JPH0243799B2 - SUISENTOIRETSUTOYOSEIJOZAISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for preventing stains caused by silicic acid scale, excrement, etc. adhering to the ceramic surface of a flush toilet bowl. The black or brownish stains found on the interface of the water reservoir and the area where flush water flows into a ceramic flush toilet are extremely stubborn stains, and are caused by harsh chemicals such as strong acids, strong alkalis, and bleach. It was difficult to remove even with the use of This is not limited to flush toilets, but also when tap water containing trace components is used as water (supply water), and this water repeatedly comes into contact with ceramic or glass surfaces such as water reservoirs or water receivers. This was a common phenomenon in situations where the material was brought into contact and dried. As a result of intensive study on this stain, the present inventors discovered that the main cause of the stain is silicic acid contained in the water used, such as tap water, and that it is firmly adhered to the ceramic surface as silicic acid scale. Ta. In addition, there is a load of feces and urine inside the flush toilet bowl, and stains caused by these excreta adhere to the interface of the standing water. An object of the present invention is to provide a composition having an effect of preventing the adhesion of stains caused by silicic acid scale, excrement, and the like. That is, the flush toilet cleanser composition of the present invention comprises (a) a cationic surfactant, (b) a polyoxyethylene alkyl ether type or polyoxyethylene alkyl phenyl ether type nonionic surfactant, and (c) maleic acid. Alternatively, it is characterized by containing a homopolymer of maleic anhydride, a copolymer obtained from a monomer copolymerizable with these, or a water-soluble salt of these polymers (hereinafter referred to as maleic acid polymer). Among the cationic surfactants as component (a), quaternary ammonium salt type cationic surfactants having 1 to 3 alkyl groups having 12 to 22 carbon atoms are preferred, and in particular, the following general formula () ~ () is shown. (In the formula, R ₁ is an alkyl group having 12 to 22 carbon atoms,
X represents a halogen such as chlorine or bromine, methyl sulfate or ethyl sulfate. ) (In the formula, R ₂ and R ₃ are alkyl groups having 12 to 20 carbon atoms.) (In the formula, R ₄ , R ₅ and R ₆ are alkyl groups having 12 to 18 carbon atoms.) (In the formula, R ₇ is an alkyl group having 12 to 22 carbon atoms.) Specific examples of the above cationic surfactants include the following. (1) Stearyltrimethylammonium chloride (2) Distearyldimethylammonium chloride (3) Dimyristyldimethylammonium chloride (4) Stearylbenzyldimethylammonium chloride (5) Cetyldiethylmethylammonium chloride (6) Dimyristyldimethylammonium methyl sulfate ( Among the polyoxyethylene alkyl phenyl ether type or polyoxyethylene alkyl ether type nonionic surfactants that are component b), those represented by the general formula () are preferred. R ₈ O(C ₂ H ₄ O) nH () (In the formula, R ₈ represents an alkyl group having 8 to 18 carbon atoms or an alkylphenyl group having 6 to 12 carbon atoms in the alkyl group, and n is 6 to 12 carbon atoms. (Represents an integer of 15.) Among these, particularly preferred is one in which R ₈ has 8 carbon atoms.
~14 alkyl group or alkyl group has 6 carbon atoms
-12 alkylphenyl group, where n is 7-12
belongs to. Specific examples of the above-mentioned nonionic surfactants include the following. Here, represents the average number of added moles of polyoxyethylene. (1) Polyoxyethylene (=8) lauryl ether (2) Polyoxyethylene (=10) nonylphenyl ether (3) Polyoxyethylene (=12) octyl ether (4) Polyoxyethylene (=7) octyl ether Among the maleic acid polymers serving as the enyl ether (C) component, preferred are homopolymers or copolymers represented by the general formula () or salts thereof. (In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a carboxyl group or an alkoxyl group having 1 to 3 carbon atoms, M is hydrogen, Represents an alkali metal or alkanolamine, with an n/m molar ratio of 1/10 to 1/
30 and the molecular weight is approximately 3,000 to 100,000. Note that the above general formula () simply indicates a copolymer (a homopolymer when m is zero), including a random copolymer, and does not indicate a block copolymer. A specific example of a copolymer of general formula () is

