JP2002194668A - Softening agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a softening agent composition having excellent softening effects, and capable of imparting fresh feeling without oily feeling to clothes. SOLUTION: This softening agent composition contains (a) a compound selected from a tertiary amine with a specific structure or its salt, and a quaternary ammonium salt with a specific structure, (b) an anionic surfactant having a 16-36C alkyl group or alkenyl group, and a -SO3M group and/or a -CSO3M group [M is a counter ion] in the molecule, and (c) water in each specific proportion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a softener composition.

[0002]

2. Description of the Related Art
As the softener, a quaternary ammonium salt having a long-chain alkyl group or an acid salt of a tertiary amine is used. These softeners have a good softening effect on various fibers in a small amount, but are known to give fibers a greasy finish, and a softener that improves the texture of clothing is desired.

In order to solve this drawback, Japanese Patent Publication No.
No. 37387 discloses a method in which a dialkyl quaternary ammonium compound and an anionic surfactant are used in combination. Japanese Patent Application Laid-Open No. 9-111660 discloses a softening component having two or more cationic groups in one molecule. Softener compositions combining anionic surfactants are disclosed. However, these techniques are not compatible with the flexibility and texture of the finished garment.

[0004] On the other hand, it is already known to use mono-long chain alkyl tertiary amines as softeners. JP 7
JP-A-268773 discloses a softener composition using a mono-long-chain alkyl tertiary amine having an ester group or an amide group and a specific ester compound. JP-A-5-132865 discloses a softener composition in which an amine compound and an anionic surfactant are supported on a substrate without being mixed. However, even the compositions disclosed therein cannot improve the oily texture.

[0005] Accordingly, an object of the present invention is to provide a softener composition having a high softening effect and imparting a favorable texture to clothing.

[0006]

The present invention provides (a) a tertiary amine represented by the following general formula (1) or a salt thereof and a quaternary ammonium salt represented by the following general formula (2). one or more compounds [hereinafter, (a) referred to as component] 3 to 40 wt%, and an alkyl group or alkenyl group having 16 to 36 carbon atoms in the (b) molecule, -SO ₃ M group and / or -OSO ₃ M group [M: counter ion] and an anionic surfactant having an [hereinafter, (b) that component] of 1 to 30 wt%, and (c) a water containing 30 to 95 wt%, (a)
/ (B) relates to a softener composition having a molar ratio of 9/1 to 4/6.

[0007]

Embedded image

Wherein R ¹ and R ⁵ are each independently an alkyl or alkenyl group having 9 to 23 carbon atoms;
R ² and R ⁶ are each independently an alkylene group having 1 to 6 carbon atoms. R ³ , R ⁴ , R ⁷ , R ⁸ , and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. A and B are each independently -COO-,
A group selected from -OCO-, -CONH- and -NHCO-, wherein n is 0 or 1; Y ^- is an anion. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION <Component (a)> In the general formula (1), R ¹ has 11 to 21 carbon atoms and further has 15 to 2 carbon atoms.
One alkyl or alkenyl group is preferred. R ² is
An alkylene group having 1 to 4 carbon atoms is preferred. R ³ and R ⁴ are
Each independently is preferably a methyl group, an ethyl group or a hydroxyethyl group. n is preferably 1. Particularly preferred compounds of the general formula (1) include the compounds of the following general formulas (1-1) and (1-2).

[0010]

Embedded image

Wherein R ¹⁰ is an alkyl or alkenyl group having 15 to 20 carbon atoms, and m is 2 or 3.
R ¹¹ and R ¹² are each independently a methyl group, an ethyl group or a hydroxyethyl group, preferably a methyl group or an ethyl group].

The compounds of the general formulas (1-1) and (1-2) can be prepared by reacting a fatty acid represented by R ¹⁰ -COOH or an alkyl (C1-5) ester or acid chloride thereof with N-hydroxyalkyl It can be easily synthesized by reacting -N, N-dialkylamine or N-aminoalkyl-N, N-dialkylamine, and R ¹⁰ may have a single alkyl chain length or a mixed alkyl chain length. .
In particular, it is preferable that R ¹⁰ is a single alkyl group having 17 carbon atoms, or R ¹⁰ is a mixed alkyl group having 15 carbon atoms and 17 carbon atoms. / 30 to 0/100, preferably 50/50 to
0/100 is preferred from the viewpoint of the softening effect and the improvement of the texture.

