JPS6241998B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an alkaline cleaning composition suitable for cleaning and removing organic and inorganic dirt and deposits stuck to the inner and outer surfaces of metal machines and containers, the inner walls of boilers, and the like. Detergents made of inorganic alkali salts such as carbonates and silicates and higher alcohol-based nonionic surfactants have traditionally been used as detergents in various fields, and detergents containing percarbonate have recently been used as well. ing. However, conventional cleaning agents generally remove simple stains, but are not effective against tough stains. Among them, those containing percarbonate have a strong effect on tough stains, but they are highly alkaline. Due to its oxidizing properties, it corroded metals and caused wear and tear on the objects it was used for. In addition, anionic and nonionic surfactants are generally added to abrasives, polishing sand, etc. to enhance cleaning power, but especially when used for tableware and baths, it is important to ensure that they are biodegradable and safe. Nothing that is fully satisfactory in terms of sex has yet to be developed. The inventors of the present invention have conducted extensive research to overcome the drawbacks of these conventional cleaning agents, and have developed a cleaning composition in which a surfactant component consisting of an amide nonionic surfactant and a metal soap is added to sodium percarbonate. The present inventors have discovered that a product can satisfy the purpose, and based on this knowledge, they have accomplished the present invention. That is, the present invention provides an alkaline cleaning composition characterized by containing 30 to 80% by weight of sodium percarbonate, 3 to 10% by weight of an amide nonionic surfactant, and 0.5 to 3.0% by weight of metal soap. It is something to do. As the amide nonionic surfactant used in the cleaning composition of the present invention, there is an oxyfatty acid amide polyoxyalkylene ether represented by the following general formula. (In the formula, R is a hydrocarbon group having 7 to 21 carbon atoms,
R' is a hydrogen atom or a lower alkyl group such as a methyl group or an ethyl group, Y is an integer from 1 to 50, and Z is an integer from 1 to 5.
). This oxyfatty acid amide polyoxyalkylene ether is a mono- or polyoxyfatty acid ester having a hydroxyl group such as castor oil, hydrogenated castor oil, methyl ricinoleate, 12-oxystearate, tetraoxystearate, etc., and ethylene oxide, propylene oxide. The oxyfatty acid ester polyoxyalkylene ether obtained by addition reaction with an alkylene oxide such as is further ammoniolyzed with liquid ammonium, or the above oxyfatty acid ester is ammoniolyzed to form an oxyfatty acid amide, and then alkylene oxide is added to this. It can be obtained by a method such as an addition reaction. Specific examples of this include, for example, castor oil fatty acid amide polyoxyethylene ether,
Examples include ricinoleic acid amide polyoxypropylene ether and hydrogenated castor oil fatty acid amide polyoxyethylene ether. In the composition of the present invention, a small amount of the oxyfatty acid amide polyoxyalkylene ether/metal soap system is sufficient, for example, 5 to 20% by weight in the composition. In the composition of the present invention, the metal compound has the general formula (R″COO) _x M (wherein R″ is an aliphatic residue such as oleyl or hydroxy oil, and M is Na, K, Li, Ca, A metal such as Mg (x is an integer corresponding to the valence number of the metal M) is used. Such metal soaps include saturated, unsaturated, hydroxy, straight chain, and branched chain fatty acids having 5 to 21 carbon atoms, and metal salts such as naphthyronic acid and rosin acid.
All of these substances are conventionally known substances. In this case, the metals are from the periodic table ~
Various valent metals may be used, but from the viewpoint of toxicity, low toxicity metals such as lithium, calcium, magnesium, etc. are preferred. By adding this metal soap, the effects of the amide nonionic surfactant, such as detergency, toxicity, and antirust ability, are further improved. In this case, the preferred addition ratio is 1 to 1/100 of the weight of the amide nonionic surfactant. In the composition of the present invention, an amide nonionic surfactant with low toxicity is used. For example, castor oil fatty acid amide polyoxyethylene ether (7 mol adduct) has an extremely low LD50 of 20 ml/Kg (mouse/acute toxicity). It is toxic. Furthermore, in a mixed system with metal soap, for example, the molar ratio of the above ether and castor oil fatty acid magnesium is 5:1.
