JP3365878B2 - Liquid softener composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides various fibers with excellent flexibility and elasticity (puffiness), excellent storage stability, excellent water absorption, and biodegradability. The present invention relates to a liquid softening finish which is excellent in nature and is friendly to the natural environment.

[0002]

2. Description of the Related Art Currently,
Commercially available products as household softening agents generally have a composition containing di (hardened beef tallow alkyl) dimethylammonium chloride as a main component. The reason for this is that this quaternary ammonium salt exerts a good softening effect on various fibers even in a small amount. However, the fourth
Although the high-grade ammonium salt has a high softening effect, if it is treated at a high concentration in order to obtain a higher softening effect, its elasticity may be reduced especially for cotton and the texture may be impaired. Further, the softener composition using the quaternary ammonium salt may easily thicken, become a gel or separate due to its physicochemical properties when stored for a long period of time. In addition to the above-mentioned quaternary ammonium salt, polyoxyethylene-based nonionic activators, additives such as electrolytes and solvents are added to commercially available softeners to improve long-term storage stability. The effect is still insufficient.

Further, in order to improve the drawbacks of the conventional quaternary ammonium salt by introducing an ester group between the quaternary nitrogen atom and the long-chain alkyl chain, various softening agents have been proposed. There is. For example, JP-A-3-90677 discloses a softener composition using an ester group-containing quaternary ammonium salt which is well dispersed without gel formation, and JP-A-1-162872 discloses a high temperature storage. Disclosed is a softener composition using an ester group-containing quaternary ammonium salt, which has good viscosity stability at the time. However, the softening finish containing these quaternary ammonium salts has a softening property, storage stability and water absorbency (fibers treated with a softening finish having poor water absorbency tend to repel water, and the feeling of use is reduced. However, it was not enough. Therefore, an object of the present invention is to provide a liquid softening agent composition exhibiting sufficiently satisfactory performances in terms of softening performance, storage stability and water absorption, and having excellent biodegradability and being friendly to the natural environment. is there.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a liquid softener finishing composition containing a quaternary ammonium salt having a very specific structure. The present invention has been completed. That is, the present invention contains the following components (A) and (B), and the mixing ratio of these components is [(A) component] by weight ratio.
/ [(B) component] = 2/1 to 1/9 The liquid softening finishing composition is provided.

[Component (A)] A compound represented by the following general formula (I) (hereinafter referred to as compound (I)), a compound represented by the following general formula (II) (hereinafter referred to as compound (II)) To tell)
, A compound represented by the following general formula (III) (hereinafter, compound
(III)) and a compound represented by the following general formula (IV) (hereinafter referred to as compound (IV)). (However, compound (I), compound (II), compound (III) and compound (I
The mixing ratio of V) is [compound (I)] / [total weight of compounds (I), (II), (III) and (IV)] = 0.040 to 0.527 [compound (II)]. / [Total weight of compounds (I), (II), (III) and (IV)] = 0.133 to 0.469 [compound (III)] / [compounds (I), (II), (III) and (IV) Total weight] of 0.013 to 0.661 [compound (IV)] / [total weight of compounds (I), (II), (III) and (IV)] = 0.001 to 0.417, and compound (I), ( II), (III) and (IV)
Griffin's HLB of the above mixture is 5-15. )

[0006]

[Chemical 7]

[In the formula, A ¹ , A ² , and A ³ represent an RCO group or an H atom. However, A ¹ group, A ²
One of the groups A ³ is an RCO group, and the other two are H atoms. Here, the R group is a linear or branched chain carbon number 7 to 23
Is an alkyl group or an alkenyl group. Q: An alkylene group having 2 to 3 carbon atoms is shown, and the alkylene group having 2 carbon atoms and the alkylene group having 3 carbon atoms may be mixed. a, b, c: Indicates a number of 0 or more, and a + b + c is 1 to 50 as an average value. ]

[0008]

[Chemical 8]

[In the formula, B ¹ , B ² , B ³ : RCO group or H atom is shown. However, B ¹ group, B ²
Two of the groups, B ³ groups, are RCO groups, and the other one is an H atom. Here, the R group has the above-mentioned meaning. Q, a, b, c: Indicates the above meaning. ]

[0010]

[Chemical 9]

[In the formula, D ¹ , D ² and D ³ : RCO groups are shown. Here, the R group has the above-mentioned meaning. Q, a, b, c: Indicates the above meaning. ]

[0012]

[Chemical 10]

[In the formula, Q, a, b, and c: have the above meanings. [Component (B)] A quaternary ammonium salt represented by the following general formula (V).

[0014]

[Chemical 11]

[In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 20 to 44 carbon atoms. ^{R 2, R 3, R 4} : identical or different and represent an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms. Z: An alkylene group having 2 to 3 carbon atoms is shown, and the alkylene group having 2 carbon atoms and the alkylene group having 3 carbon atoms may be mixed. m: Indicates a number from 0 to 20. n: shows the number of 1-6. X ⁻ : Indicates an anionic group. The present invention will be described in detail below.

[Component (A)] In the component (A) used in the present invention, the mixing ratio of the compounds (I), (II), (III) and (IV) is [the compound (I)]
/ [Total weight of compounds (I), (II), (III) and (IV)] is 0.040 to 0.527, preferably 0.040 to 0.346, more preferably 0.040 to 0.327, [compound (II)]
/ [Total weight of compounds (I), (II), (III) and (IV)] is 0.133 to 0.469, preferably 0.298 to 0.469, and [compound (III)] / [compound (I), (II ), (II
The total weight of (I) and (IV)] is 0.013 to 0.661, preferably 0.154 to 0.661, more preferably 0.173 to 0.661, and [compound (IV)] / [compound (I), (II), (I
The total weight of (II) and (IV)] is 0.001 to 0.417, preferably 0.001 to 0.096, and more preferably 0.001 to 0.077. When the mixing ratio is out of the widest range defined above, the stability of the softening agent composition decreases. The reason for this phenomenon is not always clear, but when the mixing ratio is within this range, the crystallinity of the component (A) decreases, and the precipitation of the component (A) in the softening agent composition is suppressed, As a result, it is presumed that the softening agent composition does not thicken, gel, or change in appearance.

