JPS6116794B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a detergent composition that can also impart flexibility to clothes during washing operations, and more particularly to a detergent composition containing an anionic surfactant and a specific quaternary ammonium salt. . Conventionally, detergent compositions containing anionic surfactants as a main ingredient have been widely used for washing clothes, but clothes washed with such detergent compositions have a rough texture. This tendency was particularly pronounced for items that had been washed repeatedly. Therefore, in general, after washing, a softening agent called a softer is often used to perform treatments such as softening and antistatic treatment. In recent years, cleaning compositions have been developed and marketed that eliminate the double effort of cleaning and finishing treatments, and which simultaneously perform cleaning and finishing treatments in one process.
However, since these commercially available products use cationic surfactants to impart effects such as soft finishing and antistatic treatment, interactions with anionic surfactants, which are the main components of cleaning compositions, occur. ,
Mere mixing of the two components does not fully achieve the desired effect, and various improvements have been made. For example, by mixing a quaternary ammonium salt with a sparingly water-soluble organic dispersion inhibitor such as paraffin wax or higher alcohol, or by coating it with a special film, the swelling and dispersion of the quaternary ammonium salt is delayed and the anion is removed. There are known methods to avoid interaction with surfactants (U.S. Patent No.
No. 3936537, JP-A-49-98403, JP-A-50-
(See No. 77406, etc.) However, these methods are effective to some extent under washing conditions, especially when the temperature of the water used is relatively high, and if the drying is performed at a relatively high temperature using an electric dryer, etc., but if the temperature of the washing water is below 25°C. Under such conditions, the swelling and dispersion of the quaternary ammonium salt is excessively delayed, and the quaternary ammonium salt particles tend to adhere to the cloth being washed. When this is air-dried, there is almost no possibility that the quaternary ammonium salt particles adhering to the cloth to be washed will melt and spread, and it cannot be expected to impart a soft finishing effect to the cloth to be washed. In addition, there was another drawback in that the remaining particles adhering to the cloth to be washed were conspicuous. Alternatively, a water-soluble inorganic salt such as sodium carbonate may be added in excess to an alcoholic solution, aqueous solution, or aqueous alcoholic solution of a quaternary ammonium salt.
A method of mixing and then intimately mixing with an anionic surfactant is also known.
−8927). This method utilizes the fact that a quaternary ammonium salt and an inorganic salt are mixed in a solution to partially form a composite salt, and furthermore, due to the presence of an excess of an inorganic salt, The attack of detergent ingredients, especially anionic surfactants, is alleviated, and a certain degree of softening effect can also be obtained. However, due to the formation of complex salts and the presence of excess inorganic salts, the cationic and hydrophobic properties of quaternary ammonium salts are also considerably lost, and furthermore, since they are used after being intimately mixed with anionic surfactants, The adsorption property is weak, and the softening effect is still insufficient. Essentially, when a quaternary ammonium salt is incorporated into a detergent composition based on an anionic surfactant, it is desirable that the quaternary ammonium salt be present as a single particle. However, according to conventional knowledge,
When a quaternary ammonium salt is blended alone, it is susceptible to attack by anionic surfactants in solution, so in order to obtain a sufficient softening effect,
It has been necessary to incorporate a quaternary ammonium salt that remains in excess even after being consumed by the anionic surfactant. However, with this method, a large amount of expensive quaternary ammonium salt must be used, and although the softening effect can be achieved to some extent, the cleaning power of the cleaning agent itself decreases as the anionic surfactant is consumed. However, it also had the disadvantage of impairing its foaming properties, making it impractical. However, when the present inventors conducted various studies regarding the physical properties of quaternary ammonium salts, it was unexpectedly discovered that certain quaternary ammonium salts do not form at the anionic interface even when incorporated alone in cleaning compositions. The present invention was completed based on the discovery that it is less susceptible to attack by activators and exhibits an excellent softening effect even in small amounts. That is, the present invention provides powdery detergent fabric containing an anionic surfactant with the following formula () or (), (In the formula, R ₁ and R ₂ are C ₁₀ to _{C 22} alkyl or alkenyl groups, R ₃ and R ₄ are lower alkyl groups, and R is a lower alkyl group.) The present invention provides a cleaning