JP2822031B2 - Cleaning compositions for flush toilets - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a detergent composition for flush toilets, and more particularly, to a detergent composition for flush toilets having an excellent dirt removing effect and an excellent stain preventing effect. [Prior art] Conventionally, for washing flush toilets and the like, a detergent composition comprising a surfactant, a solvent, an abrasive and the like in addition to an acidic detergent containing hydrochloric acid as a main component, an alkaline detergent such as sodium hydroxide and the like. Had been used in general. However, even if such a detergent composition can temporarily remove dirt, it can hardly be expected to have an effect of preventing contamination, and requires sufficient care in use from the viewpoint of safety such as skin irritation. In addition, there are various drawbacks, such as the necessity of using a toilet brush and the need for labor. In view of such workability and safety, in recent years, the toilet bowl is continuously cleaned by discharging water into the flush water from a flush auto cleaner (toilet ball auto cleaner) installed in a flush tank or a toilet bowl. Detergent compositions have been used to prevent, wash and keep clean. This detergent composition includes a liquid type and a solid type, and these surfactants, fragrances, and pigments are used as basic components, and a solidifying agent, a bactericide, and a deodorant are used as necessary. The cleaning and antifouling effect on toilet bowl stains is extremely poor, and in most cases, the content of the flushing water does not exceed the range of toilet fragrances that release coloring agents and fragrances. As a result, even with trays using the conventional flushing auto cleaner, yellowing is seen on the inner surface of the toilet bowl, and a ring of dirt is formed on the water seal portion at present. Therefore, even when such a detergent composition is used, it has been necessary to clean the toilet bowl with a conventional cleaning agent. [Problems to be Solved by the Invention] Accordingly, there is a need for a detergent composition for a flush auto cleaner that can advantageously remove dirt adhering to the flush toilet and has an effect of preventing the adherence of dirt. Was. [Means to solve the problem] If the flush toilet is used continuously for a long period of time, colored stains will be deposited on the inner surface of the toilet and on the water storage surface, particularly on the water seal portion. The stains are mainly calcium phosphate and iron oxide. And organic excretions such as crude protein and bile decomposition products, microorganisms and metabolites thereof. Then, the present inventor studied the nature of the dirt, the contamination mechanism, and the dirt removal method and the dirt prevention method based thereon, and as a result, the threshold was determined.
The present inventors have found that the above problems can be solved by using an effective water-soluble substance and a bleaching agent in combination, and completed the present invention. That is, the present invention relates to a polycarboxylic acid polymer having an average molecular weight of 100 to 1500, a water-soluble substance having a threshold effect selected from hydroxypolycarboxylic acids, polyaminophosphonic acids and salts thereof, of 0.1 to 60% by weight, and a bleaching agent. A first invention relating to a flush toilet composition containing 0.5 to 80% by weight and a second invention relating to a flush toilet detergent composition further containing 1 to 50% by weight of a water-soluble surfactant. The invention is provided. The water-soluble substance having a threshold effect used in the present invention is a water-soluble substance having a function of suppressing crystal nucleus growth of inorganic substances such as calcium phosphate, and is a polycarboxylic acid polymer having an average molecular weight of 100 to 1500, Carboxylic acids, polyaminophosphonic acids and their salts are used. Examples of the polycarboxylic acid polymer having an average molecular weight of 100 to 1500 include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyacetal carboxylic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic anhydride copolymer, and methacrylic acid. An acid-maleic anhydride copolymer is exemplified. Examples of the hydroxypolycarboxylic acid include citric acid, malic acid, tartaric acid, gluconic acid and the like. Examples of the polyaminophosphonic acid include ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and aminotrimethylenephosphonic acid. These compounds can be used in the acid form or as alkali metal, alkaline earth metal, ammonium or amine salts. Among these aqueous substances, hydroxypolycarboxylates, especially citrates, especially sodium citrate, are preferred. These water-soluble substances having a threshold effect may be liquids or solids, but are particularly preferably solids, and they can be used alone or in combination of two or more. The threshold effect of such a water-soluble substance, which suppresses the growth of crystal nuclei of inorganic substances such as calcium phosphate, is exhibited at 0.1 ppm or more. However, when the concentration is too high, salting out occurs and an adverse effect is exhibited. Therefore, it is necessary to adjust the concentration of the water-soluble substance in the present invention at the time of action to be 0.1 to 60 ppm, preferably 0.3 to 30 ppm. ~ 60%,
