JP2009149858A - Cleaning agent composition for hard surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning agent composition for a hard surface effectively removing composite fouling of a biofilm and the other dirt. <P>SOLUTION: This cleaning agent composition for the hard surface includes components (A), (B), and (C). (A) A basic amino acid derivative represented by a general formula (1) or a salt thereof. In the formula (1), R<SP>1</SP>indicates a C4-18 straight-chain or branched alkyl or alkenyl group; and m indicates an integer 1-5. (B) An alkaline agent. (C) A surfactant except the (C) component. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a hard surface cleaning composition, and more particularly, to hard surface cleaning capable of effectively removing composite soils of biofilms and other soils in various fields involving microorganisms. The agent composition.

A biofilm is also called a biofilm or slime, and generally refers to an aqueous system in which microorganisms adhere to and grow on the surface of substances to produce macromolecular substances such as polysaccharides and proteins from within microbial cells to form structures. . When a biofilm is formed, harm caused by microorganisms occurs, causing problems in various industrial fields. For example, when a biofilm is formed in the piping of a food plant, the biofilm peels off and leads to contamination by foreign substances in the product, and causes food poisoning due to microorganism-derived toxins. Furthermore, biofilm formation on the metal surface causes metal corrosion and promotes aging of the equipment.
Furthermore, compared to microorganisms that are dispersed and suspended in an aqueous system, microbial control agents such as bactericides and bacteriostatic agents are often unable to exert sufficient effects on microbial aggregates that have formed biofilms. . For example, in the medical field, many cases of nosocomial infections have been reported in recent years due to microorganisms remaining in narrow gaps and holes in medical devices to form biofilms. In the human oral cavity, it is well known that biofilms formed on teeth, so-called dental plaque (plaque), cause caries and periodontal disease, and these problems have been studied for a long time.

  Until now, in order to prevent the harm of biofilm, the idea of not allowing bacteria to grow by giving bactericidal action or bacteriostatic action to microorganisms, particularly bacteria, has been generally studied. Patent Document 1 describes an antibacterial preparation containing arginine hydrochloride, arginine ethyl ester, arginine glutamic acid or other arginine or a derivative thereof and a compound exhibiting antibacterial activity, but the effect is not yet satisfactory. In addition, this document shows an antibacterial effect on microbial aggregates and is not intended to remove biofilms.

  As a method for removing a biofilm, a method using a bactericide, a method using a chelating agent, a method using an enzyme, and the like have been tried. In Patent Document 2, hypochlorite, alkali metal hydroxide and a surfactant are used. A method of using these in combination is disclosed. However, none of the methods has been able to remove the biofilm effectively, and it still remains a big problem.

Biofilms are easily formed in an environment where there is a lot of moisture, such as bathrooms, kitchens, kitchens, toilet toilets, drainage lectures, drain pipes, and medical equipment. Yes. For example, oil stains are mainly used around kitchens, metal soaps, particularly fatty acid calcium salts in bathrooms, inorganic stains in toilets, and protein stains such as blood and body fluids in medical instruments. Biofilms coexist with such stains to form composite stains, and it is desired to effectively remove these composite stains.
JP-A-8-151324 JP 2005-75873 A

  Accordingly, an object of the present invention is to provide a hard surface cleaning composition capable of effectively removing microorganisms and biofilms composed of microorganism-producing substances and other soiled composites in various regions.

  The present inventor has conducted earnest research to obtain an agent that can effectively remove composite stains of biofilm and other stains, and contains a specific amino acid derivative, an alkaline agent, and a surfactant other than the specific amino acid derivative. The present invention has been completed by finding that there is a remarkable effect on the hard surface cleaning composition.

That is, this invention provides the cleaning composition for hard surfaces containing the following component (A), (B) and (C).
(A) The following general formula (1)

(In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 4 to 18 carbon atoms, and X and Y represent the following formulae:

And m represents an integer of 1 to 5. )
A basic amino acid derivative represented by:
(B) alkaline agent,
(C) Surfactant other than component (A).

Moreover, this invention provides the cleaning composition for hard surfaces containing the following component (A), (B) and (C).
(A) Arginine derivative or a salt thereof obtained by reacting arginine or a salt thereof with glycidyl ether,
(B) alkaline agent,
(C) Surfactant other than component (A).

