WO2002016536A1

WO2002016536A1 - Bactericidal antifouling detergent for hard surface

Info

Publication number: WO2002016536A1
Application number: PCT/JP2001/006869
Authority: WO
Inventors: Shin Aihara; Noriyuki Morii; Kazunori Tsukuda; Hiroyuki Yamada
Original assignee: Kao Corporation
Priority date: 2000-08-23
Filing date: 2001-08-09
Publication date: 2002-02-28
Also published as: TWI283267B; JP2002060786A

Abstract

A bactericidal antifouling detergent for hard surfaces which comprises (a) a polymer which has a weight-average molecular weight of 1,000 to 6,000,000 and in which monomer units having at least one group selected among quaternary ammonium groups and tertiary amino groups account for 10 to 100 mol% of all the monomer units, (b) a bactericidal compound having a molecular weight lower than 1,000 and having a quaternary ammonium group, and (c) a surfactant, and in which when the surfactant comprises an anionic surfactant (cA), the proportion of (cA) to (b) by weight does not exceed 1.0. The bactericidal antifouling detergent sterilizes hard surfaces and shows antifouling properties, i.e., prevents fouling substances from adhering thereto and enables fouling substances adherent thereto to be easily removed. When used in a whole house, especially when applied to the walls and floors of the kitchen, bathroom, toilet, washstand, etc. and to instruments and apparatuses placed therein, the detergent enables sterilization, prevention of fouling substance adhesion, and easy cleaning.

Description

Description Sterilizing and antifouling detergent for hard surfaces Technical field to which the invention pertains

The present invention relates to a cleaning composition for hard surfaces that can disinfect hard surfaces and prevent soiling, that is, prevent adhesion of dirt, and easily remove attached dirt. In particular, when used on walls, floors, utensils, equipment, etc. in kitchens, bathrooms, toilets, washbasins, etc. . Conventional technology

Dirt occurs in various places in daily life. Various cleaning agents have been developed to remove such dirt, and studies have been made to enhance their cleaning power. With these efforts, many measures have been proposed to remove stubborn dirt.

In addition, while developing a cleaning agent that is excellent in the removal of dirt, a technology that makes it difficult to remove dirt and a technology that makes it easy to remove dirt attached to it (hereinafter referred to as antifouling properties) Many related technologies are also being studied, and technologies applied as cleaning agents have been found. For example, Japanese Unexamined Patent Publication No. 2-1456977 discloses a flush toilet detergent containing a sulfobetaine-type amphoteric surfactant having a specific structure, and Japanese Unexamined Patent Publication No. 3-35097. Japanese Patent Laid-Open Publication No. Hei 10-16797 discloses a water-based toilet cleaner containing a sulfosuccinic acid ester, which is excellent in loose stool adhesion and has a high cleaning effect. Detergents to be mixed in proportions are described. In particular, Japanese Unexamined Patent Application Publication No. Hei 9-16995 describes that a cleaning agent having a water contact angle of 30 degrees or less with a hard surface after treatment shows excellent antifouling property. As an antifouling base, a combination of an anionic surfactant with a surfactant containing a quaternary ammonium group in a molecule or a water-soluble polymer is mentioned.

As described above, many antifouling technologies have been studied. However, the conventional technology mainly suppresses the generation of stains due to adhesion of water scales and stool, etc., and is insufficient for stains related to darkening caused by microorganisms and mold. In addition, recently, with the improvement of living environment, more and more people are concerned about hygiene problems in addition to visible dirt, and the demand for sterilization is increasing.

As a concept regarding such disinfection, the formulation of a disinfectant is proposed. However, when a bactericide, which is generally used for home use, is added to the above-mentioned cleaning agent, the effects of both the antifouling property and the bactericidal property are offset, and satisfactory bactericidal properties and antifouling properties are achieved. It was extremely difficult to do so.

An object of the present invention is to provide home use, and in cleaning hard surfaces such as toilets, bathrooms, and kitchen surroundings, not only excellent detergency but also sterilization and antifouling properties can be imparted at a satisfactory level. Agent. Disclosure of the present invention

The present invention relates to (a) a compound having a weight-average molecular weight of 1,000 to 6,000, and at least one group selected from a quaternary ammonium group and a tertiary amino group; A polymer having a monomer unit content of 0.1 to 100 mol% with respect to one monomer unit; (b) a sterilizer having a molecular weight of less than 1,000 and having a quaternary ammonium group (CA) / (b) when the surfactant contains (cA) anionic surfactant, and (cA) a surfactant. It is a germicidal and antifouling detergent for hard surfaces not exceeding 1.0 by weight.

It is preferable to contain 0.01 to 30% by weight of the component (a), 0.001 to 30% by weight of the component (b), and 0.01 to 50% by weight of the component (c).

The present invention relates to a method for cleaning and disinfecting a hard surface by applying the above composition to a hard surface and for preventing the adhesion of dirt to the hard surface. Provide use for preventing the adhesion of dirt to the surface. Detailed description of the invention

The component (a) of the present invention is a polymer containing 10 to 100 mol% of a monomer unit having a quaternary ammonium group and / or a tertiary amino group (hereinafter, referred to as a monomer unit A).

Monomer unit A is obtained by polymerizing a monomer (hereinafter, referred to as monomer A) containing a quaternary ammonium group (or a plurality of monomers) or a tertiary amino group (or a plurality of monomers). The monomer unit may be a monomer unit obtained by polymerizing a contained monomer (hereinafter, referred to as monomer A ′), or may be a quaternary ammonium obtained by quaternizing a tertiary amino group.

