JPH0668113B2 - Cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is excellent in the ability to remove protein stains adhering to clothing, and is extremely effective in preventing yellow bunting in repeated wearing and selection of clothing such as underwear. Cleaning composition.

[Conventional technology and problems]

In recent years, due to the problem of eutrophication of water quality by phosphate builder, as an alternative substance thereof, the following general formula X (M ₂ O) ・ Al ₂ O ₃・ Y (SiO ₂ ) ・ W (H ₂ O) ( In the formula, M is Na or K, X is a number of 0.7 to 1.5, and Y is 0.
The numbers from 8 to 6.0, and W represents an integer including 0. ) A low-phosphorus or phosphorus-free detergent compounded with an aluminosilicate is becoming the mainstream.

However, the phosphorus-free detergent according to the prior art is not satisfactory in cleaning performance at low temperature because the ion exchange capacity of aluminosilicate is low at low temperature. Therefore, it is known that various substances such as a bleaching agent, an enzyme and a nonionic surfactant are blended as a detergency enhancer for a phosphorus-free detergent. Of these, enzymes, especially proteases, are effective for skin stains and protein stains such as collars, sleeves, etc., but the proteases conventionally used have a high optimum temperature for exerting their enzyme activity, so that particularly low temperature In the range, the effect of blending with a phosphorus-free detergent was not sufficient, and performance enhancement in the low temperature range was strongly desired. Therefore, a low-temperature protease having optimum conditions in the low-temperature range has been developed and compounded in a detergent for clothes, and has a great effect (see JP-A-60-84397).

However, even with such a low-temperature protease, the cleaning performance in the low-temperature range (20 ° C. or lower) is not yet perfect, and the conventional protease is completely insufficient in performance. Further, even when a protease-containing detergent is used, yellow blemishes such as underwear due to sebum remaining after repeated wearing and washing have often been a cause of concern for consumers.

[Means for solving problems]

Therefore, as a result of intensive investigations by the present inventors to overcome such problems, a mixture of anionic surfactant in a specific ratio range with a specific amount of alkaline protease and a specific polymer was added to the detergent. According to the above, the cleaning performance for sebum stains and protein stains is remarkably improved in a wide temperature range even with not only low temperature proteases but also conventional alkaline proteases. The present invention has been completed by finding out that it is effective.

That is, the present invention includes (a) a linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 and an olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule. Α-sulfo fatty acid salt or ester represented by the general formula (I) (In the formula, R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, Y represents an alkyl group having 1 to 3 carbon atoms or a counter ion, and Z represents a counter ion.) (B) Alkaline protease (c) General formula (II) (In the formula, M is a group selected from the group consisting of alkali metals, ammonium, alkyl groups and alkanolamine groups, and p is an average value of 4 to 200.) consisting only of a polyacetal carboxylate segment. Or, mainly such segments,
A polymer which is stabilized against alkali and contains the above three components, and the content of the component (a) is 5 to 30% by weight (however, the compounding ratio of ,, in the component (a) is a polymerization ratio / / = 80/10 / 10-30 / 60 / 10-30 / 35/35
Limited to within the range surrounded by 4 points of ~ 55/10/35. ),
There is provided a detergent composition, wherein the content of the component (b) is 0.001 to 10% by weight and the content of the component (c) is 0.1 to 30% by weight.

Anionic surfactant (a) used in the present invention
Is an alkylbenzene sulfonate, an olefin sulfonate, an α-sulfo fatty acid salt or ester, and an alkali metal salt, an ammonium salt or an alkanolamine salt can be used as the salt, but a sodium salt is preferable. However, when these are used alone or in an appropriate combination, the effect intended by the present invention cannot be obtained, and the weight ratio of, is: / = 80/10/10 to 30
/ 60/10 to 30/35/35 to 55/10/35, and the total amount of the mixture should be 5 to 30% by weight. If the ratio is outside the range surrounded by the above four points, the cleaning performance is not improved, and if the total content is less than 5% by weight, the cleaning performance is insufficient and the effect of the present invention cannot be obtained. If it exceeds 5% by weight, the powder physical properties deteriorate.

