JP2994990B2 - Liquid soft finish composition and novel quaternary ammonium salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art
Commercially available products as household softeners are generally compositions containing di (hardened tallow alkyl) dimethylammonium chloride as a main component. This is because the quaternary ammonium salt exerts a good softening effect on various fibers in a small amount. However, the fourth
Although the quaternary 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 particularly for cotton, and the texture may be impaired. Further, the softener composition using the quaternary ammonium salt may easily thicken, gel, or separate due to its physicochemical properties when stored for a long period of time. Commercially available softeners are blended with additives such as polyoxyethylene-based nonionic activators, electrolytes and solvents in addition to the above-mentioned quaternary ammonium salts to improve long-term storage stability. The effect is still inadequate.

Further, in order to improve the disadvantages of the conventional quaternary ammonium salts by introducing an ester group between a quaternary nitrogen atom and a long alkyl chain, various softening agents have been proposed. I have. For example, JP-A-3-90677 discloses a softener composition using a quaternary ammonium salt containing an ester group which does not form a gel and disperses well, and JP-A-1-162872 discloses a softener composition. There is disclosed a softener composition using a quaternary ammonium salt containing an ester group, which has good viscosity stability at the time. However, the soft finish containing these quaternary ammonium salts has a soft performance, storage stability and water absorbency (fibers treated with a soft finish having poor water absorbency tend to repel water and have a feeling of use. Was not good enough). Therefore, an object of the present invention is to provide a liquid soft finish composition which shows satisfactory performance in terms of soft performance, storage stability and water absorbability, and is excellent in biodegradability and is friendly to the natural environment. is there.

[0004]

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a liquid softener composition containing a quaternary ammonium salt having a very specific structure. Thus, the present invention has been completed. That is, the present invention contains the following component (A) and water,
(A) The present invention provides a liquid soft finish composition characterized in that the content of the component is 3 to 40% by weight in the composition. (A) Component: quaternary ammonium salt represented by general formula (I)

[0005]

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[Wherein, R ^{1 represents a} linear or branched alkyl or alkenyl group having 20 to 44 carbon atoms (preferably an alkyl group)]. R ² , R ³ , R ⁴ : same or different and represents an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms. n: Indicates the number of 1 to 6. X ^-: represents an anion group. ]

[0007]

Embodiments of the present invention will be described below in detail. [Component (A)] In the present invention, as the component (A), a quaternary ammonium salt represented by the general formula (I) (hereinafter referred to as a quaternary ammonium salt) is used.
Quaternary ammonium salt (I)) is used. Group is represents an anion group, as the anionic group, such as halogen anion group ^- X in this case (Cl ^-, Br ^-, etc.), alkyl sulfate anionic group having 1 to 5 carbon atoms (CH ₃ S
O ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , C ₃ H ₇ SO ₄ ⁻ ) and the like. Here, the quaternary ammonium salt (I) is exemplified as follows.

[0008]

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[0009]

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In these quaternary ammonium salts (I), from the viewpoint of imparting flexibility, the R ¹ group is preferably a linear or branched alkyl or alkenyl group having 28 to 44 carbon atoms (preferably an alkyl group). And more preferably a linear or branched alkyl group or alkenyl group having 36 to 44 carbon atoms (preferably an alkyl group). Particularly preferred as the quaternary ammonium salt (I) is a quaternary ammonium salt represented by the following general formula (I-1).

[0011]

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[Wherein, R ² , R ³ , R ⁴ , n, X ⁻ : have the above meanings. Examples of the quaternary ammonium salt corresponding to the quaternary ammonium salt represented by the formula (I-1) include the following.

[0013]

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In these quaternary ammonium salts (I), a quaternary ammonium salt represented by the following general formula (I-2) and a quaternary ammonium salt represented by the above general formula (I-1)
A quaternary ammonium salt is a novel compound.

[0015]

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[In the formula, R ^{1-2 represents a} linear or branched alkyl or alkenyl group having 36 to 44 carbon atoms (preferably an alkyl group). R ² , R ³ , R ⁴ , n, X ⁻ : Represents the above-mentioned meaning. The quaternary ammonium salt (I) is produced, for example, by the following production method 1.
And manufacturing method 2, but the present invention is not limited by these manufacturing conditions.