As a preferred example of the monomer A having a quaternary ammonium group, that is, as an example from which the monomer unit A is derived, a compound represented by the following formula (4) can be mentioned.

R12R13Q2 C (FS4) — X \ R15, γ-

R> in ⁶ R ¹⁷ ^{^{formula, R 12, R 13, R}} " are each independently hydrogen atom, a hydroxyl group or a § alkyl group having 1 to 3 carbon atoms. X represents an alkylene group having 1 to 12 carbon atoms , —COOR ¹⁸ —, — CONHR ¹⁸ —, — OCOR ¹⁸ —, — R ¹⁹ —〇CO—R ¹⁸ — where R ¹⁸ and R ¹⁹ are each independently carbon An alkylene group having a number of 1 to 5. R ¹⁵ is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms or R ¹² R ¹³ C = C (R ¹⁴ ) —X— R ¹⁶ has a carbon number R ¹⁷ is an alkyl group having 1 to 3 alkyl groups, hydroxyalkyl group, or benzyl group; and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group, a carbonyl group, a sulfonic acid group or a sulfate group. Or, when R ¹⁷ is an alkyl group, a hydroxyalkyl group or a benzyl group, Y— represents an anion.

When R ¹⁷ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Y— does not exist, and these groups in R ¹⁷ become anions. Examples of the anion of Y— include a halogen ion, a sulfate ion, an alkyl sulfate ion having 1 to 3 carbon atoms, an aromatic sulfonate ion optionally substituted by an alkyl group having 1 to 3 carbon atoms, and a hydroxy ion. Can be mentioned. Among them, acryloyl (or methacryloyl) aminoalkyl (1 to 5 carbon atoms) -N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, acryloyl (or methacryloyl) 1-5 carbon atoms) -N, N, N-trialkyl (1-3 carbon atoms) quaternary ammonium salt, N— (ω-alkenyl (3-3 carbon atoms: L 0)) — Ν, Ν, Ν- Trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, Ν, —-di (ω-alkenyl (3 to 10 carbon atoms)) — ジ, Ν-dialkyl (1 to 3 carbon atoms) quaternary ammonium salt is preferred Especially, the diaryl dimethyl ammonium pier is good.

Preferred examples of the tertiary amino group monomer A ′, that is, a compound derived from a monomer unit Α ′, include a compound represented by the following formula (5). (Five)

R ² R ¹³ C:

^{^{Wherein, R l2, R l3, R}} l R 15 and R ¹⁶ are the same as above described.

Among them, N, N-dialkyl (C1-3) aminoalkyl (C1-5) acrylate (or methacrylate), N, N-dialkyl (C1-3) aminoalkyl (C1-5) ) Acrylamide, N, N-di (ω-alkenyl (C 3 -L 0))-Ν-methylamine is preferred, and diarylmethylamine is particularly preferred.

When quaternizing monomer A ', quaternizing agents such as methyl chloride, methyl bromide, benzyl chloride, dimethyl sulfate, getyl sulfate, monochloroacetic acid or a salt thereof, chlorsulfuric acid or a salt thereof, and 3-chloro-2 -It is preferably carried out using hydroxypropanesulfonic acid or a salt thereof, ethylene oxide, propylene oxide, or glycidyl ether. When ethylene oxide, propylene oxide, or glycidyl ether is used, it is preferable to react after neutralizing the monomer units with sulfuric acid, hydrochloric acid, a carboxylic acid having 1 to 12 carbon atoms, or arylsulfonic acid in advance. .

The component (a) of the present invention includes not only a polymer composed of monomer units A (a plurality of types may be used), but also a monomer unit A (a plurality of types may be used) and another monomer unit (hereinafter, referred to as “a”). Or a polymer composed of 6 units. (When monomer A 'is used, it may have an amine type monomer unit.) In this case, the arrangement of monomer unit A and monomer unit B (there may be plural types) , Block, alternating, periodic, statistical (including random), or graft type.

The polymer composed of the monomer units A and B can be obtained, for example, by copolymerizing the respective precursor monomers. In this case, the monomer unit B is preferably a monomer unit derived from a monomer selected from the following monomer groups (i) to (V), and is preferably a monomer unit derived from the monomers described in (i) to (iii) or (V). A monomer unit is more preferred, and a monomer unit derived from the monomer (i), (ii) or (V) is most preferred, particularly from the viewpoint of antifouling effect.

(i) Acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, styrenesulfonate, sulfopropyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid or a salt thereof Anion group-containing compounds selected from mono-ω-methacryloyloxyalkyl phosphates (1 to 12 carbon atoms)

(ii) Acrylic (or methacrylic) amide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N-vinyl-1-2-prolactam, N -Amide-containing compounds selected from vinyl-2-pyrrolidone

(iii) Alkyl acrylate (or methacrylic acid) alkyl (1-5 carbon atoms), acrylic acid (or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) 1 N, N-dimethyl Ester group-containing compounds selected from luminoalkyl (C1-5) and vinyl acetate

(iv) Ethylene, propylene, N-butylene, isobutylene, N-pentene, isoprene, 2-methyl-1-butene, N-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-11 Penten, 2-ethyl 1-butene, styrene, vinyl tol Benzene, α-methylstyrene, arylamine, Ν, Ν-diallylamine, Ν, Ν-diaryl-l-alkyl (1-5 carbon atoms) amine, ethyleneoxide, propyleneoxide, 2-vinylpyridine, 4-vinyl Compound selected from pyridine

(V) Sulfur dioxide.

