JPS62167399A - 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 [Field of Industrial Application] The present invention relates to a high-density granular detergent, and more particularly to a high-density granular detergent composition that has excellent dispersion and solubility even in cold water.

[Conventional technology]

In recent years, demand for high-density powder detergents has been increasing from the viewpoint of resource conservation, detergent transportation, and convenience for 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/cn+' or more, and a particle size within a range of 0.5 mm to 5 m+a. . Further, JP-A-53-36508 discloses a detergent having a bulk density of 0.55 g/cm' or more, which is dry blended with 30 to 70% of a surfactant and a specific amount of various detergent builders.

Further, JP-A-58-132093 discloses granular detergent compositions containing intimately mixed anionic surfactants and anionic polymers. It is prepared by adding water-soluble neutral or alkaline salts and mixtures thereof by preparing a non-soap anionic surfactant that is previously intimately mixed with certain water-soluble anionic polymers. Even in high-density (e.g. 0.67 g/cm3) granular detergents obtained by blending other detergent ingredients into a spray-dried granular mixture, water and anionic surfactants act to retard the dissolution of granules. The purpose is to improve the dispersion and solubility of granular detergents by eliminating or delaying the formation of highly viscous rgumJ phases.

[Problem that the invention seeks to solve]

However, such high-density powder detergents generally do not have satisfactory dispersion and solubility;
In the example described in Publication No. 2093, some effect is recognized, but if the detergent particle group is left for a certain period of time without being subjected to a relatively large mechanical force in cold water, which is commonly used in winter in Japan. Under such conditions, its dispersion and solubility are still insufficient, and no fundamental solution has been reached.

For example, cold water of 5° C. is water at a temperature that can generally be used for home laundry in Japan in winter. When using a normal fully automatic washing machine with cold water like this, the washing cycle starts by pouring water by first adding the laundry and detergent and then turning on the start switch. During the water injection period, a group of detergent particles is slowly penetrated by water without being subjected to much physical mechanical force, and at the same time, a paste-like mixture of detergent components and water at a very high concentration is formed on the particle surface. Phases are formed and particles coalesce. The entire population of particles is covered with a hydrated, highly viscous paste-like phase that cannot be redispersed by the mechanical force of subsequent stirring and cannot be completely dissolved within the normal washing time. , which was highly undesirable to consumers. Further, the formation of such a highly viscous pasty phase is particularly likely to occur when the surfactant component in the composition is mainly an anionic surfactant.

On the other hand, with low-density detergents such as conventional spray-dried detergents, the detergent particles are porous and contain a large amount of air, so they easily float on water (disperse due to buoyancy, and if particles combine in water). Even so, the density of the group itself is low (it contains a relatively large amount of air, so it is easily redispersed and dissolved by mechanical force,
Such problems are unlikely to occur.

From these viewpoints, in the case of high-density granular detergents, we focused on surfactants, especially anionic surfactants, in detergent compositions, as in the example of JP-A-58-132093 mentioned above, and developed highly viscous detergents. In order to suppress the formation of a paste-like phase, attempts were made to add various thinners and hydrotropes, but as mentioned above, under Japanese winter washing conditions, a slight improvement effect was observed. A fundamental solution has not been reached, and therefore the formation of a highly viscous pasty phase between the anionic surfactant and water is a contributing factor to the inhibition of dispersion and solubility of high-density granular detergents, but is not the main cause. It was revealed.

[Means for solving problems]

The inventors of the present invention further investigated the main cause and found that when high-density granular detergent is placed in extremely low-temperature water, water penetrates through the surface of the detergent particle group, resulting in surface activity. The agent hydrates, and the water-soluble salts hydrate while emitting heat of hydration, and then elute, and as the water that has eluted the salts further penetrates into the mass, it becomes a more highly concentrated salt solution. Eventually, heat is taken away by the surrounding low-temperature system and the temperature drops, reaching a supersaturated state and precipitating crystals.The presence of these crystals makes the viscous paste-like phase of the surfactant harder, and changes the phase itself into a strong hydrated solid phase by connecting the precipitated crystals,
It has become clear that this makes it difficult to easily disperse and dissolve even if mechanical force is applied afterwards. In other words, it has been revealed that the presence of water-soluble and crystalline salts is the main cause of inhibiting the dispersion and solubility of high-density granular detergents in cold water.