<Production Method 1>

[0018]

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[Wherein, R ¹ , R ² , R ³ , n: have the above-mentioned meanings. R ⁵ : represents an alkyl group having 1 to ⁵ carbon atoms. Y: represents a halogen atom. Z ^-: represents a group represented by ^- halogen ion or R ⁵ SO _4. However R ⁵ have the same meanings as defined above. That is, first, a halocarboxylic acid (II) and a higher alcohol (II
I) is reacted to obtain a halocarboxylic acid ester (IV).
In this case, examples of halocarboxylic acids (II) include:
What is represented by a following formula is mentioned, Preferably it is monochloroacetic acid. ClCH ₂ COOH, ClCH ₂ CH ₂ CH ₂ COOH, Cl (CH ₂ ) ₅ COOH, BrCH ₂
COOH Examples of the higher alcohol (III) include those represented by the following formulas, and these may be used alone or as a mixture, and preferably 2-hexadecyl eicosyl alcohol.

[0020]

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Here, the charged amounts of the halocarboxylic acid (II) and the higher alcohol (III) are [halocarboxylic acid (II)] / [higher alcohol (III)] = 0.8 to 1.5 in molar ratio.
The reaction temperature is preferably from 120 ° C to 160 ° C, and the reaction time is preferably from 2 to 10 hours.

The halocarboxylic acid ester (IV) thus obtained is reacted with a secondary amine (V). Examples of the secondary amine (V) include dimethylamine, diethylamine, diethanolamine, methylethanolamine, dipropylamine, di (isopropyl) amine,
Examples thereof include dibutylamine and the like, preferably dimethylamine and diethylamine. Here, the charged amount of the halocarboxylic acid ester (IV) and the secondary amine (V) is [secondary amine (V)] / [halocarboxylic acid ester (IV)] = 0.8 to 3. 0 is preferable, the reaction temperature is preferably 30 to 80 ° C, and the reaction time is preferably 3 to 15 hours.

The esteramine thus obtained
(VII) is reacted with a quaternizing agent (VIII). Quaternizing agent (VIII)
Examples of the alkyl halide (methyl chloride,
Methyl bromide and the like), dialkyl sulfate (the alkyl group has 1 to 5 carbon atoms) and the like, and preferred are methyl chloride and dimethyl sulfate. The reaction between the esteramine (VII) and the quaternizing agent (VIII) is carried out in the presence of a solvent such as isopropanol, ethanol, acetone and the like. In this case, the charged amounts of the esteramine (VII) and the quaternizing agent (VIII) are in a molar ratio of [esteramine (VII)] / [quaternizing agent.
(VIII)] = 0.8-1.5, and the reaction temperature is 80-120.
C is preferred. The quaternary ammonium salt (IX) thus obtained can be exchanged for its counter ion, if necessary, to obtain the quaternary ammonium salt (I) of the present invention.

<Production Method 2>

[0025]

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[Wherein, R ¹ , R ² , R ³ , R ⁴ , n, Y: have the above meanings. Y ^-: a halogen ion. That is, the halocarboxylic acid ester (IV) is reacted with the tertiary amine (X). In this reaction, a solvent such as no solvent or, if necessary, a solvent such as isopropanol, ethanol, or acetone can be used. The charged amounts of the halocarboxylic acid ester (IV) and the tertiary amine (X) are preferably in a molar ratio of [tertiary amine (X)] / [halocarboxylic acid ester (IV)] = 0.8 to 2.5. Is 80-16
0 ° C. is preferred. The quaternary ammonium salt (XI) thus obtained exchanges its counter ion if necessary,
The quaternary ammonium salt (I) of the present invention can be obtained.