  ADVANTAGE OF THE INVENTION According to this invention, the composite stain | pollution | contamination of the biofilm which consists of microorganisms and a microorganism-producing substance, and another dirt can be effectively removed in various areas.

  The hard surface cleaning composition of the present invention has the following general formula (1) as the component (A).

(In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 4 to 18 carbon atoms, and X and Y represent the following formulae:

And m represents an integer of 1 to 5. )
Containing at least one basic amino acid derivative represented by the formula:

The alkyl group or alkenyl group represented by R ¹ may be linear or branched, but has 4 to 18 carbon atoms, preferably 6 to 14 carbon atoms from the viewpoint of the effect of removing a biofilm. Those having 8 to 14 are more preferable, and those having 10 to 14 carbon atoms are more preferable. Specific examples include an n-hexyl group, a 2-ethylhexyl group, an n-octyl group, a decyl group, a dodecyl group, and a myristyl group. The alkyl group or alkenyl group represented by R ¹ may be single or mixed. Moreover, the mixed alkyl composition derived from natural origin, for example, palm oil or palm kernel oil, may be sufficient.
In general formula (1), m represents an integer of 1 to 5, preferably 2 to 4, and more preferably 3. X is preferably —OCH ₂ —CH (—OH) CH ₂ —, and Y is preferably —NH—C (—NH ₂ ) ═NH.

  Examples of the salt of the basic amino acid derivative (1) include salts of inorganic acids such as hydrochloride, sulfate and phosphate, and salts of organic acids such as acetate, lactate, citrate and acidic amino acid salt. Preferable examples include hydrochloride, acetate, lactate and citrate.

  The basic amino acid derivative (1) can be obtained by reacting a basic amino acid such as arginine, lysine, ortinine, histidine, hydroxyhistidine and the like with a compound such as glycidyl ether, fatty acid chloride, fatty acid anhydride, or epoxyalkane. Preferred is a compound obtained by reacting arginine with a compound such as glycidyl ether, acid chloride, or epoxyalkane, more preferably an arginine derivative obtained by reacting arginine with glycidyl ether, that is, the following general formula ( 2).

(R ² represents a linear or branched alkyl or alkenyl group having 4 to 18 carbon atoms.)
These reaction products may contain unreacted substances and by-products as long as they do not impair the cleaning effect and the storage stability of the preparation.

  JP-A-9-271655 discloses a cosmetic and a detergent composition containing a basic amino acid derivative or a salt thereof obtained by reacting glycidyl ether with a basic amino acid or a salt thereof. This is less irritating to the skin and mucous membranes, and is used for the purpose of improving the conditioning effect on hair and the like. It cannot be foreseen or guessed.

  The concentration of the component (A) in the hard surface cleaning composition of the present invention is preferably 0.001 to 10% by weight, more preferably 0.002 in terms of cost, handleability, and biofilm composite soil removal performance. -5 wt%, more preferably 0.005-3 wt%.

  The hard surface cleaning composition of the present invention contains an alkaline agent as the component (B). As component (B), hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, sodium orthosilicate, sodium metasilicate, sodium sesquisilicate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, etc. Silicates, phosphates such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, carbonates such as disodium carbonate, sodium bicarbonate, dipotassium carbonate, potassium bicarbonate, Borates such as sodium borate, organic acid salts such as sodium acetate, potassium acetate, sodium lactate and potassium lactate, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, basic amino acids such as lysine and arginine , Ethylenediamine, diechi Ntoriamin, spermine, and the like and polyamines spermidine. Two or more alkali agents may be used in combination. Among these alkali agents, sodium hydroxide, potassium hydroxide, sodium orthosilicate, sodium metasilicate, and monoethanolamine are preferable.

  These alkali agents can be used in combination at any ratio depending on the purpose within a range that can be stably blended in the hard surface cleaning composition. A preferred ratio is, in terms of cleaning effect, in terms of weight ratio, the sum of component (A) and component (C): alkaline agent = 90: 10 to 1:99, more preferably 50:50 to 10:90. It is.

  These alkaline agents are used to make the pH in the working system alkaline when using the hard surface cleaning composition of the present invention, and the pH at the working concentration is 8.0 or more, preferably 8.0. 13.5 is good, and more preferably, it is blended so as to be 8.5 to 13.0.

  The detergent composition for hard surfaces of the present invention can be used in combination with a surfactant other than the component (A) for the purpose of increasing the solubility of the component (A) or improving the biofilm removal performance. As the said surfactant, 1 or more types chosen from anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be used.