The polymer having the monomer unit Α and the monomer unit は may be synthesized by the above-mentioned copolymerization method, or may be formed into a polymer containing the monomer unit A by one of the monomers (i) to (

It may be obtained by graft polymerization of the monomers of (i) and (ii), or may be obtained by graft polymerization of the monomer of the general formula (4) to a polymer containing the monomers of (i) to (v). Or a polymer containing the monomers (i) to (V), particularly preferably a polymer containing the monomers (i) and (ii), graft-polymerized with the monomer of the general formula (5). After that, it may be quaternized.

The most preferred monomer unit B of the present invention is a monomer having one or more groups selected from a carboxylic acid group and a sulfonic acid group (but not having a quaternary ammonium group), ie, the monomer of the above (i) Monomer unit (hereinafter referred to as monomer unit B ').

Although the polymer constituting the component (a) of the present invention may be obtained by any polymerization method, a radical polymerization method is particularly preferable, and the polymerization can be carried out in a bulk, solution, or emulsion system. Radical polymerization may be initiated by heating, but the initiators are 2,2'-azobis (2-amidinopropane) dihydrochloride and 2,2'-azobis (N, N-dimethyleneisobutylamidine). Azo initiators such as dihydrochloride, and organic peroxides such as hydrogen peroxide and benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methylethylketone peroxide, perbenzoic acid, etc. Existing radical initiators such as oxides, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, etc., redox initiators such as hydrogen peroxide-Fe ³⁺ , etc. may be used, and photosensitizers may be used. Polymerization may be started by light irradiation or radiation irradiation in the presence or absence of a compound.

The component (a) of the present invention may be a homopolymer of the monomer unit A or a mixture of plural kinds of polymers selected from a copolymer of the monomer unit A and the monomer-unit B.

A more preferred constitution in the component (a) of the present invention is that the total of the monomer units A and B ′ is 50 to 100 mol% based on all the monomer units, and most preferably the monomer unit A, The molar ratio of B ′ is such that monomer unit A / [monomer unit A + monomer unit B ′] = 0.3-0.99, particularly 0.4-0.99.

Component (a) of the present invention contains another water-soluble polymer that does not contain polymer A, as long as it does not significantly inhibit the bactericidal and antifouling properties of the germicidal and antifouling detergent for hard surfaces of the present invention. You may. The component (a) of the present invention has a weight average molecular weight of 1,000 to 6,000,000, preferably 10,000 to 6,000,000, particularly preferably 100,000 to 6,000,000, The weight average molecular weight was obtained by gel permeation chromatography using polyethylene glycol as a standard substance, using a mixed solvent of acetate nitrile and water (phosphate buffer) as a developing solvent.

The component (a) is preferably present in the germicidal and antifouling detergent of the present invention in an amount of 0.01 to 30% by weight. In the case of cleaning a hard surface, the concentration of the component (a) is 0.01 to 10% by weight, more preferably 0.02 to 5% by weight. On the other hand, in the cleaning method using water in the toilet tank, Or use it as an auto cleaner for toilets that can apply an appropriate amount of cleaning liquid to the water in the evening water by installing a device in an optional water supply channel.If it is used, use 1 to 30% by weight, more preferably 2 to 20% by weight. % By weight. The concentration of the component (a) in the tank is preferably from 0.1 to 10 ppm. The component (b) of the present invention is a fungicidal compound having at least one quaternary ammonium group having a molecular weight of less than 1000, preferably 500 or less. The bactericidal compound referred to in the present invention refers to a compound having a property that the number of mouths measured by the following method is 10 or less.

Germicidal compound measurement method>

As test bacteria, Escherichia coli (IF と 3972) and Staphylococcus aureus (Staphylococcus aureus: IFQ12732) are used. IF03972 and IF012732 have been deposited at the Institute for Fermentation, Osaka, located at 17-85, Jusanhoncho, Yodogawa-ku, Osaka, Japan and can be sold. Prepare a 1% by weight aqueous solution of the test compound [component (b)], add 50 μl of 10 ⁸ to 10 ⁹ bacterial suspensions to 2 ml of the aqueous solution, mix well, and allow to stand for 5 minutes. After standing, 0.1 ml of this mixture was taken, added to 0.9 ml of LP diluent, and mixed well to reduce the effect of the compound on the bacteria. Culture on E. coli at 37 for 24 hours and Staphylococcus aureus at 37 for 48 hours. Count the number of grown colonies after culture. Perform the sterilization test for the same compound 5 times each (5 times X3). In the results of this experiment, those with less than 10 colonies of both E. coli and Staphylococcus aureus are considered bactericidal. For details of experimental conditions other than the above, see the Handbook

In accordance with the floating test method (quantitative test method) described in p. 686 of the Japan Society of Antibacterial and Fungicide, edited by Gihodo.

As the bactericidal compound having a molecular weight of less than 1000 as the component (b), compounds represented by the following formulas (1) to (3) are preferable, and among them, water-soluble compounds are particularly preferable. Here, "water-soluble" means that the amount dissolved in 1 L of water at 20 is 1 g or more.

FT

(3)

γ-

Ten

R ⁸ R

In the formula, R ¹ and R ^s are each independently an alkyl group or alkenyl group having 6 to 18 carbon atoms, preferably 8 to 16 carbon atoms, preferably an alkyl group, and R ³ and R ⁴ are each independently It is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. X is an aromatic ring or an ester group or an amide group selected from —COO—, one CONH—, one OC〇-one, and one NHCO—, and R ² is a hydroxyl group when X is an ester group or an amide group. An alkylene group having 1 to 6 carbon atoms which may be substituted, and when X. is an aromatic ring, an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or one (0-RU) _k — Here, R ¹¹ is an ethylene group or a propylene group, preferably an ethylene group, and k is an average number of 1 to 10, preferably an average number of 1 to 5. is there. R ⁵ is an alkylene group having 1 to 3 carbon atoms. R ⁷ to R ^1!) Is one or more, preferably one or two of them, an alkyl group having 8 to 18, preferably 8 to 14, more preferably 8 to 12 carbon atoms, and the remaining Is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. M is a number of 0 or 1. Further, Y— is an anion, particularly preferably a halogen ion, a sulfate ion, an alkyl sulfate ion having 1 to 3 carbon atoms, or an aromatic sulfonate ion which may be substituted with an alkyl group having 1 to 3 carbon atoms.