[Soft Finishing Composition] The soft finishing composition of the present invention contains the component (A) in an amount of 3 to 40% by weight, preferably 5 to 30% by weight.
% By weight, more preferably 10 to 30% by weight, with the balance being water. When the amount of the quaternary ammonium salt (I) is less than 3% by weight, the desired softening effect of the present invention cannot be obtained,
If it exceeds 40% by weight, the viscosity of the composition increases and the handling properties are poor. For the purpose of further improving the flexibility performance and storage stability of the composition of the present invention, a linear or branched saturated or unsaturated alcohol having 8 to 44 carbon atoms can be further blended as the component (B). Component (B) is added in an amount of 110% by weight or less, preferably 1 to 10% by weight, based on component (A).
0% by weight. Examples of the straight-chain or branched-chain saturated or unsaturated alcohol having 8 to 44 carbon atoms of the component (B) include the following.

[0028]

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

The composition of the present invention contains 1 to 1 carbon atoms for adjusting the viscosity of the composition and improving the storage stability (eg, prevention of gelation).
4 monohydric alcohol (component (D)). The amount of component (D) in the composition of the present invention is not more than 60% by weight, preferably 5 to 50% by weight, more preferably 10 to 45% by weight, based on the weight of component (A). (D)
Examples of the monohydric alcohol having 1 to 4 carbon atoms include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, and butyl alcohol.

The composition of the present invention contains a known cationic compound (quaternary ammonium salt, imidazolinium salt, etc.), an ester or an amide, or a mixture of two or more of these as a soft finish base. can do. Examples thereof include quaternary ammonium salts represented by the following general formula (XXI) and the following general formulas (XXII-1) to (XXI).
Compounds represented by II-8) are exemplified.

[0032]

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Wherein R ¹¹ represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. A ¹ , A ² , A ³ : the same or different, a hydrogen atom or
R ¹² CO- (where R ¹² is a straight-chain or branched-chain carbon having 7 to 35 carbon atoms)
Represents an alkyl or alkenyl group). However, at least one of A ¹ , A ² and A ³ is R ¹² CO
— (Where R ¹² is as defined above). Q ^-: represents an anion group. ] Where Q ^- Examples of, Cl ^-, Br ^- is a halogen ion, and alkyl sulfate group having 1 to 5 carbon atoms, such as. In the composition of the present invention, Q ⁻ in the quaternary ammonium salt represented by the general formula (XXI) may be the same as or different from X ⁻ in the quaternary ammonium salt (I) used simultaneously. Is also good.

[0034]

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Wherein R ¹⁵ and R ¹⁶ are the same or different and each represents 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)} m H ( wherein m is 1-3
Represents a number). 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) _m H (where m is as defined above) Show. Q ^-: is as defined above. ]

[0036]

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[0037] ^{wherein, R 17, R 18, Q} -: is as defined above. R ¹⁹ and R ²⁰ are the same or different and each represents a linear or branched alkyl, alkenyl or 2-hydroxyalkyl group having 9 to 23 carbon atoms. ]

[0038]

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[0039] ^{wherein, R 17, R 18, R} 19, Q -: is as defined above. ]

[0040]

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[0041] ^{wherein, R 18, R 19, R} 20, Q -: is as defined above. B: represents a group represented by the formula -OCO- or -NHCO-. ]

[0042]

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[0043] ^{wherein, R 18, R 19, R} 20, B, Q -: is as defined above. ]

[0044]

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Wherein R ¹⁹ is as defined above. ]

[0046]

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

[0048]

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Wherein R ¹⁹ and R ²⁰ are as defined above. R ^{21 represents a} straight-chain or branched-chain alkyl, alkenyl or 2-hydroxyalkyl group having 9 to 23 carbon atoms. When the concentration of the component (A) in the soft finish composition of the present invention is high, the composition tends to thicken during storage. In order to suppress the tendency to increase the viscosity, a compound having three or more active hydrogens is added with ethylene oxide and, if necessary, propylene oxide and / or trimethylene oxide, and has a weight average molecular weight of 5,000 to 2,000,000. It is preferable to blend a polyether compound or a derivative thereof (component (E)) in which the proportion of the oxyethylene group portion occupies 55% by weight or more.