For a mixture of , the toxicity is even lower, with an LD50 of 22ml/Kg. Also, in skin irritation and skin hypersensitivity tests, for example, the above surfactants and their mixtures with metal soaps have almost no irritation.
It has been determined to be equivalent to Tween20. In addition, it is less hemolytic and biodegradable than castor oil fatty acid amide polyoxyethylene ether (7mol adduct).
96.7% of its castor oil fatty acid magnesium:
Even a mixture with a molar ratio of 1 is extremely good at 97.0%. Further, the cleaning composition of the present invention may contain an appropriate chelating agent. This chelating agent is
(1) Polybasic carboxylic acids and their salts (2) Oxymonocarboxylic acids and their salts (3) Imido sulfates (4) Polyphosphates (5) Amines (6) Amino acids and their salts (7) Polyaminocarboxylic acids Examples include salts (8) sulfur-containing carboxylates. The polybasic carboxylic acids and their salts mentioned in (1) above include chain and cyclic di- to hexabasic acids. Specific examples include dibasic carboxylic acids such as malonic acid, tartaric acid, malic acid, maleic acid, fumaric acid, and oxadipropionic acid, and tribasic acids such as nitrilotriacetic acid, citric acid, and O-(carboxymethyl)tartaric acid. There are carboxylic acids. Also, oxadisuccinic acid, 2,5-dioxa-1,3,4,6
Examples include mono- or tetrasodium salts or potassium salts of hexanetetracarboxylic acid, aromatic tetrabasic carboxylic acids such as benzenetetracarboxylic acid, or alicyclic tetrabasic carboxylic acids such as cyclohexanetetracarboxylic acid. Basic carboxylic acids and their alkali metal salts, 1, 2,
3,4,5,6-hexanehexacarboxylic acid, benzenehexacarboxylic acid, 2,5-dioxa-
Examples include hexabasic carboxylic acids such as 1,1,3,4,6,6-hexanehexacarboxylic acid and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid and their alkali metal salts. can.
These polybasic carboxylic acids and their salts can be used alone or in combination of two or more. In addition, the oxymonocarboxylic acids and their salts in (2) above include gluconic acid, lactic acid, glycolic acid,
These include hydroacrylic acid, β-oxybutyric acid, and their salts. Examples of the imido sulfate in (3) above include:
Imidobis sulfates (neutral) such as (NH ₄ SO ₃ ) ₂ NH, (NaSO ₃ ) ₂ NH・2H ₂ O, (NH ₄ SO ₃ ) ₂ NNH ₄・H ₂ O,
Examples include imidobis sulfates (basic) such as (NaSO ₃ ) ₂ NNa·H ₂ O and (NaSO ₃ ) ₂ NNa·12H ₂ O. This imide sulfate has a >NH bond in its molecule and can be used in various surfactant compositions as a new type of builder that is chemically structurally different from conventional chelating builders. In the present invention, this imidosulfate exhibits the effect as a builder similar to the above-mentioned compounds (1) and (2) at the same time as making the metal soap water-soluble. That is, the aqueous solution is neutral or weakly alkaline, and the trisodium salt has excellent alkaline buffering power and sufficient water solubility, and it also has low toxicity, which has recently become an increasingly essential characteristic for builders. Acute to chronic toxicity, skin irritation, fish toxicity, hemolysis,
Condensability is extremely low. This substance can also be easily produced from sulfur and ammonia, and its price is low. Furthermore, the nitrogen content is particularly low in the case of alkali metal salts, and the sulfur content is high in some substances. Furthermore, this salt has the advantage of being less corrosive to copper, iron, etc. Therefore, this imidosulfate salt has extremely high practical formulation value for the composition of the present invention. Examples of the polyphosphate in (4) above include sodium, potassium, and lithium salts of pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, and hexametaphosphoric acid, but generally sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, Sodium tetrapolyphosphate, sodium hexametaphosphate, etc. are used. These materials may be used alone or in the form of a mixture. Examples of the amine (5) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, triethanolamine, and monoethanolamine. Further, examples of the amino acids and salts thereof in (6) include lysine, taurine, glutamic acid, alanine, phenylalanine, and salts thereof. Furthermore, examples of the polyaminocarboxylic acid and its salt in (7) include nitrilotriacetic acid, 1,2-
