JP6681283B2 - Liquid bleach composition for textiles - Google Patents

Description

  The present invention relates to liquid bleach compositions.

  The liquid bleach composition has an effect of bleaching stains attached to clothes, tableware and the like. Among them, liquid bleach compositions containing hydrogen peroxide are widely used because they are easy to use for colored patterns. Liquid stain bleach compositions require additional soil cleaning power.

  Patent Document 1 further improves the detergency by adding a surfactant and a cyclodextrin to a liquid bleaching agent composition containing hydrogen peroxide.

JP, 2011-225743, A

However, the composition of Patent Document 1 has a problem that hydrogen peroxide is easily decomposed. Gas is generated when hydrogen peroxide is decomposed. In addition, the transparent appearance is impaired due to the composition becoming cloudy (the appearance stability is low).
Further, if the viscosity of the composition is increased, it is easier to apply it directly to the stains, and thus the usability is improved and the usability can be improved. However, the composition of Patent Document 1 has a problem that the usability is poor because the viscosity is low.
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid bleaching composition having improved detergency against dirt, improved stability of hydrogen peroxide, and improved usability. It is an issue.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by combining hydrogen peroxide, a specific anionic surfactant, and a specific semipolar surfactant, and completed the present invention. It was

（式（ＩＩ）中、Ｒ^１１は炭素数１２のアルキル基又は炭素数１２のアルケニル基であり、Ｒ^１２、Ｒ^１３はそれぞれ独立に炭素数１〜３のアルキル基又は炭素数１〜３のヒドロキシアルキル基である。）
［２］（Ｂ１）成分／（Ｂ２）成分で表される質量比が、１〜１０である、［１］に記載の液体漂白剤組成物。 The liquid bleach composition of the present invention has the following aspects.
[1] component (A): hydrogen peroxide, and component (B): a surfactant,
The component (B) includes a component (B1): polyoxyalkylene alkyl ether sulfuric acid or a salt thereof, and a component (B2): a semipolar surfactant represented by the following general formula (II),
pH is below 7,
The liquid bleaching composition, wherein the content of the component (B) is 1 to 20% by mass based on the total mass of the liquid bleaching composition.

(In the formula (II), R ¹¹ is an alkyl group having 12 carbon atoms or an alkenyl group having 12 carbon atoms, and R ¹² and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. It is a hydroxyalkyl group.)
[2] The liquid bleach composition according to [1], wherein the mass ratio represented by the component (B1) / the component (B2) is 1 to 10.

  According to the present invention, it is possible to provide a liquid bleaching composition having improved detergency against dirt, improved stability of hydrogen peroxide, and improved usability.

  The liquid bleaching composition of the present invention is a composition containing the following component (A) and component (B).

≪ (A) ingredient: Hydrogen peroxide≫
The component (A) is hydrogen peroxide and has a bleaching effect. Particularly, it exhibits a high bleaching effect against water-based stains.
The content of the component (A) in the liquid bleaching composition is preferably 0.1 to 6% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the liquid bleaching agent composition. 0.5 to 4 mass% is more preferable. When the content of the component (A) is at least the lower limit value of the above range, the cleaning power against dirt is likely to be improved. When it is at most the upper limit value of the above range, the stability of hydrogen peroxide is likely to be improved.

≪ (B) component: Surfactant≫
The component (B) is a surfactant, and contains the component (B1): polyoxyalkylene alkyl ether sulfuric acid or a salt thereof, and the component (B2): a semipolar surfactant represented by the general formula (II). .

<Component (B1): polyoxyalkylene alkyl ether sulfuric acid or salt thereof>
The component (B1) is polyoxyalkylene alkyl ether sulfuric acid or a salt thereof. Specifically, a compound represented by the following general formula (I) is preferable.
^{_{R 1 - [(EO) m}} / (PO) n] -SO 3 - M + ··· (I)
(In the formula (I), R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, PO represents an oxypropylene group, and m represents EO. It represents the average number of repetitions and is a number of 0 or more.n represents the average number of repetitions of PO and is a number from 0 to 6. 0 <m + n. M ⁺ is a counter cation.]
As the polyoxyalkylene alkyl ether sulfate, those having a linear or branched alkyl group having 10 to 20 carbon atoms and having an average of 1 to 5 mol of alkylene oxide added thereto are preferable.
10-20 are preferable and, as for carbon number of R < ¹ >, 12-14 are more preferable.
0-5 are preferable and, as for the average repetition number of EO, 0.5-3 are more preferable.
The average repeating number of PO is preferably 0 to 3, and more preferably 0.
Examples of M ⁺ include alkali metal ions such as sodium ions and potassium ions, alkaline earth metal ions such as magnesium ions, and cations derived from alkanolamines such as monoethanolamine and diethanolamine.
In (EO) _m / (PO) _n , EO and PO may be random addition or block addition.
As the component (B1), a commercially available product may be used, or a known synthesis method may be used. As a known production method, a method of reacting polyoxyalkylene alkyl ether with sulfuric anhydride or with chlorosulfonic acid can be mentioned.
The component (B1) may be one type or two or more types.