On the other hand, water-soluble and crystalline inorganic salts are essential components required to improve the manufacturing suitability and washing performance of detergents.

As a result of intensive studies to solve these problems, the present inventors have limited the content of water-soluble and crystalline salts, which are the main cause of inhibiting dispersion and solubility in high-density granular detergent fabric, to below a specific amount. By dry mixing and localizing alkaline water-soluble and crystalline salts in the form of particles in a specific proportion to the fabric, a high quality product with excellent dispersion solubility and cleaning performance in cold water can be obtained. It was discovered that a dense granular detergent could be obtained, and the present invention was completed.

That is, the present invention comprises (a) 20 to 60% by weight of an organic surfactant, and (b) 2 to 15% by weight of a water-soluble and crystalline inorganic salt.
% and (c) other inorganic salts and/or organic divalent metal ion scavengers for high-density granular detergent fabric containing 25 to 78% by weight, and further 5 to 25% of granular water-soluble and crystalline alkaline inorganic salts. The present invention provides a high-density granular detergent composition characterized in that it is dry blended in a weight percent manner.

In the present invention, high density refers to a bulk density of 0.5 g/cm' or more, preferably 0.6 g/cm' or more.

Examples of the organic surfactant used in the high-density granular detergent fabric of the present invention include the following.

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 carboxylate, α-sulfo fatty acid salt or ester,
Examples of amphoteric surfactants include amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl acid phosphate esters, alkyl or alkenyl phosphate esters or their salts, carboxy or sulfobetaine type surfactants, etc. Examples of nonionic surfactants include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid glycerin heptanoester, alkylamine oxide, etc. Examples of cationic surfactants include quaternary ammonium salts.

Preferred 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, carboxy or sulfonate sulfonates. Examples include betaine type surfactants, polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or salts thereof.

The blending amount of the organic surfactant is in the range of 20 to 60% by weight, preferably 25 to 60% by weight. Contains 20% by weight
If it is less than 60% by weight, sufficient washing performance cannot be obtained, and if it exceeds 60% by weight, the manufacturing suitability and the powder physical properties of the resulting detergent will deteriorate, which is not preferable.

Among these organic surfactants, anionic surfactants in particular tend to form a viscous paste-like phase in water and are easily affected by the presence of large amounts of water-soluble and crystalline salts. When an ionic surfactant was mainly used, its dispersion solubility in cold water was particularly insufficient. Therefore, the effects of the present invention are particularly significant when the anionic surfactant content in the organic surfactant used is 70% by weight or more.

Examples of water-soluble and crystalline inorganic salts whose content is limited in the present invention include alkali metal or ammonium chlorides, sulfates, hydrogen sulfates, sulfites, hydrogen sulfites, carbonates, hydrogen carbonates, Sesquicarbonates, borates, inorganic phosphates (e.g. tripolyphosphate, pyrophosphate, ca.
polymeric metaphosphates, orthophosphates, etc. having a degree of polymerization of ~21) and silicates with a molar ratio of 5iOz to alkali metal oxide of 1.0 or less, such as orthosilicates, metasilicates, etc. , in particular the sodium salts of those mentioned above. More specifically, among the above-mentioned salts, sodium carbonate, sodium sulfate, sodium tripolyphosphate, sodium pyrophosphate, sodium orthophosphate, etc. may be mentioned. These salts have a relatively larger difference in solubility depending on temperature than other salts, so they easily precipitate crystals from an aqueous solution (in addition, they take up a relatively large amount of crystallization water at low temperatures, making it easy to connect crystals together, making their structure strong). This is a major factor that inhibits the dispersion and solubility of high-density detergents.In particular, sodium carbonate has a large calorific value due to hydration, and in addition to the same reason, it elutes in high concentration with heat generation even in cold water, and therefore it can be dissolved in the surrounding low temperature. When heat is taken away by the system and the temperature drops, a large solubility difference occurs and crystals tend to precipitate.
By becoming a hydrate salt and taking in a large amount of crystal water, the undissolved crystal itself becomes a hydrated crystal and expands in volume, making it easier to connect hydrated crystals together and making the structure stronger. Its content is particularly limited.

