JP2001181601A - Antifouling composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous antifouling composition capable of exhibiting antifouling properties by allowing an active ingredient present in the composition system to be adsorbed on an objective surface while preventing the active ingredient from being flowed out by rinse even in a washing step accompanied by the rinse with water. SOLUTION: This aqueous antifouling composition contains an amphoteric polyelectrolyte. The amphoteric polyelectrolyte contains a quarternary ammonium group or a tertiary amino group. The aqueous antifouling composition is a detergent composition for a hard surface. The method of antifouling treatment is characterized in that the amphoteric polyelectrolyte is adsorbed on the surface, and the resultant surface is brought into contact with water to form a water screen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous antifouling composition. More specifically, the present invention relates to a hard surface cleaning composition containing such an aqueous antifouling composition.

[0002]

2. Description of the Related Art Hitherto, compositions have been developed which increase the antifouling property against hard surfaces and the like. For example, dirt such as sebum and scum easily adheres to the surface of a bathtub or a sink, and particularly the bathtub has a large amount of dirt adsorbed on a draft surface, and the draft surface after draining water is remarkably rough. In addition, if left for a long time after rinsing with water, the adsorbed dirt becomes difficult to remove, which may cause discoloration and may leave roughness. For these reasons, developments have been made to enhance the antifouling properties of various surfaces. As a related document, JP-A-6-279687 discloses a unit obtained by polymerizing a (meth) acrylate containing a polyfluoroalkyl group, a unit obtained by polymerizing a (meth) acrylate containing a blocked isocyanate group, and A polymer having a unit in which an (oxy) alkylene chain-containing (meth) acrylate is polymerized is disclosed. Further, JP-A-8-41416 discloses a composition for a fluororesin coating composition comprising a fluorine-based copolymer and a water-soluble polyether-modified silicone oil. JP-A-11-21511 discloses a photocatalytic hydrophilic member having a surface layer containing acrylic silicon and a photocatalytic oxide.

[0003] JP-A-6-17007 discloses an aqueous polishing composition obtained from a polyurethane prepolymer obtained by reacting a macromonomer, a long-chain polyhydroxy compound, and an organic isocyanate with a polyfunctional organic amino compound. Is disclosed, JP-A-9-137119,
A non-fouling coating composition containing a polyol, an alkoxysilane, an alkyl silicate and a polyisocyanate is disclosed. Further, JP-A-9-273079 discloses an antifouling agent composition applied to a textile product in a wet state, wherein the antifouling agent composition is dried without being rinsed with water after application. An antifouling agent composition containing is disclosed, and JP-A-10-7742 discloses a function imparting agent containing a fluorosilicone oligomer. Thus, various developments have been made on the antifouling agent composition.For example, as an antifouling agent composition for treating the surface of a bathtub or a sink, the antifouling property after rinsing with water has been improved. In addition to being provided, the active ingredient does not flow down in the water at the time of bathing or cooking, exhibits an antifouling function, there is no roughness when the hot water is drained after bathing, the active ingredient is It is desired that the active ingredient is desorbed by the used washing and a new active ingredient film is formed again.

[0004]

