JPH10168482A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition having excellent detergency for clothes, can simultaneously perform washing and softening without adding any additional softener in the step of rinsing and has a minimized content of nitrogen compounds which cause the eutrophication of lakes and marshes by using a fatty acid soap and a carboxyalkyl thiosuccinic acid or a carboxyalkyloxysuccinic acid or a salt thereof. SOLUTION: This composition contains a fatty acid soap (A) and a compound (B) represented by the formula (R is a 1-30C alkylene or a carboxyl-substituted alkylene; X is oxygen or sulfur; M<1> , M<2> and M<3> are each hydrogen, a monovalence-equivalent metal or an unsubstituted or organo-substituted ammonium salt, provided they may be different from each other). The ratio of component A to component B is 1/2 to 50/1 by weight, and the content of component B is 0.1-30wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a cleaning composition. More specifically, the present invention relates to a detergent composition that has excellent detergency for clothing fabrics and can impart flexibility after washing and drying.

[0002]

2. Description of the Related Art Conventionally, in general washing at home, in order to impart flexibility after washing to a garment cloth to be washed, a rinsing step performed after a washing step with a detergent is used for washing clothes. The purpose has been achieved by re-adding a softening agent to adsorb a specific compound on the fibers of the garment fabric. These specific compounds include, for example,
"Oil", Vol. 48, No. 5, pp. 44-57 (199
5 years), compounds containing nitrogen in the molecule, particularly quaternary ammonium salts, tertiary amine salts and imidazolinium salts having a long-chain alkyl group or acyl group in the molecule are typical examples. It is mentioned as a typical thing. Also,
Compounds that do not contain nitrogen in the molecule have also been studied, such as sulfoxides, sulfates of long-chain fatty acid glycerides and partial esters of long-chain fatty acids and pentaerythritol, and the like. Compared with compounds containing nitrogen therein, the effect is not sufficient. As described above, the nitrogen-containing compound is excellent in imparting flexibility to the clothing fabric, but is difficult to decompose by microorganisms after being released to the environment after use, and is excellent in degradability. Even compounds are inherently concerned about eutrophication of lakes, as they contain nitrogen in the molecule. In addition, the method of using the softener for clothing involves the complexity of adding and adding a drug again in the rinsing step. In order to solve this complication, studies have been made to incorporate a compound that imparts flexibility into the detergent formulation, and to simultaneously perform washing and imparting flexibility. For example, Japanese Patent Application Laid-Open No. Sho 50-4 discloses a combination of a soap compound, a dispersant for a card, a smectite-type clay, a water-insoluble quaternary ammonium salt, an adhesion promoter and an alkaline builder salt. JP-A-1-266199 discloses a combination of a surfactant, diamide of diethylenetriamine and an imidazoline compound. However, the water-insoluble quaternary ammonium salts, diamides of diethylenetriamine and imidazoline compounds contained in these compositions are not easily decomposed by microorganisms after being released to the environment after use, and are not suitable for closed water bodies such as lakes and marshes. It is a source of eutrophication.

[0003]

DISCLOSURE OF THE INVENTION The present invention has an excellent detergency for a garment fabric, and can provide flexibility at the same time as washing without adding a softening agent again in the rinsing step. Another object of the present invention is to provide a detergent composition containing as little as possible nitrogen compounds that cause eutrophication of lakes and marshes.

[0004]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that washings containing fatty acid soap and carboxyalkylthiosuccinic acid or carboxyalkyloxysuccinic acid or salts thereof. It has been found that the agent composition has a sufficient detergency and can impart flexibility simultaneously with cleaning, and based on this finding, the present invention has been completed. That is, the present invention comprises (1) a fatty acid soap as the component (A) and a compound represented by the general formula [1] as the component (B).
A detergent composition wherein the weight ratio (A) / (B) of the component (B) is 1/2 to 50/1, and the content of the component (B) is 0.1 to 30% by weight. Stuff,

