JP2002060786A - Germicidal stainproofing agent for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a germicidal stain-proofing agent usable in the home, capable of providing hard surfaces around the circumference of a toilet, a bathroom, a kitchen, etc., with both excellent antimicrobial properties and soil resistance. SOLUTION: This germicidal strain-proofing agent for a hard surface comprises (a) a polymer which has 1,000-6,000,000 weight-average molecular weight and 10-100 mol% ratio of a quaternary ammonium group-containing monomer unit to the whole monomer units and (b) a quaternary ammonium group-containing antimicrobial compound having <1,000 molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to sterilization of hard surfaces,
And anti-fouling property, that is, a bactericidal anti-fouling agent for hard surfaces that enables the prevention of the adhesion of dirt and the easy removal of the adhering dirt, in general in a house, especially kitchens, bathrooms, toilets, wash basins, etc. The present invention relates to a bactericidal and antifouling agent for hard surfaces which can be used for walls, floors, appliances, equipment, etc., and which can sterilize, prevent the adhesion of dirt, and easily clean.

[0002]

2. Description of the Related Art Dirt is generated in various places in a living scene. Various cleaning agents have been developed to remove such stains, and studies have been made to enhance their cleaning power. With these efforts, many means for removing stubborn dirt have been proposed.

[0003] In addition, while developing such a cleaning agent excellent in dirt removal properties, a technique for making dirt less likely to adhere and a technique for easily removing dirt attached by performing treatment (hereinafter referred to as antifouling property). ) Technologies are also being considered,
Techniques for application as cleaning agents have been found. For example,
JP-A-2-14597 discloses a flush toilet detergent containing a sulfobetaine-type amphoteric surfactant having a specific structure, and JP-A-3-35097 discloses a soft fecal adhesion-preventing agent containing a sulfosuccinic diester. Japanese Unexamined Patent Publication No. 10-1697 discloses a cleaning agent which is excellent in cleaning effect and has a high cleaning effect, in which a specific surfactant and a water-soluble solvent are mixed at a specific ratio. In particular, Japanese Patent Laid-Open No. 9-1
No. 69,995 discloses that a detergent having a water contact angle of 30 ° or less with a hard surface after treatment exhibits excellent antifouling property. Specifically, an anionic surfactant is used as an antifouling base. A combination with a surfactant containing a quaternary ammonium group in the molecule or a water-soluble polymer is mentioned.

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

[0005] As a concept regarding such sterilization, blending of a fungicide is proposed. However, when a disinfectant commonly used for home use is added to the antifouling agent, the effects of both the antifouling property and the bactericidal property are offset, and satisfactory bactericidal and antifouling properties are obtained. It was extremely difficult to achieve.

An object of the present invention is to provide an agent which can be used at home and which can impart both sterilizing and antifouling properties to hard surfaces such as toilets, bathrooms and kitchens at a satisfactory level.

[0007]

According to the present invention, there is provided (a) a polymer having a weight average molecular weight of 1,000 to 6,000,000,
A polymer in which the ratio of the monomer unit having a quaternary ammonium group is 10 to 100 mol% based on all monomer units (hereinafter, referred to as component (a)), and (b) a molecular weight of 1,
The present invention relates to a bactericidal antifouling agent for hard surfaces containing a bactericidal compound having a quaternary ammonium group of less than 000 [hereinafter referred to as the component (b)]. Here, sterilization includes the meaning of antibacterial. Further, the monomer unit refers to a repeating unit derived from a monomer constituting the polymer, and the monomer refers to a low molecular substance from which the polymer is formed.

[0008]

BEST MODE FOR CARRYING OUT 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 (hereinafter, referred to as monomer unit A).

The monomer unit A is obtained by polymerizing a monomer containing a quaternary ammonium group (which may be plural) (hereinafter, referred to as monomer A) or by forming a tertiary amino group (which may be plural). It is obtained by subjecting a monomer unit obtained by polymerizing a contained monomer (hereinafter, referred to as monomer A ′) to quaternary ammonium.

Preferred examples of the monomer A include a compound represented by the following general formula (4).

[0011]

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Wherein R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen 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, -CO
^{OR 18 -, - CONHR 18 -} , - OCOR 18 -, - R 19
It is a group selected from —OCO—R ¹⁸ —. Where R ¹⁸ ,
R ¹⁹ is each independently an alkylene group having 1 to 5 carbon atoms. R ¹⁵ is 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 has 1 to 10 carbon atoms which may be substituted with a hydroxy group, a carboxyl 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. 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. be able to. ].