More preferred component (b) is a compound of the above general formula (1) or (3), most preferably a compound of the following general formula.

In the formula, R represents an alkyl group having 8 to 6 carbon atoms.

In the formula, R represents an optionally branched alkyl group having 6 to 12 carbon atoms, and m represents a number of 1 to 5 on average.

In the formula, two Rs represent an alkyl group having 8 to 12 carbon atoms which may be different.

The component (b) is preferably 0.001 to 30% by weight in the disinfectant and antifouling detergent of the present invention. Specifically, the hard surface of the object is washed by a spraying device such as a trigger or an aerosol, or by a method such as application. In the case of cleaning, the concentration of the component (b) is 0.001 to 5% by weight, more preferably 0.005 to 2% by weight. On the other hand, in the cleaning method using water in the toilet tank, When it is used in a toilet cleaner that can administer an appropriate amount of cleaning liquid to the water in the tank by providing a device in the water supply path, it is contained in an amount of 0.1 to 30% by weight, more preferably 1 to 20% by weight. You. The concentration of the component (b) in the tank is preferably 0.01 to: LOp pm.

In the present invention, the component (a) / component (b) is preferably 3'0Zl to 1Z50 in weight ratio, and 20/1 to 1/20 in order to obtain a bactericidal effect while maintaining sufficient antifouling properties. More preferably, 10/1 to 1/10 is most preferable.

The germicidal antifouling detergent for hard surfaces of the present invention further contains (c) a surfactant other than the component (b) [hereinafter referred to as the component (c)]. Nonionic surfactants, amphoteric surfactants It is preferable to add one or more surfactants selected from surfactants and anionic surfactants.

Examples of the nonionic surfactant include compounds represented by the following formulas (c1) to (c3). R ^cl -0 (EO) _n H (c 1)

[Wherein, R ″ ¹¹ is a primary linear alkyl group, a branched alkyl group or a secondary alkyl group having an average carbon number of 10 to 20, preferably 10 to 18. EO is ethylene oxide and n Is 5 to 20 as an average number of added moles.]

R ^c2 -0 (EO) _p / (PO) _q H (c 2)

[In the formula, R ^c2 is a primary alkyl group having an average carbon number of 10 to 20, preferably 10 to 18; EO indicates ethylene oxide, and PO indicates propylene oxide. k and 1 are the average number of added models, p is 5 to 15, and q is 1 to 5. EO and PO may be added randomly, or PO may be added after adding EO, or vice versa. Further, the block additional body may be three or more blocks. ]

R ^c3 — (〇R ^c4 ) _x G _y (c 3)

Wherein R ^e3 is a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms or an alkylphenyl group having an alkyl group having 8 to 18 carbon atoms, is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, preferably a glucose residue, X is a number having an average value of 0 to 6, and y is a number having an average value of 1 to 10. ].

Examples of the amphoteric surfactant include an aminoxide represented by the following general formula (c4) and a betaine represented by the following general formula (c5).

Wherein, R ^{c 5} is an alkyl or alkenyl group having 8 to 18 carbon atoms, R ^c6 is an alkylene group having 5 to several atoms. R ^c7 and R ^c8 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. A is a group selected from one COO—, one CONH—, one C—one, —NH CO—, —0—, and r is a number of 0 or 1.

(c 5)

In the formula, R ^c5 , R ^c6 , R ^c7 , R′K A and r are the same as those described in the general formula (c 4). R ^c9 is an alkylene group which ~ 1 carbon atoms which may be 5 substituted by a hydroxyl group, T is ten S 0 ₃ -, - CO_〇-, an anionic group selected from a S Of. r is a number of 0 or 1. ].

Examples of the anionic surfactant include alkylbenzene sulfonates having 8 to 18 carbon atoms in the alkyl group, alkane sulfonates, α'-olefin sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, and the like. Polyoxyethylene alkyl ether acetate And the like.

In the present invention, in particular, blending one or more of the surfactants selected from the above formulas (c3), (c4) and (c5) provides excellent detergency without impairing the antifouling effect. It is preferable for obtaining. (C) The amount of the surfactant is preferably 0.01% by weight or more and less than 50% by weight, more preferably less than 50% by weight, in order to obtain sufficient detergency and foaming power without impairing the disinfecting and antifouling effects. Is 0.1% by weight or more, particularly preferably 0.1 to 30% by weight.

However, the anionic surfactant [hereinafter referred to as (cA)] should be blended in an amount that has no effect in order to reduce the bactericidal and antifouling properties. When (cA) is contained, (cA) ) / (b) must be present in a proportion by weight not exceeding 1.0, preferably not exceeding 0.75. Beyond this range, both antifouling and disinfecting effects cannot be obtained.

