JP4030996B2 - Bleach activator and bleach composition containing the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a bleach activator and a bleach composition, and more particularly, cleaning of stains on hard surfaces such as mold removal, clothes, tableware, pottery, glass, plastic, dentures, bleaching / disinfection, washing A bleach activator capable of improving the bleaching performance of peroxy compounds widely used for tank washing, pulp bleaching, dyeing waste water treatment, prevention of dye transfer during washing, and the like The present invention relates to a bleach composition to be contained.

  Conventionally, hydrogen peroxide, an inorganic persalt that liberates hydrogen peroxide in an aqueous solution, an inorganic persalt that itself has a peracid bond, and an organic peracid (hereinafter these compounds are referred to as “peroxy compounds”). Abbreviated), and organic peracid precursors that react with hydrogen peroxide in a bleaching bath to generate organic peracids are widely used as active ingredients in bleaching agents.

However, the hydrogen peroxide, the inorganic persalt that liberates hydrogen peroxide in the aqueous solution, and the inorganic persalt itself having a peracid bond have a relatively low bleaching effect under low temperature conditions. Various proposals have been made to obtain a sufficient bleaching effect by these compounds at low temperatures.
For example, as a method for improving the bleaching power of the compound using a bleach activator, an O-acetylated product such as glucose pentaacetate (GPAC), an N-acylated product such as tetraacetylethylenediamine, and an acid such as maleic anhydride Examples thereof include a method using a bleach activator such as an anhydride.

  The organic peracid precursor exhibits a bleaching effect by reacting with hydrogen peroxide in a bleaching solution to produce an organic peracid. The organic peracid precursor is a bleach activator. Various molecular structures have been proposed for more effective use. Examples of the molecular structure include esters composed of aliphatic carboxylic acids and phenols, phenyl benzoate, and nitro-substituted phenyl benzoate (see, for example, Patent Documents 1 and 2).

  However, many organic peracids generated from the organic peracid precursor have low water solubility or high water solubility but weak bleaching power. For example, bleaching high-concentration dirt such as mold Therefore, both the bleaching power and the water solubility necessary for this were not satisfactory.

Then, the ester which has the substituted benzoic acid containing a cationic group as an organic peracid precursor which improved water solubility is proposed (for example, refer patent documents 3 and 4).
However, the ester having a substituted benzoic acid containing a cationic group has a problem of practical use due to concern about environmental pollution by a quaternary amine.

Further, as a type of ester having a charge in the leaving group, an ester having a leaving group containing a cationic group, an ester having a leaving group containing an anionic group, and the like have been proposed (for example, Patent Documents 5 and 6). reference).
However, although the ester having a charge in the leaving group has improved solubility as an organic peracid precursor, the organic peracid generated by the perhydrolysis reaction has low water solubility, and precipitation occurs during bleaching. Therefore, there is a problem that the bleaching efficiency is lowered.

  Therefore, a bleach activator capable of imparting high water solubility to the organic peracid and improving the bleaching performance, and a bleaching composition containing the bleach activator have not yet been provided, and further improvements have been made. What is desired is the current situation.

British Patent No. 864798 Japanese Patent Laid-Open No. 5-31845 Japanese Patent Laid-Open No. 2-147698 JP-A-1-190654 JP 7-216396 A JP 59-22999 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention is a bleach activator that is an organic peracid precursor capable of improving the bleaching performance of a peroxy compound, in particular, imparting high water solubility to the organic peracid even at low temperatures and improving the bleaching performance. It is an object of the present invention to provide a bleach activator that can be prepared and a bleach composition containing the bleach activator.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, by using sulfobenzoic anhydride as a bleach activator, a sulfone group is introduced into the organic peracid to be produced, resulting in water solubility. It was found that the bleaching performance was improved and the generation efficiency of the organic peracid became freely controllable, and it was found that the above problems could be solved, and the present invention was completed.

