JP3398230B2 - Liquid softener composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid soft finish composition for clothes used in a washing and rinsing bath, which is capable of imparting excellent flexibility and antistatic property to various fibers.

[0002]

2. Description of the Related Art Clothes have an undesired texture due to the fiber treatment agent being washed off or hardened due to deterioration of the fibers themselves during repeated wearing and washing. . Therefore, in recent years, in many households, a softening agent that can impart flexibility and antistatic properties to fibers has been used. The softening effect of these softening agents is that the friction coefficient of the fiber surface decreases due to the lubricating effect of the lipophilic sites in the base molecule adsorbed on the fiber surface, but the softening agent having an excellent softening effect. The agent inevitably gives the treated clothing a Greasy feel. The degree of this Greasy varies depending on the type of fiber and the method of knitting, but underwear that directly contacts the skin, such as cotton knitted underwear,
For nylon, tricot, slip, or towels that are directly touched by the hand and whose texture is felt sensitively,
There was a problem that it became greesy due to the flexible processing, or it felt sticky. In addition, although the softening effect increases as the processing concentration of the softening agent increases, this
The sy feeling has further increased, and it has been considered that the softening effect and the Greasy feeling have a correlation in the conventional softener finishing compositions.

Under these circumstances, a softening agent for clothing containing a quaternary product of a triethanolamine ester of a fatty acid, a fatty acid dialkanolamide and water (East German Patent Publication No. 270638); quaternary ammonium A water-based softening finish for clothing containing a salt, a fatty acid dialkanolamide and water (JP-A-60-231868, West German Patent Publication No. 1469497); a rinsing rinse containing a quaternary ammonium salt and a fatty acid dialkanolamide Softening finish composition for clothing used in a bath (East German Patent Publication No. 2
22893, East German Patent Publication No. 154712);
A fabric softener composition containing a specific quaternary ammonium salt and a fatty acid dialkanolamide (JP-A-58-1)
86673, Japanese Patent Publication No. 60-14146);
A softening agent composition for clothing or hair containing a specific quaternary ammonium salt and a fatty acid dialkanolamide (JP-A-58-186674); a quaternary ammonium salt and a fatty acid derivative alkylene oxide adduct. Softener composition for clothing containing fatty acid dialkanolamide and water (JP-A-60-231866, JP-A-59-1)
30369 gazette) etc. are proposed. However, when the fabric is treated with these softening finish compositions, excellent softness may not be observed or softness may be excellent, but an undesired Greasy feeling may be exhibited. Not obtained.

[0004] Therefore, the problem to be solved by the present invention is to provide a liquid softening finish composition for use in a rinse bath in a washing tub, which can impart excellent flexibility to a cloth without giving a feeling of Greasy. Is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the above objects can be achieved by combining extremely selected components, and completed the present invention. . That is, the present invention includes the following (A)
Ingredients and (B) components are contained, and the mixing ratio of these is [(A) component] / [(B) component] = 2/1 to 1
/ 9 liquid soft finish composition. [Component (A)] A compound represented by the following general formula (I).

[0006]

[Chemical 3]

[In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 7 to 23 carbon atoms. M: represents an alkylene group having 2 to 3 carbon atoms. m, n: indicates a number of 0 or more, and m + n is 0 as an average value.
It is 4. [Component (B)] A compound represented by the following general formula (II).

[0008]

[Chemical 4]

[Wherein R ² and R ^{3 are the} same or different and are linear or branched and have 7 carbon atoms]
23 represents an alkyl group or an alkenyl group. R ⁴ and R ^{5 are the} same or different and each represents an alkyl group having 1 to 4 carbon atoms. X ⁻ : Indicates a halogen ion or R ⁴ SO ₄ ⁻ . Here, R ⁴ has the above-mentioned meaning. The present invention will be described in detail below.

[Component (A)] In the present invention, the compound represented by the above general formula (I) is used as the component (A). In the general formula (I), m + n is 0 as an average value.
It is 4. When m + n exceeds 4, a high softening effect cannot be obtained. Those in which m and n are 0 are particularly preferable. Further, when a fatty acid monoethanolamide or an ethylene oxide adduct thereof having a chemical structure similar to that of the component (A) is used instead of the component (A), a composition having good storage stability cannot be obtained. In the general formula (I), as the R ¹ group, an alkyl group derived from coconut oil fatty acid, an alkyl group derived from palm kernel oil fatty acid, an alkyl group derived from palm oil fatty acid, an alkyl group derived from palm stearic acid, a hardened palm stearic acid Examples thereof include at least one selected from the group consisting of an alkyl group derived from a tallow fatty acid, an alkyl group derived from a tallow fatty acid, and an alkyl group derived from a hardened tallow fatty acid. here,
The component (A) is exemplified below.