The component (c) is preferably 0.1 to 30% by weight in the germicidal and antifouling detergent of the present invention. Specifically, the target hard surface is directly cleaned by a spraying device such as a trigger or an aerosol, or by a method such as application. In such a case, the concentration of the component (j) is 0.1 to 20% by weight, more preferably 0.2 to 10% by weight. On the other hand, in the cleaning method using water in the toilet tank, the water in the tank or any water supply When used in toilet cleaners that can administer an appropriate amount of washing liquid to the water in the tank by providing a device in the route, the content is 0.5 to 30% by weight, more preferably 1 to 30% by weight. . The concentration of the component (c) in the toilet tank is preferably 0.1 to 20 ppm. In the present invention, a water-soluble solvent [hereinafter referred to as “component (d)”] is preferably blended as an optional component for the purpose of improving detergency against organic stains. [1] A monovalent alcohol having 1 to 5 carbon atoms [2] a polyhydric alcohol having 4 to 12 carbon atoms, [3] a compound represented by the following general formula (dl), [4] a compound represented by the following general formula (d2), and [5] One or more compounds selected from the compounds represented by the following general formula (d3) are preferable.

R ^dl O (C ₂ OHC ₃₀ ) R ^d , ² _(D D

R ^d5 OC (CH ₃ ) ₂ C¾C¾OH (d 3)

In the formula, R ^dl and R ^d2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and both R ^dl l and R ^d2 are hydrogen atoms Except in cases. s and t each independently represent a number from 0 to 10, except when both s and t are 0. R ^d3 and R ^d4 represent an alkyl group having 1 to 3 carbon atoms. R ^d5 represents an alkyl group having 1 to 3 carbon atoms. Show.

Examples of the monohydric alcohol having 2 to 5 carbon atoms in [1] generally include ethanol, propyl alcohol, and isopropyl alcohol. By incorporating these lower alcohols, the stability of the system at low temperatures can be further improved.

Examples of the polyhydric alcohol having 4 to 12 carbon atoms of [2] include isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,5-pentanediol, 1,8-octanediol, In addition to 9-nonanediol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and glycerin, monoalkyl glyceryl ethers having an alkyl group having 3 to 8 carbon atoms and the like are included.

In the compound of [3], in the general formula (dl), when R ^dl and R ^d2 are an alkyl group, the number of carbon atoms is particularly preferably 1 to 4. In the general formula (dl), s and t, which are the average addition mole numbers of ethylene oxide (hereinafter, referred to as EO) and propylene oxide (hereinafter, referred to as PO), are 0 to 10, respectively. The order of addition is not particularly limited, and may be randomly added. Specific examples of the compound of [3] include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, polyoxyethylene (average number of moles = 2-3) polyoxypropylene (average number of moles = 2-3) glycol dimethyl Ether, polyoxyethylene (average number of added moles = 1 to 4) Glycol phenyl ether, phenyl carbitol, phenyl sorbitol, benzyl carbitol and the like. Among these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, and polyoxyethylene (average number of moles = 1 to 4) glycol phenyl ether are preferred from the viewpoints of detergency and usability. Further, as the compound of [4], 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone are exemplified as preferable ones, and as the compound of [5], 3- (3-dimethyl-2-imidazolidinone) is used. Preference is given to methoxy-3-methylbutanol, 3-ethoxy-3-methylbutanol and the like. Among these, a water-soluble solvent selected from the compounds of [1], [2] and [3] is preferable from the viewpoint of damage to the base material, and in particular, ethanol, isopropyl alcohol, ethylenedaricol, propylene glycol, diethylene glycol, dipropylene Glycol, daliserine, isoplendaricol, propylene glycol monomethyl ether, propylene dalicol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and monoalkyl glyceryl ether having 3 to 8 carbon atoms in the alkyl group And a water-soluble solvent selected from

The component (d) is preferably 0.1 to 50% by weight in the germicidal antifouling detergent of the present invention. In such cases, the concentration of component (d) is 0.! 20% by weight, more preferably 0.5% to 10% by weight. On the other hand, in a cleaning method using water in the toilet tank, an appropriate amount of water in the tank is provided by installing a device in the tank or an arbitrary water supply path. When it is used for an auto cleaner for a toilet which can administer a suitable washing liquid, it is contained in an amount of 1 to 50% by weight, more preferably 5 to 30% by weight. The concentration of the component (d) in the toilet tank is preferably 0.01 to 20 ppm. In the present invention, for the purpose of dissolving the inorganic dirt, and improving the detergency and the sterilizing effect, (e) It is preferable to add a chelating agent as a component. Examples of the chelating agent include (1) tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and alkali metal salts thereof, (2) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethyldalicin, nitrilotriacetic acid, Hydroxyethylene diamine triacetic acid, diethylene triamine pentaacetic acid, triethylene tetramine hexaacetic acid and their metal salts or alkaline earth metal salts, (3) aminotrimethylene phosphonic acid, 1-hydroxyethylidene 1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, N-oxide of aminotrimethylenephosphonic acid and alkali metal or alkaline earth metal salts thereof, (4) acrylic Select from acid and methacrylic acid Homopolymers or copolymers of monomers, acrylic acid-maleic acid copolymer, poly-α-hydroxyacrylic acid and its alkali metal salts, (5) citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, At least one selected from the group consisting of polycarboxylic acids selected from malonic acid and maleic acid and alkali metal salts thereof; (6) alkyl glycine mono-, di-acetic acid, aspartic acid-Ν, di-acetic acid, and serine Mono-, di-acetic acid, glutamic acid diacetate, ethylenediamine disuccinic acid or salts thereof are preferred, and the compounds of (2), (3) and (5) are particularly preferred.

The component (e) is preferably 0.1 to 20% by weight in the germicidal antifouling detergent of the present invention. More specifically, the hard surface of the object is sprayed with a trigger or aerosol, or by a method such as coating. In the case of washing, the concentration of the component (e) is 0.1 to 10% by weight, more preferably 0.3 to 7% by weight. On the other hand, in the washing method using water in the toilet tank, 1-20% by weight, more preferably 2-20% by weight when used in toilet auto cleaners that can supply an appropriate amount of cleaning liquid to the water in the tank by installing a device inside or in an optional water supply path It is contained. The concentration of the component (e) in the toilet tank is preferably 0.01 to 20 ppm.

