JPS6042279B2 - cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel cleaning composition, and more particularly, a novel cleaning composition which does not deposit water-insoluble aggregates on objects to be washed and which does not lose its free-flowing properties even after long-term storage. The present invention relates to a granular or powdered aluminosilicate-containing cleaning composition.

In heavy household detergents used for washing clothes, it has conventionally been essential to include alkali metal silicates such as sodium silicate.

In addition to its bilter action (alkaline action, alkaline buffering action, hard water softening action), the alkali metal silicate has the action of preventing corrosion of metal parts of washing machines, clothing hooks, decorative items, etc. Furthermore, in the spray drying process when making granular or powdered cleaning agents, the granules (powder) have excellent free-flowing properties by preventing pulverization, coarsening, irregular shapes, etc. It had the function of forming (skeleton formation). However, this alkali metal silicate
The substance itself is originally water-soluble, but when exposed to high temperatures during spray drying during detergent manufacturing, it becomes detergent particles, and when exposed to the air for a long time, it turns into a water-insoluble substance. However, as a result, there was a drawback that undesirable deposits were formed on the items to be washed.

Thus, insolubilization due to heat can be avoided to some extent by controlling manufacturing conditions, but on the other hand, it is unavoidable that detergents are exposed to air when used by consumers.

In fact, looking at the usage of heavy-duty powder detergents in general households these days, it is common to purchase a large amount (extra large size) of the detergent at one time and then transfer it to a plastic container before use. You can't avoid being exposed. Also, in recent years,
Due to the problem of eutrophication caused by phosphates used as builders in powdered detergents, low-phosphorus or phosphorus-free detergents have come on the market.

In this low-phosphorus or phosphorus-free detergent, the following general formula (1) is used as a substance that replaces the metal ion-trapping effect of conventional phosphates, (where M is Na or K, and X is 0.7 to 1.
5, Y is a number from 0.8 to 6.0, and W is a positive number including 0) is often blended.

Although this aluminosilicate itself is water-insoluble, since it is extremely fine particles (particle size 1 μm), it does not deposit on the items to be washed.

However, when an alkali metal silicate is blended with this aluminosilicate, when the alkali metal silicate transforms into a water-insoluble substance as described above, the aluminosilicate is incorporated into relatively large water-insoluble particles. This results in the formation of deposits on the items being washed. Due to the insolubilization of such alkali metal silicates. The flocculate can be collected using a two-tank system or a fully automatic one.
This is relatively rare when using conventional washing machines such as tank type washing machines, but when using washing machines that use water-saving or time-saving rinsing methods called shower rinses and spin rinses, which have recently become popular. During rinsing, the rinsing water is drawn through the clothes, which increases the amount of deposits. As a method to solve this problem, it has been suggested, for example, to reduce the amount of alkali metal silicate that is involved in the formation of water-insoluble substances (Special Japanese Patent Application No. 1987-1-1).
No. 2805).

In this case, an alkaline agent (generally an alkali metal carbonate), an alkaline buffer, a chelating agent, a rust preventive, etc. are blended as substitutes for the effects of the alkali metal silicate. With such a composition, detergent particles obtained by spray drying have the same cleaning performance as those containing alkali metal silicic acid salts and do not generate water-insoluble substances. It is brittle and crumbles easily, resulting in caking and loss of free-flowing properties. This decrease in free flow has a significant impact on ease of use and significantly reduces product value. Under these circumstances, the present inventor has developed an aluminosilicate-containing cleaning agent that does not impair conventional cleaning performance, does not cause aggregates to be deposited on items to be washed even when exposed to air, and has excellent free-flowing properties. As a result of intensive research to develop a composition, the present invention was completed.

