JPS6254360B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a detergent composition with excellent restaining properties. It is known to add carboxymethylcellulose soda salt and polyvinyl alcohol having various degrees of polymerization and saponification to detergents in order to prevent recontamination by insoluble substances in cleaning solutions. However, although the addition of these water-soluble polymers exhibits a certain degree of recontamination prevention effect, the effect is still not sufficient. It is also known to use polyvinyl alcohol copolymerized and modified with an allyl compound, an unsaturated carboxylic acid, and propylene as a polymer that has superior re-staining prevention properties compared to the above-mentioned carboxymethylcellulose soda salt and polyvinyl alcohol. However, there is a problem that the anti-recontamination effect is still not completely satisfactory, and there is a desire to develop an even stronger anti-recontamination agent. The present invention meets this demand, and the detergent composition of the present invention has a copolymer composition containing olefin sulfonic acid or a salt thereof (A).
Modified polyvinyl acetate containing 0.2 to 15 mol%, vinyl acetate (B) 99.8 to 60 mol%, and vinyl monomers other than the above (C) 0 to 40 mol% is blended into the detergent component. The detergent components used in the present invention are not particularly limited, but include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene acyl ester,
polyoxyethylene sorbitan fatty acid ester,
Examples include nonionic surfactants such as sorbitan fatty acid esters, and anionic surfactants such as higher alcohol sulfate ester salts, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene sulfates, and soaps. Activators can also be used.
Although soaps tend to have poor solubility in cold water and inferior cleaning power compared to synthetic detergents, if a specific modified polyvinyl acetate is added as in the present invention, in addition to preventing re-staining, soaps also have a tendency to be resistant to cold water. Improvements in solubility and detergency can also be expected. Detergent ingredients include builders such as sodium tripolyphosphate, sodium sulfate, and sodium silicate as necessary.
Auxiliary agents or additives such as fluorescent brighteners, enzymes, skin roughness preventive agents, solubilizers, disinfectants, bleaching agents, and softeners may be added. The modified polyvinyl acetate to be added to the detergent has the above-mentioned copolymer composition. The main component constituting the copolymer is vinyl acetate (B), which contains at least 60 mol%, preferably
It needs to be 70 mol% or more. Another essential component constituting the copolymer is an unsaturated sulfonic acid or a salt thereof (A) such as ethylene sulfonic acid, allyl sulfonic acid, methalylsulfonic acid, N-sulfoalkyl acrylamide, N-sulfoalkyl methacrylamide. The copolymerization ratio of this component is 0.2 to 15 mol%, preferably 0.5 to 15 mol%.
It is required to be 10 mol%. The copolymerization ratio of (A) is
If it is less than 0.2 mol%, the water solubility is insufficient and the re-staining prevention effect is insufficient, while if it exceeds 15 mol %, the re-staining prevention property is reduced and the production of the copolymer itself becomes industrially difficult. I'm getting old. The copolymer contains a vinyl monomer (C) other than the above (A) and (B) as an optional component of 40 mol% or less, preferably 30 mol% or less.
There is no problem even if the content is less than mol%. Such vinyl monomers include vinyl alcohol and other copolymerizable vinyl monomers. The amount of the modified polyvinyl acetate added to the detergent can be arbitrarily selected. The concentration of detergent in water during use
It is desirable to determine the blending amount of the two so that the concentration of the modified polyvinyl acetate is approximately 0.01 to 10 g/approximately. The detergent composition of the present invention can be applied to cleaning any type of fabric, including cotton fabric, fabric made of synthetic fibers such as polyester, nylon, polyacrylonitrile, vinylon, etc., or fabrics blended with cotton and synthetic fibers. It shows excellent recontamination prevention properties. Next, the detergent composition of the present invention will be further explained by giving examples. Example 1 A recontamination test was conducted under the following conditions. Detergent Nonionic detergent sample cloth made of polyoxyethylene nonyl phenyl ether (HLB=12.9, cloud point 50-55℃) 1 Polyester cloth (pretreated with pancreatin and washed with a nonionic surfactant) Trial cloth Cloth 2 Cotton cloth (pretreated with diastase and then washed with nonionic surfactant) Dirt α-Fe ₂ O ₃ modified polyvinyl acetate Allyl sulfone with sodium allylsulfonate content of 2.5 mol% and vinyl acetate content of 97.5 mol% Prepare a contaminated solution at a temperature of 40℃ consisting of 1 g of acid soda vinyl acetate copolymer detergent, 0.5 g of dirt, and 0.5 g of modified polyvinyl acetate, and add a 5 cm x 5 cm sample cloth to 100 ml of this contaminated solution. and in a round-o-meter type washing machine.
A cleaning test was conducted for 30 minutes at 42 rpm. The sample fabric was then shaken at 40°C for 1 minute, air-dried, and ironed. The reflectance of Hiranuma SPR-3 was measured for this contaminated cloth (and the original cloth), and the recontamination rate = Reflectance of the original cloth - Reflectance of the contaminated cloth / Reflectance of the original cloth x 10
The recontamination rate was calculated using the formula 0. The smaller the recontamination rate, the better the recontamination prevention property. The results are shown in Table 1. Control Examples 1 to 9 When addition of modified polyvinyl acetate was omitted (Control Example 1), carboxymethylcellulose soda salt (Control Example 2) was used instead of modified polyvinyl acetate, polyvinyl with a degree of polymerization of 500 and a degree of saponification of 98.5 mol% Alcohol (Control Example 3), polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 88.0 mol% (Control Example 4), Example 1
The vinyl acetate component of the modified polyvinyl acetate used in
Modified polyvinyl alcohol obtained by saponifying 85 mol% (Control Example 5), polyvinylpyrrolidone (Control Example 6), polyacrylic acid (Control Example 7), allyl glycol-vinyl acetate copolymer with an allyl glycol content of 8 mol% Allyl glycol-modified polyvinyl alcohol obtained by saponifying 98 mol% of the vinyl acetate component of (Comparative Example 8), and saponifying 99 mol% of the vinyl acetate component of a propylene-vinyl acetate copolymer with a propylene content of 3 mol%. Experiments were conducted in the same manner as in Example 1 using the obtained propylene-modified polyvinyl alcohol (Comparative Example 9). The results are shown in Table 1.

[Table] Examples 2 to 5 In place of the modified polyvinyl acetate used in Example 1, polyvinyl acetate obtained by saponifying 20 mol% of the vinyl acetate component of the modified polyvinyl acetate used in Example 1 (Example 2), Sodium methallylsulfonate-vinyl acetate copolymer (Example 3) with sodium allylsulfonate content of 2.2 mol% and vinyl acetate content of 97.8 mol%, 35 mol% of the vinyl acetate component of the copolymer used in Example 3 was saponified. (Example 4), ethylene sulfonic acid content 1.5
An experiment was carried out in the same manner as in Example 1, except that the ethylene sulfonic acid-vinyl acetate copolymer (Example 5) having a vinyl acetate content of 98.5 mol % was used. The results are shown in Table 2.

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Claims (1)

[Claims] 1 Copolymerization composition: unsaturated sulfonic acid or its salt (A) 0.2 to 15 mol% Vinyl acetate (B) 99.8 to 60 mol% Vinyl monomer other than the above (C) 0 to 40 mol% A detergent composition containing a certain modified polyvinyl acetate as a detergent ingredient.