JPS58206696A - 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 The present invention relates to detergent compositions containing novel phosphorus-free pilters.

Currently, phosphates, especially sodium tripolyphosphate, which are widely used as filters for detergents, have excellent properties as filters, but on the other hand, they can cause water pollution due to eutrophication in closed water systems such as lakes, marshes, and inland seas. It is cited as one of the causes of this and has become a social problem. For this reason, measures are being taken to reduce the content of phosphates, and ultimately there is a trend towards phosphorus-free products. Therefore, there is an urgent need for the development of a pirter that can replace the above-mentioned phosphates.

In recent years, synthetic olide, which has been used as a filter for phosphorus-free detergents, not only has problems with its supply capacity, but also because it is water-insoluble, causing problems such as abrasion of the top shaft of the washing machine and precipitation during drainage. There are drawbacks. In addition, carposi acid salts such as sodium decacetate, sodium zirconate, and sodium quesitate are used as filters for phosphorus-free detergents.
Polycarbo:J acid salts such as sodium polyacrylate and sodium polyitaconate are being considered, but among these, sodium osadiacetate has safety problems such as 11% travel in the skin, and zirconate When sodium is used, the detergency is not sufficient, and polycarposis salts such as sodium polyacrylate and sodium polyitaconate have a problem of extremely poor biodegradability, so they have not been put into practical use. Quesitate, which is used in a small amount, is not only a joint, but also has a fermentation method, so it is difficult to supply and has not been used continuously.

In view of the above-mentioned current situation, the present inventor has developed a product that does not contain lysates that cause eutrophication, has good biodegradability, does not cause pollution, and has excellent filter performance such as calcium iodine sequestration ability and dispersion ability. Moreover, as a result of intensive research to develop a detergent pilter that would not cause problems in terms of supply, the present invention was completed by discovering that a certain type of polycarposi acid salt satisfies all of these conditions.

That is, according to the present invention, the general formula [in the formula 5. V represents sodium, potassium or aci7nium, and X represents a hydrogen atom or -CCH2)5COOM.

indicates an integer from 1 to 3. ] It concerns on the detergent composition characterized by containing the polycarposis acid salt represented by these as a pirter.

Although the polycarboxylic acid salt represented by the general formula (1) is known as a compound, it has never been used in detergents and was newly developed by the present inventor as a detergent pilter. be.

The polycarposi acid salt having the general formula fl+ is suitably produced according to a known method, for example, the method described in JP-A-55-139336, but the method is not limited thereto.

That is, the polycarposis acid salt of general formula (1) is obtained by converting a polyharbosic acid ester obtained by reacting at least one of maleic acid ester, maleic acid anhydride, and Nisder fumarate with cyclohexane and hydrogen peroxide. It can be obtained by

The above manufacturing method will be explained more specifically. In the presence of an acid catalyst, cyclo+saccharide reacts with hydrogen peroxide to produce al]+cyclosulfuride. There is no particular limitation on the ratio of the ratio of nitrogen peroxide to hydrogen peroxide, but the ratio of the former to 0.5 to 2 (&
It's good to have 4 people. Hydrogen peroxide is usually used in the form of an aqueous solution with a concentration of about 30 to 40%, and as the acid catalyst, a wide range of known mineral acids can be used, including phosphoric acid, ricic acid, hydrochloric acid, etc. I can do it. The line used for such an acid catalyst is Schiff D.
It is recommended that the ratio of 100 parts to 100 parts is usually 0.5 to 10 parts.

Examples of alcohols that can be used include methanol, ethanol, tart-butanol, iso-durobanol, tart-ttanol, and the like. The amount of alcohol to be used is usually about 200 to 1000 parts by weight per 100 parts by weight of cyclohe+satsushi.

The reaction is generally carried out at a pressure of about 0 to 30 tT, usually 5 tT.
The reaction is complete in about 60 minutes. maleic acid ester,
At least one of maleic anhydride and fumaric acid ester may be present at the beginning of the reaction, or may be added after the completion of the reaction. For example, when using maleic anhydride, the solvent alcoholic acid and
It becomes a maleic acid ester.

Then, the alkyl dicyclosilyl oxide and the maleic acid ester or/and fumaric acid ester are reacted in the presence of a ferrous salt. The ratio of alco + dicyclo + silver oxide and maleic acid ester or (and) fumaric acid ester to be used is not particularly limited, but it is generally recommended to use about 1 to 3 times more of the latter to the former. good.

