JP2003155668A - Softener composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a softener composition capable of improving hand feeling of clotjing and imparting strong softening effect to the clothing independent of a condition of rinsing water. SOLUTION: This softener composition comprises (a) a compound expressed by formula (1) or formula (2), (b) a compound expressed by formula (3) or formula (4) and (c) a specific anionic surfactant (wherein R<1> and R<5> express each a 13-36C alkyl or the like; R<10> , R<12> , R<15> and R<17> express each an 8-36C alkyl or the like; R<2> , R<6> , R<11> , R<13> , R<16> and R<18> express each a 1-6C alkylene; R<3> , R<4> , R<7> , R<8> , R<9> , R<14> , R<19> and R<20> express a 1-3C alkyl or the like; A, B, D, E, F and G espress each COO, CONH or the like: a to f express 0 or 1; Y<-> and Z<-> express each an anion group). The molar ratio of (a), (b) and (c) satisfies the equation: [(a)+(b)]/(c)=9/1-4/6.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a softener composition.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As the softening agent, a quaternary ammonium salt having a long-chain alkyl group or an acid salt of a tertiary amine is used. Although these softening agents have a good softening effect on various fibers even in a small amount, it is known that the fibers give an oily finish, and a softening agent for improving the texture of clothes is desired.

In order to solve this drawback, Japanese Patent Publication No. 61-
No. 37387 discloses a method of using a dialkyl quaternary ammonium compound in combination with an anionic surfactant, and JP-A No. 9-111660 discloses a softening component having two or more cationic groups in one molecule. Disclosed are softener compositions that combine an anionic surfactant. However, these techniques cannot achieve both flexibility and texture of finished clothing.

The softening agent is added at the rinsing stage after washing with a general weak alkaline detergent.
And the amount of residual activator vary depending on the amount of laundry, the amount of wash water, or the amount of detergent used. Therefore, it is desired that the softening agent is not affected by the softening effect even if the condition of the rinse water changes.

On the other hand, it is already known to use a mono-long-chain alkyl type soft base as a softener. JP 7-2
Japanese Patent No. 687773 discloses a softener composition using a mono-long-chain alkyl tertiary amine having an ester group or an amide group and a specific ester compound. In addition, JP-A-5
JP-A-132865 discloses a softener composition in which an amine compound and an anionic surfactant are supported on a substrate without being mixed with each other. However, even the compositions disclosed therein cannot improve the oily texture. Further, there is a problem that the softening effect is reduced when the rinse water has a weak alkaline pH and there are many residual activators.

An object of the present invention is to improve the texture of clothing,
Moreover, it is to provide a softener composition capable of imparting a high softening effect to clothing regardless of the state of rinse water.

[0007]

The present invention comprises the following components (a), (b) and (c):
The molar ratio of the component (b) and the component (c) is [(a) +
(B)] / (c) = 9/1 to 4/6 is provided. (A) From a tertiary amine represented by the general formula (1) or a salt thereof (hereinafter referred to as compound (1)) or a quaternary ammonium salt represented by the general formula (2) (hereinafter referred to as compound (2)) One or more compounds selected

[0008]

[Chemical 3]

[In the formula, R ¹ and R ⁵ are each independently an alkyl group or an alkenyl group having 13 to 36 carbon atoms,
R ² and R ⁶ are each independently an alkylene group having 1 to 6 carbon atoms, and R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxy group. Is an alkyl group, A and B are each independently -COO-,
It is a group selected from —OCO—, —CONH— and —NHCO—, a and b are each independently a number of 0 or 1, and Y ⁻ is an anionic group. (B) A tertiary amine represented by the general formula (3) or a salt thereof (hereinafter referred to as the compound (3)), or a quaternary ammonium salt represented by the general formula (4) (hereinafter referred to as the compound (4)). One or more compounds selected from

[0010]

[Chemical 4]

[Wherein R ¹⁰ , R ¹² , R ¹⁵ and R ¹⁷ are each independently an alkyl group or an alkenyl group having 8 to 36 carbon atoms, and R ¹¹ , R ¹³ , R ¹⁶ and R ¹⁸ are respectively Independently, it is an alkylene group having 1 to 6 carbon atoms, and R ¹⁴ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a formula R ¹⁰
A group represented _by- [D-R ¹¹ ] _c- , wherein R ¹⁹ has 1 carbon atom.
To 3 alkyl group, hydroxyalkyl group or the formula R ¹⁵ -
[F-R ^16] _e - is a group represented by, R ²⁰ is C 1 -C
~ 3 alkyl group or hydroxyalkyl group,
D, E, F and G are each independently -COO-, -O.
A group selected from CO-, -CONH- and -NHCO-, wherein c, d, e and f are each independently 0 or 1
, And Z ⁻ is an anionic group. ] (C) In the molecule, a hydrocarbon group having 8 to 36 carbon atoms and -S
O ₃ M group and / or -OSO ₃ M group [M: counter ion] anionic surfactants having a

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION [Component (a)] The component (a) of the present invention is at least one compound selected from the compound (1) and the compound (2). In the compound (1), R ¹ has 13 carbon atoms.
To 36, preferably 14 to 24, alkyl or alkenyl groups. R ² is preferably an alkylene group having 1 to 4 carbon atoms. R ³ and R ⁴ are preferably each independently a methyl group, an ethyl group or a hydroxyethyl group. a is preferably 1.

Among the compounds (1), particularly preferred compounds include one or more selected from the compounds represented by the general formula (1-1) and the compounds represented by the general formula (1-2).