General formulas (I), (II), (III) and (IV)
In, a + b + c has an average value of 1 to 50, preferably 4 to 18. When a + b + c is less than 1 on average, a stable softening agent composition cannot be obtained, and when it is more than 50, the softening effect desired by the present invention cannot be obtained.

The HLB of Griffin (A) is 5 to 15,
It is important that it is preferably 5.6 to 12. If the HLB is less than 5, a stable softening agent composition cannot be obtained,
If it is larger than that, sufficient softening effect cannot be obtained. Here, regarding fatty acid esters of polyhydric alcohols, Griff
The HLB of in is calculated by the following formula.

Griffin's HLB = 20 × (1-S / A) [wherein S: saponification value of fatty acid ester of polyhydric alcohol (mg-KOH)
/ G). A: Shows the acid value (mg-KOH / g) of the fatty acid constituting the fatty acid ester of polyhydric alcohol. In the general formulas (I) to (III), the R group is
Palm oil fatty acid-derived alkyl group, palm kernel oil fatty acid-derived alkyl group, palm oil fatty acid-derived alkyl group, palm stearic acid-derived alkyl group, hardened palm stearic acid-derived alkyl group, tallow fatty acid-derived alkyl group,
And at least one selected from the group consisting of an alkyl group derived from a hardened tallow fatty acid, an alkyl group derived from a beef tallow fatty acid, an alkyl group derived from a hardened beef tallow fatty acid, an alkyl group derived from a palm stearic acid and a hardened palm stearic acid At least one selected from the group consisting of alkyl groups is preferable.

The component (A) is obtained, for example, by the following synthesis method (i).
~ (Iv). Synthetic Method (i) Glycerin is esterified with a fatty acid, and then ethylene oxide, propylene oxide or both are added to obtain component (A). When both ethylene oxide and propylene oxide are added, the order may be either first or both may be added at the same time, but it is preferable to add ethylene oxide after the addition of propylene oxide, and the addition mole number of propylene oxide is It is preferably 3 mol or less with respect to the glycerin skeleton.

The esterification conditions in this synthesis method (i) may be catalyst-free, but acid catalysts such as sulfuric acid, hydrochloric acid and paratoluenesulfonic acid may be used. Fatty acids used in this case include, for example, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, coconut oil, palm kernel oil, uncured or hardened. beef tallow,
Fatty acids obtained from lard, palm oil, rapeseed oil, fish oil, palm stearin, hardened palm stearin and the like can be mentioned, and these can be used alone or in a mixture. Of these, coconut oil fatty acid, palm kernel oil fatty acid, palm oil fatty acid, uncured or hardened beef tallow fatty acid, and uncured or hardened palm stearic acid are used alone or as a mixture. As the alkylene oxide addition conditions, NaOH, KOH, NaOCH ₃ , KOCH ₃ or an alkali metal salt of a fatty acid or the like is used as a reaction catalyst, but the acid catalyst used at the time of esterification should be added in excess to neutralize the acid catalyst. Is preferred.

Synthetic method (ii) Glycerin is transesterified with a fatty acid ester,
Then, alkylene oxide addition is performed to obtain the component (A). The reaction catalyst used in the transesterification reaction in the present synthesis method (ii) is NaOH, KOH, NaOCH ₃ , KOCH.
₃ etc. Examples of the fatty acid ester used in the present synthesis method (ii) include, for example, the fatty acid methanol ester, ethanol ester, propanol ester, butanol ester, ethylene glycol ester, glycerin ester, erythritol ester, and pentaerythritol described in the synthesis method (i). Esters, xylitol esters, sorbitol esters, sorbitan esters and the like are used. Of these, the following are preferred.

[0023]

[Chemical 12]

The conditions for the addition of alkylene oxide in the synthetic method (ii) include NaOH, KOH and Na as reaction catalysts.
OCH ₃ , KOCH ₃ or an alkali metal salt of a fatty acid or the like is used, but the catalyst used in the transesterification reaction may be used subsequently. The type of alkylene oxide and the order of addition are in accordance with the conditions described in the synthesis method (i).

Synthetic Method (iii) Addition of alkylene oxide to glycerin, followed by esterification with fatty acid to obtain component (A). The reaction conditions for alkylene oxide addition and esterification in this synthetic method (iii) are the same as those described in the synthetic method (i).
The fatty acid used for esterification in the synthetic method (iii) is
It is as described in the synthesis method (i).

Synthetic method (iv) Addition of alkylene oxide to glycerin, followed by transesterification with fatty acid ester to obtain component (A). The reaction conditions for alkylene oxide addition and transesterification in the synthetic method (iv) are in accordance with the conditions described in the synthetic method (ii). Examples of the fatty acid ester used for transesterification in the synthesis method (iv) include the following.

R-COOCH ₃ , R-COOCH ₂ CH ₃ [wherein R has the above-mentioned meaning. Here, as a specific example of the component (A), an alkylene oxide adduct of a mixture of beef tallow fatty acid ester of glycerin and glycerin, an alkylene oxide adduct of a mixture of partially hardened beef tallow fatty acid ester of glycerin and glycerin,
Glycerin palm stearates and glycerin mixtures alkylene oxide adducts, glycerin hardened palm stearates and glycerin mixtures alkylene oxide adducts, glycerin laurate esters and glycerin mixtures alkylene oxide adducts, glycerin Examples include an alkylene oxide adduct of a mixture of palm kernel oil fatty acid ester and glycerin, an alkylene oxide adduct of a mixture of glycerin palm oil fatty acid ester and glycerin, an alkylene oxide adduct of a mixture of glycerin palm oil fatty acid ester and glycerin, and the like. . Of these alkylene oxide adducts, ethylene oxide adducts are preferred.