Among them, acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N,
N-trialkyl (C1-3) quaternary ammonium salt, acryloyl (or methacryloyl) oxyalkyl (C1-5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt , N- (ω-alkenyl (3 to 10 carbon atoms))-N, N, N-trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, N, N-di (ω-alkenyl (3 to 10 carbon atoms) 10)) -N, N-dialkyl (C1-3) quaternary ammonium salts are preferred, and diallyldimethylammonium salts are particularly preferred.

Preferred examples of the monomer A 'include a compound represented by the following general formula (4').

[0015]

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Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶
Is the same as described above. Among them, N, N-dialkyl (C1-3) aminoalkyl (C1-5)
Acrylate (or methacrylate), N, N-dialkyl (C1-3) aminoalkyl (C1-5)
Acrylamide and N, N-di (ω-alkenyl (3 to 10 carbon atoms))-N-methylamine are preferred, and diallylmethylamine is particularly preferred.

The quaternizing agent used for converting the monomer A 'into a quaternary ammonium includes methyl chloride, methyl bromide, benzyl chloride, dimethyl sulfate, diethyl sulfate, monochloroacetic acid or a salt thereof, chlorosulfonic acid or a salt thereof. , 3-chloro-2-hydroxypropanesulfonic acid or a salt thereof, ethylene oxide, propylene oxide, glycidyl ether and the like.
When ethylene oxide, propylene oxide, or glycidyl ether is used, it is preferable that the monomer unit is neutralized with sulfuric acid, hydrochloric acid, a carboxylic acid having 1 to 12 carbon atoms, allylsulfonic acid, or the like before the reaction.

The component (a) of the present invention comprises a monomer unit A
(May be plural kinds),
It may be a polymer composed of a monomer unit A (which may be plural kinds) and another monomer unit (hereinafter, referred to as a monomer unit B). (When the monomer A 'is used, it may have an amine type monomer unit.)
In this case, the arrangement of the monomer unit A and the monomer unit B (there may be plural types) may be any of block, alternating, periodic, statistical (including random), and 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, as the monomer unit B, the following monomer group (i)
To (v) are preferred, and monomer units derived from the monomers described in (i) to (iii) or (v) are more preferred, and (i) and (ii) are particularly preferred from the viewpoint of antifouling effect. ) Or a monomer unit derived from the monomer (v) is most preferred. (I) acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, styrene sulfonate, sulfopropyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, phosphoric acid Anionic group-containing compound selected from mono-ω-methacryloyloxyalkyl (C 1 to C 12) (ii) acrylamide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacryl ( Or methacryl) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2 -An amide group-containing compound selected from pyrrolidone (iii) Acrylic acid (or methacrylic acid) alkyl (C1-5), acrylic acid (or methacrylic acid) of 2-hydroxyethyl, acrylic acid (or methacrylic acid) -
An ester group-containing compound selected from N, N-dimethylaminoalkyl (1-5 carbon atoms) 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-1-pentene, 2
-Ethyl-1-butene, styrene, vinyltoluene, α
-Methylstyrene, allylamine, N, N-diallylamine, N, N-diallyl-N-alkyl (having 1 to 1 carbon atoms)
5) amines, ethylene oxide, propylene oxide,
Compounds selected from 2-vinylpyridine and 4-vinylpyridine (v) Sulfur dioxide.

The polymer having the monomer unit A and the monomer unit B can be synthesized by the above-mentioned copolymerization method. Alternatively, the polymer containing the monomer unit A can be added to the monomers (i) to (iv), particularly preferably The polymer may be obtained by graft polymerization of the monomers (i) and (ii), or a polymer containing the monomers (i) to (iv), and particularly preferably the polymers (i) and (i).
The polymer containing the monomer of i) may be obtained by graft polymerization of the monomer of the general formula (4),
After graft-polymerizing the monomer of the general formula (4 ′) onto the polymer containing the monomer of (iv), particularly preferably the polymer containing the monomer of (i) or (ii), it is quaternized. Good.

