JPH0931493A - Cleaning agent for inorganic structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleaning agent for removing stains on concrete, stone, mortar, tile, etc., by using an aqueous solution containing phosphoric acid, formic acid, hydrochloric acid, etc., a fatty acid diethanol amide and a polyoxyalkylene alkyl ether as essential components. SOLUTION: This cleaning agent contains an aqueous solution containing (A) a mixed acid component produced by compounding (a) 100 pts.wt. of phosphoric acid with (b) 100-300 pts.wt. of formic acid and (c) 10-50 pts.wt. of hydrochloric acid and/or phytic acid, (B) 0.03-1wt.% (based on the component A) of a fatty acid diethanol amide, (C) 0.2-5wt.% of a polyoxyalkylene alkyl ether and preferably further (D) 5-40wt.% of ammonium chloride and/or ammonium sulfate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a structure made of an inorganic material such as concrete, stone, mortar, tile,
The present invention relates to a cleaning agent used to remove stains generated on the surface of structures such as outer walls and floors made of bricks and plaster.

[0002]

2. Description of the Related Art Generally, the surface of a structure exposed to the outside air such as the outer wall or floor of a building adheres to or adsorbs dust, rust, carbon (soot), oils, molds, algae, etc. floating in the outside air. It gradually becomes dirty as it breeds. In particular, in concrete and mortar structures, fouling occurs due to repeated chemical changes of themselves and repeated absorption and release of water. For example,
When rainwater seeps into concrete or mortar, calcium hydroxide elutes and reacts with carbon dioxide in the air on the surface to precipitate calcium carbonate, and at the seaside, magnesium chloride and magnesium sulfate contained in seawater droplets, Ammonium bicarbonate and the like combine with the lime content in concrete and mortar, and the product spreads on the surface, and both become dirt.

There are a chemical removal method and a physical removal method as means for removing dirt on the surface of a structure made of such an inorganic material. As the chemical removal method, a cleaning treatment with a cleaning agent containing ammonium acid fluoride as a main component has been widely used. Physical removal methods include high pressure or ultra high pressure water washing, high temperature water washing, steam washing,
Dry blast using sand and abrasives, wet blast using water and cleaning agents together with sand and abrasives, etc. are used.

[0004]

However, in the above-mentioned conventional cleaning treatment with a cleaning agent, in order to remove stubborn stains on outer walls, floors, etc., harmful ammonium acid fluoride has a high concentration of 18 to 30%. Since it uses the cleaning agent contained in, there is a risk that it may harm the human body and the surrounding environment due to its harmfulness, and has the drawback of eroding or discoloring the metal surface when there is a metal part in the cleaning part or the surrounding area, and It was necessary to carry out water curing for a long time as a pretreatment for the cleaning work. Further, in the above conventional physical removal methods, the surface layer of the structure is scraped off, which causes surface roughness along with this, and salts and white flowers (subflorescence) that are stably present under the surface layer are also generated. ) Was exposed to the surface to cause a rapid white bloom phenomenon, or exudation due to a water-soluble precipitate or a wet color.

In view of the above situation, the present invention is capable of exerting excellent cleaning / removing property against various stains accumulated on the surface of a structure for many years without causing surface roughness, and the cleaning operation is easy, Moreover, it is an object of the present invention to provide a cleaner for inorganic structures, which has higher safety and storage stability than conventional cleaners.

[0006]

In order to achieve the above object, the cleaning agent for an inorganic structure according to the invention of claim 1 comprises:
(A) phosphoric acid, (b) formic acid, (c) hydrochloric acid or / and phytic acid, (d) fatty acid diethanol amide, and (e) a polyoxyalkylene alkyl ether. is there.

Further, the invention of claim 2 is such that the cleaning agent for an inorganic structure of claim 1 contains (f) ammonium chloride or / and ammonium sulfate together with the components (a) to (e) as essential components. It was adopted.

According to a third aspect of the present invention, in the detergent for an inorganic structure according to the first or second aspect, (b) formic acid is 100 to 200 parts by weight, (c) is 100 parts by weight of phosphoric acid.
It employs a composition in which 10 to 50 parts by weight of hydrochloric acid or / and phytic acid are blended.

A fourth aspect of the present invention provides the detergent for inorganic structures according to the first to third aspects, wherein the mixed acid component comprises (a) phosphoric acid, (b) formic acid, and (c) hydrochloric acid or / and phytic acid. In contrast, (d) fatty acid diethanol amide was 0.0
3 to 1% by weight and (e) polyoxyalkylene alkyl ether in an amount of 0.2 to 5% by weight are adopted.

