JPH06166893A - Detergent composition - Google Patents

Abstract

PURPOSE:To obtain a detergent compsn. improved in hygienic effect and detergency by blending a water-insoluble solid having a quaternary ammonium salt of an organosilicon compound immobilized thereon with a specific surfactant. CONSTITUTION:A water-insoluble inorg. or org. solid is spray coated with a 0.25-10wt.% soln. of a quaternary ammonium salt of an organosilicon compound of the formula (wherein R1 is 8-22C alkyl) in water or an org. solvent, air-dried, heated to fix the latter on the former, and then further heated at 65 to 100 deg.C for a few seconds to firmly immobilize the latter on the former, and, if necessary, admixed with a silanol-condensation catalyst to obtain a water-insoluble solid (A) having the quaternary ammonium salt of the organosilicon compound immobilized thereon. 0.1-30wt.% component (A) is blended with 1-40wt.% at least one surfactant (B) selected from among polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, alkylol-amide surfactants, and pluonic surfactants. The resulting detergent compsn. is used in the form of a liq., a solid, a powder or a paste.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a detergent composition, more specifically, a detergent composition having an excellent hygienic effect by sterilizing and removing microorganisms adhering to adherends such as clothes, dishes and bath tubs. Regarding

[0002]

2. Description of the Related Art It is known that a water-insoluble solid having an organosilicon quaternary ammonium salt immobilized thereon (hereinafter referred to as an organosilicon-type immobilized bactericide) exhibits antibacterial activity. No. 177284 discloses a method for antibacterial treatment of synthetic fibers with such organosilicon quaternary ammonium. However, application of an organosilicon-type immobilized bactericide in the field of detergent has not been proposed yet.

[0003]

Although conventional detergents for clothes have a cleaning effect of removing dirt such as oil stains, they cannot be said to have sufficient sanitary effects such as bactericidal effect. When washing socks and so on, the conventional cleaning agent causes other bacteria to adhere to other clothes in the same bath.
For this reason, most housewives sort the laundry and wash it separately. That is, the present invention solves the problem that microbial contamination occurs in the cleaning bath with the conventional cleaning agent, and reduces the time and effort at the time of washing.

Therefore, in view of this actual situation, the present inventors have
As a result of intensive studies to solve the problem, by blending an organosilicon-type immobilized bactericide, it has excellent hygiene effects, and has found a cleaning agent having a good cleaning effect, and has completed the present invention. It was

[0005]

The present invention provides a detergent composition comprising a water-insoluble solid having an organosilicon quaternary ammonium salt immobilized thereon and one or more surfactants. The cleaning composition of the present invention efficiently sterilizes and removes microorganisms in the bath to prevent microbial contamination of other objects to be cleaned in the bath.

In the present invention, an organosilicon quaternary ammonium salt is immobilized and used as a bactericide. This organosilicon quaternary ammonium salt is a known compound represented by the formula: R13N + R2SiR3nX3-n.Y- (I), and is usually commercially available as an alcohol solution. In the formula (I), X is a hydrolyzable group such as a halogen atom, an alkoxy group or an acyl group,
Y is chlorine or bromine. R1 independently has 1 to 2 carbon atoms
It is preferable that it is a monovalent aliphatic hydrocarbon group of 2 and especially two of the three R1 are methyl groups and the other one is an alkyl group having 8 to 22 carbon atoms. R2 is a divalent hydrocarbon group, particularly an alkylene group having 2 to 4 carbon atoms or --CH
It is preferably 2CH2CH2NHCH2CH2-. R3 is a lower alkyl group such as a methyl group, a phenyl group or a CF3CH2CH2 group. n represents 0, 1 or 2, and is preferably 0.

Among the organosilicon quaternary ammonium salts of the formula (I), those represented by the following formulas are particularly preferable in the present invention.

