TWI283267B - Bactericidal antifouling detergent for hard surface - Google Patents

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 from 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 detergent comprises an anionic surfactant (cA), the ratioof (cA) to (b) by weight (i.e., cA/b) 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

5. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a detergent composition for a hard surface which can be used for sterilization of a hard surface, and antifouling property, that is, adhesion prevention of dirt, and easy removal. Adhesive dirt can be used for sterilization and dirt adhesion and easy to clean when used in general homes, especially kitchens, bathrooms, toilets, washstands, walls, floors, appliances, machines, etc. 'Knowledge technology can cause dirt in all kinds of places in life. In order to remove such dirt, various cleaning agents have been developed, and research to enhance the detergency has followed. By doing so, many proposals have been made to remove stubborn dirt. In addition, a technique for decontaminating excellent cleaning agents has been developed, and a technique for making it difficult to adhere to dirt and a technique for easily removing the adhered dirt (hereinafter referred to as antifouling property) have been frequently studied and found to be applied. Come as a cleaning agent technology. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A water-based toilet cleaner having an excellent adhesion prevention property and a high cleaning effect has been described. In Japanese Laid-Open Patent Publication No. Hei-1697, a detergent having a specific ratio of a specific surfactant and a water-soluble solvent has been described. In particular, in the Japanese Patent Publication No. Hei 9-169995, the cleaning agent having a water contact angle of 30° or less on the hard surface after the treatment exhibits excellent antifouling properties. Specifically, the antifouling agent can be exemplified by an anionic interface activity. A combination of a surfactant and a surfactant having a level 4 ammonium group or a water-soluble polymer in the molecule.

The paper ruler ^ @@家_石石格格(露297公爱) 1283267

As above, techniques related to antifouling have been studied from the past. However, conventional techniques are produced by inhibiting the adhesion of scales or the like (the scale is a scar of the black spots caused by microorganisms or molds on the main axis. In addition, recently, as the living environment improves, the eyes see it. Dirt, the number of people who are concerned about hygiene problems is increasing, and the requirements for sterilization are also high. The idea of such a design is to propose a formula of a fungicide. However, when it is used in a household fungicide, the above-mentioned fungicide is used. Both the antifouling property and the bactericidal effect are mutually versatile, and it is extremely difficult to achieve satisfactory bactericidal and antifouling properties. The object of the present invention is to provide a home, a toilet, a bathroom, a room, etc. In the cleaning of the hard surface, not only the excellent detergency but also the sterilizing and antifouling properties of the cleaning agent can be satisfied. The present invention relates to a sterilizing and antifouling cleaning agent for hard surfaces, It comprises (a) a weight average molecular weight of a monomer (having up to V units selected from the group consisting of a 4-stage group and a 3-stage amine group) in a ratio (relative to the all monomer unit) 10 to 100 mol %, (b) a bactericidal compound having a molecular weight of 1 Å or less, having a 4-stage ammonium group, and (c) a surfactant; when a (CA) anionic surfactant is contained as a surfactant When the ratio of (cA)/(b)^ is not more than 1.0. (a) Component: E contains 〇·〇ι~3〇% by weight, (b) component preferably contains 0.001 to 30% by weight, and (c) The composition contains 〇〇1~5 〇% by weight. The present invention provides a method for applying the above composition to a hard surface to clean the surface of the cleaning agent and sterilizing, thereby preventing the scale from adhering to the hard surface. (CNS) -5- 1283267 A7 B7 V. Inventive Note (3), and a use of the above composition for cleaning a hard surface and preventing dirt from adhering to a hard surface. DETAILED DESCRIPTION OF THE INVENTION (a) The component is a polymer having a 4-stage ammonium group and/or a 3-stage amine group (hereinafter referred to as a monomer unit) in an amount of from 1 to 100 mol%. The monomer unit A may contain a 4-grade ammonium. a monomer (also referred to as a plurality of monomers) (hereinafter referred to as monomer A) is polymerized or contained a monomer unit obtained by a monomer having a 3-stage amine group (which may also be a plural number) (hereinafter referred to as a monomer A'), or a level 3 amine group may be classified into a 4-stage ammonium group by 4 stages. A preferred example of the monomer A of the fourth-order ammonium group, that is, an example derived from the monomer unit a, may be exemplified by the compound of the following formula (4).

Rl2Rl3c = c(Fi4)- /15 R16 R17 γ- (4) wherein R12, R13 and R14 are each a hydrogen atom, a few groups or an alkyl group having a number of 1 to 3. X is selected from the group consisting of a hydrocarbon group having 1 to 12 carbon atoms, -COOR18-, -CONHR18-, -OCOR18-, -R19-OCO-R18. Here, R18 and R19 are each an anthracene hydrocarbon group having 1 to 5 carbon atoms. R15 is an alkyl group having 1 to 3 carbon atoms or a burnt group or R12R13C = C(R14)-X-. R16 is a vinyl group having 1 to 3 moles, a hydroxyalkyl group or a benzyl group, and R 1 7 is a hydroxyl group, a carboxy group, a carboxylic acid group or a sulfate group substituted with an alkyl group having 1 to 10 carbon atoms or a benzyl group. When R1 7 is an alkyl group, a hydroxyalkyl group or a benzyl group, Y· is an anion. -6- This paper scale applies to Chinese National Standard (CNS) A4 specification (21〇χ297 mm) 1283267 A7 B7

Further, when R17 contains a hydroxyl group, a sulfonic acid group or a sulfate group, γ· does not exist, and these groups in R17 are anions. The anion of γ- can be exemplified by a halogen ion, a sulfate ion, an alkyl sulfate ion having 1 to 3 carbon atoms, an aromatic sulfonate ion substituted with an alkyl group having 1 to 3 carbon atoms, and a hydroxyl ion. Among these, it is preferably a propylene fluorenyl (or methacrylamido)aminoalkyl group (carbon number 15)-fluorene, fluorene, fluorene-dialkyl (carbon number 1 to 3) , propionic acid (or methyl propyl hydrazine) oxyalkyl (carbon number 1 to 5) - hydrazine, hydrazine, hydrazine - trialkyl (carbon number 1 to 3) 4th ammonium salt, Ν-[ω-alkane Sulfhydryl (carbon number 3 to 10) diterpenoid, anthracene, fluorene-trialkyl (carbon number 1 to 3) 4-grade ammonium salt, hydrazine, hydrazine-bis(ω-alkenyl group (carbon number 3 to 1 0) ]-Ν, Ν-dialkyl (carbon number 1 to 3) 4-grade ammonium salt, especially dialkyldicylidene ammonium salt. Preferred examples of the tertiary amine-based monomer oxime From the monomer unit, the compound of the following formula (5) can be exemplified. R12 13 /R15R C=C(R14)—X—Ν (5)

