JPS6262899A - High density granular detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] The present invention relates to a dense granular detergent composition having improved dispersion solubility in water.

[Conventional technology]

In recent years, demand for high-density powder detergents has been increasing from the viewpoint of resource conservation, the transportation of detergents, and the convenience of housewives in terms of carrying and storing detergents.

As a high-density powder detergent, for example, JP-A-48-615
Publication No. 11 discloses a granulated detergent composition containing 30% or more of a surfactant, a bulk density of 0.5 g/cm" or more, and a particle size in the range of 0.5 mm to 5 mm. Also, in JP-A No. 53-36508, surfactant 3
A detergent having a bulk density of 0.55 g/cm' or more is disclosed, which is dry-blended with specific amounts of 0 to 70% and various detergent virgoos.

[Problem that the invention seeks to solve]

However, such dense powder detergents generally do not have satisfactory dissolution rates. For example, in the case of a general fully automatic washing machine, the washing cycle begins by pouring water by first adding laundry and detergent and then turning on the start switch. When the group of detergent particles is slowly immersed in water without being subjected to much physical force,
As water penetrates into a group of detergent particles, hydration and dissolution begin from the particle surface, but at this stage, at the stage where the particle surface is hydrated, a paste containing extremely high concentrations of detergent ingredients and water is formed on the particle surface. At that point, particles coalesce, and the entire group of particles is covered with a hydrated paste-like layer, which, together with the solidification of inorganic bilgoo due to hydration, forms one large mass. The problem arises that the mechanical force of the subsequent stirring cannot completely redisperse the product, and that it cannot be completely dissolved within the normal washing time, which is extremely undesirable for consumers.

Such a case is particularly likely to occur when the detergent particles have a wide particle size distribution and contain a large amount of fine powder.

This is because if the particle size distribution is wide and there are a lot of fine powders, the fluidity and dispersibility of the powder will be poor, and the powder will tend to be put in blocks during washing, and it will easily become a joint powder when it is put in. In addition, the fine powder will quickly hydrate in water and become a binder. This is because the particles become associated with each other.

Moreover, such a phenomenon is particularly likely to occur when the detergent composition contains a specific amount of anionic surfactant.

On the other hand, with low-density detergents, detergent particles easily float on water (and disperse due to buoyancy, and even if particles coalesce in water, the density of the group itself is low and it contains a relatively large amount of air). Therefore, it is easy to redisperse and dissolve by mechanical force, and such problems are unlikely to occur.

[Means for solving problems]

As mentioned above, in high-density powder or granular detergent,
In order to satisfy the solubility, it is most important to increase the dispersibility of detergent into primary particles in water, that is, to prevent detergent particles from aggregating, coalescing, or solidifying in water. .

The present inventors focused on this point, and as a result of conducting intensive studies, the above-mentioned problem could be solved by blending a specific amount of powder or granular organic acid particles into high-density detergent particles containing carbonate inside. The inventors have discovered that these problems can be solved, leading to the present invention.

That is, the present invention provides a high-density granular detergent containing 5% by weight or more of alkaline carbonate and having a bulk density of 0.5 g/cm' or more,
The present invention provides a high-density granular detergent composition with excellent dispersibility and solubility in water, which is characterized by containing 1 to 10% by weight of one or more types of powder or granular organic acids or acid anhydrides thereof. be.

The effect of the present invention is that when the detergent is permeated with water, the alkaline carbonate in the detergent particles is eluted and reacts with the organic acid, producing carbon dioxide gas and organic acid salts. This is obtained by lowering the apparent bulk density of the detergent particle population in water and increasing its dispersibility into primary particles using carbon dioxide gas.

As the alkaline carbonate used in the present invention, sodium carbonate is most preferably used, but 1-lium hydrogen carbonate or their respective potassium salts may also be used.

The content of alkaline carbonate in granular detergent is 5%
That's all.

Below this, the effects intended by the present invention cannot be obtained. These are usually 5 to 70% by weight, preferably 10 to 50% by weight.
Contains. Further, the particle size of the granular detergent (detergent dough) containing these alkaline carbonates is 40 to 2000 microns, preferably 125 to 1500 microns.

The organic acid or its acid anhydride can be in the form of powder or granules, and any organic acid that can react with alkaline carbonate to generate carbon dioxide gas when dissolved in water can be used.

Among these, organic carboxylic acids or acid anhydrides are preferred, and particularly organic carboxylic acids or acid anhydrides having as many carboxyl groups as possible in the molecule or per unit molecule (the number of carboxyl groups or carboxyl anhydrides in the molecular weight) When the ratio of group substitution is at least 20% or more, preferably 50% or more, the reaction rate with the alkaline carbonate per unit amount added is high, and the organic carboxylate produced by the reaction becomes a cleaning builder. , is very suitable to act primarily as a chelating agent.