[Component (B)] In the present invention, as the component (B), a quaternary ammonium salt represented by the general formula (V) (hereinafter abbreviated as quaternary ammonium salt (V)) is used. To be done. In this case, the X ^- group represents an anion group, and the anion group is, for example, a halogen anion group.
(Cl ⁻ , Br ^−, etc.), an alkyl sulfate anion group having 1 to 5 carbon atoms (CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , C ₃ H ₇ SO ₄ ^−, etc.) and the like. Examples of the quaternary ammonium salt (V) used in the present invention are as follows.

[0029]

[Chemical 13]

[0030]

[Chemical 14]

Of these quaternary ammonium salts (V), from the viewpoint of imparting flexibility, the R ¹ group is preferably a linear or branched alkyl group or alkenyl group having 28 to 44 carbon atoms, and Preferably linear or branched carbon number 36 ~
44 alkyl or alkenyl groups. Particularly preferred as the quaternary ammonium salt (V) is a quaternary ammonium salt represented by the following general formula (V-1).

[0032]

[Chemical 15]

[0033] ^{wherein, R 2, R 3, R} 4, n, X -: The meanings of the. Examples of the quaternary ammonium salt corresponding to the quaternary ammonium salt represented by the general formula (V-1) include the following.

[0034]

[Chemical 16]

The quaternary ammonium salt (V) is produced, for example, by the following production method 1 and production method 2, but the present invention is not limited by these production conditions.

<Production Method 1>

[0037]

[Chemical 17]

[In the formula, R ¹ , R ² , R ³ , Z, m, and n are as defined above. R ⁵ : Shows an alkyl group having 1 to ⁵ carbon atoms. Y: Indicates a halogen atom. L: represents a halogen atom or a group represented by R ⁵ SO ₄ . However, R ⁵ has the above-mentioned meaning. L ⁻ : represents a halogen ion or a group represented by R ⁵ SO ₄ ^— . However, R ⁵ has the above-mentioned meaning. That is, first, a halocarboxylic acid (VI) and a higher alcohol or an alkylene oxide adduct of a higher alcohol (VII)
Is reacted to obtain a halocarboxylic acid ester (VIII). In this case, examples of the halocarboxylic acid (VI) include those represented by the following formula, and monochloroacetic acid is preferable. ClCH ₂ COOH, ClCH ₂ CH ₂ CH ₂ COOH, Cl (CH ₂ ) ₅ COOH, BrCH ₂
COOH Moreover, examples of the higher alcohol (VII) include those represented by the following formula, and the alkylene oxide adduct of the higher alcohol is the alkylene oxide adduct of the following formula. These may be used alone or in a mixture,
Preferred is 2-hexadecyl eicosyl alcohol.

[0039]

[Chemical 18]

Here, halocarboxylic acid (VI) and higher alcohol or its alkylene oxide adduct (VII)
The charged amount of [halocarboxylic acid (VI)] /
[Higher alcohol or its alkylene oxide adduct (VII)] = 0.8 to 1.5 is preferable, and the reaction temperature is 120 ° C.
The temperature is preferably ˜160 ° C., and the reaction time is preferably 2 to 10 hours.

The halocarboxylic acid ester (VIII) thus obtained is reacted with the secondary amine (IX). Second
Examples of the primary amine (IX) include dimethylamine, diethylamine, diethanolamine, methylethanolamine, dipropylamine, di (isopropyl) amine, dibutylamine and the like, with preference given to dimethylamine and diethylamine. Here, the charged amount of the halocarboxylic acid ester (VIII) and the secondary amine (IX) is preferably [secondary amine (IX)] / [halocarboxylic acid ester (VIII)] = 0.8 to 3.0 in molar ratio, Reaction temperature is 30 ~ 8
0 ° C. is preferable, and the reaction time is preferably 3 to 15 hours.

The ester amine (X
XI) is reacted with a quaternizing agent (XXII). Examples of the quaternizing agent (XXII) include alkyl halide (methyl chloride, methyl bromide, etc.), dialkyl sulfuric acid (alkyl group having 1 to 5 carbon atoms), and the like, preferably methyl chloride, dimethyl sulfuric acid. . Esteramine (XXI) and 4
The reaction with the grading agent (XXII) is carried out in the presence of a solvent such as isopropanol, ethanol or acetone. In this case, the charged amounts of the ester amine (XXI) and the quaternizing agent (XXII) are
The molar ratio of [ester amine (XXI)] / [quaternary agent (XXI
I)] = 0.8 to 1.5 is preferable, and the reaction temperature is preferably 80 to 120 ° C. The counter ion of the quaternary ammonium salt (XXIII) thus obtained can be exchanged, if necessary, to obtain the quaternary ammonium salt (V) of the present invention.

<Production Method 2>

[0044]

[Chemical 19]

[In the formula, R ¹ , R ² , R ³ , R ⁴ , Z, m, n, and Y: have the above-mentioned meanings. Y ^-: a halogen ion. ] That is, halocarboxylic acid ester (VIII) and tertiary amine (X
React with XIV). In this reaction, a solvent may be used without a solvent, or if necessary, a solvent such as isopropanol, ethanol or acetone may be used. Halocarboxylic acid ester
(III) and the tertiary amine (XXIV) are charged at a molar ratio of [tertiary amine (XXIV)] / [halocarboxylic ester
(VIII)] = 0.8 to 2.5 is preferable, and the reaction temperature is 40 to 120.
C is preferred. The counter ion of the quaternary ammonium salt (XXV) thus obtained can be exchanged, if necessary, to obtain the quaternary ammonium salt (V) of the present invention.