  Examples of the anionic surfactant include lignin sulfonate, alkylbenzene sulfonate, alkyl sulfonate, polyoxyethylene (hereinafter referred to as POE) alkyl sulfonate, POE alkylphenyl ether sulfonate, and POE alkylphenyl. Ether phosphate ester salt, POE aryl phenyl ether sulfonate, alkyl sulfate ester salt, POE alkyl ether sulfate ester salt, POE aryl phenyl ether phosphate ester salt, naphthalene sulfonate, naphthalene sulfonate formalin condensate, POE tribenzyl Phenyl ether sulfonate, alkyl phosphate, POE alkyl phosphate, POE tribenzyl phenyl ether phosphate ester salt, dialkyl sulfosuccinate, fatty acid salt (soap), P E alkyl ether acetate and the like, it is more preferable to use inter alia alkyl sulfate and POE alkyl ether sulfate or POE alkyl ether acetates.

  Nonionic surfactants include monohydric alcohol derivative type nonionic surfactants such as POE alkyl ether, POE alkyl phenyl ether, POE aryl phenyl ether, POE styrenated phenyl ether, POE tribenzyl phenyl ether, (poly ) Polyglyceride fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, POE sorbitan fatty acid ester, alkylpolyglycoside, polyhydric alcohol derivative type nonionic surfactants such as fatty acid alkanolamide, etc., among others POE alkyl ether, ( It is more preferable to use poly) glycerin fatty acid ester, alkyl polyglycoside, sorbitan fatty acid ester or POE sorbitan fatty acid ester.

  Examples of amphoteric surfactants include alkyl carboxybetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, fatty acid amide betaines, and alkyldimethylamine oxides. Among them, alkyldimethylamine oxides and alkylhydroxysulfobetaines are preferably used.

  Examples of the cationic surfactant include alkyltrimethylammonium salts and dialkyldimethylammonium salts. Among them, alkyltrimethylammonium salts are preferable. As said salt, a halide is preferable and a chloride and a bromide are more preferable.

  These surfactants can be used in combination at any ratio depending on the component (A) and purpose. A preferable ratio is a component (A): component (C) = 90: 10 to 1:99, more preferably 50:50 to 50% by weight in terms of solubility of the component (A) and cleaning effect. 10:90.

  The hard surface cleaning composition of the present invention can be used in combination with a chelating agent as component (D) for the purpose of enhancing its effect. Chelating agents include aminocarboxylic acid derivatives such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, iminodisuccinic acid, aspartic acid diacetic acid, aminomethylglycine diacetic acid and / or their salts, organic acid salts such as citric acid, tartaric acid and gluconic acid Polyacrylic acid and / or salt thereof, polyelectrolyte compound such as polyacrylic acid / maleic acid copolymer and / or salt thereof, phosphoric acid compound such as tripolyphosphate, orthophosphate, pyrophosphate, Phosphonic acid compounds such as 1-hydroxyethane-1,1-diphosphonic acid and / or salt thereof, aminotri (methylenephosphonic acid) and / or salt thereof, ethylenediaminetetra (methylenephosphonic acid) and / or salt thereof, type A Examples include aluminosilicates such as zeolite and B-type zeolite. Nitrilotriacetic acid salts, salts of ethylenediaminetetraacetic acid, tripolyphosphates, 1-hydroxyethane-1,1-diphosphonic acid and / or its salts are preferred.

  These chelating agents can be used in combination at any ratio depending on the purpose and the compound of general formula (1). A preferred ratio is, in terms of washing effect, in a weight ratio, [total of components (A), (B) and (C)]: [component (D)] = 1:99 to 10:90, and more preferably Is 5: 95-50: 50.

  As the dosage form of the hard surface cleaning composition of the present invention, depending on the application and purpose, a solution dissolved in a solvent such as water, ethanol, isopropanol, or a solid, gel, emulsion / dispersion, powder, Aerosol etc. are mentioned, It can select suitably from these.

  The concentration in the product form of the hard surface cleaning composition of the present invention can be appropriately determined depending on the use and dosage form, but from the viewpoint of product difficulty and effects, (A), (B) and The total of component (C) is preferably 0.01 to 80% by weight, more preferably 0.02 to 60% by weight, even more preferably 0.05 to 40% by weight.

