JP2003301373A - Softening agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a transparent liquid softening agent composition for markedly reducing a stain occurring in the case of direct adhesion to clothing. <P>SOLUTION: The O/W-type transparent liquid softening agent composition comprises (a) 3-50 mass % of a compound containing one or more 12-36C hydrogen group in the molecule which may be interrupted by an unsaturated group, an amide group, an ester group or an ether group and a tertiary amino group or its acid salt or a quaternary ammonium group, (b) 3-35 mass % of an organic solvent having 0.5-3 logP, (c) 0.1-10 mass % of at least one compound selected from a paraffin being liquid at 20°C and a 12-30C alcohol being liquid at 20°C and (d) 40-90 mass % of water. The method for reducing viscosity of the O/W- type transparent liquid softening agent composition in dilution with water is provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent liquid softening agent composition having a stain suppressing effect.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Liquid softeners for clothing used in ordinary households have had an opaque appearance in which a water-insoluble quaternary ammonium salt is emulsified and dispersed in water, but in recent years, it is transparent or translucent from an aesthetic point of view. Development of various softeners. Japanese Patent Application Laid-Open No. 7-229061 discloses a composition using a softener having an unsaturated alkyl group and a non-aqueous solvent. JP-A-9-250085 discloses a softening agent composition using a softening base material having a specific iodine value.

These softeners are generally added at the rinsing stage during washing, and in some cases, the softener composition may be directly attached to clothing. When the conventional emulsified dispersion type softener composition is used, even if it is directly attached to the clothing, the softening agent can be uniformly adsorbed to the clothing by stirring in the rinse water to exert the softening effect. However, it has been found that when a softener having a transparent appearance is directly attached to clothes, stains remain on the clothes after drying even after sufficient rinsing, and improvement thereof is required.

On the other hand, the use of hydrocarbon compounds in softener compositions is already known. Japanese Patent Laid-Open No. 58-1096
No. 81 discloses a paraffin compound for the purpose of facilitating the production of a softener composition. Japanese Patent Laid-Open No. 4-2
28680 discloses a softener composition containing a hydrocarbon having a preferable viscosity. British Patent 16
No. 01360 discloses a technique of using a hydrocarbon compound for the purpose of stabilizing dispersion of a water-insoluble cationic flexible substrate. However, since the softener compositions disclosed therein are emulsified and dispersed, there is no problem of stain generation when directly attached to clothing, and a technique for suppressing this is not disclosed.

Furthermore, WO 01/04254 and EP
No. 829531 discloses a technique of using oil in a concentrated softener composition having a low water content. EP125103 discloses a technique of using a hydrocarbon compound for the purpose of enhancing the softening effect. However, even these techniques do not suggest any method for suppressing the generation of stains.

[0006] Therefore, an object of the present invention is to provide a transparent liquid softener composition in which stains generated when it is directly applied to clothing is significantly reduced.

[0007]

According to the present invention, (a) a hydrocarbon group having 12 to 36 carbon atoms, which may be divided by an unsaturated group, an amide group, an ester group or an ether group, is used in the molecule.
3 to 50% by mass of a compound having one or more and a tertiary amino group or an acid salt thereof, or a quaternary ammonium group,
(B) 3 to 35% by mass of an organic solvent having a logP of 0.5 to 3, and (c) at least one compound selected from paraffin that is liquid at 20 ° C. and alcohol having 12 to 30 carbon atoms that is liquid at 20 ° C. 0.1-10% by mass, and (d) water 40
Provided is an O / W transparent liquid softener composition containing ~ 90% by mass.

Further, the present invention has (a) one or more hydrocarbon groups having 12 to 36 carbon atoms which may be divided by an unsaturated group, an amide group, an ester group or an ether group in the molecule, And a compound having a tertiary amino group or an acid salt thereof, or a quaternary ammonium group, and (b) logP of 0.5 to
To a mixture containing the organic solvent of 3 and (d) water,
(C) At least one selected from paraffins liquid at 20 ° C. and alcohols having a carbon number of 12 to 30 at 20 ° C.
Provided is a method for reducing the viscosity of the above O / W transparent liquid softener composition when diluted with water, which comprises adding a certain compound.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION [Component (a)] The component (a) of the present invention is a hydrocarbon group having 12 to 36 carbon atoms which may be divided by an unsaturated group, an amide group, an ester group or an ether group. Is a compound having at least one in the molecule and having a tertiary amino group or an acid salt thereof, or a quaternary ammonium group, and is particularly represented by the general formula (1) and having an iodine value of 30 to 13
0, preferably 35 to 120, particularly preferably 40 to 1
A compound of 10 (hereinafter referred to as compound (1)), a compound represented by the general formula (2) (hereinafter referred to as compound (2)),
Alternatively, a compound represented by the general formula (3) (hereinafter, compound (3)
Is preferable in terms of transparency of the composition.