The polymer constituting the component (a) of the present invention may be obtained by any polymerization method, but a radical polymerization method is particularly preferred, and the polymerization can be carried out in a bulk, solution or emulsion system. The radical polymerization may be initiated by heating, but 2,2′-azobis (2-
Amidinopropane) dihydrochloride, 2,2′-azobis (N, N-dimethyleneisobutylamidine) dihydrochloride,
Azo initiators such as hydrogen peroxide and benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, organic peroxides such as perbenzoic acid, sodium persulfate, potassium persulfate, An existing radical initiator such as a persulfate such as ammonium persulfate, a redox initiator such as hydrogen peroxide-Fe ³⁺ may be used, or light irradiation in the presence / absence of a photosensitizer or Alternatively, the polymerization may be started by irradiation with radiation.

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

The proportion of the monomer unit A in the component (a) of the present invention is from 10 to 100 mol%, preferably from 20 to 100 mol%.

The component (a) of the present invention contains another water-soluble polymer which does not contain the polymer A, as long as the bactericidal and antifouling properties of the bactericidal and antifouling agent for hard surfaces of the present invention are not significantly impaired. May be.

The component (a) of the present invention has a weight average molecular weight of 1,000 to 6,000,000, preferably 10,000.
00 to 6,000,000, particularly preferably 100,0
The weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent.

The component (a) is preferably contained in the bactericidal antifouling agent of the present invention in an amount of 0.01 to 30% by weight, more preferably 0.01 to 30% by weight.
-20% by weight, most preferably 0.01-10% by weight.

The component (b) of the present invention has a molecular weight of 1,000.
Fungicidal compounds having at least one quaternary ammonium group of less than 500, preferably less than 500. The term "bactericidal" as used in the present invention means that the number of colonies measured by the following method is 10 or less.

<Method of measuring bactericidal property> Escherichia coli (IFO397) was used as a test bacterium.
2) and Staphylococcus
aureus IFO12732). A 1% by weight aqueous solution of the test compound [component (b)] is prepared, and 50 μl of 10 ⁸ to 10 ⁹ bacterial suspensions are added to 2 ml of the aqueous solution, mixed well, and allowed to stand for 5 minutes. After standing, 0.1 ml of this mixture is collected and added to 0.9 ml of LP diluent and mixed well to reduce the effect of the compound on the bacterium. Then, this mixture is applied on an SCDLP agar medium. E. coli for 24 hours at 37 ° C, Staphylococcus aureus for 48 hours at 37 ° C.
Incubate for hours. Count the number of grown colonies after culturing.
The bactericidal test is carried out simultaneously 5 times for the same compound (5 times 3). In this experimental result, those in which the number of colonies of both Escherichia coli and Staphylococcus aureus are 10 or less are regarded as bactericidal. The details of the experimental conditions other than the above-mentioned rules are based on 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).

As the fungicidal compound having a molecular weight of less than 1,000, which is the component (b), compounds represented by the following general formulas (1) to (3) are preferable, and among them, water-soluble compounds are particularly preferable. Here, the term "water-soluble" means that the amount dissolved in 1 L of water at 20 ° C is 1 g or more.

[0030]

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Wherein R ¹ and R ⁶ are each independently an alkyl 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 is independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. X is an aromatic ring or -CO
O -, - CONH -, - OCO -, - is an ester group or amide group selected from NHCO-, R ² is, X
Is an ester group or an amide group, is an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group,
When X is an aromatic ring, it is an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, or-(OR ¹¹ ) _k- . Here, R ¹¹ is an ethylene group or a propylene group, preferably an ethylene group, and k is a number of 1 to 10 on average, preferably 1 to 5 on average. R ⁵ is an alkylene group having 1 to 3 carbon atoms. R ⁷ to R ¹⁰ is one or more of these, preferably one or two C8 to C18, preferably 8-1
4, more preferably an alkyl group of 8 to 12, and the rest being an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. M is a number of 0 or 1. Further Y
^- is an anion, especially a halide ion, sulfate ion, alkyl sulfate ion having 1 to 3 carbon atoms, 1 to 3 carbon atoms
Aromatic sulfonate ions which may be substituted with an alkyl group are preferred. ].

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

[0033]

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Component (b) is preferably present in the fungicidal and antifouling agent of the present invention in an amount of 0.001 to 30% by weight, more preferably 0.01 to 30% by weight.
The content is from 0.01 to 20% by weight, most preferably from 0.005 to 5% by weight.

In the present invention, the weight ratio of component (a) / component (b) is preferably from 20/1 to 1/50 in order to obtain a bactericidal effect while maintaining sufficient antifouling properties. ~ 1 /
20 is more preferable, and 5/1 to 1/10 is most preferable.