  The hard surface cleaning composition of the present invention is a thickener, a viscosity modifier, a pH adjuster, a solvent, a fragrance, a colorant, an antioxidant, an antiseptic, and a fluorescent agent, as long as the object of the present invention is not impaired. , Excipients, soil release agents, bleaching agents, bleach activators, powdering agents, granulating agents, coating agents, and the like.

  The hard surface cleaning composition of the present invention can be used in a wide range of fields where there is a concern about the danger of biofilms. For example, the present invention can be applied to detergents for food production or beverage production plants with a high risk of bacterial contamination, kitchens, kitchens, bathrooms, toilets, drains for kitchens, kitchens, etc., drain pipes. It can also be applied to cooling water systems such as industrial cooling towers, desalination equipment, pulp and paper manufacturing systems, and circulating water systems such as bathtubs, pools, and artificial ponds. The present invention can also be applied to medical devices in which biofilms are easily formed, such as cleaning agents such as endoscopes, catheters, and artificial dialysis machines. Furthermore, it can also be used for denture care agents, contact lens cleaners, and the like.

  The hard surface cleaning composition of the present invention exhibits an effect by bringing an aqueous solution into contact with the surface on which the biofilm is formed. Examples of the method include immersion, coating, or spraying. Further, physical force such as sponge, towel, brush, water flow, etc. may be applied. In addition, the time for which the hard surface cleaning composition is allowed to act varies depending on the amount of biofilm adhered, the concentration at which the hard surface cleaning composition acts, the working temperature, and the presence or absence of physical force, but usually Is in the range of seconds to hours. In addition, it is desirable that the removed biofilm is immediately rinsed away with running water after the action.

Production Example 1
Production of N- [2-hydroxy-3- (2-ethylhexyl) oxypropyl] -L-arginine hydrochloride Into a 200 mL four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer and a stirring blade, was added L ( +)-Arginine (9.4 g, 53.7 mmol), water (50.0 g), and ethanol (50.0 g) were added, and the mixture was heated to 78 ° C. with stirring in a nitrogen atmosphere. Next, 10.0 g (53.7 mmol) of 2-ethylhexyl glycidyl ether was added dropwise while maintaining the reaction system at 78 to 80 ° C. Then, after aging at 78-80 ° C. for 4 hours, the temperature was returned to room temperature. Next, neutralization was performed by adding 9.8 g (53.7 mmol) of 6 mol / L hydrochloric acid aqueous solution. Water and ethanol were completely distilled off from the reaction solution under reduced pressure to obtain 21.6 g of N- [2-hydroxy-3- (2-ethylhexyl) oxypropyl] -L-arginine hydrochloride as a white solid. This compound corresponds to Compound 2 in Table 1.
In the same manner, compounds having C10 (isodecyl) and C12 (straight chain) were produced. These compounds correspond to the compounds 3 and 4 in Table 1, respectively.

Example 1
<Biofilm removal ability test>
Pseudomonas aeruginosa NBRC13275, Serratia marcescens NBRC12648, Staphylococcus epidermidis ( Klebsiella pneumoniae ATCC13883), soybean-Casein Digest Agar (SCD agar medium: manufactured by Nippon Pharmaceutical Co., Ltd.) ], A very small amount of bacterial mass from a colony formed by pre-culturing at 37 ° C. for 24 hours, and using a sterilized bamboo skewer, 1.5 mL each of Mueller Hinton medium was added to each well. Inoculated into plates. After culturing at 37 ° C. for 24 hours, the culture solution was discarded, and each well was rinsed 5 times with 2 mL of purified water to form and attach a biofilm to the microplate wall. Immediately, 2 mL of a solution obtained by diluting the prepared preparations shown in Table 2 (invention products 1 to 15 and comparative products 1 to 7 as a control) 10-fold with purified water was added and allowed to act at room temperature for 10 minutes. Later, the biofilm control agent in each well was discarded. Each well was rinsed twice with 2 mL of purified water, and then 2 mL of 0.1% crystal violet was added to stain the biofilm remaining on the microplate wall. After rinsing the excess staining solution with water, 2 mL of 80% ethanol was added, and the crystal violet stained biofilm was uniformly dissolved, and then the absorbance was measured at 570 nm to obtain a measured value. Similarly, after the well not treated with the hard surface cleaning composition was treated with 0.1% crystal violet, the absorbance was measured to obtain an initial value. In addition, 1.5 mL each of Mueller Hinton medium in 24 wells but not inoculated with the bacterial mass was performed in the same manner, and the absorbance was measured to obtain a blank value. Each test was performed five times and the average value was used. The removal rate was calculated by the following formula. Concentrations in the table are shown as effective concentration (% by weight) based on the total amount, and pH was adjusted using potassium hydroxide or citric acid as necessary.

