JP5062966B2 - Chelate compound-containing composition and its use as a cleaning agent - Google Patents

Description

The present invention relates to a chelate compound-containing composition and its use for a cleaning agent. More specifically, organic chelating agents, scale inhibitors, water treatment agents, detergent builders, bleaching aids, masking agents, fiber treatment agents, paper and pulp additives, semiconductor detergents, photographic agents, soil modifiers, etc. Chelate compound-containing composition useful for food, and chelate compound-containing composition useful for various cleaning in various fields such as food industry, chemical industry and machine industry, and cleaning by automatic dishwashers for home use and business use It relates to the use for cleaning agents.

Since the composition containing a chelate compound is capable of forming a complex with various metal ions and the like, an organic chelating agent, a scale inhibitor, a water treatment agent, a builder for detergents, a bleaching aid, a masking agent, It is suitably used in various applications such as fiber treatment agents, paper / pulp additives, semiconductor detergents, photographic agents, soil modifiers and the like. Examples of such a composition include those in which a chelate compound is dissolved in an alkaline aqueous solution. For convenience in transportation and storage, the chelate compound is highly concentrated and stable in a high-concentration alkaline solution. What is dissolved is desired.

Concerning a conventional aqueous solution composition containing a chelate compound, it contains an iminocarboxylate having a specific structure, and the isomer ratio of the aspartic acid skeleton portion of the iminocarboxylate (D-form / L-form (molar ratio)) Is 1/0 to 0.7 / 0.3 or 0/1 to 0.3 / 0.7, and the content of the iminocarboxylate is disclosed to be 40 to 70% by weight. (For example, refer to Patent Document 1). In such an aqueous solution composition, there is no description about dissolving an iminocarboxylate in a high-concentration alkaline solution. Further, it is disclosed that the detergent composition contains an alkali metal hydroxide and a disuccinic acid compound having a specific structure and is used for cleaning a hard surface (for example, see Patent Document 2). In this detergent composition, it is described that the alkali compound concentration is preferably 2 to 10% by weight, and the chelate compound concentration is preferably 0.05 to 10% by weight. The solution is about 0.4% of a chelate compound. In such a composition, the concentration of the alkali or the chelate compound is not sufficient, and a composition having a further increased concentration is not disclosed.

Further, the present invention relates to a detergent composition for an automatic dishwasher, containing 20 to 70% alkali salt and 1 to 30% glutamic acid diacetate having a specific structure or a salt thereof as essential components, and the pH value of a 1 weight percent aqueous solution is 9 A composition exhibiting the above is disclosed (for example, see Patent Document 3), and in a liquid composition containing NaOH and glutamic acid-N, N-diacetic acid (GLDA), preparation of a stable composition is possible at a GLDA of 35% or more. It is stated that it is difficult.
When the chelate compound contained in such a composition is dissolved in a high-concentration alkaline aqueous solution at a high concentration, it precipitates or the aqueous solution is layered. There was room for a device to be a stable composition with improved strength and glass corrosivity.
Japanese Patent No. 2644977 (page 1-2) JP 11-302691 A (second page) JP 2000-63894 A (2nd and 4th pages)

The present invention has been made in view of the above-described situation, has excellent stability under high-concentration alkaline conditions, is stable even in the case of long-term storage, improves transport efficiency, and is advantageous for storage. It is an object of the present invention to provide a concentration chelate compound-containing composition and a method for using the high concentration chelate compound-containing composition capable of improving detergency and exhibiting low corrosiveness to glass.

The inventors of the present invention have studied various compositions obtained by dissolving a chelate compound in an alkaline aqueous solution. As a result, 3-hydroxy-2,2′-iminodisuccinic acid (HIDS) is highly soluble in a highly concentrated aqueous alkaline solution. The present inventors have found that a composition containing a stable high concentration chelate compound can be obtained. If the alkaline compound concentration is specified and the dissolved concentration of HIDS is specified, not only excellent stability as a composition is maintained, but also advantageous in transportation and storage. Organic chelating agents, scale inhibitors, water treatment agents, detergent builders, bleaching aids, masking agents, fiber treatment agents, paper and pulp additives, semiconductor cleaners, photographic agents, soil modifiers, etc. The inventors have found that it can be suitably used for applications and have come up with the idea that the above problems can be solved brilliantly. In addition, when a composition for which the content of alkaline compound and HIDS is specified is used as a cleaning composition, it has been found that, together with the above-described effects, the cleaning power can be enhanced and the glass has a low corrosiveness. The invention has been reached.

