JPH09111658A - Concentrated softener composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a concentrated softener composition used for clothes, containing a specific surfactant, an alkyl quaternary ammonium compound and an organic polybasic acid in a specified ratio, giving soft and comfortable touches to the clothes, and excellent in antistaticity, absorbability, dispersive solubility and pH stability. SOLUTION: This concentrated softener composition comprises (A) 10-30wt.% of a composition containing two or more mater-insoluble quaternary ammonium cation surfactants selected from compounds of formulas I-IV (R1 is a 8-22C alkyl, a 8-22C alkenyl; R2 is a 1-4C alkyl, a hydroxyethyl, etc.; X is methylsulfate), (B) 0.2-10wt.% of a single long chain alkyl quaternary ammonium compound of formula V (R3 is a 1-30C (un)saturated hydrocarbon; R4 -R6 are each methyl, a 1-4C hydroxyalkyl; X<-> is an anion), and (C) 0.01-5wt.% of one or more low mol.wt. organic polybasic acids selected from the group consisting of ethylenediaminetetraacetoacetic acid, nitrilotriacetoacetic acid and kojic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a concentrated type softener composition for clothes.

[0002]

2. Description of the Related Art Clothes give a rough and strong feeling as the fiber treatment agent comes off as they are repeatedly worn and washed, or the fibers themselves become fluffed due to curing due to deterioration of the fibers themselves. Therefore, recently, many homes use a large amount of a fabric softener that imparts flexibility to the fiber. The function of the fabric softener is to provide a soft and fluffy texture or feel (ie, softness) when clothing or the like comes into contact with the skin.

[0003] At present, most commercially available textile softeners are di (hardened tallow alkyl) dimethyl, a cationic surfactant having a long alkyl chain of 1-2 in one surfactant molecule. A softener containing ammonium as a main component, and thus a softener containing a quaternary ammonium salt as a main component, is hardly soluble in water, and is usually produced in the form of a 3 to 6% by weight aqueous dispersion or suspension. I have. This quaternary ammonium salt can impart a good softening effect to various fibers in a small amount.

[0004] The softening effect is caused by a decrease in the coefficient of friction of the fiber surface due to the lubricating effect of the lipophilic site in the base molecule adsorbed on the fiber surface. Seems to have inevitable lipophilic properties. However, this lipophilicity has a drawback that it makes treated clothes waterproof and lowers the absorbability, and particularly when the concentration of the soft base is high, the absorbency is significantly lowered and it is difficult to concentrate.

[0005] From such a viewpoint, it has been necessary to study a soft base capable of improving the absorbability. On the other hand, as the number of garments using the softener increases, distribution costs and packaging costs for the softener must be reduced, and storage space at homes and retail stores must be reduced. The need for concentrated clothing-type fabric softeners, which are aqueous dispersions, has emerged.

[0006] Dioleyldimethyl quaternary ammonium salts having an unsaturated alkyl group are known as one of the flexible bases having excellent absorbency, but there is a limit in improving the absorbency and concentration. Was. In this regard, JP-A-2-11248
No. 1 discloses that if a finely dispersed state is obtained by using silicon in combination with dioleyl quaternary ammonium, the absorbability is increased without damaging the flexibility. It is stated that it can be significantly improved.

However, when the concentration of the soft base is 6% by weight or more, the viscosity of the dispersion of dioleyldimethyl quaternary ammonium salt significantly increases, causing problems in handling and use. Product value will be lost. Conventionally, in order to produce such a high-concentration softener, (1) a method of adding a water-soluble cationic surfactant,
(2) a method of adding higher alcohol and ethylene oxide of alkylphenol, (3) a method of adding urea, ethylene glycol and propylene glycol,
(4) A method of adding a water-soluble inorganic electrolyte is known.

However, in the cases (1) to (3),
Since the degree of concentration is not sufficient and the viscosity increases with time, a satisfactory effect cannot be obtained. In the case of the above (4), although the effect is that the initial viscosity is low, the effect of suppressing the viscosity that increases with time is low. Furthermore, when a large amount of salt is added, the aqueous dispersion tends to separate easily, and a satisfactory concentrated type fabric softener cannot be obtained.