The present invention may use a pH adjuster when adjusting pH. Examples of pH adjusters include inorganic acids such as hydrochloric acid and sulfuric acid, acid agents such as citric acid, co-octanoic acid, malic acid, fumaric acid, tartaric acid, malonic acid, and maleic acid; sodium hydroxide; Alkaline agents such as sodium carbonate and potassium carbonate, such as potassium hydroxide, ammonia and derivatives thereof, and amine salts such as monoethanolamine diethanolamine and triethanolamine, may be used alone or in combination. Further, these acid agents and alkali agents may be used in combination as a buffer system. .

The hard surface sterilizing and antifouling detergent of the present invention is preferably adjusted by the above-mentioned pH adjuster so that ^ 1 in 20 becomes 2 to 12 and particularly pH 3 to 1 It is preferable to set it to 1 from the viewpoint of the antifouling effect.

In the present invention, one or more water-soluble polymers can be added for the purpose of imparting adhesion during use and improving ease of use. The water-soluble polymer is not particularly limited, but may be one selected from water-soluble polymers described in JP-A-8-209194, page 6, column 10 to page 7, column 11. The above is preferred.

In addition to the above-mentioned components, the hard surface sterilizing and antifouling detergent of the present invention contains additives, such as fragrances, antibacterial agents, and viscosity modifiers, which are blended with ordinary detergents within a range that does not impair the effects of the present invention. Agents, pigments, dyes, suspending agents and the like can be added. In addition, for the purpose of enhancing the foaming property at the time of use, at least one selected from foaming aids such as toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, arkeel succinic acid, and metal salts of these metals is added. I can do it.

When the present invention is used, even if the polymer of the component (a) and the germicidal compound of the component (b) are dissolved or dispersed as a single agent in a solvent, any one of the optional agents may be used in combination with the optional component. In numbers No problem. One or more powders or tablets may be used in the form of one or more powders which can be immediately dissolved in a solvent such as water or provided with sustained release by combining optional components. Further, any one of the component (a) and the component (b) or the optional component may be used in a liquid state, and the other may be used in a solid state such as a powder.

The form of the sterilizing and antifouling detergent of the present invention at the time of use is not particularly limited, but is preferably a liquid composition containing component (a), component (b) and optional components, with the balance being water. When used as a solid, a solid or gel composition may be formed using a coagulant such as polyethylene glycol, polyethylene glycol fatty acid ester, polyethylene glycol fatty acid diester, fatty acid, or salt. The content of water is preferably 10 to 98% by weight, more preferably 20 to 95% by weight in the case of a liquid composition or a gel composition. In the case of a solid composition, it is preferably at most 30%, more preferably at most 20%. Example

Example 1>

A germicidal antifouling detergent having the composition shown in Table 1 was prepared, and its antifouling property and bactericidal property were evaluated by the following methods. Table 1 shows the results.

(1) Easy cleaning

After sterilizing antifouling agent LML, applied to porcelain tiles surface area 10 cm ^2, left for 5 minutes, water

20 Flow of 01111 ^ at an angle of 45 ° at a flow rate of 25 mL / sec, and drying is repeated 5 times. Then, 0.5 g of oleic acid is dropped on the surface of the ceramic tile in the form of spots. The pottery tiles with the drop of oleic acid are allowed to stand at the bottom of the tank so that the oleic acid does not flow, and the tank is gently filled with water so that the pottery tiles are not directly exposed to water. At that time, the ratio of the area where oleic acid was removed from the ceramic tile surface was determined, and evaluated in the following five steps. The percentage of dirt removal was the average value of five model contamination plates.

5: Stain removal is 80% or more

4: Stain removal is 60% or more and less than 80%

3: Stain removal is 40% or more and less than 60%

2: Stain removal is 20% or more and less than 40%

1: Stain removal is less than 20%.

(2) Dirt adhesion prevention

Using a commercially available toilet bowl (C 730 B, manufactured by Tohoku Kiki Co., Ltd.), the evaluation of the difficulty of soiling was performed. That is, the toilet was washed with the composition, and the difficulty of attaching the stain after being left for one week was visually measured based on the following criteria.

(Evaluation criteria)

A: No dirt.

〇: Slightly adhered.

Δ: Slightly adhered.

X: There is considerable dirt.

Escherichia coli (IFO 3972) and Staphylococcus aureus (Staphylococcus cauruseus: IFO 12732) were used as test bacteria. The bactericidal test was conducted by adding 50 μl of 10 ⁸ to 10 ³ bacterial suspensions to 2 ml of the germicidal antifouling agent shown in Table 1 and mixing well. Was. After standing, the mixture 0.1 ml is collected and added to 0.9 ml of LP diluent and mixed well to reduce the effect of the washing solution on the bacteria, then this mixture is spread on S CDLP agar medium, and the E. coli is 37t: Incubate for 24 hours at 37 ° C for 48 hours. Count the number of grown colonies after culture. In the sterilization test, the same sterilizing and antifouling agent was tested in five test plots for each standing time, and the sterilizing property was evaluated according to the following scores.

The details of the experimental conditions other than the above-mentioned rules conform to the floating test method (quantitative test method) described in P. 686 of the Bacterial and Fungicide Handbook (edited by the Japan Society of Bacterial and Fungicide, published by Gihodo).

〇: The number of colonies becomes less than 10 ^{4 in} 5 minutes.