ただし、前記構造式（Ｉ）において、Ｘは、ＳＯ_３Ｍ基、及びＣＯ_２Ｍ基（ただし、Ｍは、水素原子、又は塩を形成可能なカチオンを表す）のいずれかを表し、ｎは、０〜３の整数を表す。
＜２＞ ２−スルホ安息香酸環状無水物、２−スルホ安息香酸環状無水物−４−スルホン酸、２−スルホ安息香酸環状無水物−５−スルホン酸、２−スルホ安息香酸環状無水物−４−カルボン酸、２−スルホ安息香酸環状無水物−５−カルボン酸から選択される少なくとも１種である前記＜１＞に記載の漂白活性化剤である。
＜３＞ 前記＜１＞から＜２＞のいずれかに記載の漂白活性化剤と、ペルオキシ化合物とを含有することを特徴とする漂白剤組成物である。
＜４＞ 漂白活性化剤とペルオキシ化合物との配合割合のモル比が、（漂白活性化剤）：（ペルオキシ化合物）＝１：１〜１：１００である前記＜３＞に記載の漂白剤組成物である。
＜５＞ 界面活性剤、キレート剤、ビルダー、酵素、及び香料から選択される少なくとも１種を含有する前記＜３＞から＜４＞のいずれかに記載の漂白剤組成物である。
＜６＞ 前記＜３＞から＜５＞のいずれかに記載の漂白剤組成物を用いて漂白を行うことを特徴とする漂白方法である。
＜７＞ 前記＜３＞から＜５＞のいずれかに記載の漂白剤組成物を用いて漂白されたことを特徴とする被漂白物である。 This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is,
<1> A bleaching activator represented by the following structural formula (I).

In the structural formula (I), X represents an SO ₃ M group and a CO ₂ M group (where M represents a hydrogen atom or a cation capable of forming a salt), and n represents Represents an integer of 0 to 3;
<2> 2-sulfobenzoic acid cyclic anhydride, 2-sulfobenzoic acid cyclic anhydride-4-sulfonic acid, 2-sulfobenzoic acid cyclic anhydride-5-sulfonic acid, 2-sulfobenzoic acid cyclic anhydride-4 -The bleach activator according to <1>, which is at least one selected from carboxylic acid and 2-sulfobenzoic acid cyclic anhydride-5-carboxylic acid.
<3> A bleach composition comprising the bleach activator according to any one of <1> to <2> and a peroxy compound.
<4> The bleaching agent composition according to <3>, wherein the molar ratio of the blending ratio between the bleaching activator and the peroxy compound is (bleaching activator) :( peroxy compound) = 1: 1 to 1: 100. It is a thing.
<5> The bleaching composition according to any one of <3> to <4>, which contains at least one selected from a surfactant, a chelating agent, a builder, an enzyme, and a fragrance.
<6> A bleaching method wherein bleaching is performed using the bleach composition according to any one of <3> to <5>.
<7> A product to be bleached, characterized by being bleached using the bleaching composition according to any one of <3> to <5>.

  According to the present invention, a bleach activator that is an organic peracid precursor capable of improving the bleaching performance of a peroxy compound, in particular, imparting high water solubility to the organic peracid even at a low temperature and improving the bleaching performance. A bleach activator that can be applied, and a bleach composition comprising the bleach activator.

(Bleaching activator)
The bleach activator of the present invention is represented by the following structural formula (I).

In the structural formula (I), X represents an SO ₃ M group or a CO ₂ M group (where M represents a hydrogen atom or a cation capable of forming a salt), and 3 of the benzene ring The hydrogen at position 6 is replaced with any n X. Among these, those in which the hydrogen atoms at the 4th and 5th positions are substituted with n X atoms are preferable. n represents an integer of 0 to 3, and is preferably 0 or 1.
In M, examples of the cation capable of forming the salt include sodium, potassium, triethylamine, and triethanolamine. M is preferably a hydrogen atom, potassium, or sodium, and a hydrogen atom and sodium. Is more preferable.

  Examples of the compound represented by the structural formula (I) include 2-sulfobenzoic acid cyclic anhydride represented by the following structural formula (1) and 2-sulfobenzoic acid represented by the following structural formula (2). Cyclic anhydride-5-sulfonic acid, 2-sulfobenzoic acid cyclic anhydride-5-sulfonic acid potassium salt represented by the following structural formula (3), 2-sulfobenzoic acid represented by the following structural formula (4) Cyclic anhydride-5-sulfonic acid sodium salt, 2-sulfobenzoic acid cyclic anhydride-4-sulfonic acid represented by the following structural formula (5), 2-sulfobenzoic acid represented by the following structural formula (6) Cyclic anhydride-4-sulfonic acid sodium salt, 2-sulfobenzoic acid cyclic anhydride-4-sulfonic acid potassium salt represented by the following structural formula (7), 2-sulfo represented by the following structural formula (8) Benzoic acid cyclic anhydride-4-carboxylic acid sodium salt, 2-sulfobenzoic acid cyclic anhydride-4-carboxylic acid represented by the structural formula (9), 2-sulfobenzoic acid cyclic anhydride-5-carboxylic acid represented by the following structural formula (10), the following structure 2-sulfobenzoic acid cyclic anhydride-5-carboxylic acid sodium salt represented by formula (11) and 2-sulfobenzoic acid cyclic anhydride-5-carboxylic acid potassium salt represented by the following structural formula (12) Etc.

There is no restriction | limiting in particular as a manufacturing method of the bleach activator represented by the said structural formula (I), For example, it can manufacture by a well-known method, For example, Azerbaidzhanskii Kimicheskii Zhurnal, (1), 41,2002 description Methods and the like.
Moreover, as a bleaching activator represented by the said structural formula (I), you may use a commercial item (For example, Tokyo Chemical Industry Co., Ltd. product, S0124 (2-Sulfobenzoic anhydride) etc.).

(Bleach composition)
The bleaching composition of the present invention contains the bleach activator and a peroxy compound, and further contains other components such as a surfactant, a chelating agent, a builder, an enzyme, and a fragrance as necessary. .

<Bleaching activator>
As the bleach activator, the compound represented by the structural formula (I) described above is used, and the blending amount is preferably 0.1 to 20% by mass with respect to the total amount of the bleach composition. 10 mass% is more preferable.
If the blending amount of the bleach activator is less than 0.1% by mass with respect to the total amount of the bleaching composition, sufficient bleaching performance may not be obtained. There is a case where the matching effect cannot be obtained.

<Peroxy compound>
Examples of the peroxy compound include peroxides such as hydrogen peroxide, an inorganic persalt that liberates hydrogen in an aqueous solution, and an inorganic persalt that itself has a peracid bond. Examples thereof include alkali metal percarbonates, perborates, perphosphates, persilicates, and persulfates.
Among these, hydrogen peroxide, sodium perborate, and sodium percarbonate are preferable.

  As a compounding quantity of the said peroxy compound, 0.5-50 mass% is preferable with respect to the bleaching agent whole quantity, and 1-20 mass% is more preferable.

  In the bleach composition of the present invention, the molar ratio of the blending ratio of the bleach activator and the peroxy compound is (bleach activator) :( peroxy compound) = 1: 1 to 1: 100. Is more preferable, and 1: 1 to 1:10 is more preferable.

<Other ingredients>
In addition to the bleach activator and the peroxy compound, the bleach composition of the present invention includes a surfactant, a chelating agent, a builder, an enzyme (such as alcalase and lipase), a fragrance, a fluorescent agent, a fiber damage preventing agent, Antifoaming agents such as silicone, peroxide stabilizers, metal ions (Ca, Mg, Si, Al, Zn, etc.) and the like can be used in combination.
Further, when the bleaching composition is liquid, it is preferable to contain a pH buffer or the like so that the pH of the bleaching composition is 1 to 11, and when the bleaching composition is liquid or powdery It is preferable to contain a pH buffering agent or the like so that the pH in the bleaching bath is 7 to 10.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylbenzene sulfonic acid, alkyl sulfuric acid, alkyl polyethoxy ether sulfuric acid, alkyl phenyl ether sulfuric ester, paraffin sulfonic acid, α-olefin sulfonic acid , Α-sulfocarboxylic acid and water-soluble salts such as esters thereof, anionic surfactants such as soap; ethoxylated nonions such as polyoxyalkyl ethers and polyoxyalkylphenyl ethers, sugar esters, glucoside esters, methyl glucoside esters, Nonionic surfactants such as sugar activators such as ethyl glucoside ester and alkyl polyglucooxide, amide activators such as alkyl diethanolamide and fatty acid N-alkyl glucamide; alkyl carboxybetaines and alkyls Amphoteric surfactants such as aminocarboxylates such as sulfoxybetaine, alkylamidopropylbetaine, and alkylalaninate, imidazoline derivatives, and alkylamine oxides; and cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts It is done.
There is no restriction | limiting in particular as a compounding quantity of the said surfactant, Although it can adjust suitably according to the objective, 0-40 mass% is preferable with respect to the said bleaching agent whole quantity.

-Chelating agent-
The chelating agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylenediaminetetraacetate, aluminate, citrate, succinate, and acrylic acid / maleic acid copolymer salt. Can be mentioned.

-Builder-
The builder is not particularly limited and may be appropriately selected depending on the purpose. For example, aluminosilicate such as zeolite, layered silicate, alkali metal carbonate, bicarbonate, borate, phosphate, polyphosphate And inorganic builders such as tripolyphosphates; organic builders such as polycarboxylates such as nitrilotriacetic acid, lactic acid, citric acid, glycolic acid, succinic acid, and polyacrylic acid.
There is no restriction | limiting in particular as a compounding quantity of the said builder, Although it can adjust suitably according to the objective, 0-40 mass% is preferable with respect to the said bleaching agent whole quantity.

  The bleaching composition of the present invention exhibits an excellent bleaching effect under cold water to lukewarm water, specifically 5 to 40 ° C temperature conditions. Moreover, the bleaching effect outstanding in the neutral to alkaline area | region, specifically the area | region of pH 7-10 is shown.

  There is no restriction | limiting in particular as a form of the bleaching agent composition of this invention, According to the objective, it can select suitably, For example, liquid form, solid form, powder form, foam form, paste form etc. are mentioned. Further, in the case of powder, a single use amount may be packaged in a water-soluble package or the like, and in the case of liquid, it may be impregnated into a sheet or solid.

<Bleaching method>
The bleaching method using the bleach composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the method of applying the bleach composition directly or diluted to the material to be bleached, the bleach Examples include a method of immersing an object to be bleached in a bleaching bath solution in which the composition is dissolved in water, and a method of immersing the object to be bleached together with an object to be bleached impregnated with the bleaching composition in water.

<To be bleached>
The bleaching composition of the present invention is not particularly limited and is appropriately selected depending on the purpose.For example, mold in a house including a bathroom, slimming of a kitchen strainer or a triangular corner, a drain outlet, Toilet bowls, clothes, towels, carpets, tableware, pottery, glass, plastics, stains attached to dentures, organic stains, yellowing substances, stains of teeth, dyes eluted from clothes during washing bath (transfer prevention), Examples include dye waste liquid, pulp, paper, woven fabric, and yarn.
In particular, examples of the stain include stains from curry, wine, fruit juice, tomato ketchup, sauce, soy sauce, blood, grass juice, tea, and coffee.

Using the bleach activator of the present invention, it can be used at room temperature against various stains and organic matter stains on molds in houses such as bathrooms, slime in kitchen strainers and triangular corners, tea astringents in tableware, clothing, etc. The bleaching of peroxy compounds can be activated in the neutral to alkaline region to perform effective bleaching.
Therefore, the bleaching composition containing the bleach activator of the present invention comprises a mold remover, a strainer / triangular corner cleaner, a kitchen bleach, a pipe clog remover, a toilet cleaner, an automatic dishwasher detergent, a denture. Wide range of detergents such as detergents for hard surfaces such as detergents, washing tank detergents, pulp bleaches, dyeing wastewater treatment agents, bleaches for various clothing, dye transfer prevention agents during washing, and disinfectants for clothes and hard surfaces Can be used.

  Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.

(Examples 1-4, Comparative Examples 1-2)
An aqueous solution was prepared so that the concentration of the bleach activator shown in Table 1 below was 100 mM, and the concentration of hydrogen peroxide as a peroxy compound was 100 mM, and the aqueous solution was used as a pH adjuster using sodium bicarbonate and sodium carbonate. The pH was 11. The aqueous solution is allowed to stand for 2 minutes at a temperature of 30 ° C. to generate peracid, and then a half amount of spatula (about 50 μg) of catalase is added and stirred for 2 minutes to react to completely remove residual hydrogen peroxide. Disassembled.
2.5 mL was weighed out from the resulting solution, 5 mL of 33% aqueous acetic acid solution and 5 nL of 10% aqueous potassium iodide solution were added, and the organic peracid concentration was 2 mmol while titrating with 0.01 N aqueous sodium thiosulfate solution. A bleach composition was obtained by adjusting the pH to 9.5.
About the said bleaching agent composition, the pigment | dye bleaching test was done with the following method.