Japanese Patent Application Laid-Open No. 1-292172 discloses a softening agent composition for improving softness and absorbability, which comprises 6 to 50% by weight of an amidoamine or imidazoline type cationic softening agent. Ionic surfactant 0.0
There is disclosed a softener composition containing 0.05 to 10% by weight, and 0.05 to 10% by weight of a water-soluble polymer obtained by adding a lower alkylene oxide to a compound containing at least one nitrogen atom. .

JP-A-2-47363 discloses that a quaternary ammonium salt having one or more alkyl or alkenyl groups is contained in an amount of 3 to 20% by weight and a molecular weight of 200 having a skeleton represented by the following formula (I). ~ 3,000 compounds 0.00
A fabric softener composition containing 1 to 0.1% by weight and 0.3 to 2.0% by weight of a nonionic surfactant having a polyoxyalkylene group is disclosed.

[0011]

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Japanese Unexamined Patent Publication (Kokai) No. 2-112482 discloses a softener composition containing a dioleyl type quaternary ammonium salt and dimethylpolysiloxane or a modified product thereof as essential components. JP-A-2-139480 discloses that a dialkyl quaternary ammonium salt, an imidazoline type and an ester ammonium are contained as one or more kinds of essential components, and a dipolysiloxane or a modified product thereof is added to the compound. Softener compositions containing 0.5 to 5% by weight are disclosed.

[0013] However, the conventional softener composition seems to be improved to some extent in terms of softness and absorbability, but does not reach a satisfactory level in terms of the degree of concentration or long-term stability. . Therefore, an object of the present invention is to provide various fibers with excellent flexibility and absorptivity, and particularly excellent in dispersibility and solubility, and even after the preparation,
It is an object of the present invention to provide a concentrated softening composition for clothing, which hardly increases the viscosity of the composition and has good pH stability.

[0014]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have evenly provided excellent flexibility and absorbability imparting performance for various fibers, particularly, excellent dispersion solubility, pH and pH. As a result of intensive studies to develop a concentrated type softening composition for clothing with excellent viscosity stability, a general quaternary ammonium salt cationic surfactant was added to the compounding of a high concentration softening base. A specific dispersant and an organic polyacid are used in combination with a composition containing two or more kinds to adjust the pH of the composition to 5.
By making the following adjustments, the initial physical properties are improved, there is almost no increase in viscosity over time, and it is possible to obtain an excellent softener composition having excellent flexibility and absorbability imparting performance for various fibers. They have discovered and completed the concentrated clothing softener composition of the present invention.

That is, the concentrated softener composition for clothing according to the present invention is selected from (a) compounds represented by the following formulas (1), (2), (3) and (4). 2 or more water-insoluble 4
Composition 1 containing quaternary ammonium cationic surfactant
0-30% by weight,

[0016]

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(In the formula, R ₁ represents an alkyl group or an alkenyl group having C _{8 to} C ₂₂ and R ₂ represents C ₁
To C ₄ alkyl group, hydroxyethyl group or hydroxypropyl group, and X represents a methylsulfate group) (b) Single long-chain alkyl 4 represented by the following formula (5)
0.2 to 10% by weight of a quaternary ammonium compound;

[0018]

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Wherein R ₃ is a linear or branched saturated and / or unsaturated hydrocarbon having ₁ to ₃₀ carbon atoms, or a group containing an amide group or an ester group in an alkyl group. Wherein R ₄ , R ₅ and R ₆ are the same or different from a methyl group or a hydroxyalkyl group having ₁ to ₄ carbon atoms, and X ⁻ is capable of adding water solubility or water dispersibility. (Representing an anion) (c) 0.01 to 5% by weight of one or more low-molecular-weight organic polyhydric acids selected from the group consisting of ethylenediaminetetraacetate, nitrilotriacetate and citric acid; It is characterized by containing.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The quaternary ammonium cationic surfactant used in the present invention is at least two kinds selected from the compounds represented by the formulas (1), (2), (3) and (4), and is flexible. Used as a base. This quaternary ammonium cationic surfactant is contained in a proportion of 10 to 30% by weight, preferably 12 to 25% by weight, based on the whole softener composition.