In particular, it is preferably set to 0.3 to 30%. In the present invention, a chlorine-based or oxygen-based bleach is used as the bleaching agent. As chlorine bleach, for example, hypochlorous acid, dichloroisocyanuric acid, trichloroisocyanuric acid or an alkali metal thereof, an alkaline earth metal salt, or an alkali metal salt of chlorite; as an oxygen bleach, for example, Percarbonic acid, perboric acid, persulfuric acid, monoperacids of aliphatic carboxylic acids, mono or diperacids of aliphatic dicarboxylic acids, mono or diperacids of aromatic carboxylic acids, or alkali metals or alkaline earths thereof Metal salts and the like. Above all, hypochlorite, percarbonate and perphthalate are particularly preferred. These bleaches may be either liquid or solid, but are particularly preferably solid. These bleaches may be used alone or in combination of two or more. The antifouling, cleaning and deodorizing action of the bleach is expressed at 0.5 to 80 ppm, preferably 1 to 70 ppm, and 80 p
Since the influence on the septic tank and the like is concerned at pm or more, the blending amount of the bleaching agent in the detergent composition of the present invention is preferably 0.5 to 80%, particularly preferably 1 to 70%. Further, the water-soluble surfactant compounded in the second invention is:
Any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant may be used, but an anionic surfactant and a nonionic surfactant are preferred. Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl sulfate, alkyl ethoxy sulfate, olefin sulfonate, alkane sulfonate, fatty acid salt, alkyl ethoxy carboxylate, α-sulfo fatty acid salt. , Α-sulfofatty acid ester salts, alkenyl succinate salts, phosphate ester salts and the like;
Nonionic surfactants include ethylene oxide
Propylene oxide block copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxypropylene alkyl ether, polyethylene glycol, polypropylene glycol, higher fatty acid alkanolamide, higher fatty acid glycol ester, sucrose fatty acid ester, etc. . Of these, alkyl ethoxy sulfates are preferred as anionic surfactants, and polyoxyethylene higher alcohol ethers are preferred as nonionic surfactants. These surfactants can be used alone or in combination of two or more, and the amount thereof is 1 to 50 in the detergent composition.
%, Especially 2 to 25%. In the detergent composition of the present invention, in addition to the above-mentioned essential components, sulfuric acid, carbonic acid, hydrochloric acid, boric acid, silicic acid, alkali metals of phosphoric acid, alkaline earth metals, ammonium salts, as long as the effect is not impaired. Or excipients such as silicic acid anhydride, flavors, pigments, bactericides, preservatives, solidifying agents, thickeners, release agents, solvents, defoamers, surfactants other than the present invention, etc. I can do it. The detergent composition of the present invention can be in various forms such as a liquid, a solid, a paste, a powder, and a granule, and it is particularly preferable to form a solid cake. Although the production method of the detergent composition of the present invention is not particularly limited,
For example, in the case of a solid cake, the above ingredients are mixed uniformly and extruded with a screw extruder. The extruded bar is cut to an appropriate length and filled into a container. Further, the above-mentioned components may be divided into two parts and molded to form a two-part type. The detergent composition of the present invention is used in a discharge container of a flush toilet. In this case, the discharge container releases a substantially constant amount of the composition during flushing during flushing, and the water-soluble substance having a threshold effect in the flush water of the flush toilet is 0.1 to 60 ppm, and the bleach is 0.5 to 80 ppm. It is necessary to be. [Examples] Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, each test in an Example was performed by the following method. (I) Preparation of model dirt A white porcelain piece is selected as a test piece, which is attached to a toilet of a flush toilet, and the dirt is adhered by a normal use. After one month's use, the test piece was taken out, dried, and a sample within a predetermined range in reflectance measurement was used as a sample for a clean test as a model stain. (Ii) Detergency test method (1) An aqueous solution prepared by dispersing and dissolving 200 mg of each composition in tap water 2 is placed in a beaker, and a test piece of a model stain prepared in advance is immersed in the beaker and stirred with a stirrer. Leave at room temperature. After 24 hours, the test piece was taken out and dried, and then the reflectance was measured, and the cleanliness was calculated by the following equation. D: clean rate (%) R _O : reflectivity of unused test piece (%) R _A : reflectivity