That is, this invention is a high concentration chelate compound containing composition containing an alkaline compound and a chelate compound, Comprising: The said chelate compound is following General formula (1);

(Wherein, X ^{1 to} X ⁴ are the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group), and the content of the chelate compound is 1 to 90. The content of the alkaline compound is 10% to 85% by mass, and the chelate compound-containing composition.

The present invention is also a use for the detergent of the chelate compound-containing composition.
The present invention is described in detail below.

The chelate compound-containing composition of the present invention contains a chelate compound containing the chelate compound represented by the general formula (1) as an essential component and an alkaline compound.
As said chelate compound, when making a chelate compound containing composition 100 mass%, it is preferable that it is 1-90 mass%. When the concentration is less than 1% by mass, it cannot be sufficiently advantageous in transportation and storage, or the cleaning power is not sufficiently improved when used as a cleaning agent. The lower limit is preferably 1% by mass, more preferably 2% by mass, still more preferably 15% by mass, particularly preferably 20% by mass, and most preferably 25% by mass. is there. Moreover, when it exceeds 90 mass%, the stability as a composition cannot fully be improved. The range of the content of the chelate compound is more preferably 15 to 90% by mass.
The chelate compound contains the compound represented by the general formula (1) as an essential component. In the ^X 1 to X ^4, as the alkali metal atom include lithium, sodium, potassium, rubidium, cesium and the like. As the ^X 1 to X ^4, it is preferably sodium or potassium.

As said alkaline compound, when making a chelate compound containing composition 100 mass%, it is preferable that it is 10-85 mass%. If the concentration is less than 10% by mass, it will not be sufficiently advantageous in transportation and storage. The lower limit is preferably 15% by mass. Moreover, when it exceeds 85 mass%, stability as a composition cannot fully be improved. The upper limit is more preferably 80% by mass.

Examples of the alkaline compound include alkali hydroxide (earth) metal salts such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali carbonates (earth) such as sodium carbonate, sodium bicarbonate (sodium bicarbonate), and potassium carbonate. ) Metal salts: Alkali silicate metal salts such as sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate, sodium sesquisilicate and potassium sesquisilicate; ethanolamines such as monoethanolamine and diethanolamine Is preferred. Among these, potassium hydroxide and sodium hydroxide are preferable.

In the chelate compound of the present invention, the compound represented by the general formula (1) is essential. As the structure of such a compound, there are L-form and D-form in the aspartic acid skeleton.
The aspartic acid skeleton portion of the compound represented by the general formula (1) is the following general formula (3) in the general formula (1);

(Wherein, ^{X 1} and ^{X 2} are the same or different and each is the same as ^{X 1} and ^{X 2} in the formula (1).) Means a structure represented by.
The L-form and D-form in the aspartic acid skeleton are compounds in which the steric configuration at the asymmetric carbon atom in the structure represented by the general formula (3) is S configuration and R configuration. In the case of the L configuration and the R configuration, the D configuration is used.

Examples of the method for preparing the compound represented by the general formula (1) include a method in which a raw material containing aspartic acid and / or a salt thereof and epoxy succinic acid is reacted in an aqueous medium.
In the said preparation method, it does not specifically limit as reaction conditions, such as the ratio of aspartic acid and / or its salt in a raw material, and an epoxy succinic acid, reaction temperature. Moreover, as epoxy succinic acid, the isomer of a cis body and a trans body can be used, and it is preferable to use a cis body among both. The aqueous medium is water or a mixture of water and a solvent that dissolves in water. Water; a mixed solvent of water and methanol, ethanol, isopropyl alcohol, acetone, acetonitrile, or the like is preferable. Is preferably used.