X: The number of colonies exceeds 10 ⁴ when the standing time is 5 minutes The components in the table are as follows.

'Polymer B: Mercoat 550 [diallyldimethylammonium chloride and acrylamide (mole ratio 30/70) copolymer (Ca1gon, weight average molecular weight 5,000,000, measured by gel permeation chromatogram, Polyethylene glycol is used as standard)] 'Polymer A: Mercoat 100 [Homopolymer of diaryldimethylammonium chloride (Ca1gon, weight average molecular weight 400,000, measured by gel permeation chromatogram) Use polyethylene glycol as standard)]

-Polymer C: Mercoto 280, manufactured by Calgon, a copolymer of diaryldimethylammonium chloride and acrylic acid

• Polymer D: A solution obtained by adding 76.41 g of N, N-dimethylaminopropylmethacrylic acid amide to a solution of 3.59 g of acrylic acid, 280 g of water, and 32 ml of 35% aqueous hydrochloric acid under cooling, and neutralized. Was heated to 70 ° C., and a polymerization initiator (W-50, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise under a nitrogen atmosphere. After aging, the mixture was cooled to obtain a polymer having an effective content of 18%. Weight average molecular weight 400,000, monomer (a) / [monomer (a) + monomer (b)] = 0.9 (molar ratio)

• Fungicidal compound A: Sanizole C [cocoalkyl dimethyl benzylammonium chloride (manufactured by Kao Corporation)]

-Bactericidal compound B: Koyinmin D 10 P [didecyldimethylammonium chloride (manufactured by Kao Corporation)]

• Fungicidal compound C: Benzetonium chloride [Wako reagent, cationic compound with the following structure]

CI "

Fungicidal compound D: Octyl dimethyl benzalgonium chloride

AO: Amphitol 2 ON [Lauryl dimethylamine oxide (Kao Corporation)]

AG: Alkyl darcoside (a mixture of straight chain alkyl groups with 12 and 14 carbon atoms, average saccharide condensation degree 1.2 [mixture of condensation degrees 1 and 2])

• ES: Polyoxyethylene lauryl ether sulfate with an average number of moles of added EO of 2.2 moles • Betaine: N-lauroylaminopropyl-N, N-dimethyl-N-potoxymethylammonium betaine • ED TA-4 Na: Ethylenediaminetetraacetic acid tetrasodium salt

• pH adjuster: hydrochloric acid and / or sodium hydroxide (all used in aqueous solution)

The toilet auto-cleaner composition shown in Table 2 was prepared and poured into a toilet tank with a spot so that the value in Kazuko (ppm) was obtained. The antifouling property when flushing was evaluated by the following method did. Table 2 shows the results.

(1) Easy cleaning

After flushing 10 times, 0.5 g of oleic acid was dropped in five spots using a toilet (C730B manufactured by Tohoku Kikai Co., Ltd.) in spots, and the area from which the oleic acid was removed after flushing Was evaluated and evaluated in the following five steps. The average of five measurements was used for the evaluation of dirt removal.

(Evaluation criteria are the same as Table 1.)

(2) Dirt adhesion prevention

A commercially available toilet bowl (C730B, manufactured by Tohoku Kikai Co., Ltd.) was used to evaluate the difficulty of getting dirty. That is, the toilet was washed with the composition, and the hardiness of the toilet when allowed to stand for one week was visually measured based on the following criteria.

(Evaluation criteria)

A: No dirt.

〇: Slightly adhered.

Δ: Slightly adhered.

X: There is considerable dirt.

(3) Bacterial growth inhibitory effect

Table 2 of well sales added a suspension 0. 05Ml and SCD medium 0. lml of Staphylococcus aureus which had been adjusted to 10 ⁴ cfu / ral to adjust the composition 2 ml concentration in Katsuko, 3 7. After standing at C for 18 hours, the bacteriostatic activity value was determined by the following formula.

Sterile water was used as a blank. Bacteriostatic activity value = log (number of viable cells after blank culture)-log (number of viable cells after culture of evaluation sample) <evaluation>

〇: Bacteriostatic activity value: greater than 0

X: Bacteriostatic activity value: 0 or less

Formulation example

One

1. O 4 Ό D 1 by I o u "r α o 1 Ί o 20

M mouth 1 A n U. u.

Satoban Mu σ / 1 female small tit 0.1 0.3 1 3

(A) component

Sitting mouth 1 flat 0.1 0.3 1 ■) 1 1 1 3

Woman _n

Sato α 1 small U 0.1 1 1 5 3 Neither soil 1 C mouth JA 0.01 1 0.1 0.3 1 0.05 0.1 0.1 0.1 0.05 Fungicidal compound Β 0.3 0.3

Hard (b) component

Fungicidal compound C 1

Fungicidal compound D 0.1 0.3 0.5 1 1 0.5 1 1 2

AO 1 1 1 1 1 1 2 '1 1 1

AG 1 3 1 1 1 1 1 3 1 1 1 3 1 1 1.5 1 0.5

(c) ingredient

ぺ 'tine 1 1 1 1 1 1 1 1 1 1 1 0.5 1

ES 0.5 0.5 0.3 0.5 Ethanol 3 3 5 3 3 3 2 5 5 5 5 2 5 5 2 Phylobilenguelicol 3 5 5 3 3