[0010]

[Chemical 3]

[In the formula, R ¹ and R ² are each independently an alkyl group or an alkenyl group having 12 to 26 carbon atoms which may be divided by an ester group, an amide group or an ether group, and R ³ is hydrogen. An atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ⁴ has 1 carbon atom
~ 3 alkyl groups or hydroxyalkyl groups. X ⁻ represents an anionic group. ]

[0012]

[Chemical 4]

[In the formula, R ⁵ and R ⁹ are each independently an alkyl group or an alkenyl group having 14 to 36 carbon atoms,
R ⁶ and R ¹⁰ are each independently an alkylene group having 1 to 6 carbon atoms. R ⁷ , R ⁸ , R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. A and B are independently -COO
It is a group selected from-, -OCO-, -CONH- and -NHCO-. a and b are 0 or 1 numbers. Y ^-
Is an anion. In the compound (1), R ¹ and R ² are preferably a compound containing an ester group, an amide group or an ether group, particularly preferably an ester group and / or an amide group. Further, the proportion of the alkyl group is 1 to 50 mol%, preferably 1 to 3 relative to the total number of moles of R ¹ and R ^2.
0 mol%, more preferably 5 to 15 mol%, and the proportion of alkenyl groups is 50 to 99 mol%, preferably 70 to 99 mol%.
It is preferably 99 mol%, more preferably 85 to 95 mol%, and the softening agent can be made transparent in such a range. The proportion of alkenyl groups having two or more carbon-carbon unsaturated bonds is 15 mol% or less, preferably 0.1 to 10 mol%, more preferably 0.5 to 7 mol%, and particularly preferably 0.5. -5 mol%, most preferably 0.5-3 mol% is suitable from the viewpoints of transparency and storage stability.

Specific preferred compounds include compounds represented by the following general formula (1-1) (hereinafter compound (1-
1)) and a compound represented by the general formula (1-2) (hereinafter referred to as compound (1-2)).

[0015]

[Chemical 5]

[In the formula, R ¹⁴ and R ¹⁵ are each independently
It is a mixed hydrocarbon group in which an alkyl group having 13 to 18 carbon atoms and an alkenyl group are mixed, and R ¹⁸ and R ¹⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. The ratio of the alkyl group to the total number of moles of R ¹⁴ and R ¹⁵ present in the molecule is preferably 1
˜50 mol%, more preferably 1 to 30 mol%, particularly preferably 5 to 15 mol%, and the proportion of alkenyl groups is preferably 50 to 99 mol%, more preferably 70.
˜99 mol%, particularly preferably 85-95 mol%. The proportion of the alkenyl group having two or more carbon-carbon unsaturated bonds is preferably 15 mol% or less, more preferably 0.1 to 10 mol%, further preferably 0.5 to.
It is 7 mol%, particularly preferably 0.5 to 5 mol%, most preferably 0.5 to 3 mol%. R ¹⁶ and R ¹⁷ are each independently an alkylene group having 1 to 6 carbon atoms. D and E are independently -COO-, -OCO-, -CO
It is a group selected from NH- and -NHCO-, and c and d are each independently a number of 0 or 1, preferably 1. X ⁻ is an anion, preferably a halogen ion, a sulfate ion, a phosphate ion, an alkylsulfuric acid ester ion having 1 to 3 carbon atoms, and benzene sulfone which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms. Acid ion, carbon number 1
.About.12 monovalent to trivalent aliphatic carboxylate ions, particularly preferably halogen ions and sulfate ions. The compound (1-1) and the compound (1-2) are saponified animal oils such as beef tallow and lard, fish oils such as sardine oil, mackerel oil and sardine liver oil, or vegetable oils such as palm oil, cottonseed oil and sunflower oil. Alternatively, it is preferable that the oleic acid (or its methyl ester) or oleyl alcohol obtained by subjecting a fatty acid or a fatty acid methyl ester obtained by methyl esterification to a purification step such as distillation is used as a raw material.
Further, such oleic acid (or lower alkyl ester thereof) and oleyl alcohol include saturated fatty acids such as stearic acid and palmitic acid and saturated alcohols such as stearyl alcohol and palmityl alcohol in an amount of 5 to 15 mol%, linoleic acid and linoleic acid. Carbon-carbon 2 such as alcohol
It contains 7 to 15 mol% of a compound having two or more heavy bonds. In the present invention, it is particularly preferable to produce the compound (1-1) or the compound (1-2) using a raw material in which linoleic acid or linoleic alcohol is reduced. As a method of reducing linoleic acid and linole alcohol, for example, a method of using a metal copper crystal as a selective hydrogenation catalyst disclosed in JP-A-8-99036 can be mentioned.
Further, in the present invention, it is preferable to reduce the content of the compound having two or more carbon-carbon double bonds to 3 mol% or less.

A fatty acid having a reduced linoleic acid and an amine compound such as methyldiethanolamine, N, N-diaminopropyl-N-methylamine, or N-hydroxyethyl-N-aminopropyl-N-methylamine. The dehydration esterification reaction of the above compound (1-
1) can be obtained, and the compound (1-2) can be obtained by alkylating the compound (1-1) with an alkylating agent such as methyl chloride, dimethylsulfate and diethylsulfate.

As the compound (1-1), it is also possible to use a salt neutralized with an inorganic or organic acid, or a salt obtained by neutralizing an amino group with an acid agent before blending with a softener composition, After blending the amine compound with the softener composition, the amino group may be neutralized with an acid agent. The acid for neutralization is preferably hydroxycarboxylic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, oxalic acid, lactic acid or citric acid, a fatty acid having 1 to 12 carbon atoms or an alkyl sulfuric acid having 1 to 3 carbon atoms, and particularly preferably Hydrochloric acid, sulfuric acid, glycolic acid, oxalic acid, lactic acid and citric acid are preferred. These acid agents used for neutralization may be used alone or in combination.

In the present invention, when the compound (1-1) and the compound (1-2) are used, the hydrocarbon group having one unsaturated bond may include a cis form and a trans form. The trans form is preferably 25/75 to 100/0, preferably 50/50 to 95/5 (molar ratio) from the viewpoint of transparency.