That is, the present invention includes the following components (a) to (e), (a)
5 to 8 weight% of a water-soluble surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, and mixtures thereof, (b) polyacrylic acid or a salt thereof, and acrylic acid-methacrylic acid copolymerization A polymer compound selected from the group consisting of compounds or salts thereof, with a degree of polymerization of 10 to 200.0.2
-4% by weight, (C) 0.2-4% by weight of polyethylene glycol with a molecular weight of 1000-50000, (d) General formula (wherein M is Na or K, and X is a number from 0.4 to 1.5) , Y is a number from 0.8 to 6.0, and W is a positive number including O) 5 to 3% by volume of aluminosilicate, (e) 10 to 6% alkali metal salt of carbonate. %, the content of phosphate is 10% by weight or less in terms of P2O5, and the content of alkali metal silicate is 5% by weight or less. The present invention provides a cleaning composition having the following properties.

Each component will be explained in more detail below.

Component (a): Water-soluble surfactants include the following anionic surfactants and nonionic surfactants. A straight or branched chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16.

2 Having a linear or branched alkyl group or alkenyl group with an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide, or ethylene oxide/propylene oxide in one molecule. D0.1/9.9~9.9/
Alkyl or alkenyl ether sulfates added in a ratio of 0.1 or ethylene oxide/butylene oxide in a ratio of 0.1/9.9-9.9/0.1.

3. An alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average carbon number of 10 to 20.

4 Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.

Anolkanesulfonate having an average of 10 to 20 carbon atoms in one molecule.

6 A saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule.

7 having an alkyl group or alkenyl group having an average carbon number of 10 to 20, and an average of 0.5 to 8 moles per molecule of ethylene oxide, propylene oxide, butylene oxide, or ethylene oxide/propylene oxide 0.1/9 .9 to 9.9/0.1 or ethylene oxide/butylene oxide 0.9 to 9.9/0.1.
Alkyl or alkenyl ether carboxylate added in a ratio of 1/9.9 to 9.9/0.1;

8 α-sulfo fatty acid salt or ester represented by the following formula (wherein Y is an alkyl group having 1 to 3 carbon atoms or a counter ion Z is a counter ion.

R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ) Here, the counter ions of the anionic surfactant include alkali metal ions such as sodium and potassium,
Examples include alkaline earth metal ions such as calcium and magnesium, ammonium ions, and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (e.g., monoethanolamine, diethanolamine, triethanolamine, triisopropylamine, etc.). It will be done.

9 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.

10 has an alkyl group with an average carbon number of 6 to 12, and 1 to 20
Polyoxyethylene alkylphenyl ether with moles of ethylene oxide added. 11 average carbon number 10-2
A polyoxypropylene alkyl or alkenyl ether having 0 alkyl or alkenyl groups and to which 1 to 20 moles of propylene oxide are added.

12 Polyoxybutylene 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 mol of butylene oxide is added 1
3 A nonionic surfactant (ethylene oxide and propylene oxide or The ratio with butylene oxide is 0.1/9.9 to 9.9/0.1).

Component (b): In addition to the homopolymer of acrylic acid, the polyacrylic acid may contain other copolymerizable monomers in an amount of 10% or less. Examples of other copolymerizable monomers include crotonic acid and maleic acid. , itaconic acid, mesaconic acid, aconitic acid, vinyl sulfonic acid, vinyl acetate, and the like.

Although the ratio of acrylic acid/methacrylic acid is not particularly limited, it is preferably acrylic acid/methacrylic acid of 911 to 1:9. These polymer compounds have a polymerization degree of 1
0 to 200 is preferable, and examples of the counter ion include sodium, potassium, lithium, ammonium, monoethanolamine, diethanolamine, triethanolamine, etc. Among them, sodium and potassium salts are preferable.

When these polymeric compounds are combined with component (C) usually in an amount of 0.2 to 4% by weight (hereinafter simply expressed as %), the free flow property is improved. Component (c): molecular weight 1,0
00 to 50,000 polyethylene glycol, which is waxy or solid at room temperature.

