JP4964516B2 - Method for producing liquid detergent composition - Google Patents

Description

  The present invention relates to a method for producing a liquid detergent composition.

Conventionally, various liquid detergent compositions containing boric acid and / or a salt thereof have been proposed for the purpose of improving detergency.
For example, it contains an acid such as boric acid or a salt thereof, a nonionic surfactant or an amphoteric surfactant, a specific monohydric or polyhydric alcohol, and water, so that the color inherent to the hard surface is vivid. A liquid detergent composition that can be recovered has been proposed (see Patent Document 1).
Further, it comprises an aqueous solution containing boric acid, boron oxide or alkali metal borate, an anionic surfactant, a nonionic surfactant, and an alkaline protease and having an enzyme storage stability and a pH of 8-11. An enzyme-containing liquid cleaning agent has been proposed (see Patent Document 2).

Further, boric acid and / or a salt thereof is dissolved in an alkaline aqueous solution to prepare an aqueous solution having a concentration of boric acid and / or a salt thereof of 5 to 30% by mass, and then the aqueous solution is mixed with a desired cleaning agent component. A method for producing a liquid detergent composition has been proposed (see Patent Document 3).
JP-A-9-202900 JP-A-5-156294 JP 2001-164297 A

In boric acid and / or a salt thereof, for example, sodium borate is a powder raw material, has low solubility in water, and dissolves up to about 4% by mass at room temperature.
When manufacturing a liquid detergent composition, when sodium borate is added directly to the main compounding tank, it takes time to dissolve the sodium borate and the production efficiency is poor and it is difficult to input it directly to the main compounding tank. It is. Therefore, the method of melt | dissolving previously beforehand and throwing into a main compounding tank as a sodium borate solution (premix) can be considered.
However, as described above, since sodium borate has low solubility in water, it must be dissolved in a large amount of water, and a large-capacity dissolution tank is required, which requires equipment costs. There is a problem that it is bad and inferior in productivity.

In the liquid detergent composition described in Patent Document 1, no particular study has been made regarding its production method, and it is possible to restore the color of the hard surface by using an acid such as boric acid or a salt thereof. The problem is different from that of the present invention.
The method for producing an enzyme-containing liquid detergent composition described in Patent Document 2 is a method in which water is added to the above four components and the pH is adjusted to 8 to 11 using a pH adjuster, and boric acid and / or It takes time to dissolve the salt, resulting in poor production efficiency.

In the method for producing a liquid detergent composition described in Patent Document 3, the solubility of boric acid and / or its salt is improved by dissolving boric acid and / or its salt in an aqueous alkali solution having a specific concentration in advance. I am letting.
For example, in the case of sodium borate, by dissolving sodium borate in a 10% by weight alkaline aqueous solution, the solubility of sodium borate is reduced to an aqueous solution containing no alkali (in this case, the solubility of sodium borate is It is possible to make it 5 times larger (that is, it dissolves up to about 25% by mass) than in the art. Thereby, it becomes possible to perform dissolution in a small-capacity dissolution tank, and the manufacturing efficiency can be improved and the productivity can be improved.
However, since the manufacturing method of the liquid detergent composition described in Patent Document 3 uses an alkaline aqueous solution, the pH of the dissolution tank exhibits strong alkalinity of about 12 or more.
In addition, once a sodium borate solution (premix) is prepared, when the premix is stored for several days in a dissolution tank, sodium borate may precipitate during storage.

  The present invention has been made in view of the above circumstances, and the production of a liquid detergent composition having high solubility of boric acid and / or a salt thereof, excellent work safety, and good storage stability. It is an object to provide a method.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, in the method for producing a liquid detergent composition of the present invention, boric acid and / or a salt thereof (A) is dissolved in an aqueous solution containing an acidic component (B), and the boric acid and / or a salt thereof (A) is dissolved. A premix having a content of 5 to 30% by mass and a pH of 25 to 8 at 5 to 8 is prepared in advance.
Moreover, in the manufacturing method of the liquid cleaning composition of this invention, it is preferable to use the said acidic component (B) containing a metal ion scavenger.
Moreover, in the manufacturing method of the liquid cleaning composition of this invention, it is preferable to mix the said premix and hydrogen peroxide (C).

In the present invention, the “liquid detergent composition” includes a liquid detergent composition, a liquid bleach composition and the like. The liquid bleach composition means one containing bleach components such as hydrogen peroxide and a bleach activator.
“Premix” means, for example, a solution of boric acid and / or a salt thereof previously dissolved in a solvent (preferably water or the like) in advance before adding boric acid and / or a salt thereof to the main compounding tank. means.