In the formula, ^^, ^^, ^^, ^^, and ruler are the same as described above. Among these, it is preferably hydrazine, hydrazine, dialkyl (carbon number 1 to 3) aminoalkyl (carbon number 1 to 5) propionate (or methyl propionate), ν, ν- Dialkyl (carbon number: 3) amino group (carbon number: 1 to 5) acrylamide, ν, Ν-bis(ω-alkenyl (carbon number: 3 to 10))-fluorene-methylamine, Particularly preferred is diallylmethylamine. When the monomer A' is 4-staged, it is preferred to use a gasification lake, a brominated methane, a benzyl gas, a dimethyl sulfate, a diethyl sulfate, a mono-acetic acid or the like.

1283267 A7 _____B7 _ V. Description of invention (5 ) ~ ----- Salt, gas sulfonic acid or its salt, 3-gas 2 - hydroxypropane sulfonic acid or its salt, ethylene oxide, propylene oxide, shrinkage It is carried out with glyceryl ether. Further, when ethylene oxide, propylene oxide or glycidyl ether is used, it is preferred to neutralize the monomer unit with sulfuric acid, hydrochloric acid, a carboxylic acid having a carbon number of 1 to 12, or propyl sulfonic acid, and then react it. The component (a) of the present invention is a polymer composed not only of the monomer unit A (may be a plurality of types) but also a monomer unit A (may also be a plurality of types) and other monomer units (hereinafter, a polymer composed of a monomer unit. (A monomer unit having an amine type may be used when the monomer A is used.) In this case, the monomer unit A and the monomer unit B (may be plural) The arrangement pattern may also be any one of block, interaction, period, statistics (including random), and graft type. The polymer composed of monomer unit A and monomer unit B may be, for example, individual precursors. The monomer unit B is preferably selected from the monomer units (i) to (v) of the following monomer groups, more preferably derived from or one monomer unit, especially The point of the antifouling effect is most preferably derived from the monomer unit of (丨), (ii) or (v). (i) The anionic compound is selected from the group consisting of propionic acid or its salt, methyl propionate or a salt thereof, maleic acid or a salt thereof, maleic acid, phenethyl phthalate, propyl propyl methacrylate, 2-propenylamine-2-methylpropane sulfonic acid or a salt thereof嶙 单 ω ω ω ω 甲基 ( ( ( ( ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii N-Dimethylaminopropylpropionic acid (or acenaphthyl acrylate) decylamine, N,N-monomethylpropenyl (or methacrylic acid), N-ethyl fluorenyl 2 - Caprolactam, Ν _ vinyl-2-pyrrole _. -8- 1283267 A7 B7 V. Description of invention (6) (iii) The ester-containing compound is selected from the group consisting of acrylic acid (or methacrylic acid) alkyl (carbon) Number 1 to 5), acrylic acid (or methyl procyanoate) 2-hydroxyethyl, acrylic acid (or methacrylic acid)-hydrazine, fluorenyl-dimethylaminoalkyl group (carbon number 1 to 5), acetic acid The oxime ester 0 (iv) compound is selected from the group consisting of acetamidine, propylene, oxime-butene, isobutylene, hydrazine-pentane, isoprene, 2-methyl-1-butane, N-Hexole, 2 -Methyl-1-pentene, 3-methyl-1-pentene, 4·methyl-1-pentene, 2-ethyl-1-butene, phenylethylene, vinyltoluene, α-A Acetophenone, allylamine, N,N-diallylamine, N,N-diallyl-N-alkyl (carbon number 1 to 5) amine, epoxy ethene, ring emulsion tiger 2_ B Xi base ϊ? Than the lake, 4_ B Xi base π than the disease. Billion) sulfur dioxide. The polymerization of the monomer unit A and the monomer unit B can be carried out in the same manner as the above-mentioned copolymerization synthesis method, and the monomer of the above (i) to (v) can be particularly preferably used in the polymer containing the monomer unit ( i) or (ii) a monomer obtained by graft polymerization to obtain 'or a polymer obtained by containing the monomer of the above (i) to (v), wherein the monomer of the above formula (4) is graft-polymerized, Or a polymer containing a monomer of the above (丨) to (v), particularly preferably a polymer of the monomer of the above (i), (ii), after graft-polymerizing a monomer of the above formula (5), Then carry out 4 levels. The monomer unit B of the present invention preferably has a monomer selected from the group consisting of an acid group and a remnant group (but not having a grade 4 ammonium group), that is, derived from the aforementioned (i) monomer. The monomer unit (hereinafter referred to as monomer unit B). The polymer constituting the component (a) of the present invention can be obtained by any polymerization method, but it is preferably a radical polymerization method, and it can be carried out in the form of a block, a solution or an emulsion. Free radical polymerization can be started by heating, but the initiator -9-

