JPH10298867A - Softening agent composition at high concentration and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a composition, good in fluidity thereof in spite of a softening base without causing environmental problems contained at a high concentration, excellent not only in biodegradability but also in usability land useful especially as a concentrated type softening agent. SOLUTION: This softening agent composition at a high concentration is produced by compounding a sugaralcohol in an amount of 0.5-20 wt.% based on the whole composition in the softening agent composition at a high concentration containing a quaternary ammonium salt having hydrolyzable groups as a softening base at 10-30 wt.% concentration thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-concentration softener composition in which a soft base for imparting flexibility to fibers and clothing is blended in a high concentration, and a method for producing the same. The present invention relates to a low-viscosity, high-concentration softener composition whose rise is suppressed and a method for producing the same.

[0002]

2. Description of the Related Art
In general households, in order to impart flexibility and antistatic properties to textiles and clothing, a softening agent is added to the rinsing water during washing, and the softening agent contained in the rinsing water during the final rinsing is used. Such a softening agent is generally made of a di-long-chain alkyl di-short-chain alkyl quaternary ammonium salt as a softening base. However, the softener containing the di-long-chain alkyl-di-short-chain alkyl quaternary ammonium salt can impart a good softening effect and an antistatic effect to various kinds of clothing, but is drained together with the rinsing water. In this case, the biodegradability is likely to contribute to river pollution due to poor biodegradability.In recent years, as a softener without such defects, long-chain alkyl groups have been separated by ester groups or amide groups. Those containing a quaternary ammonium salt having such a hydrolyzable group as a softening base have attracted attention.

[0003] Recently, concentrated softeners having an increased soft base content have become mainstream due to demands for cost reduction during production and transportation, and usability of consumers. In the case of such a concentrated softener, since the base concentration is high, the viscosity becomes high due to the interaction between the softener particles and the like,
Its handling and usability have been problems. On the other hand, conventionally, as a method for reducing the viscosity of a softening agent, a method of adding an inorganic salt to an aqueous phase in the production process to reduce the viscosity is known, but in this method, the base concentration is reduced. If the value is increased, the amount of the inorganic salt must be increased. for that reason,
Not only does the composition cause a problem, but also affects the stability of the preparation, causing problems such as separation over time.

The present invention has been made in view of the above circumstances, and does not cause environmental problems such as river pollution, is reduced in viscosity without impairing its separation stability and the like, and is suitable as a concentrated softener. It is an object of the present invention to provide a high-concentration softener composition that can be used for a composition and a method for producing the same.

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that the hydration of an emulsion in which a sugar alcohol is highly blended with a quaternary ammonium salt. The structure of water can be made dense,
It has been found that the storage stability of the hydrolyzable group in the soft base during storage of the softener is not affected, and therefore, high-concentration softener using sugar alcohol as the soft base is a quaternary ammonium salt having a hydrolyzable group. It has been found that the viscosity can be reduced without impairing the stability and the like of the composition by blending the composition with the agent composition, and the present invention has been accomplished.

That is, the present invention relates to a fourth compound having a hydrolyzable group.
A high-concentration softener composition having a quaternary ammonium salt as a softening base and having a concentration of 10 to 30 wt%, wherein sugar alcohol is blended in an amount of 0.5 to 20 wt% based on the whole composition. A high-concentration softener composition and a method for producing the same are provided.

Hereinafter, the present invention will be described in more detail. The high-concentration softener composition of the present invention contains a quaternary ammonium salt having a hydrolyzable group at a high concentration as a softening base and increases its viscosity. Is suppressed by blending a sugar alcohol.

The type of the quaternary ammonium salt having a hydrolyzable group is not particularly limited as long as it is used as a softening agent of a softening agent. For example, it is represented by the following general formula (1). One or more selected from dilong-chain alkyl-type quaternary ammonium salts are suitably used.

[0009]

Embedded image (Wherein, R ¹ has 14 to 24 carbon atoms, preferably 14 carbon atoms)
To 18 alkyl groups or alkenyl groups, and R ² has 1 carbon atom.
4 to 24, preferably 14 to 18, alkyl or alkenyl groups, wherein at least one of R ¹ and R ² is —O
It is a compound which is divided by an ester group or amide group such as-, -CONH-, -COO-, or substituted with -OH or the like.
R ³ and R ⁴ are an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, respectively, and X is a halogen atom or a monoalkyl sulfate group. Here, in the case of the present invention, the ratio of saturation / unsaturation of the long-chain alkyl group in the above formula is not particularly limited.