Examples of the compound having three or more active hydrogens as a starting material for obtaining the component (E) include the following. As polyhydric alcohols, trimethylolpropane, diethanolamine, triethanolamine, glycerin, pentaerythritol, sorbitol, sucrose,
Partially saponified products of polyglycerin, polyvinyl alcohol and polyvinyl acetate are exemplified. Examples of the polyhydric phenol include a phenol resin and a formalin condensate of an alkylphenol. Examples of the polyamine compound include ethylenediamine and polyethyleneimine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Also, partially amidated or N-alkylated derivatives of these polyamine compounds can be used as starting materials for obtaining the component (E) as long as three or more active hydrogens remain.

The production of the component (E) can be obtained by adding ethylene oxide and, if necessary, propylene oxide and / or trimethylene oxide to a compound having three or more active hydrogens by a conventional method.
As the component (E), 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 alkylene oxides are added to a compound having three or more active hydrogens, the order of addition may be any order,
Propylene oxide (hereinafter abbreviated as PO) is added first and then ethylene oxide (hereinafter abbreviated as EO) is added to the composition of the present invention having a high concentration of component (A) during storage. Is preferred for suppressing the tendency to thicken in

The molecular weight of the component (E) is from 5,000 to 2,000,000
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 of the total molecular weight, and is preferably
80% by weight or more. In this case, when the molecular weight of the component (E) is less than 5,000, the effect of suppressing the tendency of thickening during storage of the soft finish composition is low, while 2,000,00
If it exceeds 0, the viscosity of the soft finish composition will increase remarkably, and disadvantages such as difficulty in taking out from the bottle will occur. Also,
When the proportion (total weight) of oxyethylene groups in the molecular weight of the component (E) is less than 55% by weight, the effect of suppressing the tendency of the soft finish composition to thicken during storage is low.

The derivative of the polyether compound as the component (E) includes a cross-linked reaction product obtained by the reaction of the polyether compound with a compound having an isocyanate group, and a sulfuric acid at a terminal hydroxyl group of the polyether compound. Compounds, phosphoric oxides, carboxyalkylated compounds, fatty acid esterified products, and those obtained by cationizing some of the nitrogen atoms of the 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 ester preferably has 7 to 23 carbon atoms. However, the number of double bonds, the presence or absence of branching, and the like do not significantly affect the performance. As the cationized compound, a compound obtained by partially cationizing a part of nitrogen atoms in a polyether compound with dialkyl sulfate, alkyl halide, or the like, or after cationization, is obtained by neutralizing with acetic acid, alkylbenzene sulfonic acid, or the like. And cationized products.

The soft finish composition of the present invention contains the component (E) in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the composition. The weight ratio of the component (E) to the component (A) [component (E)] / [component (A)] is 1/100 to 1
/2.5, preferably 1/50 to 1/5. The total content of the component (A) and the component (E) of the softener composition of the present invention is 4 to 45% by weight, preferably 11 to 39% by weight, and more preferably, based on the total weight of the composition. Is from 14 to 32% by weight. When the amount of the component (E) is within the above range, the soft finish composition of the present invention exhibits a desired level of soft performance according to 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 compounding amount of the inorganic electrolyte is 0 to 2% by weight, preferably 0.01 to 1% by weight in the composition. The soft finish composition of the present invention may further contain an acidic or alkaline substance for adjusting the pH of the composition. In this case, it is desirable to add an acidic or alkaline substance so that the pH of the composition of the present invention is in the range of 1.5 to 6.5 from the viewpoint of the viscosity and storage stability of the composition.

The soft finish composition of the present invention has a high stability even when stored for a long period of time. However, in order to stabilize it under severe storage conditions, 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 such as urea may be added to the composition of the present invention. In addition, the composition of the present invention may contain a pigment or dye for improving its appearance, silicone for defoaming at the time of rinsing, and a fragrance for improving taste at the time of use and after finishing. .

One example of the method for preparing the soft finish composition of the present invention is described below.
It is not limited to this manufacturing method. The component (A) is melted, or a mixture of the component (A) and other components (excluding the component (E)) is melted.
The solution is gradually dropped into deionized water held in the above to prepare an emulsion. Thereafter, if necessary, the component (E) may be added to the emulsion thus formed. Furthermore, instead of deionized water in advance,
A nonionic surfactant aqueous solution may be used, or (A)
After the addition of the component (E), an inorganic salt may be added to adjust the viscosity of the composition.