1283267 A7 B7 V. Description of the invention (7 can also use 2,2,-azobis(2-aminopropane) dihydrochloride, 2,2'-azobis(N,N-dimethylene) An azo initiator such as butylamine) dihydrochloride, hydrogen peroxide, and benzoic acid peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, mercaptoethyl ketone peroxidation Organic peroxides such as benzoic acid, sodium persulfate, potassium persulfate, ammonium persulfate, persulfate, hydrogen peroxide-Fe3+ and other reducing oxidation initiators, and other existing free radical initiators The polymerization may also be initiated by light irradiation in the presence or absence of a photosensitizer or by irradiation with radiation. The component (a) of the present invention may be a single polymer of monomer unit a and selected from the group consisting of a plurality of polymers of the copolymer of the bulk unit A and the monomer unit B. A more preferable composition of the component (a) of the present invention is that the total amount of the monomer unit a and the monomer unit B' is relative to the total The monomer unit is 50 to 1 〇〇 mol%, and the optimum monomer units A and B have a molar ratio of monomer unit A/[monomer unit a+ monomer unit Β'] = 0 3 to 0.99, especially 〇.4 to 0.99. The component (a) of the present invention may contain a bactericidal or antifouling property of the hard surface antifouling detergent of the present invention as long as it does not significantly hinder the hard surface of the present invention. The other water-soluble polymer of the present character A. The component (4) of the present invention has a weight average molecular weight of from 1 〇〇〇 to 6 〇〇〇〇〇〇 八 10,000 to 6,000,000, particularly preferably 1 〇〇, _ 〜 6 〇 〇〇, _, and the average molecular weight is the solvent of the mixed solvent of B guess and water (10), and the gel permeation chromatography is used to obtain the β-Xiao Ma’s quasi-substance i as 0.01 ~3 〇 Heavy (a) component is in the sterilizing and antifouling detergent of the present invention -10-

1283267 A7 B7 V. INSTRUCTIONS (8) Quantities, in detail, when the hard surface of the object is washed by a spray device such as a trigger or a sprayer, or by a coating method, the concentration of the component (a) is 0.01 to 10% by weight, more preferably 0.02 to 5% by weight, and in the washing method using the water in the toilet tank, an appropriate amount of the cleaning liquid can be put into the water tank or any water supply path. The water in the sink is 1 to 30% by weight, more preferably 2 to 20% by weight, when using the automatic washing device for the toilet. Further, the concentration of the component (a) in the water tank is preferably 0.1 to 10 ppm. The component (b) of the present invention is a bactericidal compound having a molecular weight of 1,000 or less, preferably at least one of the quaternary ammonium groups of 500 or less. The bactericidal compound referred to in the present invention is a compound having a property in which the number of colonies measured by the following method is 10 or less. <Method for measuring bactericidal compound> Escherichia Coli (IF 03972) and Staphylococcus aureus (IFO12732) were used as test bacteria. IF03972 and IF012732 are attached to the Institute for Fermentation, Osaka, the No. 85, No.15, Sakamotocho, Yodogawa-cho, Yodogawa-ku, Osaka, Japan. A 1% by weight aqueous solution of the test compound [(b) component] was prepared, and 2 8 to 10 9 of the bacterial floating liquid 50 " 1, was added to 2 ml of the aqueous solution, and the mixture was thoroughly mixed and allowed to stand for 5 minutes. After placing, 0.1 ml of this mixture was added to 0.9 ml of the LP dilution, and the mixture was thoroughly mixed to reduce the effect of the above compound on the bacteria. Then, the mixture was applied to SCDLP agar medium at 37 °. The culture was carried out for 24 hours at C, and the yellow grape balls were cultured at 37 ° C for 48 hours. The number of colonies born after cultivation was counted. In addition, the sterilization test is applicable to the same national standard (CNS) A4 specification (210 X 297 mm) for the same -11 - paper scale.

Binding

1283267

V. Description of the invention (9) ~ ~ - 7 = object = do not perform 5 times at the same time (5 times X 3). In the results of this experiment, the number of colonies of both the large intestine and the more staphylococcus was less than 10 as sterilization. In addition, the details of the experimental conditions other than the above-mentioned regulations are based on the floating test method (quantitative test method) of p686, which is described in the Anti-mite and Anti-Molding Handbook (published by the Japan Society for the Prevention of Bacterial and Mildew, and published by the Technical Bulletin). The bactericidal compound having a molecular weight of 1,000 or less in the component (b) is preferably a compound represented by the following formulas (1) to (3), and particularly preferably water-soluble. Here, the so-called water solubility is dissolved in 2 (the amount of water η is lg or more.

Wherein R 1 and R 6 are each a C 6-18, preferably an alkyl or alkenyl group of 8 to 16, more preferably an alkyl group, and R 3 and R 4 are each an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms; . X is an aromatic ring or an ester group selected from the group consisting of -COO-, -CONH-, -0C0-, -NHCO- or a guanamine group, and when the R2 system X is an ester group or a guanamine group, the carbon number may be substituted by a hydroxyl group. 1 to 6 of the olefin group, when X is an aromatic ring, it is replaced by a hydroxyl group. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1283267 A7

The number of oxime hydrocarbon groups or gas (1) RlV is broken. Here, R11 is a vinyl group or a propyl group. The ethyl group is preferably an ethyl group, and k is an average of 1 to 1 Å, preferably an average number. R5 is an olefin group having a carbon number of 丨3. R7~r1〇 are more than one or more of these and are 1 or 2 carbon numbers 8 to 18, preferably 8 to 14, more preferably 8 to 12, and the rest are carbon numbers i to 3. Alkyl or hydroxyalkyl. Also, the number is 〇 or 1 number. Further, γ- is an anion, particularly an aromatic sulfonate ion substituted with a halogen ion, a sulfate ion, an alkyl sulfate ion having 1 to 3 carbon atoms, or an alkyl group having 3 carbon atoms. More preferably, the component (b) is a compound of the above formula (丨) or (3), and is preferably a compound of the formula below. CH〇

In the formula, R represents an alkyl group having 8 to 16 carbon atoms.