Specific examples include oxycarboxylic acids such as malic acid, tartaric acid, and citric acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, and diglycolic acid, sulfamic acid, paratoluenesulfonic acid, and acid anhydrides thereof. can.

Solids that are stable at room temperature and have low hygroscopicity are particularly desirable because they have high storage stability, and succinic acid and/or succinic anhydride are most preferably used.

The blending amount of these is 1 to 10% by weight, preferably 1 to 8% by weight, particularly preferably 1 to 5% by weight.

The organic acid or its acid anhydride used in the present invention is mixed into detergent particles as individual organic acid particles (preferably having an average particle size of 500 μm or less), which are separate from detergent particles containing an alkaline carbonate therein.

This is preferable because it has higher storage stability than when it is included in the detergent particles like the alkaline carbonate. Furthermore, in order to further improve storage stability, the surface of the organic acid particles may be coated with polyethylene glycol, a nonionic surfactant, or the like.

The high-density powder detergent of the present invention is composed of the same components as ordinary powder detergents other than the above-mentioned components, namely, a surfactant, an inorganic or organic builder, and other additives.

Examples of these components include the following.

[1] Surfactant Anionic surfactants include linear or branched alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or Unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfo fatty acid salts or esters thereof, amino acid type surfactants, N-acylamino acid type surfactants, alkyl or alkenyl acid phosphate esters, alkyl or alkenyl phosphate esters, or Examples of amphoteric surfactants include carboxy or sulfobetaine type surfactants, and nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides, and their salts. Examples of the cationic surfactant include alkylene oxide adducts, sucrose fatty acid esters, fatty acid glycerin 7-esters, alkylamine oxides, and quaternary ammonium salts.

Preferred surfactants include linear or branched alkyl hanzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, carboxy or sulfobetaine type surfactants, polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or salts thereof.

In addition, these surfactants account for 10 to 75% of the total amount of the detergent composition.
% by weight is added.

[2] Divalent metal ion scavenger phosphates such as tripolyphosphate and birophosphate, phosphonic acid salts such as ethane-1,1-diphosphonate, 2-phosphonobutane-1,2-dicarboxylic acid, etc. Salts of phosphonocarboxylic acids, salts of amino acids such as aspartic acid and glutamic acid, aminopolyacetates such as nitrilotriacetate and ethylenediaminetetraacetate, polymer electrolytes such as polyacrylic acid and polyaconitic acid, polyethylene glycol, polyvinylpyrrolidone non-dissociated polymers such as, salts of organic acids such as oxalic acid and citric acid, aluminosilicates, etc.

[3] Alkaline agent or inorganic electrolyte Sodium silicate, sodium sulfate, etc.

[4] Re-staining prevention agents polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc.

[5] Bleaching agents, fluorescent dyes, enzymes, etc. Soda percarbonate, sodium percarbonate, sodium sulfate hydrogen peroxide adduct, sodium chloride hydrogen peroxide adduct, etc. are used as bleaching agents, and commercially available fluorescent dyes are used as brighteners. In addition, fragrances, enzymes such as protease, amylase, lipase, and cellulase, blue tint agents, bleach activators, and the like can be added as necessary.

Although there are no particular limitations on the method for producing the high-density granular detergent of the present invention, in terms of -G, after intimately mixing the surfactant and the detergent builder, drying as the case may be,
By after-blending organic acid or its acid anhydride particles of a desired particle size into a high-density granular detergent obtained by crushing and granulating it with a granulator until the desired particle size and bulk density are obtained, A high density granular detergent of the invention is obtained.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited by the following examples.

Example 1 A high-density granular detergent having the composition shown in Table 1 was manufactured according to the manufacturing method described below, and the bulk density and dispersion solubility of the detergent were compared and examined. The results are shown in Table 2. The type, particle size, and amount of the organic acid particles added are also shown in Table 2.

Table-1 Detergent composition (numbers in the table are weight %) (it) LAS: Direct IJt alkylbenzene sulfonic acid sodium (C+z~c13) AS: Alkyno I-isolated soda (C14~C15) ES: Polyoxyethylene Alki/L4JW Soda (C14-C15, EO=1.5
) AO5: α-olefin sulfonic acid soda (016~
Cue) Nonion: Polyoxyethylene alkyl ether (C92-CI3+ EO=10) Hereinafter, a method for producing a high-density granular detergent and a method for measuring bulk density and dispersion solubility will be described.

l) Detergent manufacturing method ■ Manufacturing method 1 In this manufacturing method, the anionic surfactant as a starting material was used in an unneutralized acid form, but the detergent composition in Table 1 was described as the final detergent composition.