Embedded image (Wherein, R is an alkylene group having 1 to 30 carbon atoms or a carboxyl group-substituted alkylene group, X is oxygen or sulfur, M ¹ , M ² and M ³ are hydrogen, a metal equivalent to monovalent, Or an unsubstituted or organic-substituted ammonium group, which may be the same or different.) And (2) in the compound represented by the general formula [1], X is sulfur A cleaning composition according to Item (1).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the cleaning composition of the present invention, fatty acid soap is used as the component (A). Examples of the fatty acid as a raw material of the fatty acid soap as the component (A) of the composition of the present invention include coconut oil fatty acids, palm kernel oil fatty acids,
Palm oil fatty acids, soybean oil fatty acids, rapeseed oil fatty acids, sunflower oil fatty acids, rice bran oil fatty acids, corn oil fatty acids, cottonseed oil fatty acids, tall oil fatty acids, castor oil fatty acids, hydrogenated castor oil fatty acids, tallow fatty acids, tallow fatty acids, hardened fish oil fatty acids Mixed fatty acids produced by hydrolyzing and optionally hydrogenating oils and oils of natural origin such as lauric acid, myristic acid, palmitic acid, stearic acid ,
Examples include behenic acid, palmito oleic acid, oleic acid, linoleic acid, erucic acid, ricinoleic acid, and hydroxystearic acid. One of these fatty acids can be used alone, or two or more can be used in combination. Furthermore, the fatty acid used as the raw material of the fatty acid soap used in the composition of the present invention is not limited to a naturally occurring fatty acid, but a petrochemically derived fatty acid can also be used. When a petrochemical-derived fatty acid is used, it preferably has 12 or more carbon atoms. In the composition of the present invention, the fatty acid used as the raw material of the fatty acid soap is more preferably a fatty acid having 16 or more carbon atoms in order to achieve both the good performance of detergency and the softening effect. When a mixture of fatty acids is used, the proportion of fatty acids having 16 or more carbon atoms in the total fatty acid composition is preferably 50% by weight or more. further,
Among fatty acids having 16 or more carbon atoms, unsaturated fatty acids are more preferable than saturated fatty acids. Examples of such unsaturated fatty acids include palmito oleic acid, oleic acid,
Monounsaturated fatty acids having 16 or more carbon atoms, such as gadolinic acid and erucic acid, can be mentioned.

Examples of the fatty acid soap used in the composition of the present invention include fatty acid sodium soap and potassium soap, as well as ammonium soap and amine soap. Examples of the basic component forming such a fatty acid soap include an alkali metal such as sodium and potassium, and an unsubstituted or organic group-substituted ammonium group. Examples of the unsubstituted or organic group-substituted ammonium group include an NH ₄ group, an ammonium group having one substituted organic group, an ammonium group having two substituted organic groups, and an ammonium group having three substituted organic groups. As the organic group of the organic group-substituted ammonium group, an aliphatic group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms,
Examples thereof include an aromatic group having 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms, and a hydroxyalkyl group having 2 to 24 carbon atoms, preferably 2 to 18 carbon atoms. When two or more organic groups are substituted, the plurality of organic groups may be the same or different, and may be combined with each other to form a ring structure. . Examples of the organic amine forming such an organic group-substituted ammonium group include, for example, methylamine, ethylamine, propylamine, butylamine, hexylamine, aliphatic amines such as octylamine, ethanolamine, diethanolamine,
Examples thereof include alkanolamines such as triethanolamine, isopropanolamine, diisopropanolamine, and triisopropanolamine; aromatic amines such as aniline; and heterocyclic amines such as morpholine, pyridine, pyrrolidine, and piperidine.

In the composition of the present invention, a compound represented by the general formula [1] is used as the component (B).

Embedded image In the general formula [1], R is an alkylene group having 1 to 30 carbon atoms or a carboxyl group-substituted alkylene group, more preferably an alkylene group having 1 to 18 carbon atoms or a carboxyl group-substituted alkylene group. The alkylene group or the carboxyl group-substituted alkylene group represented by R can be either linear or branched. Examples of such an alkylene group include ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, and hexadecylene. Group, heptadecylene group,
Octadecylene group, nonadecylene group, icosylene group,
Examples include a henicosylene group, a docosylene group, a trichosylene group, a tetracosylene group, a pentacosylene group, a hexacosylene group, an octakosilene group, a nonacosilene group, and a triaconylene group. Examples of the carboxyl group-substituted alkylene group include a carboxyethylene group and a 2-carboxy-1,3-propylene group. In the general formula [1], X is oxygen or sulfur. Since a detergent composition containing a compound in which X is sulfur is superior to a detergent composition containing a compound in which X is oxygen in terms of overall detergency and flexibility, X is sulfur. Is more preferable.