[0011]

[Chemical 5]

[Component (B)] As the component (B) in the present invention, the compound represented by the above general formula (II) is used. In the general formula (II), X ⁻ is a halogen ion (Cl ⁻ , Br ^−, etc.) or CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , C ₃ H ₇ SO.
₄ ^- and the like. Fourth used as component (B)
The secondary ammonium salt (II) is produced, for example, by the following reaction formula.

[0013]

[Chemical 6]

[In the above formula, R ² , R ³ , R ⁴ , R ⁵ and X ⁻ : have the above meanings. E: represents a halogen atom or R ⁵ —SO ₄ ^— . Here, R ⁵ has the above-mentioned meaning. ] That is, first, N- (2-aminoethyl) ethanolamine
Imidazoline (V) by reacting (III) with fatty acid (IV)
To get In this case, N- (2-aminoethyl)
Ethanolamine (III) / fatty acid (IV) molar ratio is 1.0
~ 2.0, preferably 1.1-1.5, the reaction temperature is 150
The temperature is ˜250 ° C., preferably 180˜230 ° C., and it is desirable to gradually evacuate the reaction system from atmospheric pressure to about 5 Torr in order to enhance the dehydration efficiency. Fatty acids used here (IV)
Generally, natural oils and fats such as palm oil, palm oil, beef tallow, rapeseed oil and fish oil are used, but chemically synthesized fatty acids having 8 to 24 carbon atoms may be used.

The imidazoline (V) thus obtained is hydrolyzed in a mixed solvent such as water / ethanol or in water with NaOH as a catalyst or without a catalyst to give a ring-opened product (VI). obtain. In this case, water is 1 to 10 times mol, preferably 2 to 5 times mol to imidazoline (V), and ethanol is 0 to 50% by weight, preferably 10 to 30% by weight of the total weight of imidazoline (V) and water. Use to some extent. NaOH is used in an amount of 0 to 10 mol%, preferably 0 to 5 mol% based on the imidazoline (V). The ring-opened product (VI) thus obtained was treated under normal conditions with an aldehyde (VII) such as formaldehyde or acetaldehyde.
Leukart reaction, or reductive alkylation reaction (after reacting the ring-opened compound (VI) with the aldehyde (VII),
Hydrogenation is performed in the presence of a hydrogenation catalyst) to carry out amidation
The primary amine (VIII) is obtained. Then, the amidated tertiary amine (VIII) is subjected to an esterification reaction with a fatty acid (IX) to obtain an amidoesterified tertiary amine (X). The fatty acid (IX) used here is coconut oil,
Generally, natural oils and fats such as palm oil, beef tallow, rapeseed oil and fish oil are derived, but chemically synthesized fatty acids having 8 to 24 carbon atoms may be used.

The amide esterified tertiary amine (X) thus obtained is quaternized by a known method.
The quaternization reaction is carried out with (XI) to obtain a quaternary ammonium salt, and the counter ion thereof is exchanged if necessary to obtain a quaternary ammonium salt (II). As the quaternizing agent (XI),
An alkyl halide (eg, methyl chloride, ethyl chloride, methyl bromide, etc.), a dialkyl sulfuric acid (eg, dimethyl sulfuric acid, diethyl sulfuric acid, etc.) and the like are used. In the quaternization reaction, a lower alcohol such as ethanol, isopropanol or butanol, the component (A) of the present invention, or a mixture thereof may be used as a solvent. The counter ion of the quaternary ammonium salt (II) thus obtained can be exchanged with an ion exchange resin or the like, if necessary. Here, the component (B) is exemplified below.

[0017]

[Chemical 7]

[In the above series of formulas, R ^2-1 and R ^3-1 are alkyl groups derived from hardened tallow fatty acid. R ^2-2 and R ^3-2 : Indicates an alkyl group derived from hydrogenated palm oil fatty acid. [Softening agent composition] The composition of the present invention contains the component (A) and the component (B). The blending ratio of the component (A) and the component (B) is a weight ratio, [(A) component] / [(B) component] = 2
/ 1-1 / 9, preferably 1 / 1-1 / 9, and more preferably 1 / 2-1 / 9. When the ratio exceeds 2/1, the softening effect desired by the present invention cannot be obtained, while
When it is less than 1/9, the garment treated with the composition exhibits a greasy feeling which is not preferable to consumers.