In the above formulas (1) to (4), X ⁻
It is not particularly limited as long as it is an anion capable of adding water solubility or water dispersibility, and examples thereof include halides such as chlorides, bromides, and iodides, as well as sulfates, methyl sulfates, and ethyl sulfates. , One or more of these are used. Among the above-mentioned anions, methyl sulfate is particularly desirable.

Specific examples of the quaternary ammonium cationic surfactant represented by the above formula (1) are not particularly limited. For example, di (hydrogenated tallow) dimethyl ammonium chloride, di (hydrogenated tallow) Dimethyl ammonium methyl sulfate, distearyl dimethyl ammonium chloride and the like. Specific examples of the quaternary ammonium cationic surfactant represented by the formula (2) are not particularly limited, and include, for example, methyl bis (tallowamidoethyl) -2-hydroxyethylammonium methyl sulfate, methylbis (tallowamidoethyl) )
-2-hydroxypropyl ammonium methyl sulfate, methyl bis (oleylamidoethyl) -2-hydroxyethyl ammonium methyl sulfate, and the like.

Specific examples of the quaternary ammonium cationic surfactant represented by the formula (3) are not particularly limited. For example, methyl bis (ethyl tallowate) -2-
Hydroxyethylammonium methyl sulfate, methyl bis (ethyl palmitate) -2-hydroxyethylammonium methyl sulfate and the like can be mentioned. Specific examples of the quaternary ammonium cationic surfactant represented by the formula (4) are not particularly limited, but include, for example, methyl-1-tallowamidoethyl-2-hydroxyethylammonium methyl sulfate, cocoimidazoline betaine , 2-coco-1- (ethyl-β-oxypropionic acid) imidazoline, cocoampopropionate, and the like.

The alkyl quaternary ammonium compound, which is one of the essential components of the softener composition of the present invention, has the formula (5)
Which is used as a dispersant. This alkyl quaternary ammonium compound is used in an amount of 0.2 to 10% by weight, preferably 0.5 to 10% by weight, based on the entire softener composition.
It is contained at a ratio of 5% by weight. R ₃ in the formula (5) is as described above, and the number of carbon atoms is preferably C 3
₁ -C _30, and more preferably a C ₁ -C _20.

Specific examples of the alkyl quaternary ammonium compound represented by the above formula (5) include, but are not limited to, tallow trimethylammonium chloride. The alkyl quaternary ammonium compound is
One type may be used alone, or two or more types may be used in appropriate combination. The low-molecular-weight organic polyacid, which is another essential component of the softener composition of the present invention, is one selected from the group consisting of ethylenediaminetetraacetate, nitrilotriacetate and citric acid (citric acid). As described above, the content is 0.01 to 5% by weight, preferably 0.01 to 3% by weight, based on the whole softener composition.

The pH of the softener composition of the present invention is preferably maintained at 5 or less. The softener composition of the present invention, if necessary, as an optional ingredient, a fragrance, an organic solvent, a dye, a pigment, an opacifier, a bactericide, an antifoaming agent, a corrosion inhibitor,
It may contain one or more additives selected from the group consisting of preservatives, protein extracts, and ironing aids such as silicone. When these components are added, they are each added in such an amount that the proportion thereof is 15% by weight or less, preferably 10% by weight or less, based on the whole composition of the present invention.

The remainder of the softener composition is not particularly limited, but may be, for example, distilled water, deionized water, tap water, or the like. The organic solvent that can be added as the optional component is not particularly limited, and includes, for example, propylene glycol, ethylene glycol, diethylene glycol, and the like. One or more of these can be selected and used.

The protein extract that can be added as the optional component is not particularly limited. For example, a protein extract having an average molecular weight of 500 to 2,000 obtained by hydrolyzing a protein such as keratin, collagen, casein or soybean protein can be used. One or more of the polypeptides or derivatives thereof may be used. These can impart excellent coating performance to animal natural fibers such as wool and silk, and are easily used since they are commonly used.

