JPS5941677B2 - Alkaline detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for removing inorganic and
The present invention relates to an alkaline detergent composition suitable for cleaning and removing organic dirt and deposits.

Conventionally, inorganic alkali salts such as carbonates and silicates and LA
Cleaning agents made of S higher alcohol-based nonionic surfactants are used as cleaning agents in various fields.

However, conventional cleaning agents are generally effective at removing simple stains, but are less effective against stubborn stains, and strongly alkaline cleaning agents are effective to some extent, but they can be used to clean metals, especially aluminum,
It has the significant drawback of corroding copper and other materials and damaging the object to be cleaned. Furthermore, there are degreasing agents for treating chemical conversion coatings that mainly contain oils and fats attached to metal surfaces, but many of them contain hydrochloric acid, sulfuric acid, sulfamic acid, etc., and remove scales attached to metal surfaces. Although it is effective for removal, it has the drawback that it is a strong acid and can also dissolve a considerable amount of the metal surface, damaging the skin. On the other hand, alkali metal salts such as citric acid, succinic acid, and malic acid are used as chelating scale removers, but in this case, the metal surface dissolves less than those containing hydrochloric acid or sulfuric acid. If used regularly, it can cause considerable damage to the scalp.

Also, the scale removal effect is inferior to those of those inorganic acids. Additionally, in general, abrasives, polishing sand, etc. with anionic or nonionic surfactants added are used to enhance cleaning power, but especially for tableware,
When considering household use such as bathing, there are few products that are satisfactory in terms of cleanability, biodegradability, and safety notes.

As a result of intensive research to overcome the drawbacks of these conventional detergents, the present inventors added a chelating agent to metal soap, and added a chelating agent selected from sodium silicate, sodium borate, sodium carbonate, etc. A composition comprising one or more of these is extremely effective in removing scale adhering to metal surfaces, and is also extremely resistant to damage to metal surfaces, and can also be effectively used on plastic and other surfaces. The present invention was developed based on this finding. That is, in the present invention, 0.1 to 20% by weight of Ll or a valent metal, and 5% by weight of a chelating agent.
~60% by weight, and at least one selected from alkali silicate salts, alkali borate salts, and alkali carbonate salts2
The present invention provides a water-soluble alkaline detergent composition characterized by comprising 0 to 97% by weight.

In the composition of the present invention, the metal set has the general formula (RCOO)NM (wherein, R is an aliphatic residue such as oleyl or hydroxy oil, and M is Ll or a metal with a valence (Mg, Ca).
, Zn, Mn, Fe, CO, Ni, etc.), n is an integer corresponding to the valence number of the metal M).

Such metal sets include saturated carbon atoms with 5 to 21 carbon atoms,
Included are unsaturated, hydroxy, straight chain, branched chain fatty acids and metal salts of naphthenic acids, rosin acids, etc., all of which are conventionally known substances. In addition, the chelating agents used in the present invention include (1) polybasic carboxylic acids and their salts, (2) oxymonocarboxylic acids and their salts, (3) imido sulfates, and (4) polyphosphates.
(5) Amines (6) Amino acids and their salts (7) Polyaminocarboxylic acid salts (8) Sulfur-containing carboxylic acid salts.

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, oxadipropionic acid, nitrilotriacetic acid, citric acid, O
- Tribasic carboxylic acids such as (carboxymethyl)tartaric acid. Also, oxadisuccinic acid, 2,5-dioxa-
Examples include mono- or tetrasodium salts or potassium salts of 1,3,4,6-hexanetetracarboxylic acid, and aromatic tetrabasic carboxylic acids such as benzenetetracarboxylic acid, or cyclohexanetetracarboxylic acid. Alicyclic tetrabasic carboxylic acids and their alkali metal salts such as 1,2,3,4,5,6-hexanehexacarboxylic acid, benzenehexacarboxylic acid, 2,5-
Six-base carboxylic acids such as dioxa-1,1,3,4,6,6-hexanehexacarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid and their alkali metal salts. I can give it to you. These polybasic/carboxylic acids and their salts can be used alone or in combination of two or more. Further, the oxymonocarboxylic acids and salts thereof in (2) above include gluconic acid, lactic acid, glycolic acid, hydroacrylic acid, β-oxybutyric acid, and salts thereof.

As the imido sulfate of (3) above, for example, (NH
4SO3)2NH1 (NaSO3)2NH・2H20 and other imidobis sulfates (neutral), (NlI4SO3)2
NNHcH20, (NaSO3)2NNa-H2O, (
Examples include imidobis sulfates (basic) such as NaSO3)2NNa.12H20.