[Softening Finishing Composition] The composition of the present invention contains the above-mentioned component (A), component (B), and water. The mixing ratio of these components is [(A) component] / [(B) by weight ratio.
Ingredient] = 2/1 to 1/9, preferably 1/1 to 1/9,
It is particularly preferably from 1/2 to 1/9, and a good softening effect can be obtained within the above range. In the present invention, the total compounding amount of the soft base (A) component and (B) component is 3 to.
It is 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 25% by weight. When the content is less than 3% by weight,
If the softening effect desired by the present invention is not obtained and the amount exceeds 40% by weight, the viscosity of the composition increases, which causes problems such as difficulty in coming out of the bottle.

For the purpose of further improving the softening performance and the storage stability of the composition of the present invention, a straight chain or branched chain saturated or unsaturated alcohol having 8 to 44 carbon atoms may be further added as the component (C). it can. The blending amount of component (C) is
The amount is 110% by weight or less, preferably 1 to 100% by weight, based on the weight of the component (B). Examples of the straight chain or branched chain C8-C44 saturated or unsaturated alcohol of the component (C) include the following.

[0048]

[Chemical 20]

In order to improve the softening performance and the storage stability of the softening agent composition of the present invention, a straight chain or branched chain saturated or unsaturated fatty acid having 8 to 36 carbon atoms (component (D)) is blended. be able to. The amount of the component (D) in the composition of the present invention is 100% by weight or less, preferably 0.5 to 50% by weight, based on the weight of the component (B). Examples of the fatty acid of the component (D) used here include stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, oleic acid, isostearic acid, and coconut oil, palm oil, beef tallow, rapeseed oil. And fatty acids having an alkyl composition derived from natural oils and fats such as fish oil.

The composition of the present invention has 1 to 1 carbon atoms in order to adjust the viscosity of the composition and improve the storage stability (prevention of gelation, etc.).
Monohydric alcohol No. 4 (component (E)) can be blended. The amount of the component (E) in the composition of the present invention is 60% by weight or less based on the weight of the component (B), preferably 5 to 50%.
%, More preferably 10 to 45% by weight. Examples of the monohydric alcohol having 1 to 4 carbon atoms as the component (E) include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol and butyl alcohol.

In the composition of the present invention, a known cationic compound (quaternary ammonium salt, imidazolinium salt, etc.), ester or amide, or a mixture of two or more thereof is added as a softening agent base. can do. Examples of these include quaternary ammonium salts represented by the following general formula (XXVI) and the following general formulas (XXVII-1) to (XXV).
Illustrative are compounds represented by II-8).

[0052]

[Chemical 21]

[In the formula, R ¹¹ represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. E ¹ , E ² , and E ³ are the same or different from each other, a hydrogen atom or
R ¹² CO- (wherein R ¹² is a linear or branched carbon number 7 to 35
Represents an alkyl or alkenyl group). However, at least one of E ¹ , E ² and E ³ is R ¹² CO
A group represented by — (wherein R ¹² is as defined above). G ⁻ : Indicates an anionic group. Examples of G ⁻ are halogen ions such as Cl ⁻ and Br ⁻ , and an alkylsulfate group having 1 to 5 carbon atoms. In the composition of the present invention, G ⁻ in the quaternary ammonium salt represented by the general formula (XXVI) may be the same as or different from X ⁻ in the quaternary ammonium salt (V) used at the same time. Good.

[0054]

[Chemical formula 22]

[Wherein R ¹⁵ and R ¹⁶ are the same or different from each other and represent a linear or branched alkyl, alkenyl or 2-hydroxyalkyl group having 10 to 24 carbon atoms. R ^17: alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group, or the formula _{- (C 2 H 4 O)} p H ( wherein p is 1-3
Represents the number of). R ¹⁸ : a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group or a group represented by the formula — (C ₂ H ₄ O) _pH (where p is as defined above); Show. G ^-: is as defined above. ]

[0056]

[Chemical formula 23]

[Wherein R ¹⁷ , R ¹⁸ and G ⁻ are as defined above]. R ¹⁹ and R ²⁰ are the same or different from each other and represent a linear or branched alkyl, alkenyl or 2-hydroxyalkyl group having 9 to 23 carbon atoms. ]

[0058]

[Chemical formula 24]

[In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , and G ⁻ : are as defined above. ]

[0060]

[Chemical 25]

[Wherein R ¹⁸ , R ¹⁹ , R ²⁰ , and G ⁻ are as defined above]. J: represents a group represented by the formula -OCO- or -NHCO-. ]

[0062]

[Chemical formula 26]

[Wherein R ¹⁸ , R ¹⁹ , R ²⁰ , J, and G ⁻ are as defined above]. ]

[0064]

[Chemical 27]

[Wherein R ¹⁹ is as defined above]. ]

[0066]

[Chemical 28]

[Wherein R ¹⁹ and R ²⁰ are as defined above]. ]

[0068]

[Chemical 29]

[Wherein R ¹⁹ and R ²⁰ are as defined above]. R ^21: a straight chain or branched chain alkyl having a carbon number of 9 to 23, alkenyl or 2-hydroxyalkyl group. When the concentration of the component (B) in the softening agent composition of the present invention is high, the composition tends to thicken during storage. In order to suppress this tendency of thickening, ethylene oxide and, if necessary, propylene oxide and / or trimethylene oxide are added to a compound having three or more active hydrogens, and the weight average molecular weight is 5,000 to 2,000,000. The ratio of the oxyethylene group part in it is 5
It is preferable to add 5% by weight or more of the polyether compound or its derivative (component (F)).

