JP7109017B2 - Aqueous hydrogen peroxide solution - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aqueous hydrogen peroxide solution with excellent stability of hydrogen peroxide.

Hydrogen peroxide is a compound that decomposes very easily. Especially in a system in which transition metals such as Fe and Cu coexist, even under acidic conditions, these transition metals act as catalysts and decompose in a short period of time. and loses its oxidative activity. In order to solve these problems, stabilizers such as phenacetin, aliphatic alcohols, aliphatic amines, glycols and glycol ethers have been investigated.

However, these stabilizers are insufficient in the stabilizing effect in a high temperature range of 50°C or higher. Representative phenyl glycol ethers have been proposed (Patent Document 1). However, even with this stabilizer, the stabilizing effect during long-term storage is still insufficient.

On the other hand, the present inventors have found a hydrogen peroxide-containing aqueous liquid containing phosphonic acid or a salt thereof in addition to phenylglycol ethers as a hydrogen peroxide-containing aqueous liquid having excellent stability even under high-temperature acidic conditions. We are developing a liquid (Patent Documents 2 and 3).

JP-A-6-115909 JP-A-2000-203813 Japanese Patent No. 4062569

As described above, the present inventors have developed hydrogen peroxide-containing aqueous liquids containing phenyl glycol ethers and phosphonic acid or salts thereof as stabilizers.
However, phenoxyethanol and the like, which are major phenyl glycol ethers, have a stabilizing effect against hydrogen peroxide, exhibit superior antiseptic action compared to paraoxybenzoic acid esters, and are less irritating, but are toxic and human. It is required to reduce the amount used because it may show irritation depending on the case.
In addition, 1-hydroxyethane-1,1-diphosphonic acid, which is the main phosphonic acid used as a stabilizing agent for hydrogen peroxide, is water-soluble and is considered harmless as long as it remains in food. However, it is a type of oxyphosphonic acid listed in the list of pharmaceutical ingredients in Hong Kong's Pharmacy and Poison Ordinance. A stop is requested.
Therefore, the present invention provides a hydrogen peroxide stabilizer excellent in hydrogen peroxide stability, even though the amount of phenyl glycol ether used as a hydrogen peroxide stabilizer is reduced and oxyphosphonic acids are not blended. The object is to provide a hydrogen aqueous liquid.

The present inventors have made intensive studies to solve the above problems. As a result, by blending specific polyoxyethylene alkyl ether phosphates or salts thereof in addition to phenyl glycol ethers, even when the amount thereof is relatively small, the stability of hydrogen peroxide is excellent. The inventors have completed the present invention by discovering that an aqueous hydrogen peroxide solution can be obtained.
The present invention is shown below.

[1] As a hydrogen peroxide stabilizer, a phenyl glycol ether represented by the following formula (I) and a polyoxyethylene alkyl ether phosphoric acid represented by the following formula (II) or a salt thereof,
_{C6H5 -} O-( _CH2CH2O ) _{m -} H (I)
R ¹ —(OCH ₂ CH ₂ ) _n —OP(═O)(OH) ₂ (II)
[In the formula, R ¹ represents a C _8-18 alkyl group, m represents an integer of 1 or more and 5 or less, and n represents an integer of 1 or more and 6 or less. ]
The total concentration of the phenyl glycol ether represented by the above formula (I) and the polyoxyethylene alkyl ether phosphoric acid represented by the above formula (II) or a salt thereof is less than 0.1% by mass. Aqueous hydrogen peroxide solution.

[2] The aqueous hydrogen peroxide solution according to [1] above, which further contains a nonionic surfactant.

[3] The aqueous hydrogen peroxide solution according to [1] or [2] above, wherein the mass ratio of the phenyl glycol ether to the polyoxyethylene alkyl ether phosphoric acid or salt thereof is 1 or more.

[4] The aqueous hydrogen peroxide solution according to [2] above, wherein the concentration of the nonionic surfactant is 0.001% by mass or more and 0.05% by mass or less.

[5] The aqueous hydrogen peroxide solution according to any one of [1] to [4] above, further comprising a polyalkylene glycol represented by the following formula (III).
R ² —[OC(R ³ )(R ⁴ )-C(R ⁵ )(R ⁶ )-] _l —OH (III)
[In the formula, R ² to R ⁶ independently represent H or a C _1-4 alkyl group, and l represents an integer of 2 or more and 5 or less. ]

[6] The aqueous hydrogen peroxide solution according to [5] above, wherein the concentration of the polyalkylene glycol represented by formula (III) is 0.001% by mass or more and 0.05% by mass or less.