Further, in the present invention, when the compound (1-1) and the compound (1-2) are used, it is preferable to use the compound (1-1) and the compound (1-2) in combination from the viewpoint of the softening effect. When used in combination, the mass ratio of compound (1-1) / compound (1-2) is 1/99 to 50/50, preferably 5/95 to 40/60, more preferably 10/90 to.
30/70 is preferable from the viewpoint of improving the softening effect.

In the compound (2), R ⁵ has 14 carbon atoms.
To 36, preferably 14 to 24, alkyl or alkenyl groups. R ⁶ has 1 to ⁶ carbon atoms, preferably 1 to 4 carbon atoms
Is an alkylene group, more preferably an ethylene group or a propylene group. R ⁷ and R ⁸ are preferably each independently a methyl group, an ethyl group or a hydroxyethyl group. a is preferably 1. Among the compounds (2), particularly preferable compounds are compounds represented by the following general formula (2-1) (hereinafter referred to as compound (2-1)) and compounds represented by the general formula (2-2) (hereinafter One or more compounds selected from the compound (2-2)).

[0022]

[Chemical 6]

[Wherein R ²⁰ is an alkyl group or alkenyl group having 15 to 35 carbon atoms, preferably 17 to 21 carbon atoms,
e is 2 or 3. R ²¹ and R ²² are each independently a methyl group, an ethyl group or a hydroxyethyl group, preferably a methyl group or a hydroxyethyl group. Compound (2-1) and compound (2-2), R ²⁰ -CO
Fatty acid represented by OH or this alkyl (C1-C1
5) It can be easily synthesized by reacting an ester or an acid chloride with N-hydroxyalkyl-N, N-dialkylamine or N-aminoalkyl-N, N-dialkylamine, and R ²⁰ is a single alkyl. It may have a chain length or a mixed alkyl chain length.

The compound (2) 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. Acids for neutralization include hydrochloric acid, sulfuric acid, phosphoric acid,
Glycolic acid, hydroxycarboxylic acid, carbon number 1-12
Is preferably a fatty acid or an alkyl sulfuric acid having 1 to 3 carbon atoms,
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 (3), R ⁹ has 14 carbon atoms.
To 36, preferably 14 to 24, alkyl or alkenyl groups. R ¹⁰ has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms
Is an alkylene group, more preferably an ethylene group or a propylene group. R ¹¹ , R ¹² and R ¹³ are preferably each independently a methyl group, an ethyl group or a hydroxyethyl group. b is preferably 1. Among the compounds (3), particularly preferable compounds are compounds represented by the following general formula (3-1) (hereinafter referred to as compound (3-1)) and general formula (3-
A compound represented by 2) (hereinafter referred to as compound (3-2))
One or more selected from

[0026]

[Chemical 7]

[In the formula, R ²³ is an alkyl group or alkenyl group having 15 to 35 carbon atoms, preferably 15 to ²³ carbon atoms,
f is 2 or 3. R ²⁴ , R ²⁵ and R ²⁶ are each independently a methyl group, an ethyl group or a hydroxyethyl group,
It is preferably a methyl group or an ethyl group. Y ⁻ is substituted with an anion, preferably a halogen ion, a sulfate ion, a phosphate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. It may be one or more selected from aryl sulfonate ions which may be present. Compound (3-1) and compound (3-2), R ²³ -CO
Fatty acid represented by OH or this alkyl (C1-C1
5) An ester or an acid chloride is reacted with N-hydroxyalkyl-N, N-dialkylamine or N-aminoalkyl-N, N-dialkylamine, and further with an alkylating agent such as alkyl halide, dialkyl sulfuric acid or alkylene oxide. It can be easily synthesized by quaternization. Further, N, N, N- trialkyl -N- hydroxyalkyl quaternary ammonium salts, N, N, N- trialkyl -N- aminoalkyl quaternary ammonium salt and a fatty acid or the alkyl represented by R ²³ -COOH It is also possible to synthesize it by reaction with a (carbon number 1-5) ester or acid chloride. R ²³ may have a single alkyl chain length or a mixed alkyl chain length.

Further, in the present invention, when the compound (2) and the compound (3) are used, it is preferable to use the compound (2) and the compound (3) together from the viewpoint of the softening effect. The mass ratio of 2) / compound (3) is 1/99 to 50/50, preferably 5/95 to 40/6.
0, more preferably 10/90 to 30/70, is preferable from the viewpoint of improving the softening effect.

In the present invention, it is also preferable to use the compound (1) in combination with the compound (2) and / or the compound (3) since the softening effect can be improved. + Compound (3)) / Compound (1)
Is preferably 1/99 to 20/80, and particularly preferably 5/95 to 15/85 by mass ratio.

