JPS6131497A - 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 application field] FIELD OF THE INVENTION This invention relates to detergent compositions.

[Conventional technology]

Conventionally, phosphates, especially sodium tripolyphosphate, have been mainly used as detergent builders, but as problems of eutrophication of rivers and lakes have arisen, phosphorus-free products have been considered.
Currently, synthetic zeolites are mainly used instead of phosphates. However, since synthetic zeolite is water-insoluble, it has drawbacks such as damaging washing machines and clogging drain pipes.

In addition, polycarboxylate salts such as sodium polyacrylate and sodium polyitaconate are being considered as detergent builders, but they have not been put into practical use due to the problem of extremely poor biodegradability.

[Problems to be solved by the present invention]

The present inventors have arrived at the present invention as a result of intensive studies aimed at finding a detergent composition with further improved biodegradability and detergency.

[Means for solving problems]

The present invention contains [1] a graft polymer (A) of a polysaccharide (a1) as a builder and a water-soluble ethylenically unsaturated monomer (a2), and [2] a surfactant (A). and the content of (A) is 6 based on the weight of the detergent composition.
50%.

In the present invention, the polysaccharide (a1) in the graft polymer (3) includes natural starch (for example, sweet potato starch, wheat starch, corn starch, etc.), modified starch (for example, pregelatinized starch, dextrin, oxidized starch, aldehyde starch, alkyl etherified starch, aryl etherified starch,
oxyalkylated starches and carboxymethylated starches), natural celluloses (such as celluloses obtained from wood, confectionery and gin bark etc.) and modified celluloses (such as alkyl etherified celluloses, organic acid esterified celluloses and carboxymethylated celluloses). can be given. These can generally be used without particular limitation, but from the viewpoint of cost, natural starch and dextrin are preferred.

The water-soluble ethylenically unsaturated monomer (a2) in the graft polymer (A) has at least one hydrophilic group (for example, an anionic group such as a carboxyl group, a carboxylic anhydride group, a carboxylic acid group, or a sulfonic acid group). group, hydroxyl group,
Nonionic groups such as ether groups and amide groups; amino groups,
A monomer having a cationic group (such as a quaternary ammonium base) can be used. Specific examples of such monomers include the following. These can also be used as a mixture of two or more types.

[■] Anionic monomer (■) Carboxyl group-containing monomer: Monoethylenically unsaturated mono- or polycarboxylic acid such as (meth)acrylic acid (means acrylic acid and methacrylic acid. The same expressions will be used hereinafter. ) Maleic acid, itaconic acid, fumaric acid, α-hydroxyacrylic acid, etc.

2. Carboxylic anhydride group-containing monomer: monoethylenically unsaturated polycarboxylic anhydride such as maleic anhydride.

3. Carboxylic acid group-containing monomer: water-soluble salt of monoethylenically unsaturated mono- or polycarboxylic acid, for example (meth)
Sodium acrylate, sodium maleate, sodium itaconate, sodium fumarate, sodium α-hydroxyacrylate, etc.

4. Sulfonic acid group-containing monomer: aliphatic or aromatic vinyl sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, etc.

4. Sulfonic acid group-containing monomer: 4. above. Water-soluble salt of sulfonic acid group-containing monomer. For example, sodium vinylsulfonate, sodium allylsulfonate, sodium vinyltoluenesulfonate, etc.

[■] For details on water-soluble monomers such as nonionic monomer 6, hydroxyl group-containing monomer S, monoethylenically unsaturated alcohol, and (meth)allylic alcohol, see JP-A-57-2100.
It is described in Publication No. 71.

(3) may be a graft polymer obtained by polymerizing (a1) with an ethylenically unsaturated monomer that becomes water-soluble by hydrolysis, and performing hydrolysis if necessary. Examples of ethylenically unsaturated monomers that become water-soluble upon hydrolysis include monomers having at least one group that becomes a hydrophilic group upon hydrolysis (ester group, nitrile group, amide group, etc.). These can also be used as a mixture of two or more types.

Examples of the ester group-containing monomer include lower alkyl Gl~3) esters of monoethylenically unsaturated carboxylic acids, such as methyl (meth)acrylate; esters of monoethylenically unsaturated alcohols, such as vinyl acetate acetic acid (meth)acrylate; It will be done. (Meth)acrylonitrile is an example of the monomer containing a nido9 group. Examples of the amide group-containing monomer include the above-mentioned amide group-containing monomers. The details are also described in Japanese Unexamined Patent Publication No. 57-210071.

Among the ethylenically unsaturated monomers mentioned above, carboxyl group-containing monomers are preferred, and particularly preferred are acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid.

Furthermore, among water-soluble monomers and monomers that become water-soluble by hydrolysis, the former are preferred.

In (A), the weight ratio of (a+) and (a2) can be varied, but is usually 100:5 to 2000, preferably 100:50 to 300. If (a2) is not 5, the performance as a bilgoo will be insufficient, and 2
If it exceeds 000, biodegradability decreases.

Graft polymerization can be carried out in a conventional manner. For example, the method described in Japanese Unexamined Patent Publication No. 57-210071 is used.

The molecular weight of the resulting graft polymer can be varied depending on the polymerization length, but is usually 1000 to 200.
The number is preferably 50,000 to 1,000,000.

Grafting rate is usually 1-100%, preferably 20-80%
%. If the grafting rate is less than 10%, biodegradability is poor. The grafting rate can be measured by a solvent extraction method (using methanol as a solvent), and can be determined by the following formula.