Examples of the compound having three or more active hydrogens as a starting material for obtaining the component (F) include the following. Examples of the polyhydric alcohol include trimethylolpropane, diethanolamine, triethanolamine, glycerin, pentaerythritol, sorbitol, sucrose, polyglycerin, polyvinyl alcohol, and partially saponified polyvinyl acetate. Examples of the polyphenols include phenol resins and formalin condensates of alkylphenols. Examples of the polyamine compound include polyethylenedimine such as ethylenediamine and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
Further, partial amidated products and N-alkylated products which are derivatives of these polyamine compounds can also be used as starting materials for obtaining the component (F) as long as three or more active hydrogens remain.

The component (F) can be produced by adding ethylene oxide and, if necessary, propylene oxide and / or trimethylene oxide to a compound having 3 or more active hydrogens by a conventional method.
As the component (F), an adduct of ethylene oxide alone, a block adduct of ethylene oxide and propylene oxide, and a partially block adduct of ethylene oxide and propylene oxide are particularly preferable. When two or more kinds of alkylene oxides are added to a compound having three or more active hydrogens, the order of addition may be any,
Propylene oxide (hereinafter, abbreviated as PO) was first added, and then ethylene oxide (hereinafter, abbreviated as EO) was added to the composition of the present invention having a high concentration of the component (B) during storage. It is preferable for suppressing the tendency of thickening.

The molecular weight of the component (F) is 5,000 to 2,000,00.
It is 0, and preferably in the range of 10,000 to 100,000.
The proportion of the oxyethylene group (EO chain) in the molecule is 55% by weight or more, preferably 80% by weight or more, of the total molecular weight. In this case, when the molecular weight of the component (F) is less than 5,000, the effect of suppressing the thickening tendency during storage of the softening agent composition is low, while 2,000
If it exceeds 000, the viscosity of the softening agent composition remarkably increases, and it is difficult to take it out of the bottle. When the proportion (total weight) of oxyethylene groups in the molecular weight of the component (F) is less than 55% by weight, the effect of suppressing the thickening tendency of the softening agent composition during storage is low.

As the derivative of the polyether compound as the component (F), a crosslinking reaction product obtained by the reaction of the polyether compound with a compound having an isocyanate group, or sulfuric acid having a terminal hydroxyl group of the polyether compound is used. Compounds, phosphorus oxides, carboxyalkylated products, fatty acid esterified products, and those obtained by cationizing a part of nitrogen atoms of the above-mentioned polyether compound. Among them, fatty acid esterified products and cationized products are particularly preferable. The fatty acid used in the production of the fatty acid esterified product preferably has 7 to 23 carbon atoms, but the number of double bonds, the presence or absence of branching, etc. do not significantly affect the performance. As the cationized compound, a compound obtained by cationizing a part of nitrogen atoms in the polyether compound with a dialkyl sulfuric acid or an alkyl halide, or after cationization and neutralizing with acetic acid, alkylbenzenesulfonic acid or the like can be obtained. Examples include cationized compounds.

The softening agent composition of the present invention contains the component (F) in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the composition. (F) for component (B)
The weight ratio of the components [(F) component] / [(B) component] is 1 /
It is 100 to 1 / 2.5, preferably 1/50 to 1/5. The total content of the component (B) and the component (F) in the softener composition of the present invention is 4 to 45% by weight, preferably 11 to 39% by weight, based on the total weight of the composition. It is preferably 14 to 32% by weight. When the amount of the component (F) is within the above range, the softening agent composition of the present invention exhibits the level of softening performance desired by the present invention, and at the same time, the tendency of thickening during storage of the composition is suppressed. .

The composition of the present invention may contain an inorganic electrolyte such as NaCl, CaCl ₂ or MgCl ₂ for adjusting the viscosity of the composition. In this case, the content of the inorganic electrolyte in the composition is 0 to 2% by weight, preferably 0.01 to 1% by weight. The softening agent composition of the present invention may further contain an acidic or alkaline substance in order to adjust the pH of the composition. In this case, it is desirable from the viewpoint of the viscosity and storage stability of the composition to add an acidic or alkaline substance so that the pH of the composition of the present invention is within the range of 1.5 to 6.5.

The softening agent composition of the present invention has a high stability even after being stored for a long period of time, but the polyoxyethylene (5
50 mol) and alkyl or alkenyl (C ₁₂ -C ₂₄₎ ethers, polyoxyethylene (5-50 moles) alkyl or alkenyl (C ₁₂ -C ₂₄₎ nonionic surfactant, such as an amine, ethylene glycol, propylene glycol, A hydrotrope agent such as urea may be added to the composition of the present invention. Further, the composition of the present invention may contain a pigment or dye for improving its appearance, silicone for defoaming during rinsing, and fragrance for improving taste after use and after finishing. . The balance of the softener composition of the present invention excluding the above-mentioned essential components and optional components is water.

An example of the method for preparing the softener composition of the present invention will be described below.
The manufacturing method is not limited to this. (A) and (B)
The components are melted or a mixture of the components (A) and (B) and the other components (excluding the component (F)) is melted, and the melt is deaerated under stirring at 60 ° C. An emulsion is prepared by gradually dropping into ionized water. afterwards,
If desired, the component (F) may be added to the emulsion thus produced. Further, in advance, a nonionic surfactant aqueous solution may be used in place of the deionized water, or an inorganic salt may be added in order to adjust the viscosity of the composition after the addition of the components (A) to (F). May be added.

[0078]

EFFECTS OF THE INVENTION The softening agent composition of the present invention imparts sufficient flexibility and excellent elasticity to various fibers, and also has storage stability (does not gel or thicken after storage,
The softening agent base does not hydrolyze after storage) and the water absorption is extremely good.