[0014]

[Chemical 5]

[In the formula, R ²¹ represents an alkyl group or an alkenyl group having 13 to 35 carbon atoms, preferably 15 to 23 carbon atoms,
g is 2 or 3. R ²² and R ²³ are each independently a methyl group, an ethyl group or a hydroxyethyl group, preferably a methyl group or a hydroxyethyl group].

The compound represented by the general formula (1-1) or (1-2) is, for example, a fatty acid represented by R ²¹ -COOH or its alkyl (C 1-5) ester or acid chloride and N. -Hydroxyalkyl-N, N-dialkylamine or N-aminoalkyl-N, N-dialkylamine can be easily synthesized, and R ²¹ may be a single alkyl chain length or a mixed alkyl chain. May be long.

The compound (1) may be a salt neutralized with an inorganic or organic acid. When used as a salt, an amino group neutralized with an acid agent can be used before blending with the softener composition. After blending the component (a) with the softener composition, the amino group can be used. May be neutralized with an acid agent. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, hydroxycarboxylic acid, fatty acid having 1 to 12 carbon atoms or alkyl sulfuric acid having 1 to 3 carbon atoms is preferable, and hydrochloric acid, sulfuric acid and glycolic acid are particularly preferable. . These acid agents used for neutralization may be used alone or in combination.

In the compound (2), R ⁵ has 13 carbon atoms.
To 36, preferably 14 to 24, alkyl or alkenyl groups. R ⁶ is preferably an alkylene group having 1 to 4 carbon atoms. R ⁷ , R ⁸ and R ⁹ are each independently preferably a methyl group, an ethyl group or a hydroxyethyl group. Among the compounds (2), particularly preferred compounds are those represented by the general formula (2
One or more kinds selected from the compound represented by -1) and the compound represented by the general formula (2-2) can be mentioned.

[0019]

[Chemical 6]

[Wherein R ²⁴ is an alkyl group or an alkenyl group having 13 to 35 carbon atoms, preferably 15 to 23 carbon atoms,
h is 2 or 3, R ²⁵ , R ²⁶ and R ²⁷ are each independently a methyl group, an ethyl group or a hydroxyethyl group,
It is preferably a methyl group or a hydroxyethyl group. Y
^- is an anionic group, preferably a halogen ion, sulfate ion, phosphate ion, alkyl sulfate ion having 1 to 3 carbon atoms, fatty acid ion having 1 to 12 carbon atoms, 1 to carbon atoms
It is one or more selected from aryl sulfonate ions which may be substituted with an alkyl group of 3. ] The compound represented by the general formula (2-1) or (2-2) is
For example, R ²⁴ fatty acids or alkyl represented by -COOH (1 to 5 carbon atoms) ester or acid chloride with N
-Hydroxyalkyl-N, N-dialkylamine or N-aminoalkyl-N, N-dialkylamine is reacted, and further quaternized with an alkylating agent such as alkyl halide, dialkyl sulfuric acid or alkylene oxide to facilitate quaternization. Can be synthesized. Further, N, N, N-trialkyl-N-hydroxyalkyl quaternary ammonium salt, N, N, N-trialkyl-N-aminoalkyl 4
It can also be synthesized by the reaction of grade ammonium salt and a fatty acid or its alkyl represented by R ²⁴ -COOH (1 to 5 carbon atoms) ester or acid chloride. R ²⁴ may have a single alkyl chain length or a mixed alkyl chain length.

The component (a) of the present invention has a softening effect,
It is preferable to use the compound (1) or the compound (1) and the compound (2) in combination, and in the case of using them in combination, the mass ratio of compound (1) / compound (2) is preferably 1/1000 to 1000/1.

[Component (b)] The component (b) of the present invention is at least one selected from the compound (3) and the compound (4). In the compound (3), R ¹⁰ and R ¹² each independently represent an alkyl group or an alkenyl group having 8 to 36 carbon atoms, preferably 8 to 24 carbon atoms, more preferably 13 to 24 carbon atoms, and particularly preferably 8 to 12 carbon atoms. 16, more preferably 1
It is an alkyl group having 3 to 16 or an alkenyl group having 16 to 20 carbon atoms. R ¹¹ and R ¹³ are each independently preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably an alkylene group having 2 or 3 carbon atoms. c and d are preferably 1, D and E are independently -COO- and / or
Or, -CONH- is preferable. R ¹⁴ is preferably a methyl group, an ethyl group or a hydroxyethyl group.

The compound (3) may be a salt neutralized with an inorganic or organic acid. When used as a salt, it is also possible to use a product obtained by neutralizing an amino group with an acid agent before blending with the softener composition, and after blending the component (b) with the softener composition, the amino group is added. May be neutralized with an acid agent. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, hydroxycarboxylic acid, fatty acid having 1 to 12 carbon atoms or alkyl sulfuric acid having 1 to 3 carbon atoms is preferable, and hydrochloric acid, sulfuric acid and glycolic acid are particularly preferable. . These acid agents used for neutralization may be used alone or in combination.

