JP2013194064A - Detergent composition, manufacturing method therefor and method for storing and transporting the detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition having excellent low-temperature stability.SOLUTION: A detergent composition includes an alkaline silicate-containing aqueous solution comprising potassium ions, sodium ions, a water-soluble anhydride silicate compound and water. Potassium, in terms of KOH, is at least 10.0 mass% mass of the anhydrous silicate-containing aqueous solution; the molar ratio of potassium to sodium in the anhydrous silicate-containing aqueous solution is greater than or equal to 0.5; the water-soluble silicic-anhydride compound, in terms of SiO, is 1.0-24 mass% of the silicate-containing aqueous solution; water is at most 75 mass% of the silicate-containing aqueous solution; and the anhydrous silicate-containing aqueous solution exhibits fluidity even if allowed to stand for 500 hours at -20°C.

Description

  The present invention relates to a cleaning composition, a method for producing the same, and a method for storing and transporting the cleaning composition.

  Liquid detergent composition (in the present specification, “liquid detergent composition” means not only a liquid detergent composition, but also a lower limit fluidity (specifically, a liquid detergent composition that can be normally used as a detergent composition). Includes a cleaning composition in which solids are dispersed within a range that maintains a viscosity of 4500 mPa · s or less.) Is a cleaning function, that is, components to be removed such as oil adhering to the member to be cleaned. In addition to being excellent in the function of removing water, it may be required to be excellent in stability during storage.

  One of the factors for losing stability during storage of the liquid detergent composition is that the storage environment is low temperature. Therefore, liquid detergent compositions are usually used even when the detergent composition is in a low-temperature environment because the detergent composition is frozen or precipitates are generated in the detergent composition. It may be required as low temperature stability that the possibility of occurrence of less than the lower limit flowability (hereinafter referred to as “flow failure”) is sufficiently reduced. If the cleaning composition is excellent in low-temperature stability, the supply of cleaning composition into the cleaning tank by replenishing the pump, etc. may cause problems such as reduced controllability of the supply amount or inability to supply. Hateful.

  The lower limit temperature at which low temperature stability can be ensured is set according to the assumed use environment of the liquid detergent composition, but the lower limit temperature is usually −5 ° C., as described in Patent Document 1, for example. It is often said.

  However, when the manufactured liquid detergent composition is transported to a destination, or when the storage environment is not particularly controlled, the liquid detergent composition is placed in almost the same environment as the outside air. −20 ° C. may be required as a lower limit temperature (hereinafter, also referred to as “storage lower limit temperature”) that can secure the properties. When the minimum storage temperature of the liquid detergent composition is −20 ° C., it is almost the same as the outside air, except for a limited part such as part of Siberia or the north part of North America, even in the world. Even if the liquid detergent composition is placed in the environment, the possibility of freezing and poor flow is sufficiently low.

  In order to realize such a liquid detergent composition having a storage minimum temperature of −20 ° C., for example, as disclosed in Patent Documents 2 and 3, a component for improving low-temperature stability is used as a liquid detergent composition. It is common to make it contain in a thing.

  Specifically, Patent Document 2 discloses a transparent liquid detergent composition containing a surfactant in a range of 20 to 50% by weight, comprising (a) alpha-olefin sulfonic acid or an alkali metal salt thereof, (B) polyoxyethylene alkylsulfuric acid or an alkali metal salt thereof, and (c) a magnesium salt, wherein the component (a) / component (b) is in the range of 90/10 to 10/90 by weight ratio, And {(a) component + (b) component} / (c) component is the range of 99/1-75/25 by molar ratio, The transparent liquid detergent composition characterized by the above-mentioned is disclosed. In the composition disclosed in Patent Document 2, alpha olefin sulfonic acid or its alkali metal salt and polyoxyethylene alkylsulfuric acid or its alkali metal salt and magnesium salt are positioned as freeze inhibitors.

  Patent Document 3 discloses a high concentration characterized by blending 0.1 to 10% by weight of phosphonobutanetricarboxylic acid or a salt thereof in an alkaline liquid detergent composition containing 20 to 60% by weight of an alkaline agent. An alkaline liquid detergent composition is disclosed. In the composition disclosed in Patent Document 2, at least one of phosphonobutanetricarboxylic acid and a salt thereof is positioned as a freezing inhibitor.

JP 2009-242643 A JP-A-6-346099 JP 2000-303099 A

  However, in recent years, there may be a problem that the quality of a product including a member to be cleaned is deteriorated due to the components contained in the cleaning composition remaining in the member to be cleaned, and such a problem may occur. In some cases, it is required that the cleaning composition has an ability to reduce the amount. In addition to such a viewpoint, the number of components contained in the cleaning composition tends to decrease from the viewpoint of reducing the waste liquid treatment load and reducing the manufacturing cost.

  In the case of such a simplified composition, the technique as shown in the above-mentioned Patent Documents 2 and 3 can no longer be applied, and cleaning with excellent low-temperature stability can be set at a storage minimum temperature of −20 ° C. It is difficult to obtain an agent composition.

  This invention makes it a subject to provide the fluid detergent composition which has the outstanding low-temperature stability in view of this present condition. In the present specification, “having fluidity” means that the above-mentioned flow failure does not occur, and specifically means that the viscosity is 4500 mPa · s or less.

The present invention provided to solve the above problems is as follows.
(1) An alkaline silicate-containing aqueous solution comprising potassium ions, sodium ions, a water-soluble anhydrous silicic acid compound and water, and having a fluidity, wherein the silicate-containing aqueous solution The potassium content is 10.0% by mass or more in terms of KOH, the molar ratio of the potassium content to the sodium content in the silicate-containing aqueous solution is 0.5 or more, and the water-soluble silicic acid anhydride in the silicate-containing aqueous solution. The content of the compound is 1.0% by mass or more and 24% by mass or less in terms of SiO ₂ , and the content of water contained in the silicate-containing aqueous solution is 75% by mass or less, and the silicate content A cleaning composition, wherein the aqueous solution has fluidity even when left in a -20 ° C environment for 500 hours.

(2) Freezing inhibitor containing polyether polyol (A); Freezing inhibitor (B) containing at least one of phosphonobutanetricarboxylic acid and its salt; and alpha olefin sulfonic acid or its alkali metal salt and polyoxyethylene alkyl The cleaning composition according to the above (1), which does not contain any of the freezing inhibitor (C) containing sulfuric acid or its alkali metal salt and magnesium salt.

(3) The silicate-containing aqueous solution contains potassium hydroxide and sodium hydroxide and aqueous solutions of these hydroxides; a mixture of potassium oxide and silicic anhydride and a mixture of sodium oxide and anhydrous silicic acid. And an aqueous solution of a mixture thereof; and the cleaning composition according to the above (1) or (2), comprising two or more selected from the group consisting of water.

(4) The detergent composition according to (3), wherein the silicate-containing aqueous solution includes an aqueous solution of sodium hydroxide, an aqueous solution of a mixture of potassium oxide and anhydrous silicic acid, and water.

(5) The cleaning composition according to any one of (1) to (4), further including a chelating agent.

(6) The cleaning composition according to (5), wherein the chelating agent contains at least one of a nitrogen-containing substance and a phosphorus-containing substance.

(7) The cleaning composition according to (5) or (6), wherein the chelating agent has a chelating function with respect to an alkaline earth metal.

(8) The cleaning composition according to any one of (2) to (4), which is contained in a surfactant.

(9) The cleaning composition according to any one of (5) to (7), further including a surfactant.

(10) An aqueous composition for preparing the cleaning composition described in any one of (1) to (9) above, which is any one of (1) to (4) above An aqueous composition comprising the silicate-containing aqueous solution described.

(11) It is obtained by the manufacturing method provided with the process of mixing the aqueous composition and chelating agent described in said (10), It is described in any one of said (1) to (4) A detergent composition comprising a silicate-containing aqueous solution and the chelating agent.

(12) The method according to any one of (1) to (4), which is obtained by a production method including a step of mixing the aqueous composition described in (10) and a surfactant. A detergent composition comprising the described silicate-containing aqueous solution and the surfactant.

(13) Any one of (1) to (4) above, which is obtained by a production method comprising a step of mixing the aqueous composition, chelating agent and surfactant described in (10) above. A cleaning composition containing the silicate-containing aqueous solution described in 1., the chelating agent and the surfactant.

(14) An aqueous composition for preparing the cleaning composition described in any one of (1) to (9) above, which is any one of (1) to (4) above An aqueous composition comprising the described silicate-containing aqueous solution and a chelating agent.

(15) Any one of (1) to (4) above, which is obtained by a production method comprising a step of mixing the silicate-containing aqueous solution described in (14) above and a surfactant. A cleaning composition containing the silicate-containing aqueous solution described in the paragraph, the chelating agent, and the surfactant.

(16) The method for producing a cleaning composition according to any one of (9), (13) and (15) above, with respect to the content of the surfactant in the cleaning composition. method for producing a detergent composition the ratio R _c of the content of the chelating agent, and setting in response to the removal target components to be attached to the cleaning member.

(17) The manufacturing method according to (16), wherein the ratio _Rc is increased when the component to be removed has an alkaline earth metal.

(18) A cleaning method for cleaning a member to be cleaned using the cleaning composition described in any one of (1) to (9), (11) to (13) and (15).

(19) A cleaning method for cleaning a member to be cleaned using the cleaning composition produced by the production method described in (16) or (17) above.

(20) Store the cleaning composition described in any one of (1) to (9), (11) to (13) and (15) in an environment of -20 ° C or higher and lower than -5 ° C. Storage method of cleaning composition.

(21) A method for storing an aqueous composition, wherein the aqueous composition described in (10) or (14) is stored in an environment of -20 ° C or higher and lower than -5 ° C.

(22) Transport the cleaning composition described in any one of (1) to (9), (11) to (13) and (15) in an environment of -20 ° C or higher and lower than -5 ° C. A method for transporting a cleaning composition.

(23) A method for transporting a cleaning composition, which transports the aqueous composition described in (10) or (14) in an environment of -20 ° C or higher and lower than -5 ° C.

  According to the present invention, there is provided a cleaning liquid composition having excellent low-temperature stability, which can have a storage lower limit temperature of −20 ° C. or lower.

An embodiment of the present invention will be described.
The cleaning composition according to this embodiment has fluidity. In this embodiment, having fluidity means that the viscosity is 4500 mPa · s or less as described above. The cleaning composition according to the present embodiment is preferably a colloid or a liquid and is substantially free of visible-size solids. In the case of containing such a solid, there is a possibility that crystallization will proceed with this as a nucleus at a low temperature, or the temperature at which such crystallization starts may increase.

1. Silicate-containing aqueous solution The cleaning composition according to this embodiment contains an alkaline silicate-containing aqueous solution composed of potassium ions, sodium ions, a water-soluble anhydrous silicic acid compound, and water.

  Here, in the present embodiment, “water” is a general term for a group of substances consisting of water molecules, hydrogen ions and hydroxide ions, and the silicate-containing aqueous solution according to the present embodiment is alkaline. The hydrogen ion concentration contained in water is lower than the hydroxide ions contained in water.

In the present embodiment, “containing a silicate-containing aqueous solution” includes the following cases.
(A) When manufacturing the cleaning composition which concerns on this embodiment at the time of making silicate containing aqueous solution at least one part of a raw material (B) The cleaning composition which concerns on this embodiment other than silicate containing aqueous solution A hypothetical silicate obtained by theoretically excluding the second component from the composition of the cleaning agent composition according to the present embodiment in the case of containing the component (referred to as “second component” in the present embodiment) When the aqueous solution contains the following compositional requirements

  In the silicate-containing aqueous solution according to the embodiment, potassium ions and sodium ions are hydrated or chemically interact with each other through silicic anhydride and water.

In the present embodiment, the “water-soluble silicic acid anhydride compound” refers to other substances (such as water) in which the silicic acid (SiO ₂ ) molecule and the silicic acid anhydride are contained in the silicate-containing aqueous solution according to the present embodiment, such as water. Specifically, water molecules and other silicic acid molecules are exemplified.) A general term for those in a state of chemically interacting with each other.

  The silicate-containing aqueous solution according to the present embodiment is substantially free of components other than potassium ions, sodium ions, water-soluble anhydrous silicate compounds, and water. Here, “substantially free” means that the silicate-containing aqueous solution may contain impurities (lithium component, magnesium component, aluminum component, etc.) that are inevitably mixed in the production process. .

(1) Composition By satisfying the following compositional conditions, the silicate-containing aqueous solution according to the present embodiment can have fluidity even when left in an environment at −20 ° C. for 500 hours.

(1-1) Potassium content Potassium content of the silicate-containing aqueous solution according to the present embodiment (in the present embodiment, "potassium content" refers to the content of components containing potassium contained in the silicate-containing aqueous solution. Means 10.0% by mass or more in terms of KOH. Since the solubility in water is higher in potassium than in sodium, when the potassium content of the silicate-containing aqueous solution is less than 10.0% by mass in terms of KOH, it has fluidity if it is up to about −5 ° C. Even in some cases, when it is cooled to −20 ° C., precipitation occurs and the fluidity is lost. Therefore, problems such as poor flow occur in the cleaning composition containing such a silicate-containing aqueous solution. From the viewpoint of further reducing the possibility of problems such as poor flow in the cleaning composition when stored at −20 ° C., the potassium content of the silicate-containing aqueous solution according to this embodiment is 11 mass in terms of KOH. % Or more, more preferably 18% by mass or more, and further preferably 25% by mass or more.
The upper limit of the potassium content of the silicate-containing aqueous solution according to the embodiment should be appropriately set in relation to other components such as a water-soluble silicic acid anhydride compound and water.

(1-2) Molar ratio of potassium to sodium content The molar ratio of potassium to sodium content in the silicate-containing aqueous solution according to this embodiment (also referred to as “K / Na ratio” in this embodiment) is 0. .5 or more. A detergent composition in which the K / Na ratio is 0.5 or more and the above-mentioned conditions such as the potassium content are satisfied, so that problems such as poor flow are unlikely to occur even when placed in an environment at −20 ° C. for 500 hours. Is realized. When the K / Na ratio is less than 0.5, it becomes difficult to satisfy the above-mentioned conditions regarding the potassium content, and problems such as poor flow may occur in the cleaning composition when stored at −20 ° C. Rise. From the viewpoint of more stably reducing the possibility of occurrence of poor flow over a longer period, for example, 800 hours or more, the K / Na ratio of the silicate-containing aqueous solution according to this embodiment may be 0.6 or more. Preferably, it is 1.5 or more, more preferably 5 or more.
The upper limit of the K / Na ratio of the silicate-containing aqueous solution according to the present embodiment should be appropriately set in relation to other components such as a water-soluble silicic acid anhydride compound and water.

(1-3) Content of water-soluble anhydrous silicic acid compound The content of the water-soluble anhydrous silicic acid compound in the silicate-containing aqueous solution according to this embodiment is 1.0% by mass or more and 24% by mass or less in terms of SiO _2. It is. By being in this range, the possibility that the silicate-containing aqueous solution loses fluidity when stored at −20 ° C. can be reduced. In particular, when the SiO ₂ equivalent content of the water-soluble silicic acid compound is less than 1.0% by mass, it is −20 ° C. even if it is in a state of fluidity up to about −5 ° C. When it is cooled down, the possibility of losing fluidity increases due to precipitation. From the viewpoint of more stably reducing this possibility, the content of the water-soluble silicic acid compound in terms of SiO ₂ is preferably 1.0% by mass or more and 20.0% by mass or less, and 5.0% by mass or more. More preferably, it is 15.0% by mass or less.

(1-4) Water Content The water content in the silicate-containing aqueous solution according to this embodiment is 75% by mass or less. By being in this range, the possibility that the silicate-containing aqueous solution loses fluidity when stored at −20 ° C. can be reduced. If the water content is excessively high, it becomes difficult to obtain the effect of freezing prevention due to the freezing point depression, and the silicate-containing aqueous solution tends to lose its fluidity. From the viewpoint of more stably reducing the possibility of such a tendency, the water content is preferably 70% by mass or less. Moreover, by reducing the water content, a relatively large amount of the water-soluble silicic anhydride compound can be contained. In such a case, the detergency may increase, so it may be more preferable to increase the content of the water-soluble silicic acid anhydride by setting the water content to 65% by mass or less depending on the application.
On the other hand, the lower limit of the moisture content is not singly defined. For example, if the water content decreases and, as a result, the content of the water-soluble silicic acid anhydride compound in terms of SiO ₂ increases, the possibility that the aqueous solution containing silicate loses fluidity increases. In addition, when the potassium content is low or the K / Na ratio is low, the content (sodium content) of sodium-containing components with relatively low solubility increases, so that the silicate-containing aqueous solution is fluid. The tendency to lose is easily manifested. From the viewpoint of more stably reducing the possibility of such a problem, the lower limit of the moisture content is preferably 40% or more, and more preferably 45% or more. Reduce the possibility of the above problems more stably, reduce the possibility of poor handling, avoid the possibility of safety management problems due to excessively concentrated liquids, etc. From this viewpoint, the water content in the silicate-containing aqueous solution is preferably 49.0% by mass or more, and more preferably 50.0% by mass or more. From the viewpoint of stably reducing the possibility of problems due to lowering of fluidity particularly over a long period of time, the water content in the silicate-containing aqueous solution is preferably 51% by mass or more, 52 It is more preferable to set it as mass% or more.

(2) Material component The material component which comprises the silicate containing aqueous solution which concerns on this embodiment is not specifically limited. For example, you may make it consist of 2 or more types chosen from the group which consists of the following component.
Potassium hydroxide,
Sodium hydroxide,
Aqueous solution of potassium hydroxide,
Aqueous solution of potassium hydroxide,
A mixture of potassium oxide and silicic anhydride,
A mixture of sodium oxide and silicic anhydride,
An aqueous solution of a mixture of potassium oxide and silicic anhydride,
An aqueous solution of a mixture of sodium oxide and silicic acid, and water.

  As a more specific example, the silicate-containing aqueous solution may be composed of an aqueous solution of sodium hydroxide, an aqueous solution of a mixture of potassium oxide and anhydrous silicic acid, and water. Alkali metal hydroxides and a mixture of potassium oxide and silicic anhydride are easier to handle if they are previously stored as an aqueous solution. In addition, since both are strong alkaline substances, handling them as solids such as powder increases the possibility of problems in health and safety.

2. Second Component The cleaning composition according to the present embodiment may further contain a component (including a solvent) other than the components constituting the silicate-containing aqueous solution as the second component. As described above, from the viewpoint of meeting the recent demand for simplifying the composition of the cleaning composition, the cleaning composition according to the present embodiment includes only the above-mentioned silicate-containing aqueous solution or a solvent. A diluted one may be used.

  In addition, the cleaning composition according to the present embodiment includes at least one of a freeze inhibitor (A) containing a polyether polyol (phosphonobutanetricarboxylic acid and a salt thereof) as disclosed in Patent Documents 2 and 3. Freezing inhibitor (B); and none of freezing inhibitor (C) containing alpha olefin sulfonic acid or its alkali metal salt and polyoxyethylene alkylsulfuric acid or its alkali metal salt and magnesium salt are contained as the second component It is preferable. Moreover, it is preferable not to contain the polyethylene glycol often used for antifreeze as a second component.

(1) Chelating agent The second component may contain a chelating agent. The specific kind of chelating agent is not particularly limited. The composition of the member to be cleaned, the composition of the component to be removed adhering to the surface of the member to be cleaned, the quality required in the state after cleaning of the member to be cleaned (such as the allowable level of surface residual substances), and the composition of the cleaning composition It may be set as appropriate in consideration of the above.

  Examples of chelating agents include aminopolycarboxylic acid chelating agents, aromatic or aliphatic carboxylic acid chelating agents, amino acid chelating agents, ether carboxylic acid chelating agents, phosphonic acid chelating agents, and hydroxycarboxylic acid chelating agents. , Polymer electrolyte (including oligomer electrolyte) chelating agents, nitrogen-containing chelating agents such as polyalcohol and dimethylglyoxime, and sulfur-containing chelating agents such as thioglycolic acid.

  The form of these chelating agents is arbitrary. For example, in the case of an acid-based chelating agent, it may be in the free acid form or in the form of a salt such as sodium salt, potassium salt or ammonium salt. Furthermore, they may be in the form of their ester derivatives which are hydrolysable.

  Examples of aminopolycarboxylic acid chelating agents include ethylenediaminetetraacetic acid (EDTA), ethylenediaminediacetic acid, hydroxyethylethylenediaminetriacetic acid (HEDTA), dihydroxyethylethylenediaminetetraacetic acid (DHEDDA), nitriloacetic acid (NTA), and hydroxyethyl. Iminodiacetic acid (HIDA), β-alanine diacetic acid, cyclohexanediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, diethylenetriaminepentaacetic acid, N- (2-hydroxyethyl) ethylenediaminetriacetic acid, Glycol ether diamine tetraacetic acid, glutamic acid diacetic acid, aspartic acid diacetic acid, methylglycine diacetic acid, iminodisuccinic acid, serine diacetic acid, hydroxyiminodisucci , Dihydroxyethyl glycine, aspartic acid, and glutamic acid, as well as derivatives such as their salts and esters.

  Examples of aromatic or aliphatic carboxylic acid-based chelating agents include glyoxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, itaconic acid, aconitic acid, and pyruvic acid. , Gluconic acid, pyromellitic acid, benzopolycarboxylic acid, cyclopentanetetracarboxylic acid, salicylic acid, acetylsalicylic acid, hydroxybenzoic acid, aminobenzoic acid (including anthranilic acid), phthalic acid, fumaric acid, trimellitic acid, gallic acid And hexahydrophthalic acid, and salts and derivatives thereof.

  Examples of the amino acid chelating agent include glycine, serine, alanine, lysine, cystine, cysteine, ethionine, tyrosine, and methionine, and salts and derivatives thereof.

  Ether carboxylates include carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid monosuccinate, and tartaric acid disuccinate, and salts and derivatives thereof.

  Examples of phosphonic acid chelating agents include iminodimethylphosphonic acid, alkyldiphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and phytic acid, and salts and derivatives thereof.

  Examples of the hydroxycarboxylic acid chelating agent include malic acid, citric acid, glycolic acid, gluconic acid, heptonic acid, tartaric acid, and lactic acid, and salts and derivatives thereof.

  Examples of the polymer electrolyte (including oligomer electrolyte) chelating agent include acrylic acid polymer, maleic anhydride polymer, α-hydroxyacrylic acid polymer, itaconic acid polymer, and two constituent monomers of these polymers. The copolymer which consists of the above and an epoxy succinic acid polymer are mentioned.

  Polyalcohols include ethylene glycol, pyrocatechol, pyrogallol, bisphenol, and tannic acid, and derivatives thereof. In addition, it is preferable not to use a polyol polyalcohol such as polyethylene glycol which has been used for enhancing the low-temperature stability of the cleaning composition.

  The chelating agent to be contained as the second component may be composed of one kind of substance or may be composed of two or more kinds of substances.

  When the chelating agent to be contained as the second component contains at least one of a nitrogen-containing substance and a phosphorus-containing substance, the cleaning performance is often improved. In the above examples, at least an aminopolycarboxylic acid chelating agent, an amino acid chelating agent and a nitrogen-containing chelating agent are contained in the nitrogen-containing material, and at least a phosphonic acid chelating agent is contained in the phosphorus-containing material.

  Depending on the material of the member to be cleaned, when the member to be cleaned is machined, the processing oil may contain a component containing an alkaline earth metal such as calcium. In such a case, the chelating agent to be contained as the second component has a chelating function with respect to the alkaline earth metal, so that the removal target component composed of the component containing the alkaline earth metal can be efficiently cleaned. It can be removed from the member.

  The content of the chelating agent to be contained as the second component should be set by appropriately considering the same factors as in the case of the type of chelating agent. This point will be described later.

(2) Surfactant The cleaning composition according to this embodiment may contain a surfactant as the second component. The kind is not particularly limited. Further, the surfactant may be composed of one type of substance or may be composed of a plurality of types of substances.

  Specific examples of the surfactant include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a semipolar surfactant, and an anionic surfactant.

  Specific examples of the anionic surfactant include polyoxyethylene alkyl sulfate, alkyl or alkenyl sulfate, polyoxyethylene alkyl or alkenyl sulfate, alkyl benzene sulfonate, alkane sulfonate, alkyl or alkenyl ether. Carboxylate, α-sulfo fatty acid derivative, α-olefin sulfonate, α-sulfo fatty acid alkyl ester salt, sulfosuccinate, alkyl phosphate ester salt, natural fatty acid soap, alkyl ethoxy sulfate, amide ether carboxylic acid, amino acid anion activator Etc. are exemplified.

  Specific examples of the nonionic surfactant include polyoxyalkylene alkyl ether, fatty acid alkanolamide, polyoxyethylene sorbitan ester, sorbitan ester, sorbitol ester, sucrose fatty acid ester, methyl glucoside ester, methyl mannoside ester, ethyl Glucoside ester, N-methyl glucamide, cyclic N-methyl glucamide, alkyl glucoside, alkyl polyglucoside, alkyl glyceryl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene acyl ester, fatty acid glycoside ester, fatty acid methyl glycoside Examples include esters and alkylmethylglucamides.

  Specific examples of the amphoteric surfactant include carboxybetaine, aminocarboxylate, alkylsulfobetaine, hydroxyalkylsulfobetaine, alkylimidazolinium betaine, alkylbetaine, and alkylamidopropylbetaine.

  Specific examples of the semipolar surfactant include alkylamine oxide, alkylamidoamine oxide, alkylhydroxyamine oxide and the like.

  Specific examples of the cationic surfactant include dilong chain alkyldimethyl quaternary ammonium ions, long chain alkyldimethyl quaternary ammonium ions, alkylammonium ions, and quaternary ammonium ions. These are usually blended in the form of hydrochloride.

  Of these surfactants, anionic surfactants and nonionic surfactants are preferred. Furthermore, specific examples of preferable surfactants include alkyl ether sulfate, sodium alkylbenzene sulfonate, polyoxyethylene alkyl ether, coconut fatty acid alkanolamide, and fatty acid amidopropyl betaine.

In the case where the cleaning composition according to the present embodiment contains a chelating agent and a surfactant as the second component, the content of the chelating agent with respect to the content of the surfactant in the cleaning composition according to the present embodiment the ratio R _c of the amount, it is preferably set according to the removal target components to be attached to the cleaning member. For example, when the main component of the component to be removed is mineral oil and hardly contains any added component, it is preferable to use a large amount of a surfactant having an excellent ability to clean the oily substance. Therefore, in such a case, the ratio _Rc may be lowered when manufacturing the cleaning composition. On the other hand, for example, a calcium-based additive is added to the processing oil for the purpose of improving processability when the member to be cleaned is manufactured by machining, and therefore a lot of such substances are included in the components to be removed. It is preferable to use a large amount of a chelating agent having an excellent ability to wash such substances. Therefore, in such a case, the ratio _Rc may be increased when manufacturing the cleaning composition.

(3) Other components The cleaning composition according to the present embodiment may contain components other than the chelating agent and the surfactant as the second component, as long as the low temperature stability is not significantly inhibited. Examples of such components include sequestering agents, neutral inorganic salts, antioxidants and antifoaming agents. What is necessary is just to set these content suitably. A solvent may be included as a second component for concentration adjustment. As a solvent in this case, a polar solvent such as an alcohol may be used in addition to water, but the type and amount used should not significantly inhibit the low-temperature stability of the cleaning composition according to this embodiment. It is.

3. Manufacturing method The manufacturing method of the cleaning composition which concerns on this embodiment is not specifically limited. Raw material that provides ingredients to be included as a detergent composition, that is, a potassium source that provides potassium ions, a sodium source that provides sodium ions, a silicic acid source and water that provides a water-soluble silicic acid compound, and, if necessary, a chelate A second component such as an agent and a surfactant may be appropriately mixed to form a solution. In preparing a solution, a mixture of some or all of these components may be heated. The heating temperature for heating is arbitrary. In order to mitigate the influence of the component that generates heat of dissolution, the above mixture may be cooled.

  When an aqueous composition (hereinafter, also referred to as “first aqueous composition”) used for preparing the cleaning composition according to the present embodiment is one comprising the above-mentioned silicate-containing aqueous solution. Since the cleaning composition which concerns on this embodiment can be manufactured only by mixing this 1st aqueous composition and 2nd component, it is preferable. Moreover, since the first aqueous composition itself has excellent low-temperature stability, it can be stably stored even in a low-temperature environment as high as −20 ° C.

  If the specific example of the cleaning composition which concerns on this embodiment manufactured using this 1st aqueous composition is shown, a manufacturing method provided with the process of mixing a 1st aqueous composition and a chelating agent will be implemented. By this, the cleaning composition which concerns on this embodiment containing a silicate containing aqueous solution and a chelating agent is obtained. By performing the manufacturing method including the step of mixing the first aqueous composition and the surfactant, the cleaning composition according to this embodiment containing the silicate-containing aqueous solution and the surfactant is obtained. A cleaning agent according to this embodiment containing a silicate-containing aqueous solution, a chelating agent, and a surfactant by carrying out a production method comprising a step of mixing the first aqueous composition, the chelating agent, and the surfactant. A composition is obtained.

  As another one of the aqueous compositions used for preparing the cleaning composition according to this embodiment (hereinafter, also referred to as “second aqueous composition”), the silicate-containing aqueous solution described above and When a composition comprising a chelating agent that is one of the second components is used, the second aqueous composition and the second component (which may be a chelating agent) are simply mixed and the present embodiment is applied. Since a cleaning composition can be manufactured, it is preferable. Moreover, unless the content of the chelating agent contained in the second aqueous composition is excessively high, the second aqueous composition itself has excellent low-temperature stability, so that it reaches -20 ° C. Even in a low temperature environment, it can be stably stored. In addition, since the upper and lower limits of the content of the chelating agent that can be contained in the second aqueous composition are determined by the type of chelating agent, the composition of the silicate-containing aqueous solution, etc., it cannot be defined definitely. However, it is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 2.5% by mass or more and 25% by mass with respect to the silicate-containing aqueous solution.

  If the specific example of the cleaning composition concerning this embodiment manufactured using this 2nd aqueous composition is shown, a manufacturing method provided with the process of mixing the 2nd aqueous composition and surfactant will be carried out. By doing, the cleaning composition which concerns on this embodiment containing a silicate containing aqueous solution, a chelating agent, and surfactant is obtained.

4). Cleaning Method, Storage Method, Transport Method (1) Cleaning Method The cleaning composition according to this embodiment described above can be obtained as it is or by appropriately diluting with a solvent such as water. The dilution ratio is arbitrary, and is set as appropriate according to the type and amount of the component to be removed (oil etc.) adhering to the member to be cleaned.

  The member to be cleaned can be cleaned by bringing the obtained cleaning liquid into contact with the member to be cleaned. The material of the member to be cleaned is not particularly limited, but unless the cleaning composition according to the present embodiment contains a special second component, since the cleaning liquid is alkaline, its surface is constituted by a material that is not easily affected by alkali. It is preferable. As an example of such a member to be cleaned, a member to be cleaned having a surface made of a metal-based material such as an iron-based material is exemplified. The shape of the member to be cleaned is also arbitrary, and may be a primary processed product such as a plate, bar, wire, or the like, or a secondary processed product such as a bolt, nut, pressed product, bent product, forged product, or cast product. It may be a processed product or a product being processed.

  The contact method between the member to be cleaned and the cleaning liquid is arbitrary, and the member to be cleaned may be immersed in the cleaning liquid, or the cleaning liquid may be sprayed onto the member to be cleaned. During cleaning, the member to be cleaned may be rubbed with a brush, waste cloth, sponge, or the like. Further, the member to be cleaned may be cleaned while applying an ultrasonic impact, or the cleaning liquid may be heated. Thereafter, by washing with water and drying, the member to be cleaned from which the object to be removed attached thereto has been removed can be obtained.

(2) Storage method, transportation method As described above, the cleaning composition and the aqueous composition (first aqueous composition, second aqueous composition) according to this embodiment have excellent low-temperature stability. Therefore, even if these cleaning compositions or aqueous compositions are stored in an environment of -20 ° C or higher and lower than -5 ° C, the possibility that they will cause problems such as poor flow during storage is sufficiently reduced. Yes. Moreover, even if these detergent compositions or aqueous compositions are transported in an environment of −20 ° C. or higher and lower than −5 ° C., the possibility that they cause problems such as poor flow is sufficiently reduced.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

Example 1
Potassium source and 48% aqueous solution of KOH as part of the water supply source, sodium source and a 50% aqueous solution of Na _{2 O} · SiO 2 as a part of the water supply source, and a source of water needed As a part, pure water is mixed in an amount as shown in Tables 1 to 3 (units are parts by mass), and the test solutions of Test Nos. 1 to 27 are composed of a silicate-containing aqueous solution. Created as a thing. Specifically, a 48% aqueous solution of KOH and / or a 50% aqueous solution of Na ₂ O · SiO ₂ were mixed, or these were added to pure water. Since heat was generated when these components were mixed, a colorless and transparent test solution could be obtained without particular heating by adjusting the mixing amount and addition amount of these components.

  For each of the obtained test solutions, 125 ml of the test solution was placed in two 250 ml plastic (polypropylene) containers, the upper part of the container was covered with a transparent sheet, and the inside of the container was sealed. One container with the test solution was allowed to stand in an environment at −5 ° C., and the other container with the test solution was left in an environment at −20 ° C.

  Three weeks after standing, the test liquid in each container was visually observed in an environment of −20 ° C., and the liquid property was confirmed by rocking the container as necessary. As a result, the low temperature stability of each test solution was evaluated by determining which of the following states “A” to “F” belonged to. When the state of the test solution in the container placed in an environment of −20 ° C. is any one of “A”, “B”, and “C”, the silicate-containing aqueous solution and the washing related to the test solution The agent composition was determined to be excellent in low temperature stability. When evaluating the fluidity, the viscosity of the viscometer calibration standard liquid (type: JIS14000) based on JIS Z8809 at 30 ° C. (corresponding to a viscosity of approximately 4800 mPa · s) is shown. It was determined whether the test liquid to be evaluated has fluidity.

A: The transparent appearance is maintained and has fluidity equivalent to that at the beginning of manufacture. B: The transparent appearance is maintained and has fluidity, but the viscosity is slightly higher than that at the beginning of manufacture. C: The transparent appearance is maintained and manufactured. D: Transparent appearance is maintained, but fluidity is poor E: Precipitation is observed and the transparent appearance is not maintained, fluidity is increased. F: Frozen, transparent appearance is not maintained

  The evaluation results are shown in Tables 1 to 3. In addition, even if the liquid of test number 1 was evaluated when the standing time in an environment of −20 ° C. passed 1300 hours, it was still determined as B. Further, the solutions of Test Nos. 3, 9 and 10 were also determined as A even when evaluated when the standing time in an environment of −20 ° C. passed 1300 hours. Even if the solutions of Test Nos. 11 to 14, 17 to 21, 23, and 24 were evaluated when the standing time in an environment of −20 ° C. passed 800 hours, the results were evaluated when 500 hours passed. The result was the same. The solution of test number 25 was determined to be E when evaluated when the standing time in an environment of −20 ° C. passed 800 hours.

The present invention provided to solve the above problems is as follows.
(1) A detergent composition comprising an alkaline silicate-containing aqueous solution comprising potassium ions, sodium ions, a water-soluble silicic acid anhydride compound and water, and having fluidity, wherein potassium of the detergent composition The amount is 10.0% by mass or more in terms of KOH, the molar ratio of potassium to sodium in the cleaning composition is 0.5 or more, and the water-soluble silicic acid compound is contained in the cleaning composition The amount is 1.0% by mass or more and 24% by mass or less in terms of SiO ₂ , the water content contained in the detergent composition is 75% by mass or less, and the detergent composition is −20 ° C. also it is 500 hours standing under environment all SANYO having fluidity, the detergent composition is a colloidal or liquid, anti-freezing agent comprising a polyether polyol (a); Hosuhonobutanto Freezing inhibitor (B) containing at least one of recarboxylic acid and its salt; and Freezing inhibitor (C) containing alpha olefin sulfonic acid or its alkali metal salt and polyoxyethylene alkylsulfuric acid or its alkali metal salt and magnesium salt A cleaning composition containing none of the above.

(2) The silicate-containing aqueous solution includes potassium hydroxide, sodium hydroxide, potassium hydroxide aqueous solution, potassium hydroxide aqueous solution, a mixture of potassium oxide and anhydrous silicic acid, oxidation The above (1) comprising at least two selected from the group consisting of a mixture of sodium and anhydrous silicic acid, an aqueous solution of a mixture of potassium oxide and anhydrous silicic acid, an aqueous solution of a mixture of sodium oxide and anhydrous silicic acid, and water detergent composition according to.

(3) The cleaning composition according to (3), wherein the silicate-containing aqueous solution includes an aqueous solution of potassium hydroxide, an aqueous solution of a mixture of sodium oxide and anhydrous silicic acid, and water.

(4) The cleaning composition according to any one of (1) to (3) , further including a chelating agent.

(5) The cleaning composition according to (4) , wherein the chelating agent contains at least one of a nitrogen-containing substance and a phosphorus-containing substance.

(6) The cleaning composition according to (4) or (5) , wherein the chelating agent has a chelating function for alkaline earth metals.

(8) The cleaning composition according to any one of (1) to (6) , which contains a surfactant.

Claims (23)

An alkaline silicate-containing aqueous solution comprising potassium ions, sodium ions, a water-soluble silicic acid anhydride compound and water, and a fluidity cleaning composition comprising:
The potassium content of the silicate-containing aqueous solution is 10.0% by mass or more in terms of KOH,
The molar ratio of potassium to sodium in the silicate-containing aqueous solution is 0.5 or more,
The content of water-soluble silicic anhydride compound in the silicate-containing aqueous solution is not more than 24 mass% 1.0 mass% or more in terms of SiO _2,
The water content contained in the silicate-containing aqueous solution is 75% by mass or less,
The detergent composition according to claim 1, wherein the silicate-containing aqueous solution has fluidity even when left in an environment of -20 ° C for 500 hours.   Freezing inhibitor (A) containing polyether polyol; Freezing inhibitor (B) containing at least one of phosphonobutanetricarboxylic acid and its salt; and alpha olefin sulfonic acid or its alkali metal salt and polyoxyethylene alkyl sulfuric acid or its The cleaning composition of Claim 1 which does not contain any of the freezing inhibitor (C) containing an alkali metal salt and a magnesium salt.   The silicate-containing aqueous solution comprises potassium hydroxide and sodium hydroxide and aqueous solutions of these hydroxides; a mixture of potassium oxide and anhydrous silicic acid and a mixture of sodium oxide and anhydrous silicic acid and these The cleaning composition according to claim 1 or 2, comprising an aqueous solution of a mixture; and two or more selected from the group consisting of water.   The cleaning composition according to claim 3, wherein the silicate-containing aqueous solution comprises an aqueous solution of sodium hydroxide, an aqueous solution of a mixture of potassium oxide and anhydrous silicic acid, and water.   The cleaning composition according to any one of claims 1 to 4, further comprising a chelating agent.   The cleaning composition according to claim 5, wherein the chelating agent contains at least one of a nitrogen-containing substance and a phosphorus-containing substance.   The cleaning composition according to claim 5 or 6, wherein the chelating agent has a chelating function for an alkaline earth metal.   The cleaning composition according to any one of claims 2 to 4, which is contained in a surfactant.   The cleaning composition according to any one of claims 5 to 7, further comprising a surfactant.   It is an aqueous composition for preparing the cleaning composition as described in any one of Claims 1-9, Comprising: From the silicate containing aqueous solution as described in any one of Claims 1-4. An aqueous composition characterized by comprising:   The silicate-containing aqueous solution according to any one of claims 1 to 4, which is obtained by a production method comprising a step of mixing the aqueous composition described in claim 10 and a chelating agent. A cleaning composition containing the chelating agent.   The silicate-containing composition according to any one of claims 1 to 4, which is obtained by a production method including a step of mixing the aqueous composition described in claim 10 and a surfactant. A cleaning composition comprising an aqueous solution and the surfactant.   The silicate as described in any one of Claim 1 to 4 obtained by the manufacturing method provided with the process of mixing the aqueous composition described in Claim 10, a chelating agent, and surfactant. A cleaning composition comprising a containing aqueous solution, the chelating agent, and the surfactant.   An aqueous composition for preparing the cleaning composition according to any one of claims 1 to 9, wherein the silicate-containing aqueous solution according to any one of claims 1 to 4. And an aqueous composition comprising a chelating agent.   The silicic acid as described in any one of Claim 1 to 4 obtained by the manufacturing method provided with the process of mixing the silicate containing aqueous solution described in Claim 14, and surfactant. A detergent composition comprising a salt-containing aqueous solution, the chelating agent, and the surfactant. It is a manufacturing method of the cleaning composition described in any one of Claim 9, 13, and 15, Comprising: Ratio of content of the said chelating agent with respect to content of the said surfactant in the said cleaning composition. _Rc is set according to the removal object component adhering to a member to be cleaned, The manufacturing method of the cleaning composition characterized by the above-mentioned. The manufacturing method according to claim 16, wherein the ratio _Rc is increased when the component to be removed has an alkaline earth metal.   A cleaning method for cleaning a member to be cleaned using the cleaning composition according to any one of claims 1 to 9, 11 to 13 and 15.   A cleaning method for cleaning a member to be cleaned using the cleaning composition manufactured by the manufacturing method according to claim 16.   The storage method of the cleaning composition which stores the cleaning composition as described in any one of Claims 1-9, 11-13, and 15 in the environment of -20 degreeC or more and less than -5 degreeC.   The storage method of the aqueous composition which stores the aqueous composition described in Claim 10 or 14 in the environment of -20 degreeC or more and less than -5 degreeC.   The conveyance method of the cleaning composition which conveys the cleaning composition as described in any one of Claims 1-9, 11-13, and 15 in -20 degreeC or more and less than -5 degreeC environment.   The transportation method of the cleaning composition which conveys the aqueous composition described in Claim 10 or 14 in the environment of -20 degreeC or more and less than -5 degreeC.