Those with a molecular weight larger than this are not preferred because they have poor solubility. When used in combination with component (b), this significantly improves free flow properties and prevents caking. This blending amount is preferably 0.2 to 4%. Component (d): the above formula (1
) is used, among which the following general formula (■), (where n is 1.8 to 3.0
and w represents a number from 1 to 6) is particularly preferred.

These are blended in an amount of 5 to 30%. Component (e): Examples of the alkali metal salt of carbonic acid include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, etc., of which sodium carbonate is particularly common. .

The combined acid content is preferably 10 to 60%. This alkali metal salt of carbonic acid can be blended in its entirety into the raw materials used to manufacture detergents, but a portion of it can be blended into the raw materials to make a detergent slurry, and after spray-drying this, 114 or more When an amount of an alkali metal salt of carbonic acid is mixed as a powder, a product with particularly excellent free-flowing properties can be obtained.

Furthermore, the above-mentioned essential component 2(a) is contained in the cleaning composition of the present invention.
In addition to ~(e), if necessary, known cleaning agent components,
Examples include concealment of other surfactants, divalent metal ion scavengers, alkali agents or inorganic electrolytes, anti-recontamination agents, bleaching agents, blue tinting agents, fluorescent dyes, enzymes, and factors that inhibit enzyme activity. Agents, enzyme activators, solubilizers such as acid oxidation inhibitors, etc. can be added.

The cleaning composition of the present invention is prepared by mixing the above components in a conventional manner,
It is manufactured by forming it into granular or powdered form.
The detergent composition of the present invention obtained in this manner also has a low content of alkali metal silicate, so there is almost no deposit of aggregates on the objects to be washed, and the detergent composition of the present invention is free from phosphates and alkali. Even when compared with those containing metal silicate, there is no inferiority at all.

Moreover, it is excellent in that it does not lose its free-flowing properties even after long-term storage. Next, an example will be given and explained.

(1) Preparation method of detergent sample Detergent slurry obtained from 60% detergent ingredients and 40% water was
A detergent powder was prepared by stirring three powders at 0° C. and spray drying.

When powdered carbonate was mixed with detergent powder, both were placed in a plastic bag and shaken well to mix. The water content of the detergent samples was measured in accordance with JIS 3362-1978. (■) Test and evaluation method (1) Measurement of water-insoluble matter Take 10'Cllf tap water in a 1e beaker, add 1.33g of detergent sample, and stir vigorously with a magnetic stirrer for 10 minutes.

Next, this solution was cut into a circular shape (about 12 cm in diameter).
After passing through a 200-mesh gilt copper sieve (opening 74 μm) using a JIS standard sieve of known weight, drying the gilt copper together in an electric dryer (105°C) for 30 minutes, and cooling it in a dencator for about 3 minutes. Measure the weight and subtract the weight of the gold-copper itself determined earlier to determine the amount of water-insoluble matter (the amount of gold-copper residue).
seek. The water-insoluble content is calculated from the obtained amount of water-insoluble matter and the amount of detergent sample used (1.33 g) according to the following formula. In addition, the changes over time in the water-insoluble components of detergents were measured in the same manner as above, using detergent samples placed in a shear tray and left indoors for two weeks without a lid. It was measured using

(2) Free flow test Free flowability was evaluated from the caking property of the powder.

Consolidation property was measured by placing a 12.5 g sample in a box made of Fuchi paper (
7.4cTn x 4.4cm x 2.8α (height)), flattened, placed a 7.2cm x 4.2cm iron plate on top, and kept at constant temperature and humidity at 30℃ and 80% RH. Leave it in the box for 7 days. Next, this detergent powder is poured onto a 47m×4T0n sieve. The powder weight A (g) remaining on the sieve and the weight B (g) passing through the sieve are measured, and the passage rate is calculated from the following formula: The larger the value, the less caking.

(3) Deposition test of water-insoluble substances on black cloth clothing (practical evaluation)
Pulsator type electric washing machine with shower rinse method (
Toshiba), add 30' of 10°C tap water, add 40g of detergent sample, and stir to dissolve.