[Table] The composition of the present invention contains the above-mentioned components (a), (b), and (c) as essential components, and if desired, a coloring agent such as Blue No. 1 to impart freshness, deodorization, and fragrance. In addition to fragrances for use, chelating agents, bactericidal agents, stabilizers, fillers, etc. can be added. The antifouling mechanism of the composition of the present invention is thought to be as follows. When a cationic surfactant is added to water, it adsorbs to the ceramic or glass surface and makes the ceramic (glass) surface hydrophobic, increasing the contact angle between the water surface and the ceramic (glass) surface.
Moisture evaporation from the interface is suppressed, making it difficult for dirt to adhere to the interface, that is, the ceramic surface. In order to produce such an effect, it is appropriate to contain the cationic surfactant in water in an amount of 0.05 to 20 ppm, preferably 0.1 to 2 ppm. This amount
If it is less than 0.05 ppm, the adsorption area of the cationic surfactant will be small and the effect will not be sufficient, and if it exceeds 20 ppm, the ceramic surface will become hydrophilic again and a sufficient effect will not be obtained. However, if a cationic surfactant is used alone, as it is repeatedly used, the cationic surfactant will accumulate and the ceramic surface will become hydrophilic again, reducing the effect of preventing the adhesion of silicic acid scale. However, when a nonionic surfactant coexists, this decrease can be suppressed and the effect of preventing the adhesion of silicic acid scale can be continuously maintained. Note that the details of the contribution mechanism of nonionic surfactants are unknown. It is appropriate to add the composition of the present invention so that the nonionic surfactant concentration in the water used is 1 to 50 ppm, preferably 3 to 10 ppm. If the amount is less than 1 ppm, sufficient effect of nonionic surfactant addition cannot be obtained, and
If it exceeds 50 ppm, the nonionic surfactant itself will be concentrated and adhered at the interface, which is not preferable. In this way, by using cationic and nonionic surfactants in combination, it is possible to prevent scale build-up on flush toilet bowls or flush tanks, but it is also possible to prevent stains caused by excrement.
In particular, it is less effective against adhesion of organic matter. (c) The maleic acid polymer effectively prevents the adhesion of such organic substances, and together with components (a) and (b), effectively prevents the flush toilet from becoming soiled. In addition, tap water also contains substances such as iron and manganese in addition to silicic acid, but the chelating or dispersing power of (c) the maleic acid polymer prevents the adhesion of stains based on these substances. (c) The concentration of the maleic acid polymer in the water used is suitably 0.1 to 5 ppm, preferably 0.2 to 3 ppm. If the concentration is less than 0.1ppm, sufficient effect will not be obtained, and if it exceeds 5.0ppm,
(c) This is not preferable because the maleic acid polymer itself adheres to the interface. As mentioned above, the composition of the present invention is used by being administered into washing water at a predetermined concentration.
The composition can be in various forms such as liquid, powder, or supported on other carriers, and the concentration or content of each component in the composition can be selected as appropriate. However, in the composition, (a) the cationic surfactant is 0.05
~20ppm, (b) nonionic surfactant 1~50ppm,
Since it is appropriate to add (c) maleic acid polymer to the washing water so that it contains 0.1 to 5 ppm, the content ratio of each component in the composition is (c) maleic acid polymer per 1 part by weight of (a )Cationic surfactant is 0.01~
200 parts by weight, and (b) nonionic surfactant is suitably 0.2 to 500 parts by weight. When preparing a liquid composition, the following composition is preferable from the viewpoints of liquid properties, ease of handling, and economical efficiency. (a) Cationic surfactant 0.05-20% by weight (b) Nonionic surfactant 1.0-50% by weight (c) Maleic acid polymer 0.1-5% by weight Water Balance As explained above, the composition for flush toilets of the present invention According to the invention, scale adhesion and organic stains caused by excrement in flush toilets can be effectively prevented. Example 1 Each composition shown in Table 1 was diluted 10,000 times with tap water and tested, and the results are shown in Table 1. (1) Adhesion of silicic acid scale A tile was placed in a test tank in an upright position, and the tap water was added to the tank every hour, taking care not to completely submerge the tile. The state of the silicic acid scale was determined using the following criteria. ○: Silicate scale does not adhere. ×: Silicic acid scale adheres. (2) Stains caused by excrement, etc. Using tiles on which silicic acid scale has been applied in advance, human urine, which has been left for 12 to 48 hours after collection, is diluted 10,000 times with tap water to a concentration of 10%. The following criteria were used to examine whether this colored substance would adhere to the areas where silicic acid scale had adhered. ○: Does not adhere. ×: Adheres.

【table】

[Table] Example 2 The effectiveness of the product of the present invention was investigated in actual household flush toilets, and as shown in Table 2, it was clearly found to be effective in preventing dirt adhesion. The survey was conducted in 15 households for one month, and each composition was used for 20,000
The test was carried out using a container that can be diluted twice as much.

【table】

Claims (1)

[Claims] 1 (a) Cationic surfactant, (b) polyoxyethylene alkyl ether type or polyoxyethylene alkyl phenyl ether type nonionic surfactant, and (c) maleic acid or maleic anhydride homopolymer or copolymerizable with these. 1. A cleaning agent composition for flushing toilets, comprising a copolymer obtained from a monomer such as a copolymer or a water-soluble salt of these polymers.