Diaminocyclohexanetetraacetic acid, ethylene glycol bis(β-aminoethyl ether)tetraacetic acid,
Examples include ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid and their salts,
As the sulfur-containing carboxylic acid and its salt in (8) above,
Examples include xanthic acid and its salts. In the composition of the present invention, in order to mix with percarbonate, the amide nonionic surfactant, metal soap, and chelating agent must be water-soluble, have low hygroscopicity, and are usually solid (powder or granule). Preferably. Therefore, it is preferable to form a solid by appropriately combining a metal soap and a chelating agent, such as a melt of an alkaline earth metal soap and a solid chelating agent. The content of sodium percarbonate in the cleaning composition of the present invention is determined in the range of 30 to 80% by weight. If the amount is larger than this range, the alkalinity will be too strong, promoting corrosion or reducing the stability of the sample during long-term storage, while if the amount is smaller than this range, the effect of oxidation will be insufficient. In addition, the amount of the amide nonionic surfactant is preferably set in the range of 3% to 10% by weight; if the amount exceeds this, granular samples may be obtained due to hygroscopicity and low melting point. It becomes difficult. The amount of metal soap used in the cleaning composition of the present invention usually ranges from 0.1 to 15% by weight. If this amount is less than 0.1% by weight, the effects of rust prevention and penetration will be somewhat insufficient, and if it exceeds 15% by weight, the amount of activator or chelating agent to dissolve it will be large, making it relatively difficult for other As the amount of ingredients decreases, the overall effect gradually decreases. The amount of metal soap added is preferably 0.5 to 3.0% by weight from the viewpoint of hygroscopicity, melting point, etc. when used together with an amide nonionic surfactant. Further, when a chelating agent is added to sodium percarbonate together with a metal soap as a surface-active component, the amount of the chelating agent in the cleaning composition is preferably in the range of 5 to 60% by weight. In this case, if the amount of the chelating agent is less than the lower limit of the above range, the effect will be insufficient because the amount of dissolved metal soap and the absolute amount of the chelating agent that does not participate in dissolution will be small, and if the amount exceeds the upper limit, the effect will be insufficient. As the content decreases, the effectiveness decreases. The alkaline cleaning composition of the present invention may contain a dye or a pigment to serve as a cleaning liquid indicator, and the amount thereof is usually in the range of 0.01 to 0.5% by weight. In addition, sodium silicate, sulfate, sodium carbonate, borates such as CMC (carboxymethyl cellulose) perborate, aluminosilicates, etc. may be added to the alkaline cleaning composition of the present invention as appropriate. Good too. Also, diatomaceous earth,
Polishing and cleaning may be performed by adding solid powder such as bentonite or clay. In the alkaline cleaning composition of the present invention, percarbonate oxidizes and decomposes stains such as grime firmly adhered to metal surfaces etc. with its strong arranging and foaming effects. Moreover, the amide nonionic surfactant imparts surface activity to the detergent composition. That is, it penetrates into the inside of dirt, etc. and swells, thereby promoting the peeling, dispersion, and foaming effects of the cleaning agent. Furthermore, the effect of this amide nonionic surfactant is promoted by adding metal soap. On the other hand, this metal soap can impart antibacterial and antirust properties to the cleaning agent. For this reason, the target metals for which the cleaning composition of the present invention is used include:
Aluminum, copper, iron, etc. are easily attacked by ordinary inorganic salts and alkali compounds, causing discoloration and pitting corrosion.
I was able to solve those problems. Furthermore, by adding a chelating agent, calcium salts in dirt are chelated, dissolved, peeled off, or dispersed.