[Component (b)] The component (b) of the present invention comprises:
ogP is 0.5 to 3, preferably 0.5 to 2, more preferably 0.5 to 1.8, and particularly preferably 0.5 to 1.6.
It is an organic solvent. Here, logP is a coefficient indicating the affinity of an organic compound for water and 1-octanol. The 1-octanol / water partition coefficient P is a partition equilibrium when a trace amount of an organic compound is dissolved as a solute in a solvent of two liquid phases of 1-octanol and water, and is a ratio of the equilibrium concentration of the organic compound in each solvent. Yes, and is generally shown in the form of their logarithm logP to the base 10.
LogP values for many compounds have been reported, Daylight Chemi
Many values are listed in the database available from cal Information Systems, Inc. (Daylight CIS), etc. If there is no actual logP value, the program "CLOGP" that can be obtained from Daylight CIS
It is most convenient to calculate with. This program uses Hansch, Leo, along with the actual logP values, if any.
Calculated by the fragment approach of
gP (ClogP) ”. The fragment approach is based on the chemical structure of the compound, taking into account the number of atoms and the type of chemical bond (cf. A. Leo, Co.
mprehensive Medicinal Chemistry, Vol.4, C. Hansch,
PG Sammens, JB Taylor and CA Ramsden, Eds.,
p.295, Pergamon Press, 1990). Since this ClogP value is the most general and reliable estimation value at present, it can be used in place of the measured logP value when selecting a compound. In the present invention, if there is a measured value of logP, it is used, and if not, the ClogP value calculated by the program CLOGP v4.01 is used.

As the organic solvent having such LogP, the following general formula (4), general formula (5) or general formula (6) can be used.
Compounds represented by are preferred.

R ²⁷ --OH (4) [In the formula, R ²⁷ is a hydrocarbon group having 4 to 8 carbon atoms, preferably an alkyl group, an aryl group or an arylalkyl group. ^{] R 28 - (O-R} 29) g -O-R 30 (5) [ wherein, R ²⁸ and R ³⁰ each independently represent a hydrogen atom, R
³¹ CO— (wherein R ³¹ is an alkyl group having 1 to 3 carbon atoms) or a hydrocarbon group having 1 to 7 carbon atoms, preferably a hydrogen atom, an alkyl group, an aryl group or an arylalkyl group,
R ²⁹ is an alkylene group having 2 to 9 carbon atoms and optionally having a branched chain. However, the case where R ²⁹ is an alkylene group having 2 to 3 carbon atoms and both R ²⁸ and R ³⁰ are hydrogen atoms is excluded. g is a number from 1 to 5. R ³² —O—CH ₂ CH (O—R ³³ ) CH ₂ —O—R ³⁴ (6) [In the formula, R ³² is an alkyl group having 3 to 8 carbon atoms, and R ³³
And R ³⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydroxy group. ] More specifically preferable 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,
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,
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, 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, 2-propoxy-1-propanol, dipropylene glycol monopropyl ether and pentyl glyceryl ether are preferable, and the most preferable component (b) is 2-phenoxyethanol and diethylene glycol monophenyl ether from the viewpoint of transparency and storage stability of the composition. And at least one selected from triethylene glycol monophenyl ether.

[Component (c)] The component (c) of the present invention is 20
Paraffin liquid at ℃ and carbon number 12 at liquid at 20 ℃
It is a compound selected from 30 alcohols.

The transparent softener composition of the present invention is presumed to form an O / W type microemulsion by using the components (a) and (b) together. Such emulsions often change as the water content changes,
It easily takes the structure of liquid crystal and thickens or gels.
As a result, gelling of the composition occurs on the garment when rinse water enters the softener composition directly attached to the garment. as a result,
Rinsing like normal washing does not disperse in water,
The present inventors presume that it may cause stains on clothing. In order to suppress gelation and improve the dispersibility in water, a method of decreasing the viscosity by adding an electrolyte and a method of adding a nonionic surfactant or a hydrotrope are generally considered. However, surprisingly,
By containing the water-insoluble paraffin or liquid alcohol as the component (c), which is generally considered to be prone to stains,
The generation of spots was improved. Presumably, since the component (c) of the present invention has an effect of suppressing such thickening and gelation and an action of promptly forming an O / W type macroemulsion upon dilution, it contains rinsing water. Also, it seems that the softener composition can be easily dispersed and stains can be suppressed.

As liquid paraffin at 20 ° C., n-
Paraffin, isoparaffin, and liquid paraffin can be used. The paraffin used in the present invention is JI.
The viscosity at 37.8 ° C. determined by the measuring method described in S-K2283 is preferably 50 to 600 SSU, and more preferably 5.
0 to 400 SSU, particularly preferably 150 to 350 SS
It is preferable to use U paraffin from the viewpoint of the stain suppression effect.

Specifically, high call K manufactured by Kaneda Co., Ltd.
-160, K-105, K-305, K-285, K-
Liquid paraffin sold under the trade name of 300, K-350, Benol, Brightol, Gloria, Caidol, Clairol, Rudol, available from Crompton Corporation, Sumol P-55 available from Matsumura Oil Research Institute Co., Ltd. , P-100, P-150, P-20
0, P-260, P-300, P-350, Moresco White P-500, P-55, P-60, P-70, P
-80, P-85, P-100, P-120, P-15
0, P-200, P-230, P-260, P-30
0, P-350P, Cristol 52, Cristol J-72, Cristol 72, Cristol 172, Cristol J-26 available from Esso Petroleum Ltd.
2, Cristol J-352, Cristol 542, Whiterex 3 available from Mobile Oil Co., Ltd.
07,309,326,335, liquid paraffin 40-S, 55-S, 60-S, 70- manufactured by Chuo Kasei Co., Ltd.
S, 80-S, 90-S, 100-S, 120-S, 1
50-S, 260-S, 350-S and Daphne oil 15N, 32N, 38N, 68N manufactured by Idemitsu Kosan Co., Ltd. can be used.