In the above reaction, for example, when D-form aspartic acid and / or a salt thereof is used as a raw material, an aspartic acid skeleton in the structural formula of the compound represented by the above general formula (1) that generates a configuration derived therefrom. The compound is represented by the above general formula (1) in which the isomer in the aspartic acid skeleton portion is the D isomer by being held in the asymmetric carbon atom of the portion as the R configuration. Such a compound represented by the above general formula (1) is prepared by adding epoxysuccinic acid to a reaction solution obtained by neutralizing a part or all of the carboxylic acid of aspartic acid, thereby allowing the compound to react. It can be prepared by a method for obtaining an aqueous solution containing a compound represented by

The compound represented by the general formula (1) may have optical isomers, but the content ratio of each optical isomer is not particularly limited, and L-form or D-form is synthesized, By dividing the racemate, the L-form or D-form may be used alone. In addition, since the biodegradability of HIDS differs among isomers and increases in the order of D-form, racemate, and L-form, it is preferable to use a racemate as the HIDS to be used, and more preferably L-form. preferable. Thus, as a method of adjusting the isomer ratio in the aspartic acid skeleton part of the compound represented by the general formula (1) to a specific range, the ratio of D-form to L-form is a specific range in the above preparation method. A method of performing a reaction using a raw material containing aspartic acid and / or a salt thereof in the above, a compound represented by the general formula (1) in the D form and a compound represented by the general formula (1) in the L form Are preferably prepared separately and mixed at a specific ratio.

The chelate compound in the present invention contains the compound represented by the general formula (1) as an essential component. As such a chelate compound, X ^{1 to} X ⁴ in the compound represented by the general formula (1) are, for example, the same or different, and a hydrogen atom, an alkali metal atom, an ammonium group, an alkaline earth metal atom, or You may contain the compound which is an organic ammonium group.
As the alkali metal atom, those described above can be preferably used. Examples of the alkaline earth metal atom include magnesium, calcium, strontium, barium, and the like, and an organic ammonium group (organic amine group) For example, alkylamine groups such as monoethylamine group, diethylamine group and triethylamine group; alkanolamine groups such as monoethanolamine group, diethanolamine group and triethanolamine group; polyamine groups such as ethylenediamine group and triethylenediamine group, etc. Can be mentioned.
In the said chelate compound, you may add another chelate compound in the range which does not inhibit the effect of the chelate compound containing composition of this invention.

The chelate compound-containing composition can be produced by mixing the above-described chelate compound, alkaline compound, and other compounds as necessary. Examples of these compounds to be mixed include powders, slurries, and solutions. Any form may be used. As a preferred mixed form, when the composition of the present invention is in a liquid state, for example, a form in which an alkaline compound aqueous solution and a chelate compound aqueous solution are mixed, or a form in which a solid chelate compound is added to the alkaline compound aqueous solution and mixed Etc. are suitable. In addition, in the case of a solid form, a form in which a chelate compound powder and a solid alkaline compound are mixed, a form in which a solid alkaline compound is added to a chelate compound aqueous solution, and kneading are suitable.

The form of the chelate compound-containing composition of the present invention is not particularly limited as long as the effects of the present invention are exhibited. For example, the chelate compound-containing composition may be used in any form such as powder, slurry, solution, and solid. Among these, the chelate compound-containing composition is preferably liquid.
When the chelate compound-containing composition is in a liquid form, the chelate compound concentration is preferably 1 to 50% by mass at any concentration of 10 to 45% by mass of the alkaline compound. As a result, the stability as a composition can be maintained even in high-concentration alkali, and it can be advantageous in transportation and storage. For example, when used as a cleaning agent, the detergency is improved and the stability against glass is reduced. Corrosiveness can be exhibited. That is, the chelate compound-containing composition is an aqueous solution, the chelate compound content is 1 to 50% by mass, and the alkaline compound content is 10 to 45% by mass. Is also one of the preferred embodiments of the present invention.
That the chelate compound-containing composition is stabilized is a state in which a precipitate is not substantially formed when left at 40 ° C. for 1 month.