The compound of the general formula (1) may be a salt neutralized with an inorganic or organic acid. When used as a salt, a compound obtained by neutralizing an amino group with an acid agent before blending in the softener composition can be used. After blending the compound of the general formula (1) in the softener composition, The amino group may be neutralized with an acid agent. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, hydroxycarboxylic acid, a fatty acid having 1 to 12 carbon atoms or an alkyl sulfuric acid having 1 to 3 carbon atoms is preferable, and hydrochloric acid, sulfuric acid, and glycolic acid are particularly preferable. . These acid agents used for neutralization may be used alone or in combination.

In the compound of the general formula (2), R ⁵
Is preferably an alkyl group or alkenyl group having 11 to 21 carbon atoms, more preferably 15 to 21 carbon atoms. R ⁶ has a carbon number of 1 to
An alkylene group of 4 is preferred. R ⁷ , R ⁸ and R ⁹ are each independently preferably a methyl group, an ethyl group or a hydroxyethyl group. As a particularly preferred compound as the compound of the general formula (2), the following general formula (2-1) or (2-2)
The compound of.

[0015]

Embedded image

Wherein R ¹³ is an alkyl or alkenyl group having 15 to 20 carbon atoms, and 1 is 2 or 3. R
¹⁴ , R ¹⁵ and R ¹⁶ are each independently a methyl group, an ethyl group or a hydroxyethyl group, preferably a methyl group or an ethyl group. Z ⁻ is substituted with an anion, preferably a halogen ion, a sulfate ion, a phosphate ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. At least one selected from aryl sulfonic acid ions which may be used. The compounds of the general formulas (2-1) and (2-2) are represented by R
Reacting a fatty acid represented by ^13- COOH or its alkyl (C1-5) ester or acid chloride with N-hydroxyalkyl-N, N-dialkylamine or N-aminoalkyl-N, N-dialkylamine And can be easily synthesized by quaternizing with an alkylating agent such as an alkyl halide, dialkyl sulfate, or alkylene oxide. N, N, N-trialkyl-N-hydroxyalkyl quaternary ammonium salts;
N, can be synthesized by reaction with N- trialkyl -N- aminoalkyl quaternary ammonium salt and a fatty acid or the alkyl represented by R ¹³ -COOH (1 to 5 carbon atoms) ester or acid chloride . R ¹³ may have a single alkyl chain length or a mixed alkyl chain length. Especially R
¹³ is a single alkyl group having 17 carbon atoms, or R
^It is preferable that ¹³ is a mixed alkyl group having 15 carbon atoms and 17 carbon atoms, and the ratio of 15 carbon atoms / 17 carbon atoms is 7 by weight.
0/30 to 0/100, preferably 50/50 to 0/1
00 is preferred from the viewpoint of softening effect and improvement of texture.

The component (a) of the present invention is preferably used in combination with the compound of the general formula (1) or the compound of the general formula (1) and the compound of the general formula (2) from the viewpoint of a softening effect. The weight ratio of the compound of the general formula (1) / the compound of the general formula (2) is preferably from 1/100 to 100/1.

<Component (b)> The component (b) of the present invention comprises an alkyl or alkenyl group having 16 to 36, preferably 16 to 24, particularly preferably 16 to 20 carbon atoms in the molecule;
-SO ₃ M group and / or -OSO ₃ M group [M: counter ion]
Anionic surfactant having the above-mentioned carbon number, specifically, alkylbenzene sulfonic acid, alkyl (or alkenyl) sulfuric acid, polyoxyalkylene alkyl (or alkenyl) ether sulfuric acid, olefin sulfonic acid, alkane sulfonic acid, α -Sulfo fatty acids, α-sulfofatty acid esters and salts thereof are preferred. Among these, alkyl (or alkenyl) sulfate having an alkyl or alkenyl group having 16 to 20 carbon atoms, an alkyl or alkenyl group having 16 to 20 carbon atoms, and ethylene oxide (hereinafter referred to as EO) average addition The number of moles is 1 to 6, preferably 1 to 4, particularly preferably 1 to 3.
Polyoxyethylene alkyl (or alkenyl)
It is preferable to mix one or more selected from ether sulfuric acid and salts thereof. As the salt, a sodium salt,
Potassium salts, ammonium salts and alkanolamine salts are good from the viewpoint of storage stability.

[Softener composition] The softener composition of the present invention contains the component (a) in an amount of 3 to 40% by weight, preferably 5 to 40% by weight, particularly preferably 5 to 35% by weight, and (b) The component is contained in an amount of 1 to 30% by weight, preferably 2 to 25% by weight, particularly preferably 3 to 20% by weight. Also, (a) /
(B) is a molar ratio of 9/1 to 4/6, and further 9/1 to 5 /
5, especially 8.5 / 1.5 to 6.5 / 3.5 is desirable from the viewpoint of flexibility and texture. further,
It is preferable to contain the component (a) and the component (b) in a total amount of 5 to 60% by weight, particularly 10 to 50% by weight, from the viewpoint of the softening effect and the storage stability.

