examples 9 to 13 are

shown in Table 13 below. Table 13

Through Table 13 above, it is seen that the fiber softening compositions

according to Examples 33 to 56 comprising the amido ammonium salt

represented by formula 1 having an amide group and a hydroxyl group within molecules of the present invention have excellent properties in softening

properties, anti-electrostatic properties, diameter of dispersion particles,

bio-degradability and stability.

As described in the above, the cationic surfactants of formulae 1 and 2

prepared according to the methods of the present invention have excellent

solubility in water by possessing an amide group or a hydroxyl group, which is

hydrophilic, within molecules, and have very excellent physicochemical

characteristics such as softening properties, anti-electrostatic properties and

dispersion properties.

Also, the fiber softening composition of the present invention has

excellent uniform adhesion effects onto clothes, and thus is excellent in softening

properties, anti-electrostatic effects, and absorption as well as excellent in

storage stability, dispersion in water, and bio-degradability, at the same time.

Claims

WHAT IS CLAIMED IS:

1. A process for preparing a cationic surfactant represented by the following

formula 1 :

wherein R^ is a linear or branched alkyl group, alkenyl group, or a mixed

group comprising one or more kinds of C₇-C₂₁; X is CH₃, (CH₂)_mOH,

(CH₂)_mOCOR₂, (CH₂)_mNH₂, or (CH₂)_mNHCOR₂, wherein R₂is a linear or branched

alkyl group, alkenyl group, or a mixed group comprising one or more kinds of

C₇-C₂₁, and m is an integer of 2 to 6; Y is a hydrogen atom, CH₂CHOHCH₂OH,

CH₂CHOHCH₂CI, CH₂CH₂CN, CH₂CH₂COOCH₃, CH₂CH₂COOH, or CH₂CH₂OH;

Z is a hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glyconic acid,

apple acid, tin acid, tartaric acid; and n is an integer of 2 to 6;

comprising the steps of:

a) reacting an amine and a higher fatty acid;

b) tertiarizing the reactant obtained from step a); and

c) quaternarizing the tertiary amine obtained from step b) by neutralizing

it with an acid.

2. The process for preparing the cationic surfactant according to claim 1

characterized in that the reaction of step a) is carried out at reaction temperature

of 100 - 180 °C and for reaction time of 1 - 20 hours after 0.5 to 1.0 equivalent

of the amine are added with regard to 1 equivalent of the higher fatty acid.

3. The process for preparing the cationic surfactant according to claim 1 characterized in that the amine in step a) is aminoethylaminoethanole or

diethylenetriamine.

4. The process for preparing the cationic surfactant according to claim 1

characterized in that the higher fatty acid in step a) is a mixture of one or more

kinds having a linear or branched alkyl group or alkenyl group of C₈-C₂₂.

5. The process for preparing the cationic surfactant according to claim 1

characterized in that the tertiarization reaction of step b) is carried out at reaction

temperature 30 — 100 ^°C and for reaction time of 0.1 — 5 hours after less than 1

equivalent of a tertiarizing agent is added with regard to 1 equivalent of the

reactant obtained from step a)

6. The process for preparing the cationic surfactant according to claim 5

characterized in that said tertiarizing agent is selected from the group of glycidol,

ephichlorohydrine, acrylonitrile, methyl acrylate, acrylic acid, and vinyl alcohol.

7. The process for preparing the cationic surfactant according to claim 1

characterized in that the acid of step c) is hydrochloric acid, sulfuric acid, nitric

acid, phosphoric acid, glyconic acid, apple acid, tin acid or tartaric acid.

8. A fiber softening composition comprising the compound represented by the

following formula 1 :

ft x

R¹CNH(CH₂)_nN' Z

^Nγ

wherein Ri is a linear or branched alkyl group, alkenyl group, or a mixed

group comprising one or more kinds of C₇-C₂ι; X is CH₃, (CH₂)_mOH,

(CH₂)_mOCOR₂, (CH₂)_mNH₂, or (CH₂)_mNHCOR₂, wherein R₂is a linear or branched alkyl group, alkenyl group, or a mixed group comprising one or more kinds of

apple acid, tin acid, tartaric acid; and n is an integer of 2 to 6.

9. The fiber softening composition according to claim 8 wherein the content of the

compound represented by the formula 1 is 1 to 30% by weight.

10. The fiber softening composition according to claim 8 further comprising 0.1 to

30 parts by weight of a non-ionic surfactant with regard to 100 parts by weight of

the compound represented by formula 1.

11. The fiber softening composition according to claim 10 wherein said non-ionic

surfactant is one or more selected from the group of polyoxyethylene (2 to 50

mol) alkyl-alkenylether or polyoxyethylne (2 to 50 mol)-alkyl phenyl ether (2 to 50

mol) of Cιo-C₂₀; polyoxyethylene (2 to 50 mol) alkyl-alkenylester or

fatty acid alkyl ester or its ethylene oxide (15 to 40 mol) additives,

polyoxyethylene (1 to 30 mol) alkyl-alkenylamide; polyoxyethylene (1 to 50 mol)

to 50 mol) of cured castor oil; alkylamineoxide; and amidopropylamineoxide.

12. The fiber softening composition according to claim 8 further comprising 0.1 to

30 parts by weight of a dispersion stabilizer with regard to 100 parts by weight of

the compound represented by formula 1.

13. The fiber softening composition according to claim 12 wherein said dispersion stabilizer is one or more selected from the group consisting of lower alcohol or

glycols of Ci to C₈, higher alcohols of Cι₂ to C₂₀, iodide, magnesium, sodium

chloride, calcium chloride and sodium nitrate.