In the general formula [1], M ¹ , M ² and M ³
Is hydrogen, a monovalent metal or an unsubstituted or organic group-substituted ammonium group, which may be the same or different. As a metal, for example,
Examples thereof include lithium, sodium, potassium, calcium, magnesium, zinc, aluminum, iron, cobalt, nickel, copper, and tin. Among these,
Lithium, sodium, potassium, calcium, magnesium are particularly preferred. Regarding the metal of the general formula [1],
The metal equivalent to monovalent refers to a virtual metal obtained by dividing the metal by its valence. For example, when the metal is a divalent metal such as calcium and magnesium, Ca _1/2 , Mg
_It is virtually represented as _1/2 , and when it is a trivalent metal such as aluminum, it is virtually represented as Al _1/3 . Divalent one metal corresponds to 2 out of M ^1, M ² and M ^3, M ¹ in the general formula in one molecule of the compound represented by [1],
It may correspond to two of M ² and M ³ , or two molecules M ¹ , M ² and M of the compound represented by the general formula [1]
^It may correspond to 2 of ³ and may have a structure that crosslinks two molecules. Further, the trivalent metal corresponds to ^one of M ¹ , M ² and M ³ of one to three molecules of the compound represented by the general formula [1]. When the metal is a monovalent metal such as sodium or potassium, one metal ion is a metal equivalent to monovalent.

In the general formula [1], the unsubstituted or organic group-substituted ammonium group is an NH ₄ group, an ammonium group substituted with one organic group, an ammonium group substituted with two organic groups, or substituted with three organic groups. Ammonium group. The organic group of the organic group-substituted ammonium group has 1 to 1 carbon atoms.
24, preferably 1 to 18 aliphatic groups, 6 to 2 carbon atoms
4, preferably 6 to 18 aromatic groups, 2 to 24 carbon atoms,
Preferably, there may be mentioned 2 to 18 hydroxyalkyl groups. When two or more organic groups are substituted, a plurality of organic groups may be the same or different, and may be combined with each other to form a ring structure. Examples of the organic amine forming such an organic group-substituted ammonium group include, for example, aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, and octylamine, ethanolamine, diethanolamine, triethanolamine, and isopropanolamine. , Diisopropanolamine, alkanolamines such as triisopropanolamine, aromatic amines such as aniline, morpholine,
Heterocyclic amines such as pyridine, pyrrolidine and piperidine can be mentioned, among which morpholine and alkanolamine are particularly preferable. In the composition of the present invention, it is preferable that two-thirds or more of the carboxyl groups of the compound represented by the general formula [1] form a salt.

The method for producing the compound represented by the general formula [1] used in the composition of the present invention is not particularly limited.
It can be manufactured by any known method. For example, thioglycolic acid or a salt thereof is added to maleic anhydride to produce carboxymethylthiosuccinic anhydride or a salt of carboxymethylthiosuccinic anhydride, which is then hydrolyzed and further neutralized with an appropriate basic compound. By adding them to form a salt, carboxymethylthiosuccinic acid or a salt thereof can be obtained. In the cleaning composition of the present invention, the weight ratio (A) / (B) between the component (A) and the component (B) is 1/2 to 50/1, more preferably 1/1 to 20/1. It is. Weight ratio (A) / (B) is 1 /
If it is less than 2, sufficient detergency may not be obtained. If the weight ratio (A) / (B) exceeds 50/1, a sufficient softening effect may not be obtained. In the composition of the present invention, the content of the component (B) is 0.1 to 30% by weight, and more preferably 0.5 to 10% by weight. When the content of the component (B) is less than 0.1% by weight, a sufficient softening effect may not be obtained. The content of the component (B) is 30% by weight.
If it exceeds 300, the detergency may be impaired.