[0058]

Industrial Applicability The soft finish composition of the present invention imparts sufficient flexibility, antistatic property and excellent elasticity to various fibers, and has storage stability (gelation or increase after storage). Not sticky; the soft finish base does not hydrolyze after storage) and water absorption is extremely good.

[0059]

EXAMPLES Examples of the novel quaternary ammonium salt (I-1) of the present invention, examples of the synthesis of the quaternary ammonium salt (I) according to the present invention, and examples of the liquid softener of the present invention will now be described. The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 34 g of chloroacetic acid and 2-hexadecyleicosyl alcohol.
56 g was added and the temperature was raised to 140 ° C. After reacting at the same temperature for 7 hours while distilling off generated water, excess chloroacetic acid was removed by washing with water, and 175 g of chloroacetic acid ester was removed.
Obtained. Then, 64 g of a 50% aqueous solution of dimethylamine and water 1
After adding 00 g, the temperature was raised to 55 ° C., and the mixture was reacted at the same temperature for 10 hours. After the reaction, excess dimethylamine was removed by washing with water to obtain 170 g of a glycine ester. Next, the glycine ester 90 was placed in an autoclave equipped with a stirrer and a thermometer.
g, methyl chloride 15g, acetone 70g, 90 ℃
For 6 hours. After the reaction, crystallization was performed with acetone, and after drying, 85 g of the target substance as a white powder was obtained. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0061]

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[0062]

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IR spectrum (KBr tablet) 1746 cm ^-1 , 1206 cm ^-1 Example 2 44 g of chlorobutyric acid, 2-hexadecyl eicosyl alcohol 1 were placed in a four-necked flask equipped with a stirrer, thermometer and condenser.
56 g was added and the temperature was raised to 140 ° C. After reacting at the same temperature for 7 hours while distilling off generated water, excess chlorobutyric acid was removed by washing with water, and 185 g of chlorobutyrate was removed.
Obtained. Then, 64 g of a 50% aqueous solution of dimethylamine and water 1
After adding 00 g, the temperature was raised to 55 ° C., and the mixture was reacted at the same 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 reacted at 90 ° C. for 6 hours. After the reaction, crystallization with acetone was performed, and after drying, 90 g of the target substance as a white powder was obtained. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0064]

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[0065]

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IR spectrum (KBr tablet) 1731 cm ^-1 , 1182 cm ^-1 Example 3 45 g of chlorohexanoic acid and 156 g of 2-hexadecyl eicosyl alcohol were placed in a four-necked flask equipped with a stirrer, thermometer and cooling tube. The temperature was raised to 140 ° C. The reaction was carried out at the same temperature for 10 hours while distilling off generated water 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 mixture was reacted 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, the above 6-aminohexanoic acid ester was placed in an autoclave equipped with a stirrer and a thermometer.
g, methyl chloride 15 g, isopropyl alcohol 80
g was added and reacted at 90 ° C. for 8 hours. After the reaction, crystallization was performed with acetone, and after drying, 1030 g of the target substance as a white powder was obtained. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0067]

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[0068]

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IR spectrum (KBr tablet) 1730 cm ^-1 , 1185 cm ^-1 Synthesis Example 1 34 g of chloroacetic acid, 2-dodecylhexadecyl alcohol 123 were placed in a four-necked flask equipped with a stirrer, thermometer and cooling tube.
g was added and the temperature was raised to 140 ° C. After reacting at the same temperature for 5 hours while distilling off generated water, excess chloroacetic acid was removed by washing with water to obtain 145 g of chloroacetic acid ester. Then, 64 g of a 50% aqueous solution of dimethylamine and 100
g was added and 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 a glycine ester. Next, the glycine ester 75 was placed in an autoclave equipped with a stirrer and a thermometer.
g, methyl chloride 15g, acetone 50g, 90 ℃
For 6 hours. After the reaction, crystallization was performed with acetone, and after drying, 70 g of the target substance as a white powder was obtained. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0070]