As the quaternary ammonium salt, specifically, distearoyloxyethyldimethylammonium chloride, dioleoyloxyethyldimethylammonium chloride, dipalmitoyloxyethyldimethylammonium methylsulfate, distearoyloxyisopropyldimethylammonium chloride,
And di-long-chain alkyl ammonium salts such as dioleoyloxyisopropyldimethylammonium chloride and dioleoyloxybutyldimethylammonium chloride. Among these, dioleoyloxyethyldimethylammonium chloride and distearoyloxyethyldimethylammonium chloride The di-long chain (C ₁₄ -C ₁₈ ) alkyl diester type ammonium salt is more preferable.

The concentration of the ammonium salt in the composition of the present invention is 10 to 30% (% by weight, the same applies hereinafter), preferably 12 to 27%, more preferably 13 to 26%.
If the concentration of the ammonium salt is too low, it cannot be used as a concentrated softener, and if the concentration is too high, the viscosity reducing effect is reduced.

The sugar alcohol which is the viscosity reducing agent of the present invention is not particularly limited in its kind, and is, for example, sorbitol,
Talit, alit, mannitol, tetrit, erythrit, glucose, fructose, idit, galactit, pentit, xylit, hexit and the like can be mentioned, and these can be used alone or in an appropriate combination of two or more. Although it is possible, in the case of the present invention, among these, sorbitol is particularly preferably used.

The amount of the sugar alcohol is 0.5 to 20%, preferably 2 to 10%, more preferably 4 to 6%, based on the whole composition. If the amount is too small, the effect of reducing the viscosity cannot be obtained. If the amount is too large, no further effect can be obtained, which is uneconomical. The mixing ratio of the sugar alcohol to the quaternary ammonium salt is preferably 1 to 200%, more preferably 6 to 100%, particularly preferably 13 to 60% of the quaternary ammonium salt. If the blending ratio of alcohol is too large, no further blending effect can be obtained, which may be uneconomical,
If the mixing ratio of the sugar alcohol is too small, the viscosity reducing effect may not be obtained.

The softener composition of the present invention is intended to suppress the increase in viscosity of the composition due to the high content of the quaternary ammonium salt by blending the above-mentioned predetermined amount of sugar alcohol as described above. In the case of the softener composition of the invention,
When compared with a composition having the same composition except that the sugar alcohol is not blended, the blending amount of the sugar alcohol is usually 0.5 to 0.5% of the total composition, though depending on the combination of the quaternary ammonium salt and the sugar alcohol. As it increases to 20%,
The viscosity of the composition decreases from 1/8 to 1/65. The viscosity of the softener composition of the present invention varies depending on the type, blending amount, composition and the like of the quaternary ammonium salt. The viscosity of the composition at 25 ° C. is measured using a BL-type rotational viscometer and a rotor. Is generally 1,500 cP (centipoise) or less, particularly preferably 500 cP or less, when represented by the viscosity measured after rotating at 30 rpm for 20 seconds.

The softener composition of the present invention is a liquid composition containing the above-mentioned quaternary ammonium salt having a hydrolyzable group, which is a softening base, and the above-mentioned sugar alcohol, the state of which is particularly limited. However, it is usually prepared as a liquid such as an O / W emulsion or an aqueous dispersion of vesicles containing an oily component described below in a bilayer membrane structure of the quaternary ammonium salt. During the preparation of the composition of the present invention, in addition to the above essential components, various components which are usually compounded in a softener can be added. When a quaternary ammonium salt is used, depending on the pH of the composition, the base may be hydrolyzed during storage. Therefore, the pH of the composition is usually adjusted to pH 2 to 5 which is a region where the hydrolyzable group is stabilized. The composition of the present invention is preferably adjusted to the above pH. in this case,
As the acidic compound, for example, aqueous solutions of hydrochloric acid, sulfuric acid, citric acid, phosphoric acid and the like are suitably used. Further, in the present invention, in order to facilitate film formation by the surfactant,
Organic solvents such as polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, and lower alcohols such as ethanol and isopropyl alcohol, fatty acids such as stearic acid and oleic acid, polyoxyethylene alkyl ethers and sorbitan fatty acid esters together with the above surfactants Various emulsifiers such as polyoxyethylene sorbitan fatty acid ester and additives such as fatty acid alkanolamine can be blended in usual amounts.

The composition of the present invention may further contain an oily component, if necessary, in addition to the above-mentioned surfactants. Such oily components include oil-soluble fragrances, silicone oils, oil-soluble Antibacterial agents and the like can be mentioned, and the amounts of these compounds can be appropriately selected within a range not to impair the effects of the present invention.