The softener composition of the present invention is in the form of an aqueous solution obtained by diluting the components (a) and (b) with water as the component (c), and the water used is distilled water or ion-exchanged water. Is preferred. In terms of storage stability, water is present in the composition in an amount of from 30 to
95% by weight, preferably 50 to 85% by weight.

Furthermore, the composition of the present invention can be adjusted to have a pH of 20 to 8.5, more preferably 1 to 7, especially 2 to 5, at 20 ° C., from the viewpoint of storage stability. It is preferable in terms of texture and texture.

In the present invention, in addition to the components (a) to (c), the component (d) has 12 to 36 carbon atoms, preferably 14 carbon atoms.
It is preferable from the viewpoint of the softening effect and the improvement of the feeling that it contains a saturated or unsaturated fatty acid or a salt thereof of from 24 to 24, more preferably from 14 to 20. Specifically, it is lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, or a mixture thereof. In particular, at least one selected from palmitic acid, stearic acid, and oleic acid is preferable. Further, fatty acids having an alkyl composition derived from palm oil and tallow are also preferable. When a salt is used, a sodium salt, a potassium salt, a magnesium salt, and an alkanolamine salt are preferable.
The potassium salt is good. The above fatty acids or salts thereof (d)
Is contained in the composition in an amount of 0.01 to 5% by weight, particularly 0.3% by weight.
~ 3% by weight is preferred. The component (d) / component (a) is 1/100 to 1/2 by weight, preferably 1/50 to 1/2.
1/5 is favorable from the viewpoint of the softening effect.

In the present invention, from the viewpoint of storage stability, the above (a)
It is preferable to add a nonionic surfactant as the component (e) in addition to the components (c) to (c). As the nonionic surfactant, a polyoxyethylene alkyl ether having an alkyl group or an alkenyl group having 8 to 20 carbon atoms is preferable, and a nonionic surfactant represented by the following general formula (3) is particularly preferable. R ¹⁷ -T-[(R ¹⁸ O) _p -H] _q (3) [wherein R ¹⁷ has 10 to 18 carbon atoms, preferably 12 to 12 carbon atoms.
And R ¹⁸ is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. p represents a number of 2 to 100, preferably 5 to 80, particularly preferably 10 to 60. T is -O-, -CO
Q is 1 when T is -O-, and q is 2 when T is -CON- or -N-. ].

Specific examples of the compound of the general formula (3) include the following compounds. During ^{_{R 17 -O- (C 2 H 4}} O) r -H [wherein, R ¹⁷ have the same meanings as defined above. r is a number of 8 to 100, preferably 10 to 60. ] ^{_{R 17 -O- (C 2 H 4}} O) r - in _{(C 3 H 6 O) t} -H [wherein, R ¹⁷ have the same meanings as defined above. s and t are each independently a number of 2 to 40, preferably 5 to 40;
And propylene oxide may be a random or block adduct. ]

[0025]

Embedded image

From the viewpoint of stability, the amount of the nonionic surfactant is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight in the composition. In addition, from the viewpoint of texture and storage stability,
(E) component / [(a) component + (b) component] is 1 in weight ratio.
/ 100 to 1/2, more preferably 1/50 to 1/2, especially 1/1
0 to 2/5 is good.

In the present invention, further from the viewpoint of storage stability,
As the component (f), an ester compound of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol is added to the composition in an amount of 0.1 to 10%.
It is preferable to add 1 to 10% by weight, particularly 0.5 to 5% by weight. As the ester compound, triglyceride, diglyceride, monoglyceride and pentaerythritol mono, di, triester and sorbitan ester are preferable.

The softener composition of the present invention may contain an inorganic salt as the component (g). As the inorganic salt, sodium chloride is preferred from the viewpoint of storage stability, and 0 to 1000 ppm, preferably 10 to 500 ppm in the composition.
It is good to add. However, surfactants such as fatty acid salts include sodium salts and potassium salts, but the inorganic salts mixed into the composition by use of such surfactants are not limited to the above.

Further, the softener composition of the present invention can contain a solvent as the component (h). As the solvent,
It is preferable from the viewpoint of storage stability to mix a solvent component selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and polyoxyethylene phenyl ether. These solvent components are preferably incorporated in the composition in an amount of 0 to 20% by weight, particularly 0.5 to 10% by weight. When ethanol is used, it is desirable to use polyoxyethylene alkyl ether sulfate-modified ethanol or 8-acetylated sucrose-modified ethanol.

