JP3224191B2 - Liquid softener composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides liquid softness which imparts excellent flexibility and elasticity (fluffiness) to various fibers, has excellent storage stability, is excellent in biodegradability and is friendly to the natural environment. It relates to a finish composition.

[0002]

2. Description of the Related Art
Commercially available products as a household softening agent are generally composed mainly of di (hardened tallow alkyl) dimethylammonium chloride. This is because the quaternary ammonium salt exerts a good softening effect on various fibers in a small amount. However, although the quaternary ammonium salt has a high softening effect, there is a problem in that when the residue after treatment is released into the natural world such as a river, it is hardly biodegraded, and adversely affects organisms.
As means for solving this, dimethyldi (alkanoyloxyethyl) ammonium chloride and methyldi (alkanoyloxyethyl) 2-hydroxyethylammonium methylsulfate have been marketed, but these have been compared with the above quaternary ammonium salts. Thus, the biodegradability has been improved, but the flexibility and the storage stability are still insufficient.

Accordingly, an object of the present invention is to provide a liquid soft finish composition which exhibits satisfactory performance in terms of soft performance and storage stability, has excellent biodegradability, and is friendly to the natural environment. That is.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a liquid soft finish composition containing a quaternary ammonium salt having a very specific structure, a nonionic surfactant and a hydrotrope agent. As a result, the inventors have found that the above problem can be solved, and have completed the present invention.

That is, the present invention relates to the following component (A):
30% by weight, 0.5 to 5% by weight of component (B) and component (C)
It is intended to provide a liquid soft finish composition characterized by containing 0.5 to 20% by weight. (A) component: a quaternary ammonium salt represented by the general formula (I)

[0006]

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Wherein R ^{1 represents a} linear or branched alkyl or alkenyl group having 18 to 44 carbon atoms. R ² , R ³ , R ⁴ : same or different and represents an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. Y: a linear or branched alkylene group having 2 to 4 carbon atoms. m: 0 to 20 indicating the average number of moles of alkylene oxide added
Is the number of n: represents an integer of 1 to 6. X ^-: represents an anion group. ] (B) component; polyoxyethylene (P = 10 to 60) alkyl or alkenyl (C ₈ ~C ₂₂₎ ether, polyoxyethylene (P = 10 to 60) alkyl or alkenyl (C ₈ ~C ₂₂₎ phenyl ether And polyoxyethylene (P = 10-60)
At least one selected from alkyl or alkenyl (C ₈ -C ₂₂ ) amines (where P represents the average number of moles of ethylene oxide added) (C) component; Tropic

[0008]

Embodiments of the present invention will be described below in detail.

[Component (A)] In the present invention, a quaternary ammonium salt represented by the general formula (I) (hereinafter abbreviated as quaternary ammonium salt (I)) is used as the component (A). In this case, the X ^- group represents an anionic group,
Examples of the anionic group include a halogen anionic group (Cl ⁻ ,
Br ^-, etc.), alkyl sulfate anionic 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.

Here, the quaternary ammonium salt (I) is exemplified as follows.

[0011]

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[0012]

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[0013]

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[0014]

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Among these quaternary ammonium salts (I), from the viewpoint of imparting flexibility, R ¹ is a linear or branched alkyl or alkenyl group having 28 to 44 carbon atoms and Y is an ethylene group. A certain quaternary ammonium salt is preferable, and a quaternary ammonium salt represented by the general formula (I-1) is particularly preferable.

[0016]

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[Wherein, R ² , R ³ , R ⁴ , X ⁻ , m, n: have the above meanings. R ^5: an alkyl group having a carbon number of 10 to 22 straight chain. R ⁶ : represents a linear alkyl group having 8 to 20 carbon atoms. In the general formula (I), R ² , R ³ and R ⁴ are preferably a methyl group, and n is preferably 1. Further, m is preferably from 0 to 8, and particularly preferably from 0 to 5. More particularly preferred quaternary ammonium salts (I) are quaternary ammonium salts represented by the following general formula (I-2).

[0018]

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Wherein m ′ is 0 or 2. The quaternary ammonium salt (I) is produced, for example, by the following production methods 1 and 2, but the present invention is not limited by the production conditions.