The bactericidal and antifouling agent for hard surfaces of the present invention has good bactericidal and antifouling properties, and further comprises (c) a surfactant other than the component (b) [hereinafter referred to as (c) Component)], thereby imparting detergency and being able to be used as a hard surface sterilizing and antifouling detergent. As surfactants, nonionic surfactants, amphoteric surfactants,
It is preferable to add one or more surfactants selected from anionic surfactants.

Examples of the nonionic surfactant include compounds represented by the following general formulas (c1) to (c3). R ^c1 —O (EO) _n H (c1) wherein R ^c1 has an average carbon number of 10 to 20, preferably 10
~ 18 primary linear alkyl group, branched alkyl group or secondary alkyl group. EO is ethylene oxide, and n is 5 to 20 as an average number of added moles. R ^c2 —O (EO) _p / (PO) _q H (c2) wherein R ^c2 has an average carbon number of 10 to 20, preferably 10
~ 18 primary alkyl groups. EO indicates ethylene oxide, and PO indicates propylene oxide. k and l
Is the average number of moles added, p is 5 to 15, and q is 1 to 5. EO and PO may be added randomly, or PO may be added after EO is added, or vice versa. Further, the block additional body may be three or more blocks. R ^c3- (OR ^c4 ) _x G _y (c3) wherein R ^c3 is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms or an alkyl group having an alkyl group having 8 to 18 carbon atoms. Phenyl group, R ^c4 has 2 to 2 carbon atoms
The alkylene group of 4, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, preferably a glucose residue, x represents a number having an average value of 0 to 6, and y represents a number having an average value of 1 to 10. ].

As the amphoteric surfactant, the following general formula (c)
The amine oxide represented by 4) and betaine represented by the general formula (c5) can be exemplified.

[0039]

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[Wherein, R^c5Is alkyl having 8 to 18 carbon atoms
Or an alkenyl group,^c7, R ^c8Is German
Standing, an alkyl group having 1 to 3 carbon atoms or hydroxyal
It is a kill group. R^c6Is an alkylene group having 1 to 5 carbon atoms
You. A represents -COO-, -CONH-, -OCO-, -N
HCO- or -O-, wherein r is 0 or 1
Is the number of ]

[0041]

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[Wherein R ^c5 , R ^c6 , R ^c7 , R ^c8 , A and r are the same as those described in the general formula (c4). R ^c9
Is an alkylene group of 1 to 5 carbon atoms which may be substituted with a hydroxyl group, T is _{^{-OSO 3 -, -COO -, -SO}} 3 -
An anionic group selected from r is a number of 0 or 1. ].

Examples of the anionic surfactant include an alkylbenzene sulfonate having 8 to 18 carbon atoms, an alkane sulfonate, an α-olefin sulfonate, an alkyl sulfate, a polyoxyethylene alkyl ether sulfate, and a polyoxyalkylene sulfonate. Examples thereof include ethylene alkyl ether acetate.

In the present invention, it is particularly preferable to incorporate at least one of the surfactants selected from the general formulas (c3) and (c4) in order to obtain excellent detergency without impairing the antifouling effect. The amount of the surfactant (c) is preferably 0.01% by weight or more and less than 20% by weight in order to obtain a sufficient detergency without impairing the sterilizing and antifouling effects.
It is more preferably at least 0.1% by weight, particularly preferably from 0.1 to 15% by weight.

However, anionic surfactants and betaine-type amphoteric surfactants (amphoteric surfactants having a quaternary ammonium group and a sulfonic acid group or a carboxy group) reduce bactericidal and antifouling properties. , In an amount that does not affect, specifically, an amount that does not exceed 5.0% by weight, more preferably 3.
0% by weight or less, most preferably 1.0% by weight or less.

In the present invention, it is preferable to add a water-soluble solvent as component (d) for the purpose of improving the detergency against organic stains, [1] a monohydric 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 (d1), [4] a compound represented by the following general formula (d2), and [5] the following The general formula (d
One or more compounds selected from the compounds represented by 3) are preferable.

[0047]

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[0048] wherein, R ^d1 and R ^d2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, but a phenyl group or a benzyl group, both R ^d1 1 and R ^d2 is a hydrogen Except when it becomes an atom. 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 each represent an alkyl group having 1 to 3 carbon atoms. R ^d5 represents an alkyl group having 1 to 3 carbon atoms. ].

