JPH0853405A - Production of acyloxybenzenesulfonate - Google Patents

Abstract

PURPOSE:To obtain the subject compound in high selectivity and yield at a low cost and simultaneously suppress side reaction by the coexistence of a specific carboxylic acid in reacting a phenolsulfonate with a carboxylic acid halide. CONSTITUTION:This method for producing an acyloxybenzenesulfonate of formula III [R<1> is a 1-4C alkyl; R<2> is a 1-21C alkyl or alkenyl (which can be substituted with a halogen or phenyl or an ester, amide, an ether or phenylene may be inserted) or phenyl; (n) is 0-2; M is an alkali metal, an alkaline earth metal or ammonium] is to react a phenolsulfonate of formula I with a carboxylic acid halide of formula II (X is F, Cl, Br or I). In the process, the reaction is carried out in the presence of a carboxylic acid of formula V (R<3> is same as R<2>). An 8-16C acyloxybenzenesulfonate is preferred as the carboxylic acid of formula IV. The carboxylic acid is preferably used in an amount of 0.05-20 pts.wt. based on 1 pt.wt. compound of formula I. The compound of formula III is useful especially as a bleaching activator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an acyloxybenzene sulfonate useful as a bleach activator in an oxygen bleach. More specifically, the present invention relates to a method for producing an acyloxybenzene sulfonate having less side reaction by allowing a specific carboxylic acid to coexist when a carboxylic acid halide acts on a phenol sulfonate.

[0002]

2. Description of the Related Art Acyloxybenzene sulfonate is
Hydrogen peroxide generating substrate and hydrogen peroxide represented by PC (sodium percarbonate) and PB (sodium perborate),
It is a compound which is particularly useful as a bleach activator because it can easily produce an organic peracid at low temperature by contacting in water and exerts an effective bleaching performance against stains and stains on clothes and the like (JP-A-59). No. 22999). In this method for producing an acyloxybenzene sulfonate, as a representative method of using a phenol sulfonate as a raw material, acetic anhydride is allowed to act to form Na acetyloxybenzenesulfonate, and then a fatty acid having a desired alkyl chain is added. Then, a method of causing a transesterification reaction (Japanese Patent Publication 4-1)
No. 739), and phenol sulfonic acid diNa salt, 20
Method of reacting carboxylic acid halide in an aprotic solvent having a dielectric constant of 20 or more at -25 ° C (Japanese Patent Application No. 5-6001)
No. 8) is known. However, in the former case, a large amount of acetic acid is by-produced and the production cost is very high. In the latter case, it is necessary to use a reaction solvent for dispersing or dissolving the diphenol phenolsulfonic acid salt. Recovery and purification are required, and in either case, there is a problem in terms of economy. Furthermore, in any case, a relatively high-purity product cannot be obtained, and a refining operation using a solvent is indispensable, which is unsuitable as a commercial production process.

Therefore, it has been desired to develop a method capable of industrially producing an acyloxybenzene sulfonate with high selectivity and high yield. An object of the present invention is to provide an industrial production method capable of producing an acyloxybenzene sulfonate with high selectivity and high yield in producing a high-purity acyloxybenzene sulfonate. .

[0004]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have made earnest studies on the reaction between a phenol sulfonate and a carboxylic acid halide, and as a result, carry out the reaction in the presence of a specific carboxylic acid. Then, surprisingly, the inventors have found that higher conversion and selectivity than ever have been obtained and that a high-purity acyloxybenzene sulfonate can be produced, and have completed the present invention. That is, the present invention is
Substantially anhydrous general formula (1)

[0005]

[Chemical 5]

(In the formula, R ¹ represents a linear or branched lower alkyl group having 1 to 4 carbon atoms. N: represents a number of 0 to 2, and when n = 2, two R ^1's are the same. M: Alkali metal, alkaline earth metal or ammonium is shown) to the phenol sulfonate represented by
General formula (2)

[0007]

[Chemical 6]

(In the formula, R ² is a straight chain having 1 to 21 carbon atoms, which may be substituted with a halogen or a phenyl group, and in which an ester group, an amide group, an ether group or a phenylene group may be inserted. Represents a branched alkyl group or an alkenyl group, or represents a phenyl group which is unsubstituted or substituted with a halogen or an alkyl group, X: represents a halogen atom selected from F, Cl, Br or I). A carboxylic acid halide represented by the formula (3)

[0009]

[Chemical 7]

In the production of the acyloxybenzenesulfonate represented by the formula (wherein R ¹ , R ² , n and M have the above-mentioned meanings), the general formula (4)

[0011]

Embedded image

(In the formula, R ³ is a straight chain having 1 to 21 carbon atoms, which may be substituted with a halogen or a phenyl group, and an ester group, an amide group, an ether group or a phenylene group may be inserted. Which represents a branched alkyl group or an alkenyl group, or represents a phenyl group which is unsubstituted or may be substituted with a halogen or an alkyl group). The present invention provides a method for producing an acyloxybenzene sulfonate.