The alcohol having 12 to 30 carbon atoms which is liquid at 20 ° C. has a branched alkyl group having 16 to 28 carbon atoms or a hydrocarbon group having 1 to 3 unsaturated bonds.
Grade alcohols are preferred. Specific preferred compounds include isostearyl alcohol, oleyl alcohol, oxo alcohol obtained by hydroformylating 1-olefin having 15 to 27 carbon atoms with carbon monoxide and hydrogen, tetraisobutylene or pentaisobutylene with carbon monoxide and hydrogen. One or more selected from the polymethyl branched primary alcohols obtained by hydroformylation and the Guerbet alcohols having 16 to 28 carbon atoms are preferable. As the Guerbet alcohol, a primary alcohol having a total carbon number of 16 to 28 in which an alkyl group is branched at the 2-position obtained by a reaction of an aldehyde having an alkyl group having 8 to 16 carbon atoms with an alkali, a Ni catalyst or the like is used. The thing obtained by making a dehydrogenation reaction and a hydrogenation reaction generate | occur | produce, and performing a Guerbet reaction is mentioned.

In the present invention, at least one selected from liquid paraffin and Guerbet alcohol is most preferable from the viewpoint of the stain suppressing effect.

[Component (d)] The component (d) of the present invention is water, and water obtained by removing hardness components such as calcium and magnesium present in a trace amount in water and heavy metals such as iron is preferable,
Ion exchange water or distilled water can be used. Also,
A small amount of chlorine may be contained for the purpose of sterilizing or sterilizing water.

[Other Components] In the present invention, an anionic surfactant (hereinafter referred to as the component (e)) is preferably contained in the present invention for the purpose of improving the softening effect, and in particular, the compound (in the component (a)) ( When 2) and / or compound (3) is used, the softening effect can be remarkably improved.

The component (e) has 14 to 20 carbon atoms,
Preferably, it has a saturated or unsaturated fatty acid having 16 to 18 or an alkali metal or alkaline earth metal salt thereof, or an alkyl group or alkenyl group having 16 to 36, preferably 16 to 28 carbon atoms, and a -SO ₃ M group. And / or -O
Anionic surfactants having SO ₃ M groups [M: counterion] are preferred. Specifically, a fatty acid selected from myristic acid, palmitic acid, stearic acid, oleic acid, and palmitoleic acid, alkylbenzenesulfonic acid having the above carbon number, alkyl (or alkenyl) sulfuric acid ester, 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 16 to 28 carbon atoms, and 1 carbon atom
A polyoxyethylene alkyl (having 6 to 28 alkyl groups or alkenyl groups and having an average number of added ethylene oxide (hereinafter referred to as EO) moles of 1 to 6, preferably 1 to 4, particularly preferably 1 to 3 Alternatively, it is preferable to add one or more selected from alkenyl) ether sulfates and salts thereof. As the salt, sodium salt and potassium salt are preferable from the viewpoint of storage stability.

The softener composition of the present invention may use a solvent other than the above-mentioned component (b), but it is preferable that the effect of making the softener transparent is not impaired. Solvents that can be used other than the component (b) (hereinafter referred to as the component (f))
Is a solvent selected from ethanol, isopropanol, glycerin, ethylene glycol, and propylene glycol, and ethanol is particularly preferable from the viewpoint of odor.

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), it is preferable to further blend a nonionic surfactant as the component (g). The nonionic surfactant is preferably a polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and / or a compound obtained by adding an alkylene oxide to a fat or oil or a partial hydrolyzate of a fat or oil. A particularly preferable example of the polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 8 to 20 carbon atoms is a nonionic surfactant represented by the following general formula (7). Further, as a particularly preferable example of the compound obtained by adding an alkylene oxide to a fat or oil or a partial hydrolyzate of a fat or oil, a polyoxyalkylene adduct of hydrogenated castor oil (average addition mole number: 30 to 100, more preferably 5)
0-80).

[0045] ^{R 35 -G - [(R 36} O) h -R 37] i (7) [ wherein, R ³⁵ is 8 to 18 carbon atoms, preferably 10 to 16
Is an alkyl group or an alkenyl group, wherein R ³⁶ has 2 carbon atoms.
Or an alkylene group of 3 and preferably an ethylene group. R ³⁷ is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. h represents a number of 2 to 100, preferably 5 to 80, more preferably 5 to 60, particularly preferably 10 to 40. G is -O-, -COO-, -CON- or -N-, i is 1 when G is -O- or -COO-, and when G is -CON- or -N-. i is 2.
Here, a plurality of R ³⁶ and R ³⁷ may be the same or different. ] Specific examples of the compound represented by the general formula (7) include compounds represented by the following general formulas (7-1) to (7-4).

R ³⁵ —O— (C ₂ H ₄ O) _j —H (7-1) [In the formula, R ³⁵ has the above-mentioned meaning. j is a number of 8 to 100, preferably 10 to 60. _{^{] R 35 -O- (C 2 H}} 4 O) k - (C 3 H 6 O) m -H (7-2) wherein, R ³⁵ have the same meanings as defined above. k and m are each independently a number of 2 to 40, preferably 5 to 40, and (C
₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. ]

[0047]

[Chemical 8]

[Wherein R³⁵Indicates the above meaning. p,
q, r and s are each independently a number from 0 to 40, and p
+ Q + r + s is a number of 5 to 60, preferably 5 to 40.
, (C ₂H_FourO) and (C₃H₆O) is random or
It may be a lock addition body. R ³⁶And R³⁷Are each
Independently, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
It ] In addition, the softener composition of the present invention has an inorganic component (h).
It may contain a salt and / or an organic acid salt having 1 to 7 carbon atoms.
it can. Inorganic salts include sodium sulfate and magnesium sulfate.
Cium, sodium chloride, calcium chloride, and sodium chloride
Gnesium, glycolic acid as organic acid salt, p-tolu
Metal salts of ensulfonic acid are preferred for storage stability.
Yes. However, sodium salts are used for surfactants such as fatty acid salts.
And potassium salts, but such surfactants
Inorganic salts incorporated into the composition due to the use of
It's not something you can do.