14. The fiber softening composition according to claim 8 further comprising 0.01

to 3 parts by weight of one or more additives selected from the group consisting

of fragrants, antiseptic agents.disinfectants, fluorescent whitening agents,

colorants, anti-oxidants and anti-foaming agents.

15. A process for preparing a cationic surfactant represented by the following

formula 2:

wherein R³ is a linear or branched alkyl group, alkenyl group, or a mixed

group comprising one or more kinds of C₇-C₂₁;

one or more kinds of C C₂ι;

comprising one or more kinds of C₇-C₂₁, m is an integer of 2 to 6;

Y is a hydrogen atom, CH₂CHOHCH₂OH, CH₂CHOHCH₂CI, CH₂CH₂CN,

CH₂CH₂COOCH₃, CH₂CH₂COOH, or CH₂CH₂OH;

M is a sulfate or halogen atom; and

n is an integer of 2 to 6; comprising the steps of:

a) reacting a fatty acid of the following formula 6:

O o il R³COH

wherein R³ is as defined above;

and an amine of the following formula 7:

H₂N(CH₂)_nNH-X

wherein n and X are as defined above;

to prepare an amido amine of the following formula 5:

O

3¹¹ FrCNH(CH₂)nNH— X

wherein R³, n and X are as defined above;

b) tertiarizing the amido amine of the above formula 5 with a tertiarizing

agent (Y) to prepare a compound of the following formula 4:

wherein R³, n, X and Y are as defined above;

c) quaternarizing the compound of above formula 4 with a compound of

the following formula 3:

R⁴-M

wherein R⁴and M are as defined above.

16. The process for preparing the cationic surfactant according to claim 15

characterized in that the amido amine of formula 5 in step a) is prepared without solvents at reaction temperature of 100 - 180 ^°C for reaction time of 1 — 20

hours.

17. The process for preparing the cationic surfactant according to claim 15

characterized in that the amine of formula 7 in step a) is

aminoethylaminoethanole or diethylenetriamine.

18. The process for preparing the cationic surfactant according to claim 15

characterized in that the content of the amine of formula 7 in step a) is 0.5 to 1.0

equivalent with regard to 1 equivalent of the fatty acid.

19. The process for preparing the cationic surfactant according to claim 15

characterized in that the tertiarization of step b) is carried out at reaction

temperature of 30 - 100 °C and for reaction time of 0.1 ~ 5 hours.

20. The process for preparing the cationic surfactant according to claim 15

characterized in that the tertiarizing agent of step b) is selected from the group of

glycidol, ephichlorohydrine, acrylonitrile, methyl acrylate, acrylic acid, and vinyl

alcohol.

21. The process for preparing the cationic surfactant according to claim 15

characterized in that the content of the tertiarizing agent of step b) is 0.5 to 1.0

equivalent with regard to 1 equivalent of amido amine.

22. The process for preparing the cationic surfactant according to claim 15

characterized in that the compound of formula 3 is dimethylsulfate or an alkyl

halide having an alkyl group of C C₂₁.

23. A fiber softening composition comprising an amido ammonium salt

represented by the following formula 2:

wherein R³ is a linear or branched alkyl group, alkenyl group, or a mixed

group comprising one or more kinds of C₇-C₂₁;

R⁴ is a linear or branched alkyl group, alkenyl group, or a mixed group

comprising one or more kinds of C C₂ι;

comprising one or more kinds of C₇-C₂ι, m is an integer of 2 to 6;

Y is a hydrogen atom, CH₂CHOHCH₂OH, CH₂CHOHCH₂CI, CH₂CH₂CN,

CH₂CH₂COOCH₃, CH₂CH₂COOH, or CH₂CH₂OH;

M is a sulfate or halogen atom; and

n is an integer of 2 to 6.

24. The fiber softening composition according to claim 23 wherein the amido

ammonium salt represented by formula 2 is prepared by reacting a fatty acid and

an amine, tertiarizing it with a tertiarizing agent and quaternarizing with a

dimethylsulfate or alkylhalide.

25. The fiber softening composition according to claim 23 wherein the amido

ammonium salt represented by formula 2 is comprised in an amount of 1 to 30

parts by weight with regard to 100 parts by weight of the fiber softening

composition.

26. The fiber softening composition according to claim 23 further comprising 0.1 to 30 parts by weight of one or more non-ionic surfactants selected from the

group of polyoxyethylene (2 to 50 mol) alkyl-alkenylether or polyoxyethylne (2 to

50 mol)-alkyl phenyl ether (2 to 50 mol) of C₁₀-C₂₀; polyoxyethylene (2 to 50 mol)

of Cιo-C₂₀; sorbitane fatty acid alkyl ester or its ethylene oxide (15 to 40 mol)

50 mol) alkyl-alkenylamine, glyceryl monoalkyl-alkenyl ester; ethylene oxide

additives (2 to 50 mol) of cured castor oil; alkylamineoxide; and

amidopropylamineoxide, with regard to 100 parts by weight of the amido

ammonium salt.

27. The fiber softening composition according to claim 23 further comprising 0.1

to 30 parts by weight of one or more dispersion stabilizer selected from the group

consisting of lower alcohol or glycols of Ci to C₈, higher alcohols of C₁₂ to C₂₀,

iodide, magnesium, sodium chloride, calcium chloride and sodium nitrate with

regard to 100 parts by weight of the amido ammonium salt.

28. The fiber softening composition according to claim 23 further comprising 0.01

of fragrants, antiseptic agents, disinfectants, fluorescent whitening agents,

colorants, anti-oxidants and anti-foaming agents.