of test piece with model dirt (%) R _B : reflectivity of test piece after clean (%) (iii (2) Detergency test method (2) A test piece of the model dirt was attached to the toilet of a flush toilet, and 80 g of each composition was dispersed and dissolved in tap water 2 to prepare a supernatant of an aqueous solution of 5 ml per flush using a metering pump. Discharged. After being used for one month, the test piece was taken out, dried and the reflectance was measured, and the cleaning rate was calculated by the formula (I). (Iv) Detergency test method (3) Cleaning of the toilet in the flush toilet was suspended for one month, and the detergency of each composition against accumulated dirt (particularly dirt on the ring portion and the water seal portion) was examined. For the composition of the present invention, after the aqueous solution was discharged for one month in the same manner as in the cleaning power test (2), and for the comparative product, after cleaning according to the specified use method, the cleanliness of the toilet bowl surface was measured. Was evaluated by visual judgment. The evaluation criteria are as follows. ：: Almost no dirt △: Dirt is partially left ×: Dirt is left on the whole surface (v) Antifouling force test method An unused test piece is attached to the toilet of a flush toilet,
A supernatant of an aqueous solution prepared by dispersing and dissolving 80 g of each composition in tap water 2 was discharged at a rate of 5 ml per flush using a metering pump. After one month of use, the test piece was taken out and dried to measure the reflectance, and the cleanliness was calculated by the following equation. SR: Antifouling rate (%) R _E : Reflectance of test piece after cleaning for one month (%) R _C : Reflectivity of test piece after uncleaning for one month (%) R _O : Same meaning as above In addition, for the comparative product, after cleaning the test piece according to the specified use, affix it to the toilet of the flush toilet,
After one month of use, the test piece was taken out and dried to measure the reflectance, and the antifouling rate was calculated by the following equation. SR: Antifouling rate (%) R _D : Reflectivity of test piece washed with comparative product (%) R _G : Reflectivity of test piece washed with comparative product before use for one month (%) R _F : Reflectance (%) of untreated test pieces after one month use (vi) Workability evaluation Ten panelists actually used the product of the present invention and the comparative product, and one month later, the workability was easy. investigated. The criteria are as follows. ：: Cleaning work is easy. Δ: Washing work is somewhat difficult. ×: Cleaning work is difficult. Example 1 With respect to the compositions shown in Table 1, the cleaning power against the model soil was measured based on the cleaning power test (1). Table 1 shows the results. * 1 Molecular weight 6000 * 2 Molecular weight 500 * 3 Ethylenediaminetetramethylenephosphonic acid * 4 High-grade powder (60%) Example 2 The compositions shown in Table 2 were tested for cleanability test method (2) and antifouling test method. Each was measured based on the following. Table 2 shows the results. Example 3 Using the composition of the present invention and the comparative product shown in Table 3, the cleaning power against the model soil was measured by the cleaning power test method (2), and the cleaning power against the toilet soil was measured by the cleaning power test method (3). The antifouling power and workability were examined based on the antifouling power test method and the workability evaluation method, respectively. According to the designated use method, the comparative products were washed with the standard amount of No. 23 and No. 24 using a toilet brush, and No. 25 was evaluated by installing a container in a low tank. Table 3 shows the results. [Effects of the Invention] The detergent composition of the present invention exhibits excellent effects in both detergency and antifouling power, and not only keeps flush toilets clean, but also has extremely easy workability. Was observed. On the other hand, cleaning with a comparative product requires the use of a toilet brush and the like, and although a temporary cleaning power is recognized to some extent, there is no antifouling power and much labor is required for the work. In addition, the comparative product (No. 25) aimed at simplicity did not have cleanliness and antifouling functions, and a satisfactory comparative product, such as necessitating cleaning work with another comparative product, was not found.

Claims (1)

(57) [Claims] 0.1 to 60% by weight of a water-soluble substance having a threshold effect selected from a polycarboxylic acid polymer having an average molecular weight of 100 to 1500, hydroxypolycarboxylic acid, polyaminophosphonic acid and salts thereof, and 0.5 to 80% by weight of a bleaching agent. A detergent composition for flush toilets, comprising: 2. Water soluble substance with threshold effect 0.1-6
A detergent composition for flush toilets, comprising 0% by weight, 0.5 to 80% by weight of a bleaching agent and 1 to 50% by weight of a water-soluble surfactant.