In the compound (4), R ¹⁵ and R
Each of ¹⁷ independently has 8 to 36 carbon atoms, preferably 8 to 36 carbon atoms.
An alkyl group having 24 carbon atoms or an alkenyl group, particularly preferably an alkyl group having 8 to 16 carbon atoms or 16 to carbon atoms.
20 alkenyl groups. R ¹⁶ and R ¹⁸ are each independently preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably an alkylene group having 2 or 3 carbon atoms. e and f are preferably 1, F and G are each independently -CO
O- and / or -CONH- are preferred. R ¹⁹ and R ²⁰
Are each preferably a methyl group, an ethyl group or a hydroxyethyl group. Z ⁻ is an anion group, preferably a halogen ion, a sulfate ion, a phosphate ion, and a carbon number of 1 to
It is one or more selected from the group consisting of alkyl sulfate ester ion of 3, a fatty acid ion of 1 to 12 carbon atoms, and an aryl sulfonate ion which may be substituted with an alkyl group of 1 to 3 carbon atoms.

More preferred compounds among the compounds (3) are compounds represented by the general formulas (3-1) to (3-3), and more preferred compounds among the compounds (4) are the general formula (4). Examples thereof include compounds represented by -1) to (4-3).

[0026]

[Chemical 7]

[Wherein R ²⁷ is an alkyl group or alkenyl group having 9 to 21 carbon atoms, preferably an alkyl group or oleyl group having 9 to 16 carbon atoms, i and j are numbers of 2 or 3, and R ²⁸ is a methyl group, an ethyl group, a hydroxyethyl group or a group represented by the formula R ²⁷ —COO (CH ₂ ) _i —, R ²⁹ is a methyl group, an ethyl group or a hydroxyethyl group, and Z ⁻ is It has the same meaning as described above. The component (b) of the present invention is a compound (3) from the viewpoint of the softening effect,
Alternatively, the compound (3) and the compound (4) are preferably used in combination, and when they are used in combination, the mass ratio of compound (3) / compound (4) is preferably 1/1000 to 1000/1.

[Component (c)] The component (c) of the present invention comprises a hydrocarbon group having 8 to 36 carbon atoms, preferably 14 to 36 carbon atoms such as an alkyl group or an alkenyl group, a —SO ₃ M group and / or a hydrocarbon group. -OSO ₃ M group [M: counterion] is an anionic surfactant having in the molecule, and specifically, an alkylbenzene or alkenyl group is an alkylbenzenesulfonic acid having the above carbon number, alkyl (or alkenyl) Sulfate, polyoxyalkylene alkyl (or alkenyl)
Ether sulfate, olefin sulfonic acid, alkane sulfonic acid, α-sulfo fatty acid, α-sulfo fatty acid ester and salts thereof are preferred. Among these, alkyl (or alkenyl) sulfuric acid esters having an alkyl group or an alkenyl group having 14 to 26 carbon atoms, and 1 carbon atom
4 to 26 having an alkyl group or an alkenyl group and having an ethylene oxide (hereinafter referred to as EO) average addition mole number of 1
One or more selected from polyoxyethylene alkyl (or alkenyl) ether sulfates having 1 to 6, preferably 1 to 4, and particularly preferably 1 to 3 and salts thereof are preferable. As the salt, sodium salt, potassium salt,
Ammonium salt and alkanolamine salt are preferable from the viewpoint of storage stability.

[Softener composition] In the softener composition of the present invention, the component (a) is preferably 3 to 40% by mass, more preferably 5 to 40% by mass, particularly preferably 5 to 35% by mass.
It is preferable that the component (b) is contained in an amount of preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 2 to 15% by mass from the viewpoint of softening effect and texture. Further, the component (c) is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, and particularly preferably 2
It is preferable that the content is -20% by mass from the viewpoint of softening effect and texture.

The softener composition of the present invention comprises the component (a),
The molar ratio of the component (b) and the component (c) is [(a) +
(B)] / (c) = 9/1 to 4/6, and further 9/1 to 5 /
It is preferable that it is 5, especially 8.5 / 1.5 to 6.5 / 3.5 from the viewpoint of flexibility and texture. From the viewpoint of the influence on the rinse water, the mass ratio of the component (a) and the component (b) is (a) / (b) = 1/10 to 100/1, preferably 1/3 to 50/1, and further Preferably 1 / 2-50
/ 1, particularly preferably 1/1 to 25/1, most preferably 2/1 to 25/1. Also,
5 to 6 in total of component (a), component (b) and component (c)
It is preferable that the content is 0% by mass, particularly 10 to 50% by mass from the viewpoint of softening effect, texture and storage stability.

The softener composition of the present invention comprises the component (a),
It is in the form of an aqueous solution prepared by diluting the components (b) and (c) with water, and the water used is preferably distilled water or ion-exchanged water. From the viewpoint of storage stability, water is added to the composition in an amount of 30 to 95% by mass, preferably 50 to 85% by mass.

Further, the pH of the composition of the present invention at 20 ° C. is preferably adjusted to 1 to 8.5, more preferably 1 to 8, and especially 2 to 8 from the viewpoint of storage stability.