The total blending amount of the components (A) and (B) is
It is 3 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 25% by weight. If the total content of the components (A) and (B) is less than 3% by weight, the desired softening effect of the present invention cannot be obtained, and if it exceeds 40% by weight, the viscosity of the composition increases and Inconvenience such as difficulty in coming out occurs. Furthermore, in the softening agent composition of the present invention, when the components (A) and (B) are blended in a high concentration, the composition is further treated with active hydrogen as a component (C) in order to suppress thickening tendency during storage. 2 to 3 carbon atoms in a compound having 3 or more
Alkylene oxide adduct of (wherein the total weight of oxyethylene groups in the molecule of component (C) is 55% by weight or more), and a polyether compound having an average molecular weight of 5,000 to 2,000,000 or a derivative thereof is blended. be able to.

Examples of the compound having 3 or more active hydrogens as a starting material for obtaining the component (C) are as follows. As polyhydric alcohols, trimethylolpropane, diethanolamine, triethanolamine, glycerin, pentaerythritol, sorbitol, sucrose,
Examples thereof include polyglycerin, polyvinyl alcohol, and partially saponified polyvinyl acetate. Examples of polyhydric phenols include phenol resins and formalin condensates of alkylphenols. Examples of the polyamine compound include polyethyleneimine such as ethylenediamine, 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 long as the number of active hydrogens remains 3 or more.

The component (C) can be produced by adding an alkylene oxide essentially containing ethylene oxide to a compound having 3 or more active hydrogens by a conventional method. Of these, ethylene oxide alone or a block or partial block adduct of ethylene oxide and propylene oxide is particularly preferable, and the order of addition may be any, but propylene oxide (hereinafter, referred to as P
In the composition (A), ethylene oxide (hereinafter abbreviated as EO) is added after the first addition of O).
And (B) is preferable because it suppresses the thickening tendency during storage of the composition when the component (B) is used in a high concentration.

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

As the derivative of the polyether compound as the component (C), a crosslinking reaction product of a compound having an isocyanate group or the like, or a sulfated product of a terminal hydroxyl group of the polyether compound,
Examples thereof include phosphorus oxides, carboxyalkylated products, fatty acid esterified products, and those obtained by cationizing a part of nitrogen atoms. Of these, fatty acid esterified products and cationized products are particularly preferable. In the case of a fatty acid esterified product, it is preferable that the fatty acid used has 7 to 23 carbon atoms, but the number of double bonds, branching, etc. do not significantly affect the performance. Examples of the cationized compound include a compound obtained by cationizing a polyether compound with a dialkyl sulfuric acid, an alkyl halide, or the like, or a cationized compound obtained by neutralizing with an acetic acid or an alkylbenzenesulfonic acid.

The content of the component (C) is 0.5 to 5% by weight, preferably 1 to 5% by weight in the softener composition.
3% by weight, and the mixing ratio of the (C) component and the (B) component is a weight ratio of [(C) component] / [(B) component] = 1/100 to 1
/2.5, preferably 1/50 to 1/5, and the total blending amount of the components (B) and (C) is 4 to 50% by weight, preferably 11 to 40% by weight, more preferably 14 to It is desirable to adjust the content to be 32% by weight in order to achieve the desired level of softening performance of the present invention and at the same time suppress the tendency of thickening during storage of the composition.

Further, 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 24 carbon atoms is used as the component (D). It can be blended. The blending amount of the component (D) is [(D) component] / [(B) component] = 0.5 / 100 to 1/1, preferably 1/100, in the weight ratio of the (D) component and the (B) component. ~ 1/2 is more preferable. Further, the total blending amount of the component (B) and the component (D) is preferably 4 to 50% by weight in the composition. Examples of fatty acids used here include 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. And fatty acids obtained from pork fat, palm oil, rapeseed oil, fish oil and the like. Further, in the present invention, a softening agent base represented by the following general formulas (XII-1) to (XII-3) can be blended. In this case, the content of the softening agent base is 0 to 15% by weight in the composition.
Is.