The method for producing the cleaning composition of the present invention is not particularly limited. For example, after saponifying and decomposing fats and oils with an alkali component and water, other components are added, spray-dried and pulverized. Method, dissolving fatty acid soap in water, adding other compounding ingredients, spray drying and pulverizing, adding other compounding ingredients to fatty acid soap, mixing and pulverizing without adding water, and the like. it can. Among these methods, fatty acids have an alkaline component,
Add water not exceeding 15% by weight to the compound represented by the general formula [1], other components and the total composition, and mix with a pressure kneader, a Loedeger mixer, a Henschel mixer, a high speed mixer, etc. A method of neutralizing and mixing with a machine and pulverizing to produce is preferred. The detergent composition of the present invention can contain one or more surfactants that are generally used in detergents, as long as the effects of the present invention are not impaired.
For example, alkyl benzene sulfonate, alkyl ether or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, alkyl ether or alkenyl ether carboxylate, α-sulfo fatty acid ester salt, acylmethyltaurine Salts, N-acyl amino acid salts, alkyl or alkenyl phosphates or salts thereof, anionic surfactants such as sulfated oils and sulfated fatty acid salts, amphoteric interfaces such as carboxybetaine, imidazolinium betaine, and sulfobetaine Activator, polyoxyalkylene alkyl or alkenyl ether, polyoxyalkylene alkyl phenyl ether, fatty acid alkanolamide or its alkylene oxide adduct, fatty acid sorbitan ester, fatty acid Esters of fatty acids with polyhydric alcohols such as Noguriserido, such as non-ionic surfactants such as alkylamine oxide can be exemplified. In addition, builders, which are generally added to detergent compositions,
It may contain a fluorescent whitening agent, an enzyme, a redeposition inhibitor, a chelating agent, a bleaching agent, a bleaching activator, a preservative, a dye, a fragrance, and the like.