In the present invention, the above-mentioned component (a), component (b),
In addition to the component (c), logP is 0.2 as the component (d).
To 3.0, preferably 0.5 to 3.0, more preferably 0.8 to 2.0, still more preferably 1.0 to 1.9, most preferably 1.1 to 1.6. Is preferable from the viewpoint of the preferable appearance and storage stability of the composition.
The preferable appearance here means a uniformly dispersed state or a transparent state of the softening agent composition, and in the present invention, a particularly aesthetically preferable transparent state. Also, log P is a coefficient indicating the affinity of an organic compound for water and 1-octanol, and the 1-octanol / water partition coefficient P is a trace amount of a compound as a solute in a solvent of two liquid phases of 1-octanol and water. The distribution equilibrium when dissolved, is the ratio of the equilibrium concentrations of the compounds in the respective solvents, and is generally shown in the form of their logarithm logP to the base 10. The logP values of many compounds have been reported, Daylight Chemical Inform
Many values can be found in the databases available from ation Systems, Inc. (Daylight CIS). If there is no measured logP value, Daylight C
It is most convenient to calculate with the program "CLOGP" available from IS. This program calculates "calculated logP (ClogP)" by Hansch Leo's fragment approach along with the measured logP value, if any.
The value of is output. The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo Comprehensive Medicinal
Chemistry, Vol.4 C. Hansch, PG Sammens, JB Tayl
or and CA Ramsden, Eds., P.295, Pergamon Press,
1990). Since this ClogP value is the most general-purpose and reliable estimation value at present, the measured lo
It can be used instead of the gP value. In the present invention, l
If there is an actual measured value of ogP, it is used, and if not, the ClogP value calculated by the program CLOGP v4.01 is used.

As the organic solvent having such log P, the following general formula (5), general formula (6) and general formula (7) are given.
Compounds represented by are preferred.

R ³⁰ --OH (5) [wherein R ³⁰ is a hydrocarbon group having 4 to 8 carbon atoms, preferably an alkyl group, an aryl group, or an arylalkyl group. ] ^{R 31 - (O-R 32} ) k -O-R 33 (6) : wherein, R ³¹ and R ³³ are each independently a hydrogen atom, R
^{A group represented by 34} CO— (R ³⁴ is an alkyl group having 1 to 3 carbon atoms), a hydrocarbon group having 1 to 7 carbon atoms, preferably a hydrogen atom, an alkyl group, an aryl group or an arylalkyl group, R ³² Is an alkylene group having 2 to 9 carbon atoms and optionally having a branched chain. k is a number from 1 to 5. ] _{^{R 35 -O-CH 2 CH (}} O-R 36) CH 2 -O-R 37 (7) [wherein R ³⁵ represents an alkyl group having 3 to 8 carbon atoms,
R ³⁶ and R ³⁷ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydroxy group. More specifically preferred compounds include n-butanol, isobutanol, 2-butanol, n-hexanol, cyclohexanol, phenol, benzyl alcohol, phenethyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, diethylene glycol monobenzyl ether. , Diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether,
2-ethylhexane-1,3-diol, hexane-
1,6-diol, nonane-1,6-diol, nonane-1,9-diol, 2-methyloctane-1,8-diol, 2-butoxyethanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 2- (2-Methyl) propoxyethanol, diethylene glycol mono-2-methylpropyl ether, 2-propoxy-1-propanol, dipropylene glycol monopropyl ether, 2-butoxy-
1-propanol, propylene glycol monobutyl ether, propylene glycol monophenyl ether,
Dipropylene glycol monobutyl ether, 2-t-
Butoxy-1-propanol, 2-phenoxy-1-propanol, 2-ethoxypropyl-1-acetate,
2-propoxypropyl-1-acetate, 1,2-diacetoxypropane, 3-dimethyl-3-methoxy-
Examples thereof include 1-propanol, 1,3-dimethylbutyl glyceryl ether, pentyl glyceryl ether, and hexyl glyceryl ether.

Among these, particularly n-hexanol, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, hexane-1,6-diol. , Nonane-1,6-
Diol, nonane-1,9-diol, diethylene glycol monobutyl ether, 2-propoxy-1-propanol, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monobutyl ether, pentyl glyceryl ether, Hexyl glyceryl ether is preferred.

Further, among these, benzyl alcohol,
2-phenoxyethanol, 2-benzyloxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, nonane-1,
Most preferred are 9-diol, propylene glycol mono (n-butyl) ether, propylene glycol monophenyl ether, dipropylene glycol monobutyl ether, hexyl glyceryl ether.

The composition of the present invention preferably contains the component (d) in an amount of 0.5 to 40% by mass, more preferably 1 to 35% by mass, and particularly preferably 5 to 30% by mass.

In the present invention, the above-mentioned component (a), component (b),
In addition to the components (c) and (e), the number of carbon atoms is 12
~ 36, preferably 14-24, more preferably 14-
It is preferable to contain 20 saturated or unsaturated fatty acids or salts thereof in order to improve the softening effect and the texture effect. Specifically, it is lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, or a mixture thereof, and one or more kinds selected from palmitic acid, stearic acid, and oleic acid are particularly preferable. Further, a fatty acid having an alkyl composition derived from palm oil or beef tallow is also preferable. When a salt is used, sodium salt, potassium salt, magnesium salt and alkanolamine salt are preferable, and sodium salt and potassium salt are particularly preferable from the viewpoint of storage stability. The compounding amount of this component (e) is 0.01 in the composition.
-5% by mass, particularly preferably 0.05-3% by mass. The mass ratio of component (e) / [component (a) + component (b)] is preferably 1/500 to 1/10, particularly 1/300 to 1/50 from the viewpoint of the softening effect.

In the present invention, from the viewpoint of storage stability, the above (a)
In addition to the component, the component (b) and the component (c), (f)
It is preferable to add a nonionic surfactant as a component. As the nonionic surfactant, a polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 8 to 20 carbon atoms is preferable, and a nonionic surfactant represented by the general formula (8) is particularly preferable.