The parts other than the zeolites of compositions 1 to 3 and sodium tripolyphosphate were supplied to an FM-NIES-120 type Nesco kneader (manufactured by Tomito Sangyo! 11) and kneaded to neutralize the anionic surfactant. After that, add a part of the fine zeolite powder or sodium tripolyphosphate, grind it to the desired particle size with a hammer mill, and then add the remaining fine zeolite powder.
The mixture was mixed using a Shugi mixer to obtain a high-density granular detergent.

■ Manufacturing method 2 Prepare a slurry (solid content 60% by weight) with a composition excluding the components added in the steps after compositions 1 to 3, obtain detergent powder by spray drying, and then use a high-speed mixer (stir transfer granulation). A high-density granular detergent was obtained by crushing and granulating the detergent to a desired particle size using a machine.

The second part of water or nonion in the composition can be added as a granulation aid during crushing and granulation, and may contain small amounts of thermally unstable additives such as enzymes, bleaching agents, and inorganic bilges that do not require drying. For example, sodium sulfate, zeolite fine powder, etc. are optionally added in a step after spray drying.

■ Manufacturing method 3 Prepare slurry of compositions 1 to 3 (solid content 60% by weight),
It was dried with a drum dryer, then granulated with a screw extrusion granulator, and crushed and sized to a desired particle size to obtain a high-density granular detergent.

The high-density granular detergents produced by each of the above-mentioned manufacturing methods were prepared to have a particle size in which the average particle diameter was in the range of 250 μ to 450 μ without substantially containing particles with a particle size of 1500 μ or more, and used for experiments. The organic particles were added to these high-density granular detergents by after-blending.

2) Measurement of detergent bulk density (apparent specific gravity) , IIS K-3362.

3) Measurement of detergent dispersion solubility Fully automatic laundry 82.8 kg Aozora PF-265 manufactured by Hitachi Co., Ltd.
Place 40g of detergent in one place at one end of the bottom of the U gutter, add 2kg of clothing (60% by weight cotton underwear and 40% by weight polyester/cotton blend dress shirt) onto the detergent, and heat at 10°C. Tap water was poured slowly at a flow rate of 8β/min over 5 minutes until the detergent reached a flow rate of 40j2, avoiding direct contact with the detergent. Thereafter, stirring was started, and after 3 minutes and 5 minutes of stirring, stirring was stopped, water was drained, and residual scattering was visually determined after 3 minutes of dehydration. The judgment criteria are shown below.

○: No residual detergent ◎: Slightly small particles of residual detergent △: Many small particles of residual detergent or a few lumps of residual detergent ×: Considerable lumps of residual detergent In this measurement method, the detergent particle population is During water injection, the receiver is exposed to water for 5 minutes without receiving any physical mechanical force, and after being exposed to water, it is subjected to mechanical force due to stirring.

Example 2 A high-density granular detergent having the formulation shown in Table 3 was manufactured, and Example 1
Similarly, the bulk density and dispersion solubility of detergent powders were compared and studied. The results are shown in Table 4.

Table 3 Detergent composition (The numbers in the table are weight%.) [Note] LAS, AS, and nonion are the same as in Table 1. [Effects of the invention] As described above, the dispersion solubility of high-density detergents is A remarkable difference was observed between the product of the present invention to which acid particles were added and the comparative product, and the product of the present invention showed excellent dispersion solubility in both cases. In both comparative products, water gradually penetrates from the surface of the detergent particle group during the 5-minute water injection period, forming a viscous gel or paste-like layer of highly concentrated detergent ingredients and water on the surface. Furthermore, due to the hydration of the inorganic building blocks such as sodium carbonate inside, the detergent particles solidify together, turning into a lump covered with a viscous paste-like layer, which is completely dispersed and dissolved by subsequent stirring. I realized that I couldn't finish it and stayed. In contrast, in the product of the present invention, the sodium carbonate in the detergent reacts with the organic acid from the area where water has penetrated, generating carbon dioxide gas, resulting in the above-mentioned paste-like layer and inorganic building block. It has been found that the detergent particles can be prevented from caking by the detergent particles, reduce the bulk density of the detergent particle population, and exhibit good dispersion and solubility similar to that of general low-density detergents.

High-density granular detergents have excellent dispersion, especially when they are used in ways such as when the detergent particles are put into water in a state where they are bound to a certain extent, such as when they are packaged in a water-soluble film or the like. A dissolving effect is essential, and the high-density granular detergent of the present invention is preferably used.

The amount of organic acid added is the minimum amount necessary for the detergent to obtain an evaluation result of ○ in the dispersion solubility test method shown in this example, and is considered to cause no practical problems at all. . In addition, the amount added can be reduced by reducing the particle size of the organic acid particles and increasing the probability that the organic acid particles exist between detergent particles.

Claims (1)

[Claims] 1 A granular detergent containing 5% by weight or more of an alkaline carbonate and having a bulk density of 0.5 g/cm^3 or more is blended with 1 to 10% by weight of a powder or granular organic acid or its acid anhydride. High-density granular detergent composition.