Removal rate (%) = 100 × [{(initial value−blank value) − (measured value−blank value)} / (initial value−blank value)]

The obtained biofilm removal rate is shown in Table 2.
In addition, the compounds 1-4 in a table | surface are shown in following Table 1.

  From the above results, it can be seen that the biofilm can be satisfactorily removed by using the hard surface cleaning composition of the present invention.

Example 2 Cleaning test for bath stains A test piece made of polypropylene measuring 80 mm long × 20 mm wide × 1 mm thick is placed in the drainage groove of a family of four people, leaving it to stand for 2 months, and then used as a test piece. Evaluation was performed as follows. The same size as a test piece containing 3 mL of a test solution obtained by diluting the detergent composition for hard surface shown in Table 2 (inventive products 1 to 15 and comparative products 1 to 7 as a control) 10 times with purified water. After the cotton cloth was adhered to the test piece for 1 minute, the state of soiling after rubbing with a sponge was visually evaluated in the following five stages. Table 2 shows the results of detergency against bath dirt as an average of 5 times.
5: Very good dirt removal 4: Good dirt removal 3: Unevenness in dirt removal 2: Slight dirt removal degree 1: Almost no dirt removal

Example 3 Cleaning test for kitchen dirt A stainless steel test piece of length 80 mm x width 20 mm x thickness 1 mm was placed in the drainage ditch of a family of four people in a family. Evaluation was performed as follows. The same size as a test piece containing 3 mL of a test solution obtained by diluting the detergent composition for hard surface shown in Table 2 (inventive products 1 to 15 and comparative products 1 to 7 as a control) 10 times with purified water. After the cotton cloth was adhered to the test piece for 1 minute, the state of soiling after rubbing with a sponge was visually evaluated in the following five stages. Table 2 shows the results of detergency against kitchen soil as an average of 5 times.
5: Very good dirt removal 4: Good dirt removal 3: Unevenness in dirt removal 2: Slight dirt removal degree 1: Almost no dirt removal

Example 4 Soil cleaning test in toilet bowl The cleaning power against inorganic and organic composite stains in a flush toilet bowl that does not fall off when rubbed with a brush was evaluated as follows. 10 mL of a test solution obtained by diluting the prepared hard surface cleaning compositions (inventive products 1 to 15 and comparative products 1 to 7 as a control) shown in Table 2 10 times with purified water is uniformly sprayed on the soil. The state of removal of dirt after rubbing with a brush after standing for a minute was visually evaluated as follows, and the results of cleaning properties against toilet dirt are shown in Table 2.
◎: Good ○: Somewhat good △: Somewhat bad ×: Bad

  As shown in Examples 2 to 4, as compared with comparative products 1 to 3, 6 and 7 which are conventional techniques, which are modeled on a commercially available bathroom stain detergent, a commercially available kitchen stain detergent, and a stain detergent in a commercial toilet bowl, It can be seen that the product of the present invention exhibits excellent detergency against composite dirt in which a biofilm on a hard surface coexists.

Claims (5)

Hard surface cleaning composition containing the following components (A), (B) and (C):
(A) The following general formula (1)

(In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 4 to 18 carbon atoms, and X and Y represent the following formulae:

And m represents an integer of 1 to 5. )
A basic amino acid derivative represented by:
(B) alkaline agent,
(C) Surfactant other than component (A). The hard surface cleaning composition according to claim 1, wherein m is 3 and Y is —NH—C (—NH ₂ ) ═NH in the general formula (1). Formula (1), X is -OCH ₂ -CH (-OH) CH ₂ - in which claim 1 or 2 hard surface detergent composition. Hard surface cleaning composition containing the following components (A), (B) and (C):
(A) Arginine derivative or a salt thereof obtained by reacting arginine or a salt thereof with glycidyl ether,
(B) alkaline agent,
(C) Surfactant other than component (A).   The hard surface cleaning composition according to any one of claims 1 to 4, further comprising (D) a chelating agent.