R ³⁸ -U-[(R ³⁹ O) _m -H] _n (8) [wherein R ³⁸ has 10 to 18 carbon atoms, preferably 12 to 1 carbon atoms]
8 is an alkyl group or an alkenyl group, R ³⁹ is an alkylene group having 2 or 3 carbon atoms, and preferably an ethylene group. m represents a number of 2 to 100, preferably 5 to 80, particularly preferably 10 to 60. U is -O-, -CON
<Or -N <, n is 1 when U is -O-, and n is 2 when U is -CON <or -N <. ].

The following compounds can be mentioned as specific examples of the compound represented by the general formula (8).

R ³⁸ --O-(C ₂ H ₄ O) _p --H [wherein R ³⁸ has the above-mentioned meaning. p is a number of 8 to 100, preferably 10 to 60. _{^{] R 38 -O- (C 2 H}} 4 O) q - (C 3 H 6 O) in _r -H [wherein, R ³⁸ have the same meanings as defined above. q and r are each independently a number of 2 to 40, preferably 5 to 40, and EO
And propylene oxide (hereinafter referred to as PO) may be random or block adducts. ]

[0044]

[Chemical 8]

[In the formula, R ³⁸ has the above-mentioned meaning. s,
t, u and v are each independently 0 to 40, preferably 5
-40, and s + t + u + v is 5-60, preferably 5-40. EO and PO may be random or block adducts. ] The blending amount of the nonionic surfactant of the component (f) is 0.
5 to 10% by mass, particularly 1 to 8% by mass is preferable.

Further, the softener composition of the present invention may contain an inorganic salt as the component (g). As the inorganic salt, at least one selected from sodium chloride, calcium chloride and magnesium chloride is preferable from the viewpoint of storage stability, and is 0 to 1000 ppm, preferably 10 in the composition.
It is preferable to add ~ 500 ppm. However, surfactants such as fatty acid salts include sodium salts and potassium salts, but the inorganic salts mixed in the composition by the use of such surfactants are not limited to the above.

In the softener composition of the present invention, a solvent other than the component (d) can be used as the component (h). Specific preferred component (h) is a solvent selected from ethanol, isopropanol, glycerin, ethylene glycol and propylene glycol, and these component (h) are contained in the composition in an amount of 0 to 20% by mass, particularly 0.5. It can be blended in an amount of 10 to 10% by mass. When ethanol is used, it is desirable to use polyoxyethylene alkyl ether sulfate modified ethanol or 8-acetylated sucrose modified ethanol.

In the present invention, an ester compound of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol can be blended as the component (i) for the purpose of improving the storage stability. Specific preferred compounds include triglyceride, diglyceride, monoglyceride, pentaerythritol mono-, di-, triesters, and sorbitan esters, and the compounding amount thereof is preferably 5% by mass or less, more preferably 3% by mass or less. It is particularly preferably 1% by mass or less.

The softening agent composition of the present invention may contain a generally known sequestering agent or antioxidant in order to improve the color and odor after storage. As the sequestering agent, aminocarboxylic acids represented by ethylenediaminetetraacetic acid salt, diethylenetriaminepentaacetic acid salt, etc., inorganic phosphorus compounds represented by tripolyphosphate, pyrophosphate, 1
-Hydroxyethane-1,1-diphosphonate, polyphosphonic acids, and organic phosphoric acids typified by phytic acid can be mentioned, and the antioxidant is 2,6-di-te.
Examples include rt-butyl-4-methylphenol and 2 (3) -butyl-4-oxyanisole. These may be added as an acid or a salt. These sequestering agents and antioxidants are added to the softener composition of the present invention in the range of 0.1 to 1000 ppm with respect to the component (a).

In the softener composition of the present invention, silicones and fragrances which are usually added to fiber treatment agents (particularly preferred are the components (c) and (d) described in JP-A-8-11387). A combination of aroma components) or components such as pigments may be added.

As the method for producing the softener composition of the present invention, the components (f) and (h) are dissolved in water, if necessary, and heated to 40 to 70 ° C, preferably 45 to 65 ° C. Warm, then (a) component, (b) component, (c) component,
If necessary, component (d), component (e), component (g) and component (i) are added and mixed by stirring, adjusted to a predetermined pH with an acid agent, and after cooling, other components are added. The method is preferable from the viewpoint of storage stability.

[0052]

EXAMPLES Synthesis Example 1: Synthesis of (a-1) Palmitic acid / stearic acid mixed at 50/50 (mass ratio) mixed fatty acid and N-hydroxyethyl-N, N-.
By dehydration esterification reaction with dimethylamine (a-
1) was synthesized. That is, N-hydroxyethyl-
N, N-dimethylamine 132 g, palmitic acid 200
g and 200 g of stearic acid were placed in a four-necked flask equipped with a stirrer, a thermometer, and a dehydration tube, and heated to 150 ° C.
The mixture was heated and stirred while distilling off water produced at that temperature for 4 hours. The temperature was further raised to 180 ° C., and N-hydroxyethyl-
While stirring dropwise addition of 66 g of N, N-dimethylamine, heating and stirring were continued for 10 hours. Then, the mixture was cooled to 120 ° C., unreacted amine was distilled off under reduced pressure, and the target N-alkanoyloxyethyl-N, N-dimethylamine (a-
1) 473 g was obtained.