In the formula, R may also be an alkyl group having a branched carbon number of 6 to 12, and melon means an average number of 1 to 5. -13- The paper music scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1283267 V. Invention description

R

〆

R /CH3 N xch3 cr The two-version R table cannot be a different alkyl group having 8 to 12 carbon atoms. (8) It is preferable to use the sterilizing and antifouling cleaning agent of the present invention as the amount of the smear 30: the amount = in detail, when the surface of the object is cleaned by a fogging device such as a trigger or a sprayer, or by a coating method The concentration of the component #(b) is 0.001 to 5% by weight, more preferably 5% to 2% by weight, and is provided in the reading or passage when using the washing of the water in the sink. The device can inject a proper amount of washing liquid into the water in the water tank. When the automatic washing device for the toilet is used, it contains 〇1 to 3〇% by weight, more preferably 20% by weight. Further, the concentration of the component (b) in the water tank is preferably 〇〇i to i 〇 ppm °. In the present invention, in order to maintain sufficient antifouling property, in order to obtain a sterilizing effect, (a) component/(b) component is weighed. The ratio is preferably 30^4/50, more preferably 2〇/1 〜1/20, and most preferably 1〇/1~mo. The sterilizing and antifouling cleaning agent for hard surfaces of the present invention further contains (b) a surfactant other than (hereinafter referred to as component (c)) as (c). It is preferable to add one or more kinds of surfactants selected from the group consisting of nonionic surfactants, amphoteric surfactants, and @ionic surfactants. The nonionic surfactant can be exemplified by the following formula (c 1) to formula (c 3 ).

Rcl-〇(EO)nH (cl) -14-

1283267 A7 _______B7 V. INSTRUCTION DESCRIPTION (12) [wherein, Rcl is an average carbon number of 1 〇 to 2 Å, preferably 1 〇 to 18, a linear alkyl group, a branched alkyl group or a secondary alkyl group. E〇 is ethylene oxide, and the n-type average addition molar number is]

Rc2-0(E0)p/(P0)qH (c2) [wherein R 2 is an average carbon number of 10 to 2 Å, preferably a mono-alkyl group of 1 〇 18 18 . E0 is ethylene oxide and p〇 is propylene oxide. The upper and lower 丨 are the average addition moiré, p is 5 to 15, and q is 1 to 5. E0 and p〇 are randomly added or added to E0, and may be added to p〇, or may be the opposite block addition. Further, the block addition product may be three or more blocks. ]

Rc3-(ORc4)xGy (c3) [wherein Re3 is a linear or branched chain having 8 to 18 carbon atoms or an alkylphenyl group having a decyl group or an alkyl group having 8 to 18 carbon atoms; R "is an alkyl group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar having a carbon number of 5 or 6, or a glucose residue, χ is an average number of 値0 to 6, and y is an average 値1 to 10 The number of the surfactants can be exemplified by the amine oxide represented by the following formula (c4) and the beet of the formula (c5): rC5 — (ARC6^-Ni-►0 r iC8 -15 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210x297 mm) 1283267 A7 B7 V. Inventive Note (13 where Rc) is an alkyl or alkane group with a carbon number of 8 to 18, and R is a carbon number. ^ 烟 烟 ° ° RC7, 8 are alkyl 1 or 3 alkyl or hydroxyalkyl, respectively. a is selected from - COO-, -CONH-, -〇c〇...-NHC〇_, the base, Γ The number is 0 or 1. (c 5) RC7 rc5 - (arC6^n+-^r«_t r iC8 where Rc5, Rc6, Rc7, rc8, A&r are the same as those described in the above formula (c4) The same. r. 9 is a hydrocarbon group having a carbon number of 丨~5 which may be substituted by a hydroxyl group, and T is selected from the group consisting of 〇S〇3-, -C〇〇, and -S〇3. Ionic group. r is the number of hydrazine or work.] Anionic surfactants can be exemplified by alkyl benzene sulfonates, alkane sulfonates, alpha sulfonium sulfonates, alkyl sulphates having 8 to 18 carbon atoms in the alkyl group. An ester salt, a polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl ether acetate, etc. In the present invention, interfacial activity selected from the above formulas (c3), (c4), and (c5) is especially formulated. One or more kinds of agents can provide excellent detergency without impairing the antifouling effect. The amount of the surfactant of the component (C) is such that the antibacterial and antifouling effects are not impaired, and sufficient detergency or rise is obtained. The foaming force is preferably 001% by weight or more and 50% by weight or less, more preferably 〇丨% by weight or more, particularly preferably 0.1% by weight to 30% by weight. However, the anionic surfactant [hereinafter (cA)] is for reducing sterilization. Sex and antifouling properties should be formulated in an amount that does not affect. When (cA) is contained, (£person)/(1)) is not more than 1.0, and more preferably not more than 〇.75. To adjust-16- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1283267 A7 _— __ _B7 V. Invention description (Μ) If it exceeds this range, both antifouling and bactericidal effects cannot be obtained. (c) The composition is preferably 〇"~3 〇% by weight in the sterilizing antifouling detergent of the present invention, in detail, with a trigger Or a spray device such as a sprayer, or when the hard surface of the object is directly washed by the coating method, the concentration of the component (c) is 〜·1 to 20% by weight, more preferably 〇2 to 1% by weight, and In the method of washing water in the toilet water tank, a device is provided in the water tank or in any water supply passage, and an appropriate amount of the washing liquid can be put into the water in the water tank, and when the automatic washing device for the toilet is used, The concentration of the component (4) in the water tank containing 〇·5~3〇% by weight, and the amount of collapse is preferably L; ~20 ppm 〇 In the present invention, it is suitable for the purpose of improving the detergency of organic dirt. (4) [The component (4) below] is preferably a component selected from the group consisting of [1] a monovalent alcohol having 1 to 5 carbon atoms, [2] a polyvalent alcohol having 4 to 12 carbon atoms, and [3] having the following general formula (4). ) the compound shown, (4) a compound represented by the following formula (d2), and [5] a compound represented by the following formula (d3) One or more.