  In the liquid bleach composition, the content of the component (B1) is preferably 0.1 to 18% by mass, more preferably 1 to 10% by mass, and 2 to 5 with respect to the total mass of the liquid bleach composition. Mass% is more preferable. When the content of the component (B1) is at least the lower limit value of the above range, the detergency against dirt can be easily improved, and the viscosity can be increased, whereby the usability can be easily improved. When it is at most the upper limit value of the above range, the low temperature appearance stability will be easily improved, and the usability will be easily improved by increasing the viscosity.

The mass ratio (hereinafter, also referred to as B1 / A ratio) represented by the component (B1) / the component (A) is preferably 0.1 to 20, more preferably 0.2 to 5, and 0.3 to 2. More preferable.
When the B1 / A ratio is at least the lower limit value in the above range, the stability of hydrogen peroxide is easily improved and the cleaning power against dirt is easily improved. When it is at most the upper limit value of the above range, the cleaning power against dirt can be easily improved.

<Component (B2): Semipolar Surfactant Represented by General Formula (II)>
The component (B2) is a semipolar surfactant represented by the following general formula (II).

(In the formula (II), R ¹¹ is an alkyl group having 12 carbon atoms or an alkenyl group having 12 carbon atoms, and R ¹² and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. It is a hydroxyalkyl group.)

  In the present specification, the "semipolar surfactant" is a surfactant having a semipolar bond (a bond having an intermediate property between a nonpolar bond and a polar bond), and the semipolar surfactant dissolves in the surfactant. Depending on the pH of the solution to be dispersed or the dispersion system to be dispersed, it may be cationic, anionic, or amphoteric.

In formula (II), R ¹¹ is an alkyl group having 12 carbon atoms or an alkenyl group having 12 carbon atoms. The alkyl group having 12 carbon atoms and the alkenyl group having 12 carbon atoms may be linear or branched.

R ¹² and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
The alkyl group having 1 to 3 carbon atoms and the hydroxyalkyl group having 1 to 3 carbon atoms may be linear or branched.
Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group and propyl group.
Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include hydroxyethyl group and hydroxypropyl group.
The component (B2) may be one type or two or more types.

  In the liquid bleach composition, the content of the component (B2) is preferably 0.1 to 8% by mass, more preferably 0.3 to 3% by mass, and 0 based on the total mass of the liquid bleach composition. 0.5-2 mass% is more preferable. When the content of the component (B2) is at least the lower limit value of the above range, the viscosity can be increased and the usability can be easily improved. When it is at most the upper limit value of the above range, the appearance stability is likely to be improved.

The mass ratio (hereinafter, also referred to as B2 / A ratio) represented by the component (B2) / the component (A) is preferably 0.05 to 10, more preferably 0.1 to 8, and 0.2 to 3. More preferable.
When the B2 / A ratio is not less than the lower limit value in the above range, the viscosity can be increased and the usability is likely to be improved. When it is at most the upper limit value of the above range, the cleaning power against dirt can be easily improved.

1-10 are preferable, as for the mass ratio (henceforth B1 / B2 ratio) represented by (B1) component / (B2) component, 2-8 are more preferable, and 3-5 are more preferable.
When the B1 / B2 ratio is not less than the lower limit value of the above range, the cleaning power against stains is likely to be improved, and the appearance stability of the liquid is likely to be improved. When it is at most the upper limit value of the above range, the viscosity can be increased and the usability can be easily improved.

  Examples of the surfactant other than the component (B1) and the component (B2) include anionic surfactants other than the component (B1), nonionic surfactants, cationic surfactants, amphoteric surfactants, and semi-components other than the component (B2). Examples include polar surfactants.

  Examples of the anionic surfactant other than the component (B1) include linear alkylbenzene sulfonic acid or its salt, α-olefin sulfonate, linear or branched alkyl sulfate ester salt, alkane sulfonate having an alkyl group, Examples include α-sulfofatty acid ester salts. Examples of the salt in these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine.

As the linear alkylbenzene sulfonic acid or a salt thereof, a linear alkyl group having 8 to 16 carbon atoms is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate preferably has 10 to 20 carbon atoms.
The alkyl sulfate ester salt preferably has an alkyl group having 10 to 20 carbon atoms.
As the alkane sulfonate, those having an alkyl group having 10 to 20 carbon atoms are preferable, and those having 14 to 17 are more preferable. Among them, those in which the alkyl group is a secondary alkyl group (that is, secondary alkane sulfonate) are particularly preferable.
As the α-sulfo fatty acid ester salt, one having a fatty acid residue having 10 to 20 carbon atoms is preferable.