× 100 The detergent composition of the present invention contains (~ as a builder) and a surfactant. As the surfactant, anionic surfactants (alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfate ester salt) , alkanesulfonates, sulfo fatty acid ester salts, fatty acid salts, etc.); Nonionic surfactants (higher alcohol ethoxylates, higher fatty acid ethoxylates, coconut oil fatty acid jetanolamide, etc.); Cationic surfactants (alkyltrimethylammonium chloride) , dialkyldimethylammonium chloride, etc.); amphoteric surfactants (alkyldimethylaminoacetic acid betaine, etc.).In addition, other builders (sodium tripolyphosphate,
sodium metasilicate, sodium aluminosilicate, nitrilotriacetate, triethanolamine hydrochloride, etc.);
Inorganic compounds (mirabilite, urea, etc.); Alkali (caustic soda, soda carbonate, sodium silicate, triethanolamine, etc.); Acids (hydrochloric acid, citric acid, etc.); Solvents (ethanol,
Isopropyl alcohol, butyl alcohol, ethylene glycol, etc.); Water; Oxidizing agents (hydrogen peroxide, sodium percarbonate, etc.); Reducing agents (sodium bisulfite, etc.);
Chelating agents (e.g. ethylenediaminetetraantherate); anti-recontamination agents (e.g. carboxymethyl cellulose); abrasives (e.g.
Components such as talc, finely powdered silica, etc.); clouding agents; enzymes; fragrances; colorants; fluorescent dyes; and preservatives can be blended.

The amount of builder (A) in the detergent composition of the present invention is usually 6 to 50%, preferably 8 to 30%, based on the weight of the detergent composition. If the amount of builder (A) is less than 6%, the calcium ion trapping ability will be insufficient and the effects of the present invention cannot be expected. Moreover, even if more than 50% is mixed, the performance does not improve and it is economically disadvantageous.

The amount of surfactant (A) is usually 1 to 50%, preferably 5 to 40%, based on the weight of the detergent composition.

The amount of total builders [sum of (A) and other builders] is usually from 6 to 50%, preferably from 8 to 40%.

The detergent composition of the present invention can be prepared into a solid, powder, liquid, paste, slurry, etc. by a conventional method.

The method of using the detergent composition of the present invention is not particularly limited, and it is usually diluted with water to a ratio of about 100 to 10,000 times.

The composition of the present invention can be preferably used as a detergent composition for textile products. Textile products include natural fibers such as cotton, wool, and silk, recycled fibers such as cotton wool and rayon,
Textile products such as knitted fabrics made of semi-synthetic fibers such as acetate, synthetic fine fibers such as nylon, acrylic, polyester, and polypropylene, and various fibers that are a mixture of these, especially household products (underwear, diapers, lingerie, etc.)
, sweaters, etc.).

The method for applying it to textile products is, for example, by diluting it with water to prepare a cleaning bath, immersing the textile product in it, stirring it, rinsing it, and then squeezing it dry.

〔Example〕

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Examples 1-3. Comparative Examples 1-2 Using the builders shown in Table 1, detergent compositions were obtained with the following formulations.

Table-1 al: Polysaccharide sulfate) a2: Amount of water-soluble ethylenically unsaturated monomer (5') Immediately before composition of detergent Sodium alkylbenzenesulfonate 20 parts by weight Builder 20 Sodium silicate 8 Sodium carbonate
8CMC1 Total: 100 The detergency of this composition was tested in the following manner. The results are shown in Table 2. As shown in Table 2, the detergent composition of the present invention is comparable in detergency to synthetic zeolite, and the biodegradability of the builder graft polymer (A) is also superior to conventional polycarboxylic acid type products. There is.

Table 2 Biodegradability was measured according to the Ministry of International Trade and Industry law.

(Cleaning power) An artificial dirt was prepared by mixing the following organic dirt components, fired clay, and carbon black in a ratio of 69.7:29.8:0.5 (weight ratio).

Organic dirt components (weight ratio) Oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin
2.5 squalene
2.5 cholesterol 1
．． 6 Gelatin 7.0 Using this artificial dirt, a contaminated cloth was created using a water-based wet method.
This was cut into 5cm x 5cm and the reflectance was 38±2%.
Tests were conducted in the following range. For the test, this contaminated cloth 1
Washing was carried out under the following conditions using 0 cloth and 3 sheets of additive cloth to which 607n9 of organic dirt was attached per cloth.

Washing condition tester: Ter g-0-Tome ter rotation speed: 12 Orpm Washing liquid amount: 90 (lyn, l!) Water hardness: 90 ppm (CaCOa conversion) Detergent concentration: 0.10% Temperature: 30°C Bath ratio: 30 times (adjusted with clean knitted cloth) Washing time:
10 minutes rinsing time; 3 minutes x 2 drying; 3 iron drying between sheets of paper.Then, the surface reflectance of the cloth before and after washing was measured, and the detergency was determined from the following formula.

K/S-(1-R)/2RR: Surface reflectance of cloth [Effect of the invention] The detergent composition of the present invention exhibits good detergency for textile products even in hard water.

Additionally, the builder used is highly biodegradable and water-soluble, so there is no need to worry about damaging your washing machine or clogging drain pipes. Furthermore, there is no problem of eutrophication of rivers, lakes and marshes due to phosphorus.

Claims (1)

[Scope of Claims] 1. [1] A graft polymer of a polysaccharide (a1) as a builder and a water-soluble ethylenically unsaturated monomer (a2) (
A) and [2] surfactant (B), and the content of (A) is 6 to 5 based on the weight of the detergent composition.
A detergent composition characterized in that it contains 0%.