RdlO(C2B4〇HC3ii6〇)Rd:1 s t h2c - ch2 R^~N\ /N-Rd4 (d 2) II a ο -17-

1283267 A7 B7 V. Description of invention (15)

Rd5OC(CH3)2CH2CH2OH (d3) wherein Rd and Rd2 each represent a hydrogen atom, an alkyl group having a carbon number of 8, or a phenyl group or a benzyl group, and the case where both of Rdd and Rd2 are a hydrogen atom is removed. S and t respectively represent the number of 〇~1 ,, but the case where both S and t are 〇 is removed. Rd3 and Rd4 represent an alkyl group having a carbon number of i to 3. Rd5 represents a burnt group having a carbon number of 1 to 3. The monovalent alcohol having 2 to 5 carbon atoms in [1] is generally exemplified by ethanol, propanol or isopropanol. By adjusting these lower alcohols, the stability in the low temperature system can be further improved. [2] After the polyvalent alcohol of 4 to 12, for example, isopropanol, 22,4-trimethyl-1,3-pentanediol, iota, 5-pentanediol, [,8•xin A monoalkyl glyceryl ether having a carbon number of 3 to 8 in addition to a diol, a decanediol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, or glycerin. The compound of [3] is preferably in the formula (d1), and the carbon number of the case where Rcu or Rd2 is an alkyl group is =1 to 4. Further, in the general formula (d1), s&t of the average addition molar number of ethylene oxide (hereinafter referred to as e〇) and propylene oxide (hereinafter referred to as P0) are respectively the number of 〇..., but E0 The order of addition to P0 is not particularly limited, and γ is a random addition. Specific examples of the compound of [3] include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethyl ether monoethylene diethylene glycol monobutyl ether, and propylene glycol monomethyl H alcohol monopropyl group. Ether, diol monoethyl (tetra), propylene glycol dimethyl acid, polyoxyethylene (average addition mole number = 2 to 3) polyoxypropylene (average addition mole number = 2 -18- A7 B7

1283267 V. Description of Invention (16) Glycol dimethyl ether, polyoxyethylene (average addition molar number = 1 to 4) glycol phenyl ether, phenyl carbitol, phenyl cellosolve, benzo Kikabi alcohol and the like. Among them, in terms of detergency and feeling of use, it is preferably propylene glycol monomethyl acid, diethylene glycol early butyl ether, polyoxyethylene (average addition molar number = 1 to 4) diol phenyl ether. Further, the compound of [4] can be exemplified by i, 3-dimethyl-2-butyrene, 1 3 diethyl-2-carbobutyl ketone, and the compound of [5] is preferably 3-A. Oxy 3-methylbutanol, 3·ethoxy-3-methylbutanol, and the like. The water-soluble solvent of the compound selected from [i], [2], and [3], particularly preferably selected from the group consisting of ethanol, isopropanol, ethylene glycol, propylene glycol, and the like. Ethylene glycol, dipropylene glycol, glycerin, isopropyl glycol, propylene glycol monomethyl ether, propylene glycol monoethyl acid, propylene glycol monopropyl bond, propylene glycol monobutyl ether and a single alkyl group with a carbon number of 3 to 8 A water-soluble solvent of glyceryl hydrazine. The component (d) is preferably 〇1 to 5 〇% by weight in the sterilizing and antifouling cleaning agent of the present invention, and in detail, the object is washed by a spray device such as a trigger or a sprayer, or by a coating method. When the surface is used, the concentration of the component (d) is 0.1 to 20 parts by weight. /〇, more preferably 5 to 10% by weight, and in the washing method using the water in the water tank, a device is provided in the water tank or in any water supply passage, and the water can be appropriately washed in the water in the water tank. The cleaning solution, when using the automatic cleaner for the toilet, contains 1 to 50% by weight, more preferably 5 to 30% by weight. Further, the concentration of the component (d) in the water tank of the toilet is preferably 1 to 20 ppm. In the present invention, in order to dissolve the inorganic soil to enhance the detergency and the bactericidal effect, the further component (e) is preferably formulated with a chelating agent. The chelating agent should be (1) 3-19- This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1283267 A7 B7 V. Invention description (17) Polyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, six partial Phosphoric acid and alkali metal salts thereof, (2) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrostriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid , triethylenetetramine hexaacetic acid and the metal salt or soil test group metal salt, (3) aminotrimethylene phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine four a methylene phosphonic acid, a diethylenetriamine penta methylene phosphonic acid, an N-oxide of an aminotrimethylene phosphonic acid, and an alkali metal or alkaline earth metal salt thereof, (4*) selected from the group consisting of acrylic acid and Single polymer or copolymer of methacrylic acid monomer, propionate-maleic acid copolymer, polypyridyl citrate and its metal salt, (5) transgenic acid, calo acid, apple (1) an alkenyl glycine-ruthenium, an anthracene-acid, a carboxylic acid, a malonic acid, a malonic acid, a polyvalent carboxylic acid, or an alkali metal salt selected from the group consisting of Diacetate, aspartic acid, hydrazine, ν_ diacetic acid, serine, hydrazine, hydrazine diacetate, glutamic acid diacetic acid, ethylenediamine bis-succinic acid or the like, especially (2), (3 The compound of (5) is preferred. The component (e) is preferably 〇1 to 2% by weight in the sterilizing antifouling detergent of the present invention, and more specifically, a spray device such as a trigger or a sprayer, or a hard surface for washing the object as a coating method The concentration of the component (e) is 0.1 to 10% by weight, more preferably 3% to 7% by weight, and in the washing method using the water in the toilet tank, the water tank or any water supply passage is provided. There is a device that can put a proper cleaning solution into the water in the water tank. When using the automatic cleaning device for the toilet, it contains 1 to 2% by weight, more preferably 2 to 2 inches. /〇. In addition, the concentration of the components in the water tank of the temple should be 〇 〇 1~2 〇 ppm °. The pH adjuster can also be used when the pH of the invention is reduced. pH adjuster can also be -20- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1283267 A7 __-____B7 _ V. Invention description (18) Use inorganic acid such as hydrochloric acid or sulfuric acid, or An acid such as an organic acid such as an organic acid such as citric acid, succinic acid, anaphoric acid, succinic acid, tartaric acid, malonic acid or maleic acid, or sodium hydroxide or potassium hydroxide or ammonia Or a derivative thereof, an amine salt such as monoethanolamine or diethanolamine or triethanolamine, or a test agent such as sodium citrate carbonate dance, may be used singly or in combination. Further, these acid agents may be used in combination with an alkali agent as a buffer system. The sterilizing and antifouling cleaning agent for hard surfaces of the present invention should be adjusted to a pH of 2 to 12 ′ at 20 C, especially at a pH of 3 to 11 by the above-mentioned pH adjusting agent, and it is preferable that the effect is low. In the present invention, the water-soluble polymer may be added for the purpose of improving the adhesion and ease of use at the time of use. The water-soluble polymer is not particularly limited, but is preferably selected from the group consisting of 〇 4 4 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 In the hard surface sterilizing antifouling detergent of the present invention, in addition to the above components, additives which are formulated with general detergents, such as perfumes, antibacterial agents, viscosity modifiers, pigments, dyes, are also added without extracting the effects of the present invention. Suspended knowledge and so on. Further, in order to improve the foaming property at the time of use, a foaming auxiliary agent selected from the group consisting of toluic acid, xylene acid, cumenesulfonic acid, alkenyl succinic acid, and the like may be added. More than one species. In the case of using the present invention, the bactericidal compound of the (&) component and the bactericidal compound of the hydrazine component may be dissolved or dispersed in a solvent to form a single agent, and any number of components may be combined. Further, the components are combined and dissolved or imparted with a solvent such as water, and used in the form of one or more powders or tablets. Furthermore, it is also possible to apply the Chinese National Standard (CNS) A4 specification (210 X 297 public |) 1283267 A7 ___B7 to the (a) component and the component (b) or any component. The invention specification (19) One is liquid, and the other is a solid such as a powder. The sterilizing antifouling detergent of the present invention is not particularly preferred in the form of use, but preferably contains the component (a), the component (b), and an optional component, and the remainder is a liquid composition of water, and when used as an automatic cleaner, A solid or gel-like composition is used by 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 from 1 to 98% by weight, more preferably from 20 to 95% by weight, based on the liquid composition or the gel composition. When the solid composition is used, it is preferably 3 % by weight or less, more preferably 20% or less. EXAMPLES A sterilizing antifouling detergent having the composition shown in Table 1 was prepared, and its antifouling property and bactericidal property were evaluated by the following methods. The results are shown in Table 1. <Evaluation of antifouling property> % (1) Washability 1 ml of a bactericidal antifouling agent was applied to the surface of a ceramic tile having an area of 10 em2, and after standing for 5 minutes, water was 200 ml to 45. The flow rate of the angular flow rate was 25 ml/sec, and it was dried. After repeated 5 times, 0.5 g of oleic acid was dropped on the surface of the pottery brick. Drip the oleic acid pottery tiles so that the oleic acid does not flow, and it is placed at the bottom of the sink. The water is not directly applied to the pottery tiles, and it is quietly filled with water in the sink to judge the oleic acid from the pottery tiles. The ratio of the area where the surface was removed was evaluated in the following five stages. Further, the % of the antifouling drop is the average enthalpy of the five pieces of the model contamination plate. 5: The dirt falls to more than 80%. _ 4 : The dirt falls to 60% or more and 80% or less. -22- 1283267 A7 B7 - --- V. Description of invention (2〇) 3 : The dirt falls to 40% or more and 60% or less. 2: The dirt falls to 2% or more and 40% or less. 1 : The dirt falls below 20%. (2) Prevention of dirt adhesion The use of a commercially available toilet (C730B, manufactured by Kaneka Machine Co., Ltd.) was used to evaluate the difficulty of adhesion of dirt. In other words, the toilet was washed with the composition, and it was difficult to adhere the dirt at the time of the i week, and the measurement was carried out visually according to the following criteria. (Evaluation criteria) ◎: The scale was not attached. 〇: The dirt is slightly attached. △ •• The dirt is rarely attached. X ··The dirt is attached a lot. <Bactericidal evaluation> Escherichia Coli (IF03972) and Staphylococcus aureus (IF012732) were used as test bacteria. In the bactericidal test, 2 ml of the bactericidal antifouling agent shown in Table 1 was added to the bacteria floating liquid 5 a 1 ' of 丨〇 8 to 1 and thoroughly mixed, and the bacteriostatic property was set for 5 minutes. After placing, take 1 ml of the mixture and add it to the LP dilution of 〇9, mix well, and reduce the effect of the washing solution on the bacteria. Then, apply the mixture on SCDLP agar medium, coliform at 37 C. The culture was carried out for 24 hours, and the Staphylococcus aureus was cultured at 3.7 π for 48 hours. The number of colonies that were born after the cultivation was counted. Further, the sterilizing test was carried out for each of the same sterilizing and antifouling agents in five test zones, and the following evaluations were used to evaluate bactericidal properties. -twenty three-