[Chemical 1] [In the formula, R1 means an alkyl group having 8 to 22 carbon atoms. ]

In the present invention, the water-insoluble solid for fixing the organosilicon quaternary ammonium salt may be any water-insoluble solid including an inorganic substance and an organic substance,
The solid may be synthetic or natural. Examples thereof include metal oxides and metal carbonates, siliceous substances, cellulosic substances, resins and plastics. Examples of particularly preferred solids include metals and metal oxides such as iron, aluminum, copper, nickel,
Titanium dioxide, alumina, zinc oxide, magnesium oxide, iron oxide, calcium carbonate, calcium hydrogen phosphate and magnesium carbonate; siliceous materials such as glass,
Silica, diatomaceous earth, ground quartz, mica, zeolite, aluminum silicate, aluminum calcium silicate, magnesium silicate and zirconium silicate; resins and plastics such as polyester, polyamide, cellulose acetate, rayon, polystyrene, polyethylene, polypropylene, epoxy resin, phenolic resin , Silicone resins and polycarbonate resins; cellulosic materials such as wood, cotton and hemp, and other natural organic materials such as silk and wool.

The organosilicon quaternary ammonium salt can be immobilized on the water-insoluble solid by a method known per se.
For example, a solution of an organosilicon quaternary ammonium salt can be applied to the water-insoluble solid by dipping or spraying and then immobilized by drying the coating material or heating after the coating step. Preferably, the water-insoluble solid is coated with an aqueous or organic solvent solution of the organosilicon quaternary ammonium salt. Such solutions are readily prepared by adding the corresponding hydrolyzable silane to water or an organic solvent such as methanol, ethanol or hexane.

Satisfactory results are obtained when the concentration of the organosilicon quaternary ammonium salt in the treatment solution is 0.25 to 10% by weight. When the treated surface is air dried or heated, the organosilicon quaternary ammonium salt coating is immobilized on the surface of the solid. When this treated solid is heated at 65 to 100 ° C. for several minutes, the organosilicon quaternary ammonium salt coating is more firmly fixed on the surface of the solid. If desired, a conventional silanol condensation catalyst (eg water) can be added to the treatment solution to enhance the silanol condensation properties and form an improved bond of the compound.

The detergent composition of the present invention contains the organosilicon-type immobilized bactericide thus obtained in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total amount of the composition. Blend in proportion. If the blending amount is less than 0.1% by weight, a sufficient bactericidal effect is not exhibited, and if it exceeds 30% by weight, the cleaning performance is impaired.

The surfactant that can be used in the present invention is preferably one or more selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, either alone or in combination. it can. The anionic surfactant may be one known per se, for example, a sulfate ester type anionic surfactant, a sulfonate type anionic surfactant, a carboxylic acid type anionic surfactant and a phosphate ester salt type anion. And a surface active agent.

The sulfate ester type anionic surfactant is, for example, an alkyl or alkenyl sulfate ester salt (alkali metal salt or alkaline earth salt of a sulfate ester of a linear and / or branched higher alcohol having 8 to 24 carbon atoms). Metal salts, ammonium salts and alkanolamine salts), polyoxyalkylene alkyl or alkenyl ether sulfuric acid ester salts (alkali metal salts of sulfuric acid esters of linear and / or branched higher alcohols having 8 to 24 carbon atoms, alkaline earth metals) Salt, ammonium salt and alkanolamine salt, alkylene oxide addition mole number is 1 to 10), polyoxyalkylene alkylaryl ether sulfuric acid ester salt (alkylphenol or alkylnaphthol sulfuric acid ester containing one or more alkyl groups having 4 to 18 carbon atoms) Alkali metal salts, alkaline earth metal salts, ammonium salts and alkanolamine salts, the number of added moles of alkylene oxide from 1 to 20), sulfuric acid ester salts of higher fatty acid ester (number of carbon atoms from 8 to 24
Sulfate ester salt of saturated and / or unsaturated fatty acid monoglyceride), higher fatty acid alkylolamide sulfate ester salt and polyoxyalkylene higher fatty acid alkylolamide sulfate ester salt;

Sulfonate type anionic activators are, for example, funnel oil and sulfated sodium salt of oleic acid,
α-olefin sulfonic acid sodium salt, alkylbenzene sulfonic acid sodium salt, alkane sulfonic acid sodium salt, and alkyl-substituted aryl ether sulfonic acid sodium salt; carboxylate type anionic surfactants include, for example, alkali metal salts of higher fatty acids or Alkanolamine amine salts and acylated amino acid salts, etc .; Phosphate ester type anionic surfactants include, for example, alkyl phosphate ester salts and polyoxyalkylene alkyl ether phosphate ester salts.