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

The polyhydric alcohol having 4 to 12 carbon atoms [2] includes isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, and 1,9-nonanediol , Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, and monoalkyl glyceryl ether having an alkyl group having 3 to 8 carbon atoms.

The compound of [3] has a carbon number of 1 to 1 when R ^d1 and R ^d2 are alkyl groups in the general formula (d1).
4 is particularly preferred. Further, in the general formula (d1), s and t are average addition mole numbers of ethylene oxide (hereinafter, referred to as EO) and propylene oxide (hereinafter, referred to as PO).
Is a number from 0 to 10, respectively, but the order of addition of EO and PO is not particularly limited, and may be random addition. Specific examples of the compound [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, and propylene glycol monoethyl. Ether, propylene glycol dimethyl ether, polyoxyethylene (average addition mole number = 2-3) polyoxypropylene (average addition mole number = 2-3) glycol dimethyl ether, polyoxyethylene (average addition mole number = 1-4) glycol phenyl Ether, phenyl carbitol, phenyl cellosolve, 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.

The compound of [4] includes 1,3-
Dimethyl-2-imidazolidinone, 1,3-diethyl-
2-imidazolidinone is exemplified as being preferred,
As the compound of [5], 3-methoxy-3-methylbutanol, 3-ethoxy-3-methylbutanol and the like are preferable.

Among these, water-soluble solvents selected from the compounds [1], [2] and [3] are preferable from the viewpoint of damage to the substrate, and particularly ethanol, isopropyl alcohol, ethylene glycol, propylene glycol and diethylene glycol. , Dipropylene glycol,
A water-soluble solvent selected from glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and monoalkyl glyceryl ether having an alkyl group having 3 to 8 carbon atoms is preferable.

The water-soluble solvent of the component (d) is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, most preferably 1 to 10% by weight in the germicidal antifouling agent of the present invention. % By weight.

In the present invention, for the purpose of dissolving the inorganic soil and improving the detergency and the sterilizing effect, it is preferable to further add a chelating agent as the component (e). 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, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and alkali metal salts or alkaline earth metal salts thereof, (3) N-oxides of aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid and alkali metal salts or alkaline earth metals thereof Salt, (4) a homopolymer or copolymer of a monomer selected from acrylic acid and methacrylic acid, an acrylic acid-maleic acid copolymer, poly α-hydroxyacrylic acid and its alkali gold Salts, (5) one or more polycarboxylic acids selected from citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and alkali metal salts thereof, and (6) alkylglycine- N, N
-Diacetic acid, aspartic acid-N, N-diacetic acid, serine-
N, N-diacetate, glutamic acid diacetate, ethylenediamine disuccinic acid or salts thereof are preferred, and particularly (2)
The compounds (3) and (5) are preferred.

The chelating agent of the component (e) is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, most preferably 0.5 to 10% by weight in the germicidal antifouling agent of the present invention. 1
0% by weight is contained.

In the present invention, a pH adjuster may be used when adjusting the pH. Examples of the pH adjusting agent include inorganic acids such as hydrochloric acid and sulfuric acid, and acid agents such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and other organic acids, sodium hydroxide and potassium hydroxide, Alkaline agents such as sodium carbonate and potassium carbonate such as ammonia and derivatives thereof, 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 germicidal antifouling agent of the present invention comprises the above p
It is preferable to adjust the pH at 20 ° C. to 2 to 12 with an H adjuster, and it is particularly preferable to adjust the pH to 3 to 11 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 is disclosed in JP-A-8-209194, p.
Column 1 to page 7 column 11 are preferably one or more selected from the water-soluble polymers.

The hard surface germicidal antifouling agent of the present invention includes, in addition to the above-mentioned components, additives incorporated in ordinary detergents as long as the effects of the present invention are not impaired, such as fragrances, antibacterial agents, and viscosities. Adjusters, pigments, dyes, suspending agents and the like can be added. Further, for the purpose of enhancing the foaming property at the time of use, at least one selected from foaming assistants such as toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, alkenylsuccinic acid and alkali metal salts thereof is added. Can be done.