[0012]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The following raw materials were used for the cleaning compositions prepared in the examples. (A) Component Fatty acid soap (1): sodium salt of NAA-34 [Nippon Yushi Co., Ltd.]. Fatty acid composition: 3% by weight of myristic acid, 5% by weight of palmitic acid, 8% by weight of palmito oleic acid, 1% by weight of stearic acid, 74% by weight of oleic acid, 7% by weight of linoleic acid, 2% by weight of linolenic acid. Fatty acid soap (2): sodium salt of a mixed fatty acid of coconut oil fatty acid 40% by weight and tallow fatty acid 60% by weight. Fatty acid composition: 2% by weight of caprylic acid, 3% by weight of capric acid, 20% by weight of lauric acid, 9% by weight of myristic acid, 21% by weight of palmitic acid, 2% by weight of palmitooleic acid, 13% by weight of stearic acid, 28% of oleic acid % By weight, 2% by weight of linoleic acid. (B) component disodium carboxymethylthiosuccinate (SCM
TS) disodium carboxyethylthiosuccinate monosodium salt (SCETS) disodium carboxymethyloxysuccinate (SC
MOS) Trisodium oxydisuccinate (SODS) Other components Nonionic activator (1): 9 mol of ethylene oxide adduct of alcohol having 12 to 14 carbon atoms. Nonionic activator (2): 9 mol of ethylene oxide of nonylphenol. Anionic activator (1): sodium salt of a sulfuric acid ester of an ethylene oxide 3 mol adduct of an alcohol having 12 to 14 carbon atoms. Anionic activator (2): sodium salt of n-dodecylbenzenesulfonic acid. TMS: sodium salt of monosuccinate of tartaric acid. DMDTAC: dimethyldi-tallowalkylammonium chloride. Further, the detergency test and evaluation were performed by the following methods. (1) Artificial stained cloth 15.0% by weight of oleic acid, 7.5% by weight of palmitic acid,
7.5% by weight of myristic acid, 30.0% by weight of tallow hardened oil,
Cholesterol 10.0% by weight, squalene 5.0% by weight, cetyl alcohol 10.0% by weight and paraffin 1
A mixture of 5.0% by weight of carbon black dispersed therein was used as artificial stain, and the artificial stain was used to contaminate a cotton white cloth to obtain an artificially stained cloth. (2) Washing test Using a washing machine [AW-65VF3, manufactured by Toshiba Corporation], a washing test was performed at a standard course water level. Tap water 63 in the washing machine
Liters and 63.0 g of the detergent composition were added and uniformly dissolved, and 30 cotton towels (about 2 kg in weight) and 10 cm × 10
A 30 × 30 cm cotton cloth was sewn with four artificial contaminated cloths, and washed at a washing temperature of 25 ° C. for a washing time of 10 minutes, and then rinsed twice and dehydrated for 40 seconds. (3) Evaluation of detergency The color computer [Suga Test Machine] was used for the original white cloth before contamination, the artificially stained cloth before cleaning, and the artificially stained cloth after cleaning.
The surface reflectance was measured using SM-4 manufactured by Co., Ltd., and the detergency was calculated from the following equation. Detergency = {(R ₂ −R ₁ ) / (R ₀ −R ₁ )} × 100
(%) Where R ₀ is the reflectance of the original white cloth before contamination,
R ₁ is the reflectivity of the artificially stained cloth before washing, R ₂ is the reflectivity of the artificially stained cloth after washing. When the value of the cleaning power is 35% or more, the cleaning effect is sufficient, and when the cleaning power is less than 35%, the cleaning effect is insufficient. (4) Evaluation of Flexibility The washed cotton towel was dried in the shade, and three sets were stacked to prepare 10 sets of samples. The three cotton towels were subjected to a sensory evaluation of flexibility by ten panelists. As a control, a triple-layered cotton towel washed similarly using a commercially available synthetic compact detergent and prepared in the same manner was used. 2 points when showing much better flexibility compared to the control, 1 point when showing better flexibility,
0 if equal, -1 if less flexible
Points were given, and the total of the evaluation scores by ten panelists was obtained. Example 1 50 parts by weight of fatty acid soap (1) as the component (A) and disodium carboxymethylthiosuccinate 5 as the component (B)
A detergent composition was prepared by mixing 35 parts by weight of soda ash, 5 parts by weight of No. 2 sodium silicate and 5 parts by weight of zeolite as other components. When a cleaning test was performed using this cleaning composition, the cleaning power was 38% and the flexibility was 1%.
8 points. Example 2 50 parts by weight of fatty acid soap (2) as a component (A), 5 parts by weight of disodium monopotassium carboxyethylthiosuccinate as a component (B), 35 parts by weight of soda ash as other components, No. 2 silicate A cleaning composition was prepared by blending 5 parts by weight of soda and 5 parts by weight of sodium percarbonate. When a cleaning test was performed using this cleaning composition, the cleaning power was 38.
% And flexibility were 17 points. Example 3 50 parts by weight of a fatty acid soap (1) as a component (A), 5 parts by weight of disodium carboxymethyloxysuccinate as a component (B), and 10 parts of a nonionic surfactant (1) as other components
A detergent composition was prepared by mixing 10 parts by weight of anionic surfactant (1), 5 parts by weight of soda ash, 5 parts by weight of sodium metasilicate and 15 parts by weight of zeolite. When a cleaning test was performed using this cleaning composition, the cleaning power was 40.
%, Flexibility was 14 points. Example 4 30 parts by weight of fatty acid soap (1) as component (A), 5 parts by weight of trisodium oxydisuccinate as component (B), 20 parts by weight of nonionic activator (2) as other components, and 15 parts by weight of soda ash Parts, 10 parts by weight of sodium metasilicate and 20 parts by weight of zeolite were blended to prepare a detergent composition. When a cleaning test was performed using this cleaning composition, the cleaning power was 37% and the flexibility was 14 points. Examples 5 to 10 Each component shown in Table 1 was blended to prepare a detergent composition,
A cleaning test was performed. The evaluation results of detergency and flexibility are
It is shown in the table. Comparative Example 1 50 parts by weight of fatty acid soap (1) as the component (A), 35 parts by weight of soda ash as the other components, No. 2 sodium silicate 5
Parts by weight, 5 parts by weight of sodium metasilicate and 5 parts by weight of zeolite were blended to prepare a detergent composition. When a cleaning test was performed using this cleaning composition, the cleaning power was 38.
% And flexibility were 5 points. Comparative Example 2 50 parts by weight of fatty acid soap (1) as the component (A), 0.5 parts by weight of disodium monopotassium carboxyethylthiosuccinate as the component (B), and soda ash 3 as the other component
5 parts by weight of No. 2, 4.5 parts by weight of sodium silicate, 5 parts by weight of sodium metasilicate and 5 parts by weight of zeolite were blended to prepare a detergent composition. When a cleaning test was performed using this cleaning composition, the cleaning power was 38% and the flexibility was 5 points. Comparative Example 3 10 parts by weight of fatty acid soap (1) as a component (A), 30 parts by weight of disodium carboxymethyloxysuccinate as a component (B), and a nonionic activator (2) 1 as another component
0 parts by weight, 10 parts by weight of anionic activator (1), 10 parts by weight of anionic activator (2), 10 parts by weight of soda ash, 10 parts by weight of sodium percarbonate and 10 parts by weight of zeolite to form a detergent composition Prepared. When a cleaning test was performed using this cleaning composition, the cleaning power was 32% and the flexibility was 8 points. Comparative Examples 4 to 8 Each component shown in Table 2 was blended to prepare a detergent composition,
A cleaning test was performed. The evaluation results of detergency and flexibility are
It is shown in the table. Comparative Example 9 A cleaning test was performed using a commercially available synthetic compact detergent. Table 2 shows the evaluation results of detergency and flexibility.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