composition characterized in that it contains powder particles. The quaternary ammonium salt of formula () or () used in the present invention is a known compound and can be prepared by a conventional method. The quaternary ammonium salt powder particles preferably have an average particle size of 100 to 350μ and do not substantially contain particles larger than 500μ; if this particle size is too small, the surface area of the particles increases. Therefore, they are susceptible to the action of anionic activators, and if they become too large, they may easily fall off even if they adhere to clothing, or the particles adhering to clothing may become noticeable. Further, the apparent specific gravity of the powder particles of the quaternary ammonium salt should be at least 0.25, and is particularly preferably at least 0.4. The quaternary ammonium salt powder used in the present invention is preferably prepared, for example, by the following method. First, the lower alcohol/water mixture solution of the quaternary ammonium salt is desolvated under high temperature and reduced pressure conditions. In the desolvation operation, it is necessary to minimize the residence time in order to prevent thermal decomposition, coloration, odor deterioration, etc. of the quaternary salt due to thermal history. For this purpose, for example, thin-film evaporators are advantageously used. In addition, the desolvation temperature needs to be higher than the melting point of the quaternary ammonium salt in order to ensure the flow of the liquid into the evaporator and the pumping transport of the desolvated quaternary ammonium salt. There is a problem of quality deterioration due to history, so it is preferable to operate at as low a temperature as possible. Among the liquid mixture for dissolving the quaternary ammonium salt, isopropyl alcohol, ethanol, methanol, etc. are used as the lower alcohol.
Isopropyl alcohol is particularly preferred. Also,
The amount of water added to the liquid mixture is preferably 20 to 40 parts per 100 parts of lower alcohol. By doing so, during desolvation, even if the lower alcohol falls below a predetermined concentration, some water remains, so the quaternary ammonium salt maintains fluidity even at temperatures below the melting point of the quaternary ammonium salt. It is easy to handle, and it is possible to suppress quality deterioration such as coloration and odor deterioration of the quaternary ammonium salt. The quality deterioration of quaternary ammonium salts due to thermal history has a remarkable temperature dependence, and lowering the operating temperature even a little is very effective. Next, the quaternary ammonium salt from which the solvent has been removed as described above is made into powder by a cooling solidification pulverization method, an extrusion granulation method, a spray cooling method, or the like. (1) Cooling, solidification, and pulverization method The desolventized molten quaternary ammonium salt is cooled and solidified to around room temperature while passing through a cooler, such as a kneader cooler, and is taken out as a lump of about 20 mm or less. This is finely ground using a suitable grinder. At this time, the fourth
In order to prevent the softening and adhesion of ammonium salts, it is important to introduce cold air at 5 to 10°C into the grinder. In addition, in order to increase the yield of the desired particle size after pulverization, after cooling the quaternary ammonium salt, a granule of approximately 20 mm or less is first obtained using an extrusion granulator, and then finely divided into granules. A method of crushing is also effective. The fourth result obtained in this way
If necessary, powders with a desired particle size range are prepared from grade ammonium salt powders. (2) Extrusion granulation method The desolventized quaternary ammonium salt is
It is cooled to 50° C. and extruded into rods through a screen with constant pores in an extruder granulator. The pore size of the extruding screen should be close to the desired particle size, for example 0.3 mm to 1.0 mm, and the pore shape should be close to circular, for example circular to square. In this way, the rod-shaped quaternary ammonium salt granules that have been extruded and granulated are subjected to subsequent crushing and sizing.
If necessary, the particles are adjusted to a desired particle size by sieving. (3) Spray cooling method A method of obtaining powder by spraying a heated molten quaternary ammonium salt that has been desolvated from a nozzle at a certain pressure or higher into a cold space. The heating temperature needs to be set to a predetermined temperature such that the quaternary ammonium salt has sufficient fluidity and is atomized when sprayed from the nozzle, for example, 120 to 150°C.