The softener composition of the present invention may contain a conventionally known antioxidant in order to improve the color and odor after storage. As antioxidants, aminocarboxylic acids represented by ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid, etc., inorganic phosphorus compounds represented by tripolyphosphate, pyrophosphate, 1-hydroxyethane-1,1-diphosphonate, Polyphosphonic acids,
Organic phosphoric acids represented by phytic acid, 2,6-di-t
tert-butyl-4-methylphenol and 2 (3)-
Examples thereof include butyl-4-oxyanisole and the like, and these may be added as an acid or a salt. These antioxidants are
In the softener composition of the present invention, 0.1 to component (a) is used.
It is blended in the range of 1000 ppm.

The softener composition of the present invention contains silicones and fragrances (particularly preferably those represented by components (c) and (d) described in JP-A-8-11387) which are usually added to a fiber treatment agent. Or a combination of components such as pigments.

The method for producing the softener composition of the present invention is as follows. Component (e), component (g) and component (h) are dissolved in component (c) water, if necessary, at 40 to 70 ° C.
Preferably, the temperature is raised to 45 ° C. to 65 ° C. and then (a)
Component, component (b), and if necessary, component (d) and component (f)
A method of adding the components, stirring and mixing, adjusting the pH to a predetermined value with an acid agent, cooling, and then adding other components is preferable from the viewpoint of storage stability.

[0033]

EXAMPLES Synthesis of Synthesis Example 1 (a-1) A mixed fatty acid obtained by mixing palmitic acid / stearic acid at a weight ratio of 50/50 and N-hydroxyethyl-N, N-
By the dehydration esterification reaction with dimethylamine, (a-
1) was synthesized. That is, N-hydroxyethyl-
132 g of N, N-dimethylamine, 200 palmitic acid
g and 200 g of stearic acid were placed in a four-necked flask equipped with a stirrer, thermometer, and dehydration tube, and the temperature was raised to 150 ° C.
The mixture was heated and stirred at that temperature for 4 hours while distilling off the water produced. The temperature was further raised to 180 ° C., and heating and stirring were continued for 10 hours while dropping 66 g of 2-dimethylaminoethanol. Thereafter, the mixture was cooled to 120 ° C. and unreacted amine was distilled off under reduced pressure to obtain 473 g of a desired 2-dimethylaminoethanol fatty acid ester.

Synthesis Example 2 Synthesis of (a-2) (a) was obtained by demethanolamidation of methyl stearate with N, N-dimethyl-1,3-propanediamine.
-2) was synthesized. That is, N, N-dimethyl-1,
161 g of 3-propanediamine and methyl stearate 4
48 g was put into a four-necked flask equipped with a stirrer, a thermometer and a dehydrating tube, and the temperature was raised to 180 ° C. The mixture was heated and stirred at that temperature for about 5 hours while distilling off the methanol produced. Thereafter, the mixture was cooled to 120 ° C., and unreacted amine was distilled off under reduced pressure to obtain 545 g of the target N, N-dimethyl-N′-stearoyl-1,3-propanediamine.

Synthesis of Synthesis Example 3 (a-3) Synthesis was performed using (a-1) produced in Synthesis Example 1 above and methyl chloride. That is, 100 g of (a-1) and 300 g of isopropanol were charged into an autoclave,
After the replacement with nitrogen, the temperature was raised to 100 ° C. with stirring. Thereafter, 18 g of methyl chloride was injected by an injection pump and reacted for 3 hours. After cooling, isopropanol was distilled off under reduced pressure to obtain the desired N-alkanoyloxyethyl-N, N, N-trimethylammonium chloride.

Synthesis of Synthesis Example 4 (a-4) In the same manner as in Synthesis Example 3 using (a-2) produced in Synthesis Example 2 and methyl chloride, the desired N-alkanoylaminopropyl-N, N, N-trimethylammonium chloride was obtained.