The nonionic surfactant used in the present invention is, for example, polyoxyethylene (1 to 20 mol) alkyl ether (having 8 to 22 carbon atoms), polyoxyethylene (1 to 20 mol) alkyl. Phenyl ether (having 8 to 18 carbon atoms), polyoxyethylene (1 to 20)
Polyoxyethylene polyoxypropylene block polymer such as polyoxypropylene (1 to 20 mol) alkyl ether (C8 to C22), higher fatty acid alkanolamide or alkylene oxide adduct thereof (C8 to C18, alkylene oxide). Addition mole number 0
10), polyalkylene oxide adducts of higher fatty acid polyhydric alcohol esters, and tertiary alkylamine oxides (having 8 to 22 carbon atoms).

The amphoteric surfactant may be one known per se,
Examples thereof include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. The amount of these surfactants is 1 to 40% by weight, preferably 5 to 20% by weight. If the amount is less than 1% by weight, the cleaning effect cannot be sufficiently obtained, and if the amount exceeds 40% by weight, it is economical. It is a problem from the point of.

The composition of the present invention can be used as a detergent for clothes, kitchens such as cleansers, and households, and can be provided in the form of liquid, solid, powder and paste. Depending on its properties, known components can be appropriately blended within a range that does not impair the effects of the present invention. For example, in a liquid detergent, lower alcohol such as ethanol, hydrotrope such as ethylene glycol and propylene glycol can be used. For agents, fluorescent agents, antioxidants, pigments, fragrances, and powder cleaners, zeolite,
Examples include builders such as carbonates and silicates, fluorescent agents, antioxidants, pigments, and fragrances.

[0018]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "%" is "% by weight".
Is.

[0019]

[Table 1]

Using the composites shown in Table 1, the bactericidal effect and the detergency were evaluated.

[0021]

[Table 2]

[In the table, LAS-Na; sodium salt of linear alkylbenzene sulfonic acid having an alkyl group having an average carbon number of 12; AE; polyoxyethylene addition mole number: 10
A sodium salt of a straight-chain alkyl ether sulfate having 12 to 14 carbon atoms in the alkyl group, LAS-TEA; a triethanolamine salt of a straight-chain alkylbenzenesulfonic acid having an alkyl group having an average carbon number of 12, sodium silicate;
Na2O: SiO2 = 1: 2.2 sodium silicate (JIS No. 1), zeolite; A type synthetic zeolite (manufactured by Mizusawa Chemical Co., Ltd., Shilton B). ], The ingredients other than the organosilicon-type immobilizing germicide in the clothing detergent composition are mixed by using a mixing device such as spray granulation or a ribbon mixer, and the organosilicon-type immobilizing germicide is mixed therein. Then, the detergency and the bactericidal effect were evaluated by the methods described below.

(Detergency) (1) Preparation of artificial soil cloth Clay containing crystalline minerals such as kaolinite and vermiculite dried at 200 ° C for 30 hours was used as inorganic soil. After dissolving 3.5 g of gelatin in 950 cc of water at about 40 ° C., 0.25 g of carbon black was dispersed in water with a powerful emulsifying machine, Polytron (KINEMATICA, Switzerland). Next, add 14.9 g of inorganic dirt and disperse with Polytron.
Further, 31.35 g of organic dirt was added and emulsified and dispersed to prepare a stable dirt bath. 10cm × 20c in this dirt bath
After dipping a predetermined clean cloth of m (cotton cloth No. 60 designated by Japan Oil Chemistry Association), water was squeezed by a two-roll rubber roll to make the amount of adhered dirt uniform. After drying this dirty cloth for 30 minutes at 105 ° C., both sides of the dirty cloth were rubbed 25 times on each side. This is cut into 5 cm x 5 cm and the reflectance is 42 ±
The range of 2% was used as a soiled cloth. The soil composition of the thus obtained soil cloth

[0024]

[Table 3]