The silicon that can be added as the optional component is not particularly limited, but linear polydialkyl or alkylallyl siloxane (wherein alkyl contains 1 to 4 carbon atoms) is particularly desirable. The siloxane can be replaced with an amide or amine. If the siloxane is replaced with an amine, the amine group can also be quaternized. One or more types of silicon can be selected and used.

The fragrances, dyes, pigments, opacifiers, bactericides, defoamers, corrosion inhibitors and preservatives which can be added as optional components are commonly used in conventional clothing softener compositions. One or more may be appropriately selected and used.
Various conventional fabric softeners include isopropyl alcohol,
It is generally provided in the form of a solution or paste containing ethanol or other solvent substances. Therefore,
Such minimal amounts of isopropyl alcohol, ethanol or other solvent materials can be present in the composition, but do not affect the basic properties of the composition, ie, softness and physical properties.

The method for preparing the softener composition of the present invention is not particularly limited.
To 5 are continuously performed. Step 1: Two or more quaternary ammonium cation surfactants represented by the above formulas (1) to (4) are weighed simultaneously, and the quaternary ammonium cation is heated at a temperature of 60 to 65 ° C. in a temperature-controllable preliminary water tank. A molten mixture is prepared by melting the ionic surfactant.

Step 2: Measure the water at a temperature of 60 to 65 ° C. into the mixing tank, and add the molten mixture obtained in Step 1 while stirring appropriately. Step 3: As the dispersant, a part of the alkyl quaternary ammonium compound represented by the formula (5) is added. Step 4: After lowering the temperature of the blending tank to 35 ° C. or less, a necessary amount of an organic solvent is added and stirred.

Step 5: Inject the organic polyacid (and optionally further additives) and stir for 2-3 minutes,
Adding the remainder of the alkyl quaternary ammonium compound,
By stirring, a concentrated softener composition is obtained. The above method does not cause the gelation problem that is usually associated with the conventional method for producing a concentrated softener composition, and is, for example, 10 to 40.
A concentrated softener composition having a viscosity of about 0 cps can be obtained. The obtained concentrated softener composition has excellent stability characteristics, and therefore has no layer separation and is particularly excellent in dispersibility.

[0034]

EXAMPLES Hereinafter, the present invention will be described based on more specific examples and comparative examples, but the present invention is not limited to the following examples. Examples 1-4 and Comparative Examples 1-4 : According to the composition ratio (% by weight) shown in Table 1 below, by performing the following steps 1 to 5 continuously, each softener composition was prepared. Was performed by the method described below.

Step 1: A quaternary ammonium cationic surfactant is weighed and placed in a temperature-adjustable pre-water bath at 60 to 65 ° C.
A molten mixture is prepared by melting the quaternary ammonium cationic surfactant at a temperature of. Step 2: Measure the water at a temperature of 60 to 65 ° C. into the mixing tank, and add the molten mixture obtained in Step 1 with appropriate stirring.

Step 3: A part of the alkyl quaternary ammonium compound is added as a dispersant. Step 4: After lowering the temperature of the blending tank to 35 ° C. or less, a necessary amount of an organic solvent is added and stirred. Step 5: Citric acid and other additives are injected, and after stirring for 2 to 3 minutes, the rest of the alkyl quaternary ammonium compound is added and stirred to obtain a concentrated softener composition.

Comparative Examples 1 to 4 Each softener composition was prepared in the same manner as in the example according to the composition ratio (% by weight) shown in Table 1 below, and each performance evaluation test was performed by the method described later. . In addition, Comparative Example 1 shows a composition ratio of a conventional softener composition, Comparative Examples 2 to 4 are cases where betaine, coconut diethanolamine or alkyl polyethoxylates were used as a dispersant instead of the alkyl quaternary ammonium compound. It is shown.