<Production Method 1>

[0021]

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[Wherein, R ¹ , R ² , R ³ , R ⁴ , Y, n, m: have the above meanings. Z: represents a halogen atom. W ^-: represents a group represented by ^- halogen ion or R ⁴ SO _4. However R ⁴ have the same meanings as defined above. That is, first, a halocarboxylic acid (II) is reacted with a higher alcohol or its alkylene oxide adduct (III) to obtain a halocarboxylic acid ester (IV). In this case, examples of the halocarboxylic acid (II) include those represented by the following formula, and preferably monochloroacetic acid. ClCH ₂ COOH, ClCH ₂ CH ₂ CH ₂ COOH, Cl (CH ₂ ) ₅ COOH, BrCH ₂ COOH Also, examples of higher alcohols or their alkylene oxide adducts (III) include higher alcohols represented by the following formulas: Ethylene oxide or propylene oxide adducts thereof can be mentioned, and these alone or in combination can be used, and preferably 2-hexadecyl eicosyl alcohol or its ethylene oxide adduct.

[0023]

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The higher alcohol or its alkylene oxide adduct (III) used in the present invention is disclosed in JP-B-61-5.
No. 9612 can be obtained. That is,
It can be obtained by subjecting a primary alcohol to a heat condensation reaction in the presence of an alkali or an alkali and a cocatalyst, and adding an alkylene oxide as necessary.

Here, the charged amounts of the halocarboxylic acid (II) and the higher alcohol or its alkylene oxide adduct (III) are in a molar ratio of [halocarboxylic acid (II)] / [the higher alcohol or its alkylene oxide adduct ( III))
= 0.8 to 1.5, 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 amounts of the halocarboxylic acid ester (IV) and the secondary amine (V) are preferably in a molar ratio of [secondary amine (V)] / [halocarboxylic acid ester (IV)] = 0.8 to 3.0, Reaction temperature is 30-80
C is preferable, and the reaction time is preferably 3 to 15 hours.

The thus obtained esteramine (V
I) is reacted with a quaternizing agent (VII). Examples of the quaternizing agent (VII) include alkyl halides (methyl chloride, methyl bromide, etc.), dialkyl sulfates (the alkyl group has 1 to 5 carbon atoms), and preferably methyl chloride and dimethyl sulfate. . The reaction between the esteramine (VI) and the quaternizing agent (VII) is carried out by isopropanol, ethanol,
The reaction is performed in the presence of a solvent such as acetone. In this case, the charged amounts of the esteramine (VI) and the quaternizing agent (VII) are in a molar ratio of [esteramine (VI)] / [quaternizing agent (VII)].
= 0.8-1.5, and the reaction temperature is preferably 80-120 ° C. The quaternary ammonium salt thus obtained (V
In III), the counter ion can be exchanged as necessary to obtain the quaternary ammonium salt (I) of the present invention.

<Production Method 2>

[0029]

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[Wherein, R ¹ , R ² , R ³ , R ⁴ , Y, n, m, and Z have the above-mentioned meanings. Halocarboxylic acid ester (IV) in the same manner as in Production method 1
Is obtained, the halocarboxylic acid ester (IV) is reacted with a tertiary amine (IX). 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 (IX) are preferably in a molar ratio of [tertiary amine (IX)] / [halocarboxylic acid ester (IV)] = 0.8 to 2.5. Is 40 to 120
C is preferred. The quaternary ammonium salt (X) thus obtained can be exchanged for its counter ion, if necessary, to obtain the quaternary ammonium salt (I) of the present invention.

[Component (B)] As the component (B) used in the present invention, polyoxyethylene (P = 10 to 60) alkyl or alkenyl (C _{8 to} C ₂₂ ) ether, polyoxyethylene (P = 10 60) alkyl or alkenyl (C ₈ -C ₂₂₎ phenyl ether, and polyoxyethylene (P = 10-6
0) At least one selected from the group consisting of alkyl or alkenyl (C ₈ -C ₂₂ ) amines is preferred, and particularly preferred is an ethylene oxide adduct of a primary alcohol having 12 to 14 carbon atoms (P = 18 to 40). ), An ethylene oxide adduct of a secondary alcohol having 12 to 14 carbon atoms (P = 18 to 40).

[Component (C)] The hydrotrope used in the present invention is at least one selected from polyhydric alcohols, and preferably at least one selected from ethylene glycol, propylene glycol and glycerin.

[Liquid Soft Finishing Composition] The liquid soft finishing composition of the present invention contains 3 to 30% by weight of the component (A), 0.5 to 5% by weight of the component (B) and 0.5 to 5% by weight of the component (C). It contains 0.5 to 20% by weight, with the balance being water and optional components.