Synthesis Example 2: Synthesis of (a-2) Dehydration amidation of N, N-dimethyl-1,3-propanediamine with a mixed fatty acid obtained by mixing palmitic acid / stearic acid at a ratio of 40/60 (mass ratio). (A-2) was synthesized by the reaction. That is, 161 g of N, N-dimethyl-1,3-propanediamine and 273.3 g of mixed fatty acid were placed in a four-necked flask equipped with a stirrer, a thermometer, and a dehydration tube, and 1
The temperature was raised to 80 ° C. The mixture was heated and stirred while distilling off water produced at that temperature for about 5 hours. Then, the mixture was cooled to 120 ° C., unreacted amine was distilled off under reduced pressure, and the target N-
Alkanoylaminopropyl-N, N-dimethylamine (a-2) was obtained.

Synthesis Example 3: Synthesis of (a-3) N-oleoylaminopropyl-N, N-dimethyl was prepared in the same manner as in Synthesis Example 2 except that oleic acid was used instead of the mixed fatty acid in Synthesis Example 2. The amine (a-3) was obtained.

Synthesis Example 4: Synthesis of (a-4) Synthesis was carried out using the component (a-1) produced in Synthesis Example 1 and methyl chloride. That is, 100 g of the component (a-1)
Then, 300 g of ethanol and 300 g of ethanol were charged into the autoclave and, after purging with nitrogen, the temperature was raised to 100 ° C. with stirring. Then, 18 g of methyl chloride was press-fitted with a press-fitting pump and reacted for 3 hours. After cooling, ethanol was distilled off under reduced pressure to obtain the desired N-alkanoyloxyethyl-N, N, N-trimethylammonium chloride (a-4).

Synthesis Example 5: Synthesis of (a-5) Using the component (a-2) prepared in Synthesis Example 2 and methyl chloride, synthesis was carried out in the same manner as in Synthesis Example 4, and the desired N-alkanoylaminopropyl was obtained. -N, N, N-trimethylammonium chloride (a-5) was obtained.

Synthesis Example 6: Synthesis of (a-6) Using the component (a-3) prepared in Synthesis Example 3 and methyl chloride, a synthesis was carried out in the same manner as in Synthesis Example 4 to obtain the desired N-oleoylamino. Propyl-N, N, N-trimethylammonium chloride (a-6) was obtained.

Synthesis Example 7: Synthesis of (ab-1) Oleic acid and N-methyl-N-hydroxyethyl-1,
(Ab-1) was synthesized by a dehydration esterification reaction and a dehydration amidation reaction with 3-propanediamine. That is, 119.2 g (1.00 mol) of N-methyl-N-hydroxyethyl-1,3-propanediamine and 434.5 g (1.53 mol) of oleic acid were mixed with a stirrer, a thermometer, a nitrogen introduction pipe, and a dehydration pipe. A 1000 ml four-neck round bottom flask equipped with was charged, the pressure was reduced to 26.7 kPa, and the temperature was raised to 180 ° C. After reacting for 7 hours as it is, it is cooled and N-oleoylaminopropyl-N-hydroxyethyl-N-
A mixture of methylamine and N-oleoylaminopropyl-N-oleoyloxyethyl-N-methylamine was obtained. Of these, 300.0 g and ethanol 58.5 g
Was charged into an autoclave equipped with a stirrer, a thermometer, and an introduction tube, and 38.8 g (0.768 mol) of methyl chloride was press-fitted at room temperature. Then, it heated up at 80 degreeC and reacted for 4 hours. After cooling to 60 ° C., the residual pressure was blown to obtain the desired N-oleoylaminopropyl-N-hydroxyethyl-N, N-dimethylammonium chloride and N-oleoylaminopropyl-N-oleoyloxyethyl-N. , N-dimethylammonium chloride mixture (weight ratio 65/35) (ab-1) was obtained.

Synthesis Example 8: Synthesis of (ab-2) (ab-2) was synthesized by dehydration esterification reaction of oleic acid and N, N-dihydroxyethyl-N-methylamine. That is, N, N-dihydroxyethyl-N
-Methylamine 132.2 g (1.00 mol) and oleic acid 437.4 g (1.54 mol) were stirred, a thermometer,
A 1000 ml four-neck round bottom flask equipped with a nitrogen introduction tube and a dehydration tube was charged and the temperature was raised to 190 ° C. 9 under normal pressure
After reacting for a time, the mixture was cooled and N-oleoyloxyethyl-N-hydroxyethyl-N-methylamine and N,
A mixture of N-dioleoyloxyethyl-N-methylamine was obtained. Of this, 300.0g and ethanol 5
8.4 g was charged into an autoclave equipped with a stirrer, a thermometer, and an introduction tube, and 39.9 g of methyl chloride (0.791) was added.
Mol) at room temperature. Then, raise the temperature to 100 ° C,
Reacted for 6 hours. After cooling to 60 ° C., the residual pressure was blown to obtain the desired N-oleoyloxyethyl-N-hydroxyethyl-N, N-dimethylammonium chloride and N, N-dioleoyloxyethyl-N, N-dimethyl. Mixture of ammonium chloride (weight ratio 65/3
5) (ab-2) was obtained.

Example 1 Softener compositions shown in Tables 1 to 5 were prepared using the following ingredients. At that time, the component (d), the component (f), the component (g) and the component (h) were dissolved in water and the temperature was raised to 60 ° C.
Component (a) while stirring with a stirring blade at 60 ° C.,
The components (b), (c), and optionally the components (e) and (i) are added and adjusted to a predetermined pH with a 35% hydrochloric acid aqueous solution and a 48% sodium hydroxide aqueous solution, and then the remaining (j) The ingredients were added and cooled to room temperature. In addition, in the pH range shown in Tables 1 to 5, (a-1), (a-2), (a-
3), (b-1), (b-2), (b-3), (b-
7) The component is almost entirely present in the composition in the form of its hydrochloride salt.