(d) Component 5 3

Jim Brovilengeliko

Five

Chill ether

Query acid 2 2 2 5 1 1 1 1 2 2 4 2 2 2 2 5 2 2

(Ingredients

EDTA- 4N a 3 3 3 2 2 5 2 2 2 3 3 3 Ion-exchanged water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Total 100 100 100 100 100 100 100 100 100 100 100 1.00 100 100 100 100 100 100 100 100 pH 7 7 11 3 7 7 7 7 7 7 7 7 3 10 7 7 7 3 6 6 Easy cleaning 4.0 5.0 5.0 5.0 4.0 5.0 5.0 5.0 4.6 5.0 5.0 5.0 4.6 4.6 5.0 5.0 4.2 4.2 5.0 5.0 Anti-fouling properties 〇 ◎ ◎ ◎ 〇 ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ Sterilization

瑯 ¾

Comparison example

1 2 3 4 5 6 F Polymer A 1

Polymer B 1

(A) component

Polymer C 1

Polymer D 1 Fungicidal compound A 0.1

Bactericidal compound B 0.3

Hard (b) component

Sterilization 1 Raw compound G

Pledge

Table ¾ _ Bacteria monomerized n D 1 1 AO 1

1.5 1 1 kill '* ~,

(c) component η

Bacterium 1 1 U.0 1 1 ES

Dirty%

Ethanol

Washing

Pure (d) Ingredients

Agent Propylene gericol monomer

Chill ether

Cuenoic acid 1 1 2 2 2

(e) component

EDTA-4Na 2 3.5 2 Ion-exchanged water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining

C3. 100 100 100 100 100 100 100

ΡΗ. 7.7 7 7 7 7 7 7 Easy cleaning 2.0 1.0 2.0 2.0 2.0 2.0 2.4 Stain adhesion prevention △ X Δ X X X X

¥ £ Bacterial XXXX 〇 XX

Table 2

-15-

Claims

The scope of the claims

1. (a) A monomer unit having a weight average molecular weight of 1,000 to 6,000,000 and having at least one group selected from quaternary ammonium groups and tertiary amino groups (B) a bactericidal compound having a molecular weight of less than 1,000 and having a quaternary ammonium group, and (c) a surfactant. When (cA) an anionic surfactant is contained as a surfactant, a (cA) / (b) weight ratio of (cA) / (b) does not exceed 1.0, which is a bactericidal and antifouling detergent for hard surfaces.

2. The germicidal and antifouling detergent for hard surfaces according to claim 1, wherein (b) is at least one bactericidal compound selected from the compounds represented by the following formulas (1) to (3).

Wherein, R ¹ and R ⁶ are each independently an alkyl group or alkenyl group having 6 to 18 carbon atoms, 1 ³ and 1 ⁴ are each independently alkyl or hydroxyalkyl of 1 to 3 carbon atoms It is an alkyl group. X is an aromatic ring or an ester group or an amide group selected from —COO—, one CONH—, one OCO—, and —NHCO—, and R ² is a hydroxyl group when X is an ester group or an amide group. And when X is an aromatic ring, an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or one (O—R n ) _k —. Here, R ¹¹ is an ethylene group or a propylene group, and k is a number of 1 to 10 on average. R ⁵ is alkylene having 1 to 3 carbon atoms. ! ¾ ⁷ to 1 ^ ¹⁾ is an alkyl group of 1 Tsu or more of these carbon number 8 to 18, the remainder being Argyle or hydroxy aralkyl kill groups of 1 to 3 carbon atoms. M is a number of 0 or 1. Furthermore, Y— is an anion. ]

3. The germicidal and antifouling detergent for hard surfaces according to claim 1, wherein the monomer unit having a quaternary ammonium group in (a) is derived from a compound represented by the following formula (4).

-16- [Wherein, R ¹² , R ¹³ and R ¹⁴ are each independently a 7K element atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. X is an alkylene group having 1 to 12 carbon atoms, -COOR ¹⁸ -, -CONHR ¹ ⁸ - one OCOR ¹⁸ - a group selected from - one R ¹⁹ - OC_〇 one R ^18. Here, R ¹⁸ and R ¹⁹ are each independently an alkylene group having 1 to 5 carbon atoms. 1 to ¹⁵ are an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms or R ¹² R ¹³ C = C (R ¹⁴ ) -X—. R ¹⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group; and R ¹⁷ is a C 1 to C 3 group which may be substituted with a hydroxy group, a carbonyl group, a sulfonic acid group, or a sulfate group. When R ¹⁷ is an alkyl group, a hydroxyalkyl group, or a benzyl group, Y— represents an anion. ]

4. The germicidal and antifouling detergent for hard surfaces according to claim 1, wherein the monomer unit having a tertiary amino group in (a) is derived from a compound represented by the following formula (5).

_R 15 (5)

_R 12 _R 13 _c _ _{cf R} 14 no

■ X—N

_R 16

^{^{Wherein, R. 12, R 13, R}} 14, R 15 and R ¹⁶ are the same as above described. ]

5. (a) The polymer of component is a monomer unit A having at least one group selected from quaternary ammonium groups and tertiary amino groups, and at least one selected from carboxylic acid groups and sulfonic acid groups. Is a polymer containing a monomer unit B 'having a group [but not having a quaternary ammonium group] and wherein the sum of monomer units A and B accounts for 50 to 100 mol% of all monomer units. Item 6. The sterilizing and antifouling detergent for hard surfaces according to Item 1.

6. The hard surface according to claim 1, wherein the component (a) contains 0.01 to 30% by weight, the component (b) contains 0.001 to 30% by weight, and the component (c) contains 0.01 to 50% by weight. Sterilizing and antifouling detergent.

7. A method for cleaning and disinfecting a hard surface by applying the composition according to claim 1 to the hard surface and preventing adhesion of dirt to the hard surface.

8. Use of the composition according to claim 1 for cleaning and disinfecting hard surfaces and preventing the adhesion of dirt to hard surfaces.

■ 17-