  ADVANTAGE OF THE INVENTION According to this invention, the solubility of boric acid and / or its salt is high, it can provide the manufacturing method of the liquid detergent composition which is excellent in safety | security at work, and also has favorable storage stability.

≪Method for producing liquid detergent composition≫
In the method for producing a liquid detergent composition of the present invention, boric acid and / or a salt thereof (A) (hereinafter sometimes referred to as (A) component) is converted into an acidic component (B) (hereinafter referred to as (B) component). In other words, a premix dissolved in an aqueous solution is prepared in advance.
After preparing the said premix previously, the liquid detergent composition which concerns on this invention can be manufactured by mixing this premix and arbitrary components, such as a washing | cleaning component.
Hereinafter, as an example, the method for producing the liquid detergent composition of the present invention will be described by dividing it into <a step of preparing a premix in advance> and <a step of mixing a premix and an optional component>.

<Step of preparing premix in advance>
In this step, the (A) component is dissolved in an aqueous solution containing the (B) component, the content of the (A) component is 5 to 30% by mass, and the pH at 25 ° C. is 5 to 8 premix. Is prepared in advance.

・ Boric acid and / or its salt (A)
Examples of the component (A) include orthoboric acid (H ₃ BO ₃ ); a salt formed by borate ions BO ₃ ^3- and BO ₄ ^5- , or an anion salt (condensed borate) obtained by condensing them. Can be mentioned.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt; ammonium salt and the like. Of these, alkali metal salts are preferable, and sodium salts and potassium salts are more preferable.
Among the above components (A), preferred are orthoboric acid (H ₃ BO ₃ ), sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium tetraborate, and ammonium tetraborate. And sodium tetraborate is more preferable.
In the present invention, it is particularly preferable to use sodium tetraborate · pentahydrate or sodium tetraborate · 10 hydrate because of good detergency and solubility.
(A) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
For example, when sodium tetraborate (anhydride) is used alone, the pH of a 3% by mass aqueous solution of sodium tetraborate is about 9.

・ Acid component (B)
In this invention, (B) component is used in order to adjust the 25 degreeC pH of a premix in the range of 5-8. The effect of the present invention can be obtained by adjusting the pH of the premix within this range.
Examples of the component (B) include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; and organic acids such as p-toluenesulfonic acid, citric acid, and phosphonic acid derivatives.
Among inorganic acids, it is preferable to use sulfuric acid. Among organic acids, it is preferable to use an organic acid that is also used as a metal ion scavenger (hereinafter simply referred to as “metal ion scavenger”).
Among the above, it is more preferable to use an organic acid, and it is particularly preferable to use a metal ion scavenger. By using a metal ion scavenger, the pH of the premix is adjusted, and metal ions such as iron ions contained in raw materials used as component (A) (for example, industrial grade borate) are captured. Is done. Thereby, the precipitation derived from this metal ion by storage time is suppressed and the storage stability of a premix improves more. Moreover, it is estimated that the effect of the improvement of a detergency and the improvement of stabilization of the bleaching component mix | blended arbitrarily is acquired.
Specific examples of such metal ion scavengers include, for example, citric acid; organic phosphonic acid derivatives such as 1-hydroxyethane-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid; nitrilotriacetic acid, ethylenediaminetetra Examples thereof include aminopolyacetic acids such as acetic acid, hydroxyethylethylenediamine triacetic acid, diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid; organic acids such as dicarboxymethylglutamic acid; and polymer chelating agents such as polyacrylic acid. Of these, organic phosphonic acid derivatives are preferable, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable because it has good solubility and a good effect of improving the storage stability of the premix.
Examples of suitable commercial products of 1-hydroxyethane-1,1-diphosphonic acid include BRIQUEST ADPA (trade name) manufactured by Rhodia, CHIRES PH-210 (trade name) manufactured by CHIRES, and DEQUEST 2010 (manufactured by Monsanto). (Product name) and the like, and the same effect can be obtained by using any of them.
(B) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.