When the chelate compound-containing composition is less than 1% by mass when the chelate compound-containing composition is 100% by mass, it is not sufficiently advantageous in transportation and storage, or the cleaning power is sufficient when used as a cleaning agent. It will not improve. The lower limit is preferably 2% by mass, more preferably 15% by mass, and still more preferably 20% by mass. Moreover, when it exceeds 50 mass%, stability as a composition cannot fully be improved. The upper limit is preferably 45% by mass, and more preferably 40% by mass. In addition, as a range of content of the said chelate compound, it is more preferable that it is 15-50 mass%.
When the chelate compound-containing composition is 100% by mass, the alkaline compound concentration is less than 10% by mass, which is not sufficiently advantageous for transportation and storage. The lower limit is preferably 15% by mass, and more preferably 20% by mass. Moreover, when it exceeds 45 mass%, the stability of a composition cannot fully be improved. The upper limit is preferably 40% by mass, and more preferably 35% by mass.
The chelate compound and the alkaline compound are the same as described above.

The chelate compound-containing composition of the present invention contains a specific range of a chelate compound and an alkaline compound. Among them, the alkaline compound is preferably potassium hydroxide or sodium hydroxide. More preferably. The chelate compound has the following general formula (2):

And a chelate compound-containing composition containing sodium hydroxide as an essential component is also a preferred embodiment of the present invention.

Both chelate compound-containing compositions containing potassium hydroxide or sodium hydroxide as the alkaline compound exhibit sufficient detergency. A chelate compound-containing composition containing potassium hydroxide can easily form a stable composition with not only the compound represented by the general formula (1) but also a general chelate compound. It can be used suitably. On the other hand, in the chelate compound-containing composition containing sodium hydroxide, the compound represented by the general formula (1) can be suitably used because the stable region of the composition is wide as compared with the conventional chelate compound. Further, sodium hydroxide is less expensive than other alkaline compounds such as potassium hydroxide, and has an advantage that it is advantageous in terms of cost.
Thus, a stabilized high-concentration chelate compound-containing composition containing sodium hydroxide and a chelate compound, wherein the composition is an aqueous solution, and the chelate compound is represented by the general formula (1). The chelate compound-containing composition having the above-described compound as an essential component, the content of the chelate compound is 15 to 50% by mass, and the content of the sodium hydroxide is 10 to 45% by mass. This is one of the preferred forms.

The chelate compound-containing composition can be produced by mixing the above-mentioned chelate compound, sodium hydroxide, and other compounds as necessary. Examples of these compounds to be mixed include powders, slurries, solutions, etc. Any of these forms may be used. Preferred mixing forms include, for example, a form in which a sodium hydroxide aqueous solution and a chelate compound aqueous solution are mixed, a form in which a powdered chelate compound is added to and mixed with a sodium hydroxide aqueous solution, and solid or molten sodium hydroxide in water. The form etc. which add and mix a chelate compound aqueous solution are suitable.

The present invention is also a use for the detergent of the chelate compound-containing composition.
When the chelate compound-containing composition is used as a cleaning agent, it may be used as it is depending on the use, or may be used after diluting to an appropriate concentration with a diluent or the like according to the purpose. It can be suitably used for food production equipment (food and beverage equipment, food factory tanks and piping, etc.), various bottles such as beer bottles and milk bottles, and automatic dishwasher applications. In such applications, washing is performed by spraying with an alkaline cleaning liquid. Conventionally, at this time, insoluble silicate scales are generated on the surface of glass and ceramics due to the elution of a small amount of silicic acid by the detergent, and white The dirt will adhere and cause fogging and loss of gloss. When the chelate compound-containing composition of the present invention or a diluted solution thereof is used, the glass corrosivity is lower than that of an EDTA solution (ethylenediaminetetraacetic acid solution). The effect can be demonstrated.

The chelate compound-containing composition of the present invention and its diluted solution also have excellent solubility in water-insoluble Ca salt, so it is suitable for washing equipment and containers that produce insoluble calcium salt in the course of use. Can be used. Such facilities and containers include, for example, sake brewing tanks. Conventionally, brewing tanks such as beer tanks produce insoluble calcium salts, mostly calcium oxalate, and wine As aging progresses, white crystals of calcium tartrate will form at the bottom of tanks and bottles. The chelate compound-containing composition of the present invention and its diluted solution can effectively dissolve these insoluble calcium salts. For example, calcium oxalate can be dissolved with performance equivalent to that of an EDTA solution, and thus can be effectively used as a scale dissolving agent. Further, the chelate compound-containing composition of the present invention and the diluted solution thereof have a remarkably large ability to dissolve calcium tartrate compared to EDTA, and can be used for washing wine brewing tanks.