96· 96· Γ:..Γ

I2832ffc ° ° Patent Application A Wenming Book Replacement Page (April 1996) --------- V. Invention Description (21 also 'Details> The details of the experimental conditions are based on the sterilization and anti-mildew manual The floating test method (quantitative test method) described in p686 (published by the Japan Society for the Prevention of Bacterial and Antimicrobial Diseases), 〇: The number of colonies with a standing time of 5 minutes is less than 1 〇 4. X: Colonies with a standing time of 5 minutes The number exceeds 丨〇 4. The ingredients in the table are as follows: • Polymer B: Merquat (Υ — π — Bu) 550 [diallyldimethylammonium chloride and acrylamide (Morby 3〇/ 7〇) Copolymer (manufactured by Calg〇n, weight average molecular weight 50,000, measured by gel permeation chromatography, using polyethylene glycol as standard)] • Polymer A: Merquat (Y-mouth Ib) i均 [homopolymer of diallyldimethylammonium chloride (manufactured by Calgon, weight average molecular weight 40,000, gel permeation chromatography, using polyethylene glycol as a standard) )] • Polymer C: Merquat (Y — π - Bu) 280, manufactured by Calgon, ratified with propyl propyl Co-polymer of base and propionic acid • Polymer D: n,N-dimethylaminopropyl was added under cooling in a solution of 3.59 g of acrylic acid, 280 g of water, and 3 2 ml of aqueous hydrochloric acid solution of 3 2 m 1 76.41 g of decylamine methacrylate was heated to 7 Torr in a neutralized solution, and a polymerization initiator (V - 50 from Wako Pure Chemical Industries, Ltd.) was added dropwise under nitrogen. After curing, it was cooled to obtain a polymer and weight of 18% of the active ingredient. Average molecular weight of 40,000, monomer / [monomer (a) + monomer (b)] = 0 · 9 mole ratio) • bactericidal compound A: 廿2 V° - small [cocoalkyl dimethyl benzene Methylammonium chloride (King) (manufactured by Kao): • Bactericidal compound B:] Less than $VD 10P [Dimercaptodimethylammonium chloride-24 - This paper scale applies to China National Standard (CNS) Α4 specification ( 210X 297 mm) 1283267 A7 B7 Description of the invention (22~~ compound (King)) • Acaricidal compound C · gasification \ y 7 Bu 々 a [and photochemical reagents, cationic compounds of the structure] (ch3)3cch2c(ch3)2