  Among these, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, and α-olefin sulfonate are preferable in terms of excellent detergency and stability, and linear alkylbenzene sulfonic acid or a salt thereof and alkane sulfone. Acid salts are more preferable, and linear alkylbenzene sulfonate sodium (LAS) and secondary sodium alkanesulfonate having 14 to 17 carbon atoms (SAS) are particularly preferable.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers (AE), polyoxyethylene polyoxypropylene alkyl ethers (EOPO type nonions), and other polyoxyalkylene alkyl ethers, alkyl (poly) glycosides, sorbitan fatty acid esters, polyoxyethylene. Examples thereof include sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ester oxyethylene propylene block polymer, and fatty acid monoglyceride.
Among the above, from the viewpoint of stability in a liquid bleaching composition containing a bleaching component such as hydrogen peroxide, ease of controlling the dissolved gas amount of the liquid bleaching agent composition, and the like, a polyoxyalkylene alkyl ether. Is preferable, and a polyoxyalkylene alkyl ether represented by the following general formula (III) is particularly preferable.

_{^{R 10 -O- (AO) p -H}} ··· (III)
(In the formula (III), R ¹⁰ is a linear or branched alkyl group having 8 to 16 carbon atoms or a linear or branched alkenyl group having 8 to 16 carbon atoms; AO is 2 to 2 carbon atoms. 5 represents an alkyleneoxy group; p represents the average number of AO repeats, and is 1 to 20, preferably 3 to 15.)

The carbon number of R ¹⁰ in the formula (III) is 8 to 16, preferably 10 to 14 and more preferably 12 to 14 in any case of an alkyl group or an alkenyl group. When the carbon number is 8 or more, the detergency becomes good, and when the carbon number is 16 or less, the solubility is improved.
R ¹⁰ is preferably an alkyl group, specifically, a heptyl group, 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, The tetradecyl group is particularly preferred.
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 alone or in combination of two or more.
Although depending on the type of the AO, p is preferably 3 to 15 when AO is an oxyethylene group and / or an oxypropylene group.
When AO is an oxyethylene group and / or an oxypropylene group, these may be random addition or block addition.

  In the liquid bleach composition, the content of the nonionic surfactant is preferably 0.1 to 18% by mass, more preferably 0.5 to 12% by mass, based on the total mass of the liquid bleach composition. It is more preferably from 10 to 10% by mass. When the content of the nonionic surfactant is at least the lower limit value of the above range, the cleaning power against dirt can be easily improved. When it is at most the upper limit of the above range, the appearance stability of the liquid is likely to be improved.

Examples of the semipolar surfactant other than the component (B2) include trialkylamine oxide represented by the following general formula (IV).
R ³¹ R ³² R ³³ N → O ... (IV)
(In the formula (IV), R ³¹ is a linear or branched alkyl group having 8 to 11 carbon atoms, a linear or branched alkyl group having 13 to 18 carbon atoms, or a linear chain having 8 to 11 carbon atoms. A branched or branched alkenyl group, or a linear or branched alkenyl group having 13 to 18 carbon atoms, and R ³² and R ³³ each independently have a linear or branched carbon number of 1 to 3 is an alkyl group or a linear or branched hydroxyalkyl group having 1 to 3 carbon atoms.)

In the liquid bleach composition, the content of the component (B) is 1 to 20% by mass, preferably 2 to 18% by mass, and 6 to 15% by mass with respect to the total mass of the liquid bleach composition. More preferable.
When the content of the component (B) is at least the lower limit value of the above range, the cleaning power against stains can be easily improved and the usability can be easily improved by increasing the viscosity. If it is at most the upper limit of the above range, the effect of the present invention can be easily obtained.

<Arbitrary ingredients>
The liquid bleaching composition of the present invention may contain, in addition to the components (A) and (B) described above, optional components usually used in liquid bleaching compositions.
Examples of optional components include polymers, pH adjusters, chelating agents, radical trapping agents, organic solvents, buffers, fragrances, solvents, hydrotropes, and bleach activators.

The polymer is not particularly limited, and examples thereof include polymers commonly used in detergents for textile products. An example is a polymer having at least one repeating unit (c1) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and an oxyalkylene unit (c2).
In addition, in this specification, a "repeating unit" means the monomer unit which comprises a polymer.

-About specific repeating unit (c1) Among the specific repeating units (c1), the alkylene terephthalate unit (hereinafter, this repeating unit is also referred to as "repeating unit (c11)") has the following general formula (c1-1). The repeating unit represented by

In the formula (c1-1), R ²¹ is a lower alkylene group. The lower alkylene group for R ²¹ preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 2 to 4 carbon atoms.
Specific examples of the repeating unit (c11) include an ethylene terephthalate unit, a propylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit and a tert-butylene terephthalate unit. Of these, a propylene terephthalate unit is preferable.
As the repeating unit (c11), one type may be used alone, or two or more types may be used in combination.

  Among the specific repeating unit (c1), examples of the alkylene isophthalate unit (hereinafter, this repeating unit is also referred to as “repeating unit (c12)”) include a repeating unit represented by the following general formula (c1-2). To be

In the formula (c1-2), R ²² is a lower alkylene group. The lower alkylene group for R ²² preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 2 to 4 carbon atoms.
Specific examples of the repeating unit (c12) include ethylene isophthalate units, propylene isophthalate units, n-butylene isophthalate units, sec-butylene isophthalate units, and tert-butylene isophthalate units. Of these, a propylene isophthalate unit is preferable.
As the repeating unit (c12), one type may be used alone, or two or more types may be used in combination.

The polymer may have only one type of repeating unit (c1), or may have two or more types. That is, the polymer may have only the repeating unit (c11) as the repeating unit (c1), or may have only the repeating unit (c12) in one molecule thereof. ) And the repeating unit (c12). Moreover, you may have 2 or more types of repeating units (c11), and / or 2 or more types of repeating units (c12).
The repeating unit (c1) may be introduced in one unit in one molecule, or in two or more units (that is, in a block form).

The repeating number of the repeating unit (c1) contained in one molecule of the polymer is preferably 1 to 10, more preferably 1 to 6, and further preferably 2 to 4.
When the number of repeating units (c1) is at least the above preferred lower limit, the deodorizing effect on the textile product after washing will be easily enhanced. When it is at most the preferable upper limit value, the appearance stability when used as a liquid detergent is likely to be enhanced.

-About oxyalkylene unit (c2) As an oxyalkylene unit (henceforth this repeating unit is also called a "repeating unit (c2)"), the repeating unit represented by the following general formula (c2-1) is mentioned.

In the formula (c2-1), R ²³ is a lower alkylene group. The lower alkylene group for R ²³ preferably has 1 to 4 carbon atoms, more preferably 2 to 4 carbon atoms, further preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
Examples of the repeating unit (c2) include an oxyethylene unit, an oxypropylene unit and an oxybutylene unit. Of these, oxyethylene units and oxypropylene units are preferable, and oxyethylene units are more preferable.

The polymer may have only one type of repeating unit (c2) or may have two or more types. That is, the polymer may have, for example, only an oxyethylene unit or only an oxypropylene unit as a repeating unit (c2) in its one molecule, and may have an oxyethylene unit and an oxypropylene unit. It may have both units. Among them, it is preferable to have only an oxyethylene unit.
Further, the polymer may have an oxyalkylene group (having a repeating number of repeating unit (c2) of 1) as a repeating unit (c2) in one molecule thereof, and a polyoxyalkylene group (repeating unit). (C2) has a repeating number of 2 or more), and may have both an oxyalkylene group and a polyoxyalkylene group.

The number of repeating units (c2) in one molecule of the polymer is 1 or more, preferably 5 to 150, more preferably 10 to 100.
When the number of repeating units (c2) is not less than the above preferred lower limit, the appearance stability when used as a liquid detergent is more likely to be increased. When it is at most the above preferable upper limit value, the deodorizing effect on the object to be washed after washing tends to be enhanced.

  The polymer may be a polymer in which the repeating unit (c1) and the repeating unit (c2) are polymerized in a block form, or may be a polymer in which the repeating units are polymerized in a random form. Among these, a polymer polymerized in a block form is preferable as the polymer.

The polymer may have other repeating units in addition to the repeating unit (c1) and the repeating unit (c2). Examples of the other repeating unit include a repeating unit derived from a polymerization initiator, a polymerization terminator and the like, a repeating unit derived from a monomer capable of copolymerizing with the monomer providing the repeating unit (c1) or the repeating unit (c2), and the like. To be
When the polymer has other repeating units, the total of the repeating unit (c1) and the repeating unit (c2) is preferably 80 mol% or more based on the total of all repeating units constituting the polymer. More preferably 90 mol% or more, and may be 100 mol%. When the total of the repeating unit (c1) and the repeating unit (c2) is at least the above preferred lower limit, the deodorizing effect on the object to be washed after washing will be easily enhanced.

The polymer is preferably a water-soluble polymer from the viewpoint of its own solubility and liquid stability of the liquid detergent.
The term "water-soluble polymer" used herein means that 10 g of the polymer is added to 1000 g of water in a 1 liter beaker under the condition of 40 ° C. and stirred for 12 hours by a stirrer (thickness 8 mm, length 50 mm) (200 rpm). What is dissolved after being done.

The weight-average molecular weight of the polymer is preferably 500 or more, more preferably 800 or more, and further preferably 1000 or more, since the solubility and dispersibility in water is enhanced. On the other hand, the preferable upper limit value is 10,000 or less, more preferably 8,000 or less, and further preferably 7,000 or less. When the weight average molecular weight of the polymer is equal to or more than the preferable lower limit value, the deodorizing effect on the washed object is easily enhanced. When the weight average molecular weight of the polymer is equal to or less than the preferable upper limit value, the solubility and dispersibility of the polymer in water is more likely to be improved, and the appearance stability when blended in the liquid detergent is likely to be increased.
The "weight average molecular weight" as used herein refers to a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent and converted based on a calibration curve for PEG (polyethylene glycol).

  Polymers are synthesized by various methods disclosed in various documents, textbooks, patent documents, and the like, for example, Journal of Polymer Science, Volume 3, 609 to 630 (1948); Journal of Polymer Science, Volume 8, 1 Page 22 (1951); can be produced by the method described in JP-A-61-218699.

  Preferable specific examples of the polymer include those containing a polymer compound represented by the following formula (C1), a polymer compound represented by the formula (C2), or a mixture thereof.

In the formulas (C1) and (C2), R ²⁰ and R ³⁰ are each independently a hydrogen atom or a methyl group, preferably a methyl group, and more preferably a methyl group. .
R ²⁴ and R ²⁷ each represent a methyl group or a hydrogen atom, and each preferably represents a methyl group.
R <^25> , R <^26> , R <^28> and R <^29> are each independently an alkylene group having 2 to 4 carbon atoms.
s1 and s2 are each 0 to 10, preferably 0.5 to 5, and more preferably 0.5 to 2.5. t1, t2, u1 and u2 are each independently 1 to 100, preferably 1 to 80, and more preferably 1 to 50. When s1, s2, t1, t2, u1 and u2 are in the above preferred ranges, the blending effect of the polymer is likely to be sufficiently exhibited. Further, the solubility in water is further improved, and a liquid detergent having a high transparency is easily obtained.

As the polymer, one type may be used alone, or two or more types may be used in combination.
As the polymer, a synthetic product or a commercially available product may be used.
Commercially available products of the polymer include trade name TexCare SRN-100 (Germany, Clariant Gmb H, weight average molecular weight 3000), trade name TexCare SRN-300 (Germany, Clariant Gmb H, weight average molecular weight 7,000) and the like. .
Among these, TexCare SRN-100 is preferable because it has a high solubility in water and a liquid detergent having a high transparency can be easily obtained.

  The content of the polymer is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, and further preferably 0.2 to 1% by mass, based on the total mass of the liquid bleaching agent composition.

Examples of the pH adjusting agent include sodium hydroxide, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, ammonia and the like.
The pH of the liquid bleach composition of the present invention is 7 or less, preferably 2 to 7, more preferably 3 to 6. When the pH is at least the lower limit value of the above range, the appearance stability of the liquid is likely to be improved. When it is at most the upper limit of the above range, the stability of hydrogen peroxide is likely to be improved, and the viscosity is increased, whereby the usability is easily improved.
The pH of the liquid bleaching composition (adjusted to 25 ° C.) is a value measured by a pH meter (manufactured by Toa DKK Co., Ltd., “HM-30G”) or the like.

Examples of the chelating agent include phosphonic acid type chelating agents such as 1-hydroxyethane-1,1-diphosphonic acid. The content of the chelating agent in the liquid bleach composition is preferably 0.1 to 2% by mass based on the total mass of the liquid bleach composition.
Examples of the radical trapping agent include p-methoxyphenol and dibutylhydroxytoluene. The content of the radical trapping agent in the liquid bleaching composition is preferably 0.01 to 1 mass% with respect to the total mass of the liquid bleaching composition.
Examples of the organic solvent include aromatic compounds such as phenyldiglycol. The content of the organic solvent in the liquid bleaching composition is preferably 0.1 to 3 mass% with respect to the total mass of the liquid bleaching composition.
Examples of the buffer include citric acid. The content of the buffer in the liquid bleach composition is preferably 0.01 to 2% by mass based on the total mass of the liquid bleach composition.
The perfume includes a perfume raw material alone, or a perfume composition comprising a perfume raw material, a perfume solvent, a perfume stabilizer, etc., a liquid detergent for clothes, a liquid bleaching detergent, a liquid bleaching agent. For example, a fragrance that is usually used can be blended. The content of the fragrance in the liquid bleach composition is preferably 0.01 to 1% by mass based on the total mass of the liquid bleach composition.
Water is preferably used as the solvent. The content of water in the liquid bleach composition is preferably 40 to 95% by mass based on the total mass of the liquid bleach composition.
Examples of the hydrotrope include water-miscible organic solvents such as alcohols having 2 to 4 carbon atoms, glycols, polyglycols, and alkyl ethers; toluenesulfonic acid, xylenesulfonic acid, benzoate, urea, and the like. To be The content of the hydrotrope agent in the liquid bleaching agent composition is preferably 0.01 to 15% by mass based on the total mass of the liquid bleaching agent composition.
A bleach activator is a substance that does not have a bleaching effect by itself, but reacts with hydrogen peroxide in a liquid bleach composition to be converted into a highly oxidizing organic peracid.
Known compounds can be used as the bleach activator. For example, tetraacetylethylenediamine; an alkanoyloxybenzenesulfonic acid having an alkanoyl group having 1 to 18 carbon atoms, preferably 8 to 12 carbon atoms, or a salt thereof; an alkanoyl group having 1 to 18 carbon atoms, preferably 8 to 12 carbon atoms. Alkanoyloxy benzoic acid or its salt which has is mentioned. Of these, 4-decanoyloxybenzoic acid (DOBA), sodium 4-dodecanoyloxybenzenesulfonate (DOBS), and sodium 4-nonanoyloxybenzenesulfonate (NOBS) are preferable.
These bleach activators may be used alone or in combination of two or more.
The content of the bleaching activator is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and 0.4 to 1% by mass based on the total mass of the liquid bleaching agent composition. % Is more preferable. When the content of the bleach activator is at least the above lower limit, the bleaching power against yellowing in the liquid bleach composition is increased, and when it is at most the above upper limit, the stability of hydrogen peroxide can be improved.
The total content of the components contained in the liquid bleaching composition does not exceed 100% by mass.