With respect to the obtained softening agent composition, the softness and texture were evaluated by the following methods, and further, Table 3, Table 4 and Table 5 were used.
The appearance of the composition shown in 1 above was also evaluated. The results are shown in Tables 1 to 5.

<Ingredients> (A-1): N-alkanoyloxye obtained in Synthesis Example 1
Cyl-N, N-dimethylamine (A-2): N-alkanoylaminopine obtained in Synthesis Example 2
Ropil-N, N-dimethylamine (A-3): N-oleoylaminopro obtained in Synthesis Example 3
Pill-N, N-dimethylamine (A-4): N-alkanoyloxye obtained in Synthesis Example 4
Chill-N, N, N-trimethylammonium chloride (A-5): N-alkanoylaminopine obtained in Synthesis Example 5
Ropil-N, N, N-trimethylammonium chloride (A-6): N-oleoylaminopro obtained in Synthesis Example 6
Pill-N, N, N-trimethylammonium chloride (B-1): N, N-distearoyloxyethyl-N
-Methylamine (B-2): N, N-dioleoyloxyethyl-N-
Methylamine (B-3): N-alkanoylaminopropyl-N-a
Lucanoyloxyethyl-N-methylamine (alkano
Ile group: stearoyl group / palmitoyl group in a molar ratio of 5
0/50) (B-4): N, N-distearoyloxyethyl-
N, N-dimethylammonium chloride (B-5): N, N-dioleoyloxyethyl-N,
N-dimethylammonium chloride (B-6): N-alkanoylaminopropyl-N-a
Lucanoyloxyethyl-N, N-dimethylammonium
Muclide (alkanoyl group: stearoyl group / palmi
(50/50 molar ratio of toyl groups) (B-7): N-alkanoylaminopropyl-N-a
Lucanoyloxyethyl-N-methylamine (alkano
Ile group: lauroyl group / myristoyl group in a molar ratio of 50
/ 50) (B-8): N-alkanoylaminopropyl-N-a
Lucanoyloxyethyl-N, N-dimethylammonium
Muchloride (alkanoyl group: lauroyl group / myristo
(Ile group is 50/50 in molar ratio) (B-9): dialkyldimethylammonium chloride
[Carbon number C₁₂/ C₁₃/ C ₁₄/ C₁₅Is 20/30/30 /
A 1-alkene in a molar ratio of 20 was hydroformated with carbon monoxide.
Oxo-type alcohol obtained by milling (the alcohol
The content of methyl-branched alkyl alcohol is 25 mol.
%) And monomethylamine with nickel catalyst
React to obtain dialkylmethylamine, and
Obtained by alkylation with chlorchloride] (B-10): dialkyldimethylammonium chloride
De (alkyl group: lauryl group / myristyl group in molar ratio
50/50) (C-1): sodium stearyl sulfate (C-2): polyoxyethylene hardened beef tallow composition alkyl
Sodium sulfate (EO average addition mole number 2.3,
Hardened beef tallow composition is 40/6 palmitic / stearyl groups
0 mass ratio) (C-3): Guerbet type sodium alkyl sulfate
(2-octyldodecyl sulfate sodium salt) (2
Sulfate octyl-1-dodecanol with sulfur trioxide
And neutralized with sodium hydroxide) (C-4): Guerbet type alkyl (C_{twenty four}) Sulfate ester
Thorium (2-decyl tetradecyl sulfate ester Natri
Umm) (D-1): 2-phenoxyethanol (logP =
1.19) (D-2): diethylene glycol monophenyl ether
Le (logP = 1.25) (D-3): dipropylene glycol monopropyl ether
Tell (logP = 1.0) (E-1): stearic acid (E-2): Oleic acid (E-3): Lauric acid / myristic acid = 50/50
(Weight ratio) (F-1): EO averaged in saturated alcohol having 12 carbon atoms
20 mol added (f-2): stearylamine
EO added with an average of 30 mol (G-1): Sodium chloride (G-2): magnesium chloride (H-1): ethanol (I-1): Exel 150 [stearic acid mono, di,
Triglyceride mixture (mono: di: tri = 60: 35:
5) Made by Kao Corporation] (J-1): Silicone (Toray Dow Corning Siri
Corn-16, BY-16-891) (J-2): Dye (Acid Blue 9) (J-3): fragrance [hexyl cinnamic aldehyde
(18), Nerolyn Yala Yala (4), Tricyclodeceni
Lu acetate (4), benzyl acetate (10), mu
Skoketone (5), anisylacetone (2), sandals
Mysore core (2), aldehyde C14 peach
(1), linalool (18), dihydroxymyrceno
Le (8), Borneol (4), Cedrol (4), Mu
Goal (5), benzyl alcohol (5), dipropile
Mixture of glycol (10): quality in perfume in parentheses
amount%]. (J-4): 2,6-ditert-butyl-4-methylphene
Noor <Evaluation method of flexibility and texture> Bath towel (cotton 100
%) 5 sheets of commercially available weak alkaline detergent (Kao Corporation
Was washed in a washing machine (Toshiba 2-tank washing machine V
H-360S1, detergent concentration 0.0667 mass%, tap water
Use 30 L, water temperature 20 ° C., 10 minutes). Then wash solution
Drain, dehydrate for 3 minutes, then inject 30 L of tap water for 5 minutes
It was rinsed for a while, and drained and dehydrated for 3 minutes. Then re
30L of tap water is poured and rinsed and dehydrated similarly.
It was. After repeating this operation once more,
PH of 20 ° C to 8.0 with
Number 12 to 15 sodium alkylbenzene sulfonate
Of 30 L of tap water (evaluation
Aqueous solution) and add 7 ml of the softener composition of Tables 1 to 5
The mixture was added and stirred for 5 minutes. Then, it was dehydrated and naturally dried.