This imidosulfate has an NH bond in its molecule,
It can be used as a new type of chelating agent. In terms of low toxicity, it has no acute or chronic toxicity, skin irritation, fish toxicity,
Hemolysis and 11 concentration surnames are 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 an alkali metal salt, and the sulfur content is high. Furthermore, this salt has a feature of low corrosion resistance against 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, bentaethylenehexamine, triethanolamine, and monoethanolamine. Examples of the amino acids and salts thereof in (6) include glycine, taurine, glutamic acid, alanine, phenylalanine, and salts thereof.

Furthermore, examples of the polyaminocarboxylic acids and salts thereof in (7) include nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid, ethylene glycol bis(β-aminoethylethenolytetraacetic acid, ethylenediaminetetraacetic acid,
Examples of the sulfur-containing carboxylic acid and salts thereof (8) include xanthogesic acid and salts thereof. In the present invention, especially when the object to be cleaned is a food container, a biological container, etc., or when the safety of detergent users and the low pollution of waste liquid are issues, a composition of low toxicity can be used.

In such cases, calcium,
Magnesium and lithium are preferred. Particularly preferred chelating agents are salts of malic acid, succinic acid, citric acid, etc., imidosulfates, alkylolamines, aminocarboxylic acid salts, and the like. The alkali silicate used in the present invention has the general formula:
Sodium, potassium, lithium, ammonium x:
1-10y: 1-10z: O-10), and for example, sodium metasilicate, water glass, etc. are usually used.

Alkaline boric acid salt is M'4B207・1H20 (M':
Sodium, potassium, lithium, ammonium, l:
1 to 5), and the alkali carbonate is M'2C03.
It is represented by MH2O (M!: sodium, potassium, lithium, ammonium m: 1-10). All of these inorganic salts have a low toxicity range but a high pH.

In the case of dirt that is not extremely strong, when the target metal is aluminum, etc., or when it is desired to avoid skin irritation, acetic acid, lactic acid, citric acid, boric acid, etc. can be added to the composition of the present invention to adjust the pH. You may use it by lowering it to 8-10. Furthermore, the composition of the present invention may optionally contain various anionic, non-ionic and amphoteric surfactants, redeposition inhibitors such as CMC (carpoxymethylcellulose), urea, sodium toluenesulfonate, etc. By adding hydroponic agents, etc., it is possible to improve the surrounding capacity and reduce costs.

Furthermore, a dye or pigment may be added as an indicator of the cleaning liquid, and the amount thereof is usually 0.01 to 0.5% by weight.
A range of is good.

In addition, solid powders such as aluminosilicate, diatomaceous earth, bentonite, and clay may be added to the alkaline cleaning composition of the present invention for polishing and cleaning.

Aluminosilicate is PAl2O3・QNa2O・RH2
It is represented by O (p: 1-101q: 1-101r: 1-10). All of these substances have appropriate hardness and adsorption power and ion exchange power for various substances, and have a cleaning aiding effect by mechanically removing and softening adhered dirt. The particle size is suitably 0.05 to 20/t, preferably 0.05/t.
It is 2 to 10μ. There is no particular limit to the amount of surfactant added, but it is usually 1 to 100% to the sum of metal soap and chelating agent.
1001 is preferably added in an amount of 5 to 30% by weight. Examples of such surfactants include the following. (1) Examples of the anionic surfactant include commonly used ones such as alkyl sodium sulfate, sodium alkylbenzene sulfonate, sodium long-chain α-olefin sulfonate, and sodium alkyl polyoxyalkylene ether sulfate.

(2) Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene long chain fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, nonylphenyl polyoxyethylene ether, long chain fatty acid alkylol amides, polyoxyethylene long chain alkyl amides, etc.

(3) Examples of the cationic surfactant include dodecyltrimethylammonium chloride, tetradecyldiethylolbenzylammonium nitrate, tetraalkylammonium salt, N-alkylpyridinium halide,
Alkylamine salts, etc.

(4) Examples of amphoteric surfactants include alkylimidazolinium betaine, alkylglycine betaine, alkylaminoalkyl sulfuric acid, alkyldiethylenetriaminoacetate, alkylaminoalkylsulfonic acid, and N-dodecylaminomethylphosphoric acid.

These surfactants can be used alone or as a mixture.

Low-toxicity products are particularly preferred for use in kitchen utensils, baths, food industry, etc. For example, nonionic amide surfactants are all low-toxic, and LD of castor oil fatty acid amide polyoxyethylene ether (7m01 adduct)
5O has an extremely low toxicity of 20ml/K9 (mice/rapid toxicity). It also has low hemolysis and skin irritation, and has good biodegradability of 96.7%. The composition of the present invention is a solid (
It can be in the form of powder or granules), an aqueous solution, or an aqueous dispersion.

When a surfactant component is used as an auxiliary agent in a solid product, one with a high melting point is desirable. The amount of metal soap used in the cleaning composition of the present invention usually ranges from 0.1 to 20% by weight.