<< Method for producing liquid bleach composition >>
The liquid bleaching composition of the present invention is not particularly limited and can be produced by a conventionally known production method.
For example, the component (A), the component (B), and, if necessary, the optional component are mixed with a solvent (for example, water such as ion-exchanged water) and dissolved to adjust to a predetermined pH. Can be manufactured.

<< How to use the liquid bleach composition >>
The method of using the liquid bleaching composition of the present invention is, for example, a liquid bleaching agent composition alone or in a water together with a known detergent or softening agent to form a washing liquid, and the washing liquid is put into a washing machine. The method of washing with a liquid bleaching agent composition is previously dissolved in water, the article to be washed is dipped in this, and then washed with a washing machine. In addition, after applying the liquid bleaching composition to the article to be washed, it may be left as it is, and then ordinary washing may be performed.
Examples of the article to be washed include textile products such as clothing, cloth, sheets, curtains and carpets.
The content of the liquid bleaching composition in the cleaning liquid is not particularly limited. The amount of the liquid bleaching agent composition added to water is, for example, 3 to 15 mL of the liquid bleaching agent composition per 10 L of water.

  The liquid bleaching composition of the present invention contains (A) component: hydrogen peroxide and (B) component: a surfactant, and the (B) component is (B1) component: polyoxyalkylene alkyl ether sulfuric acid. Or a salt thereof, a component (B2): a semipolar surfactant represented by the general formula (II), and a trialkylamine oxide represented by the general formula (IV), and having a pH of 7 or less, The content of the component (B) is preferably 1 to 20% by mass based on the total mass of the liquid bleaching agent composition.

  The liquid bleaching composition of the present invention contains (A) component: hydrogen peroxide and (B) component: a surfactant, and the (B) component is (B1) component: polyoxyalkylene alkyl ether sulfuric acid. Or a salt thereof, a component (B2): a semipolar surfactant represented by the general formula (II), and a nonionic surfactant, and the pH is 7 or less, and the content of the component (B) is It is preferably 1 to 20 mass% with respect to the total mass of the liquid bleaching composition.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<< Examples 1-9, Comparative Examples 1-5 >>
<Preparation of liquid bleach composition>
The compositions of the respective examples were prepared according to the compounding compositions shown in Tables 1 and 2 by the production method described later (if there is any uncombined component, the component is not compounded).
Each component was mixed according to the composition shown in Tables 1 and 2, and a pH adjuster was added to adjust the pH to obtain each composition.
The unit of the compounding amount in the table is "mass%", and all the components show the pure equivalent amount.
The blank column in the table indicates that the component is not blended.
“Balance” means that water is blended so that the total blended amount (mass%) of all blended components contained in the composition of each example is 100 mass%.
The components shown in the table will be described below. In addition, Examples 5, 8 and 9 are reference examples.

<(A) component>
-A-1: Hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Inc.).

<(B1) component>
B1-1: polyoxyalkylene alkyl ether sulfate sodium salt (in the formula (I), R ¹ = alkyl group having 12 carbon atoms, m = 2, n = 0, M ⁺ = sodium ion). ("Emar 270J" manufactured by Kao Corporation)
B1-2: polyoxyalkylene alkyl ether sulfate sodium salt (in the formula (I), R ¹ = alkyl group having 12 and 14 carbon atoms, m = 1, n = 0, M ⁺ = sodium ion). (Production method of b1-2)
In an autoclave having a capacity of 4 L, 400 g of a product name CO1270 alcohol manufactured by P & G Co. (a mixture of an alcohol having 12 carbon atoms and an alcohol having 14 carbon atoms in a mass ratio of 75/25) as raw material alcohol, and potassium hydroxide as a reaction catalyst After charging 0.8 g of a catalyst and replacing the inside of the autoclave with nitrogen, the temperature was raised with stirring. Subsequently, while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization type detector (FID), column: Ultra-1 (manufactured by HP, L25m × φ0.2 mm × T0.11 μm) ) And was used, the obtained alcohol ethoxylate had an average addition mole number of ethylene oxide of 1.0. In addition, the amount of the compound to which ethylene oxide is not added (which finally becomes the compound of m = 0 and n = 0 in the general formula (I)) is 43% by mass based on the whole alcohol ethoxylate obtained. there were.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after substituting with nitrogen, 96 g of liquid anhydrous sulfuric acid (sulfane) was slowly added dropwise while keeping the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, this was neutralized with an aqueous sodium hydroxide solution to obtain b1-2.
-B1'-1: secondary sodium alkane sulfonate, manufactured by Clariant Japan Co., Ltd., trade name "SAS30".