Alizarin Red S as a dye is added to the bleach composition so as to have a concentration of 0.2 mM, the absorption after 100 seconds of a specific wavelength (510 nm) is measured with an absorptiometer, and the dye degradation rate is based on the following formula: Asked. The results are shown in Table 1.
Pigment degradation rate (%) = 100 × (1−B / A)
In the above formula, A represents the absorbance of 0.2 mM aqueous solution of alizarin red S, and B represents the absorbance after 100 seconds from the start of the test.

比較例１は、過酸化水素１００ｍＭ溶液（ｐＨ９．５）を使用。

Comparative Example 1 uses a 100 mM hydrogen peroxide solution (pH 9.5).

(Examples 5-8, Comparative Examples 3-4)
Based on the composition shown in Table 2 below, a bleaching composition was prepared by a conventional method.
The obtained bleaching agent composition was diluted 100 times with tap water, and adjusted to pH 10 using sodium bicarbonate and sodium carbonate as pH adjusting agents, and 100 mL each was used as a bleaching test solution.
In the bleaching test solution, 5 g of a test cloth contaminated with various stains was immersed and allowed to stand at room temperature (about 25 ° C.) for 10 hours.
As for the test cloth, plain weave cotton cloth (# 100) was immersed in black tea, curry, spinach extract and red wine for 30 minutes at room temperature, then lightly rinsed with tap water, and then natural at room temperature. It was prepared by drying.
The test cloth taken out from the bleaching solution was washed with water and dried. The Lab value before and after immersion of the test cloth and before contamination was measured using CHROMAMETER (CR-300, manufactured by MINOLTA), and the bleaching rate was calculated using the following equation. The results are shown in Table 2.
Bleaching rate (%): (A−B) / (A−C) × 100
In the above formula, A, B, and C represent the following values, respectively.
A: Lab value (L ² + a ² + b ² ) ^1/2 of the test cloth before immersion in the bleach test solution
B: Lab value (L ² + a ² + b ² ) ^1/2 of the test cloth after immersion in the bleach test solution
C: Lab value (L ² + a ² + b ² ) of test cloth before stain contamination ^1/2

(Examples 9-12, Comparative Examples 5-6)
An aqueous solution was prepared so that the concentration of the bleach activator shown in Table 3 below was 100 mM, and the concentration of hydrogen peroxide as a peroxy compound was 1000 mM, and the aqueous solution was used as a pH adjuster using sodium bicarbonate and sodium carbonate. A bleach composition was obtained at pH 9.5.
As a test plate, an unglazed tile (made by INAX: SPKC-1060) on which black mold (Cladosporia cladosporioides) was cultured and deposited was placed horizontally, and 0.5 g of each of the above-mentioned bleaching compositions was dropped onto the test plate. After being left for 2 minutes, washed with water and air-dried, the lightness (L value) was measured using a color difference meter (manufactured by MINOLTA; CR-200), and the bleaching rate was determined based on the following formula. The results are shown in Table 3.
Bleach rate (%) = 100 × {(L ₁ −L ₀ ) / (Ls−L ₀ )}
In the above formula, Ls, L ₀ , and L ₁ represent the following values, respectively.
Ls: L value of unglazed tile before applying mold,
L ₀ : L value of model mold plate before bleaching L ₁ : L value after bleaching

比較例５は、過酸化水素１０００ｍＭ溶液（ｐＨ９．５）を使用。

Comparative Example 5 uses a hydrogen peroxide 1000 mM solution (pH 9.5).

According to the present invention, mold removal, strainer / triangular corner cleaning, kitchen bleaching, pipe clogging removal, toilet cleaning, dishwashing with an automatic dishwasher, denture cleaning, hard surface cleaning bleaching, washing tub cleaning, pulp bleaching, Bleach activators that can improve the bleaching performance of peroxy compounds widely used for dyeing wastewater treatment, bleaching for various clothes, prevention of dye movement during washing, sterilization of clothes, hard surfaces, etc., and A bleach composition comprising the bleach activator is obtained. In addition, by using the bleach composition of the present invention, high effects of various bleaching, washing, and sterilization can be obtained.

Claims (3)

A bleaching activator represented by the following structural formula (I):

In the structural formula (I), X represents an SO ₃ M group and a CO ₂ M group (where M represents a hydrogen atom or a cation capable of forming a salt), and n represents Represents an integer of 0 to 3; A bleach composition comprising the bleach activator according to claim 1 and a peroxy compound. Bleaching using the bleach composition according to claim 2.