The content of these water-soluble and crystalline inorganic salts in the detergent fabric of the present invention is required to be 2% by weight or more from the viewpoint of powder physical properties, and 15% by weight or less from the viewpoint of low-temperature solubility.

In the case of sodium carbonate, it is desirable to suppress it to less than 10% by weight for the reasons mentioned above.

The detergent fabric of the present invention contains virgoosic substances such as water-soluble but non-crystalline inorganic salts, water-insoluble inorganic salts, and other common detergent ingredients to enhance manufacturing suitability and washing performance.

Examples of these inorganic salts include silicates with a molar ratio of 5in2 to alkali metal salt of more than 1.0 (No. 1, No.
Examples include inorganic bilges and/or organic divalent metal ion scavengers such as aluminosilicate represented by type A zeolite, etc.), and the content thereof is 25 to 78% by weight. .

The method for producing the high-density granular detergent fabric of the present invention is not particularly limited, but for example, the method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 48-61511, or the method using an alkali agent for unneutralized anionic surfactant. It can be manufactured by adding an acid-resistant detergent component, neutralizing it, and then adding zeolite and pulverizing it, or by increasing the bulk density by granulating a powdered detergent by spray drying.

The particle size of the high-density granular detergent fabric is usually in the range of 40 to 2,000 microns, particularly preferably in the range of 125 to 2,000 microns.

In the present invention, water-soluble and crystalline inorganic salts such as those described above are mixed homogeneously with other detergent ingredients including organic surfactants, rather than existing in a delocalized state. It has been found that a larger total amount of water-soluble and crystalline salts can be blended by dry mixing and localizing the particles with particles made of other detergent ingredients. This is because when the detergent particles are delocalized, when the detergent particle population is penetrated by water, the water-soluble and crystalline salts are more evenly eluted from all parts, and the surrounding low-temperature system When heat is taken away by the liquid and the temperature drops and crystals precipitate, crystals are precipitated in all parts of the paste phase where organic surfactants and other detergent components are mixed, making the paste phase even stronger. This is because it makes the crystals harder and, in turn, makes it easier for the crystals to connect with each other. In contrast, according to the present invention, water-soluble and crystalline inorganic salts are dry-mixed as particles into high-density granular detergent fabric and localized, thereby reducing the phenomenon of low-temperature solubility reduction as described above. be able to. For the same reason, even if the total amount of water-soluble and crystalline inorganic salts is the same, a larger proportion of water-soluble and crystalline inorganic salts that are dry-mixed into the detergent fabric will exhibit better dispersion and solubility than if they are blended into the detergent fabric.

In the present invention, in order to enhance washing performance, by blending 5 to 25% by weight of alkaline earth metal and crystalline inorganic salt particles into the high-density granular detergent fabric, it can be compared with conventional spray-dried detergents. A high-density granular detergent composition that can achieve equivalent washing performance and has good dispersion and solubility in cold water can be obtained by dry after-blending. Water-soluble and crystalline inorganic salt content is 20% by weight
If the washing performance is less than 1, the washing performance can be compensated for by increasing the content of other inorganic bilges and organic divalent metal ion scavengers, but in general it is better to use water-soluble and crystalline inorganic salts, which are cheaper. The alkaline water-soluble and crystalline inorganic salts, whose content is preferably 20% by weight or more, include, among the above-mentioned water-soluble and crystalline inorganic salts, for example, sodium carbonate, sodium tripolyphosphate, Examples include sodium pyrophosphate and sodium orthophosphate.