Add to this the black cloth of Cotton Prode (#40) (one piece is 30
Pour in 400ml of 400ml and stir by inverting the mixture for a little over 1 hour. Thereafter, the washed black cloth was placed in a rinsing tank, rinsed using a shower rinse method for 7 minutes, and then dehydrated for 4 minutes.

After the dehydrated black cloth was air-dried, the amount of water-insoluble matter adhering to its surface was evaluated according to the following criteria. The front and back sides of each test cloth were evaluated, and each score was totaled to give an evaluation score. Therefore, a score of O is good, and the higher the score, the greater the amount of deposits.

(4) Cleaning power test 10X10C77 in detergent aqueous solution 1e! artificially contaminated cloth 1
Add two uncontaminated cloths of the same size so that the bath ratio is 1:60, and measure 10 with a tergotometer.
Washing was carried out at 0r'Pm under the following conditions.

The cleaning conditions and oil composition of the artificially contaminated cloth are as follows. [Washing conditions] Washing time 1 powder detergent concentration 0.1% Water hardness 8. DH Water Temperature 20℃ Cedar 5 minutes in tap water [Oil composition of artificially contaminated cloth] Cottonseed oil 60% Cholesterol 10 Oleic acid 10 Palmitic acid 10 Liquid and solid paraffin 10 Washing is contaminated (carbon black is mixed in as an indicator by the usual method) The reflectance of the original cloth and the contaminated cloth before and after washing was measured using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was determined using the following formula.

(The table shows the average value of 1-geki measurements). Example 1 A powdered detergent was prepared according to the formulation shown in Table 1, and the water-insoluble content and passage rate were determined.

The results are shown in Table 1, and as is clear from this, even if the alkali metal silicate (sodium silicate) is not contained at all or is less than 3%, the material containing high molecular compounds and polyethylene glycol is The invented product was a smooth powder cleaning agent with very little water-insoluble matter after a period of time and almost no caking.

Example 2 A powder detergent was prepared by adding 3% of each of the various polymer electrolytes shown in Table 3 to the basic formulation shown in Table 2, and the water-insoluble content and passage rate were evaluated.

The results are shown in Table-3. As is clear from these results, the cleaning composition containing the water-soluble polymer electrolyte disclosed in the present invention has a low water-insoluble content, has no powder caking property, and has excellent free-flowing properties. It can be seen that it is.

Example 3 A powdered detergent was prepared according to the formulation shown in Table 4, and after being exposed to air for one month in a shear dish, a deposition test on black cloth clothing was conducted.

Even when the detergent composition of the present invention is rinsed using a shower rinse method, there is almost no water-insoluble content that would deposit and remain on the clothes to be washed, and there is no problem at all in practice.

Example 4 Detergent samples with the formulations shown in Table 5 were prepared, and their cleaning power was evaluated using artificially contaminated cloth.

Claims (1)

[Scope of Claims] 1. Components (a) to (e): (a) a water-soluble surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, and mixtures thereof;
80% by weight, (b) 0.2-4% by weight of a polymer compound selected from the group consisting of polyacrylic acid or its salt and acrylic acid-methacrylic acid copolymer or its salt, with a degree of polymerization of 10-200. %, (c) molecular weight 1000-5000
0.2-4% by weight of polyethylene glycol (d)
General formula X(M_2O)・Al_2O_3・Y(SiO_2)・
W(H_2O) (where M is Na or K, X is 0.4
~1.5, Y is a number from 0.8 to 6.0, and W is a positive number including 0).
(e) 10 to 60% by weight of an alkali metal salt of carbonic acid, the content of phosphate is 10% by weight or less calculated as P_2O_5, and the content of alkali metal silicate is 5% by weight. A cleaning composition characterized in that it is in the form of granules or powder having a content of % by weight or less.