Specific examples of maleic acid esters and fumaric acid esters include maleic acid esters such as zi-ru maleate and diethyl maleate, zi-ru-ra 0 pill maleic acid, di-butyl maleate, di-tert-butyl maleate, and the like. Examples include fumaric acid esters such as esters, di-21-butyl fumarate, diethyl fumarate, di-1-di-butyl fumarate, di-butyl-fumarate, and di-11γl-butyl fumarate.

Examples of ferrous salts include ferrous sulfate and weird ferrous salts.

Examples include ferrous acetate, ferrous sulfate, and t:dimuth salt. The amount of ferrous salt used is usually 1 to 2 for Alco + Zircro + Silver Oshido It.
It is preferable to set it to about 100 ml. The reaction is usually -10-IO"
The reaction is carried out with CK, and the reaction is completed in about 5 to 2 hours at -ffKo. In this way, a polycarposi acid ester in the general formula (1) in which M is an alkyl group is obtained.

Next, the obtained polycarboxylic acid ester is pycnized by a conventional method to obtain a polycarboxylic acid group of the general formula (1) in which M is sodium, potassium, or acynium.

The polycarposi acid salt of the general formula [l] obtained from the reaction V is usually a mixture of each compound represented by the general formula i1.
In the present invention, -C can be obtained in powder form, but in the present invention, each compound may be separated, but usually it is used as a mixture as a detergent bilter without separation.

In the detergent composition of the present invention, it is essential to contain a polycarposi acid salt of general formula (1) as a bilter. The amount used is selected from a wide range without particular limitation, but is preferably 3 to 50% by weight of the entire composition.

As the surfactant in the detergent composition of the present invention, any known surfactant can be used without particular limitation, such as linear alkylbenzexulfonate (hereinafter referred to as LAS), α -Olefin sulfonate (hereinafter referred to as AO5), olefin sulfonate (hereinafter referred to as AO5),
(hereinafter referred to as HO5), alkaline sulfate (hereinafter referred to as As), alkaline sulfate (hereinafter referred to as As), alkaline sulfate salt (hereinafter referred to as A
es), 2-sulfo fatty acid ester salt (hereinafter referred to as S
FE), secondary alkadisulfo:J salt (hereinafter referred to as S
(hereinafter referred to as -A P E), aniolytic activators such as AS), aniolytic activators such as AS), alioxylic acid activators (hereinafter referred to as -A P E), P
-Al+; Noniosilic acid activators such as lephenylbolyoxylic acid ether (hereinafter referred to as APPE) can be obtained, and at least one of these, a favorable anionic activator and a nonioral activator 2-4t combining
IIi is used.

In addition to the above-mentioned pills and surfactants, the detergent composition of the present invention may also contain various additives commonly used in compositions of this type, such as other bilter silicates such as synthetic zeolites, carbonic acid, etc. Auxiliary buildings such as salts, sulfates, borates, etc.
Carboxylic dimethylcellulose (hereinafter referred to as CAi C), polyethylene dimethylcellulose (hereinafter referred to as CAi C), polyethylene dimethylcellulose (hereinafter referred to as PEG), polyvinyl dimethylcellulose (hereinafter referred to as PVP), polyvinyl alcohol (hereinafter referred to as PVA) Anti-recontamination agents such as, other antifoaming agents, whitening agents, fluorescent whitening agents, K +:
, /di-inhibitors, enzymes, fragrances, etc. can be used in combination as appropriate.

The detergent composition of the present invention is in the form of ordinary compositions of this type, that is, powder, granules, liquid, paste, etc. = 7L
It may be in the form of , and its usage is the same as that of the conventional one.

In the dud 191 detergent composition, it is distributed as a bilter.
Polycarposis salts with the general formula +1) do not absorb phosphorus, which is a cause of water pollution due to eutrophication of lakes, etc., and are water-soluble low-molecular compounds, so they have good biodegradability and do not cause pollution. In addition, as shown in the test examples described later, it has excellent silage performance, and in terms of supply, it is easy to scale up the rashite, and can fully meet the increasing demand.

Therefore, the detergent composition of the present invention does not cause pollution, has good detergency, and is cost effective.

Below are reference examples and test examples 1. The present invention will be explained in more detail with reference to Examples, Comparative Examples, and Experimental Examples.