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[0071]

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IR spectrum (KBr tablet) 1748 cm ^-1 , 1205 cm ^-1 Synthesis Example 2 34 g of chloroacetic acid and 90 g of 2-octyl dodecyl alcohol were placed in a four-necked flask equipped with a stirrer, a thermometer, and a condenser, and were heated to 140 ° C. The temperature rose. After reacting at the same temperature for 5 hours while distilling off generated water, 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 a glycine ester. Next, 57 g of the above-mentioned glycine ester, 15 g of methyl chloride and 400 g of acetone were placed in an autoclave equipped with a stirrer and a thermometer.
Reacted for hours. After the reaction, crystallization was carried out with acetone, and after drying, 60 g of the target substance as a white powder was obtained. The following structures were confirmed from the NMR spectrum and the IR spectrum.

[0073]

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[0074]

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IR spectrum (KBr tablet) 1746 cm ^-1 , 1205 cm ^{-1 The} quaternary ammonium salts obtained in Examples 1 to 3 and Synthesis Examples 1 and 2 are summarized in Table 1.

[0076]

[Table 1]

Examples 4 to 23, Comparative Examples 1 to 6 Quaternary ammonium salts (I) (component (A)) shown in Table 1, higher alcohols (component (B)) shown in Table 2, and Table 3 fatty acid
((C) component), lower alcohol ((D) component, polyalkylene oxide compound ((E) component) shown in Table 4) and the like are shown in Tables 5 and 6.
A soft finish composition containing the components shown in the following ratio was prepared (pH = 3).
Adjusted). The obtained soft finish composition was evaluated for storage stability, flexibility, elasticity and water absorption by the following methods. The results are shown in Tables 7 and 8. In the comparative examples, the following compounds (S) to (U) were used. In the following formulas, R ²³ and R ³³ represents an alkyl group composition obtained by replacing the carboxyl group of hardened tallow fatty acid in a methylene group. R ²⁴ and R ³⁴ each represent an alkyl group having a composition obtained by removing the carboxyl group of the hardened tallow fatty acid.

[0078]

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[0079]

[Table 2]

[0080]

[Table 3]

[0081]

[Table 4]

(1) Method of evaluating storage stability The flexible finish compositions shown in Tables 5 and 6 were sealed and sealed.
The solution was stored at 25 ° C., 25 ° C., and 50 ° C. for 20 days, and the appearance and fluidity under sealed conditions were measured. (2) Evaluation method of flexibility and elasticity a) Treatment method Commercial cotton towel 1.5 kg, acrylic jersey 0.5 kg
Was washed five times with a commercially available detergent attack (manufactured by Kao Corporation, registered trademark) in 3.5 ° DH hard water using a 30 liter washing machine to remove the fiber treating agent attached to each fiber. 6 ml of the soft finish composition described in No. 6 was charged, and the mixture was treated under stirring at 25 ° C. for 1 minute. b) Evaluation method The cloth treated by the above method was air-dried at room temperature, and then left for 24 hours in a constant temperature and humidity room at 25 ° C and 60% RH. These fabrics were evaluated for flexibility and elasticity. The evaluation of flexibility and elasticity was performed by comparing one pair of cloths treated with 10 cc of a soft finishing agent comprising 15% by weight of di-hardened tallow alkyldimethylammonium chloride as a control. The evaluation is expressed as follows. +2: Softer or higher elasticity than control +1; Slightly softer or slightly higher elasticity than control 0: Softness or elasticity equal to control (3) Evaluation method of water absorption [Virex method] Flexibility The cloth treated in the same manner as in the evaluation method of elasticity was allowed to stand in a thermo-hygrostat at 25 ° C. and 65% RH for 24 hours. Among them, a cotton towel was used for evaluation of water absorption. Cut the non-pile weave of the cotton towel into a 25cm x 2cm rectangle. On the other hand, water of 25 ° C was prepared in the constant temperature and humidity chamber, and 2 cm from the bottom was immersed in water while holding the cloth vertically, and the water was absorbed. Is measured.