<(B2) component>
B2-1: a semipolar surfactant represented by the formula (II) (in the formula (II), R ¹¹ = dodecyl group, R ¹² = methyl group, R ¹³ = methyl group). Dodecyldimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Kadenax DM12D-W".
B2′-1: a semipolar surfactant represented by the formula (IV) (in the formula (IV), R ³¹ = tetradecyl group, R ³² = methyl group, R ³³ = methyl group). Tetradecyl dimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Kadenax DM14D-N".

<Other components (B)>
Polyoxyethylene alkyl ether: A mixture of an alcohol having 12 carbon atoms (C12OH) and an alcohol having 14 carbon atoms (C14OH) (mass ratio C12OH / C14OH = 75/25) to which 6 mol of ethylene oxide is added on average. Manufactured by Lion Corporation, product name "Reox CL-60".

[Arbitrary ingredients]
Phenyldiglycol: diethylene glycol monophenyl ether, trade name "PhDG (90)" manufactured by Nippon Emulsifier Co., Ltd.
-Buffer: citric acid, manufactured by Kanto Chemical Co., Inc., reagent "citric acid".
-PH adjuster: sulfuric acid (manufactured by Toho Zinc Co., Ltd.), sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.).
[Common ingredients]
Chelating agent: 1-hydroxyethane-1,1-diphosphonic acid (HEDP), manufactured by Rhodia, trade name "BRIQUEST ADPA" ... 0.75% by mass.
Radical trapping agent: p-methoxyphenol, manufactured by Kawaguchi Chemical Co., Ltd., trade name "MQ-F" ... 0.1% by mass.
Polymer: A polymer having a specific repeating unit (c1) and an oxyalkylene unit (c2). Product name "TexCare SRN-100" manufactured by Clariant GmbH, Germany, weight average molecular weight 3000, pH 4 (measured at 20 ° C, 5 mass% aqueous solution), viscosity 340 mPa · s (measured at 50 ° C), the above general formula (C1) Aggregate containing a polymer compound represented by) ... 0.2% by mass.
-Perfume: The perfume composition A of Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399 0.1% by mass.

<Evaluation of cleaning power against dirt>
0.02 ml of chili oil (manufactured by SB Foods Co., Ltd.) was dropped onto a polyester tropical cloth (Tanigami Shoten Co., Ltd.) cut into 5 cm × 5 cm, and air-dried at room temperature overnight to obtain a stain-stained soiled cloth.
0.12 mL of the same liquid cleaning agent was applied to each of the 5 stain-stained soiled cloths, and left still for 5 minutes.
Next, 900 mL of tap water at 15 ° C. and Terg-O-Tometer (manufactured by UNITED STATES TESTING) containing 0.6 g of a detergent (manufactured by Lion Corporation, trade name Top Clear Liquid) were added to 5 pieces of stain stain dirt cloth. And washed at 120 rpm for 10 minutes (bath ratio 20 times).
After that, 5 pieces of the stain-dirty soiled cloth after washing were taken out, and the oil-dirty soiled cloth was rinsed under running water for 3 minutes with a 2-tank washing machine (Mitsubishi Electric Corporation CW-C30A1 type), Then, after dehydration for 1 minute, it was air dried.
Using a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd., trade name SE2000), the Z value of the original cloth (polyester tropical cloth) before adhesion of stains and the stain stain dirt cloth before and after the cleaning test are measured, The cleaning rate was calculated from the following formula. The larger the value of the cleaning rate, the higher the coating cleaning power.
Cleaning rate (%) = (Z value of stain-stained soiled cloth after cleaning-Z value of stain-stained soiled cloth before cleaning) / (Z value of original cloth-Z-value of stain-stained soiled cloth before cleaning) ) X 100
Then, the detergency was evaluated according to the following evaluation criteria, using the average value of the detergency calculated for the 5 stain-dirty soiled cloths as an index.
<< Evaluation criteria >>
⊚: The average cleaning rate is over 45%.
◯: Average cleaning rate is 40% or more and less than 45%.
Δ: The average value of the cleaning rate is 30% or more and less than 40%.
X: The average value of the cleaning rate is less than 30%.

<Evaluation of the stability of hydrogen peroxide (gas generation suppressing effect)>
A 12 μm thick polyethylene terephthalate (PET), a 15 μm thick polyethylene (PE), a 7 μm thick aluminum foil, and a 30 μm thick PE are laminated in this order to cut a laminated film into a length of 6 cm and a width of 12 cm. Folded in half. Then, the two sides in the lateral direction were heat-sealed with a width of 0.5 cm to obtain a container. After filling 20 g of the liquid composition from the opening of the container, the opening was heat-sealed with a width of 0.5 cm to be hermetically sealed. After storing in this state in a thermostatic chamber at 50 ° C for 2 months, the appearance of the container was visually observed, and the storage stability was evaluated according to the following criteria.
<< Evaluation criteria >>
◯: The container has no bulge.
Δ: The container is slightly inflated.
X: The container is clearly inflated.