SUMMARY OF THE INVENTION According to the present invention, even in a washing step involving rinsing with water, the active ingredient in the composition system is not washed away by the rinsing, but is adsorbed on the target surface to improve the antifouling property. An object of the present invention is to provide an aqueous antifouling composition that expresses. Another object of the present invention is to provide a hard surface cleaning composition containing such an aqueous antifouling composition.
Another object of the present invention is to provide an antifouling treatment method in which the above antifouling property is exhibited.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the present inventors have solved the above-mentioned problems by including a specific polymer in an aqueous contaminant composition. . That is, the present invention provides an aqueous antifouling composition containing an amphoteric polymer electrolyte. The present invention also provides a hard surface cleaning composition containing such an aqueous antifouling composition. Further, the present invention provides an antifouling treatment method characterized in that an amphoteric polymer electrolyte is adsorbed on the surface and then brought into contact with water to form a water film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION First, examples of the amphoteric polymer electrolyte used in the present invention include those obtained by copolymerizing an anionic vinyl monomer unit (a) and a cationic vinyl monomer unit (b). Further, as other monomer units, an amphoteric polymer electrolyte copolymerized using a hydrophobic vinyl monomer unit (c) and a nonionic hydrophilic monomer unit (d) may be used. Furthermore,
The amphoteric polymer electrolyte in the present invention may be composed of a monomer having a cation group and an anion group in the same monomer, which is composed of the monomer unit (c) and / or
Or (d) may be included. Examples of the anionic vinyl monomer unit (a) include a carboxyl group-containing vinyl monomer and a sulfone group-containing vinyl monomer. Specific examples of the carboxyl group-containing monomer unit include acrylic acid, methacrylic acid, 3-butenoic acid, 3-methyl-butenoic acid, 4-pentenoic acid, 4-methyl-4-pentenoic acid, 5-hexenoic acid, and 5-hexenoic acid. Methyl-5-hexenoic acid, 8-octenoic acid, 8-methyl-8-octenoic acid, 11-dodecenoic acid, 11-methyl-11-dodecenoic acid, 15-hexadecenoic acid, 15-methyl-1
5-hexadecenoic acid and the like. Specific examples of the sulfone group-containing monomer unit include acrylamide methanesulfonic acid, acrylamidoethanesulfonic acid, methanesulfonic acid acrylate, ethanesulfonic acid acrylate, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2 -Methacrylamide-2-methylpropanesulfonic acid, 2-acrylamide-
n-butanesulfonic acid and the like. Further, as these carboxyl groups and sulfone groups, not only the acid type,
Including its salts. Further, the salt may be copolymerized alone or in combination with the acid type. As the salt of the carboxyl group-containing monomer or the sulfone group-containing monomer, respective alkali metal salts, ammonia, triethylamine,
Organic amine salts such as triethanolamine are exemplified. The polymer of the present invention may be obtained by neutralizing the carboxyl group or sulfone group-containing monomer unit of the obtained copolymer with an alkali agent. In the amphoteric polymer electrolyte of the present invention, the anionic vinyl monomer unit (a)
Is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, and still more preferably 10 to 70% by mass.
~ 65% by mass.

The cationic vinyl monomer unit (b) includes a cationic vinyl monomer having a tertiary amino group or a quaternary ammonium group. As the counter anion of this monomer, halogen, sulfate, oxalic acid, citric acid and the like are preferable, and chloride and bromide are more preferable. Concretely, dimethylaminoethyl acrylate chloride, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylamide chloride, diethylaminoethyl acrylate chloride, diethylaminoethyl methacrylate chloride, diethylaminoethyl acrylamide chloride, dimethylaminopropyl acrylate chloride, dimethylaminopropyl chloride Methacrylate, dimethylaminopropylacrylamide chloride,
Trimethylaminoethyl chloride, trimethylaminoethyl methacrylate, trimethylaminopropyl chloride, trimethylaminopropyl methacrylate, triethylaminoethyl chloride, 1-trimethylamino-2-hydroxypropyl methacrylate, [3- (meth Acrylamino)
Propyl] trimethylammonium chloride and the like. In the amphoteric polymer electrolyte of the present invention,
The cationic vinyl monomer unit (b) preferably contains 20 to 97% by mass, more preferably 30 to 97% by mass.
95% by mass, and more preferably 35 to 90% by mass.
It is.

The hydrophobic vinyl monomer unit (c) includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
Decyl acrylate, decyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-
Hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate and the like can be mentioned. In the amphoteric polymer electrolyte of the present invention, the hydrophobic vinyl monomer unit (c) preferably contains 0 to 25% by mass, more preferably 0 to 20% by mass.
% By mass.