The preparation method of a premix prepares aqueous solution (X) containing (B) component, for example by melt | dissolving the said (B) component in water.
The component (B) contained in the aqueous solution (X) is preferably blended so that the content of the component (B) in the premix is 0.5 to 15% by mass, It is more preferable to mix | blend so that it may become, and it is still more preferable to mix | blend so that it may become 5-15 mass%. By setting it as this range, it becomes easy to adjust the 25 degreeC pH of a premix in the range of 5-8. Moreover, the solubility of (A) component improves by setting it as more than the lower limit of this range. On the other hand, the storage stability of a premix improves by setting it as an upper limit or less.
The aqueous solution (X) may contain other components as needed in addition to the component (B).
For example, the pH of the premix may be adjusted using only the component (B), or may be adjusted using another pH adjuster.
Examples of the pH adjuster include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia and the like, and sodium hydroxide is preferable.
When the component (B) and the pH adjuster are used in combination, the pH adjuster is contained in the aqueous solution (X) together with the component (B) before the component (A) is dissolved in the aqueous solution (X). The component (A) is preferably contained in the aqueous solution (X) together with the component (B) before the component (A) is dissolved in the aqueous solution (X). Thereby, a premix can be prepared efficiently.

Next, the component (A) is dissolved in the obtained aqueous solution (X). Thereby, a premix is prepared.
The dissolution of the component (A) in the aqueous solution (X) is blended so that the content of the component (A) in the premix is 5 to 30% by mass, and is blended so as to be 10 to 25% by mass. It is preferable that the amount is 10 to 20% by mass. By setting it to the lower limit of the range or more, when the component (A) is preliminarily dissolved (pre-dissolved), it can be dissolved in a small-capacity dissolution tank (such as a compounding pot), and the equipment cost is reduced. This is advantageous. On the other hand, the solubility of (A) component improves by setting it as an upper limit or less, and the storage stability of a premix also improves. In addition, content of the (A) component in the said premix shows the value converted into the anhydrous salt.
In addition to the above components, the components contained in the aqueous solution (X) include components such as cleaning components generally used in liquid cleaning compositions as necessary, for example, surfactants, metal ion scavengers, radical traps. Agents, pH adjusters, hydrotropes, inorganic salts, soil release agents, silicones, bactericides, antibacterial agents, fluorescent dyes, enzymes, fragrances, pigments and the like can be appropriately blended. As these components, the same components as those exemplified for each of the corresponding components described later can be blended.
In the preparation of the premix, for stirring and mixing of each component, a stirrer, a mixer, etc., which are usually used for preparing a liquid detergent composition can be used in accordance with the blending scale and the like. .

The prepared premix has a pH of 5 to 8 at 25 ° C., preferably 6 to 7.5, and more preferably 6.5 to 7.5. By being above the lower limit of the range, the solubility of the component (A) increases. On the other hand, by being below an upper limit, it is excellent in work safety and the storage stability of the premix is good.
Here, the pH of the premix indicates a value obtained by measuring the stock solution of the premix (adjusted to 25 ° C.) with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.).

<Step of mixing premix and optional components>
In this step, the liquid detergent composition according to the present invention is produced by mixing the premix prepared in advance in the above step and an optional component such as a cleaning component.
As such an optional component, a component such as a cleaning component generally used in a liquid cleaning composition can be appropriately blended. For example, surfactants, bleach components, metal ion scavengers, radical trap agents, pH adjusters, hydrotropes, inorganic salts, soil release agents, silicones, bactericides, antibacterial agents, fluorescent dyes, enzymes, perfumes, pigments Etc. can be blended.

-Premix It is preferable to mix | blend a premix so that content of the said (A) component and the said (B) component may become the following in a liquid detergent composition.
The content of the component (A) is not particularly limited, and it is preferably blended so as to be 0.01 to 10% by mass in the liquid detergent composition, and 0.1 to 6% by mass. It is particularly preferable to blend so as to be. By setting it to be equal to or higher than the lower limit value of the range, the effect of blending the component (A) can be more easily obtained. On the other hand, by setting it to the upper limit value or less, it is possible to balance with other components in formulation design.
The content of the component (B) is not particularly limited, and it is preferably blended so as to be 0.05 to 3% by mass in the liquid detergent composition, and 0.1 to 3% by mass. It is more preferable to mix | blend so that it may become, and it is especially preferable to mix | blend so that it may become 0.3-3 mass%. By setting it to be equal to or higher than the lower limit of the range, the performance (detergency, etc.) as a liquid detergent composition is improved. In the case of a liquid bleach composition, the stability of the bleaching component is improved. On the other hand, by setting it to the upper limit value or less, the liquid appearance becomes better.

-Surfactant As the surfactant, any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants may be used, one kind alone, or two or more kinds. It can also be used in combination as appropriate.