[0026]

[Chemical 8]

[In the formula, R ⁶ and R ⁷ represent an alkyl group having 1 to 4 carbon atoms. R ⁸ : Shows a linear or branched alkyl group or alkenyl group having 7 to 23 carbon atoms. Z ⁻ : Indicates a halogen ion or R ⁹ SO ₄ ^— group. Here, R ⁹ represents an alkyl group having 1 to 4 carbon atoms. Incidentally, Z ^- is said X ^-
May be the same or different. ]

[0028]

[Chemical 9]

[In the formula, R ⁸ represents the above meaning. R ¹⁰ : Shows a linear or branched alkyl group or alkenyl group having 7 to 23 carbon atoms. ]

[0030]

[Chemical 10]

[In the formula, R ⁸ and R ¹⁰ are as defined above. R ¹¹ : represents a linear or branched alkyl group or alkenyl group having 7 to 23 carbon atoms. In addition, the composition of the present invention does not prevent the use of a conventionally known soft base as long as the object of the present invention is not impaired. Further, in the composition of the present invention, for adjusting the viscosity of the composition,
An inorganic electrolyte such as NaCl, CaCl ₂ or MgCl ₂ can be added. In this case, the compounding amount of the inorganic electrolyte is 0 to 2 in the composition.
%, Preferably 0.01 to 1% by weight.

In the softener composition of the present invention, an acid or alkaline substance can be added to adjust the pH of the composition. In this case, it is desirable to adjust the pH within the range of 1.5 to 6.5 from the viewpoint of the viscosity and storage stability of the composition. The softening agent composition of the present invention has high stability for long-term storage, but in order to be stabilized under more severe storage conditions, polyoxyethylene (5 to 50 mol) alkyl or alkenyl (C ₁₂ ~ C ₂₄ ) ether, polyoxyethylene (5 to 50 mol) alkyl or alkenyl (C ₁₂
~ C ₂₄ ) Nonionic surfactants such as amines, hydrotropes such as ethylene glycol, propylene glycol, glycerin or urea may be added. Also,
A pigment or dye for improving the appearance of the composition of the present invention,
Silicone may be added for defoaming during rinsing, and a fragrance may be added for improving the appearance during use and after finishing. The balance of the softener composition of the present invention excluding the essential and optional components is water.

An example of the method for preparing the softener composition of the present invention will be described below, but the present invention is not limited to this method. A mixture of the components (A) and (B) and other components (excluding the component (C)) is melted, and the melt is gradually added to ion-exchanged water heated to 60 ° C. with stirring. Drop it. Thereafter, if necessary, the component (C) may be added to the emulsion thus produced. Furthermore, a nonionic surfactant may be added in water in advance, or an inorganic salt may be added to adjust the viscosity after addition of the components (A) and (B) and other components. Good.

[0034]

EFFECT OF THE INVENTION The softening agent composition of the present invention can impart excellent softness to a cloth without giving a feeling of Greasy. In addition, it has excellent biodegradability, is kind to the natural environment, and has very good storage stability (no gelation or thickening after storage).

[0035]

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. In the examples,% is based on weight unless otherwise specified.

Examples 1 to 11 Component (A) shown in Table 1, component (B) shown in Table 2, component (C) shown in Table 3, component (D) shown in Table 4 and other components shown in Table 5 Using the ingredients, a liquid softener composition of the present invention having the composition shown in Table 6 was prepared.

Comparative Examples 1 to 4 A liquid softening agent composition having a composition shown in Table 6 was prepared using the component (A) shown in Table 1, the component (B) shown in Table 2 and the other components shown in Table 5. Was prepared.

The liquid softening and finishing compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were used to evaluate the flexibility and the feeling of Greasy by the following methods. Further, the storage stability was evaluated by the following method. The results are shown in Table 6.

[Evaluation of Softness and Greasy Feel] Commercially available cotton towels, acrylic fibers, and polyester fibers were repeatedly washed 5 times with a commercially available detergent “Attack” (registered trademark of Kao Corporation), and the detergent attached to the cloth. After removing the liquid softening agent composition prepared above 0.5% of the weight of the fabric
After pouring it in, treating it with stirring at 25 ℃ at a bath ratio of 1/30 for 3 minutes, air-drying it indoors, and then in a constant temperature and humidity room at 20 ℃ and 65% RH for 24 hours.
Left for hours. The softness and the feeling of Greasy were evaluated for these cloths.