As the chelate compound and the alkaline compound when the chelate compound-containing composition of the present invention is used as a cleaning agent, those described above are suitable. In addition, these contents are as described above, depending on the use of beer tank cleaning agent (CIP cleaning), liquid type of dishwasher cleaning agent, solid type of dishwasher cleaning agent, etc. Can be set as appropriate.
Thus, the chelate compound-containing composition of the present invention can be suitably used for cleaning, and is a high-concentration chelate compound-containing cleaning composition containing an alkaline compound and a chelate compound. The compound has the compound represented by the general formula (1) as an essential component, the content of the chelate compound is 15 to 90% by mass, and the content of the alkaline compound is 10 to 85% by mass. A cleaning composition containing a chelate compound is also one of the preferred embodiments of the present invention.

As the chelate compound-containing composition, in addition to the above-mentioned compounds, inorganic builders, dispersants, surfactants, antifoaming agents, scale formation inhibitors, granulating agents, extenders, bleaching agents, bleaching activator, A surface modifier, a corrosion inhibitor, a recontamination inhibitor, a fluorescent agent, a bactericidal agent, an enzyme, a fragrance, a coloring agent, a sugar or a sugar acid, or a salt thereof may be contained.
As the inorganic builder, anhydrous sodium sulfate, anhydrous potassium sulfate and the like are suitable, and as the dispersing agent, polymer carboxylate such as sodium polyacrylate and sodium salt of acrylic acid-maleic acid copolymer are suitable. As surfactants, high foaming surfactants such as alkyl sulfate salts, α-sulfo fatty acid salts, soaps, alcohol ethoxylates, alkyl polyglucosides, and low foaming nonionic interfaces such as copolymers of ethylene oxide and propylene oxide An activator is preferable, and as the antifoaming agent, a silicone-based antifoaming agent, a fatty acid-based antifoaming agent, a fatty acid ester-based antifoaming agent, or the like is preferable. As a scale formation inhibitor, hexametaphosphoric acid or an alkali metal thereof is used. Salts and the like are suitable, and the granulating agent is preferably sodium sulfate or amorphous silica. The amount include sodium and potassium sulfate, sodium chloride, potassium chloride and the like.

The chelate compound-containing composition of the present invention can be used for various applications, for example, organic chelating agents, scale inhibitors, water treatment agents, detergent builders, bleaching aids, masking agents, fiber treatment agents. It can be used as an additive for paper and pulp, a semiconductor cleaning agent, a photographic agent, a soil modifier, and the like. In addition, the chelate compound-containing composition of the present invention is suitably used for cleaning and removing dirt adhering to a hard surface such as glass, plastic or metal in various cleaning applications. As a cleaning method, methods such as immersion cleaning, spray cleaning, circulation cleaning, brush cleaning, and spray cleaning can be used.

When the composition of the present invention is used for a cleaning application, it may be used as it is depending on the application, or may be used after diluting to an appropriate concentration with a diluent or the like according to the purpose. In the food industry, chemical industry, etc., containers for loading food products such as beverages such as beer and juice, processed foods; containers for storing these containers; tanks such as fermentation tanks for beer; Equipments such as equipment piping, sterilization plates, filling machines, etc .; workplaces; suitable for washing transport vehicles such as tank vehicles and container vehicles.
Moreover, it can also be used for cleaning by an automatic dishwasher for home use or business use, metal surface cleaning, metal cleaning, precision cleaning, etc. in the chemical and machine industries.

The chelate compound-containing composition of the present invention has the above-described configuration, has excellent stability under high-concentration alkaline conditions, is stable even when stored for a long period of time, has improved transport efficiency, and is advantageous for storage. Is. In addition to such effects, the chelate compound-containing composition has enhanced detergency and has low corrosiveness to glass and the like, and thus can be used for various cleaning applications.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Examples 1-6
The alkaline compound shown in Table 1, 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium salt (HIDS · 4Na), and ion-exchanged water are mixed to the concentrations shown in Table 1 to obtain a chelate compound-containing composition. It was. Table 1 shows the change in the solution of the obtained chelate compound-containing composition at 40 ° C. for one month.

Comparative Examples 1-7
Using an alkaline compound shown in Table 1, HIDS · 4Na is mixed as shown in Table 1 with ethylenediaminetetraacetic acid tetrasodium salt (EDTA · 4Na) or nitrilotriacetic acid trisodium salt (NTA · 3Na). I got a thing. Table 1 shows the change in the solution of the obtained chelate compound-containing composition at 40 ° C. for one month.

Example 7 and Comparative Examples 8-10
The test solution was prepared by mixing the chelate compound, NaOH and ion-exchanged water so that the concentrations shown in Table 2 were obtained. The chelate compound is selected from 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium salt (HIDS · 4Na), tetrasodium ethylenediaminetetraacetate (EDTA · 4Na), and trisodium nitrilotriacetate (NTA · 3Na). did. A slide glass was suspended as a test piece in the test solution and immersed at 40 ° C. for 2 weeks. After the immersion, the test piece was washed with ion-exchanged water, then the mass and area were measured, and the corrosion degree (mg / cm ² / day) was calculated according to (Equation 1).

Evaluation Examples 1-4
The same test as Example 7 and Comparative Examples 8 to 10 was performed except that the test solution was prepared by mixing the chelate compound, NaOH and ion-exchanged water so as to have the concentration shown in Table 3.

Example 8 and Comparative Examples 11-13
The test solution was prepared by mixing the chelate compound, NaOH and ion-exchanged water so that the concentrations shown in Table 3 were obtained. The chelate compound is selected from 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium salt (HIDS · 4Na), tetrasodium ethylenediaminetetraacetate (EDTA · 4Na), and trisodium nitrilotriacetate (NTA · 3Na). did. A slide glass was suspended as a test piece in the test solution and immersed at 100 ° C. for 3 days. After the immersion, the test piece was washed with ion-exchanged water, then the mass and area were measured, and the corrosion degree (mg / cm ² / day) was calculated according to (Equation 1).

As is apparent from Tables 2-4, the composition containing HIDS is shown to be less corrosive to glass than the control containing EDTA or NTA.

Evaluation Examples 5-8
A test solution was prepared using 0.6% of a water-insoluble calcium salt, 0.2% of a chelate compound, 3% of NaOH, and the remainder as ion exchange water. As water-insoluble calcium salts, calcium tartrate and calcium oxalate were used, and chelate compounds were selected from HIDS · 4Na and EDTA · 4Na as shown in Table 4. After stirring the test solution at 80 ° C. for 1 hour, the dissolved Ca ²⁺ was quantified by ICP emission spectrometry and converted into the calcium salt weight, and the calcium salt solubility was calculated according to (Equation 2).
Calcium salt solubility (%) = (mass of dissolved calcium salt / mass of prepared calcium salt) × 100 (Formula 2)

As is apparent from Table 5, the composition containing HIDS is shown to have a water-insoluble gallium salt solubility equal to or higher than that of a comparative control containing EDTA.

Claims (5)

A high concentration chelate compound-containing composition containing an alkaline compound and a chelate compound,
The chelate compound has the following general formula (1):

(Wherein X ^{1 to} X ⁴ are the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group), and an essential component,
The content of the chelate compound is 2 to 45 % by mass,
The content of the alkaline compound, Ri 10-40% by mass,
The chelate compound-containing composition, wherein the alkaline compound is potassium hydroxide and / or sodium hydroxide . The chelate compound-containing composition according to claim 1, wherein the content of the chelate compound is 15 % by mass or more . The chelate compound-containing composition, the chelate compound-containing composition of claim 1, wherein the <br/> is an aqueous solution. The chelate compound has the following general formula (2):

The chelate compound-containing composition according to claim 1, 2 or 3 , wherein the alkaline compound contains sodium hydroxide as an essential component. The use method which uses the chelate compound containing composition of Claim 1, 2, 3 or 4 as a cleaning agent.