Can be removed. Of these, trisodium imidobis sulfate also exhibits a rust-preventing effect on copper and iron. By using the alkaline cleaning agent composition of the present invention, it is possible to exert a strong cleaning effect even on firmly adhered dirt, and it is also possible to use the alkaline cleaning agent that corrodes metals, unlike conventional alkaline cleaning agents. This has an excellent effect in that there is no risk of damaging the object. Furthermore, as mentioned above, since a metal soap is used in combination, it is possible to impart anti-corrosion ability and furthermore, it can be made antibacterial. Furthermore, the alkaline cleaning composition of the present invention basically comprises:
It has low toxicity. Therefore, the alkaline cleaning composition of the present invention can remove organic and inorganic calcium, magnesium compounds, proteins, animals and plants, and mineral oils stuck to the inner and outer surfaces of metal machines and containers, the inner walls of boilers, tiles, bathtubs, etc. It is suitable for use in cleaning and removing dirt and deposits consisting of carbohydrates and the like. In this case, it is usually used as an aqueous solution with a concentration of 0.1 to 5.0% by weight, but the concentration can be changed as appropriate depending on the usage temperature and application. Next, the present invention will be explained in more detail based on examples. Note that each test in the examples was conducted according to the following method. 1 Cleaning power 1 Preparation of test pieces Copper plate and aluminum plate (size 8 x 40 mm,
Artificial dirt with the following composition was measured by weighing (numbered) and heating it to about 50℃, then heated to about 80℃.
0.15g is dropped with a dropper and spread over the surface and left at room temperature. Artificial dirt (parts by weight) Palmitic acid 20 Cetyl alcohol 20 Cholesterin 15 Tripalmitin 15 Solid paraffin 15 Calcium oleate 15 Carbon black 0.1 100.1 2 Measurement method 4 g of sample solution with a concentration of 0.5% by weight was placed in a 12 x 65 mm test tube with a lid. Shake at a rate of once/second at an angle of about 15° from the horizontal for 30 minutes to 2 hours at 40℃ and 45℃, measure the weight change of the amount of dirt attached, and visually observe at the same time. Ivy. 2 Rust prevention power Pour approximately 4 ml of the sample aqueous solution into a test tube with a lid (same as in 1 above), and add a test metal piece (4 x 20 x 0.8 mm) to it.
(metal plate) and visually observe changes in the metal piece after 24 hours in a 90°C hot bath. The metal pieces for the corrosion test at this time were as follows.

[Table] 3 Antibacterial power Each sample aqueous solution was placed in a water sampler (manufactured by Nippon Millipore Limited), the culture medium was removed after 30 seconds, the solution was strained and exposed to the outside air for 1 hour.
The plate was left standing at 38°C for 1 to 3 days, and the number of colonies generated was measured. Example 1 Samples Nos. 1 to 24 having the compositions shown in Table 2 were prepared. Table 3 shows the results of a cleaning test performed on this sample. Table 4 shows the results of the rust prevention ability test.

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[Table] From the results of experiments No. 3, 4, and 5 in Table 3 above,
It can be seen that the composition of the present invention exhibits a significantly superior dirt removal rate to the cleaning compositions of Experiment Nos. 1, 2, 6, 7, and 8. Furthermore, by comparing Experiment No. 2 with Experiment 3, it can be seen that the addition of castor oil fatty acid magnesium (metal soap) significantly improves the stain removal rate. Furthermore, by comparing Experiment Nos. 3 and 4, it can be seen that trisodium imidobis sulfate further improves the stain removal rate. On the other hand, from the results in Table 4, in the case of the present invention (experimental
No. 2, 3, 4) It can be seen that it has an excellent rust prevention effect. Furthermore, the stain removal rates of Experiments Nos. 3, 4, and 24 in Table 3 were compared to Experiment No. 21 (combination of amide nonionic surfactant and metal soap) or Experiment No. 1 or 22 (sodium percarbonate). It can be seen that the composition containing the three components of the present invention has a cleaning effect significantly superior to that expected from Experiment Nos. 1, 21 and 22. Example 2 Various aqueous solutions shown in Table 5 were prepared, and using sample aqueous solutions 1 to 6, an antibacterial activity test was conducted according to the method described above. The results are shown in Table 6.

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[Table] The results in this table show that although trends differ slightly depending on the type of microorganism, sodium carbonate is generally less effective, and sodium percarbonate is somewhat better, but not sufficient. In the case of adding a metal mixture, the effect was fully exhibited. It can be seen that although TSIS in No. 6 has almost no antibacterial properties itself, it does not inhibit the effect of the compound.

Claims (1)

[Claims] 1 30-80% by weight of sodium percarbonate, 3-10% by weight of amide nonionic surfactant, and metal soap
An alkaline cleaning composition characterized by containing 0.5 to 3.0% by weight.