In the present invention, for the purpose of improving flexibility,
An ester compound of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol may be blended as the component (i), but care must be taken to obtain a transparent appearance. Examples of compounds that can be blended include triglyceride, diglyceride, monoglyceride, pentaerythritol mono-, di-, triesters, and sorbitan esters.

The softener composition of the present invention may contain a commonly known sequestering agent or antioxidant (hereinafter referred to as component (j)) in order to improve the color and odor after storage. . Ethylenediaminetetraacetic acid salt as a sequestering agent,
Aminocarboxylic acids typified by diethylenetriamine pentaacetate, inorganic polyphosphoric compounds typified by tripolyphosphate and pyrophosphate, 1-hydroxyethane-1,1-
Examples thereof include diphosphonates, polyphosphonic acids, and organic phosphoric acids represented by phytic acid. Examples of antioxidants include 2,6-di-tert-butyl-4-methylphenol and 2 (3) -butyl-4. -Oxyanisole and the like can be mentioned. These may be added as an acid or a salt.

The softening agent composition of the present invention has a melting point (mp) of 25 ° C. or higher, preferably 50, having a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, from the viewpoint of the effect of suppressing odor deterioration.
It is preferable to add an organic acid at ˜300 ° C., more preferably 50˜200 ° C. Specific preferred compounds include glycolic acid (mp80 ° C.) and citric acid (mp15).
3 ° C), oxalic acid (mp102 ° C), lactic acid (mp26 ° C),
Malonic acid (mp135 ° C), succinic acid (mp185
℃), maleic acid (mp130 ℃), malic acid (mp1)
00 ℃), tartaric acid (mp170 ℃), glutaric acid (mp
98 ° C), adipic acid (mp153 ° C), n-butylmalonic acid (mp102 ° C), azelaic acid (mp107)
℃), citric acid (mp153 ℃), benzoic acid (mp12
2 ° C.) and phthalic acid (mp 191 ° C.). Among these, glycolic acid, citric acid, oxalic acid, and lactic acid are particularly preferable in terms of the effect of suppressing odor deterioration.

In the softener composition of the present invention, a fragrance which is usually used in a fiber treating agent (particularly preferably JP-A-8-113) is used.
The combination of the aroma components shown in the components (c) and (d) described in Japanese Patent No. 871) or a component such as a pigment may be blended.

[Softener composition] The content of the component (a) in the softener composition according to the present invention is 3 to 50% by mass, preferably 4 to 40% by mass, particularly preferably 5 to 35% by mass. is there. Further, the content of the component (b) is 3 to 35% by mass, preferably 5 to 30% by mass, and particularly preferably 10 to 25% by mass. The content of the component (c) is 0.1-10.
%, Preferably 0.3 to 7% by weight, particularly preferably 0.5 to 5% by weight. The component (d), water, can be added to the composition in an amount of 40 to 90% by mass, particularly 45 to 70% by mass. If the content is less than this range, problems such as an increase in the viscosity of the composition occur. However, if it exceeds this range, it becomes difficult to make the composition transparent.

In the present invention, when the compound (1) is used as the component (a), it is preferable that the component (e) is 0.
1 to 10% by mass, more preferably 0.5 to 7% by mass, and particularly preferably 1 to 5% by mass. When the compound (2) and / or the compound (3) is used as the component (a), the component (e) is preferably 0.1 to 35% by mass, more preferably 0.5 to 30% by mass, and particularly preferably. Is 3 to 1
Add 5% by mass. Furthermore, when the compound (2) and / or the compound (3) is used as the component (a),
From the viewpoint of improving the softening effect, the molar ratio of component (a) / component (e) is preferably 95/5 to 52/48, more preferably 90/10 to 55/45, and particularly preferably 80/2.
0-60 / 40 is suitable.

The blending amount of the component (f) is 0 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, most preferably 1 to 2% by mass, and (g) From the viewpoint of stability, the compounding amount of the nonionic surfactant as a component is preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 8% by mass in the composition. Further, the blending amount of the component (h) is 0 to 3% by mass, preferably 0.1 to 2% by mass, and more preferably 0.2 to 0.5% by mass in the composition. The blending amount of the component (i) is preferably 5% by mass or less, more preferably 3% by mass or less,
It is particularly preferably 1% by mass or less. The sequestering agent and antioxidant as the component (j) are preferably 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 present invention, it is a transparent aqueous solution in the form of an aqueous solution in which the component (a), the component (b), and optionally other components are dissolved in water. Here, the transparency of the present invention is defined as a state in which the light transmittance at 660 nm is 30% or more, preferably 50% or more when measured with an optical path length of 1 cm. The softener composition of the present invention has a pH at 20 ° C of 1.5 to 7.5, preferably 1.8 to 6 from the viewpoint of storage stability.