Nonionic surfactants include polyoxyalkylene alkyl ether, alkyl (poly) glycoside, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ester oxyethylene propylene block polymer, fatty acid A monoglyceride etc. are mentioned.
Among the above, polyoxyalkylene alkyl ether is preferable from the viewpoint of stability in a liquid bleach composition containing a bleaching component such as hydrogen peroxide, and polyoxyalkylene alkyl ether represented by the following formula is preferable. Particularly preferred.
R—O— (AO) _n —H
[Wherein, R represents a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms; AO represents an oxyalkylene group; n represents the average number of moles of AO added;
Is the number of ]

In the above formula, in R, the alkyl group has 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms. The carbon number of the alkenyl group is the same as the carbon number of the alkyl group. When the carbon number is 8 or more, the detergency is improved, and when the carbon number is 16 or less, the solubility is improved.
Among them, an alkyl group is preferable, and specifically, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group are preferable, and a dodecyl group and a tetradecyl group are particularly preferable. preferable.
Examples of AO include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxypentylene group. Of these, an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is preferable. AO may be added individually by 1 type and 2 or more types may be added.
Although n depends on the type of AO, for example, when AO is an oxyethylene group and / or oxypropylene group, n is preferably 3-15.
In addition, n is preferably an AO adduct having a narrow ratio of 55% by mass or more, which represents a distribution ratio of AO adducts having different numbers of added moles of AO represented by the following general formula (S). The narrow ratio is preferably 55% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. By being above the lower limit of the range, the liquid stability of the liquid detergent composition is improved. The narrow rate is preferably as high as possible from the viewpoint of liquid stability.

［式中、ｎ_ｍａｘは全体のエチレンオキシド付加体中に最も多く存在するエチレンオキシド付加体のエチレンオキシドの付加モル数を示す。ｉはエチレンオキシドの付加モル数を示す。Ｙｉは全体のエチレンオキシド付加体中に存在するエチレンオキシドの付加モル数がｉであるエチレンオキシド付加体の割合（質量％）を示す。］

[ _Wherein n _max represents the number of moles of ethylene oxide added in the ethylene oxide adduct most abundant in the entire ethylene oxide adduct. i represents the number of moles of ethylene oxide added. Yi represents the ratio (% by mass) of the ethylene oxide adduct having an i added mole number of ethylene oxide present in the entire ethylene oxide adduct. ]

  The narrow rate can be controlled by, for example, a method for producing a polyoxyalkylene alkyl ether represented by the above formula. Such a production method is not particularly limited, but as a suitable method, for example, a surface-modified composite metal oxide catalyst described in JP-A No. 2000-144179 is used to convert the fatty acid alkyl ester. Examples thereof include a method of addition polymerization of ethylene oxide.

Examples of the anionic surfactant include a linear or branched alkylbenzene sulfonic acid or a salt thereof; an α-olefin sulfonate; a linear or branched alkyl sulfate ester salt; a linear or branched alkyl group Alternatively, alkyl ether sulfates or alkenyl ether sulfates having an alkenyl group and having an average addition mole number of 0.5 to 8 moles of oxyethylene added; α-sulfo fatty acid ester salts, higher fatty acid salts, and the like. .
Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt, and the like. Alkali metal salts are preferable, and sodium salts are more preferable.
Examples of the cationic surfactant include various quaternary ammonium salts such as a mono long chain hydrocarbon type quaternary ammonium salt and a di long chain hydrocarbon type quaternary ammonium salt.
Examples of amphoteric surfactants include carboxybetaine, sulfobetaine, and hydroxysulfobetaine.

  The content of the surfactant is not particularly limited depending on the type and use, but is preferably 0.5 to 40% by mass, and 3 to 40% by mass in the liquid detergent composition. More preferably, it is more preferably 8 to 30% by mass. By setting it to be equal to or more than the lower limit of the range, effects (such as a cleaning effect due to the surface active effect) by adding the surfactant are remarkably easily obtained. On the other hand, when the amount is not more than the upper limit of the range, storage stability is improved, which is economically advantageous.

-Bleaching component As a bleaching component, the component normally used for what is called oxygen type bleaching agents, such as a bleaching activator which raises the activity of hydrogen peroxide and hydrogen peroxide, for example is mentioned.
In the present invention, it is preferable to mix the premix and hydrogen peroxide (C) (hereinafter referred to as component (C)). By containing (C) component, the liquid bleaching composition which has a bleaching effect in a liquid detergent composition can be obtained easily.
The content of the component (C) is designed according to its use and is not particularly limited, but is preferably 0.1 to 10% by mass in the liquid detergent composition. More preferably, it is 2 mass%, and it is further more preferable that it is 2-6 mass%. By setting it to be equal to or more than the lower limit of the range, sufficient bleaching property can be easily obtained. On the other hand, by setting it to be equal to or less than the upper limit of the range, it is possible to balance with other components such as a surfactant, and the storage stability is improved.