In order to suppress quality deterioration due to thermal history, it is preferable to shorten the heating time as much as possible by heating the jacket in the feed line to the spray nozzle. As the spray cooling device, a spray tower type which introduces cold air is suitable, and for example, a cooling method in which cold air of 5 to 20° C. is introduced countercurrently or cocurrently with the quaternary ammonium salt is preferable. The discharge pressure of the spray nozzle varies depending on the nozzle selected depending on the desired particle size, but is usually set at a high pressure of 20 kg/cm ² G or more. The quaternary ammonium salt powder thus obtained is prepared into a powder having a desired particle size range by classification, if necessary. The quaternary ammonium salt of the present invention is different from other typical quaternary ammonium salts (i.e., the alkyl substituent is the same as the quaternary ammonium salt of the present invention, but the counterion is Cl, Br, etc.). ), it has a higher melting point and thermal decomposition point and better thermal stability.Furthermore, by using the manufacturing method described above, it is an excellent quaternary product with less deterioration in color and odor and good storage stability. Ammonium salt powder can be obtained. The quaternary ammonium salt powder particles obtained by these methods are cylindrical to nearly spherical in shape, have a relatively small specific surface area, a large apparent specific gravity, and have a smooth flowing surface. Preferably one with good quality. Among the quaternary ammonium salts of the present invention, those whose counter ion is methosulfate can be most suitably powdered. The quaternary ammonium salt powder thus prepared is mixed and blended with a granular detergent material containing an anionic surfactant as a main component by a conventional method. The amount of quaternary ammonium salt powder blended in the entire cleaning composition is 0.5 to 5% by weight (hereinafter simply %).
) is preferable. The amount of anionic surfactant to be blended is preferably 15 to 25%, which is the amount in general cleaning compositions. The effects of the present invention are exhibited even when the quaternary ammonium salt powder is combined with any commonly used anionic surfactant, but in particular, as an anionic surfactant, the following (a) average carbon number 10 Linear or branched alkylbenzene sulfonate having ~16 alkyl groups (b) Having a straight or branched alkyl group or alkenyl group having an average of 10 to 20 carbon atoms, and having an average of 10 to 20 carbon atoms per molecule.
Alkyl or alkenyl ethoxy sulfate with 0.5 to 8 moles of ethylene oxide (c) Alkyl or alkenyl sulfate with an alkyl or alkenyl group having an average of 10 to 20 carbon atoms (d) An alkyl or alkenyl ethoxy sulfate with an average of 10 to 20 carbon atoms When using one or more of the olefin sulfonate salts (the counter ions of these anionic surfactants are alkali metal ions, alkaline earth metal ions, ammonium ions, or alkanolamines) in the molecule. , good results are obtained. Further, as an example of blending a quaternary ammonium salt and an anionic surfactant to obtain particularly good results, the total weight ratio of the anionic surfactant and the quaternary ammonium salt is 5:1 to 50. :1, and the weight ratio of the sum of the anionic surfactants other than (a) and the quaternary ammonium salt is 10:1.
Hereinafter, a case will be mentioned in which (c) and the quaternary ammonium salt are used in a weight ratio of 3:1 or less. There are no particular restrictions on the mixing/blending method used in the present invention. For example, quaternary ammonium salt powder particles obtained by a spray cooling method or an extrusion granulation method are quantitatively dropped onto a detergent material that is constantly transferred from a hopper or a belt, or into a mixer such as a rotary kiln. A method is used in which a predetermined amount of detergent material and quaternary ammonium salt powder particles are added and mixed. The detergent dough used in the present invention may be manufactured by a known manufacturing method such as a spray drying method or a granulation method, and a detergent dough manufactured by a spray drying method is preferably used. There are no particular restrictions on the manufacturing conditions for the detergent fabric produced by the spray drying method, and the particle size obtained by spraying an aqueous slurry of heat-resistant components such as surfactants and builders into a heated space and drying it is approximately 50 to 100.
It is in the form of hollow particles of 700 μm, and components such as fragrances, enzymes, bleaching agents, and inorganic alkali builders such as zeolite and soda carbonate may be added after the spray drying. The detergent composition of the present invention may further contain various components that are included in common detergents, such as the following components. (1) Nonionic surfactant The nonionic surfactant is not particularly limited as long as it is used in ordinary detergent compositions, and examples of the nonionic surfactant include the following. (A) Polyoxyethylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 moles of ethylene oxide is added (B) Having an alkyl group having an average carbon number of 3 to 12 1