[0038]

[Table 1]

The annotations in Table 1 are as follows. * 1: Di (hydrogenated tallow) dimethyl ammonium chloride [Sherex Co., Ltd. Adogen 442 (Adogen)
442); Radio quote 6480 (Fad Co.)
ioquat 6480)], di (hydrogenated tallow) dimethyl ammonium methyl sulfate [Adogen 137] from Sherex Co., and distearyl dimethyl ammonium chloride [Adgen 137 from Sherex Co.] TA-101 (Adogen TA-101)].

* 2: Methylbis (tallow amidoethyl)-
2-hydroxyethylammonium methyl sulfate [Carsosoft T-90 (Loza Co.)
-90); Stepan Co.'s Akkosoft 501 (Acco
soft 501); Varisoft 222 from Sherex Co., methylbis (tallowamidoethyl) -2-hydroxypropylammonium methyl sulfate [Varisoft from Sherex Co.]
238 (Varisoft 238)], methyl bis (oleylamidoethyl) -2-hydroxyethylammonium methylsulfate (Akkosoft 780 from Stepan Co.)
(Accosoft 780); Varisoft 222LT from Sherex Co.].

* 3: Methylbis (ethyl tallowate) -2-
Hydroxyethylammonium methyl sulfate (Tetranyl L1 from Kao; Stepa
n Co.) Stepantex X 8403 (Stepantex X 8403)
And Stepantex VK-90)
Methyl bis (ethyl palmitate) -2-hydroxyethylammonium methyl sulfate [Tetranyl L5 from Kao; Dehyquart AU36 and Dehyquart AU36 from Henkel Co.]
AU46 (Dehyquart AU46)].

* 4: Methyl-1-tallowamidoethyl-2
-Hydroxyethylammonium methyl sulphate (Accosoft 801 from Stepan Co.)
801); Lonza Co.'s Cursosoft S-90 (Cars
osoft S-90); Varisoft 475 from Sherex Co.]. * 5: Tallow trimethylammonium chloride [Radioquat 647 from Fina Co.]
1)]; Sherex Co.'s Adgen 471 (Adog
en 471)].

* 6: Used in ordinary softener compositions for clothes. Performance Evaluation Test Evaluation tests of the performance (flexibility, absorbency) and dispersion stability of each of the softener compositions obtained in Examples and Comparative Examples obtained above were performed by the following methods. Table 2 shows the results.

1. Flexibility test Commercially available cotton towels (thick and thin), thin wide cotton cloth or polyester cloth are washed twice with a fully automatic washing machine at room temperature using a commercially available washing powder detergent, and at room temperature After rinsing with water, the test cloth was used. Then, at 25 ° C,
To 45 g of tap water, 10 g of a softener composition on a finished product basis was added to make a uniform solution. The test cloth was immersed in this so that the bath ratio was 20: 1, treated for 3 minutes, and dehydrated for 2 minutes. After drying the test cloth treated in this way with a fan,
A flexibility test was conducted by 10 well-trained panelists. The criteria were determined as follows.

4: Very soft. 3: Soft. 2: Slightly soft. 1: Same as before processing. 2. Absorbency test The wide cotton cloth treated with the above softener was cut into a size of 2 cm x 15 cm, dipped in a 0.01% solution of dye blue # 1 for 5 mm (25 ° C), and the height of water rising for 6 minutes. Was measured.

Assuming that the rate of increase of the softener-untreated cloth is 100,
Those that increased by 0 or more were regarded as good. 3. Normal Stability Test Viscosity Change For each softener composition, the viscosity immediately after production, the viscosity after storage for one month in a 40 ° C. incubator, and the viscosity after storage for one month at normal temperature were measured by Brookfield (Broofield).
kfield) Measured at 25 ° C. using a viscometer (unit: c)
ps).

Dispersibility and solubility For each softener composition, immediately after production, after storage at room temperature for one month, after storage at 40 ° C. for one month, low temperature (0 to 3)
C.) for one month, the dispersibility of the compositions in each case was checked as follows. After filling a 1-liter cylinder with tap water, 5 g of the softener composition was carefully poured into the top of the cylinder, and the state of dispersion was evaluated. The criteria were determined as follows.