The nonionic hydrophilic monomer unit (d) includes acrylamide, methacrylamide, polyethylene glycol acrylate (polymerization degree of ethylene oxide of 1 to 30), polyethylene glycol methacrylate (polymerization degree of ethylene oxide of 1 to 30), methoxypolyethylene Glycol acrylate (degree of polymerization of ethylene oxide 2 to 30), methoxypolyethylene glycol methacrylate (degree of polymerization of ethylene oxide 2 to 30) and the like can be mentioned. In addition, in the amphoteric polymer electrolyte of the present invention, the nonionic hydrophilic monomer unit (d) is 0 to 0.
The content is preferably 25% by mass, more preferably 0 to 20% by mass.

The amphoteric polymer electrolyte in the present invention may be a random (co) polymer or a block (co) polymer of the above components (a) to (d). Specific examples of the amphoteric polymer electrolyte in the present invention include the following compounds (a
1) and (a2). Compound (a1)
Is a compound in which the anionic group of the anionic vinyl monomer is a carboxyl group, and compound (a2) is a compound in which the anionic group of the anionic vinyl monomer is a sulfone group.

Compound (a1)

Here, R ₁ in each monomer unit represents hydrogen or a C ₁ -C ₃ alkyl chain. (A) R _{2 in the} anionic vinyl monomer unit represents a C _{0 to} C ₁₅ alkyl group, and M represents hydrogen, an alkali metal salt or an ammonium derivative, or a mixture thereof. R _{3 in the} cationic vinyl monomer unit represents a C _{1 to} C ₁₅ linear or branched alkylene group or alkenylene group, or a C ₆ cyclohexyl group or phenyl group. R ₄ and R ₅ are C ₁
An alkyl group or hydroxyalkyl group -C _3, R ₆ represents hydrogen or an alkyl group C ₁ -C _3. R ₄ ,
When R ₅ and R ₆ are simultaneously an alkyl group, the length of the alkyl groups may be the same or different. (C) R _{7 in the} hydrophobic vinyl monomer unit represents a C _{1 to} C ₁₅ linear or branched alkylene group or alkenylene group, or a C ₆ cyclohexyl group or phenyl group. (D) A non-ionic hydrophilic monomer units represents an oxygen atom or NH, R ₈
Is a hydrogen atom when A is NH, and R ₈ is represented by (CH ₂ CH ₂ O) n B when A is oxygen. Here, when n is 1, B is a hydrogen atom, and when n is 2 or more and 30 or less, B is
Represents a hydrogen atom or CH ₃ .

Compound (a2)

Here, R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , A and M are compounds (a
As in the case of 1), R ₉ represents a C ₁ -C ₁₅ linear or branched alkylene group or alkenylene group, and may contain one or more hydroxyl groups in a carbon chain. The composition ratios a, b, c, and d of the compounds (a1) and (a2) are (a
+ B) / (c + d) preferably represents 100 to 50/0 to 50% by mass, more preferably 100 to 60/0 to 40% by mass.
The ratio of a / b is preferably 20-80 / 80-20% by mole,
More preferably, it is 30 to 60/60 to 30 mol%. Each of c and d preferably represents 0 to 25% by mass, more preferably 0 to 20% by mass.

The following compounds (a3) and (a4) are examples of amphoteric polymer electrolytes comprising a monomer having a cation group and an anion group in the same monomer.

Compound (a3)

Here, R ₁ , R ₃ ,
R ₄ , R ₅ , R ₇ , R ₈ , A and M are the same as those in the compound (a1), and R ₁₀ is a C ₁ -C ₁₀ linear or branched alkylene group or a hydroxyl group. It may have a structure including one or more.

Compound (a4) Here, R ₁ , R ₃ , R ₄ , R ₅ , R ₇ ,
R ₈ , A and M are the same as those in the compound (a1),
R ₁₁ may have a structure containing one or more C ₁ -C ₁₀ linear or branched alkylene groups or hydroxyl groups.