A fifth aspect of the present invention is the detergent for an inorganic structure according to the second to fourth aspects, wherein the mixed acid component comprises (a) phosphoric acid, (b) formic acid, and (c) hydrochloric acid or / and phytic acid. In contrast, (f) ammonium chloride or / and ammonium sulfate is contained in an amount of 5 to 40% by weight.

According to a sixth aspect of the invention, the fatty acid diethanolamide (d) in the detergent for inorganic structure according to the first to fifth aspects is a dehydration condensation reaction product of 1 mol of monocarboxylic acid and 2 mol of diethanolamine. : Type 2 fatty acid diethanol amide is adopted.

In a seventh aspect of the present invention, the (e) polyoxyalkylene alkyl ether in the detergent for inorganic structure according to the first to sixth aspects is a reaction product of a monoalcohol having 9 to 14 carbon atoms and polyethylene oxide. It is a polyoxyethylene alkyl ether having the following structure.

[0013]

Detailed structure and function of the invention: In the cleaning agent of the present invention, (a)
The mixed acid component consisting of phosphoric acid, (b) formic acid, and (c) hydrochloric acid or / and phytic acid exerts a strong dissolving power for various stains, and (d) fatty acid diethanolamide (e) and (e) which are surfactants. The combined use of polyoxyalkylene alkyl ether imparts high wettability and penetrability to the surface of the inorganic structure and facilitates the release of dirt from the surface, and thus dust accumulated on the surface of the inorganic structure such as concrete for many years, Excellent cleaning and removability is obtained for stubborn dirt mixed with rust, carbon (soot), oils and fats, mold, algae, etc., and chemical deposits and reactants. Therefore, even dirt that is difficult to remove can be reliably removed. Moreover, with this cleaning agent, there is almost no risk of damaging the human body or the surrounding environment, and pretreatment for cleaning can be performed with a hose as much as water washing, and the conventional long-time water curing before cleaning is unnecessary. There is an excellent advantage that the surface of the structure can be prevented from being rough.

Furthermore, according to the cleaning agent of the present invention in which (f) ammonium chloride or / and ammonium sulfate is blended with the above-mentioned components (a) to (e), even if a metal portion exists in the cleaning portion or its periphery, It is possible to obtain an excellent cleaning action on the surface for the inorganic structure described above without causing corrosion or discoloration of the metal surface.

In the cleaning agent of the present invention, the above (a) to
The acid component (c) does not provide good detergency even if any one or two components are lacking, and is particularly strong against stains that are difficult to remove with an ordinary acid detergent when the formic acid (b) is lacking. The solubility, which is an important advantage of the present invention, is lost, and the lack of phosphoric acid (a) tends to cause corrosion or discoloration of the metal surface. As the component (c), only one of hydrochloric acid and phytic acid may be used, or both may be used in combination. In addition, phytic acid is also called mesosohexaphosphoric acid (chemical formula ... C ₆ H ₁₈ O ₂₄ P ₆ ).
-A hexaphosphoric acid ester of inositol, which has a very strong chelating action, and improves the detergency by forming a chelated product by combining with the metal existing in the surface layer of the body to be cleaned. It has a function.

Therefore, the mixing ratio of these acid components is
For 100 parts by weight of phosphoric acid in (a), 1 part of formic acid in (b) is added.
A range of 0 to 300 parts by weight and 10 to 50 parts by weight of (c) hydrochloric acid or / and phytic acid is preferable. Outside this range, the detergency is reduced and the structure surface is rough and corrosive to metals. Other problems such as Further, since the formic acid component (b) exhibits a strong solubility for stains that are difficult to remove with a normal acidic detergent as described above, it accounts for 50 to 70% by weight of the total amount of the acid component. A range is recommended.

The fatty acid diethanol amide (d) is not particularly limited, but 1: 2 type fatty acid diethanol amide is preferable. That is, this 1: 2 type fatty acid diethanol amide, as shown in the following reaction formula,
It is obtained by dehydration condensation of 1 mol of a monocarboxylic acid such as lauric acid and coconut oil fatty acid and 2 mol of diethanolamine in a nitrogen stream while stirring under heating, and an equimolar reaction product of monocarboxylic acid and diethanolamine. Compared with the 1: 1 type fatty acid diethanol amide, which has the advantage, there is an advantage that better wettability can be imparted to the surface of an inorganic structure such as concrete.

[0018]

(E) As the polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether,
Although polyoxypropylene alkyl ether, poly (oxyethylene-oxypropylene) alkyl ether and the like can be used, polyoxyethylene alkyl ether composed of a reaction product of monoalcohol and polyethylene oxide is preferable as shown in the following reaction formula, Among them, those in which R ₂ in the following general formula is an alkyl group having 9 to 14 carbon atoms and n is an integer of 9 to 12 are particularly preferable.

[0020]

The blending amount of (d) fatty acid diethanol amide and (e) polyoxyalkylene alkyl ether in the detergent is based on the mixed acid components (a) to (c).
The former component (d) is 0.03 to 1% by weight, and the latter (e) is
The content of the component is preferably in the range of 0.2 to 5% by weight, and if both are too small, good wettability and penetrability to the surface of the inorganic structure such as concrete cannot be imparted, and conversely if too much, excessive foaming occurs. However, there is a problem that it takes time to rinse. Further, even when one of these components (d) and (e) is lacking, the above-mentioned good wettability and permeability cannot be imparted.

The cleaning agent for an inorganic structure of the present invention is in the form of an aqueous solution containing the above-mentioned components (a) to (e) as essential components, but as described above, it is (f) together with the components (a) to (e). )
A structure containing ammonium chloride and / or ammonium sulfate is more preferable. This (f) component is (a)-(c)
It has a function of effectively suppressing the corrosiveness of the mixed acid with respect to metal, and the compounding amount in the detergent is from the above (a) to
The range of 5 to 40% by weight is preferable with respect to the mixed acid component of (c), and if it is too small, the above corrosion inhibiting function becomes insufficient,
On the contrary, if the amount is too large, there is a problem that the detergency is deteriorated.

In the case of cleaning with the cleaning agent for an inorganic structure of the present invention, it is not necessary to carry out water curing for a long time as in the conventional case as a pretreatment, and preferably, the surface to be cleaned is simply washed with water by a hose or the like. Then, the cleaning agent may be applied or showered, simple brushing may be added to remove stains, and finally water cleaning may be performed. However, this cleaning target is various inorganic structures such as outer walls and floors using various inorganic materials such as concrete, stone, mortar, tiles, bricks, plaster, etc. Even if it is present, it does not matter, and particularly in the case of the detergent containing the component (f), it can be applied to a portion exposed to a corrosive metal such as steel without any support. In addition, the cleaning agent of the present invention does not cause a change in composition even after a long period of time after preparation, has almost no decrease in cleaning power over time, and is extremely excellent in storage stability.

[0024]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples.

Examples 1-5, Comparative Examples 1-10 Phosphoric acid, formic acid, hydrochloric acid, phytic acid, ammonium chloride,
1: 2 type lauric acid diethanol amide, polyoxyethylene lauryl ether (n in the above-mentioned general formula I is 9 to 12 parts by weight shown in the following Table 1 is dissolved in water to make the total amount 100 parts by weight, A detergent was prepared.

[0026]

[Table 1]

The cleaning agents of these Examples and Comparative Examples were used to wash the concrete outer wall surface of the building, the brick surface, the tile surface, the stone surface, the mortar surface, and the plaster surface, and the cleaning property was tested. The results are shown in Table 2 below. In addition, about 1 to 2 liters / m ² of water is washed with a hose on the surface to be cleaned.
After pouring at a rate of 1 to wash with water, apply a cleaning agent at a rate of 100 to 200 g / m ² using a roller, brush with a brush, and finally with a hose at a rate of approximately 1 to 2 liters / m ² . It was performed by pouring in and washing with water. In addition,
The condition and evaluation of the surface to be cleaned are as follows.

Outer wall surface of concrete: darkening and rust-like substances are generated due to long-term weathering. Brick surface: The surface is white and dirty. Tile surface: Blackened spots. Stone surface: Stain-like state. Mortar surface: A state in which a black object spreads over the entire surface. Stucco surface: Stain-like state.

[Evaluation of Detergency] A ... The stain was completely removed. B: A little dirt remained. C: Remarkable stain remained. D: Dirt was hardly removed.

Next, in order to investigate the influence of each of the cleaning agents of the above-mentioned Examples and Comparative Examples on the metal surface, a stainless steel plate, a rolled iron steel plate, a brass plate, and a copper plate were added to the cleaning agent, respectively.
After dipping for a minute, it was taken out and the state of the plate surface was observed, and the results shown in Table 2 below were obtained. The evaluation was made into the following four stages.

[Evaluation of Effect on Metal Surface] ⊙: No change at all. ◯ ... Slightly discolored. B: Remarkable discoloration was observed. X: Corrosion on the surface was observed.

[0032]

[Table 2]

From the results shown in Table 2, the cleaning agent of the present invention is very effective for the stubbornly soiled surface of the structures made of various inorganic materials such as concrete, stone, mortar, tile, brick and plaster. Excellent cleaning power, especially (f)
It can be seen that the compositions containing the components ammonium chloride or ammonium sulfate (Examples 1 to 4) can reliably prevent the corrosion and discoloration of the metal surfaces of various materials. On the other hand, a conventional cleaning agent containing hydrofluoric acid as a main component (Comparative Examples 6 to 10)
So, if the concentration of hydrofluoric acid is low, a sufficient cleaning effect cannot be obtained, and if the concentration is increased by ignoring the problem of harmfulness, the cleaning effect is good but the metal surface may be attacked. it is obvious. Therefore, among the three components of (a) phosphoric acid, (b) formic acid, (c) hydrochloric acid and / or phytic acid,
The composition lacking one (Comparative Examples 1 to 3) has insufficient detergency, and particularly when (a) does not contain phosphoric acid (Comparative Example 2), even if (f) ammonium chloride is contained, rolled steel sheet, There is a problem that discoloration of the surface of a brass plate, a copper plate, etc. occurs, and a composition lacking one of (e) fatty acid diethanolamide and (f) polyoxyalkylene alkyl ether (Comparative Examples 5 and 5) results in insufficient cleaning. I understand.

[0034]

According to the invention of claim 1, as a cleaning agent for an inorganic structure, various inorganic materials such as outer walls and floors using various inorganic materials such as concrete, stone, mortar, tiles, bricks and plaster. It can exhibit excellent cleaning and removal properties against various dirt accumulated on the surface of the structure for many years without causing surface roughness, and is easy to clean, and is more safe than conventional cleaning agents. It is provided with high cost and excellent storage stability.

According to the second aspect of the present invention, as the above-mentioned cleaning agent for inorganic structures, even if the cleaning portion or the peripheral portion thereof has a metal portion, it does not corrode or deteriorate.
The thing which can exhibit the said outstanding washing | cleaning removability is provided.

According to the third aspect of the present invention, as the above-mentioned cleaning agent for an inorganic structure, particularly excellent cleaning properties and stubborn dirt can be surely removed, and surface roughness can be surely prevented.
A material that is less corrosive to metals is provided.

According to the fourth aspect of the present invention, the above-mentioned detergent for inorganic structure has good wettability and penetrability on the surface to be washed, and thus can exhibit more excellent detergency. It is provided that does not cause foaming and is easy to wash with water after washing.

According to the fifth aspect of the present invention, as the above-mentioned detergent for an inorganic structure containing ammonium chloride and / or ammonium sulfate, one which can more reliably prevent corrosion and discoloration of the metal surface and has excellent detergency. Provided.

According to the inventions of claims 6 and 7, as the above-mentioned cleaning agent for an inorganic structure, one having particularly good wettability and penetrability to the surface to be cleaned and capable of exhibiting more excellent cleaning power. Provided.

Claims (7)

[Claims] 1. An inorganic substance comprising an aqueous solution containing (a) phosphoric acid, (b) formic acid, (c) hydrochloric acid or / and phytic acid, (d) fatty acid diethanolamide, and (e) polyoxyalkylene alkyl ether as essential components. Cleaning agent for structures. 2. The cleaning agent for an inorganic structure according to claim 1, which contains (f) ammonium chloride or / and ammonium sulfate as an essential component together with the components (a) to (e). 3. (a) 100 parts by weight of phosphoric acid, (b)
The cleaning agent for inorganic structures according to claim 1 or 2, which comprises 100 to 300 parts by weight of formic acid and 10 to 50 parts by weight of (c) hydrochloric acid or / and phytic acid. 4. A mixed acid component comprising (a) phosphoric acid, (b) formic acid, and (c) hydrochloric acid or / and phytic acid,
The inorganic structure according to any one of claims 1 to 3, wherein the fatty acid diethanolamide (d) is contained in an amount of 0.03 to 1% by weight and the polyoxyalkylene alkyl ether (e) is contained in an amount of 0.2 to 5% by weight. Washing soap. 5. A mixed acid component composed of (a) phosphoric acid, (b) formic acid, and (c) hydrochloric acid or / and phytic acid,
(F) The cleaning agent for inorganic structures according to any one of claims 2 to 4, which comprises 5 to 40% by weight of ammonium chloride and / or ammonium sulfate. 6. The (d) fatty acid diethanol amide,
The cleaning agent for inorganic structures according to any one of claims 1 to 5, which comprises a 1: 2 type fatty acid diethanol amide which is a dehydration condensation reaction product of 1 mol of monocarboxylic acid and 2 mol of diethanolamine. 7. The polyoxyalkylene alkyl ether (e) is a polyoxyethylene alkyl ether composed of a reaction product of a monoalcohol having 9 to 14 carbon atoms and polyethylene oxide. Cleaning agent for inorganic structures.