In the present invention, in order to achieve localization as described above, it is better for the water-soluble and crystalline inorganic salt particles to be dry-mixed to have a large particle size rather than a fine one. Particles □ Since the dissolution rate of the particles themselves becomes too slow and is not desirable as a detergent, the average particle size is 100μ to 1000μ, preferably 200μ to 600μ.
Those are preferably used.

In addition, the bulk density of the inorganic salt particles is 0.5 g/cm" or more, preferably 0.6 g/cm3 or more, and is particularly preferably about the same as the bulk density of the detergent fabric. The bulk density of the detergent fabric and the salt particles is If the density difference is too large, the salt particles will become too localized due to particle classification, and the resulting area will become similar to one in which too many salt particles are blended, resulting in the dispersion of that area. In addition, if the particle size of the salt particles is too small, they will be delocalized too much, and the dispersion and solubility will be adversely affected, similar to when a large amount is added to detergent fabric. This is not desirable because there is a risk that the situation will be headed in the direction of

The organic divalent metal ion scavenger used in the present invention includes salts of phosphonic acids such as ethane-1,1-diphosphonate, salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, etc. , 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, salts of organic acids such as oxalic acid and citric acid, Examples include polyacetal carboxylic acid polymers or salts thereof described in JP-A-54-52196.

Furthermore, the composition of the present invention may contain the following components in appropriate amounts as required.

1) Re-staining prevention agents polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc.

2) Bleaching agents, fluorescent dyes, enzymes, etc. Bleaching agents such as sodium percarbonate, sodium percarbonate, sodium sulfate/sodium chloride hydrogen peroxide adducts, and brighteners include commercially available fluorescent dyes, fragrances, and proteases. Enzymes such as , amylase, lipase, and cellulase, blue tint agents, bleach activators, and the like may also be added as necessary.

〔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 fabric (A) having the composition shown in Table 1 was produced,
Table 2 shows the results of a comparative study on the bulk density and dispersion solubility of high-density granular detergents prepared by dry mixing water-soluble and crystalline salt particles (B) shown in Table 2 with (A).

Table 1 Composition of high-density granular detergent fabric (A) (all numbers in the table are weight%) (a) Organic surfactant LAS: Linear alkylbenzenesulfonate sodium (C
+□~C7 AS: Alkyl sodium sulfate (CI4~C1,) AES
:Polyoxyethylene alkyl sodium sulfate (014~
CIS + penalty = 1.5) AO3: α-olefin sulfonate soda (CI6~C
+ll) Nonion: polyoxyethylene alkyl ether (C,
□~C13+ plane = 10) (b) Water-soluble and crystalline inorganic salts In Table 1, (a) is an organic surfactant, and (b) is a water-soluble and crystalline inorganic salt defined by the present invention. be. Although polyethylene glycol having an average molecular weight of about 13,000 was used, it is a dispersant and is not included in the organic surfactant (a).

In addition, zeolite is water-insoluble, and sodium silicate No. 2 is amorphous and does not form regular crystals from an aqueous solution.
None of these are included in the water-soluble and crystalline salts (b).

The manufacturing method of high-density granular detergent and the measurement method of bulk density and dispersion solubility will be explained below.The manufacturing method is a preferred example of manufacturing the high-density granular detergent used in this example.
It is not particularly limited.

1) Detergent manufacturing method Prepare a slurry containing 50% by weight of water-containing bone with the composition (P) in Table 1, and spray dry it to obtain a slurry with a bulk density of 0.3 g.
A detergent powder (P) of around /cm3 was obtained.