If this amount is less than 0.1% by weight, the rust prevention, penetration, and cleaning effects will be somewhat insufficient, and if it exceeds 20% by weight, the amount of active agent or chelating agent to dissolve it will be large. As the amount of other ingredients decreases relatively, the overall effect gradually decreases. In addition, since it is rather expensive, it is not economical for the purpose of use. The concentration of this metal soap is preferably in the range of 0.1 to 30% by weight when used together with a chelating agent. Further, the amount of the chelating agent in the detergent composition prepared by adding a metal soap as a surfactant component and a chelating agent to an alkali salt is in the range of 5 to 60% by weight. In this case, if the amount of 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 chelating agent that does not participate in dissolution will be small, and if it exceeds the upper limit, the content of alkali salt will be too low. As a result, the alkalinity as a whole decreases, which is also economically disadvantageous. The total amount of metal soap and chelating agent in the alkaline detergent composition is 3 to 80% by weight, preferably 5 to 50% by weight.

Therefore, the remaining 20 alkali salts selected from alkali silicate salts, alkali borate salts, and alkali carbonate salts
It ranges from 97% by weight. The composition of the present invention is generally used at a concentration of 0.01 to 5% by weight as an aqueous solution.

It is used at a low concentration if it is used for a long period of time, including its scale prevention effect, and at a high concentration when it is used to clean stubborn dirt in a short period of time. Any method of use such as immersion, circulation, spraying, or hand wiping is possible. The operating temperature can range from room temperature to 100°C, but generally the higher the temperature, the greater the cleaning effect. In the case of a dispersion system to which clay or the like is added, a 20 to 50% by weight aqueous dispersion system is used.

In the alkaline detergent composition of the present invention, the alkaline salt has a strong saponification effect to saponify and decompose or water-solubilize stains such as dirt firmly attached to metal surfaces.

The metal chelating agent formulation also imparts a strong surface activity to the detergent composition. That is, it penetrates into the inside of dirt, etc. and swells to promote the peeling, dispersion, and foaming effects of the cleaning agent, and furthermore, through its chelating action, it captures and dissolves calcium salts, which are the main components of scale and other substances. On the other hand, this metal soap can impart antibacterial protection and anti-rust properties to the cleaning agent.

For this reason, target metals for which the cleaning composition of the present invention is used include aluminum, copper, iron, etc., and these are easily attacked by ordinary inorganic salts and alkali compounds, causing discoloration and pitting corrosion. By blending this metal soap in the appropriate proportions as described above, these problems could be solved. Furthermore, by adding a chelating agent, calcium salts and the like in the dirt can be chelated and dissolved, peeled off, dispersed, and removed. On the other hand, trisodium imidobis sulfate also has a rust-preventing effect on copper and iron. In addition, when a metal soap and a chelating agent are used together, the metal soap acts as a surfactant and exhibits various effects such as penetration, dispersion, emulsification, rust prevention, and antibacterial properties. By using the alkaline detergent composition of the present invention, it is possible to exert a strong cleaning effect even on firmly adhered dirt, and it is also less effective than conventional alkaline detergents, which corrode metals. It has an excellent effect in that there is no risk of damaging the object to be used.

Furthermore, as mentioned above, if a metal soap is used in combination, it is possible to impart anti-corrosive properties and to provide an antibacterial enclosure. Moreover, the alkaline detergent compositions of the present invention have essentially low toxicity. Therefore, the alkaline detergent composition of the present invention can be used on the inner and outer surfaces of machines and containers made of metal, plastic, ceramics, wax, glass, etc., the inner walls of boilers, piping, water tanks, bathtubs, furniture, kitchen equipment, etc. It is suitable for use in cleaning and removing dirt and deposits consisting of inorganic and organic calcium, magnesium compounds, proteins, animal and vegetable oils, mineral oils, carbohydrates, etc.

In this case, it is usually used as an aqueous solution with a concentration of 0.1 to 50% 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) PH: Measured using a PH meter manufactured by Toa Denpa.

(2) Surface tension Measured using a Rigineuil surface tension meter. (3) Pour about 3 ml of sample solution (more than 15 m 71 liters in depth) into a penetrating beaker (10 ml), lightly place a test cloth (felt, 8 x 8 mT! L) on the liquid surface with tweezers, and submerge it from the liquid surface. Count the seconds until it sinks.

(4) Pour 2.09 g of sample solution into a test tube with lifting force lifter (12 x 65 mm), shake vertically for 25 CTrL/20 times/10 seconds, leave at room temperature, and measure the height of bubbles immediately and after 30 minutes. were measured and the average value was taken. ] The stability in the father's direction is expressed as 2;;:;π;=be100 (1).