As shown in FIG. (2) Preparation of sebum cloth A cloth (cotton knitted cloth 5 cm x 5 cm) to which 60 mg of organic dirt shown in Table 2 is attached per sheet. (3) Washed knitted cloth Cotton knitted cloth (the same as that used for the sebum cloth). (4) Cleaning method S. Testing's Terg-O-
Using a Tometer, 10 artificial dirt cloths and 3 sebum cloths are put therein, and a clean knitted cloth is further put therein. The bath ratio is adjusted to 30 times, and the cloth is washed at 120 rpm for 10 minutes at 25 ° C. The cleaning liquid has a cleaning agent concentration of 0.083% 90
Use 0 ml and rinse for 3 minutes with 900 ml water. The water used was 3 ° DH. (5) Detergency evaluation method

[0026]

[Equation 1]

[In the formula, R is EL of Cari Zeiss
It is a reflectance (%) measured by a REPHO reflectometer. ] The detergency was evaluated by the average value of 10 pieces of the artificial soil cloths tested.

(Evaluation of bactericidal efficacy) 1 ml of each test strain which was pre-cultured 3 times was used as a test sample of 10 m at a concentration of 0.083%.
1 in a sterilization test tube containing 10 l at 25 ° C
After being allowed to act for 1 minute, 1 platinum loop amount was taken out from the action test tube and planted in a fresh broth medium (NaCl 0.5%, polypeptone 1.0%, meat extract 0.5%), and 37
After culturing at 48 ° C for 48 hours, the presence or absence of growth of the bacteria was determined.
(+) Indicates the survival of the bacterium, and (-) indicates the death of the bacterium.

[0029]

[Table 4]

[In the table, AES: sodium salt of straight chain alkyl sulfate ester having 3 moles of polyoxyethylene added and alkyl group having 12 to 14 carbon atoms, AS and A]
E: A triethanol salt of a linear alkyl sulfate having an alkyl group having 12 to 14 carbon atoms, AA: a fatty acid diethanolamide having an alkyl group having an average carbon number of 12 are shown. ] The detergent composition for kitchen shown in [] was prepared by a conventional method, and the detergency and sterilization ability were evaluated. (Evaluation of detergency) Dishwashing test method (oil chemistry, 24 volumes, 5
95, 1975) and a detergent composition concentration of 0.2
%, Wash the dishes to which 1.3 g of dirt has been attached per dish in a 4 l bath, and evaluate by the number of washed dishes. (Evaluation of bactericidal efficacy) Each test strain 1 which was pre-cultured 3 times
ml was put into a sterilization action test tube containing 10 ml of a test sample having a concentration of 0.2%, allowed to act for 10 minutes at 25 ° C., 1 platinum loop amount was taken out from the action test tube, and fresh broth medium (NaCl 0.5 %, Polypeptone 1.0%,
After being planted in a meat extract (0.5%) and cultured at 37 ° C. for 48 hours, the presence or absence of growth of the bacteria was determined. (+) Is the survival of the bacterium,
(-) Indicates the killing of the bacterium.

As shown in Tables 2 and 4, Examples 1 to 8 in which a fixed amount of the organosilicon-type immobilized bactericide was blended showed clear bactericidal effect and excellent detergency as compared with Comparative Examples. There is.

Example 9 A kitchen cleanser having the following formulation was produced by a conventional method. Component Blending amount (%) Sodium dodecylbenzene sulfonate 4.0 Polyoxyethylene (10) dodecyl ether 3.0 Silica powder 50.0 Complex 4 (Table 1) 5.0 Water residual total 100.0

Example 10 A liquid laundry detergent having the following formulation was produced by a conventional method. Component Blending amount (%) Dodecylbenzenesulfonic acid triethanolamine salt 20.0 Polyoxyethylene (10) Dodecyl ether 30.0 Ethanol 15.0 Complex 2 (Table 1) 10.0 Water residual amount Total 100.0 Also in Examples 9 and 10, excellent bactericidal efficacy was exhibited.

[0034]

INDUSTRIAL APPLICABILITY According to the present invention, a detergent composition having an excellent hygienic effect (bactericidal effect) containing an organosilicon type germicide can be obtained.

Claims (2)

[Claims] 1. A detergent composition comprising an organosilicon quaternary ammonium salt-immobilized water-insoluble solid and one or more surfactants. 2. A surfactant containing at least one selected from polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, alkylol amide type surfactant and pluronic type surfactant. The cleaning composition according to claim 1, which comprises: