JP2016011356A - Acidic detergent composition for foam cleaning - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-liquid type acidic detergent composition for foam cleaning which is excellent in rust removability, storage stability, and foaming properties.SOLUTION: The one-liquid type acidic detergent composition for foam cleaning with excellent rust removability, storage stability, and foaming properties contains an oxalic acid and a specific amine oxide as essential components.

Description

  The present invention relates to an acidic cleaning composition for foam cleaning.

In general, the cleaning work is roughly classified into a cleaning work by a machine and a manual cleaning work. In general, the former is used for pre-cleaning where the object to be cleaned and dirt having a fixed shape or simple shape are relatively weak, and for the pre-cleaning, and the latter is used for complicated cleaning, places where dirt is conspicuous, and finishing cleaning. In the latter, since the cleaning agent is diluted and the cleaning agent is applied and rubbed using tools such as a brush and a pad, a certain level of arm strength is required, which is a heavy labor for a weak worker. In addition, since the diluent for cleaning used for manual work has a low viscosity, it quickly drips from the surface to be cleaned, so that it is not possible to sufficiently remove dirt, generation of wasted cleaning agents, wastewater equipment There are cases where problems such as an increase in the amount of wastewater treatment occur.
As a method for solving the above problems, foam cleaning (or foam cleaning) has been proposed. This method is a method in which a foamy or foamy cleaning agent adheres to an object to be cleaned and is sufficiently brought into contact with dirt or the like to perform cleaning. Specifically, by spraying the cleaning agent in a foam using a sprayer that can be sprayed in the form of a foam, the continuous foamy bubbles are adsorbed or adhered to the surface of the object to be cleaned, and the cleaning agent is wasted. Suppresses dripping. This method can be expected to save cleaning agents, reduce wastewater treatment, and improve cleaning properties.
However, the cleaning agent usually used for foam cleaning is a two-component type of cleaning liquid and foaming aid. Therefore, it is in an environment where problems such as incorrect work at the time of mixing at the work place, problems of cost increase of the cleaning agent, problems of complicated management of the cleaning agent, problems of securing the storage location, etc. are likely to occur. It exists as an issue. And since there are differences in the type and degree of dirt depending on the object to be cleaned, there are compositions suitable for each object to be cleaned (use), and any type of foaming aid can be used. It is not always possible, and since it is a two-component type, trial and error studies are required to obtain an optimal combination of compositions.
As a specific example, there is an example of foam cleaning of a railway vehicle (Non-Patent Document 1). A cleaning agent having a derusting function is used for a vehicle cleaning agent such as a railway vehicle. As components mixed therewith, reducing treatment agents such as acidic ammonium fluoride, ammonium thioglycolate, oxalic acid, hydrochloric acid, dilute sulfuric acid, sulfamic acid, citric acid, and glycolic acid are known (Patent Document 1). ~ 5). However, even in the case of a railway vehicle having a wide range of objects to be cleaned, the present situation is that a two-pack type cleaning agent is used even though the above-described problems exist.

JP 2006-249488 A JP 2010-024366 A JP 2010-065239 A JP 2011-032495 A JP 2013-227365 A

“Kizuna” Japan Railway Transportation Service Association May 2013 P.12

  An object of the present invention is to provide an acidic detergent composition for one-pack type foam cleaning having good rust removal properties, storage stability and foam properties.

So far, a one-component acidic detergent suitable for foam cleaning has not been known. Therefore, first, the present inventor has conducted various studies on what kind of acidic cleaning agent is suitable for foam cleaning.
It has been found that oxalic acid is the best as a composition component mainly having a derusting action. Next, the functions and performance necessary for foam cleaning are foam characteristics (particularly foamability, foamability, foam sustainability). In order to impart foaming properties and foaming properties to model acidic detergents containing oxalic acid, we studied by simply adding sodium dodecylbenzenesulfonate, but sodium oxalic acid reacted to form sodium oxalate salt. However, there is a phenomenon in which the salt precipitates and precipitates in the stock solution, and a new problem of storage stability arises. Regarding the foam characteristics in the system under consideration, the foam sustainability was not satisfactory, although a good tendency was observed in the foamability (foamability) at the initial stage of foaming. The inventor has found that it is not easy to simultaneously achieve storage stability and basic performance of foam cleaning (Comparative Examples 1 to 6 described later).
Therefore, the present inventor has continued intensive studies and using oxalic acid and amine oxide as basic composition components is an essential technique for optimizing derusting property, storage stability and foam properties for foam cleaning. As a result, the present invention has been completed through further intensive studies based on the findings.

  That is, this invention provides the acidic cleaning composition for foam cleaning which makes the following items a summary.

｛式中、Ｒ^１は、炭素数８〜２２の直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基、下記式（ａ）で表される基、又は下記式（ｂ）で表される基を表す。

［式中、Ｘは、炭素数７〜２１の直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基を表す。Ｒ^４は、水素原子又は炭素数１〜３の直鎖状若しくは分岐鎖状のアルキル基を表す。ｐは、１〜４を表す。］

［式中、Ｙは、炭素数８〜２２の直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基を表す。ｔは、オキシエチレン基の平均付加モル数を示し、０．５〜１５を表す。］
またＲ^２及びＲ^３は、同一又は異なって、それぞれ、炭素数１〜３の直鎖状若しくは分岐鎖状のアルキル基又はヒドロキシエチル基を表す。｝
で表されるアミンオキシドを含有する（一液型の）泡沫洗浄用酸性洗浄剤組成物。 (Item 1) Oxalic acid and component (A): Formula (1)

{In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, a group represented by the following formula (a), or a group represented by the following formula (b). Represents.

[Wherein, X represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms. R ⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms. p represents 1-4. ]

[Wherein Y represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms. t shows the average addition mole number of an oxyethylene group, and represents 0.5-15. ]
R ² and R ³ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms or a hydroxyethyl group. }
(1 liquid type) foam cleaning acidic detergent composition containing the amine oxide represented by these.

(Item 2) The oxalic acid content is 0.1 to 15 parts by weight and the component (A) content is 0.1 to 10 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. The acidic cleaning composition for foam cleaning according to Item 1 above, wherein

(Item 3) Furthermore, the component (B): a trivalent or higher polyol compound and the component (C): at least one selected from the group consisting of amine compounds (the one-component type) ) Acid cleaning composition for foam cleaning.

(Item 4) The (single-component) foam cleaning acidic cleaning composition according to Item 3, wherein the component (C) is an alkanolamine.

(Item 5) The upper limit of the content of the component (B) is 25 parts by weight and the upper limit of the content of the component (C) is 10 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. And the total content of a component (B) and a component (C) is 0.01-35 weight part, The acidic detergent for foam cleaning of the said claim | item 3 or claim | item 4 or the claim | item 4 Composition.

(Item 6) Furthermore, the component (D): the acidic cleaning composition for foam cleaning according to any one of Items 1 to 5 containing an anionic surfactant.

(Item 7) The (single-component) foam cleaning acidic cleaning composition according to Item 6, wherein the component (D) is a sulfonic acid anionic surfactant.

(Item 8) The component (D) according to Item 6 or Item 7, wherein the content of the component (D) is 0.1 to 6 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. Acid cleaning composition for foam cleaning.

(Item 9) Further, the above items 1 to 8, further comprising at least one selected from the group consisting of component (E): sulfonic acid compound, component (F): nonionic surfactant and component (G): solvent. An acidic detergent composition for foam cleaning according to any one of (1).

(Item 10) The content of component (E) is in the range of 0.1 to 10 parts by weight, and the content of component (F) is 1 to 10 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. The acidic detergent composition for foam cleaning according to Item 9, wherein the content of component (G) is in the range of 0.1 to 30 parts by weight.

(Item 11) The acidic detergent composition for foam cleaning according to any one of Items 1 to 10, wherein the pH of the acidic detergent composition for foam cleaning is 0.1 to 4.0. .

(Item 12) In any one of Items 1 to 11, the (one-pack type) foam cleaning acidic cleaning composition is for foam cleaning of a stainless steel exterior material, an aluminum exterior material, or a painted exterior material. The (one-pack type) acidic detergent composition for foam cleaning as described.

(Item 13) The (single-component) acidic cleaning composition for foam cleaning (for a one-component type) for foam-cleaning the outer plate of a vehicle (one-component type) An acidic cleaning composition for foam cleaning.

(Item 14) The acidic cleaning composition for foam cleaning according to item 13, wherein the vehicle is a railway vehicle.

(Item 15) Further, the amphoteric surfactant, the semipolar surfactant, the cleaning aid, the antioxidant, the stabilizer, the pH adjuster, the antibacterial, excluding the oxalic acid and the components (A) to (G). Agent, antiseptic, disinfectant, thickener, thickener, viscosity modifier, chelating agent, water softener, fragrance, deodorant, pigment, colorant, hydrotope agent, anti-redeposition agent, dispersant The foaming aid, foam enhancing agent, foam modifier, hard water-resistant agent, and at least one selected from the group consisting of a rust removal aid are contained in any one of the above items 1 to 14 (one-pack type ) Acid cleaning composition for foam cleaning.

According to the inventions in Items 1 and 2, it is possible to obtain a one-component acidic detergent composition for foam cleaning that has good rust removal properties, storage stability, and foam properties. According to the inventions described in the above items 3 to 5, in addition to the effects described in the inventions of items 1 and 2, a further improvement effect in storage stability can be obtained. According to the inventions of the above items 6 to 8, in addition to the effects of the inventions of the items 1 to 5, a further improvement effect can be obtained in foaming properties and foaming properties among the foam properties. According to the inventions of the above items 9 to 10, in addition to the effects described in the inventions of the items 1 to 8, a further improvement effect and good hard water resistance effect can be obtained in the foam characteristics. According to the invention of item 11, the effect of removing rust can be obtained more stably.
The effect of said invention is acquired as a synergistic effect by making the invention of claim | item 1 and claim | item 2 into a basic composition.
Moreover, according to invention of said 12th-14th, it can be used as an acidic cleaning composition for foam cleaning of the one-pack type most suitable for the object of foam cleaning. According to the invention described in Item 15, a one-component foam cleaning acidic cleaning composition having the functions of the additive can be obtained by blending the additive having the function.

  The acidic detergent composition for foam cleaning of the present invention comprises oxalic acid and component (A): an amine oxide represented by the above general formula (1), and further component (B): trivalent or higher. A composition comprising a polyol compound and / or component (C): an amine compound, and further component (D): an anionic surfactant.

  As the oxalic acid according to the present invention, oxalic acid (anhydrous), oxalic acid dihydrate, and the like can be used, and there is no particular limitation, and those manufactured by known methods, commercially available products, reagents, etc. Can be used. Major suppliers include Mitsubishi Gas Chemical Co., Ltd. and Ube Industries, Ltd.

  The content of the oxalic acid is preferably 0.1 to 15 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning.

  The component (A) according to the present invention is at least one selected from amine oxides represented by the general formula (1). More specifically, alkylamine oxide, alkenylamine oxide, amidoamine oxide, oxyalkylene alkylamine oxide and the like are exemplified.

In the general formula (1), R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, a group represented by the above formula (a), or the above formula (b). It is a group represented. The alkyl group or alkenyl group is preferably a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, more preferably a linear or branched alkyl group having 10 to 18 carbon atoms. Is recommended.
In the group represented by the formula (a), X is a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, preferably a linear or branched chain having 9 to 17 carbon atoms. A branched alkyl group or alkenyl group, more preferably a linear alkyl group having 9 to 17 carbon atoms, is recommended. For R ⁴ , a hydrogen atom or a linear or branched chain group having 1 to 3 carbon atoms is recommended. The alkyl group is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. About p, it is 1-4, Preferably 2 or 3, More preferably, 3 is recommended.
In the group represented by the formula (b), Y is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably a linear or branched group having 10 to 18 carbon atoms. A branched alkyl group or alkenyl group, more preferably a linear alkyl group having 10 to 18 carbon atoms is recommended. t shows the average addition mole number of an oxyethylene group, and is 0.5-15, Preferably 0.7-13, More preferably, 0.8-11 are recommended.
R ² and R ³ in the general formula (1) are the same or different and are each a linear or branched alkyl group having 1 to 3 carbon atoms or a hydroxyethyl group, preferably a methyl group or a hydroxy group. Ethyl groups are recommended.

More specifically, as an example when R ¹ in the general formula (1) is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, octyldimethylamine oxide, decyldimethylamine oxide , Lauryl dimethylamine oxide, myristyl dimethyl amine oxide, palmityl dimethyl amine oxide, stearyl dimethyl amine oxide, oleyl dimethyl amine oxide, behenyl dimethyl amine oxide, coco dimethyl amine oxide, lauryl diethyl amine oxide, lauryl dipropyl amine oxide, coco diethyl amine oxide , Cocodipropylamine oxide, octyldi (hydroxyethyl) amine oxide, decyldi (hydroxyethyl) amine oxide, lauryldi (hydroxyethyl) a Minoxide, myristyldi (hydroxyethyl) amine oxide, palmityldi (hydroxyethyl) amine oxide, stearyldi (hydroxyethyl) amine oxide, oleyldi (hydroxyethyl) amine oxide, behenyldi (hydroxyethyl) amine oxide, cocodi (hydroxyethyl) amine oxide Alkyl (or alkenyl) amine oxides such as
Examples of when R ¹ in the general formula (1) is a group represented by the formula (a) include caprylic amidopropyl dimethylamine oxide, capric amidopropyl dimethylamine oxide, lauric amidopropyl dimethylamine oxide, myristic Acid amidopropyl dimethylamine oxide, palmitate amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, oleic acid amidopropyl dimethylamine oxide, palm fatty acid amidopropyl dimethylamine oxide, lauric acid amidopropyl diethylamine oxide, lauric acid amidopropyl Amidoamine oxides such as di (hydroxyethyl) amine oxide,
Examples of when R ¹ in the general formula (1) is a group represented by the formula (b) include polyoxyethylene (t = 0.5 to 15) octyl ether dimethylamine oxide, polyoxyethylene (t = 0 .5-15) Decyl ether dimethylamine oxide, polyoxyethylene (t = 0.5-15) lauryl ether dimethylamine oxide, polyoxyethylene (t = 0.5-15) myristyl ether dimethylamine oxide, polyoxyethylene (t = 0.5-15) palmityl ether dimethylamine oxide, polyoxyethylene (t = 0.5-15) stearyl ether dimethylamine oxide, polyoxyethylene (t = 0.5-15) oleyl ether dimethylamine Oxide, polyoxyethylene (t = 0.5-15) lauryl ether diethylamino Polyoxyethylene alkyl ether amines such as oxide, polyoxyethylene (t = 0.5-15) lauryl ether dipropylamine oxide, polyoxyethylene (t = 0.5-15) lauryl ether di (hydroxyethyl) amine oxide Oxides, etc. are exemplified.
Preferably, octyldimethylamine oxide, decyldimethylamine oxide, lauryldimethylamine oxide, myristyldimethylamine oxide, palmityldimethylamine oxide, stearyldimethylamine oxide, cocodimethylamine oxide, octyldi (hydroxyethyl) amine oxide, decyldi (hydroxy Ethyl) amine oxide, lauryl di (hydroxyethyl) amine oxide, myristyl di (hydroxyethyl) amine oxide, palmityl di (hydroxyethyl) amine oxide, stearyl di (hydroxyethyl) amine oxide, cocodi (hydroxyethyl) amine oxide, amidopropyl caprylate Dimethylamine oxide, capric amidopropyl dimethylamine oxide, lauric acid Dopropyldimethylamine oxide, myristic amidopropyl dimethylamine oxide, palmitic amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, coconut fatty acid amidopropyl dimethylamine oxide, lauric acid amidopropyl di (hydroxyethyl) amine oxide, Palm fatty acid amidopropylamine oxide is recommended.
These can be blended alone or in appropriate combination of two or more.

As the amine oxide represented by the general formula (1) which is the component (A) according to the present invention, commercially available products, reagents, those prepared by known synthesis methods, and the like can be used.
For example, the product name “Wandamine OX-300” (manufactured by Shin Nippon Rika Co., Ltd., lauryl dimethylamine oxide), the product name “Amphithol 20N” (manufactured by Kao Corporation, lauryl dimethylamine oxide), the product name “Unisafe A-” LM "(manufactured by NOF Corporation, lauryl dimethylamine oxide), trade name" Unisafe A-MM "(manufactured by NOF Corporation, myristyl dimethylamine oxide), trade name" Unisafe A-SM "(NOF ( Co., Ltd., stearyl dimethylamine oxide), trade name “Unisafe A-OM” (manufactured by NOF Corporation, oleyl dimethylamine oxide), trade name “Unisafe A-LE” (manufactured by NOF Corporation, di ( Hydroxyethyl) laurylamine oxide), trade name “GENAMINOX KC” (manufactured by Clariant Japan Co., Ltd., cocodimethylamine oxide), trade name “G” NAMINOX CHE "(manufactured by Clariant Japan Co., Ltd., Rauriruji (hydroxyethyl) amine oxide), trade name" GENAMINOX AP "(manufactured by Clariant Japan KK, lauric acid amidopropyl dimethylamine oxide), and the like. In addition to the above, many manufacturers are described in, for example, “2013 Chemical Product of 16313 (Issuing Office; Chemical Industry Daily, Issued January 29, 2013)”.
The polyoxyethylene alkyl ether amine oxide can also be produced in accordance with the disclosures of Japanese Patent Application Laid-Open Nos. 5-178873 and 5-11797.

  The content of the component (A): amine oxide is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. .

The trivalent or higher polyol compound as the component (B) according to the present invention means an organic compound having three or more hydroxyl groups. Examples include glycerin, diglycerin, triglycerin, polyglycerin, polyvinyl alcohol, sorbitol, xylitol, etc., preferably glycerin, diglycerin, triglycerin, polyglycerin, polyvinyl alcohol, especially glycerin and / or diglycerin and polyvinyl alcohol. A combination with is recommended.
In addition, it is recommended that the polyol compound has a solubility in water (25 ° C.) of 10% or more, more preferably 20% or more.
These can be blended alone or in appropriate combination of two or more.

There is no restriction | limiting in particular in the said polyol compound, What was manufactured by the well-known method, what can be obtained with a commercial item, a reagent, etc. can be used.
Polyvinyl alcohol is generally produced by saponifying polyvinyl acetate. Polyvinyl alcohol is roughly classified into a fully saponified type and a partially saponified type depending on the difference in the degree of saponification (degree of saponification). Preferably, a completely saponified polyvinyl alcohol is recommended. When partially saponified polyvinyl alcohol is used, a degree of saponification of 60 to 100 mol%, more preferably 90 to 100 mol%, particularly preferably 98 to 100 mol% is recommended.
The polymerization degree of polyvinyl alcohol is preferably 300 to 5000, more preferably 500 to 3500.
The polyvinyl alcohol may be a copolymer (modified polyvinyl alcohol) with a component capable of copolymerizing polyvinyl acetate.
Examples of main suppliers of polyvinyl alcohol include Kuraray Co., Ltd., Nippon Synthetic Chemical Industry Co., Ltd., Nippon Acetate / Poval Co., Ltd., etc., for example, trade name “GOHSENOL NH-18” (Nippon Synthetic Chemical Industry Co., Ltd.) For example, the product name “GOHSENOL NH-11” (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., fully saponified type) is exemplified.

The amine compound which is the component (C) according to the present invention is an organic compound having an amino group. For example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-bis (2-hydroxyethyl) -N-cyclohexylamine, 2-amino-1-butanol, 2 Alkanolamines such as amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, methylamine And alkylamines such as dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine and butylamine, and aqueous ammonia.
Among these, alkanolamine is preferable, and monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine are more preferable.
These can be blended alone or in appropriate combination of two or more.
The amine compound is not particularly limited, and those used in the field of acidic detergents, those produced by known methods, those commercially available, reagents and the like can be used.

Component (B): Trivalent or higher polyol compound and Component (C): The upper limit of the content of component (B) with respect to 100 parts by weight of the foam cleaning acidic detergent composition Is preferably 25 parts by weight, more preferably 19 parts by weight, and the upper limit of the content of component (C) is preferably 10 parts by weight, more preferably 6 parts by weight, and component (B) and It is recommended that the total content of component (C) is in the range of preferably 0.01 to 35 parts by weight, more preferably 0.03 to 25 parts by weight.
A particularly preferred embodiment is when the component (B) and the component (C) are used in combination, and the respective contents are in the range of 0.05 to 18 parts by weight and 0.1 to 5 parts by weight. It is recommended that the total content of B) and component (C) is in the range of 0.15 to 23 parts by weight. By using the component (B) and the component (C) in combination, in addition to improving storage stability, it contributes to improving rust removal.

As the anionic surfactant which is the component (D) according to the present invention, those used in the field of acidic detergents can be suitably used.
For example, polyoxyethylene (1-7) alkyl (or alkenyl) ether acetate having an alkyl group (or alkenyl group) having 8 to 18 carbon atoms, polyoxyethylene fatty acid having an aliphatic acyl group having 8 to 18 carbon atoms Monoethanolamide ether acetate, aliphatic acylamino acid salt derived from fatty acid having 8 to 18 carbon atoms (N-acylglycine salt, N-acylsarcosine salt, N-acylalanine salt, N-acyl-N-methylalanine salt, N-acyl-L-glutamate, N-acyl-L-aspartate, etc.), sulfonic acid or a salt thereof, and the like.
Among these, sulfonic acid or a salt thereof (that is, sulfonic acid anionic surfactant) is preferably recommended.
Note the sulfonic acid anionic surfactants, in the present specification and claims, Z-SO 3 _H group (Z is an aliphatic group, an alicyclic group, an aromatic group.), Z- It may be shown as SO ₃ M (Z is as defined above, M represents a counter cation).
Specific examples of the sulfonic acid-based anionic surfactant include, for example, alkane (carbon number 8 to 22) sulfonic acid, α-olefin (carbon number 10 to 22) sulfonic acid, alkyl (carbon number 8 to 22) benzene. Sulfonic acid such as sulfonic acid, alkyl (4 to 10 carbon atoms) naphthalenesulfonic acid, dialkyl (8 to 22 carbon atoms) diphenyl ether disulfonic acid, alkane (8 to 22 carbon atoms) sulfonate, α-olefin (10 carbon atoms) -22) Sulfonates such as sulfonates, alkyl (carbon number 8-22) benzene sulfonate, alkyl (carbon numbers 4-10) naphthalene sulfonate, dialkyl (carbon number 8-22) diphenyl ether disulfonate , Etc. are exemplified.
These can be blended alone or in appropriate combination of two or more.

Examples of the counter cation constituting the sulfone salt include alkali metal ions, ammonium ions, and organic ammonium ions.
Examples of alkali metal ions include lithium ions, sodium ions, potassium ions, and the like. Organic ammonium ions include monoethanolammonium ion, N-methylmonoethanolammonium ion, N-butylmonoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, isopropanolammonium ion, 2-hydroxymethyl-2-propylammonium ion Examples include alkanol ammonium ions such as ammonium ions of basic amino acids such as lysine and arginine.
Among these, sodium ions, potassium ions, diethanolammonium ions, triethanolammonium ions, and ammonium ions are recommended as preferred counter cations.

  The content of the anionic surfactant is preferably 0.1 to 6 parts by weight, more preferably 0.5 to 4 parts by weight, with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. In addition, the content range of the sulfonic acid anionic surfactant is also recommended.

As the anionic surfactant which is the component (D) according to the present invention, commercially available products, reagents and those prepared by a known synthesis method can be used.
For example, the product name “Neoperex GS” (manufactured by Kao Corporation, dodecylbenzene sulfonic acid), the product name “Eleminol MON-2” (manufactured by Sanyo Chemical Industries, Ltd., sodium dodecyl diphenyl ether disulfonate), the product name “Lipolane” PB-800CJ "(manufactured by Lion Corporation, α-olefin (C14-18) sodium sulfonate) is exemplified. In addition to the above, many manufacturers are described in, for example, “2013 Chemical Product of 16313 (Issuing Office; Chemical Industry Daily, Issued January 29, 2013)”.

  From the viewpoint of the effects of the present invention, the preferred embodiments of the content of each of the composition components (oxalic acid, component (A) to component (D)) in the acidic detergent composition for foam cleaning of the present invention are as described above. A combination of recommended ranges of the content of the composition components is recommended as a more preferred embodiment.

  Moreover, the pH of the acidic detergent composition for foam cleaning of the present invention is preferably 0.1 to 4.0, more preferably 0.2 to, from the viewpoint of the removal rate and removal time of metal oxide film and rust. 3.0 is recommended.

  The acidic detergent composition for foam cleaning of the present invention essentially contains water and is usually used or provided in the form of an aqueous solution. Examples of the water include distilled water, ion-exchanged water, purified water, tap water, and groundwater, but preferably distilled water and ion-exchanged water are recommended. In addition, when using tap water and groundwater, the hardness is preferably 200 mg / L or less, more preferably 50 mg / L or less.

  As a composition component capable of giving a good effect complementarily, supplementarily or incrementally to the effect of the present invention and the workability at the time of foam washing, component (E): sulfonic acid compound, component (F): Nonionic surfactant, component (G): solvent may be mentioned, and it is particularly recommended to blend in the range where the effects of the present invention are exhibited.

The component (E): sulfonic acid compound is a low molecular weight organic compound having no surface activity. In the present specification and claims, the “sulfonic acid compound” means a low molecular organic compound having a —SO ₃ H group (sulfonic acid group).
Specific examples include isethionic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, sulfamic acid, and the like. These can be blended alone or in appropriate combination of two or more.
There is no restriction | limiting in particular in a sulfonic acid compound, What was manufactured by the well-known method, what can be obtained with a commercial item, a reagent, etc. can be used.

［式中、Ｒ^５は炭素数８〜２２の直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基を表す。Ａはプロピレン基又はエチレン基を表す。ｎは、（ＡＯ）基の平均付加モル数を示し、３．５〜１８を表す。ｎ個の（ＡＯ）基は、同一又は異なって、それぞれ、オキシエチレン基又はオキシプロピレン基を表す。］
で表されるポリオキシアルキレンアルキル（又はアルケニル）エーテル化合物が推奨される。
より具体的には、ポリオキシエチレン(７)デシルエーテル、ポリオキシエチレン(８)デシルエーテル、ポリオキシエチレン(１０)デシルエーテル、ポリオキシエチレン(１２)デシルエーテル、ポリオキシエチレン(１５)デシルエーテル、ポリオキシエチレン(７)ラウリルエーテル、ポリオキシエチレン(８)ラウリルエーテル、ポリオキシエチレン(１０)ラウリルエーテル、ポリオキシエチレン(１２)ラウリルエーテル、ポリオキシエチレン(１５) ラウリルエーテル、ポリオキシエチレン(７)ミリスチルエーテル、ポリオキシエチレン(８)ミリスチルエーテル、ポリオキシエチレン(１０)ミリスチルエーテル、ポリオキシエチレン(１２)ミリスチルエーテル、ポリオキシエチレン(１５)ミリスチルエーテル、ポリオキシエチレン(７)パルミチルエーテル、ポリオキシエチレン(８)パルミチルエーテル、ポリオキシエチレン(１０)パルミチルエーテル、ポリオキシエチレン(１２)パルミチルエーテル、ポリオキシエチレン(１５)パルミチルエーテル、ポリオキシエチレン(８)ステアリルエーテル、ポリオキシエチレン(１０)ステアリルエーテル、ポリオキシエチレン(１２)ステアリルエーテル、ポリオキシエチレン(１５)ステアリルエーテル、ポリオキシエチレン(１０)オレイルエーテル、ポリオキシエチレン(１２)オレイルエーテル、ポリオキシエチレン(１５)オレイルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(６)デシルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(６)デシルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(６)ラウリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(６)ラウリルエーテル、ポリオキシプロピレン(３)ポリオキシエチレン(６)ラウリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(７)ラウリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(７)ラウリルエーテル、ポリオキシプロピレン(３)ポリオキシエチレン(７)ラウリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(８)ラウリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(８)ラウリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(９)ラウリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(９)ラウリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(１０)ラウリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(１０)ラウリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(１２)ラウリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(１２)ラウリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(６)ミリスチルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(６)ミリスチルエーテル、ポリオキシプロピレン(３)ポリオキシエチレン(６)ミリスチルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(７)ミリスチルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(７)ミリスチルエーテル、ポリオキシプロピレン(３)ポリオキシエチレン(７)ミリスチルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(８)ミリスチルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(８)ミリスチルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(９)ミリスチルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(９)ミリスチルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(１０)ミリスチルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(１０)ミリスチルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(１２)ミリスチルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(１２)ミリスチルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(８)ステアリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(８)ステアリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(９)ステアリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(９)ステアリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(１０)ステアリルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(１０)ステアリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(１２)ステアリルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(１２)オレイルエーテル、ポリオキシプロピレン(２)ポリオキシエチレン(１２)オレイルエーテル、ポリオキシプロピレン(３)ポリオキシエチレン(１２)オレイルエーテル、ポリオキシプロピレン(１)ポリオキシエチレン(６)アルキル(Ｃ１０〜１２)エーテル、ポリオキシプロピレン(２)ポリオキシエチレン(６)アルキル(Ｃ１０〜１２)エーテル、ポリオキシプロピレン(１)ポリオキシエチレン(７)アルキル(Ｃ１０〜１２)エーテル、ポリオキシプロピレン(２)ポリオキシエチレン(７)アルキル(Ｃ１０〜１２)エーテル、ポリオキシプロピレン(１)ポリオキシエチレン(９)アルキル(Ｃ１０〜１２)エーテル、ポリオキシプロピレン(２)ポリオキシエチレン(９)アルキル(Ｃ１０〜１２)エーテルなどが例示される。これらは、単独で又は２種以上を適宜組み合わせて配合することができる。
なお、上記の「オキシアルキレン基」、「オキシプロピレン」及び「オキシエチレン」に続く括弧内の数字は、それぞれの平均付加モル数を表す。例えば、ポリオキシプロピレン(３)ポリオキシエチレン(７)ラウリルエーテルの場合では、オキシプロピレン基の平均付加モル数が３モル、オキシエチレン基の平均付加モル数が７モルを意味する。また「アルキル」に続く括弧内の「Ｃ数字」は、アルキル基の炭素数を意味する。 As the component (F): nonionic surfactant, those usually used in the field of acidic detergents can be adopted. Specifically, polyoxyalkylene alkyl (or alkenyl) ether, polyoxyalkylene alkyl phenyl ether, alkyl monoglycerin ether, alkanediol derivatives such as PEG-1 lauryl glycol, polyoxyalkylene alkyl (or alkenyl) ether amine derivatives And alkanolamides having an aliphatic acyl group having 8 to 18 carbon atoms, polyoxyethylene (1-10) fatty acid alkanolamides having an aliphatic acyl group having 8 to 18 carbon atoms, glycerin fatty acid ester, sorbitan fatty acid ester, etc. Is done.
Of these, ether type nonionic surfactants are preferred, and polyoxyalkylene alkyl (or alkenyl) ethers are more preferred, and in particular, the following general formula (2)

[Wherein, R ⁵ represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms. A represents a propylene group or an ethylene group. n shows the average addition mole number of (AO) group, and represents 3.5-18. The n (AO) groups are the same or different and each represents an oxyethylene group or an oxypropylene group. ]
A polyoxyalkylene alkyl (or alkenyl) ether compound represented by:
More specifically, polyoxyethylene (7) decyl ether, polyoxyethylene (8) decyl ether, polyoxyethylene (10) decyl ether, polyoxyethylene (12) decyl ether, polyoxyethylene (15) decyl ether , Polyoxyethylene (7) lauryl ether, polyoxyethylene (8) lauryl ether, polyoxyethylene (10) lauryl ether, polyoxyethylene (12) lauryl ether, polyoxyethylene (15) lauryl ether, polyoxyethylene ( 7) Myristyl ether, polyoxyethylene (8) myristyl ether, polyoxyethylene (10) myristyl ether, polyoxyethylene (12) myristyl ether, polyoxyethylene (15) myristyl ether, polyoxyethylene (7) palmityl ether , Reoxyethylene (8) palmityl ether, polyoxyethylene (10) palmityl ether, polyoxyethylene (12) palmityl ether, polyoxyethylene (15) palmityl ether, polyoxyethylene (8) stearyl ether, poly Oxyethylene (10) stearyl ether, polyoxyethylene (12) stearyl ether, polyoxyethylene (15) stearyl ether, polyoxyethylene (10) oleyl ether, polyoxyethylene (12) oleyl ether, polyoxyethylene (15) Oleyl ether, polyoxypropylene (1) polyoxyethylene (6) decyl ether, polyoxypropylene (2) polyoxyethylene (6) decyl ether, polyoxypropylene (1) polyoxyethylene (6) lauryl ether, polyoxy Propi (2) Polyoxyethylene (6) lauryl ether, polyoxypropylene (3) polyoxyethylene (6) lauryl ether, polyoxypropylene (1) polyoxyethylene (7) lauryl ether, polyoxypropylene (2) poly Oxyethylene (7) lauryl ether, polyoxypropylene (3) polyoxyethylene (7) lauryl ether, polyoxypropylene (1) polyoxyethylene (8) lauryl ether, polyoxypropylene (2) polyoxyethylene (8) Lauryl ether, polyoxypropylene (1) polyoxyethylene (9) lauryl ether, polyoxypropylene (2) polyoxyethylene (9) lauryl ether, polyoxypropylene (1) polyoxyethylene (10) lauryl ether, polyoxy Propylene (2) Polyoxyethylene (10) Lauryl Ether, polyoxypropylene (1) polyoxyethylene (12) lauryl ether, polyoxypropylene (2) polyoxyethylene (12) lauryl ether, polyoxypropylene (1) polyoxyethylene (6) myristyl ether, polyoxypropylene (2) Polyoxyethylene (6) myristyl ether, polyoxypropylene (3) polyoxyethylene (6) myristyl ether, polyoxypropylene (1) polyoxyethylene (7) myristyl ether, polyoxypropylene (2) polyoxy Ethylene (7) myristyl ether, polyoxypropylene (3) polyoxyethylene (7) myristyl ether, polyoxypropylene (1) polyoxyethylene (8) myristyl ether, polyoxypropylene (2) polyoxyethylene (8) myristyl Ether, polyoxy Propylene (1) Polyoxyethylene (9) Myristyl ether, Polyoxypropylene (2) Polyoxyethylene (9) Myristyl ether, Polyoxypropylene (1) Polyoxyethylene (10) Myristyl ether, Polyoxypropylene (2) Poly Oxyethylene (10) myristyl ether, polyoxypropylene (1) polyoxyethylene (12) myristyl ether, polyoxypropylene (2) polyoxyethylene (12) myristyl ether, polyoxypropylene (1) polyoxyethylene (8) Stearyl ether, polyoxypropylene (2) polyoxyethylene (8) stearyl ether, polyoxypropylene (1) polyoxyethylene (9) stearyl ether, polyoxypropylene (2) polyoxyethylene (9) stearyl ether, polyoxy propylene( ) Polyoxyethylene (10) stearyl ether, polyoxypropylene (2) polyoxyethylene (10) stearyl ether, polyoxypropylene (1) polyoxyethylene (12) stearyl ether, polyoxypropylene (1) polyoxyethylene ( 12) oleyl ether, polyoxypropylene (2) polyoxyethylene (12) oleyl ether, polyoxypropylene (3) polyoxyethylene (12) oleyl ether, polyoxypropylene (1) polyoxyethylene (6) alkyl (C10 -12) ether, polyoxypropylene (2) polyoxyethylene (6) alkyl (C10-12) ether, polyoxypropylene (1) polyoxyethylene (7) alkyl (C10-12) ether, polyoxypropylene (2 ) Polyoxyethylene (7) alkyl (C10-12) Ether, polyoxypropylene (1) Polyoxyethylene (9) alkyl (C10～12) ether, polyoxypropylene (2) polyoxyethylene (9) alkyl (C10～12) ether can be exemplified. These can be blended alone or in appropriate combination of two or more.
The numbers in parentheses following the above “oxyalkylene group”, “oxypropylene”, and “oxyethylene” represent the average number of moles added. For example, in the case of polyoxypropylene (3) polyoxyethylene (7) lauryl ether, it means that the average added mole number of oxypropylene groups is 3 moles and the average added mole number of oxyethylene groups is 7 moles. The “C number” in parentheses following “alkyl” means the number of carbon atoms of the alkyl group.

Examples of the component (G): solvent include alcohol solvents, cellosolve solvents, glycols, glycol ethers, and the like. Alcohol solvents include alcohol solvents such as ethanol and isopropyl alcohol, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and phenyl cellosolve, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, Tylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol mono Glycol ether solvents such as butyl ether and 3-methoxy-3-methyl-1-butanol, lactam solvents such as N-methyl-2-pyrrolidone, glycol solvents such as ethylene glycol, propylene glycol, butylene glycol and polyethylene glycol Is exemplified.
Among these, butyl cellosolve, diethylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, N-methyl-2-pyrrolidone, ethylene glycol, and polyethylene glycol are recommended.
These can be blended alone or in appropriate combination of two or more.

When using the said component (E): sulfonic acid compound, the content becomes with respect to 100 weight part of acidic detergent compositions for foam cleaning, Preferably it is 0.1-10 weight part, More preferably, it is 0.5. ~ 8 parts by weight are recommended.
Moreover, when using the said component (F): nonionic surfactant, the content becomes with respect to 100 weight part of acidic detergent compositions for foam washing, Preferably it is 1-10 weight part, More preferably, it is 2 parts. ~ 8 parts by weight are recommended.
Moreover, when using the said component (G): solvent, the content becomes with respect to 100 weight part of acidic cleaning composition for foam cleaning, Preferably it is 0.1-30 weight part, More preferably, it is 5-25 weight. Is recommended.

  The method for preparing the acidic detergent composition for foam cleaning of the present invention is not particularly limited, and a preparation method generally used in the detergent field can be applied. For example, a predetermined amount of oxalic acid and component (A), and optionally component (B) to component (G), water (process agent, balance agent), and if necessary, other components described later in desired amounts, It can prepare easily by selecting the order of mixing | blending suitably and mixing suitably at room temperature or under heating as needed. As a preferable order of the blending, an order in which a composition component that is slowly dissolved in water (or a composition component that is difficult to dissolve) is mixed with water and finally oxalic acid is mixed is recommended.

  There is no restriction | limiting in particular as a usage method of the acidic cleaning composition for foam cleaning of this invention, The method normally used for foam cleaning can be used. For example, depending on the degree of rust stains on the object to be cleaned, the acidic detergent composition for foam cleaning is diluted or appropriately diluted and injected into a tank of a foam cleaning machine or an automatic machine car washer. A method for efficiently washing a washing object by generating foamy foam by spraying the acidic detergent composition for foam washing from the nozzle of the washing machine by pressure feeding with compressed air or mechanical feeding by a pump Etc. are exemplified.

In addition to the oxalic acid and components (A) to (G) according to the present invention, the “acidic detergent composition for foam cleaning of the present invention” is generally used in the field of acidic detergents, “other components”. Can be blended within the range where the effects of the present invention are exhibited.
Other components include, for example, various surfactants such as amphoteric surfactants and semipolar surfactants, excluding oxalic acid and components (A) to (G) according to the present invention, cleaning aids, and antioxidants. Agent, stabilizer, pH adjuster, antibacterial agent, preservative, disinfectant, thickener, thickener, viscosity adjuster, chelating agent, water softener, fragrance, deodorant, pigment (colorant) , Hydrotope agents, anti-redeposition agents, dispersants, foaming aids (foam enhancers), foam modifiers, hard water resistant agents, rust aids (reducing components), and the like.

  Examples of the various surfactants include alkylbetaine type amphoteric surfactants such as alkyl (carbon number 8 to 22) dimethylaminoacetic acid betaine, and amidoalkyl betaines such as fatty acid (carbon number 8 to 22) amidopropyldimethylaminoacetic acid betaine. Type amphoteric surfactant, sulfobetaine type amphoteric surfactant such as alkyl (carbon number 8-22) hydroxysulfobetaine, fatty acid (carbon number 8-22) amidopropyl hydroxysulfobetaine, 2-alkyl-N-carboxymethyl- N-hydroxyethylimidazolinium betaine and other imidazolinium betaine type amphoteric surfactants, betaine type amphoteric surfactants such as alkyl (8 to 22 carbon atoms) amine oxide, amidoamine oxide, oxyalkylene alkylamine oxide, carbon Having an alkyl group of 8 to 18 N- alkyl amino di-acid salt, N- alkylamino dipropionate salt, N- alkyldiaminoethyl N- alkyl amino acids type amphoteric surfactants such as glycine salts, and the like are exemplified.

  Examples of thickeners and viscosity modifiers include polyether-type thickeners such as polyoxyethylene (60) cetyl stearyl diether, and water-soluble polymers such as hydroxyethyl cellulose, hydroxypropyl methylcellulose, sodium polyacrylate, and xanthan gum. Examples include mold thickeners.

  Examples of the pH adjuster include organic acids such as citric acid, malic acid and lactic acid, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, triethanolamine, Ammonia and the like are exemplified. It does not specifically limit as a form to add, A powder form or a liquid thing can be used as it is or in the form of aqueous solution.

  As the foaming aid (foam enhancer), for example, fatty acid ethanolamides derived from fatty acids mainly composed of coconut oil fatty acid, palm kernel oil fatty acid, and lauric acid are recommended.

Examples of the hard water resistant agent include polymer derivatives such as polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, polystyrene sulfonic acid or a salt thereof, an acrylamide-methylpropanesulfonic acid copolymer or a salt thereof, and the like.
When using a hard water resistant agent, the content is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the acidic detergent composition for foam cleaning. Is done.

Examples of the chelating agent include ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminopentaacetic acid, triethylenetetraaminohexaacetic acid, L-glutamic acid diacetic acid, L -Aspartic acid-N, N-diacetic acid, 2-hydroxyethyliminodiacetic acid, gluconate, 3-hydroxy-2,2-iminodisuccinic acid, hydroxyethylidene diphosphonic acid, nitrilotris (methylenephosphonic acid), phosphombutane Examples of tricarboxylic acids and salts of alkali metals, ammonium, etc., are used as part or all of these acids.
When using a chelating agent, the content is preferably 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the acidic detergent composition for foam cleaning. .

Examples of the flavor include natural flavors such as lemon oil, eucalyptus oil, lime oil and rose oil, and synthetic flavors such as α-pinene, l-menthol, l-citronellol and d-limonene, and other food flavors.
When using a fragrance | flavor, the content becomes like this. Preferably it is 0.01-2 weight part with respect to 100 weight part of a rust remover composition or an acidic rust cleaning composition, More preferably, it is 0.05-5. .5 parts by weight are recommended.

Examples of the deodorant include plant essential oils, plant extracts, chemical substances such as chlorine dioxide, and more specifically, fragrances such as lily of the valley oil, linden oil, jasmine oil, gardenia oil, mint oil, violet oil and the like. Agents, masking agents such as cinnamic aldehyde, vanillin, heliotropin, coumarin, carvone, canafer, and bonol, neutralizing deodorants such as turpentine oil, clove oil, cinnamon oil, cedar oil, orange oil, orange peel oil, etc. Is mentioned.
When the deodorant is used, the content thereof is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. Recommended.

Examples of the disinfectant include amphoteric surfactants, cationic surfactants, and reverse soaps.
When using a disinfectant, the content thereof is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. Is recommended.

Examples of preservatives include benzoic acid, salicylic acid, dehydroacetic acid, sodium dehydroacetate, sorbic acid, boric acid, chlorxylenol, resorcin, paraoxybenzoic acid ester, phenoxyethanol, thymol, hinokitile, thioxolone, benzalkonium chloride, benzoic chloride Examples include tonium, lauryl di (aminoethyl) glycine, chlorhexidine gluconate, chlorobutanol and the like.
When the preservative is used, the content is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the acidic detergent composition for foam cleaning. The

Examples of the viscosity modifier include polyether type thickeners such as polyoxyethylene (60) cetostearyl hydroxymyristyl ether, polyoxyethylene (60) cetyl stearyl diether, hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyacrylic acid Examples thereof include water-soluble polymer thickeners such as sodium and xanthan gum.
When using a viscosity modifier, its content is preferably 0.01-5 parts by weight, more preferably 0.1-3 parts by weight, based on 100 parts by weight of the acidic detergent composition for foam cleaning. Is done.

Examples of antifoaming agents include oil-based, oil-compound-type, solution-type, emulsion-type, self-emulsification-type silicone-type antifoaming agents, surfactants, polyethers, organic-type antifoaming agents such as higher alcohols, and the like. Illustrated.
When using an antifoamer, the content thereof is preferably 0.001 to 0.5 parts by weight, more preferably 0.003 to 0.1 parts per 100 parts by weight of the acidic detergent composition for foam cleaning. Part by weight is recommended.

Examples of reducing components other than oxalic acid (rust removal aid) include malic acid, citric acid, tartaric acid, glycolic acid, glyceric acid, lactic acid, itaconic acid, succinic acid, thioglycolic acid, thiomalic acid, and butanetetracarboxylic acid And propanetricarboxylic acid, formic acid, acetic acid and salts thereof.
When using reducing components other than oxalic acid, the content thereof is preferably 0.01 to 8 parts by weight, more preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the acidic detergent composition for foam cleaning. Is recommended.

Antioxidants include, for example, nordihydroguaiaretic acid, guaiac fat, propyl gallate, butylhydroxyanisole, dibutylhydroxytoluene, α-tocopherol (vitamin E), sodium sulfite, potassium sulfite, sodium pyrosulfite, pyro Sulphites such as potassium sulfite, hyposulfites such as sodium hyposulfite and potassium hyposulfite, ascorbates such as isoascorbic acid, ascorbic acid, sodium ascorbate and potassium ascorbate, thiosorbitol, cysteine hydrochloride, sodium thiosulfate, Thiosulfates such as potassium thiosulfate, gallic acid, sodium gallate, pyrogallol, tannic acid, persimmon astringent, glyoxal, tartaric acid, hydroquinone, longarit, salicylic acid, gluconic acid, pyrocatechol , 3-hydroxybutyric acid, propionic acid, phthalic acid, isophthalic acid, 3-hydroxy salicylic acid, 3,5-dihydroxy salicylic acid, succinic acid, sulfosalicylic acid, and triethylene glycol acid.
When using an antioxidant, its content is preferably 0.1 to 5 parts by weight, particularly preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the acidic detergent composition for foam cleaning. Is done.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Further, physical properties and chemical properties in each of the examples and comparative examples were evaluated by the following methods.

[Derusting property]
Method for producing test piece for test The test piece (stainless steel SUS-304, 6 × 8 cm) is thoroughly washed with an alkaline detergent, then washed with acetone, and then dried, and the weight (g) of the test piece is determined by the decimal point. Weighed (A) to 4 digits. Next, the test piece was covered with Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.) wetted with an aqueous solution containing sodium chloride (5% by weight) and nonionic surfactant (1% by weight) to prevent air from entering. Sprinkle 4 g of iron powder (100 mesh, manufactured by Nacalai Tesque Co., Ltd.) and use a micro spatula to make it as uniform as possible. Next, it contains salt (5% by weight) and nonionic surfactant (1% by weight). The aqueous solution was sprayed and homogenized again. Thereafter, it was left at room temperature for 72 hours to rust. Kim wipes were removed from the rusted test pieces, washed with water, and air-dried for 24 hours to prepare test test pieces. The weight (g) of the test piece was weighed (B) to the fourth decimal place.
The nonionic surfactant is “Licanon EP-200” (trade name, manufactured by Shin Nippon Chemical Co., Ltd., polyoxyethylene (8) polyoxypropylene (4) polyoxyethylene (4) oleyl ether). used.
Test Method The acidic detergent composition for foam cleaning of the present invention is diluted 50 times with tap water, immersed in the test piece for testing for 40 minutes at 25 ° C., then washed with running water for 1 minute, and air-dried for 12 hours. The weight (g) of the air-dried test piece for testing was weighed (C) to the fourth decimal place.
This test was performed twice, and the average of the values calculated from the following formulas was taken as the rust removal rate.

Rust removal rate (%) = {(B)-(C)} × 100 / {(B)-(A)}

[Foam properties]
The acidic detergent composition for foam cleaning of the present invention is diluted 10 times with tap water, put into a pump former, the nozzle of the pump former is brought close to a 100 ml beaker and discharged 10 times, and the foam immediately after discharge is discharged. Height (foaming property) was measured.
Next, in order to evaluate the foam persistence, it was allowed to stand still for 30 minutes, and the height of the foam after 30 minutes was measured.

[Foam test by sprayer]
The acidic detergent composition for foam cleaning of the present invention was diluted 10-fold with tap water and injected into a foam sprayer. Using the foam sprayer, the diluted solution was sprayed on the vertical surface of the coated plate. The appearance of the foam sprayed visually was observed, and the foam quality of the sprayed foam was determined according to the following criteria.
Next, the adsorptivity and foam persistence were determined according to the following criteria in the same state. The adsorptivity was determined by visually observing the state of dripping of the sprayed bubbles. The foam persistence was determined by whether or not the foam was maintained for 5 minutes.
In any of the determination criteria, it can be evaluated that a superior effect is recognized.
<Criteria for foam quality>
○: Fine mousse △: Slightly coarse foam ×: Rough foam <Adsorption criteria>
○: Sprayed bubbles are adsorbed for 5 minutes or more without dripping.
Δ: Sprayed bubbles slowly fall down.
X: The sprayed bubble drips quickly.
<Criteria for foam persistence>
○: Persistence of foam for 5 minutes or more ×: No persistence of foam for 5 minutes

[Storage stability]
The acidic detergent composition for foam cleaning of the present invention is put in a 50 ml glass bottle, tightly stoppered, and stored still in a −5 ° C. incubator for 30 days. Evaluated. Judgment standard ◎ can be evaluated as having an advantageous effect, and judgment standard ◯ can be evaluated as having a good effect.
<Criteria>
(Double-circle): The generation | occurrence | production and isolation | separation of precipitation, cloudiness, and turbidity were not observed at all.
○: Slight fogging occurred.
Δ: Precipitate was generated.
X: A large amount of precipitate was generated.

[Hard water resistance]
The acidic detergent composition for foam cleaning of the present invention is diluted 10-fold with tap water, sealed in 40 ml in a 50 ml glass bottle, kept at room temperature for 3 days, and the amount of precipitates and turbidity observed visually. did. The appearance was judged according to the following criteria, and the hard water resistance was evaluated. Judgment standard ◎ can be evaluated as having an advantageous effect, and judgment standard ◯ can be evaluated as having a good effect.
<Criteria>
A: No precipitate or turbidity was observed at all.
○: Slight precipitate or turbidity occurred.
Δ: Precipitate was generated.
X: A large amount of precipitate was generated.

[Examples 1-5, Comparative Examples 1-6]
According to the composition components and composition ratios (parts by weight) shown in Table 1, these composition components were mixed at room temperature or under heating. As a common mixing order, oxalic acid dihydrate was added last. When blending polyvinyl alcohol, it was first dissolved in ion-exchanged water under heating. All other systems were mixed at room temperature. In this way, an acidic cleaning composition for foam cleaning was prepared. Using these compositions, rust removal, foam characteristics, foam test using a sprayer, storage stability, and hard water resistance were evaluated, and the evaluation results are shown in Table 1. “Parts by weight” is based on 100 parts by weight of the acidic detergent composition for foam cleaning.
As Comparative Example 6, except that oxalic acid was not used, the same procedure as in Example 1 was carried out. However, since no rust removal property was obtained, no other evaluation was performed.

  The compound of the composition component of Table 1 is as follows, and the numerical value in the table | surface has displayed the weight part of each composition component with respect to 100 weight part of foam acidic detergent composition. Moreover, when preparing the acidic detergent composition for foam cleaning of the present invention using a commercially available product in the form of an aqueous solution, the composition components are converted into pure components, the blending amount is adjusted, and the composition is mixed. A product was prepared.

<Abbreviations of compounds, etc.>
・ Oxalic acid dihydrate: Mitsubishi Gas Chemical Co., Ltd.
Ingredient (A)
Amine oxide-1: Palm oil alkyldimethylamine oxide (trade name “GENAMINOX KC”, manufactured by Clariant Japan Co., Ltd.)
・ Amine oxide-2: Dihydroxyethyl coconut oil alkylamine oxide (trade name “GENAMINOX CHE”, manufactured by Clariant Japan Co., Ltd.)
Amine oxide-3: Laurylamidopropyldimethylamine oxide (trade name “GENAMINOX AP”, manufactured by Clariant Japan Co., Ltd.)
Ingredient (B)
・ Glycerin: Trade name “Dense Glycerin S”, manufactured by Shin Nippon Rika Co., Ltd. ・ Diglycerin: Trade name “Diglycerin 801”, manufactured by Sakamoto Pharmaceutical Co., Ltd. ・ Polyvinyl alcohol: Trade name “GOHSENOL NH-18”, Japan Completely saponified by Chemical Synthesis Industry Co., Ltd.
Ingredient (C)
・ Diethanolamine: Shell Chemicals Japan Co., Ltd. ・ Triethanolamine: Trade name “TEA-99”, Shell Chemicals Japan Co., Ltd.
Ingredient (D)
・ Dodecylbenzene sulfonic acid: Trade name “Neopelex GS”, manufactured by Kao Corporation ・ Dodecyl diphenyl ether disulfonate Na: Sodium dodecyl diphenyl ether disulfonate (trade name “Eleminol MON-2” manufactured by Sanyo Chemical Industries, Ltd.)
Α-olefin sulfonic acid Na: α-olefin (C14-18) sodium sulfonate (trade name “Lipolane PB-800CJ”, manufactured by Lion Corporation)
Ingredient (E)
・ Isethonic acid: trade name “Adekatech HES-700H”, manufactured by ADEKA Corporation ・ Methanesulfonic acid: trade name “Lutropur MSA”, manufactured by BASF Japan Ltd. ・ ethane sulfonic acid: manufactured by HBCCChem, Inc.
Ingredient (F)
Polyoxyalkylene alkyl ether-1: polyoxyalkyl (7) alkyl (C10-12) ether (trade name “Conion EP-200” [The breakdown of the average number of moles of oxyalkylene group added is 1 mole of oxypropylene group , 6 mol of oxyethylene group], manufactured by Shin Nippon Rika Co., Ltd.)
Polyoxyalkylene alkyl ether-2: polyoxyethylene (10) decyl ether (trade name “Fine Surf D-1310”, manufactured by Aoki Oil & Fat Co., Ltd.)
Polyoxyalkylene alkyl ether-3: polyoxyalkylene tridecyl ether (trade name “Neugen TDX-80”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Ingredient (G)
・ N-methyl-2-pyrrolidone: manufactured by Mitsubishi Chemical Co., Ltd. ・ polyethylene glycol: trade name “PEG-400” manufactured by Sanyo Chemical Industries, Ltd.

From the evaluation results in Table 1, the following items (1) to (4) can be understood.
(1) Combining oxalic acid and component (A): amine oxide simultaneously exhibits good performance of rust removal, storage stability and foam properties, and enables use as a one-part type. It turns out that it is an essential combination (Examples 1-5 / Comparative Examples 1-6). In particular, when Example 1 and Comparative Example 1 are compared, for example, it can be read that the improvement of the foam characteristics is remarkable.
(2) When Example 3 and Comparative Example 3 are compared, component (B): trivalent or higher polyol compound and / or component (C): contributes to improvement in solubility of oxalic acid by adding an amine compound. It can be seen that this contributes to improvement of storage stability. Moreover, from Example 2 and Example 4, it turns out that a rust removal property improves more by using together a component (B) and a component (C).
(3) When Example 1 and Example 5 are compared, it turns out that foam characteristics are further improved by blending component (D): anionic surfactant.
(4) When Example 2 and Comparative Example 2 or Example 4 and Comparative Example 4 are respectively compared, the effect of improving the hard water resistance can be obtained by blending component (E): sulfonic acid compound. Recognize.

  The acidic reducing detergent composition of the present invention enables one-pack type, has high rust removal property, good storage stability (particularly low temperature stability), and good foam characteristics for foam cleaning. Therefore, it can be suitably used for foam cleaning of vehicles such as railway vehicles equipped with stainless steel exterior materials, aluminum exterior materials, painted exterior materials, stainless steel sinks, automobile brake discs, and the like.

Claims (7)

Oxalic acid and component (A): general formula (1)

{In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, a group represented by the following formula (a), or a group represented by the following formula (b). Represents.

[Wherein, X represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms. R ⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms. p represents 1-4. ]

[Wherein Y represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms. t shows the average addition mole number of an oxyethylene group, and represents 0.5-15. ]
R ² and R ³ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms or a hydroxyethyl group. }
The acidic cleaning composition for foam cleaning containing the amine oxide represented by these.   The content of the oxalic acid is 0.1 to 15 parts by weight and the content of the component (A) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. Item 10. The acidic cleaning composition for foam cleaning according to Item 1.   The acidic cleaning composition for foam cleaning according to claim 1 or 2, further comprising at least one selected from the group consisting of component (B): trivalent or higher polyol compound and component (C): amine compound. .   The upper limit of the content of the component (B) is 25 parts by weight and the upper limit of the content of the component (C) is 10 parts by weight with respect to 100 parts by weight of the acidic detergent composition for foam cleaning. The acidic cleaning composition for foam cleaning according to claim 3, wherein the total content of (B) and component (C) is 0.01 to 35 parts by weight.   Furthermore, component (D): The acidic cleaning composition for foam cleaning of Claim 3 or Claim 4 containing an anionic surfactant.   The acidic cleaning composition for foam cleaning according to any one of claims 1 to 5, wherein the acidic cleaning composition for foam cleaning is for foam cleaning of a stainless exterior material, an aluminum exterior material, or a coated exterior material. .   The acidic cleaning composition for foam cleaning according to any one of claims 1 to 5, wherein the acidic cleaning composition for foam cleaning is used for foam cleaning of an outer plate of a vehicle.