With respect to the composition ratios e, f, and g of the compounds (a3) and (a4), e / (f + g) is preferably from 100 to 50/0 to 50% by mass, more preferably from 100 to 50% by mass. 60 / 0〜4
0% by mass. Betaine conversion rate of betaine moiety-containing monomer (R ₁₀ -COOM of compound a3 or R ₁₁ -S of compound a4
Addition rate of O ₃ M to amine moiety, R ₁₀ -COOM / N (mol%), R _1
1 -SO ₃ M / N (mol%)) represents 40 mol% or more, and more preferably 45 mol% or more. f and d are each 0 to 25
% By mass, more preferably 0 to 20% by mass. The carboxylic acid group of the betaine moiety-containing monomer unit of the compound (a3) which can be used in the present invention may be not only an acid form but also a salt thereof, and the salt may be used alone or in combination with an acid form. They may be combined. As the salt of the carboxylic acid group, for example, an alkali metal salt, ammonia, an organic amine salt such as triethylamine, triethanolamine or the like can be used. The polymer of the present invention may be obtained by neutralizing the carboxylic acid group of the obtained copolymer with an alkali agent.
Examples of the counter anion in the cation portion of the quaternary ammonium salt include halogens, preferably chlorides and bromides. Specifically, for example, N-acryloyloxyethyl N, N-dimethylammonium N-methylcarboxylate, N-methacryloyloxyethyl N,
N-dimethylammonium N-methylcarboxylate, N-acryloylaminopropyl N, N-dimethylammonium N-methylcarboxylate, N-methacryloylaminopropyl N, N-dimethylammonium N-methylcarboxylate and the like can be mentioned.

The sulfonic acid group of the betaine moiety-containing monomer unit of the compound (a4) used in the present invention is not limited to an acid form, and a salt thereof may be used.
A copolymer may be used in combination with the acid type. As the salt of the sulfonic acid group, for example, alkali metal salts, ammonia, organic amine salts such as triethylamine, triethanolamine and the like can be used. The polymer of the present invention may be obtained by neutralizing the sulfonic acid group of the obtained copolymer with an alkali agent. The counter anion in the cation portion of the quaternary ammonium salt may be any counterpart as long as it is halogen, and is preferably chloride or bromide. Specifically, for example, N-acryloyloxyethyl N, N-dimethylammonium N
-(Hydroxy) propanesulfonate, N-methacryloyloxyethyl N, N-dimethylammonium N-
(Hydroxy) propanesulfonate, N-acryloyloxyethyl N, N-dimethylammonium N-propanesulfonate, N-methacryloyloxyethyl N,
N-dimethylammonium N-propanesulfonate and the like can be mentioned.

The amphoteric polymer electrolyte which can be used in the present invention preferably has a mass average molecular weight of at least 1,000, more preferably from 2,000 to 8,000,000, and still more preferably from 2,000 to 7,000,000. Further, the amphoteric polymer electrolyte as described above, for example, conventionally known solution polymerization,
It can be produced by polymerization by a polymerization method such as bulk polymerization or precipitation polymerization. The polymerization temperature varies depending on the solvent used, but is generally preferably from 30 to 100 ° C, and the polymerization time is preferably from 3 to 24 hours. At this time, various conventionally known polymerization initiators can be used, and there is no particular limitation as long as they have the ability to initiate radical polymerization.For example, benzoyl peroxide, 2,2′-azo Bisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-divaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N, N′dimethyleneisobutylamidine), sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide and the like are preferred, and azo compounds are preferred. Examples of the amphoteric polymer electrolyte that can be used in the present invention include proteins in addition to those described above. The protein is not particularly limited as long as it is an amphoteric polyelectrolyte protein, and specific examples include albumin.