Polyoxyethylene alkyl phenyl ether with ~20 moles of ethylene oxide added (C) Polyoxypropylene alkyl or alkenyl group with an average of 10 to 20 carbon atoms and with 1 to 20 moles of propylene oxide added Alkenyl ether (D) Polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group with an average carbon number of 10 to 20 and added with 1 to 20 moles of butylene oxide (E) An alkyl group or alkenyl group with an average carbon number of 10 to 20 A nonionic surfactant having an alkenyl group and adding a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide (the ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1/9.9 to 9.9) /0.1) (F) Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the general formula below [In the formula, R ₁₁ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ₁₂ is H or CH ₃ , n' is an integer of 1 to 3, and m' is an integer of 0 to 3. (2) Builder In addition, one or more of the following various alkali metal salts may be contained in an amount of 0 to 50% as a builder component. Condensed phosphates such as tripolyphosphate, pyrophosphate, metaphosphate, aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, citrate, malate, glycolate, etc. Polymer electrolytes such as oxycarboxylic acid salts, polyacrylic acid and its salts, alkali hydrolyzed salts of vinyl acetate-maleic anhydride copolymers, etc. Further water-insoluble substances include talc, finely powdered silica, clay, calcium silicate (e.g.
Microcells manufactured by Johns-Manvill, etc.) and "zeolites" having the ability to exchange divalent metal ions described below can also be blended as necessary. Crystalline or/and amorphous aluminosilicate represented by the following formula (u), x (M ₂ O)・Al ₂ O ₃・y (SiO ₂ )・w (H ₂ O)
(u) (In the formula, M represents a sodium and/or potassium atom, and x, y, and w represent the number of moles of each component within the following numerical range: 0.7≦x≦1.2 1.6≦y ≦2.8 w is any positive number including 0) Crystalline or/and amorphous zeolite represented by the following formula (v) X(M ₂ O)・Al ₂ O ₃・Y(SiO ₂ )・Z
(P ₂ O ₅ )·W(H ₂ O) (v) (In the formula, M represents Na or K, and X, Y, Z, and W represent the number of moles of each component within the following numerical range. 0.20 ≦ One or more types can be contained in the composition in an amount of 0 to 50% by weight, preferably 5 to 30% by weight. Silicates, carbonates, sulfates, and alkanolamines represented by triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, etc. can also be contained as organic alkaline agents. (4) Anti-recontamination agent In addition, one of the following compounds can be used as an anti-recontamination agent.
The species or two or more species can be contained in the composition in an amount of 0.1 to 5%. polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone,
carboxymethylcellulose etc. (5) Bleaching agents, fluorescent dyes, enzymes, etc. Bleach agents such as sodium percarbonate, sodium perborate, sodium sulfate, sodium chloride and hydrogen peroxide adducts, and brighteners such as commercially available fluorescent dyes and fragrances. Enzymes such as , protease, amylase, lipase, and cellulase, blue tinting agents, and the like may also be added as necessary. The detergent composition of the present invention thus obtained has an extremely small amount of anionic surfactant that is consumed by the quaternary ammonium salt and is wasted.
It is excellent in that it provides excellent detergency and foaming during washing, and the quaternary ammonium salt adsorbed and remaining on the cloth to be washed also exhibits excellent foam removal properties during rinsing. Next, the present invention will be explained in more detail with reference to Examples. An example of producing quaternary ammonium salt powder particles by a cooling solidification pulverization method is shown as a reference example. Reference example By adding 2% water by weight to a raw material solution of 90% quaternary ammonium salt, 9% isopropyl alcohol, and 1% water, the temperature is 10 to 20°C lower than the melting point of the quaternary ammonium salt itself, i.e. A desolvation operation is performed at 120 to 130°C, which is 10 to 20°C lower than the melting point of distearyldimethylammonium methosulfate, 140°C, and the desolventized quaternary ammonium salt is passed through cooling water in a continuous kneader cooler. While kneading, the mixture was sequentially cooled and solidified to obtain a lump of approximately 10 mm at 15 to 20°C, which was then finely pulverized using a pulverizer. after that,
The desired particle size was adjusted by classification.
(Incidentally, the mixed granules with other ingredients as a comparative sample are prepared by adding and mixing other ingredients to the molten quaternary ammonium salt that has been desolvated in the above reference example. (as powder particles)
The water content of the obtained quaternary ammonium salt powder particles is
It was 0.2% and the apparent specific gravity was 0.45. Example 1 Quaternary ammonium salt powder particles or quaternary ammonium salts shown in Table 1 with a particle size of 149 to 350μ (average particle size 250μ) were added to a detergent fabric having the following composition according to the manufacturing method of the reference example. Mixed granules with other ingredients are mixed with 1.5% pure quaternary ammonium salt (after-blend), washed under the following washing treatment conditions, and evaluated for softening effect. Sensory flexibility was evaluated by 20 professional female panelists. did. The results are shown in Table 1. (1) Detergent fabric (spray heat-dried detergent fabric)