When the content of the component (A) is less than 3% by weight,
If the softening effect desired by the present invention cannot be obtained and exceeds 30% by weight, the viscosity of the composition increases and the handling properties become poor. When the content of the component (B) is less than 0.5% by weight, the composition thickens with the lapse of time. When the content exceeds 5% by weight, the effect remains unchanged, which is economically disadvantageous. Also (C)
When the content of the component is less than 0.5% by weight, the viscosity after freezing and recovery increases, and when it exceeds 20% by weight, phase separation is observed in the composition after storage, which is not preferable.

[Optional Components] In the present invention, a linear or branched saturated or unsaturated fatty acid having 8 to 40 carbon atoms can be blended for the purpose of further improving the flexibility performance and the storage stability. The compounding amount is 110% by weight based on the component (A).
Hereinafter, it is preferably 1 to 90% by weight.

Further, for the purpose of improving the flexibility performance, a linear or branched saturated or unsaturated alcohol having 8 to 44 carbon atoms can be blended. The compounding amount is 100% by weight or less, preferably 0.5 to 50% by weight based on the component (A).

The composition of the present invention may contain a known cationic compound (quaternary ammonium salt, imidazolinium salt, etc.), an ester or an amide, or a mixture thereof as a softener base. Examples of these include compounds represented by the following general formulas (XI-1) to (XI-9).

[0038]

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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- (wherein R ¹² is a carbon number of straight or branched chain 7-35
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 (XI-1) may be the same as or different from X ⁻ in the quaternary ammonium salt (I) used simultaneously. May be.

[0040]

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[In the formula, 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)} q H ( where q is 1 to 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) _q H (where q is as defined above) Show. Q ^-: is as defined above. ]

[0042]

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[0043] [In the ^{formula, 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. ]

[0044]

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[0045] ^{wherein, R 17, R 18, R} 19, Q -: is as defined above. ]

[0046]

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[0047] ^{wherein, R 18, R 19, R} 20, Q -: is as defined above. B: represents a group represented by the formula -OCO- or -NHCO-. ]

[0048]

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[Wherein, R ¹⁸ , R ¹⁹ , R ²⁰ , B, Q ⁻ are as defined above. ]

[0050]

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Wherein R ¹⁹ is as defined above. ]

[0052]

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

[0054]

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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. The composition of the present invention, for adjusting the viscosity of the composition, NaCl, CaCl
₂ , inorganic electrolytes such as MgCl ₂ , MgSO ₄ , CaSO ₄ , and Na ₂ SO ₄ can be blended. 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 falls within the range of 1.5 to 6.5 from the viewpoint of storage stability of the composition. In addition, a pigment or dye may be added to improve the appearance, silicone may be added to defoam at the time of rinsing, and a fragrance may be added to improve the taste at the time of use and after finishing.

An example of a method for preparing the liquid softener composition of the present invention is described below, but the preparation method of the present invention is not limited to this method. (A) melting the components,
Alternatively, a mixture of the component (A) and other components is melted, and this melt is gradually dropped into deionized water maintained at 60 ° C. with stirring to prepare an emulsion. A nonionic surfactant aqueous solution may be used instead of deionized water, or after the addition of the components (A) to (C), an inorganic salt may be added as necessary to adjust the viscosity of the composition. You may.

[0058]

Industrial Applicability The liquid softener composition of the present invention imparts excellent flexibility and elasticity (fluffiness) to various fibers, and has excellent storage stability and excellent biodegradability in a natural environment. It is a gentle liquid softener composition.

[0059]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples of the quaternary ammonium salt (I) according to the present invention and Examples of the liquid softener composition of the present invention. Is not limited to these examples.

Synthesis Example 1 34 g of monochloroacetic acid and 156 g of 2-hexadecyl eicosyl alcohol were placed in a four-necked flask equipped with a stirrer, thermometer, and condenser, and the temperature was raised to 140 ° C. After reacting at the same temperature for 7 hours while distilling off generated water, excess monochloroacetic acid was removed by washing with water to obtain 175 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 170 g of a glycine ester.

Next, 90 g of the glycine ester and methyl chloride 15 were placed in an autoclave equipped with a stirrer and a thermometer.
g and acetone 70 g, and reacted at 90 ° C. 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.