The aqueous hydrogen peroxide solution according to the present invention uses a reduced amount of phenyl glycol ethers as a stabilizing agent for hydrogen peroxide, and does not need to contain phosphonic acids. Nevertheless, it exhibits relatively good hydrogen peroxide stability even under acidic conditions at elevated temperatures. Therefore, the aqueous hydrogen peroxide solution according to the present invention is industrially extremely useful as an aqueous hydrogen peroxide solution to be blended in detergents, cosmetics, and the like.

1 is a graph showing test results for hydrogen peroxide stability of various aqueous hydrogen peroxide solutions at elevated temperatures and under acidic conditions.

The aqueous hydrogen peroxide solution according to the present invention contains, as hydrogen peroxide stabilizers, phenyl glycol ethers represented by formula (I) (hereinafter abbreviated as "phenyl glycol ethers (I)"), and Polyoxyethylene alkyl ether phosphates represented by formula (II) (hereinafter abbreviated as "POE alkyl ether phosphates (II)") or salts thereof, the above phenyl glycol ethers (I) and the above POE alkyl The total concentration of ether phosphates (II) or salts thereof is less than 0.1% by mass.

The aqueous hydrogen peroxide solution according to the present invention usually contains about 0.1% by mass or more and 10% by mass or less of hydrogen peroxide. Hydrogen peroxide generally becomes unstable and easily decomposed as the liquid becomes more basic from neutral. Therefore, the aqueous hydrogen peroxide liquid according to the present invention is preferably acidic. The pH can be, for example, 6.0 or less, preferably 5.5 or less or 5.0 or less, and more preferably 4.5 or less or 4.0 or less.

Also, transition metals such as Cu, Fe, Cr, and Mn promote the decomposition of hydrogen peroxide. there is However, the transition metal concentration is preferably 100 ppm or less, more preferably 50 ppm or less or 20 ppm or less, and even more preferably 10 ppm or less or 5 ppm or less, although it depends on the type.

Phenyl glycol ethers (I) used as stabilizers for hydrogen peroxide in the present invention are represented by formula (I).
_{C6H5 -} O-( _CH2CH2O ) _{m -} H (I)
[In the formula, m represents an integer of 1 or more and 5 or less. ]

In formula (I), m is preferably 3 or less, more preferably 1 or 2, and even more preferably 1. That is, phenyl glycol ethers (I) include ethylene glycol phenyl ether (phenoxyethanol), diethylene glycol phenyl ether, triethylene glycol phenyl ether, tetraethylene glycol phenyl ether, pentaethylene glycol phenyl ether, etc. Among them, Ethylene glycol phenyl ether (phenoxyethanol) is particularly preferred.
Phenyl glycol ethers (I) are used as hydrogen peroxide stabilizers in the present invention, and also function as preservatives due to their antibacterial properties.

The POE alkyl ether phosphates (II) used as hydrogen peroxide stabilizers in the present invention are represented by formula (II).
R ¹ —(OCH ₂ CH ₂ ) _n —OP(═O)(OH) ₂ (II)
[In the formula, R ¹ represents a C _8-18 alkyl group, and n represents an integer of 1 or more and 6 or less. ]

A " _C8-18 alkyl group" refers to a linear or branched monovalent saturated aliphatic hydrocarbon group having 8 or more and 18 or less carbon atoms. Examples include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like. A C _10-18 alkyl group is preferred, and a C _10-16 alkyl group is more preferred. Moreover, as the _C8-18 alkyl group, a linear one is preferable.

In formula (II), n is preferably 2 or more, more preferably 3 or more, and preferably 5 or less, more preferably 4 or less.

The counter cations constituting the salts of POE alkyl ether phosphates (II) are not particularly limited, but examples include alkali metal ions such as lithium ion, sodium ion and potassium ion; ammonium ion (NH ₄ ⁺ ); tetraalkylammonium; Examples include organic ammonium ions such as ions, preferably alkali metal ions, and more preferably sodium ions or potassium ions.

Phenyl glycol ethers (I) and POE alkyl ether phosphates (II) or salts thereof may be used singly or in combination of two or more thereof. For example, as the POE alkyl ether phosphates (II), a mixture having two or more alkyl groups with different carbon numbers may be used. Also, two or more POE alkyl ether phosphates (II) having different degrees of polymerization of the polyoxyethylene portion may be used.

The total concentration of phenyl glycol ethers (I) and POE alkyl ether phosphates (II) or salts thereof in the aqueous hydrogen peroxide solution according to the present invention is 0.1 mass in terms of performance such as safety and cost. % is preferred. The total concentration is more preferably 0.095% by mass or less or 0.090% by mass or less, and even more preferably 0.085% by mass or less. On the other hand, in order to sufficiently exhibit the effects of the phenyl glycol ethers (I) and the POE alkyl ether phosphates (II) or salts thereof, the total concentration is preferably 0.020% by mass or more, more preferably 0.040% by mass or more. is more preferable, and 0.050% by mass or more is even more preferable.