When the present invention is used, the polymer of the component (a) and the germicidal compound of the component (b) may be dissolved or dispersed as a single agent in a solvent, or may be used in combination with an optional component. Any number of agents may be used. In addition, by combining optional components, it may be used in the form of one or more powders or tablets which are immediately dissolved in a solvent such as water or provided with sustained release. 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 mode of use of the germicidal antifouling agent of the present invention is not particularly limited, but is a liquid composition containing component (a), component (b) and optional components, with the balance being water or polyethylene glycol, A solid or gel composition may be prepared using a coagulant such as a fatty acid. When the germicidal antifouling agent of the present invention is directly applied as a liquid composition to a hard surface to be cleaned, the content of the component (a) in the composition is preferably 0.01 to 10% by weight. %, More preferably 0.0
The content of the component (b) is preferably 0.001 to 5% by weight, most preferably 0.01 to 3% by weight.
%, More preferably 0.001 to 3% by weight, most preferably 0.005 to 3% by weight, and the content of the component (c) is preferably 0.01 to 10% by weight, more preferably 0 to 10% by weight. 0.1 to 8% by weight, most preferably 0.1 to 5% by weight, and the content of the component (d) is preferably 0.1 to 5% by weight.
The content is 5% by weight, more preferably 0.5 to 5% by weight, most preferably 1 to 3% by weight, and the content of the component (e) is preferably 0.1 to 15% by weight, more preferably 0.1 to 15% by weight. 1 to
It is preferably 10% by weight, most preferably 0.5 to 10% by weight, and may be prepared by diluting a high concentration solution with tap water or the like immediately before use. Further, a thickener such as xanthan gum may be added to these liquid compositions in order to increase the adhesion to the wall surface. In the case of direct application, a container provided with a trigger sprayer capable of directly spraying, spraying or applying the sterilizing / fouling agent or the cleaning agent onto a body to be cleaned, or a container having a discharge mechanism such as a squeeze container It is most preferred that the article is filled with a.

In the case of a solid or gel, it is useful as an auto cleaner used for a toilet flush tank.

[0064]

EXAMPLES A bactericidal antifouling agent 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.

<Evaluation of antifouling property> (1) Easy cleaning property 1 mL of a sterilizing antifouling agent was applied to the surface of a ceramic tile having an area of 10 cm ² , allowed to stand for 5 minutes, and then 200 mL of water was flowed at a 45 ° angle at a flow rate of 25 mL. After repeating the flow and drying at a rate of 5 times / second, 0.5 g of oleic acid is dropped on the surface of the ceramic tile in the form of spots. The ceramic tile with the oleic acid dropped on it is kept at the bottom of the water tank so that oleic acid does not flow, and the water is gently filled with water so that the ceramic tile is not directly exposed to water. At that time, the ratio of the area where oleic acid was removed from the surface of the ceramic tile was determined, and evaluated in the following five steps. In addition, the average value of five model-contaminated plates was adopted as the percentage of stain removal. 5: The stain removal is 80% or more 4: The stain removal is 60% or more and less than 80% 3: The stain removal is 40% or more and less than 60% 2: The stain removal is 20% or more and less than 40% 1. : Stain removal is less than 20%.

(2) Antifouling property A commercially available toilet bowl (C730B, manufactured by TOTO Kiki Co., Ltd.) was used.
Evaluation of the difficulty of attaching dirt was performed. That is, the toilet was washed with the composition, and the degree of soiling when left for one week was visually measured based on the following criteria.

(Evaluation Criteria) A: There is no stain. ：: Slightly adhered. Δ: Slightly adhered. ×: There is considerable dirt.

<Evaluation of bactericidal property> Escherichia coli (Es
cherichia coli (IFO3972) and Staphylococcus aur
eus IFO12732) was used.

The bactericidal test was carried out using 2 m of the germicidal antifouling agent shown in Table 1.
After 50 μl of 10 ⁸ to 10 ⁹ bacterial suspensions were added and mixed well, the bactericidal activity when the standing time was set to 5 minutes was examined. After standing, 0.1 ml of the mixture was collected and 0.9 m
1 L of LP diluent and mixed well to reduce the effect of the washings on the bacteria, then apply this mixture on SCDLP agar medium for 24 hours at 37 ° C for E. coli and 37 ° C for Staphylococcus aureus. And culture for 48 hours. Count the number of grown colonies after culturing. In addition, the sterilization test performed the same sterilization antifouling agent by five test sections each for each leaving time, and evaluated the sterilization by the following scores.