(5) Dispersion force: Put about 3 ml of sample and about 3~ of carpon plaque into a test tube (same as in (2)), close the tube, and put 25C7rL
/20 times/10 seconds, and after 5 hours, the height (h) and turbidity of the dispersed layer were evaluated, and the average value was taken.

The evaluation criteria are as follows.

Cleaning power 1) Preparation of test piece 1 Measure the weight of a metal plate (0.8 x 8 x 40 mm with 1 number), heat it to about 50°C, and then add artificial dirt with the following composition heated to about 8°C. 0.159 is spread over the surface by dropping it with a spoonful and left at room temperature.

2 Artificial dirt 0.039 was applied to a metal plate (0.8 x 3 x 20 mm) in the same manner as in 1.

Artificial dirt is assumed to be organic dirt or scale, and contains typical organic matter and groundwater components and has a softening point of 7.
The above three types of compounds were selected as a composition that would have appropriate fluidity at 0 to 80°C, and the blending ratio was determined.

The types and specifications of the metal pieces used in Test 5 are as shown in Table 1. 2) Measurement method 1 Place the test piece in a test tube with a lid (φ 12 x 80 mm) and leave it standing upright for 3 days (step 1), then horizontally at an angle of about 15 for 1 h 145 at an amplitude of 1001 rL, 5 times in 10 seconds. It was shaken at °C (stage 2), then left standing for 27 days (stage 3), and changes in the amount of dirt attached were visually observed at each stage.

In the test, two test pieces were used for each sample, and the test pieces were left at room temperature (17
~22°C).

The evaluation criteria are as follows. 2. Place the test piece in a test tube with a lid (φ8 x 50Tn 1L) and leave it at room temperature (15-22℃).
After a certain period of time, changes in the amount of dirt attached were visually observed and evaluated.

(7) Rust prevention power After measuring the detergency of (6), the metal pieces were visually observed and evaluated.

The evaluation criteria are as follows.

Evaluation Surface condition: No change at all. Slight decrease in gloss, pitting formed in a very small area, slight staining in the solution. Change in level 4 increased slightly. Significant change. Rust appeared on about one-half of the surface. Significant change. However, the entire surface was covered with rust, and the solution significantly changed color or formed precipitates.A detergent composition was prepared with the composition shown in Table 2 of Examples, and then a detergency test, a rust prevention test, and a surface activity test were conducted. .

Test Example 1 Table 3 shows the results of cleaning stains on copper plates using various chelating agents, metal soaps, and inorganic alkali salt compounds.

Test pieces and measurement methods for detergency are (6) I)-1 and 2)-
1 was used for each. From the above results, the chelating agent is
Most of the cleaning power and rust prevention power are inferior, and the metal soap and chelating agent combination system (sample A6.5) is the most excellent. On the other hand, the inorganic salt blending system of the present invention
It is economical because the active ingredient exhibits almost the same effect at a lower concentration. That is, sample/F6. ll and 14 (use concentration 2
%), the active ingredient (Metal Setsuken +
chelating agent) respectively (16.4+1,6)XO. O
2=0.36(%, (21.4+25.0+1.6)×
0.02=0.96, sample waterfall 5 (use concentration 1%)
It is equivalent to or about 1/2 compared to (64.0+16.0)×0.010.80.

In particular, sample A6. It can be seen that ll, l4, and 5 are 0.032, 0.032, and 0.16 (1), respectively, and that in the case of sample waterfalls 11 and 14, it is sufficient to be about 1/5 of sample wash 5. Test Example 2 Table 4 shows the results of testing the cleaning power and rust prevention power of various chelating agents and compounds on steel, copper, and aluminum plates.

The test piece and measurement method were as described in (6) 1)-2 and 2)-2. From the above results, it can be seen that the cleanability and corrosivity vary considerably depending on the type of metal (Samples 1 to 4), but this combination system (Samples 13 and 14) is effective in a short period of time on average. It can be seen that this shows that Test Example 3 Table 5 shows the test results of the cleaning power and rust prevention power using various metal plate samples for various formulations and comparative substances consisting of sodium alkylbenzenesulfonate, inorganic salts, and chelating agents.

The test piece and measurement method were as described in (6)l)-2 and 2}-2. From the above results, the comparative substance (sample A6
．． 6), it can be seen that this formulation system (Samples Taki 7 to 12) exhibits excellent effects in both cleaning power and rust prevention power in most cases.

Test Example 4 Table 6 shows the results of measuring various surface activities for various chelating agents and formulations.

From the above results, it can be seen that the blended system of the present invention is excellent in various surface activities on average.

Claims (1)

[Claims] 1 Li or II-valent metal metal soap 0.1 to 20% by weight, chelating agent 5 to 60% by weight, and at least one selected from alkali silicates, alkali borates, and alkali carbonates20 97% by weight of a water-soluble alkaline detergent composition.