Valley example l 150f of dimethyl malate to 350tr of methanol
To this, add 802.35 g of Schiff D + Satsushi 802, 802 hydrogen peroxide solution and 3 g of concentrated sulfuric acid, and add 18 to 20 g
The mixture was stirred at ℃ for 30 minutes. Next, the reaction bath liquid was cooled to -5° C., ferrous sulfate 2401 was gradually added (with stirring), and the reaction was continued for 60 minutes by further stirring. After the reaction is complete, 60% sulfuric acid 182 is added, stirred, and left to separate. −
Layer E was taken, washed sequentially with dilute sulfuric acid and water, and then dehydrated to obtain liquid methyl polycarpodiaate 1601.

Add 0.5% of this methyl polycarpositate to 50y with stirring.
Ethanolic sodium hydroxide solution of N 3100+++
Add t and saponify to sodium polycarposiate 150
I got 2.

This sodium polycarposis acid has a compound of the general formula % Vi 2 as a main component, and these KAf=Na,
It was a mixture containing a small number of compounds with X=H and 7L=l.

Test Example 1 #The pH buffering abilities of sodium polycarposis acid obtained in Example 1 and commercially available sodium tripolysinate were compared side by side.

The pH buffering capacity of an aqueous solution of sodium recarbosinate or sodium tripolysilicate (nest system) and an aqueous solution containing sodium metasilicate and sodium sulfate (compound system) was investigated.

The concentration and buffer capacity of each solution are shown in Table 1 below.

Table 1 Rice test solution (+lF, initial pH of 100 ml
Amount of 02N hydrochloric acid to be reduced (ml) As is clear from Table 1, sodium polycarposiate is
It had a good buffering capacity in a single system, and showed a buffering capacity higher than that of tripolyricic acid in a blended system.

Test Example 2 The calcium iodine sequestering abilities of sodium polycarposis acid obtained in Reference Example 1 and commercially available sodium tripolysinate were investigated and compared.

That is, 1% calcium acetate was added dropwise to 50 d of a 0.6% sample solution to which sodium dodisylbecisecis sulfosinate was added as a precipitation indicator, and the calcium iodine sequestering ability was examined. The results are shown in Table 2 below.

2nd table wood Method A: Measured by adjusting P// to 10 with O, IN sodium hydroxide.

Method B: 0.5% sodium metasilicate aqueous solution
The measurements were taken in addition to

Yuzubo C method: Measured as is without pH adjustment.

As is clear from Table 2, sodium polycarboxylate is
Regardless of the presence or absence of pH adjustment, it exhibited an excellent calcium iodine sequestration ability almost equivalent to that of sodium tripolysilicate.

Test Example 3 The dispersion ability of the sodium polycarboxylate obtained in Reference Example 1 and the commercially available sodium tripolysilicate in machigan dioxide was investigated and compared.

That is, 0.19 mankasi dioxide was added to 250 ml of an aqueous solution with a sample concentration of 0.1% and a sodium dodicylbecizenesulfosinate concentration of 0.05%, and the suspension was stirred and dispersed, and the suspension was placed in a 100 ml graduated cylinder. I left it still. After 1 hour, suspension 10111 from the scale position of 80ml! The dispersion ability of each sample was investigated by measuring the mangas concentration using atomic absorption spectrometry. The results are shown in Table 3 below.

As is clear from Table 3 SA3, polycarposi acid sodium t
Ram showed good dispersion ability of Masi dioxide almost comparable to sodium tripolysilicate.

According to Test Examples 1 to 3 above, sodium polycarposis has excellent pilling performance comparable to that of sodium tripolysilicate in all categories of pH buffering capacity, calcium sulfur sequestration capacity, and carbon dioxide dispersion capacity. I understand.

Example 1 A powdered detergent composition of the present invention having the following composition was produced.

Surfactant LAS
17 Bilter auxiliary filter Sodium metasilicate 5 Sodium carbonate 3 Sodium sulfate 54 Redoiling inhibitor CMC) Example 2 A powdered detergent composition of the present invention having the following composition was produced.

Surfactant Heavy LAS
l 1AO5-11 :4 pz
3 Sodium polycarboxylate 20 Sodium luther metasilicate 5 Sodium carbonate 3 Sodium sulfate 46 Reinjection inhibitor C5 Hiki IC) Example 3 Powdered antifil of the present invention with the following composition Manufacture things (.

Surfactant) I: LAS
IIΔUS
71 APE 3 Pill Information - 1 Sodium Recarbosinate IO6 Zeolite 10 Auxiliary Sodium Metasilicate 5 Sodium Carbonate 3 Sodium Sulfate 46 Redoiling Inhibitor CMCI Example 4 A pasty cleaning composition of the present invention having the following composition was produced.