Cl. • bactericidal compound D: octyl dimethyl decyl ammonium chloride • AD · ryt 々 々 20N [lauryl dimethylamine oxide (King) (manufactured by Kao)) • AG · thioglycol Glycosides (linear alkyl groups with a carbon number of 12 and 14 mixtures, average sugar condensation degree 1.2 [condensation degrees 1 and 2 millimoles)]) • ES: E0 average addition moles of 22 moles of poly Oxyethylene vinyl lauryl ether sulfate • Betaine: N-lauroylaminopropyl _N, N•dimercapto-N. carboxymethylammonium betaine • EDTA-4Na: ethylenediaminetetraacetic acid tetrasodium salt p Η 〃 整 · · 盐酸 HCl HCl HCl 酸 酸 酸 酸 酸 酸 酸 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 In the case of (ppm), the point is put into the toilet sink, and the antifouling property at the time of flushing is evaluated by the following method. The results are shown in Table 2. -25-

1283267 A7 B7

<Evaluation of antifouling property> (1) Washability After using the flushing device 10 times (C730B, Toto Machinery Co., Ltd.), the oleic acid g was dropped in 5 points. The area ratio of oleic acid after flushing was evaluated in the following five stages. χ, the evaluation of the dirt drop is based on the average of 5 times. (Evaluation criteria are the same as in Table 1.) (2) Prevention of dirt adhesion Using a commercially available toilet (C730B, Toto Machinery Co., Ltd.), it is difficult to assess the adhesion of dirt. Namely, the toilet was washed with the composition, and the adhesion of the dirt at the time of one week was measured by the naked eye on the basis of the following criteria. (Evaluation criteria) ◎ The dirt is not attached 〇 The dirt is slightly attached △ The dirt is rarely attached X The dirt is attached a lot (3) The developmental inhibition effect of the bacteria is adjusted to 2 ml of the composition adjusted to the concentration in the brackets of Table 2

A suspension of 104 cfu/ml Staphylococcus aureus 0.05 ml with 0.1 ml of SCD medium, stir well, at 37. (: Let stand for 18 hours, and obtain the bacteriostatic activity as follows. Also, use sterile water as a blank. Static activity 値=1〇g (number of bacteria after blank culture)-log (evaluation test) Number of bacteria after sample culture) -26- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1283267 A7 B7 V. Invention description (24) <Evaluation> 〇: Static activity 値: ratio 0 is also large X: static activity 値: 0 or less -27- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1283267 A7 B7 V. Invention description (25)

Solid surface sterilizing antifouling detergent 铕 compounding component (% by weight) 1 1 s 1 1 D&gt; =? 葙m 〇&gt; 1 male 2 Q) 钸热黑 l· l· o 恭SI &gt;〇&gt; 0薛 Xue CT D&gt; Signature H? 〇 H H? CT 〇&gt; 兹mm H? CT D&gt;豸&gt; 命ο η 00 &gt; 〇〇b Ο CJ ro CJ CJ - - •Ο P 〇◎ Cn ο ο CJ ro CO a CO S δ P0 〇 ◎ pi 二ο 漭C3 ro cn o 'u\ 一- - ω ο ◎ cn CO § Ol &lt;J1 - - - - CO . 公〇〇'〇ο A CO--ρ ρ CJI ο ◎ ϋΐ ο -* o - SS ο ο ◎ • cn ο sea i. a cn a S a 0 ◎ cn b ο 漭 a CO S a - CJ 00 〇〇α&gt; ο N3 N&gt CJ ro 一一- ρ ο s Ρ (0 〇 ◎ ο fO ro Ol 一一ro 2 • ·〇CJ «α ο ο ◎ 1 A CO A S - A 〇 ◎ cn 〇ο cn cn - one • ο - Γ0 〇◎ S: CO 8 漭CJ% one-one- ω 〇◎ o ο海 N3 ro cn 一一- - 〇◎ Cn ·〇ο 漭rsj ro cn S - ρ - «Λ σι ο ◎ ΟΊ ο 海含; ro ro CO Nd - one CJ 0) 〇〇ο 者 CO ro cn一 - ρ ρ 〇〇isa o ο 告 ai CJI S - - 00 〇 ◎ cjy σ&gt; ο CJ ro cn -* - ο S cn 〇 ◎ cn bo ο 漭CJ ro Remnant, CJ ro S a S N3 CJ ro 〇 X &gt; rsj ·〇ο - XX ·〇ο - cn •S a - ρ ro X &gt; ro O ο - cn CJ S «α ω XX ro 〇ο 漭ro ro cn - a 〇X ro •O ο CO Ro cn S 一 ϋΐ XX ro ·〇ο :海cn CJ1 一一一Ο) XX fO ο ro fO cn - one - , ι Μ·δο*2 rrtftsse. order J -28-

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1283267 A7 B7 V. Invention description (26)

Table 2 Preparation examples Comparative preparation example 21 22 23 18 SV© 1? (a) Component 7 - Bu 280 polymer C 3 (1) 5 (5) 7 Bu, a / D 10 (10) (6) Ingredients 3(1) 5(5) ' 〕-^&gt;D10P B 5(5) (c) Component AO 10(3.3) 10(10) 20(20) AG 10(10) 10(10) Ion exchange water residue Residual parts. Residual parts total 100 100 100 100 pH (20°G4 7 7 7 7 Easy* 5.0 5.0 5.0 .2.0 Dirt rabbits Moss 枉 1 〇 ◎ ◎ X Bacterial development inhibition effect 〇〇〇 X