Next, in the method for producing a high-concentration softener composition according to the present invention, the above-mentioned predetermined amount of the above-mentioned ammonium salt and the above-mentioned sugar alcohol is mixed to suppress an increase in viscosity due to the high mixing of the above-mentioned ammonium salt. It is intended to produce a high-concentration softener composition, and the means for blending these components is not particularly limited. For example, an oil obtained by appropriately melting and mixing the quaternary ammonium salt and the oil-soluble component in the optional component A method of obtaining an O / W emulsion by mixing and emulsifying a water phase in which a water-soluble component in the optional component is appropriately dissolved in water under high shear, to obtain an O / W emulsion, and a part of the oil phase and the water phase ( Or the first aqueous phase) to form a liquid crystal composition, and then add and mix the remainder of the aqueous phase (or the second aqueous phase) to the liquid crystal composition. Aqueous dispersion of ER Can be employed.However, as a method for producing a high-concentration softener composition such as the present invention, the above-mentioned vesicle A method for producing a dispersion is preferred.

In the case of the production method of the present invention, the viscosity of the high-concentration softener composition as the final product is reduced by blending the above-mentioned predetermined amount of sugar alcohol. There is no particular limitation.

When an aqueous dispersion of vesicles is prepared by the above method, the mixing ratio of the oil phase and the total aqueous phase is not particularly limited and can be appropriately selected. Phase / total water phase = 1/1 to 1/5, especially 1/1.
It is preferable to set it to about 5１ ／. The mixing ratio of the aqueous phase (first aqueous phase) to be mixed with the oil phase is preferably such that the liquid crystal composition is formed immediately before the vesicle is formed from the viewpoint of the formation of the liquid crystal composition and the vesicle conversion rate of the ammonium salt. Yes,
Oil phase / first aqueous phase = 0.5 / 1 to 1.6 / at normal weight ratio
1, especially about 1.0 / 1 to 1.2 / 1, and the first aqueous phase / second aqueous phase = 20/80 to 50/50, especially about 25/75 to 40/60. Is preferred.

The temperature at which the liquid crystal composition is formed by kneading the system consisting of the aqueous phase and the oil phase must be equal to or higher than the phase transition temperature (T _c ) of the ammonium salt. If the liquid crystal composition formation temperature is _lower than _Tc , no liquid crystal is formed. The temperature difference between the temperature at which the liquid crystal composition is formed and _Tc is not particularly limited and can be appropriately selected within a temperature range in which liquid crystal can be formed. It is desirable that the temperature is higher than _c by 2 to 20 ° C., particularly 2 to 10 ° C.

When a liquid crystal composition is formed from the above system, the kneading apparatus to be used is not particularly limited, and a conventionally used apparatus can be used, but the viscosity of the system is such that the liquid crystal composition is formed. Considering that
It is desirable to be able to mix the high-viscosity material as a whole, and as such a device, for example, a line mixer, an azihomo mixer, a kneader, a paddle mixer, a screw mixer,
Examples include a spiral mixer, a Nauter mixer, a double helical ribbon mixer, and a continuous kneader. The kneading conditions at this time are within the normal use range of these devices, and it is desirable to continue stirring until the liquid crystal composition is formed and the viscosity of the system becomes high.

In the case of the above method, a liquid crystal composition is formed from the above system by such a kneading step.
Whether or not a liquid crystal composition was formed in such a step
It can be confirmed by utilizing the change (increase) in the viscosity of the system due to the formation of the liquid crystal composition. In addition, after the system in which the liquid crystal composition was formed was frozen and cut, the cut surface was taken into a mold,
Observation with a transmission electron microscope reveals the existence of a multilayer structure, and this multilayer structure is recognized as a lamellar liquid crystal formed by the bilayer film of the ammonium salt and the aqueous layer composed of the aqueous phase.

Next, the liquid crystal composition and the second aqueous phase are mixed to form a desired high-concentration softener composition (vesicle dispersion).
In this case, the mixing can be performed at a temperature lower than the phase transition temperature of the ammonium salt, but it is preferable to perform the mixing at a temperature higher than the phase transition temperature in consideration of the solidification of the ammonium salt. The order of adding the liquid crystal composition and the second aqueous phase is not particularly limited, and they may be added simultaneously, for example. The stirring device used in the mixing / dispersing step is not particularly limited, and a device used in a normal emulsifying / dispersing step can be used. In view of obtaining a composition having excellent separation stability, it is desirable to lengthen the residence time and increase the time required for shearing. Therefore, in this mixing / dispersing step, the same apparatus as in the liquid crystal composition forming step is suitably used.