[0079]

EXAMPLES The present invention will now be described in more detail by showing examples of the present invention, but the present invention is not limited to these examples. (B) Component Synthesis Example 1 34 g of chloroacetic acid and 2-hexadecyl eicosyl alcohol were placed in a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube.
56g was put and it heated up to 140 degreeC. After distilling off the produced water, the reaction was carried out at the same temperature for 7 hours, and then excess chloroacetic acid was removed by washing with water to remove 175 g of chloroacetic acid ester.
Obtained. Next, 64 g of 50% aqueous solution of dimethylamine and water 1
00 g was added, the temperature was raised to 55 ° C., and the reaction was carried out at that temperature for 10 hours. After the reaction, excess dimethylamine was removed by washing with water to obtain 170 g of glycine ester. Next, the glycine ester 90 was added to an autoclave equipped with a stirrer and a thermometer.
g, methyl chloride 15g, acetone 70g, 90 ℃
And reacted for 6 hours. After the reaction, crystallization with acetone was performed, and after drying, 85 g of the desired product as a white powder was obtained. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0080]

[Chemical 30]

[0081]

[Chemical 31]

IR spectrum (KBr tablet) 1746 cm ^-1 , 1206 cm ^-1 (B) Component synthesis example 2 44 g of chlorobutyric acid and 2-hexadecyl eicosyl were placed in a four-necked flask equipped with a stirrer, thermometer and cooling tube. Alcohol 1
56g was put and it heated up to 140 degreeC. After distilling off the produced water, the reaction was carried out at the same temperature for 7 hours, and then excess chlorobutyric acid was removed by washing with water to obtain 185 g of chlorobutyric acid ester.
Obtained. Next, 64 g of 50% aqueous solution of dimethylamine and water 1
00 g was added, the temperature was raised to 55 ° C., and the reaction was carried out at that temperature for 10 hours. After the reaction, excess dimethylamine was removed by washing with water to obtain 185 g of 4-aminobutyric acid ester. Next, 95 g of the above 4-aminobutyric acid ester, 15 g of methyl chloride and 70 g of isopropyl alcohol were placed in an autoclave equipped with a stirrer and a thermometer, and the mixture was reacted at 90 ° C. for 6 hours. After the reaction, crystallization with acetone was performed, and after drying, 90 g of the desired product as a white powder was obtained. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0083]

[Chemical 32]

[0084]

[Chemical 33]

IR spectrum (KBr tablets) 1731 cm ⁻¹ , 1182 cm ⁻¹ (B) Component synthesis example 3 In a four-necked flask equipped with a stirrer, thermometer and cooling tube, 45 g of chlorohexanoic acid, 2-hexadecyl eico 156 g of sil alcohol was added and the temperature was raised to 140 ° C. While distilling off the produced water, the reaction was carried out at the same temperature for 10 hours to obtain 195 g of chlorohexanoic acid ester. Next, 64 g of a 50% aqueous solution of dimethylamine and 100 g of water were added, the temperature was raised to 60 ° C., and the reaction was carried out at that temperature for 10 hours. After the reaction, excess dimethylamine was removed by washing with water to obtain 195 g of 6-aminohexanoic acid ester. Next, in an autoclave equipped with a stirrer and a thermometer, the above 6-aminohexanoic acid ester 100
g, methyl chloride 15g, isopropyl alcohol 80
g was added, and the mixture was reacted at 90 ° C. for 8 hours. After the reaction, crystallization with acetone was performed, and after drying, 1030 g of the desired product as a white powder was obtained. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0086]

[Chemical 34]

[0087]

[Chemical 35]

IR spectrum (KBr tablet) Synthesis example 4 of 1730 cm ^-1 , 1185 cm ^-1 (B) component 34 g of chloroacetic acid and 2-dodecylhexadecyl alcohol in a four-necked flask equipped with a stirrer, thermometer and cooling tube. one two Three
g was added and the temperature was raised to 140 ° C. The reaction was carried out at the same temperature for 5 hours while distilling off the produced water, and then excess chloroacetic acid was removed by washing with water to obtain 145 g of chloroacetic acid ester. Next, 64g of 50% aqueous solution of dimethylamine and 100 of water
g was added, the temperature was raised to 55 ° C., and the reaction was carried out at that temperature for 10 hours. After the reaction, excess dimethylamine was removed by washing with water to obtain 145 g of glycine ester. Next, add the above glycine ester 75 to an autoclave equipped with a stirrer and a thermometer.
g, methyl chloride 15g, acetone 50g, 90 ℃
And reacted for 6 hours. After the reaction, crystallization with acetone was performed, and after drying, 70 g of the desired product as a white powder was obtained. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0089]

[Chemical 36]

[0090]

[Chemical 37]

IR spectrum (KBr tablet) 1748 cm ^-1 , 1205 cm ^-1 (B) Synthesis example 5 34 g of chloroacetic acid, 90 g of 2-octyldodecyl alcohol in a four-necked flask equipped with a stirrer, thermometer and cooling tube Was charged and the temperature was raised to 140 ° C. The reaction was carried out at the same temperature for 5 hours while distilling off the produced water, and then excess chloroacetic acid was removed by washing with water to obtain 110 g of chloroacetic acid ester. Next, 64 g of a 50% aqueous solution of dimethylamine and 100 g of water were added, the temperature was raised to 55 ° C., and the reaction was carried out at that temperature for 10 hours. After the reaction, excess dimethylamine was removed by washing with water to obtain 113 g of glycine ester. Next, in an autoclave equipped with a stirrer and a thermometer, 57 g of the above glycine ester, 15 g of methyl chloride and 400 g of acetone were put, and the mixture was heated at 90 ° C. for 6 hours.
Reacted for hours. After the reaction, crystallization with acetone was performed, and after drying, 60 g of the desired product as a white powder was obtained. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0092]

[Chemical 38]

[0093]

[Chemical Formula 39]

IR spectrum (KBr tablets) 1746 cm ^-1 , 1205 cm ^{-1 The} quaternary ammonium salts obtained in Synthesis Examples 1 to 5 are shown in Table 1 together.