In the aqueous antifouling composition of the present invention, the amphoteric polymer electrolyte as described above can be contained alone, but two or more can be used in combination. The concentration of the amphoteric polymer electrolyte in the aqueous antifouling composition is preferably 0.01 to 30%, more preferably 0.01 to 20%. The balance is preferably water. The aqueous antifouling composition of the present invention,
Although any form of granular, gel, or liquid may be used, it is preferable that the liquid is used for convenience in use. Further, in the present invention, by preparing a hard surface cleaning composition containing the above-described aqueous antifouling composition, it is possible to impart cleaning properties in addition to antifouling properties and adsorptivity. Such a hard surface cleaning composition, for example, anionic surfactants, cationic surfactants, nonionic surfactants,
In addition to surfactants such as amphoteric surfactants, plasticizers (such as ethyl carbitol), chelating agents (such as EDTA), solvents (such as ethanol), pH adjusters (such as citric acid), and fragrances can be used in combination. it can. At this time, it is preferable that an anionic surfactant and / or a nonionic surfactant is contained in the hard surface cleaner in an amount of 0.1 to 10%.

In the present invention, antifouling properties can be imparted by adsorbing the amphoteric polymer electrolyte on the surface of the object and then contacting it with water to form a water film. At this time, the target surface may be an FRP plate (reinforced plastic), stainless steel enamel (glass), artificial marble, ABS resin, polypropylene plate, polyethylene plate, or the like. In addition, a water film indicates that a water layer is formed on a target surface. Such an antifouling treatment method is preferably carried out using the above-described aqueous antifouling composition or hard surface cleaning composition of the present invention.

[0024]

According to the present invention, even in a washing step involving rinsing with water, the active ingredient in the composition system is not washed away by the rinsing, but is adsorbed on the target surface to exhibit antifouling properties. It has become possible.

[0025]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 14 were performed using the following 14 types of amphoteric polymer electrolytes. Amphoteric polymer electrolytes 1 to 13 were produced by the polymerization method described below. In addition, the calculation of the following mass% was performed on the assumption that the anionic monomer or the anion group in the betaine portion was in the acid form. 1; acrylic acid / trimethylaminoethyl methacrylate
= 26/74 (mass%) (50/50 (mol%)) 2; methacrylic acid / dimethylaminoethyl methacrylate
/ t-butyl methacrylate = 25/69/6 (% by mass) 3; acrylamidopropanesulfonic acid / dimethylaminoethyl methacrylate / n-butyl methacrylate = 39.4 /
55.6 / 5 (mass%) 4; methacrylic acid / dimethylaminoethyl methacrylate
/ Methoxy (ethyleneoxy (EO = 23)) methacrylate
= 30 / 54.8 / 15.2 (mass%) 5; acrylic acid / trimethylaminoethyl methacrylate
/ Ethyl methacrylate / methoxy (ethyleneoxy (EO
= 23)) Methacrylate = 18.8 / 66.2 / 5/10 (% by mass) 6; Poly N-methacryloyloxyethyl N, N-dimethylammonium N-methylcarboxylate 7; N-Methacryloyloxyethyl N, N-dimethylammonium N -Methylcarboxylate / t-butyl methacrylate = 98/2 (% by mass) 8; N-methacryloyloxyethyl N, N-dimethylammonium N-methylcarboxylate / methoxy (ethyleneoxy (EO = 9)) methacrylate = 95 / 5 (% by mass) 9; N-methacryloyloxyethyl N, N-dimethylammonium N-methylcarboxylate / ethyl methacrylate / methoxy (ethyleneoxy (EO = 9)) methacrylate = 90/2/8 (% by mass) 10; Poly N-methacryloyloxyethyl N, N-dimethylammonium N- (hydroxy) propane sulf Sulfonate 11; N-methacryloyloxyethyl N, N-dimethyl ammonium N- (Hidokishi) propane sulfonate / t
-Butyl methacrylate = 98/2 (% by mass) 12; N-methacryloyloxyethyl N, N-dimethylammonium N- (hydroxy) propane sulfonate /
Methoxy (ethyleneoxy (EO = 9)) methacrylate = 9
5/5 (% by mass) 13; N-methacryloyloxyethyl N, N-dimethylammonium N- (hydroxy) propane sulfonate /
Ethyl methacrylate / methoxy (ethyleneoxy (EO =
9)) Methacrylate = 90/2/8 (% by mass) 14; Albumin (Tokyo Kasei Co., Ltd.)