[0083]

[Table 5]

[0084]

[Table 6]

Note) *: The numbers in brackets indicate the amount of the compound in the composition, and the unit is% by weight. The balance is water.

[0086]

[Table 7]

[0087]

[Table 8]

As is clear from Tables 7 and 8, all of the liquid softener compositions of the present invention showed little change in appearance and fluidity over time, and good storage stability. The flexibility, elasticity and water absorption were also equal to or better than the control.

Continued on the front page (72) Inventor Tohru Kato 1334 Minato, Wakayama-shi, Wakayama Prefecture, Kao Corporation (72) Inventor Nishimoto Uichiro 1334 Minato, Wakayama-shi, Wakayama Prefecture, Kao Corporation Laboratory (72) Inventor, Yasunori Ota 1334 Minato, Wakayama-shi, Wakayama Pref. Kao Corporation Laboratory (56) References JP-A-5-132865 (JP, A) JP-A-63-312399 (JP, A) JP-A-5-230764 (JP, A) JP-A-4-333669 (JP, A) JP-A-3-90677 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06M 13/46-13/467 CA (STN)

Claims (10)

(57) [Claims] 1. A liquid softener composition comprising the following component (A) and water, wherein the content of the component (A) is 3 to 40% by weight in the composition. (A) Component: quaternary ammonium salt represented by the general formula (I) [In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 28 to 44 carbon atoms. R ² , R ³ , R ⁴ : same or different and represents an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms. n: Indicates the number of 1 to 6. X ^-: represents an anion group. ] 2. A (A) a quaternary ammonium salt represented by the general formulas for the component (I), R ¹ groups of claim 1 wherein the linear or branched alkyl group having a carbon number of 36 to 44 of Liquid soft finish composition. Wherein component (A) 4 is quaternary ammonium salt according to claim 1 liquid softener composition as claimed represented by the general formula (I-1). Embedded image [Wherein, R ² , R ³ , R ⁴ , n, X ^{− have} the same meaning as above. ] 4. The composition further comprises, as a component (B), a straight-chain or branched-chain saturated or unsaturated alcohol having 8 to 44 carbon atoms,
The liquid softener composition according to any one of claims 1 to 3 , wherein the content of the component (B) is 110% by weight or less based on the weight of the component (A). 5. The composition further comprises, as the component (C), a linear or branched saturated or unsaturated fatty acid having 8 to 36 carbon atoms, wherein the content of the component (C) is based on the weight of the component (A). 100% by weight
The liquid soft finish composition according to any one of claims 1 to 4 , which is: 6. A component (D) having 1 to 4 carbon atoms.
The liquid soft finish composition according to any one of claims 1 to 5 , further comprising a polyhydric alcohol, wherein the content of the component (D) is 60% by weight or less based on the weight of the component (A). 7. As the component (E), 0.5 to 5% by weight, based on the total weight of the composition, of ethylene oxide and optionally propylene oxide and / or trimethylene oxide are added to a compound having three or more active hydrogens. A polyether compound or a derivative thereof having a weight average molecular weight of 5,000 to 2,000,000 and a ratio of an oxyethylene group portion in the molecular weight of 55% by weight or more,
Weight ratio of component (E) to component (A) [component (E)] /
((A) component) is 1/100 to 1 / 2.5, and (A)
The liquid soft finish composition according to any one of claims 1 to 6 , wherein the total content of the component and the component (E) is 4 to 45% by weight based on the total weight of the composition. 8. A quaternary ammonium salt represented by the general formula (I-2). Embedded image [Wherein, R ^{1-2 represents a} linear or branched alkyl group or alkenyl group having 36 to 44 carbon atoms. R ² , R ³ , R ⁴ , n, X ⁻ : Represents the above-mentioned meaning. ] 9. The quaternary ammonium salt according to claim 8, wherein R ^1-2 is a linear or branched alkyl group having 36 to 44 carbon atoms. 10. A quaternary ammonium salt represented by the general formula (I-1). Embedded image [Wherein, R ² , R ³ , R ⁴ , n, X ^{− have} the same meaning as above. ]