4: Completely dispersed without any particles. 3: Fine particles are present and dispersed. 2: dispersed with small particles. 1: Dispersion is poor due to large particles. 0: Not dispersed

PH Measurement Using a pH meter, the pH of the composition in each case immediately after production and after storage for one month in a 45 ° C. incubator was adjusted to 25.
Measured in ° C. Refrigeration cycle The product was stored at -15 ° C for 1 day to freeze the product, and then the process of thawing at room temperature was repeated five times, and the physical properties were measured.

[0050]

[Table 2]

As shown in Table 2, it was confirmed that the softener composition according to the example was superior in performance and physical properties as compared with the softener composition according to the comparative example.

[0052]

As described above, the concentrated softener composition for garments of the present invention is three times more than the general softener composition.
Since it can be concentrated twice or more, excellent flexibility, antistatic property and absorptivity can be obtained even if the amount used is reduced to 1/3. Further, even when stored at a high temperature for a long time, there is almost no increase in viscosity, and the resilience after freezing is excellent and practical.
Further, the pH stability is excellent under any storage conditions, and the dispersion solubility is particularly excellent, so that the performance of the active ingredient is effectively exhibited when actually used for fiber treatment.

On the other hand, transportation costs and packaging costs are reduced by high concentration. In addition, since a mixer having ordinary stirring conditions can be manufactured by using a dispersing agent, a mixer having strong stirring performance is not required, so that considerable cost savings can be obtained in terms of equipment.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jinyuan Jong, 54, Daeun-dong, Daedeok-gu, Daejeon-gu, Republic of Korea 114-403 (72) Inventor, Ike Gan ▲ Yup ▼ Bon-dong, Daedeok-gu, Daejeon, Republic of Korea 284- 1 Jugong Apartment 202-506 (72) Inventor Kim Chang-ho 137-9, 1-dong, Shinkichi, Yeongdeungpo-gu, Seoul, Republic of Korea

Claims (7)

[Claims] (A) an interface of two or more water-insoluble quaternary ammonium cations selected from the compounds represented by the following formulas (1), (2), (3) and (4): From 10 to 30% by weight of a composition containing an activator; (In the formula, R ₁ represents an alkyl group or an alkenyl group having a carbon number of C _{8 to} C ₂₂ , R ₂ represents an alkyl group having a carbon number of C _{1 to} C _4, a hydroxyethyl group or a hydroxypropyl group, and X represents Represents a methylsulfate group) (b) Single long-chain alkyl 4 represented by the following formula (5)
0.2 to 10% by weight of a quaternary ammonium compound; (In the formula, R ₃ represents a linear or branched saturated and / or unsaturated hydrocarbon having ₁ to ₃₀ carbon atoms, or a group containing an amide group or an ester group in the alkyl group,
R ₄ , R ₅ and R ₆ represent a methyl group or a group which is the same as or different from a hydroxyalkyl group having ₁ to ₄ carbon atoms,
X ⁻ represents an anion capable of adding water solubility or water dispersibility) (c) One or more low molecular weight organic compounds selected from the group consisting of ethylenediaminetetraacetoic acid, nitrilotriacetic acid and oxalic acid. A concentrated type fabric softener composition comprising: 0.01 to 5% by weight of a polyvalent acid. 2. R ₃ in the above formula (5) is the number of carbon atoms C ₁
The concentrated softener composition for clothes according to claim 1, which has C ₂₀ to C ₂₀ . 3. The concentrated fabric softener composition according to claim 1, wherein X ⁻ in the formulas (1) to (4) is a halide. 4. The concentrated type according to claim 3, wherein X ⁻ in the formulas (1) to (4) is at least one selected from the group consisting of chloride, bromide and iodide. Clothing softener composition. 5. The method according to claim 1, wherein X ⁻ in the formulas (1) to (4) is at least one selected from the group consisting of sulfate, methyl sulfate and ethyl sulfate. Concentrated softener composition for clothes. 6. The concentrated fabric softener composition according to claim 5, wherein X ⁻ in the formulas (1) to (4) is methyl sulfate. 7. The concentrated fabric softener composition according to claim 1, which has a pH of 5 or less.