Examples of the bleach activator include tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, and dodecane. Sodium noyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene And organic peracid precursors such as undecanoyloxybenzene and dodecanoyloxybenzene.
Of these, sodium nonanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, and decanoyloxybenzoic acid are preferred.
A bleaching activator can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the bleach activator is preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass in the liquid detergent composition. By setting it to be equal to or more than the lower limit of the range, it is easy to obtain a good bleaching power. On the other hand, liquid stability improves by setting it as below the upper limit of this range.

Metal ion scavenger The metal ion scavenger that can be used in this step is the same as the metal ion scavenger exemplified in the component (B), and in particular, 1-hydroxyethane-1,1-diphosphone Acid is particularly preferred.
A metal ion scavenger can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the metal ion scavenger is preferably 0.1 to 3% by mass in the liquid detergent composition.

-Radical trapping agent In the liquid cleaning composition of this invention, a radical trapping agent can be used as an arbitrary component, Preferably a phenol type radical trapping agent can be used.
For example, when hydrogen peroxide is blended, if the pH of the product is particularly 5 or more, the decomposition of hydrogen peroxide may not be suppressed with the metal ion scavenger alone. In such a case, it is preferable to use a phenol-based radical trapping agent in combination.
In addition, if it is left on for a long time after being applied to clothing due to misuse, the clothing may be damaged by abnormal decomposition of hydrogen peroxide due to metal in the soil or components that are highly reactive with hydrogen peroxide. is there. In such a case, it is possible to suppress damage to clothing as described above by adding a phenol-based radical trapping agent.
In the present invention, the phenolic radical trapping agent is phenol and a phenol derivative. Preferred examples of the phenol derivative include a compound having a phenolic OH group, an ester derivative of a phenolic OH group, an ether derivative and the like. The substitution position may be any of ortho, meta, and para positions.
Of these, compounds having a phenolic OH group are more preferred.
Among them, a more preferable compound is a redox potential (OP) ₀ of 1.25 V described in “GE Penketh, J. Appl. Chem”, pages 7,512 to 521 (1957). The following compounds are particularly preferred, and are compounds of 0.75 V or less.
Among the above compounds, dimethoxyphenol, catechol, hydroquinone, 4-methoxyphenol, dibutylhydroxytoluene (BHT) and the like are preferable, and 4-methoxyphenol is particularly preferable.
A radical trap agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the radical trapping agent is preferably 0.01 to 6% by mass in the liquid cleaning composition.
In addition, phenolic radical trapping agents have a higher effect of trapping radicals than other radical trapping agents. Therefore, decomposition of hydrogen peroxide in pharmaceutical preparations and abnormal decomposition during reaction with hydrogen peroxide stain components are not possible. It is thought that each can be suppressed. Therefore, it is estimated that the stability of the liquid detergent composition (liquid bleach composition) in the container is maintained and the effect of suppressing damage to clothing is high.

-PH adjuster pH adjusters that can be used in this step include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, citric acid and phosphonic acid derivatives; sodium hydroxide, water Examples include potassium oxide, sodium carbonate, sodium hydrogen carbonate, monoethanolamine, diethanolamine, triethanolamine, and ammonia.
The pH adjuster can be used singly or in appropriate combination of two or more, and can be used as appropriate to adjust the pH of the liquid detergent composition to the desired pH described below. .

-Hydrotrope agent In the liquid cleaning composition of this invention, various components, such as a fragrance | flavor, can be stably mix | blended by using a hydrotrope agent.
As the hydrotrope agent, monohydric alcohols such as ethanol, isopropanol and phenyl polyoxyethylene alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol and glycerin can be used.
A hydrotrope agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the hydrotrope is preferably 0.1 to 10% by mass in the liquid detergent composition.

-Inorganic salts As inorganic salts, sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate etc. can be used, for example.

-Soil release agent Examples of the soil release agent include water-soluble polymers, and specifically, from dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) or esters thereof, polycarboxylic acids, polyalcohols, polyalkylene glycols, etc. A constituted polymer or the like can be used.
A soil release agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the soil release agent is preferably 0.1 to 3% by mass in the liquid detergent composition.
The “water-soluble polymer” as used herein refers to an aqueous solution having a concentration of 1% by mass (in terms of pure content) prepared by dissolving a polymer in ion-exchanged water at a temperature of 25 ° C. It is transparent and not cloudy. Here, “transparent” means that when a glass cell having an optical path length of 10 mm is used and ion-exchanged water is added to the control side cell, the light transmittance at a wavelength of 660 nm is 95% or more.