[0062]

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[0063]

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IR spectrum (KBr tablet) 1746 cm ^-1 , 1206 cm ^-1 Examples 1 to 18 and Comparative Examples 1 to 6 Components (A) shown in Table 1, components (B) shown in Table 2, and components shown in Table 3
Using the component (C) and the other components, liquid soft finish compositions having the compositions shown in Tables 4 and 5 were prepared. The obtained liquid soft finish composition was evaluated for storage stability and flexibility by the following methods, and the results are shown in Tables 4 and 5. In each case, CaCl ₂ was added in an amount of 0.2% by weight in the composition, and the remainder other than the optional components was prepared as water. The pH of the composition was adjusted to 4.0 with an aqueous HCl solution.

(1) Method of evaluating storage stability The liquid soft finish compositions described in Tables 4 and 5 were sealed,
The appearance and the fluidity of each of the case of storing at 25 ° C. for 1 month and the case of storing (freezing) at −20 ° C. for 12 hours and then storing at 20 ° C. for 12 hours were visually measured based on the following criteria. ；: No change in appearance was observed. X: Thickening or separation phenomenon is observed.

(2) Evaluation method of flexibility (a) Treatment method 1 kg of a commercially available towel was washed 5 times with 3.5 ° DH hard water with a commercial detergent “Attack” (registered trademark, Kao Corporation) five times (30 liters). After removing the fiber treating agent attached to the fibers, 6 ml of the liquid softening finish composition shown in Tables 4 and 5 was added, and the mixture was treated with stirring for 1 minute.

(B) Evaluation method The towels treated by the above method were air-dried indoors at 25 ° C and 65%
It was left in a constant temperature and humidity chamber of RH for 24 hours. These fabrics were evaluated for flexibility. Evaluation of the softness was performed by comparing the fabric treated with the softener consisting of 15% by weight of distearyldimethylammonium chloride in Examples 1 and 2 and Comparative Examples 2 and 3 with 20 ml, and in other cases, with the fabric treated with 5 ml. .
The evaluation criteria were as follows. +2: softer than control. +1; slightly softer than the control. 0; same as control.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

[Table 5]

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

As is clear from Tables 4 and 5, all of the liquid softener compositions of the present invention had good flexibility and storage stability.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-93160 (JP, A) JP-A-4-333669 (JP, A) JP-A-58-208468 (JP, A) JP-A 64-64 65198 (JP, A) JP-A-8-217732 (JP, A) JP-A-54-130509 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 13/00-13 / 535

Claims (5)

(57) [Claims] 1. A liquid softener composition comprising the following component (A): 3 to 30% by weight, component (B): 0.5 to 5% by weight, and component (C): 0.5 to 20% by weight. object. Component (A): a quaternary ammonium salt represented by the general formula (I): [Wherein, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 18 to 44 carbon atoms. R ² , R ³ , R ⁴ : same or different and represents an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. Y: a linear or branched alkylene group having 2 to 4 carbon atoms. m: 0 to 20 indicating the average number of moles of alkylene oxide added
Is the number of n: represents an integer of 1 to 6. X ^-: represents an anion group. ] (B) component; polyoxyethylene (P = 10 to 60) alkyl or alkenyl (C ₈ ~C ₂₂₎ ether, polyoxyethylene (P = 10 to 60) alkyl or alkenyl (C ₈ ~C ₂₂₎ phenyl ether And polyoxyethylene (P = 10-60)
At least one selected from alkyl or alkenyl (C ₈ -C ₂₂ ) amines (where P represents the average number of moles of ethylene oxide added) (C) component; at least one type of hydrohydric alcohol selected from polyhydric alcohols Tropic 2. The liquid softener composition according to claim 1, wherein the component (A) is a quaternary ammonium salt represented by the general formula (I-1). Embedded image [Wherein, R ² , R ³ , R ⁴ , X ⁻ , m, n: have the above meanings. R ^5: an alkyl group having a carbon number of 10 to 22 straight chain. R ⁶ : represents a linear alkyl group having 8 to 20 carbon atoms. ] 3. R ² , R ³ and R ⁴ are all methyl groups and n = 1
The liquid soft finish composition according to claim 2, which is 4. The component (B) is composed of an ethylene oxide adduct of a primary alcohol having 12 to 14 carbon atoms (P = 18 to 40) and an ethylene oxide adduct of a secondary alcohol having 12 to 14 carbon atoms (P = 18). And at least one selected from the group consisting of polyoxyethylene alkyl ethers.
The liquid soft finish composition according to any one of the above. 5. The liquid soft finish composition according to claim 1, wherein the hydrotrope component (C) is at least one selected from ethylene glycol, propylene glycol and glycerin.