Surfactant Molded Chi AO511, 4P E I 4 Pills <- Sodium Polycarbosinate 10 Synthetic Zeolite ・□゛・4t.

Auxiliary bilter sodium metasilicate 5 Sodium carbonate 20 Sodium hydrogen carbonate 19 Sodium sulfate 1O redointment inhibitor C, MC1 Comparative example! A powder detergent composition having the following composition was produced.

Surfactant: 1 L, 4 S
] 7 Pills - Sodium silicate 20 Auxiliary pills Sodium metasilicate 5 Sodium carbonate 3 Sodium sulfate 54 Redoiling preventive agent CM CI Comparative example 2 A powdered detergent composition having the composition of Formula F was manufactured. .

Surfactant Heavy-walled Chi LAS
17 Pilter Synthetic Zeolite 20 Auxiliary Luther Sodium Metasilicate b5 Sodium Carbonate Sodium Sulfate 54 Re-staining Prevention Agent CMC' Comparative Example 3 A powder detergent composition having the following composition was produced.

Surfactant Juyarichi LAS
17 Sodium bilter tripolysilicate 20 Auxiliary pi II 7 Sodium goometa silicate 5 Sodium peroxylate 3 Sodium sulfate
54...Re-staining prevention agent CMCI Comparative Example 4 A powdered detergent composition having a Dopa-Si composition was produced.

Kai ゛9'' activator (enchi L, i
5 17shi'ru da -

0 Kamisukeji Luther Sodium Metasilicate C) Sodium Carbonate 3 Sodium Sulfate
74 Recontamination Prevention Agent CtW C1 Experimental Example! Cutting compositions of Examples 1 to 4, law compositions of Comparative Examples 1 to 4, '! The cleaning power of Shibini's commercially available thermal detergent A (surfactant content: 17% by weight) was investigated using the following artificially contaminated cloth, cleaning power test, and cleaning power calculation method.

1 Artificially contaminated cloth oil +001, air conditioning cyst 2002 and oleic acid 8
A standard cotton cloth was immersed in a continuous staining machine and contaminated by adding water to 2 tons, dried, and further aged for 3 weeks to obtain an artificially contaminated cloth. The composition of the oil is 10 parts of balmitic acid, 5 parts of stearic acid, and 1 part of oleicic acid.
Parts by weight of O, 5 parts by weight of linoleic acid, 15 parts by weight of coconut oil, 20 parts by weight of sari-zu oil, 0'715 parts by weight of whale oil, 10 parts by weight of Barafisi, 10 parts by weight of Barafishi, 5 parts by weight of Squale, 75 parts by weight of Juho, and] Reste D −
5 parts by weight.

2 Cleaning power test Artificially contaminated cloth obtained as described above (dimensions 10 x 10 c
rn) and 4 sheets of original white cloth (same dimensions) were placed in a 1z detergent solution and washed with a tertometer at the following conductivity.

Washing conditions Detergent # degree 0.133 heavy duty water Temperature 30℃ Washing time 10 minutes Water 50 ppm Hard water (C'αtan/
M, q "t=2/l) Rotation speed 12Q rprn Rinse 3 minutes 21~・1 3 Minide method of cleaning power Ro: Reflectance of original cloth R5: Reflectance of contaminated cloth before cleaning /? +71: Washing Reflectance of contaminated cloth after washing
Table 4 shows the results of the detergency test for the bi products.

Table 4 As is clear from Table 4, the detergency of the detergent composition containing the polynocarboxylic acid salt of the present invention is comparable to that of the detergent composition containing -nobolyphosphate, and is superior to the commercially available dQ Rishi detergent. It can be seen that it is significantly superior to the phosphate substitute PILTER combination antibiotic 11, which has been tested and tested in the United States.

− (hereafter −hi)′ C,,”’;j-

Claims (1)

[Claims] (f) General formula [wherein M is sodium, potassium or a:, /7nium, and X is a hydrogen atom or -(CB2')5 COO,'
71 Rizu d. indicates an integer from 1 to 3. ] A detergent composition characterized by containing a polycarposis salt represented by the following as a pilther. (Fang + l: recarbosinate, Malay:) vinegar ester,
Claim No. 1, which is obtained by converting polycarposiic acid ester J obtained by diluting at least one of maleic anhydride and fumaric acid ester with Schiff D, Sanone, and hydrogen peroxide. The detergent composition according to item 1.