The order of blending the premix and the optional components is not particularly limited. For example, in the case of manufacturing a liquid detergent composition, after adding about 90 parts by weight of water of the blend scale, the surfactant and hydrotrope are added. Agent and radical trapping agent are sequentially added and mixed. Next, a premix prepared in advance is added and mixed. Thereafter, a metal ion scavenger, a water-soluble polymer, and a fragrance are sequentially added and mixed, and then a pH adjuster is added and balanced with water so that the total amount becomes 100% by mass to obtain a liquid detergent composition. It is done.
The pH of the liquid detergent composition is preferably 5 to 11 and particularly preferably 6 to 10 from the viewpoint of detergency and storage stability of the liquid.
For example, in the case of producing a liquid bleach composition, after adding about 90 parts by mass of water of a blending scale, a surfactant, a bleach activator, a hydrotrope, and a radical trapping agent are sequentially added. And mix. Next, a premix prepared in advance is added and mixed. Thereafter, a metal ion scavenger, a water-soluble polymer, and a fragrance are sequentially charged and mixed, and then hydrogen peroxide (C) is charged. Then, a liquid bleaching agent composition is obtained by adding a pH adjuster and balancing so that the whole quantity may be 100 mass% with water. In the production of the liquid bleach composition, it is particularly preferable to add the component (C) after mixing components other than the pH adjuster. Thereby, (C) component can be mix | blended stably in a liquid bleach composition.
The pH of the liquid bleach composition is preferably 3 to 8, more preferably 5 to 7, because the stability of the component (C) is better.
Here, pH of a liquid detergent composition and a liquid bleach composition shows the value measured by the method similar to the measuring method of pH of the said premix.
In the production of the liquid detergent composition, the stirring and mixing of the premix and each optional component are usually carried out in accordance with the blending scale, etc. A machine can be used.

ADVANTAGE OF THE INVENTION According to this invention, the solubility of boric acid and / or its salt is high, it can provide the manufacturing method of the liquid detergent composition which is excellent in safety | security at work, and also has favorable storage stability.
According to the present invention, boric acid having a low solubility in water and / or a salt thereof can be blended efficiently and safely. Moreover, since boric acid and / or its salt can be melt | dissolved by high concentration by this invention, a small capacity | capacitance dissolution tank (mixing pot etc.) can be used. In addition, since pre-mixing does not cause precipitation and storage stability is good, several days of pre-mix used for product formulation can be prepared at once, enabling efficient production It becomes. Furthermore, the manufacturing cost can be reduced.
According to the present invention, since pH 5-8 of the premix at 25 ° C. is close to the pH of the liquid detergent composition to be finally produced, pH adjustment becomes easy. Further, by having such a pH range, there is almost no concern about corrosion of the production equipment.
According to the method for producing a liquid detergent composition of the present invention, a liquid detergent composition and a liquid bleach composition can be provided.
The liquid detergent composition (liquid bleach composition) produced by the production method of the present invention has good storage stability of hydrogen peroxide.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. However, Examples 1-4 and 11-14 are all reference examples. “%” Means “% by mass” unless otherwise specified.

<Premix preparation>
Using the raw materials shown in Table 1 (boric acid or its salt (A), acidic component (B), sodium hydroxide), premixes having the compositions shown in Table 2 were prepared by the following methods.
A stirrer in which two paddle blades (diameter 7 cm) were attached to a three-one motor (product name: TYPE: HEIDON 1200G, manufactured by Shinto Kagaku Co., Ltd.) was set in a 1 L beaker.
Next, the mixture was stirred and mixed while adding purified water → acidic component (B) → sodium hydroxide (Examples 6 and 9) in this 1 L beaker so that the total charged amount (blending scale) was 800 g. . During the addition of the raw material, the rotational speed of the two paddle blades was 180 rpm.
Thereafter, boric acid or a salt thereof (A) was added to the stirred and mixed solution and mixed with stirring to obtain a premix.
In addition, the compounding quantity of Table 2 shows the amount equivalent to a pure part. However, in boric acid or a salt thereof (A), the amount of sodium tetraborate hydrate is the concentration calculated in terms of sodium tetraborate (Na ₂ B ₄ O ₇ ) (ie, indicating the Na ₂ B ₄ O ₇ amount).
Moreover, the unit of the compounding quantity in Table 2 is mass%, and the quantity of purified water was adjusted so that the total quantity might be 100 mass%. Purified water was adjusted to 25 ° C.