The details of the experimental conditions other than the above-mentioned rules were as follows.
The floating test method (quantitative test method) described in p.686 of the Bactericidal and Fungicide Handbook (edited by the Japan Society of Bacterial and Fungicide, published by Gihodo). ：: The number of colonies after leaving for 5 minutes is 10 ⁴ or less. ×: The number of colonies in a standing time of 5 minutes exceeds 10 ⁴

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[Table 1]

Polymer A: Mercoat 550 [diallyldimethylammonium chloride and acrylamide (molar ratio 3
0/70) Copolymer (manufactured by Calgon, weight average molecular weight 5,000,000, measured by gel permeation chromatogram, using polyethylene glycol as a standard)] Polymer B: Mercoat 100 [diallyldimethylammonium chloride homopolymer ( Calgon, weight average molecular weight: 400,000, measured by gel permeation chromatogram, using polyethylene glycol as a standard)] Bactericidal compound A: Sanisole C [cocoalkyldimethylbenzylammonium chloride (manufactured by Kao Corporation)] Fungicidal compound B: Cotamine D10P [didecyldimethylammonium chloride (manufactured by Kao Corporation)] Fungicidal compound C: Benzethonium chloride [Wako reagent, cationic compound having the following structure]

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Embedded image

AO: Amphitol 20N [lauryl dimethylamine oxide (manufactured by Kao Corporation)] AG: Alkyl glucoside (a mixture of straight-chain alkyl groups having 12 to 14 carbon atoms, average sugar condensation degree 1.2 [condensation] Degree 1
And 2]) ES: polyoxyethylene lauryl ether sulfate having an average addition mole number of 2.2 mol betaine: N-lauroylaminopropyl-N, N-
Dimethyl-N-carboxymethylammonium betaine EDTA-4Na: tetrasodium ethylenediaminetetraacetate pH adjuster: hydrochloric acid and / or sodium hydroxide (all used in aqueous solution)

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazunori Tsukuda 1334 Minato, Wakayama City, Wakayama Pref. ED02 ED28 FA06 FA28 FA34

Claims (4)

[Claims] (1) a weight average molecular weight of 1,000 to
6,000,000, and the ratio of monomer units having a quaternary ammonium group is 10
And (b) a molecular weight of 1,
A bactericidal antifouling agent for hard surfaces containing a bactericidal compound having a quaternary ammonium group, which is less than 000. 2. The germicidal and antifouling agent for hard surfaces according to claim 1, wherein (b) is one or more germicidal compounds selected from the compounds represented by the following general formulas (1) to (3). Embedded image [Wherein, R ¹ and R ⁶ each independently represent a carbon number of ^{6 to 1} ;
8 alkyl or alkenyl groups, and R ³ and R
⁴ is independently an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. X is an aromatic ring or -COO
—, —CONH—, —OCO—, or —NHCO—, an ester group or an amide group, and R ² represents a carbon number which may be substituted with a hydroxyl group when X is an ester group or an amide group. 1 to 6 alkylene groups;
Is an aromatic ring, it is an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, or-(OR ¹¹ ) _k- . Here, R ¹¹ is an ethylene group or a propylene group,
k is a number of 1 to 10 on average. R ⁵ is an alkylene group having 1 to 3 carbon atoms. In R ^{7 to} R ¹⁰ , at least one of them is an alkyl group having 8 to 18 carbon atoms, and the rest is a C 1 to C 1 alkyl group.
3 alkyl groups or hydroxyalkyl groups. M is a number of 0 or 1. Further, Y ⁻ is an anion. ] 3. The disinfectant / fouling agent 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 general formula (4). Embedded image [In the formula, R ¹² , R ¹³ , and R ¹⁴ are each independently a hydrogen 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 18 -, - OCOR 18 -} , - R 19 -OCO-R
^18- . Here, R ¹⁸ and R ¹⁹ are each independently an alkylene group having 1 to 5 carbon atoms. R
¹⁵ hydroxy or alkyl group having 1 to 3 carbon atoms alkyl or ^{R 12 R 13 C = C (} R 14) is -X-. R ¹⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group; and R ¹⁷ has 1 to 10 carbon atoms which may be substituted with a hydroxy group, a carboxyl 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. Also, R
^{When 17} contains a carboxyl group, a sulfonic acid group, or a sulfate group, Y 2 ^- is not present, and these groups in R ¹⁷ become anions. ] 4. Further, as (c), 0.01% by weight or more and less than 20% by weight of a surfactant other than (b) (provided that an anionic surfactant and a betaine-type amphoteric surfactant in the composition are used). The germicidal and antifouling detergent for hard surfaces according to any one of claims 1 to 3, which is contained at a concentration of not more than 5.0% by weight.