Next, (P) is put into a high-speed mixer (stirring transfer granulator, manufactured by Fukae Kogyo Co., Ltd.), and composition (B) of finely powdered zeolite moistened with water is added to crush and granulate it, resulting in bulk. A high-density granular detergent with a density of 0.6 g/cm3 to 0.8 g/cm3 was obtained. At this time, the water in composition (0) acts as a granulation binder for the crushed detergent powder (P), and the water in composition (0) acts as a granulation binder for the crushed detergent powder (P).
The fine zeolite powder in b) acts as a carrier for water as a granulation binder and as a granulation aid to suppress the formation of coarse particles.

Further, as the granulation binder, the nonion in the composition (P) may be liquefied and sprayed onto the detergent powder during granulation. High-density granular detergent (P) +
By finally dry mixing (R) fine powder zeolite and water-soluble and crystalline salt particles (B) into (Q),
A high-density granular detergent with excellent fluidity and anti-caking properties was obtained.

Additionally, small amounts of thermally unstable additives, such as enzymes and bleaching agents, are preferably incorporated by dry mixing in this last step. In this example, after crushing and granulation, the mesh size was 1.
Coarse particles with a particle size of 1 mm or more were removed by passing through a 1 mm screen. According to this manufacturing method, crushing and granulation conditions (type of granulator, granulation temperature, granulation time, type of granulation binder, etc.)
The desired bulk density and density can be achieved by adjusting the opening of the screen to be passed through after granulation, by recycling coarse particles, and by selecting the blending amount, bulk density and particle size of the water-soluble and crystalline salt particles (B) to be dry mixed. A granular detergent of granular size can be obtained.

2) Measurement of detergent bulk density (apparent specific gravity) JIS K-3
3) Measurement of detergent dispersion solubility Fully automatic washing machine 2.8 kg Aozora PF-265 manufactured by Hitachi Co., Ltd.
0, place 40g of detergent at one end of the bottom of the washing tub, and place clothes (60 parts by weight of cotton underwear and polyester/
2 kg of cotton blend dress shirts (40 parts by weight) were added, and tap water at a predetermined temperature was slowly poured over 5 minutes at a flow rate of 81/min until the temperature reached 401, avoiding direct contact with the detergent. After that, start stirring and after stirring for 3 minutes,
Stop stirring, drain the water, and after 3 minutes of dehydration, visually determine the amount of detergent remaining on the clothes and in the washing tub. 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 pouring, it is exposed to water for 5 minutes with almost no physical mechanical force applied to it, and after being penetrated by water, it is subjected to mechanical force due to stirring.

Example 2 A high-density granular detergent fabric (8) having the composition shown in Table 3 was produced,
A comparative study was conducted on the bulk density and dispersion solubility of a high-density granular detergent prepared by dry mixing water-soluble and crystalline salt particles (B) with (A).

The detergent manufacturing method and various measurement methods are the same as in Example 1. The results are shown in Table 4.

Table 3 Composition of high-density granular detergent fabric (A) (all numbers in the table are weight%)

Claims (1)

[Scope of Claims] 1 (a) 20 to 60% by weight of an organic surfactant; (b)
2 to 15% by weight of water-soluble and crystalline inorganic salts and (c
) Dry blending of granular water-soluble and crystalline alkaline inorganic salts in an amount of 5 to 25% by weight to a high-density granular detergent fabric containing 25 to 78% by weight of other inorganic salts and/or organic divalent metal ion scavengers. A high-density granular detergent composition characterized by: 2. The high-density granular detergent composition according to claim 1, wherein the content of anionic surfactant in the organic surfactant is 70% by weight or more. 3. Claim 1, wherein the water-soluble and crystalline inorganic salt is one or more selected from the group consisting of sodium carbonate, sodium sulfate, sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate. The high-density granular detergent composition according to item 1 or 2. 4 The average particle size of the granular water-soluble and crystalline inorganic salt is 10
Claims 1 to 3 which are 0 to 1000μ
The high-density granular detergent composition according to any one of paragraphs.