Binding

-29 - The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

12832 Shaohao 12〇399 Patent Application Case Chinese Patent Application Range Replacement (April 1996) A hard surface sterilizing antifouling detergent comprising (a) 0.01 to 30% by weight of a polymer having a weight average molecular weight of 1,000 to 6,000,0 Å, comprising a monomer unit a having at least a group selected from the group consisting of a 4-stage ammonium group and a 3-stage amine group; and a monomer unit B selected from at least one monomer selected from the group consisting of (i) to (v); wherein the monomer unit A The molar ratio of / [monomer unit A + monomer unit B] is from 0.4 to 0.99 and the total amount of monomer unit A and single m unit B ' from the monomer described below is 5 相对 relative to the all monomer unit. ~丨〇〇莫耳% : (i) An anionic group-containing compound selected from the group consisting of propionic acid or a salt thereof, methyl acetoacetic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, styrene Sulfonate, sulfopropyl methacrylate, 2-propanyl ruthenium-2-methylpropanesulfonic acid or a salt thereof, and mono-omega-methylpropoxyalkyl phosphate (carbon number) 1~12); (Π) a compound containing a guanamine group, which is selected from the group consisting of butylamine, hydrazine, hydrazine-dimethylaminopropylpropionic acid (or methacrylic acid) decylamine, hydrazine Ν·Dimethylpropenyl Or methyl propyl ketone) decylamine, hydrazine, hydrazine-dimethylaminoethyl acrylate (or methacrylic acid) decylamine, hydrazine-vinyl-2 - caprolactam and hydrazine-vinyl-2- Pyridone; (iii) an ester group-containing compound selected from the group consisting of acrylic acid (or methacrylic acid) alkyl groups (carbon number 1 to 5), propylene glycol (or methacrylic acid) 2-hydroxyethyl group, acrylic acid ( Or methacrylic acid 73247-960427.DOC - 1 - This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 8 8 8 8 AB c D 1283267 VI. Patent application scope dimethylaminoalkane Base (carbon number 1 to 5) and vinyl acetate; (iv) selected from the group consisting of ethylene, propylene, oxime, butylene, N-pentene, isoprene, 2 · decyl-1 Butene, Ν-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butanthene, styrene , vinyl toluene, α-methylstyrene, allylamine, ν, Ν-diallylamine, Ν 5 Ν -diallyl-fluorenyl-alkyl (carbon number 1 to 5) amine, ring Compounds of oxyethane, propylene oxide, 2-vinylpyridine and 4-vinylpyridine And (ν) vaporized sulfur, (b) 0 · 〇〇1~3 〇 1% of a suitable compound having a molecular weight of 1,000 or less and having a grade 4 ammonium group; and (c) 0·0 1 to 5% by weight of the surfactant; and (cA) anionic surfactant as the surfactant, (c A) / (b) is not more than 1.0 by weight. 2. According to the scope of the patent application A sterilizing antifouling detergent for a hard surface, wherein (b) is at least one bactericidal compound R1 - (X - R2) R3 IR · Ό (1) selected from the compounds represented by the following formulas (1) to (3) -2 73247-960427.DOC This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) !283267 ABCD Rb-N Υ· (2) R, /R9'〆R10 Y· (3), Ri and R6 are each an alkyl group or alkane group having a carbon number of 6 to 18, and R3 and R are an alkane having a carbon number of 1 to 3 Or a hydroxyalkyl group, X is an aromatic ring or an ester group or a guanamine group selected from =00...-CONH-, -0C0, _NHCCU, and R is also a hydroxyl group when X is an ester group or a guanamine group. The substituted anthracene hydrocarbon group having 1 to 6 carbon atoms, when X is an aromatic ring, may also be substituted with a hydroxyl group of ^6, ΙνΤί 甘士/τη 1 1 , . . . 埽1~6 anthracene hydrocarbon group or _( 0_Rll)k·, where RI1 is an ethyl group or a propyl group, k is an average number of 10, RS is an anthracene hydrocarbon group having a carbon number of 丨(1), and 1 or more of R to R1G is a carbon number of 8 The alkyl group of ~8, the remaining alkyl group having 1 to 3 carbon atoms or the hydroxyalkyl group, and 111 is the number of ruthenium or 1, and the second step Y is an anion. 3·, according to the patent scope of the third paragraph of the hard surface sterilizing antifouling cleaner, the second unit with (4) 4 grade base unit is from the following formula (4) compound R12R13C two C (FH) - Χ \广Υ· /Ν\ # R17 73247-960427.DOC . 3 This paper scale applies to China National Standard (CNS) Α4 specification (210X 297 mm) (4) ABCD 1283267 VI. Patent application scope [in the formula, R, R, R 4 are each a hydrogen atom, a trans group or an alkyl group having a carbon number (I); X is selected from an alkenyl group having 1 to 12 carbon atoms, _c〇〇Rl8_, -CONHR18-, -OCORi, -Ri, 〇 C〇Rl8·; Here, R18 and R19 are each an alkene group having a carbon number of 1 to 5; an alkyl group or a hydroxyalkyl group having a carbon number of 丨~3 or R12R13C=C(Ri4)-X-; Fe group, sulfhydryl group, epiformyl group; R 17 is a carbon group of 1 to 1 fluorene which may be substituted by a group, a group, a group of a repeating acid group, or a sulfur group, or a When 17 is an alkyl group, a hydroxyalkyl group, or a benzyl group, γ· is an anion. 4. The sterilizing and antifouling agent for a hard surface according to the first aspect of the invention, wherein the monomer unit having the amine group of the (a) ternary group is derived from the compound 15 represented by the following formula (5) ( 5) R12R13C=C( R14 )—X—N , R16 [wherein R12, R are the same as] 0 RM, R 15 and R are related to the above-mentioned description 4- 73247-960427.DOC This paper scale applies to Chinese national standards. (CNS) A4 size (210 X 297 mm)