【table】

[Table] (2) Washing treatment conditions Cotton knitted underwear was washed using a commercially available electric washing machine under the conditions of tap water at 20°C, detergent 0.13%, and bath ratio of 1.0 kg/30, and then washed with cedar. The dehydrated and air-dried sample was used for flexibility evaluation. (3) Results

【table】

【table】

[Table] Shows the main effect values for the modified method.
Example 2 1.5% di-tallow alkyldimethylammonium methosulfate powder of various particle sizes shown in Table 2 according to the manufacturing method of the reference example was blended (after blended) to the detergent dough having the composition below, and the same method as in Example 1 was carried out. A relative comparison was made of their flexibility. Also, when cleaning,
Add cotton broad black cloth (5 pieces of 40cm square),
After washing, whether or not white particulate matter remained on the black cloth was visually judged according to the following criteria. ◎ No deposits found at all 〇 Almost no deposits found △ Slightly visible deposits × A large amount of deposits visible These results are shown in Table 2. (1) Detergent fabric (spray heat-dried detergent fabric)

【table】

【table】

【table】 (2) Results

[Composition]

Anionic surfactants (Table 3) Weight% Beef tallow alkyl fatty acid sodium 1 Sodium tripolyphosphate 17 Synthetic zeolite 2 JIS No.2 Sodium Silicate 10 Sodium carbonate 5 Carboxymethyl cellulose 1 PEG6000 1 Sodium paratoluenesulfonate 1 Enzyme 0.5 Fluorescent dye trace amount fragrance trace amount Water 5 mirabilite balance

【table】

【table】 Result:

【table】

[Table] Good, but as a powder of cleaning composition
Its physical properties are poor.
In addition, other quaternary ammonium salt powders or mixed granules of quaternary ammonium salts and other components shown in Table 1 show similar trends to the results shown in Examples 2 and 3. . However, their flexibility was generally at a lower level than the di-tallow alkyldimethylammonium methosulfate powders shown in Examples 2 and 3.

Claims (1)

[Claims] 1. A powdery detergent material containing an anionic surfactant is prepared by the following formula () or (). (In the formula, R ₁ and R ₂ are C ₁₀ to _{C 22} alkyl or alkenyl groups, R ₃ and R ₄ are lower alkyl groups, and R is a lower alkyl group.) Average particle size is 100~350μ
A cleaning composition characterized in that it contains powder particles that do not substantially contain particles with a particle size of 500μ or more.