<Evaluation of usability (viscosity (mPa · s)>)
The liquid temperature of the liquid cleaning agent of each example was adjusted to 25 ° C. in a constant temperature bath to obtain a measurement sample. The viscosity of the measurement sample was measured using a B-type viscometer (“Model BM” manufactured by Tokyo Keiki Co., Ltd.) (rotor No. 2, rotation speed 60 rpm, viscosity 60 seconds after starting rotation).
The measured viscosity values were classified and evaluated according to the following evaluation criteria. The liquid cleaning agent marked with ⊚ is very easy to apply to textiles during application cleaning. The liquid cleaning agent of ○ is easy to apply to the textile product at the time of application cleaning. The liquid cleaning agent of Δ is a little easy to apply to the textile product at the time of applying and washing. The liquid cleaning agent of × is difficult to apply by applying to the textile product at the time of applying and washing. In addition, it was 145 mPa * s in Example 1, 130 mPa * s in Example 2, 145 mPa * s in Example 3, and 147 mPa * s in Example 4.
<< Evaluation criteria >>
A: Over 100 mPa · s.
◯: 50 mPa · s or more and less than 100 mPa · s.
Δ: 25 mPa · s or more and less than 50 mPa · s.
X: Less than 25 mPa · s.

<Evaluation of appearance stability>
A transparent glass bottle was filled with 100 g of the liquid detergent of each example, and the lid was closed and sealed. In this state, it was left standing in a constant temperature bath at 50 ° C. for 24 hours and stored.
After the storage for 24 hours, the appearance of the liquid was visually observed, and the storage stability of the liquid detergent was evaluated according to the following evaluation criteria.
<< Evaluation criteria >>
◯: Colorless and transparent immediately after compounding, and colorless and transparent even after storage at 50 ° C.
Δ: Colorless and transparent immediately after compounding, precipitation and turbidity were observed after storage.
X: Precipitation / separation was observed immediately after blending.

All of Examples 1 to 9 to which the invention of the present application was applied were excellent in detergency against stains, stability of hydrogen peroxide, and usability.
Comparative Example 1 in which the component (B1) was changed to SAS was inferior in cleaning power against stains, stability of hydrogen peroxide, usability, and appearance stability.
Comparative Example 2 containing no component (B2) was inferior in stability and usability of hydrogen peroxide.
Comparative Example 3 in which the content of the component (B) was less than 1% by mass was inferior in cleaning power against stains and usability.
Comparative Example 4 having a pH of more than 7 was inferior in stability and usability of hydrogen peroxide.
Comparative Example 5 in which R ¹¹ had 14 carbon atoms had poor appearance stability.
From the above results, it was confirmed that the liquid bleaching composition to which the present invention was applied was excellent in cleaning power against stains, stability of hydrogen peroxide, and usability.

Claims (3)

Component (A): hydrogen peroxide, and component (B): a surfactant,
The component (B) is a component (B1): polyoxyalkylene alkyl ether sulfuric acid or a salt thereof, a component (B2): a semipolar surfactant represented by the following general formula (II), and a nonionic surfactant. It includes,
pH is below 7,
The content of the component (B), Ri the total mass to 1 to 20% by mass of the liquid bleach composition,
The content of the nonionic surfactant is 0.1 to 18% by mass relative to the total mass of the liquid bleaching composition,
A liquid bleaching composition for a textile product, wherein the mass ratio represented by the component (B1) / the component (B2) is 3 to 5 .

(In the formula (II), R ¹¹ is an alkyl group having 12 carbon atoms or an alkenyl group having 12 carbon atoms, and R ¹² and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. It is a hydroxyalkyl group.)   The liquid bleaching composition for textiles according to claim 1, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether represented by the following general formula (III).
  R ¹⁰ -O- (AO) _p -H ... (III)
(In the formula (III), R ¹⁰ Is a linear or branched alkyl group having 8 to 16 carbon atoms or a linear or branched alkenyl group having 8 to 16 carbon atoms; AO represents an alkyleneoxy group having 2 to 5 carbon atoms; Indicates the average number of AO repeats and is 1 to 20. )   The liquid bleaching composition for textiles according to claim 1 or 2, wherein the component (B1) is a compound represented by the following general formula (I).
  R ¹ -[(EO) _m / (PO) _n ] -SO _Three ⁻ M ⁺ ... (I)
(In the formula (I), R ¹ Is a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, and PO represents an oxypropylene group. m represents the average number of repetitions of EO and is a number of 0 or more. n represents the average number of repeated POs and is a number from 0 to 6. 0 <m + n. M ⁺ Is a counter cation. )