The flexibility and texture of the above treated bath towels were judged by the following criteria by 10 panelists (10 men in their thirties), and an average score was obtained. An average score of 0 or more and less than 1 is ◯, 1 or more and less than 1.5 is Δ, and 1.5 or more is ×.
Was judged as.

(1) Evaluation criteria for flexibility 0: Very soft finish 1: Soft finish 2: Slightly soft finish 3: No soft finish (2) Texture evaluation criteria 0: Clean without oil Texture 1: Not slightly oily, refreshing texture 2: Slightly oily texture 3: Oily texture <Appearance evaluation method> Compositions in Tables 3, 4 and 5 100 ml was put into a wide-mouth standard bottle No. 11, and the appearance was visually evaluated according to the following criteria.

[0065] ◎: transparent ○: Appears to be slightly cloudy, but almost transparent △: cloudy X: precipitation has occurred

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

Example 2 A softener composition shown in Table 6 was prepared using the following components.
At that time, the components (d), (f) and (h) were dissolved in water and the temperature was raised to 60 ° C. While stirring with stirring blades at 60 ° C., component (ab) (a mixture of component (a) and component (b)), component (c), and component (e) were added, and 35
% Aqueous solution of hydrochloric acid and aqueous 48% sodium hydroxide solution, the pH was adjusted to a predetermined level, the remaining component (j) was added, and the mixture was cooled to room temperature.

The softening agent composition thus obtained was used in Example 1.
The flexibility, texture and appearance were evaluated in the same manner as in. The results are shown in Table 6.

<Ingredients> (ab-1): N-oleoylaminopropyl-N-hydroxyethyl-N, N-dimethylammonium chloride and N-oleoylaminopropyl-obtained in Synthesis Example 7.
Mixture of N-oleoyloxyethyl-N, N-dimethylammonium chloride (weight ratio 65/35) (ab-2): N-oleoyloxyethyl-N-hydroxyethyl-N, N obtained in Synthesis Example 8. -A mixture of dimethylammonium chloride and N, N-dioleoyloxyethyl-N, N-dimethylammonium chloride (weight ratio 65/35) (c-4), (d-1), (e-2), ( f-1),
(H-1), (j-2), (j-3), (j-4): same as the first embodiment

[0074]

[Table 6]

[0075]

The softener composition of the present invention has the p
It also exhibits an excellent softening effect when H is weakly alkaline and has a large amount of residual activator, and can also improve an oily texture.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shuji Takata             Kao Co., Ltd. 1334 Minato, Wakayama City, Wakayama Prefecture             Inside the laboratory F-term (reference) 4L033 BA29 BA45 BA86 DA01 DA04

Claims (3)

[Claims] 1. The following components (a), (b) and (c):
Including the components, the molar ratio of the components (a), (b) and (c) is [(a) + (b)] / (c) = 9/1 to 4
/ 6 softener composition. (A) a tertiary amine represented by the general formula (1) or a salt thereof,
Alternatively, one or more compounds selected from the quaternary ammonium salt represented by the general formula (2): [In the formula, R ¹ and R ⁵ each independently have 13 to 3 carbon atoms.
6 is an alkyl group or an alkenyl group, R ² and R ⁶ are each independently an alkylene group having 1 to 6 carbon atoms,
R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group,
A and B are independently -COO-, -OCO-,
A group selected from -CONH- and -NHCO-,
a and b are each independently a number of 0 or 1, and Y ⁻ is an anionic group. ] (B) A tertiary amine represented by the general formula (3) or a salt thereof,
Alternatively, one or more compounds selected from the quaternary ammonium salt represented by the general formula (4): [Wherein R ¹⁰ , R ¹² , R ¹⁵ and R ¹⁷ are each independently
An alkyl group or an alkenyl group having 8 to 36 carbon atoms,
R ¹¹ , R ¹³ , R ¹⁶ and R ¹⁸ each independently have 1 carbon atom.
A 6 alkylene group, R ¹⁴ is an alkyl group having 1 to 3 carbon atoms, hydroxyalkyl group or the formula ^{R 10 - [D-R 11} ]
R ¹⁹ is a group represented by _c- , and R ¹⁹ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a formula R ¹⁵ — [F—R ¹⁶ ].
_e - in a group represented, R ²⁰ is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, D, E, F and G are each independently, -COO -, - OCO -, - CO
A group selected from NH- and -NHCO-, c,
d, e, and f are each independently a number of 0 or 1,
Z ^- is an anionic group. ] (C) In the molecule, a hydrocarbon group having 8 to 36 carbon atoms and -S
O ₃ M group and / or -OSO ₃ M group [M: counter ion] anionic surfactants having a 2. A mass ratio of the component (a) and the component (b),
(A) / (b) is 1/10 to 100/1.
The softener composition described. 3. The hydrocarbon group of component (c) has 14 carbon atoms.
The softener composition according to claim 1 or 2, wherein