Polymerization Method Amphoteric Polymer Electrolyte 2 Polymerization A methacrylic acid was placed in a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirring device.
13 g, dimethylaminoethyl methacrylate 35.6 g, t
-3.1 g of butyl acrylate, 0.3 g of 2,2'-azobis (2-methylbutyronitrile) and 100 g of ethyl alcohol were charged,
The mixture was stirred at room temperature for 30 minutes while blowing nitrogen. The reaction system
The temperature was raised to 75 ° C. and reacted for 6 hours. The product was taken out of the reactor, and the solvent was concentrated under reduced pressure and removed to obtain a polymer solid. This solid was dissolved and dialyzed for 7 days. Concentrate the aqueous solution, freeze-dry and amphoteric polymer 49g
I got The mass average molecular weight of the obtained polymer was 200,000. Amphoteric polymer electrolytes 1, 4, and 5 were also produced by the same polymerization method as above.

Polymerization of Amphoteric Polymer Electrolyte 3 In a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirrer, 14.4 g of 2-acrylamido-2-methylpropanesulfonic acid, dimethylaminoethyl Methacrylate 20.4g, n-butyl acrylate 1.8g, 2,2'-azobis (2-methylbutyronitrile) 0.2
g and N, N-dimethylformamide (100 g) were charged, and the mixture was stirred at room temperature for 30 minutes while blowing nitrogen. The reaction system was heated to 70 ° C. and reacted for 6 hours. Withdrawing the product from the reactor,
A polymer solid was obtained by reprecipitation with ethanol. This solid was dissolved and dialyzed for 7 days. The aqueous solution was concentrated and freeze-dried to obtain 34 g of an amphoteric amphiphilic polymer. The mass average molecular weight of the obtained polymer was 180,000.

Polymerization of amphoteric polymer electrolyte 7 (betaine structure) In a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirrer, 49 g of dimethylaminoethyl methacrylate, t-butyl acrylate
1.4g, 2,2'-azobis (2-methylbutyronitrile) 0.31
g and 100 g of ethyl alcohol, and reacted at 80 ° C. for 4 hours while blowing nitrogen. Next, a solution obtained by dissolving 47.4 g of bromoacetic acid in 70 g of ethanol was added to the obtained polymerization reaction solution, and after sufficiently stirring, a solution of 15 g of potassium hydroxide dissolved in 100 g of ethanol was added dropwise using a dropping funnel. Then, an amphoteric reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was allowed to cool to room temperature, filtered, and the precipitate was removed. The solvent was removed by drying under reduced pressure to obtain 64 g of a solid content. The mass average molecular weight of the obtained polymer was 120,000.
Further, in this amphoteric copolymer, the binding ratio of the carboxymethyl moiety was 100% in terms of a molar ratio with respect to all nitrogen atoms contained in the copolymer. Amphoteric polymer electrolyte 6,
8 and 9 were produced by the same polymerization method as described above.

Polymerization of amphoteric polymer electrolyte 11 (betaine structure) In a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen introducing tube and a stirring device, 49 g of dimethylaminoethyl methacrylate, t-butyl acrylate
1.9 g, 2,2'-azobis (2-methylbutyronitrile) 0.31
g and 100 g of ethyl alcohol, and reacted at 80 ° C. for 4 hours while blowing nitrogen. Next, a solution prepared by dissolving 67.5 g of sodium 2-hydroxy-3-propanesulfonate in 70 g of ethanol / water (= 50/50 mass ratio) was added to the obtained polymerization reaction solution, and the mixture was sufficiently stirred. Further, an amphoteric reaction was performed at 80 ° C. for 5 hours under a nitrogen stream. After the reaction,
The mixture was allowed to cool to room temperature, filtered, and the precipitate was removed. The solvent was removed by drying under reduced pressure to obtain 93 g of a solid content. The weight average molecular weight of the obtained polymer was 110,000. Further, in this amphoteric copolymer, the binding ratio of the sulfobetaine site was 100% in terms of a molar ratio with respect to all nitrogen atoms contained in the copolymer. Amphoteric polymer electrolytes 10, 12, and 13 were also produced by the same polymerization method as described above.