For the evaluation of softness and greasiness, a pair of comparisons were carried out using the cloth treated with the softening agent composition of Comparative Example 2 as a control. The evaluation is expressed as follows. Flexibility: +2 Softer than the control +1 Slightly softer than the control 0 Same as the control -1 The control is a little softer-2 The control is softer Greasy Sense: +2 The control is Greasy +1 The control is a little Greasy Certain 0 Same as control -1 is slightly more Greasy than control-2 is more Greasy than control <Evaluation method of storage stability> The liquid softening agent composition prepared above is hermetically sealed at 20 ° C and 40 ° C. It was stored for 20 days, and the appearance and fluidity under the closed 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.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

Note) * 1: R ³⁰ represents an alkyl group derived from hardened beef tallow fatty acid. * 2: EO means ethylene oxide. * 3: 20% by weight of a compound represented by the following formula (E-6-1),
-6-2) A mixture of 45% by weight of the compound represented by the formula and 35% by weight of the compound represented by the formula (E-6-3).

[0047]

[Chemical 11]

(In the formula, R ³¹ is a mixed group of an alkyl group derived from a hardened tallow fatty acid and an alkyl group derived from an uncured beef tallow fatty acid, and a weight ratio of [former] / [latter] = 25/75. Is shown.)

[0049]

[Table 6]

Note) In Table 6, the number in parentheses () indicates the compounding amount in the composition, and the unit is% by weight. The balance is water.

From the above results, it can be seen that the softening agent composition of the present invention can impart excellent flexibility to a cloth without giving a feeling of Greasy and has good storage stability. .

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-231866 (JP, A) JP-A-6-228865 (JP, A) US Patent 4237064 (US, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) D06M 13/00-13/535

Claims (6)

(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). [Chemical 1] [In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 7 to 23 carbon atoms. M: represents an alkylene group having 2 to 3 carbon atoms. m, n: indicates a number of 0 or more, and m + n is 0 as an average value.
It is 4. [Component (B)] A compound represented by the following general formula (II). [Chemical 2] [In the formula, R ² and R ^{3 are the} same or different and are linear or branched and have 7 carbon atoms.
23 represents an alkyl group or an alkenyl group. R ⁴ and R ^{5 are the} same or different and each represents an alkyl group having 1 to 4 carbon atoms. X ⁻ : Indicates a halogen ion or R ⁴ SO ₄ ⁻ . Here, R ⁴ has the above-mentioned meaning. ] 2. The liquid softener composition according to claim 1, wherein m and n are 0 in the general formula (I). 3. In the general formula (I), R ¹ group is an alkyl group derived from coconut oil fatty acid, an alkyl group derived from palm kernel oil fatty acid, an alkyl group derived from palm oil fatty acid, an alkyl group derived from palm stearic acid, and cured. The liquid softening agent composition according to claim 1 or 2, which is at least one selected from the group consisting of an alkyl group derived from palm stearic acid, an alkyl group derived from tallow fatty acid, and an alkyl group derived from hardened tallow fatty acid. 4. The liquid softening agent composition according to claim 1, wherein the total amount of the component (A) and the component (B) compounded is 3 to 40% by weight in the composition. 5. The composition further comprises the following component (C), wherein the content of the component (C) is 0.5 to 5% by weight in the composition, and the mixing ratio of the component (C) and the component (B) is a weight ratio. [(C) component] / [(B) component] = 1/100 to 1 / 2.5, and the total blending amount of the (B) component and the (C) component is 4 to 50 in the composition.
The liquid softening agent composition according to any one of claims 1 to 4, wherein the liquid softening agent composition is wt%. [Component (C)] An alkylene oxide adduct having 2 to 3 carbon atoms to a compound having 3 or more active hydrogens (provided that (C)
The total weight of oxyethylene groups in the component molecule is 55% by weight or more), and the average molecular weight is 5,000 to 2,000,
000 polyether compounds or their derivatives. 6. The component (D) further contains a linear or branched, saturated or unsaturated fatty acid having 8 to 24 carbon atoms,
The mixing ratio of the component (D) and the component (B) is a weight ratio [component (D)] / [component (B)] = 0.5 / 100 to 1/1
The liquid softener composition according to any one of claims 1 to 5, wherein the total amount of the components (B) and (D) is 4 to 50% by weight in the composition.