Examples of such an apparatus include a line mixer, an azimohomomixer, a homomic line mill, a homomic lineflow, a milder, and a disper mixer. The stirring conditions at this time are performed within the normal use range of these devices. In particular, when the peripheral speed at the tip of the stirring blade is used as a representative value of the shearing force, the peripheral speed at the tip of the stirring blade is 8
It is preferable to apply a shearing force of at least m / s.

The order of adding the liquid crystal composition and the second aqueous phase at this time is not particularly limited, and they may be added simultaneously, for example.
The temperature at the stage when the high-concentration softener composition is prepared may be equal to or higher than the phase transition temperature of the ammonium salt, and may be equal to or lower than the phase transition temperature to solidify the bilayer film of the bilayer multilayer structure. State. Further, cooling may be performed after the dispersion step.

According to the production method of the present invention, it is possible to produce a high-concentration softener composition in which an increase in viscosity is suppressed by blending a sugar alcohol. Otherwise, the viscosity of the resulting high concentration softener composition is typically between 3,000 and 20,000 cP.
However, the viscosity of the resulting high-concentration softener composition can be adjusted to 20 to 1,500 cP by blending the sugar alcohol.

In the case of the production method of the present invention, the high-concentration softener composition thus prepared can be used as a concentrated softener as it is, and as long as the effects of the present invention are not hindered, And the like can be added.

The pH of the high-concentration softener composition according to the production method of the present invention is desirably adjusted to a pH range in which the hydrolysis of the quaternary ammonium salt is most suppressed as described above. Depends on the type of quaternary ammonium salt, but is usually pH 2 to 5, especially pH 2.5 to 4. In the case of the production method of the present invention, the step of performing pH adjustment includes:
Depending on the specific manufacturing method, various differences occur.
In the case of a method for preparing a W-type emulsion, an acidic compound may be added to the aqueous phase in such an amount that the intended O / W-type emulsion has the above-mentioned pH. May be performed. On the other hand, in the case of the method for preparing the aqueous dispersion of the vesicles, the pH of the aqueous phase used at the time of liquid crystal formation is adjusted so that the pH of the finally obtained vesicle dispersion is in the above pH range. When the pH is adjusted during the formation of the liquid crystal, the storage stability of the quaternary ammonium salt in the dispersion is reduced as compared with the case where the pH of the vesicle dispersion is adjusted only in the final step. In addition to the improvement, it is possible to suppress an increase in the viscosity of the system due to the formation of the liquid crystal. When the pH is adjusted in the intermediate step, it is preferable to finely adjust the pH in the final step.

[0029]

The high-concentration softener composition of the present invention suppresses an increase in viscosity due to the high content of a quaternary ammonium salt having a hydrolyzable group. In spite of its containing, its fluidity is good, so it is not only excellent in biodegradability but also excellent in usability, and particularly useful as a concentrated softener. Further, the production method of the present invention is not only suitable for producing such a high-concentration softener composition, but also has good fluidity of the system at the time of production, and uniformly disperses particles composed of the soft base. Not only has the above characteristics,
A high-concentration softener composition having excellent dispersion stability can be easily produced.

[0030]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the table,% means% by weight.

Examples 1 to 6 and Comparative Example 1 Diester ammonium chloride (distearoyloxyethyldimethylammonium chloride) and an oily fragrance were melted and mixed so as to have the oil phase composition ratio shown in Table 1. Was prepared, and each aqueous phase component was dissolved in purified water so as to have the ratio of the aqueous phase composition shown in Table 1 to prepare an aqueous phase of Comparative Example 1. In Examples, sorbitol (70% aqueous solution) was added to and dissolved in the above aqueous phase so as to have a ratio shown in Table 1 to obtain an aqueous phase. A 6/10 amount in the above aqueous phase was taken to be a first aqueous phase. In addition, the remainder of the said aqueous phase was used for the 2nd aqueous phase.

Next, the oil phase and the first aqueous phase were each heated to 38 ° C. in advance, and continuously supplied to a line mixer set to the same temperature. Is kneaded while continuously supplying an acidic compound (9% hydrochloric acid aqueous solution) not shown in the above, so that the pH of the final production liquid (aqueous dispersion of vesicles) becomes pH 2.5 to 3.5 during liquid crystal formation. A liquid crystal composition was formed. The stirring conditions of the line mixer at this time are as follows. A four-bladed blade paddle 2 having a ratio d / D of the blade diameter d of the stirring blade to the stirring tank diameter D of 0.8 is 0.8.
Using a column, shearing was performed at a peripheral speed of the tip of the paddle blade of 8 m / s, and kneading was performed with an average residence time of 40 seconds.