<Ingredients> The ingredients used in the examples are shown below. (A-1): 2-dimethylaminoethanol fatty acid ester obtained in Synthesis Example 1 (a-2): N, N-dimethyl-N′- obtained in Synthesis Example 2
Stearoyl-1,3-propanediamine (a-3): N-alkanoyloxyethyl-N, N, N-trimethylammonium chloride obtained in Synthesis Example 3 (a-4): N-alkanoyl obtained in Synthesis Example 4 Aminopropyl-N, N, N-trimethylammonium chloride (a'-1): N, N-distearoyloxyxyethyl-N, N-dimethylammonium chloride (b-1): Sodium stearyl sulfate (b-2) : Polyoxyethylene cured tallow composition sodium alkyl sulfate (EO average addition mole 2.3, cured tallow composition has a weight ratio of palmityl group / stearyl group of 40/60) (b'-1): alkyl (carbon number 12-14) Sodium benzenesulfonate (b'-2): sodium myristyl sulfate (d-1): stearic acid (e-1) 21 moles of EO added to saturated alcohol having 12 carbon atoms on average (e-2): 20 moles of EO added to diethanolamide of lauric acid on average (f-1): Exel 150 [monostearic acid, The
Triglyceride mixture (mono: di: tri = 60: 35:
5) Kao Corporation] (g-1): sodium chloride (h-1): ethylene glycol (i-1): silicone (manufactured by GE Toshiba Silicone)
TSA730). (I-2): Dye (Acid Blue 9) (i-3): Fragrance [Hexylcinnamic aldehyde (18), Neroline Yarala (4), Tricyclodecenyl acetate (4), Benzyl acetate (10), Musk ketone (5), anisyl acetone (2), sandal mysole core (2), aldehyde C14 peach (1), linalool (18), dihydroxymyrcenol (8), borneol (4), cedrol (4), mugol ( 5), a mixture of benzyl alcohol (5) and dipropylene glycol (10): the weight in parentheses is the weight% in the fragrance].

Example 1 A softener composition shown in Table 1 was prepared using the above components.
Five bath towels (100% cotton) were washed with a washing machine using a commercially available weak alkaline detergent (Kao Corporation Attack) (Toshiba 2-tub washing machine VH-360S1, detergent concentration of 0.1%).
0667% by weight, use 30L of tap water, water temperature 20 ° C, 10
Minutes). After that, the washing liquid is drained, and after dehydration for 3 minutes, 30 L
Of tap water and rinsed for 5 minutes, and drained for 3 minutes. Thereafter, 30 L of tap water was again injected, and then 7 ml of the softener composition shown in Table 1 was added thereto, followed by stirring for 5 minutes. Then, it dehydrated and air-dried.

(Method for Preparing Softener Composition) The components (e), (g) and (h) were dissolved in water and heated to 60 ° C. When the temperature reaches 60 ° C., the components (a), (b), (d) and (f) are stirred with a homomixer.
The components were added and adjusted to a predetermined pH with a 35% aqueous hydrochloric acid solution and a 48% aqueous sodium hydroxide solution, and then cooled to room temperature.
The remaining component (i) was added. In the pH range shown in Table 1, almost all of the components (a-1) and (a-2) exist in the composition in a hydrochloride state.

(Evaluation of Flexibility) The treated clothing was judged by 10 panelists (10 males in their 30s) according to the following criteria, and the average score was obtained. ○: Average score of 0 or more and less than 1
Tables 1 and 2 were determined as △ and 1.5 or more as x and less than 1.5, respectively.
It was shown to. Very soft finished ... 0 Soft finished ... 1 Slightly soft finished ... 2 Not soft finished ... 3.

(Evaluation of texture) The texture is oily and refreshing. …… 0 Slightly oily and light texture …… 1 Slightly oily texture …… 2 Oily texture …… 3

[0042]

[Table 1]

In Table 1, (a) of Formulation Examples 1-9 to 1-11
/ (B) molar ratio is (a'-1), (b'-1),
(B′-2) was defined as the component (a) or the component (b).

[0044]

[Table 2]

In Table 2, (a) /
(B) The molar ratio is (a'-1), (b'-1), (b '
-2) was used as the component (a) or the component (b).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideji Takata 1334 Minato, Wakayama-shi, Wakayama Prefecture Kao Research Laboratory F-term (reference) 4L033 AC02 BA28 BA45 BA53 BA71 BA85

Claims (1)

[Claims] (A) one or more compounds selected from a tertiary amine represented by the following general formula (1) or a salt thereof and a quaternary ammonium salt represented by the following general formula (2): 40 wt%, (b) an alkyl or alkenyl group of 16 to 36 carbon atoms in the molecule, -SO ₃ M group and / or -OSO ₃ M group [M: counter ion] and an anionic surfactant having a From 1 to 30% by weight, and (c) water from 30 to 9%.
5% by weight, and (a) / (b) is in a molar ratio of 9/1 to 4
/ 6. Embedded image Wherein R ¹ and R ⁵ are each independently an alkyl or alkenyl group having 9 to 23 carbon atoms, and R ² and R ⁶ are each independently an alkylene group having 1 to 6 carbon atoms.
R ³ , R ⁴ , R ⁷ , R ⁸ , and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group.
A and B are each independently -COO-, -OCO-,
A group selected from -CONH- and -NHCO-,
n is 0 or 1. Y ^- is an anion. ]