[0095]

[Table 1]

Examples 1 to 41, Comparative Examples 1 to 16 Components (A) shown in Tables 2 and 3, (B) components shown in Table 1, (C) components shown in Table 4, and (D) ) Component, the (E) component shown in Table 6, the (F) component shown in Table 7, and the surfactants (X) and (Y) shown below are used.
A liquid softener composition having the composition shown in was prepared. In the comparative examples, the following compounds (S) to (U) were used.

Surfactant (X): polyoxyethylene (20 mol) lauryl ether Surfactant (Y): polyoxyethylene (20 mol) stearylamine

[0098]

[Chemical 40]

(In the above formula, R ²³ and R ³³ represent an alkyl group having a composition obtained by substituting the carboxy group of hardened tallow fatty acid with a methylene group. R ²⁴ and R ³⁴ exclude the carboxyl group of hardened tallow fatty acid. The resulting alkyl group is shown.)

[0100]

[Table 2]

[0101]

[Table 3]

Note) * 1: EO represents ethylene oxide. * 2: Semi-hardened beef tallow is beef tallow / hardened tallow = 1/1 (weight ratio)
Is. * 3: Semi-cured palm stearate methyl ester is palm stearate methyl ester / cured palm stearate methyl ester = 1/1 (weight ratio).

[0103]

[Table 4]

[0104]

[Table 5]

[0105]

[Table 6]

[0106]

[Table 7]

Using the liquid softening finish compositions obtained in Examples 1 to 41 and Comparative Examples 1 to 16, softness, elasticity, water absorption and storage stability were evaluated by the following methods. The results are shown in Tables 8 to 13.

<Evaluation of flexibility and elasticity> Commercially available cotton towels, acrylic fibers, and polyester fibers were repeatedly washed 5 times with a commercial detergent "Attack" (registered trademark, manufactured by Kao Corporation), and the detergent attached to the cloth. Then, 0.5% of the weight of the cloth was added to the liquid softening agent composition prepared above, and the mixture was treated at 25 ° C with a bath ratio of 1/10 under stirring for 3 minutes, and then air-dried indoors, and then at 20 ° C. The sample was left to stand in a thermo-hygrostat at 65% RH for 24 hours. The softness and elasticity of these cloths were evaluated. For the evaluation of softness and elasticity, a pair of comparisons were carried out using the cloth treated with the softening agent composition of Comparative Example 16 as a control. The evaluation is expressed as follows.

Flexibility: +2 Softer or more elastic than the control +1 Slightly softer or slightly more elastic than the control 0 Softer than the control or equivalent in elasticity -1 Slightly softer or slightly elastic in the control Higher-2 The control is softer or has higher elasticity <Water absorption evaluation method [Vailex method]> A cloth treated in the same manner as the softness and elasticity evaluation method is used at 25 ° C and 65%.
It was left for 24 hours in the constant temperature and humidity room of RH. Among them, a cotton towel was used for evaluation of water absorption. Cut the non-pile portion of the cotton towel into a 25 cm x 2 cm rectangle. On the other hand, prepare water at 25 ° C in the above-mentioned constant temperature and humidity chamber, put the cloth piece vertically so that 2 cm from the bottom is submerged in water, let it absorb water, and raise the height of water after 15 minutes. To measure.

<Evaluation Method of Storage Stability> The liquid softening agent composition prepared above was sealed and stored at 20 ° C. for 20 days, and the appearance and fluidity under the sealed condition were visually observed.
As a result, those showing no change in appearance and fluidity were regarded as good, and those showing change in state were specified as such.

[0111]

[Table 8]

[0112]

[Table 9]

[0113]

[Table 10]

[0114]

[Table 11]

[0115]

[Table 12]

[0116]

[Table 13]

Note) In Tables 8 to 13, the number in parentheses () indicates the compounding amount in the composition, and the unit is% by weight. The balance is water. The pH of the composition was adjusted to 3.

From the above results, it can be seen that the softening agent composition of the present invention can impart excellent flexibility, elasticity and water absorbability and has good storage stability.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-7-3645 (JP, A) JP-A-8-92875 (JP, A) JP-A-5-132865 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) D06M 13/00-13/535

Claims (13)