As the protease (b), an alkaline protease whose activity expression is sufficiently retained even in an alkaline state is preferably used for the purpose of the present invention. The alkaline protease that can be used includes those distributed in animals, plants, bacteria and fungi, and purified fractions thereof, and is not particularly limited. Examples of preferred proteases used in the present invention include the following, but the present invention is not limited thereto.

(1) Bacillus-derived alkaline serine protease described in JP-A-51-8401 (Novo Industries, Ltd.) (2) Strong alkaline protease derived from Fusarium-genus or Gibberella-genus described in JP-A-46-43551 (Takeda Yakuhin) (Industry) (3) Bacillus-derived alkaline protease described in JP-A-46-42956 (Gyoshu) (4) Acremonium-derived alkaline protease described in JP-A-54-62386 (Kirin beer) (5) Alkaline protease originating in the genus Achromobacter described in JP-A-59-59189 (Wako Pure Chemical Industries) (6) Alkaline protease originating in the Bacillus described in JP-A-48-2794 (RIKEN) (7) Special Alkaline protease of Bacillus origin described in Kai Sho 50-16435 (RIKEN) (8) Alkaline protease of Bacillus origin described in JP-A-53-18594 (RIKEN) (9) Alkaline protease of Bacillus origin described in JP-A-55-46711 (RIKEN) (10) Alkaline protease of Bacillus origin described in JP-A-57-42310 (Gist Brocades) (11) Bacillus-originating alkaline protease described in JP-A-56-16200 (Gist-Brocades) (12) JP-A-56-24512-Bacillus-originating alkaline protease (Gist-Brocades) (13) Bacillus-originating alkaline protease described in JP-A-47-1832 (Sanraku Ocean) (14) Bacillus-originating alkaline protease described in JP-A-52-35758 (Baxter Trabenol Laboratories) (15) JP-A-50 -34633-derived alkaline protease derived from Bacillus subtilis (Nagase & Co., Ltd.) (16) Alkaline protease derived from cephalosporium described in JP-B-46-41594 (Fuji (17) Alkaline protease of Bacillus origin described in JP-A-58-134990 (Showa Denko) (18) Alkaline protease of Bacillus origin described in JP-A-55-14086 (Gist Brocades) ( 19) Bacillus-derived alkaline protease described in JP-A-51-82783 (Gist Brocades) (20) Bacillus-derived alkaline protease described in JP-A-51-125407 (Gist-Brocades) (21) Hypoallergenic protease of Bacillus origin described in JP-A-55-39794 (Novo Industries) (22) Alkaline protease of Serratia origin described in JP-A-46-1840 (Research Corporation) (23) ) Alkaline proteases derived from the genera Acremonium, Cephalosporium and Aleurismium described in JP-A-48-23989 (Albright E. De Wilson
(24) Thermostable alkaline protease originating in the genus Sermus described in JP-A-58-152482 (Amano Pharmaceutical Co., Ltd.) The alkaline protease is a purified fraction as well as a purified fraction.
Naturally, crude enzymes and their granules can also be used.

In the detergent composition of the present invention, the alkaline protease must be contained in a necessary amount according to the purpose, that is, 0.001 to 10% by weight in terms of purified enzyme. From the viewpoint of producing a detergent composition, it is preferable to use these enzymes as enzyme granules obtained by mixing the crude enzyme or the crude enzyme with other components in the detergent composition and granulating in advance. . In this case, a crude enzyme or a granulated product is used as a purified enzyme so as to be 0.001 to 10% by weight.

Next, the polymer (c) is a polymer of acetal carboxylate and is described in JP-A-54-52196. Such a polymer (c) is disclosed in JP-A-54-52196. As described in (1), it can be prepared by mixing an ester of glyoxyaldehyde and a polymerization initiator under polymerization conditions and stabilizing the resulting polymer against rapid depolymerization in an alkaline solution. The stabilized copolymer can also be saponified to form a salt of this polymer. At this time, it is also possible to copolymerize one kind or two or more kinds of comonomer which can be polymerized with the ester of glyoxylic acid aldehyde. Suitable comonomers include, for example, epoxy compounds such as ethylene oxide, propylene oxide, epihalohydrin epoxysuccinate, aldehydes such as formaldehyde, acetaldehyde, and aldehydes containing up to 20 carbon atoms. A comonomer having 1 to 4 carbon atoms,
For example, ethylene oxide, formaldehyde or acetaldehyde is preferable.