As a method for producing the softener composition of the present invention, if necessary, the components (e), (f) and (h) are dissolved in water and the temperature is 40 to 70 ° C., preferably 45.
To 65 ° C., and then (a) component, (b) component, (c) component, and if necessary, (d) component, (g) component, (i) component and (j) component are added. And stir to mix,
From the viewpoint of storage stability, a method of adjusting the pH to a predetermined value with an inorganic acid agent and / or an organic acid agent, and then adding other components after cooling is preferable.

[0058]

Example 1 A softener composition having the composition shown in Tables 1 and 2 was prepared by the following method using the following components, and the appearance and the effect of reducing viscosity when diluted with water were evaluated by the following method. . Further, after the softening treatment by the following method, the stain suppressing effect was evaluated. The results are shown in Tables 1 and 2.

<Ingredients> The ingredients used in the examples are shown below. (A-1): Compound obtained by the following method: A fatty acid having a hydrocarbon composition shown in Example 1 in Table 2 of JP-A-8-99036, paragraph No. 0023, and N-methyl-N-hydroxyethyl-N-amino. Propylamine was subjected to dehydration condensation reaction by a conventional method at a molar ratio of fatty acid / amine = 1.86 / 1 to give N-oleoylaminopropyl-N-oleoyloxyethyl-N as a main product.
-Methylamine was obtained. Next, this compound was alkylated by a usual method using methyl chloride using ethanol as a reaction solvent, and the solvent was distilled off under reduced pressure to give N-
Oleoylaminopropyl-N-oleoyloxyethyl-N, N-dimethylammonium chloride was obtained.
The composition of the compound is N-oleoylaminopropyl-
N-oleoyloxyethyl-N, N-dimethylammonium chloride 80%, N-oleoylaminopropyl-N- (2-hydroxyethyl) -N, N-dimethylammonium chloride 7%, unreacted fatty acid 3 %, Containing 5% ethanol. (A-2): Compound obtained by the following method: A fatty acid having a hydrocarbon composition and triethanolamine shown in Comparative Example 3 in Table 2 of JP-A-8-99036, paragraph No. 0023, and fatty acid / amine = 1.7. A dehydration condensation reaction was carried out by a usual method at a molar ratio of / 1, to obtain N, N-dioleoyloxyethyl-N-hydroxyethylamine as a main product. This compound was alkylated by a conventional method with dimethylsulfate using ethanol as a reaction solvent to obtain N, N-dioleoyloxyethyl-N.
-Hydroxyethyl-N-methylammonium methylsulfate was obtained. The compound composition is N-oleoyloxyethyl-N, N-di (2-hydroxyethyl)-
27% N-methylammonium methylsulfate,
N, N-dioleoyloxyethyl-N-hydroxyethyl-N-methylammonium methylsulfate 37%, N, N, N-trioleoyloxyethylamine 16%, N, N, N-tri (2-hydroxy) Ethyl) -N-methylammonium 5% methylsulfate, 5% unreacted fatty acid, and 5% ethanol as a reaction solvent. (A-3): N-alkanoylaminopropyl-N, N
-Dimethylamine hydrochloride (alkanoyl group is a stearoyl group / palmitoyl group in a molar ratio of 95/5) (a-4): N, N-dialkyl-N, N-dimethylammonium chloride (alkyl group is lauryl group / myristyl group) Is 50/50 in molar ratio) (b-1): 2-phenoxyethanol (logP =
1.19) (b-2): Diethylene glycol monophenyl ether (log P = 1.25) (b-3): Dipropylene glycol mono n-butyl ether (log P = 1.52) (b-4): Pentyl glyceryl ether (LogP =
0.54) (c-1): Rudol (RUD) manufactured by Crompton Corporation
OL) (Viscosity 150 SSU) (c-2): Kaneda High Coal K-300
(Viscosity 200 SSU) (c-3): Kaneda High Coal K-160
(Viscosity 50 SSU) (c-4): Cristol 542 (viscosity 540 SSU) obtained from Esso Oil Co., Ltd. (c-5): C24 Guerbet alcohol (2-decyl-1)
-Tetradecanol) (e-1): oleic acid (e-2): 2-decyl-1-tetradecyl sulfate sodium salt (f-1): ethanol (g-1): polyoxyethylene lauryl ether (E
O average condensation degree 19) (g-2): polyoxyethylene hydrogenated castor oil (EO average condensation degree 60) (h-1): magnesium chloride (i-1): dehydration condensation product of lauric acid and sorbitan
The molar ratio of lauric acid / sorbitan is 1.1 / 1. (J-1): 2,6-di-tert-butyl-4-methylphenol (k-1): fragrance [hexylcinnamic aldehyde (18), neroline yarayala (4), tricyclodecenyl acetate (4) , Benzyl acetate (10), musk ketone (5), anisylacetone (2), sandal mysole core (2), aldehyde C14 peach (1), linalool (18), dihydroxymyrcenol (8), borneol (4) , Cedrol (4), Mugor (5), Benzyl alcohol (5), Dipropylene glycol (10): Mass% in perfume in parentheses].

<Evaluation Method of Appearance of Softening Agent Composition> The appearance of the softening agent composition shown in Tables 1 and 2 was evaluated according to the following criteria.

○: transparent (light transmittance at 660 nm is 30% or more) ×: opaque (light transmittance at 660 nm is less than 30%) <Evaluation method of viscosity reducing effect when diluted with water> Flexibility in Tables 1 and 2 The maximum viscosity when the agent composition was diluted 5 times with ion-exchanged water was measured at 20 ° C. using a B-type viscometer and evaluated according to the following criteria.