The above-mentioned amphoteric polymer electrolytes 1 to 14 (Examples 1 to 14) and acrylic acid (AC-30 manufactured by Nippon Pure Chemical Co., Ltd.)
Using S (Comparative Example 1) and cationized cellulose (KGP manufactured by Lion Corporation: Comparative Example 2), a detergent composition for hard surfaces was produced according to the components and concentrations shown in Table 1. In Comparative Example 3, an amphoteric polymer electrolyte was not used.
The adsorptivity, antifouling property, and finished feeling of each composition thus prepared were evaluated by the following evaluation methods. The results are shown in Table 1.

Adsorption (Hydrophilic surface by polymer) Apply 0.5 g of the preparation to each area of a FRP plate, 10 cm x 10 cm, and rinse thoroughly with water. The evaluation was based on the surface wettability. ；: The surface can be wet with water for 1 minute or more (well hydrophilized). Δ: Water can be wetted for only 10 seconds or less (not so hydrophilic). X: Water flows down and cannot be wet with water (not hydrophilized).

Antifouling stain [Artificial sebum 0.05% (oleic acid 45%, triolein
25%, stearic acid 19.5%, squalene 4%, liquid paraffin 4%, cholesterol 2.5%), carbon 0.003
%, Fatty acid soap calcium (C14 / C16 = 50/50%) 0.003
%], And as a bath material, "FRP board, area 10cm x 1
0cm ", the material of the sink is" stainless steel (SUS-316),
After applying 0.5 g of the prepared solution to an area of “10 cm × 10 cm” and thoroughly rinsing with water, the antifouling property was evaluated in the following four steps. ◎: Both materials are not stained ○: Both materials are hardly stained △: Both materials are slightly stained ×: Both materials are very stained

A feeling of finish 10 panelists took the sample home, and in each household, "bath tub (material / person; 6 FRP, 2 stainless steel,
Enamel 1 person, artificial marble 1 person) ”, used as a cleaning agent, after bathing and after removing hot water, the roughness of the draft surface was compared with the composition of the present invention and a commercial product, and evaluated on the following four scales did. ◎: No roughness was felt ○: Almost no roughness was felt △: Roughness was slightly felt ×: Roughness was felt very much

Table 1

The compositions of Examples and Comparative Examples in Tables 2, 3 and 4 below are the same as those of Example 1 except for the type and amount of the polymer compound and the amount of water.
The same as above. Table 2

Table 3

Table 4 In Comparative Examples, acrylic acid (Nippon Pure Chemical Co., Ltd.) was used as a polymer.
AC-30S), cationized cellulose (Lion Corporation)
KGP). Polymer 0%: Adsorption, antifouling properties, and finished feeling are poor.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/37 CEA C11D 3/37 CEA 17/00 17/00 // C09D 5/16 C09D 5/16 201 / 02 201/02 (72) Inventor Masanori Komatsu 1-3-7, Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4H003 AD02 AD04 BA12 DA05 EB30 FA06 4H020 AA06 AB02 AB07 4J002 BG011 BG071 BG081 BG131 FD026 FD317 GH01 4J038 CG021 CG031 CG141 CG181 CH201 CH231 CJ131 GA06 GA08 GA09 GA13 MA08 MA12 NA05 PC02

Claims (4)

[Claims] An aqueous antifouling composition containing an amphoteric polymer electrolyte. 2. The aqueous antifouling composition according to claim 1, wherein the amphoteric polymer has a quaternary ammonium group or a tertiary amino group. 3. A hard surface cleaning composition comprising the aqueous antifouling composition according to claim 1 or 2. 4. An antifouling treatment method comprising: adsorbing an amphoteric polymer electrolyte on a surface; and contacting the surface with water to form a water film.