The liquid crystal composition formed here was added to 38
The second aqueous phase heated to ° C. was continuously supplied to and mixed with the next line mixer set at the same temperature, to obtain an aqueous dispersion of vesicles. Regarding the stirring conditions of the line mixer at this time, a two-stage four-blade turbine in which the ratio d / D of the blade diameter d of the stirring blade to the stirring tank diameter D is 0.5 is used, The peripheral speed is 10m /
While applying shear as s, mixing with an average residence time of 30 seconds was added to obtain an aqueous dispersion of vesicles, and a high-concentration softener composition (concentrated softener) of Examples 1 to 6 and Comparative Example 1 was used. did.

Examples 7 to 9 and Comparative Example 2 Diester ammonium chloride (distearoyloxyethyldimethylammonium chloride) and an oily fragrance were melted and mixed so as to have the oil phase composition ratios shown in Table 2. Was prepared, and each aqueous phase component was dissolved in purified water so as to have an aqueous phase composition ratio shown in Table 2 to prepare an aqueous phase. In Examples 7 and 8, sorbitol (70% aqueous solution) was added to and dissolved in the above aqueous phase at the ratio shown in Table 2, and in Comparative Example 2, the above aqueous phase was left as it was for 30 minutes. ° C
, And continuously supplied to a line homomixer previously set to the same temperature.
The above-mentioned oil phase heated to 0 ° C. is continuously supplied, and the peripheral speed of the rotor tip of the homomixer is set to 9 m / s, shearing is performed, and emulsification is performed to obtain an O / W emulsion. A high concentration softener composition (concentrated type) of Examples 7, 8 and Comparative Example 2 was prepared by adjusting an acidic compound (9% hydrochloric acid aqueous solution) not shown in the composition so as to have a pH of 2.5 to 3.5. Softener).

Example 9 is the same as Example 1 except that the composition of the oil phase and the amount of sorbitol were changed as shown in Table 2 above. Agent composition (concentrated softener) was obtained.

For these Examples and Comparative Examples, 25 ° C.
Using a BL-type rotational viscometer, the viscosity was measured after rotating the rotor at 30 rpm for 20 seconds.
The results are shown in Tables 1 and 2.

[0037]

[Table 1]

[0038]

[Table 2]

According to Table 1, in the case of the present invention (Examples 1 to 6), by adding 1 to 20% by weight of sorbitol (viscosity reducing agent) at the time of forming the liquid crystal, the diester ammonium chloride concentration was 26%. Despite having a high concentration of 1% by weight, the viscosity at 25 ° C. is 1,350-350.
When the diester ammonium chloride concentration is 26% by weight in the absence of sorbitol in comparison with cP (Comparative Example 1), the viscosity at 25 ° C. is 20,000 cP. It is recognized that an increase in the viscosity of a high-concentration softener composition comprising an aqueous dispersion of highly mixed vesicles can be suppressed.

On the other hand, according to Table 2, the present invention (Examples 7 to 7)
In the case of 9), by adding 5% by weight of sorbitol (viscosity reducing agent) in total, the viscosity at 25 ° C. is 20 to 20% even though the diester ammonium chloride concentration is as high as 13 to 21% by weight. 150 cP O / W
A high-concentration softener composition comprising a dispersion of the emulsion and the vesicles is obtained, whereas in the case of no sorbitol (Comparative Example 2), even at a diester ammonium chloride concentration of 13% by weight at 25 ° C. A high-concentration softener composition consisting of an O / W emulsion having a viscosity of 50 cP was obtained, which composition was the same as that of Example 8 having a concentration of 17% by weight of diester ammonium chloride containing 5% by weight of sorbitol. Therefore, by adding sorbitol, it is possible to suppress the increase in viscosity of the high-concentration softener composition due to the high content of diester ammonium chloride, and to concentrate the softener without impairing its usability. It is recognized that

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuo Nagai 1-37 Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (2)

[Claims] 1. A quaternary ammonium salt having a hydrolyzable group is used as a softening base, and a sugar alcohol is added to a high-concentration softening composition having a concentration of 10 to 30% by weight based on the entire composition. A high-concentration softener composition characterized by containing 0.5 to 20% by weight. 2. When producing a high-concentration softener composition in which the concentration of a quaternary ammonium salt having a hydrolyzable group is 10 to 30% by weight, a sugar alcohol is used as a viscosity reducing agent in an amount of 0 to 30% by weight. A method for producing a high-concentration softener composition, wherein the high-concentration softener composition is mixed so as to have a viscosity of 0.5 to 20% by weight to reduce the viscosity of the high-concentration softener composition.