(57) [Claims] 1. The following component (A) and component (B) are contained, and the mixing ratio of these is [(A) component] /
[Component (B)] = 2/1 to 1/9 A liquid softening finish composition. [Component (A)] A compound represented by the following general formula (I) (hereinafter referred to as compound (I)), a compound represented by the following general formula (II) (hereinafter referred to as compound (II)), A compound represented by the following general formula (III) (hereinafter referred to as compound (III))
And a mixture of compounds represented by the following general formula (IV) (hereinafter referred to as compound (IV)). (However, the mixing ratio of the compound (I), the compound (II), the compound (III) and the compound (IV) is [compound (I)] / [compound (I), (II), ( III) and (IV) total weight] = 0.040 to 0.527 [compound (II)] / [total weight of compounds (I), (II), (III) and (IV)] = 0.133 to 0.469 [compound (III )] / [Total weight of compounds (I), (II), (III) and (IV)] = 0.013 to 0.661 [compound (IV)] / [compounds (I), (II), (III) and ( IV) total weight] = 0.001 to 0.417, and the compounds (I), (II), (III) and (IV)
Griffin's HLB of the above mixture is 5-15. ) [Chemical 1] [In the formula, A ¹ , A ² , A ³ : RCO group or H atom is shown. However, A ¹ group, A ²
One of the groups A ³ is an RCO group, and the other two are H atoms. Here, the R group is a linear or branched chain carbon number 7 to 23
Is an alkyl group or an alkenyl group. Q: An alkylene group having 2 to 3 carbon atoms is shown, and the alkylene group having 2 carbon atoms and the alkylene group having 3 carbon atoms may be mixed. a, b, c: Indicates a number of 0 or more, and a + b + c is 1 to 50 as an average value. ] [Chemical 2] [In the formula, B ¹ , B ² , and B ³ : represent an RCO group or an H atom. However, B ¹ group, B ²
Two of the groups, B ³ groups, are RCO groups, and the other one is an H atom. Here, the R group has the above-mentioned meaning. Q, a, b, c: Indicates the above meaning. ] [Chemical 3] ^{Wherein, D 1, D 2, D} 3: shows the RCO group. Here, the R group has the above-mentioned meaning. Q, a, b, c: Indicates the above meaning. ] [Chemical 4] [In formula, Q, a, b, c: shows the above-mentioned meaning. [Component (B)] A quaternary ammonium salt represented by the following general formula (V). [Chemical 5] [In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 20 to 44 carbon atoms. ^{R 2, R 3, R 4} : identical or different and represent an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms. Z: An alkylene group having 2 to 3 carbon atoms is shown, and the alkylene group having 2 carbon atoms and the alkylene group having 3 carbon atoms may be mixed. m: Indicates a number from 0 to 20. n: shows the number of 1-6. X ⁻ : Indicates an anionic group. ] 2. The component (A) is a compound (I), (II),
It is a mixture of (III) and (IV), and the mixing ratio of compound (I), compound (II), compound (III) and compound (IV) is [compound (I)] / [compound (I)] (I), (II), (III) and (IV) total weight] = 0.040 to 0.346 [compound (II)] / [compound (I), (II), (III) and (IV) total weight ] = 0.298 to 0.469 [Compound (III)] / [Total weight of compounds (I), (II), (III) and (IV)] = 0.154 to 0.661 [Compound (IV)] / [Compound (I), (II), (III) and (IV) total weight] = 0.001 to 0.096, and in the general formulas (I) to (IV), a + b
The liquid softening agent composition according to claim 1, wherein + c has an average value of 4 to 18. 3. The component (A) is a compound (I), (II),
It is a mixture of (III) and (IV), and the mixing ratio of compound (I), compound (II), compound (III) and compound (IV) is [compound (I)] / [compound (I)] (I), (II), (III) and (IV) total weight] = 0.040 to 0.327 [compound (II)] / [compound (I), (II), (III) and (IV) total weight ] = 0.298 to 0.469 [Compound (III)] / [Total weight of compounds (I), (II), (III) and (IV)] = 0.173 to 0.661 [Compound (IV)] / [Compound (I), (II), (III) and (IV) total weight] = 0.001 to 0.077, and in the general formulas (I) to (IV), a + b
The liquid softening agent composition according to claim 1, wherein + c has an average value of 4 to 18. 4. In the general formula (I) to the general formula (III),
R group is an alkyl group derived from coconut oil fatty acid, an alkyl group derived from palm kernel fatty acid, an alkyl group derived from palm oil fatty acid, an alkyl group derived from palm stearic acid, an alkyl group derived from hardened palm stearic acid, an alkyl derived from beef tallow fatty acid The liquid softening agent composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of a base and an alkyl group derived from a hardened tallow fatty acid. 5. In the general formula (I) to the general formula (III),
The R group is at least one selected from the group consisting of an alkyl group derived from tallow fatty acid, an alkyl group derived from hardened tallow fatty acid, an alkyl group derived from palm stearic acid, and an alkyl group derived from hardened palm stearic acid. 4. The liquid softening agent composition according to any one of 4 above. 6. In the general formula (I) to the general formula (IV),
The liquid softening agent composition according to claim 1, wherein the Q group is —CH ₂ CH ₂ —. 7. The quaternary ammonium salt represented by the general formula (V) as the component (B), wherein the R ¹ group is a linear or branched alkyl group having 36 to 44 carbon atoms. 7. The liquid softening agent composition according to any one of 6 above. 8. The liquid softener composition according to claim 1, wherein the component (B) is a quaternary ammonium salt represented by the general formula (V-1). [Chemical 6] ^{Wherein, R 2, R 3, R} 4, n, X -: The meanings of the. ] 9. The liquid softening agent composition according to claim 1, wherein the total amount of the components (A) and (B) is 3-40% by weight of the composition. 10. Further, as the component (C), a straight chain or branched chain saturated or unsaturated alcohol having 8 to 44 carbon atoms is contained, and the content of the component (C) is based on the weight of the component (B). 110% by weight or less, and the liquid softening agent composition according to any one of claims 1 to 9. 11. A straight or branched chain saturated or unsaturated fatty acid having 8 to 36 carbon atoms is further contained as the component (D),
The content of the component (D) is based on the weight of the component (B).
The liquid softener composition according to claim 1, which is 100% by weight or less. 12. The component (E) further has 1 to 4 carbon atoms.
The liquid softening agent composition according to any one of claims 1 to 11, containing the monohydric alcohol of (1), and the content of the component (E) is 60% by weight or less based on the weight of the component (B). object. 13. Further, as the component (F), ethylene oxide and, if necessary, propylene oxide and / or trimethylene oxide are added to 0.5 to 5% by weight, based on the total weight of the composition, of a compound having 3 or more active hydrogens. And the weight average molecular weight is 5,000 to 2,000,000,
A polyether compound or a derivative thereof in which the proportion of oxyethylene groups in the molecular weight is 55% by weight or more, and the weight ratio of the component (F) to the component (B) [(F) component] / [(B) Component] is 1/100 to 1 / 2.5, and
The liquid softener composition according to any one of claims 1 to 12, wherein the total content of the component (B) and the component (F) is 4 to 45% by weight based on the total weight of the composition.