  About the obtained premix of each example, it evaluated by the method and evaluation criteria shown below, and the result was written together in Table 2.

(Evaluation of properties)
In preparation of said premix, the borate (A) was added and the pH and liquid appearance of the premix after stirring for 10 minutes were evaluated, respectively.
The pH was measured with a stock solution of the premix (adjusted to 25 ° C.) with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.).
The liquid appearance was visually evaluated based on the following criteria.
○: Dissolved uniformly.
X: A precipitation component was observed.

(Evaluation of storage stability)
The premix of each example was transferred to a 100 mL glass bottle, sealed, and stored in a 10 ° C. thermostatic bath, and the change in liquid appearance was visually evaluated based on the following criteria.
A: Uniform after 8 days.
○ to ◎: Uniform after 6 days.
○: Uniform after 4 days.
Δ: After 2 days, a deposited component was observed.
X: Precipitated components were observed within 1 day.

  From the results of Table 2, Examples 1 to 9 according to the present invention each have a borate content in the range of 5 to 30% by mass in each premix, and boric acid and / or a salt thereof. It was confirmed that the solubility was high. Moreover, as for all of Examples 1-9, the pH of 25 degreeC was in the range of 5-8, and it has confirmed that it was excellent in the safety on operation | work. Furthermore, it was confirmed that Examples 1 to 9 all had good storage stability.

On the other hand, in Comparative Example 1 which does not contain an acidic component (B) and has a pH of 9.0 at 25 ° C., it was confirmed that the borate was precipitated immediately after preparation of the premix.
Further, in both Comparative Example 2 and Comparative Example 4 in which the pH of the premix is less than 5 and Comparative Example 3 in which the pH at 25 ° C is more than 8, borate precipitates immediately after preparation of the premix. It was confirmed.
Moreover, also about the comparative example 5 with excess borate content, it was confirmed that borate precipitates immediately after premix preparation.

From the above results, in the premixes of Examples 1 to 9, the pH at 25 ° C. is in the range of 5 to 8, and is excellent in safety in blending work. Moreover, there is almost no concern about corrosion of the manufacturing equipment.
Furthermore, since the premixes of Examples 1 to 9 can dissolve borate at a high concentration, it is possible to reduce costs by using a small-capacity dissolution tank (such as a mixing pot).
Moreover, since Examples 1-9 do not precipitate borate with time even if the premix is stored after preparing the premix, several days of premixes used for product formulation are prepared at once. Manufacturing efficiency can be increased.

<Manufacture of liquid detergent composition>
Using the premixes of Examples 1 to 9 obtained above, the liquid detergent composition having the composition shown in Table 3 (Liquid bleach composition: Examples 11, 13, 15 to 18 / Liquid detergent composition: Implementation Examples 12, 14, 19) were prepared by the following methods, respectively.
A stirrer having two paddle blades (diameter 7 cm) attached to a three-one motor (product name: TYPE: HEIDON 1200G, manufactured by Shinto Kagaku Co., Ltd.) was set in a 2 L beaker.
Next, the components shown in Table 3 were added to the 2 L beaker in accordance with the blending order and mixed to obtain a liquid detergent composition so that the total charge (blending scale) was 1800 g. During the addition of the raw material, the rotational speed of the two paddle blades was 180 rpm.
However, as for the compounding quantity in Table 3, components other than a premix show pure amount conversion amount. The premix shows the content of itself (as it is). The unit of the blending amount in Table 3 indicates mass%.
Moreover, the amount (predetermined amount) which subtracted the total compounding quantity of the raw material of the mixing | blending order 2-18 from 1700g was set and refined water 1 was mix | blended. The amount of purified water 2 was adjusted so that the total amount was 100% by mass. Purified water 1 and purified water 2 were both adjusted to 25 ° C.
In addition, since the premix of Comparative Examples 1-5 was not uniform, it was not able to mix | blend with manufacture of a liquid detergent composition.