Phenyl glycol ethers (I) and POE alkyl ether phosphates (II) or salts thereof are preferably blended in a well-balanced manner in order to fully exhibit the effects of each component. For example, it is preferable that the mass ratio of phenyl glycol ethers (I) to POE alkyl ether phosphates (II) is 1 or more. The ratio is more preferably 2 or more or 3 or more, and even more preferably 4 or more. On the other hand, if the ratio is too large, the effects of both components may not be sufficiently exhibited.

The main solvent of the aqueous hydrogen peroxide solution according to the present invention is water, but if necessary, a water-miscible organic solvent may be blended. Here, the water-miscible organic solvent refers to an organic solvent that is miscible with water without limitation under normal temperature and normal pressure. Water-miscible organic solvents include alcohol solvents such as methanol, ethanol and isopropanol; polyol solvents such as ethylene glycol, propylene glycol and glycerin; ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and dimethylacetamide. Solvent; sulfoxide solvents such as dimethyl sulfoxide can be mentioned.

When a mixed solvent of water and a water-miscible organic solvent is used as the solvent, the proportion of water in the mixed solvent is preferably 60% by mass or more, more preferably 80% by mass or 90% by mass or more, and 95% by mass or more or 98% by mass. % or more is even more preferable. Moreover, it is preferable to use substantially only water as a solvent.

In addition to phenyl glycol ethers (I) and POE alkyl ether phosphates (II) or salts thereof, nonionic surfactants may be added to the aqueous hydrogen peroxide solution according to the present invention. Addition of a nonionic surfactant may further improve the stability of hydrogen peroxide.

Examples of nonionic surfactants include sorbitan fatty acid esters and sorbitan polyoxyethylene ether fatty acid esters. Fatty acids constituting these fatty acid esters include _C8-20 long-chain fatty acids such as caprylic acid, lauric acid, palmitic acid, stearic acid and oleic acid. The fatty acid esters also include fatty acid diesters and fatty acid triesters. The polyoxyethylene polymerization degree of the polyoxyethylene ether fatty acid ester can be, for example, about 10 or more and 30 or less.

The concentration of the nonionic surfactant in the aqueous hydrogen peroxide solution according to the present invention is not particularly limited, and may be adjusted as appropriate. The concentration is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 0.04% by mass or less, and more preferably 0.02% by mass or less.

Polyalkylene glycols represented by the following formula (III) (hereinafter abbreviated as "polyalkylene glycols (III)") may be added to the aqueous hydrogen peroxide solution according to the present invention. By adding polyalkylene glycols (III), it is possible to solubilize components that are not sufficiently soluble in water, which is the main solvent, to suppress the precipitation of components, and to further stabilize hydrogen peroxide.
R ² —[OC(R ³ )(R ⁴ )-C(R ⁵ )(R ⁶ )-] _l —OH (III)
[In the formula, R ² to R ⁶ independently represent H or a C _1-4 alkyl group, and l represents an integer of 2 or more and 5 or less. ]

A “C _1-4 alkyl group” refers to a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl. A C _1-2 alkyl group is preferred, and methyl is more preferred. H or methyl are preferred for R ² to R ⁶ .

The concentration of the polyalkylene glycol (III) in the aqueous hydrogen peroxide solution according to the present invention is not particularly limited, and may be adjusted as appropriate. can. The concentration is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 0.04% by mass or less, and more preferably 0.02% by mass or less.

In the aqueous hydrogen peroxide solution according to the present invention, hydrogen peroxide is stabilized even in the presence of a transition metal that promotes decomposition of hydrogen peroxide and even at relatively high temperatures. Its oxidative activity is maintained. Therefore, the aqueous hydrogen peroxide solution according to the present invention can be widely used in bleaching agents, cosmetics, chemical polishing agents, hair dyes, etc. containing hydrogen peroxide as an oxidizing component. Phenyl glycol ethers (I) and POE alkyl ether phosphates (II) or salts thereof, which are active ingredients of the aqueous hydrogen peroxide solution according to the present invention, are blended from the beginning to stabilize hydrogen peroxide. In addition, hydrogen peroxide can be stabilized by adding it at the same time as or immediately after the addition of hydrogen peroxide in the preparation process.

The present invention is a method for stabilizing hydrogen peroxide in an aqueous liquid containing hydrogen peroxide, wherein the aqueous liquid contains phenyl glycol ethers represented by formula (I) and formula (II). It also relates to a process comprising adding the represented polyoxyethylene alkyl ether phosphates or salts thereof. In the method, the essential components phenyl glycol ethers (I) and POE alkyl ether phosphates (II), and the description and addition amounts of the above-mentioned preferred components, etc., are included in the aqueous hydrogen peroxide solution according to the present invention. The description of is incorporated.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be modified appropriately within the scope that can conform to the gist of the above and later descriptions. It is of course possible to implement them, and all of them are included in the technical scope of the present invention.