In the cleaning tests using the cleaning compositions of the present invention of Examples 1 to 10, the value of the detergency was 36 to 41%.
And all have a sufficient cleaning effect.
It is over 5%. In addition, in the sensory evaluation of the flexibility by comparing with a cotton towel washed with a commercially available synthetic compact detergent, most of the 10 panelists evaluated that the flexibility was much better or better than the control product, The total of the evaluation points has reached 14 to 18 points. In contrast, the detergent compositions of Comparative Examples 1 and 5 to 8 containing no component (B) and the weight ratio (A) / component (A) / component (B)
In a cleaning test using the cleaning composition of Comparative Example 2 in which (B) was too large, the cleaning effect was 36 to 38%, and the cleaning effect was sufficient. Only the evaluation is equal to the product or better than the control product, and the total of the evaluation points is 4 to 5 points. Further, the component (A) and
Comparative Examples 3 and 4 in which the weight ratio (A) / (B) of the component (B) is too small.
In the cleaning test using the cleaning composition of the above, the detergency was 29 to 32% and the cleaning effect was insufficient, and in the sensory evaluation of flexibility, many panelists evaluated that they were better than the control product. There are few evaluations that are far better, and the total evaluation score is only 8 to 10 points. In Comparative Example 9 using a commercially available synthetic compact detergent, the detergency was 4
At 0%, the cleaning effect is sufficient, but in terms of flexibility, it is inferior to the cleaning compositions of the present invention of the examples and of the comparative examples.

[0018]

The cleaning composition of the present invention has excellent detergency and can impart flexibility to an object to be cleaned simultaneously with cleaning.

Claims (2)

[Claims] 1. A fatty acid soap as the component (A) and a compound represented by the general formula [1] as the component (B), wherein the weight ratio of the components (A) and (B) is (A) / (B). ) Is 1/2 to 50/1, and the content of the component (B) is 0.1 to 30% by weight. Embedded image (Wherein, R is an alkylene group having 1 to 30 carbon atoms or a carboxyl group-substituted alkylene group, X is oxygen or sulfur, M ¹ , M ² and M ³ are hydrogen, a metal equivalent to monovalent, Or an unsubstituted or organic group-substituted ammonium group, which may be the same or different.) 2. A compound represented by the general formula [1]:
2. The cleaning composition according to claim 1, wherein X is sulfur.