The mixture of comonomers can be polymerized with the aldehyde ester to form a terpolymer, or a more complex polymer structure.

Such a polymer or copolymer is provided with a chemically reactive group at the end of the polymer to be stabilized against rapid depolymerization in an alkaline solution. Particularly suitable terminal groups include alkyl groups, oxygen-containing alkyl groups and oxygen-containing cyclic alkyl groups such as oxyalkyl groups such as methoxy, ethoxy, carboxylic acids such as Aldehydes, ethers and other oxygen-containing alkyl groups such as And so on. In these terminal groups, M is an alkali metal, ammonium, alkanolamine, 1 to 4
Is an alkyl group having 4 carbon atoms, and R is hydrogen or an alkyl group having 1 to 8 carbon atoms.
These chemically stable end groups at the polymer ends may be the same or different.

The polymer (c) used in the present invention is preferably a polymer containing at least 50% by weight or more of the polyacetal carboxylate segment represented by the general formula (II).

The amount of component (c) used in the present invention must be 0.1 to 30% by weight.

The effect of the present invention cannot be obtained unless this condition is satisfied.

If desired, the detergent according to the present invention can be in the form of particles, powder, solid, or the like. Further, the cleaning composition of the present invention may optionally contain the components exemplified and described below, but these are not particularly limited and may be blended according to the purpose.

<Nonionic Surfactant> Polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide, or alkylene oxide adduct thereof.

<Builder> One or more kinds of various alkali metal salts can be contained as a builder component in an amount of 0 to 50% by weight. Condensed phosphates such as tripolyphosphate, pyrophosphate, metaphosphate, nitrilotriacetate, ethylenediaminetetraacetate, aminopolyacetate such as diethylenetriaminepentaacetate, citrate, malate, glycolate, etc. Oxycarboxylates, polyacrylic acid and its salts, vinyl acetate
Polymer electrolytes such as alkali hydrolysis salts of maleic anhydride copolymers.

Further, as the water-insoluble substance, talc, finely divided silica, clay, calcium silicate, and crystalline or amorphous zeolite having divalent metal ion exchange ability can be blended as necessary.

<Alkali Agent or Inorganic Electrolyte> One or more of various alkali metal salts shown below as alkaline agents or inorganic electrolytes are used in the composition.
It may be contained in an amount of 50% by weight, preferably 5 to 30% by weight. Silicates, carbonates, sulphates, and as organic alkaline agents, triethanolamine, diethanolamine,
It can also contain alkanolamines represented by monoethanolamine and triisopropanolamine.

<Recontamination Preventing Agent> As a recontamination preventing agent, one or two or more kinds of the following compounds can be contained in the composition in an amount of 0.1 to 5% by weight. Polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyethylene glycol, etc.

<Bleaching agent, fluorescent dye, oxygen, etc.> As a bleaching agent, sodium percarbonate, sodium perborate, sodium sulfate / sodium chloride hydrogen peroxide adduct, etc., and as a whitening agent, a commercially available fluorescent dye, a fragrance, Enzymes such as amylase, lipase, and cellulase, bluing agents, bleach activators, and the like can be added as necessary.

〔Example〕

Next, the present invention will be specifically described with reference to examples, but these examples do not limit the scope of the present invention. Unless otherwise specified,% in the examples is based on weight.

The detergency of natural complex stains (sebum and protein stains) in the examples was evaluated subcutaneously.

Composite stain-contaminated cloth; natural collar cloth-contaminated cloth Cotton / polyester = 35/65 blended cloth is sewn onto the collar of the shirt, and an adult boy wears it for two days. After wearing, a cloth having a symmetrical stain with respect to the center point was selected, and the cloth was half-cut at the symmetrical point of the stain and used for the experiment.