<< Description of ingredients shown in Table 3 >>
Nonionic Surfactant-1, Nonionic Surfactant-2: Polyoxyethylene alkyl ether (ethylene oxide adduct) represented by the following general formula (I), which is represented by the general formula (S) An ethylene oxide adduct whose ratio (the proportion of the distribution of ethylene oxide adducts with different addition moles of ethylene oxide) is specified, manufactured by Lion Corporation.
^{_{R 1 O- (CH 2 CH 2}} O) n '-H ··· (I).
[Wherein, R ¹ represents an alkyl group; n represents an average number of moles of ethylene oxide added. ]

Nonionic surfactant-1: narrow ratio 84 mass%, alkyl group R ¹ = C ₁₂ H ₂₅ —, ethylene oxide (EO) average addition mole number n ′ = 5.
Nonionic Surfactant -2: Narrow ratio of 40 wt%, an alkyl group ^R 1 _{= C} 12 _{H 25} - and _C 14 _{H 29} - a mixture of (mixing ratio by mass ratio 7/3), EO average addition molar number n ′ = 15.

Nonionic surfactant-3: polyoxyethylene alkyl ether (12 carbon atoms in alkyl group, 7 average added moles of EO; trade name “EMALEX 707”, manufactured by Nippon Emulsion Co., Ltd.).
LAS-Na: C10-14 sodium alkylbenzene sulfonate, manufactured by Lion Corporation.
-AOS-Na: C14 sodium α-olefin sulfonate (product of 40% by mass) (trade name “Lipolane LB-440”, manufactured by Lion Corporation).
-Monoalkyl (C16,18) trimethylammonium chloride (mixture of trimethylammonium chloride having 16 carbon atoms in the alkyl group and trimethylammonium chloride having 18 carbon atoms in the alkyl group): trade name “ARCARD T-800”, Lion Corporation Made.
Organic peracid precursor: sodium dodecanoyloxybenzenesulfonate, lion synthetic product; manufactured according to the method for synthesizing bleach activator (I-3) described in JP-A-06-316700.
Phenyl polyoxyethylene alcohol: trade name “Phenyl Diglycol PhDG”, manufactured by Nippon Emulsifier Co., Ltd.
4-methoxyphenol: trade name “MQ-F”, manufactured by Kawaguchi Chemical Co., Ltd.
HEDP: hydroxyethane-1,1-diphosphonic acid (60% by mass product) (HEDP used in Examples 13, 16, and 17: trade name “BRIQUEST ADPA”, manufactured by Rhodia; Examples 11, 15, and 18 HEDP used: trade name “Kyrest PH-210”, manufactured by Kyrest Inc.).
Water-soluble polymer: Soil release agent (polymer having an alkylene terephthalate unit, weight average molecular weight 3000), trade name “SRN-100”, manufactured by Clariant.
Fragrances A to D: The same as the fragrance compositions A to D described in Tables 7 to 14 of JP-A-2003-268398.
Hydrogen peroxide: 35% by mass aqueous solution, manufactured by Mitsubishi Gas Chemical Company.
・ Sulfuric acid: Trade name “62.5% sulfuric acid”, manufactured by Nissan Chemical Industries, Ltd.
Sodium hydroxide: trade name “25% sodium hydroxide” manufactured by Asahi Glass Co., Ltd.

  About the obtained liquid cleaning composition of each example, it evaluated by the method and evaluation criteria shown below, and the result was written together in Table 3.

(Evaluation of storage stability 1)
The liquid detergent composition of each example was transferred to a 100 mL glass bottle, sealed, and stored in a constant temperature bath at 40 ° C., and the change in the liquid appearance after one month was visually evaluated based on the following criteria.
○: No change in appearance was observed.
X: Precipitation or phase separation occurred.

(Evaluation of storage stability 2)
The liquid detergent composition of each example was transferred to a 100 mL glass bottle, sealed, stored in a 10 ° C. constant temperature bath, and the change in the liquid appearance after 1 month was visually evaluated based on the following criteria.
○: No change in appearance was observed.
X: Precipitation or phase separation occurred.

From the results of Table 3, it was confirmed that all of the liquid detergent compositions of Examples 11 to 19 in which the premixes of Examples 1 to 9 were blended had good storage stability.

Claims (3)

Boric acid and / or its salt (A) is dissolved in an aqueous solution containing the organic phosphonic acid derivative (B),
A liquid detergent composition characterized in that the boric acid and / or salt (A) content thereof is 5 to 30% by mass and a premix having a pH of 5 to 8 at 25 ° C is prepared in advance. Production method. Method for producing the liquid detergent composition of the content of claim 1, wherein Ru 0.5 to 15% by mass of an organic phosphonic acid derivative (B) in the premix.   The manufacturing method of the liquid cleaning composition of Claim 1 or 2 which mixes the said premix and hydrogen peroxide (C).