Examples 1-4, Comparative Examples 1-3
Components were mixed according to the composition shown in Table 1 to prepare each hydrogen peroxide stabilizer. The numerical values in Table 1 are mass ratios. As polyoxyethylene (POE) alkyl ether phosphate, "Phosphanol ^(R) RS-410, 610, 710" manufactured by Toho Chemical Industry Co., Ltd. is used, and POE sorbitan monooleate is manufactured by NOF Corporation. "Nonion ^(R) OT-221" was used.

After adding 0.1% by mass of each hydrogen peroxide stabilizer to a 5.6% by mass aqueous solution of hydrogen peroxide, _{FeNH4 ( SO4} ) _2.12H2O and _{CuSO4.5H2O were} added. was added so that the concentrations of Fe and Cu were 1 ppm each, and the pH was adjusted to 3.5 with sulfuric acid or potassium hydroxide.
Each acidic aqueous hydrogen peroxide solution thus obtained was allowed to stand in a constant temperature bath adjusted to 60° C., and the hydrogen peroxide residual rate was measured over time by the cerium (IV) sulfate solution-ferroin indicator method. Two examples of each aqueous hydrogen peroxide solution were prepared, measurements were performed twice, and an average value was calculated from the measurement results of four examples. The results are shown in FIG.

As the results shown in FIG. 1, even with the hydrogen peroxide stabilizer of Comparative Example 1 containing phenoxyethanol and 1-hydroxyethane-1,1-diphosphonic acid, the sum of them in the aqueous hydrogen peroxide solution was 0. When the content was less than 1% by mass, the stabilizing effect of hydrogen peroxide was not sufficient. The same was true for the hydrogen peroxide stabilizer of Comparative Example 2 containing only phenoxyethanol.
In addition, even if polyoxyethylene alkyl ether phosphoric acid is contained in addition to phenoxyethanol, the effect of the hydrogen peroxide stabilizer of Comparative Example 3, in which the degree of polymerization of polyoxyethylene is 9, is not sufficient. rice field.
On the other hand, in the case of the hydrogen peroxide stabilizer according to the present invention containing, in addition to phenoxyethanol, a polyoxyethylene alkyl ether phosphate having a polyoxyethylene polymerization degree of 6 or less, the sum of these components is less than 0.1% by mass. Even so, the stabilizing effect of hydrogen peroxide was clearly improved. In particular, the hydrogen peroxide stabilizing effect of the hydrogen peroxide stabilizer of Example 4, in which polyoxyethylene sorbitan monooleate was used in combination, was remarkably excellent.

Claims (6)

As hydrogen peroxide stabilizers, phenyl glycol ethers represented by the following formula (I), and polyoxyethylene alkyl ether phosphoric acids represented by the following formula (II) or salts thereof,
_{C6H5 -} O-( _CH2CH2O ) _{m -} H (I)
R ¹ —(OCH ₂ CH ₂ ) _n —OP(═O)(OH) ₂ (II)
[In the formula, R ¹ represents a C _8-18 alkyl group, m represents an integer of 1 or more and 5 or less, and n represents an integer of 2 or more and 6 or less. ]
The total concentration of the phenyl glycol ether represented by the above formula (I) and the polyoxyethylene alkyl ether phosphoric acid represented by the above formula (II) or a salt thereof is less than 0.1% by mass. Aqueous hydrogen peroxide solution. The aqueous hydrogen peroxide solution according to Claim 1, further comprising a nonionic surfactant. 3. The aqueous hydrogen peroxide solution according to claim 1, wherein the mass ratio of said phenyl glycol ethers to said polyoxyethylene alkyl ether phosphates or salts thereof is 1 or more. 3. The aqueous hydrogen peroxide solution according to claim 2, wherein the concentration of the nonionic surfactant is 0.001% by mass or more and 0.05% by mass or less. The aqueous hydrogen peroxide solution according to any one of claims 1 to 4, further comprising a polyalkylene glycol represented by the following formula (III).
R ² —[OC(R ³ )(R ⁴ )-C(R ⁵ )(R ⁶ )-] _l —OH (III)
[In the formula, R ² to R ⁶ independently represent H or a C _1-4 alkyl group, and l represents an integer of 2 or more and 5 or less. ] 6. The aqueous hydrogen peroxide solution according to claim 5, wherein the concentration of the polyalkylene glycol represented by formula (III) is 0.001% by mass or more and 0.05% by mass or less.

Images