○: less than 4000 mPa · s Δ: more than 4000 mPa · s and less than 10,000 mPa · s ×… gelling or viscosity of 10,000 mPa · s or more <Preparation method of softening agent composition> Completion of the softening agent composition in a 300 mL beaker. Ion-exchanged water was added in an amount corresponding to 95% of the amount required for the mass to reach 200 g, and the temperature was raised to 60 ° C. in a water bath. While stirring with a turbine type stirring blade with three blades each having a length of 2 cm (200 r / min), a required amount of component (b),
The component (e) was dissolved. Next, a required amount of a mixture (40 ° C.) in which the components (a) and (d) were mixed in advance was added. After stirring as it is for 5 minutes, the components (c) and (f) to (k) are sequentially added, and after stirring for 5 minutes, the target pH is adjusted with a 35% hydrochloric acid aqueous solution and a 48% sodium hydroxide aqueous solution, Ion-exchanged water at 60 ° C. was added in an amount necessary to achieve the finished mass. Then, the mixture was stirred for 10 minutes, the beaker was transferred to a water bath containing water at 5 ° C, and the mixture was cooled to 20 ° C while stirring. The pH values shown in Tables 1 and 2 are the pH values after cooling (20 ° C).

<Softening Method and Evaluation Method of Stain Suppressing Effect> Five polo shirts (100% cotton, blue) were washed in a washing machine using a commercially available weak alkaline detergent (Kao Corporation Attack) (Toshiba 2 Tank type washing machine VH-360S1, detergent concentration 0.0667 mass%, tap water 30L use, water temperature 2
0 ° C., 10 minutes). After that, drain the cleaning solution, dehydrate for 3 minutes, pour 30 L of tap water and rinse for 5 minutes,
After draining, dehydration was performed for 3 minutes. Then, 5 mL of the softener composition of Table 1 and Table 2 was directly sprinkled on the obtained wet polo shirt in a circular shape having a diameter of about 5 cm and left for 5 minutes, and then 30 L of tap water was poured again and stirred for 5 minutes. Immediately after dehydration and after natural drying at 20 ° C. and 50% RH,
The stain suppression effect was visually evaluated according to the following criteria.

∘: No stain is observed at all immediately after dehydration and after drying ○: Slight stain is observed immediately after dehydration, but no stain is observed after drying ○ Δ: Immediately after dehydration and Slight stains occur after drying, but all are at acceptable level .... Staining is apparent both immediately after dehydration and after drying.

[0065]

[Table 1]

[0066]

[Table 2]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shuji Takata             Kao Co., Ltd. 1334 Minato, Wakayama City, Wakayama Prefecture             Inside the laboratory F-term (reference) 4L033 AB04 AC02 BA01 BA11 BA45                       BA85 DA01 DA02

Claims (5)

[Claims] 1. (a) 12 to 3 carbon atoms which may be divided by an unsaturated group, an amide group, an ester group or an ether group.
3 to 50 mass% of a compound having one or more hydrocarbon groups of 6 in the molecule and having a tertiary amino group or an acid salt thereof, or a quaternary ammonium group, and (b) logP of 0.5 to.
3 to 35% by mass of an organic solvent of 3 and (c) at least one compound 0.1 to 1 selected from paraffin liquid at 20 ° C. and alcohol liquid at 12 ° C. having 12 to 30 carbon atoms.
0 mass%, and (d) 40-90 mass% of water,
O / W transparent liquid softener composition. 2. The component (c) is JIS-K2283.
The viscosity at 37.8 ° C. determined by the measuring method described in 1.
The transparent liquid softener composition according to claim 1, which contains 0 SSU of paraffin. 3. The transparent liquid softener composition according to claim 1, wherein the component (a) is a compound represented by the following general formula (1) and having an iodine value of 30 to 130. [Chemical 1] [Wherein, R ¹ and R ² are each independently an alkyl group or an alkenyl group having 12 to 26 carbon atoms which may be divided by an ester group, an amide group or an ether group,
³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. X ⁻ represents an anionic group. ] 4. The component (a) according to claim 1, which is one or more selected from the compound represented by the following general formula (2) and the compound represented by the following general formula (3). Transparent liquid softener composition. [Chemical 2] [In the formula, R ⁵ and R ⁹ each independently have 14 to 3 carbon atoms.
6 is an alkyl group or an alkenyl group of R ⁶ and R ¹⁰
Are each independently an alkylene group having 1 to 6 carbon atoms. R ⁷ , R ⁸ , R ¹¹ , R ¹² and R ¹³ are each independently
It is a C1-C3 alkyl group or a hydroxyalkyl group. A and B are independently -COO-, -OC
It is a group selected from O-, -CONH- and -NHCO-. a and b are 0 or 1 numbers. Y ⁻ is an anion. ] 5. (a) 12 to 3 carbon atoms which may be divided by an unsaturated group, an amide group, an ester group or an ether group.
A compound having one or more hydrocarbon groups of 6 in the molecule and having a tertiary amino group or an acid salt thereof, or a quaternary ammonium group, (b) an organic solvent having a logP of 0.5 to 3, and ( d) To a mixture containing water, (c) at least one compound selected from paraffin liquid at 20 ° C. and alcohol having a carbon number of 12 to 30 at 20 ° C. is added. A method for reducing the viscosity of an O / W transparent liquid softener composition as described above when diluted with water.