Cleaning conditions and evaluation method When cleaning a naturally contaminated cloth, half-cut a 9 cm × 30 cm naturally contaminated cloth in symmetrical positions, clean one of a pair of 9 cm × 15 cm contaminated cloths with a standard detergent, and use one with a comparative detergent. Each was washed with a detergent of the present invention. 0.13 out of 10 pieces of naturally contaminated cloth
Put in a 3% detergent solution, 100 rpm 10 with a tergotometer
It was washed for a minute, dried and then subjected to judgment.

The half-cut cloth washed with the standard detergent and the half-cut cloth washed with the detergent of the present invention were evaluated by integral comparison by visual judgment. The cleaning cloth was ranked on the basis of the standard dirt, which was ranked in 10 levels that represent the degree of dirt. The detergency was represented by the detergency of the detergent of the present invention when the detergency of the standard detergent was 100. The difference in detergency index is 0.5 or more, which can be regarded as a significant difference.

Anionic Surfactants Used The following combinations of anionic surfactants were blended in the detergent compositions as shown in the examples.

Alkaline Protease Used The alkaline protease shown below was blended in the detergent composition as shown in the examples.

(I) Alcalase 2.0M (Novo Industries Co., Ltd.) (ii) API-21 (Showa Denko KK) (Example 1) With respect to the cleaning composition having the composition shown in the table below, the cleaning performance for the test cloth was evaluated. The results are shown in Table 1.

(Example 2) With respect to the cleaning composition having the composition shown in the table below, the cleaning performance for the test cloth was evaluated. The results are shown in Table 2.

(Example 3) With respect to the cleaning composition having the composition shown in the table below, the cleaning performance for the test cloth was evaluated. The results are shown in Table 3.

(Example 4) The yellowing prevention property of clothing was evaluated by the following method.
The results are shown in Table 4.

Test cloth A cotton underwear that has been pre-washed with JIS standard detergent three times and dried is then worn by an adult boy for 2 days. After wearing, 10 cm ×
The cloth was cut into 10 cm pieces and subjected to the following experiments.

Washing conditions and evaluation method (Washing conditions) Targotometer 100 rpm Test cloth 10 pieces / 1 Washing time 10 minutes Dewatering 1 minute Rinse 3 minutes Detergent concentration 0.133% Temperature 20 ° C Dry air Dry (yellowing test) After washing The test cloth was allowed to stand for 30 days under the conditions of 40 ° C. and 80% RH to promote yellowing, and then the yellowing preventing ability of the clothing was measured by the following method.

That is, the reflectance of the test cloth immediately after washing and after being left for 30 days at 40 ° C., 80% RH was measured at a wavelength of 460 mμ, R ₍ o ₎ ; reflectance immediately after washing R _(S) ; 40 ° C, 80% RH, reflectance after being left for 30 days The yellowing prevention rate was calculated by the formula.

Detergent formulation The same as in Example 1 except that the alkaline protease was (ii). The results are shown in Table 4.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C11D 1:14 1:28)

Claims (1)

[Claims] 1. A straight-chain or branched-chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 and an olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule. Α-sulfo fatty acid salt or ester represented by (I) (In the formula, R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, Y represents an alkyl group having 1 to 3 carbon atoms or a counter ion, and Z represents a counter ion.) (B) Alkaline protease (c) General formula (II) (In the formula, M is a group selected from the group consisting of alkali metals, ammonium, alkyl groups and alkanolamine groups, and p is an average value of 4 to 200.) consisting only of a polyacetal carboxylate segment. Or, mainly such segments,
A polymer which is stabilized against alkali and contains the above three components, and the content of the component (a) is 5 to 30% by weight (however, the compounding ratio of ,, in the component (a) is a polymerization ratio / / = 80/10 / 10-30 / 60 / 10-30 / 35/35
Limited to within the range surrounded by 4 points of ~ 55/10/35. ),
A cleaning composition, wherein the content of the component (b) is 0.001 to 10% by weight, and the content of the component (c) is 0.1 to 30% by weight.