Hereinafter, the present invention will be described in detail. The phenol sulfonate as a raw material of the present invention has the above general formula (1)
R ¹ in the formula may be any linear or branched lower alkyl group having 1 to 4 carbon atoms. The substitution number n is 0 to 2, and n is preferably 0 or 1 from the viewpoint of raw material supply and biodegradability. Particularly, n = 0 is most preferable in terms of price. M represents an alkali metal, alkaline earth metal or ammonium,
Li, Na, K, and Mg are particularly preferable in terms of water solubility and performance of the target acyloxybenzene sulfonate. Specific examples of the phenol sulfonate represented by the general formula (1) include phenol sulfonate and cresol sulfonate, and as the counter ion forming the salt,
Na, K, Li, Mg etc. are mentioned. Among these, in terms of raw material supply, cresol sulfonic acid Na salt, K salt and Mg salt
It is preferable to use a salt, a sodium salt of phenolsulfonic acid, a salt of K thereof, and a salt of Mg thereof, and particularly preferable are a sodium salt of phenolsulfonic acid, a salt of K salt, and a salt of Mg in terms of cost.

The phenol sulfonate represented by the general formula (1) is prepared by converting corresponding phenols into concentrated sulfuric acid and S.
It can be produced by a known method such as sulfonation with O ₃ gas, liquid SO ₃ and chlorosulfonic acid, followed by neutralization with an alkali agent and further drying. In addition,
Dehydration of this phenol sulfonate generally requires conditions such as high temperature (Japanese Patent Laid-Open No. 62-106072) under an inert gas stream or azeotropic dehydration, and its improvement is desired. By adding the carboxylic acid represented by the general formula (4) used in the reaction of the invention before or after neutralization, the phenol sulfonate can be dried extremely well in view of physical properties and equipment. preferable. The phenol sulfonate represented by the general formula (1) used in the present invention is preferably used in a substantially anhydrous form. Here, substantially anhydrous does not mean a completely anhydrous state, but a small amount of water contained in the raw material itself,
For example, a water content of 0.5% by weight or less is substantially anhydrous. If a substantial amount of water is present, the carboxylic acid halide represented by the general formula (2) is hydrolyzed, and the reaction yield is reduced. As the dehydration conditions, specifically, 0.05 to 20 parts by weight of the carboxylic acid represented by the general formula (4) is added to 1 part by weight of phenolsulfonic acid before or after neutralization, and the mixture is stirred or kneaded. Mix well, disperse well, and treat at 110-200 ℃ under reduced pressure of 5-500 Torr for 1-10 hours.
Those with a weight% or less can be easily obtained.

Specific examples of the carboxylic acid represented by the general formula (4) used in the present invention include acetic acid, n-propionic acid, n-butyric acid, n-hexanoic acid, n-heptanoic acid, i-
Heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid,
n-nonanoic acid, i-nonanoic acid, 3,5,5-trimethylhexanoic acid, n-decanoic acid, i-decanoic acid, n-undecanoic acid, i-undecanoic acid, lauric acid, myristic acid, palmitic acid, stearin Acid, isostearic acid,
Fatty acids typified by behenic acid, benzoic acid, methyl benzoic acid, aromatic carboxylic acids typified by octylbenzoic acid, chloroacetic acid, chlorobutyric acid, bromobutyric acid, chlorocaproic acid, bromocaproic acid, chloroundecanoic acid, etc. Examples thereof include halogenated alkylcarboxylic acids, arylphenylcarboxylic acids represented by phenylacetic acid, phenylpropionic acid, and the like. Among these carboxylic acids, acetic acid, n-propionic acid, n-butyric acid, and n-hexanoic acid are included because the function of the bleach activator of the product is not impaired by the transesterification reaction that may occur during the esterification reaction. , N-heptanoic acid, i-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, i-nonanoic acid, n-decanoic acid, i-decanoic acid, n-undecanoic acid,
i-Undecanoic acid, lauric acid, myristic acid, and palmitic acid are preferable, and particularly n-octanoic acid and 2-ethylhexanoic acid are used in order to obtain a good effect on hydrophilic stains and hydrophobic stains and water solubility. , N-nonanoic acid, i-nonanoic acid, n-decanoic acid, i-decanoic acid, n-undecanoic acid, i-undecanoic acid, lauric acid, and the like, preferably a straight or branched fatty acid having 8 to 16 carbon atoms. Further, in the sense that the same composition can be obtained by the esterification reaction, the carboxylic acid residue of the carboxylic acid represented by the general formula (4) and the carboxylic acid residue of the carboxylic acid halide represented by the general formula (2) are the same. Lauric acid is particularly preferable in order to obtain lauroyloxybenzene sulfonate having a good balance of effects on substances such as hydrophilic stains and hydrophobic stains.

Specific examples of the carboxylic acid halide represented by the general formula (2) used in the present invention include acid chlorides, acid bromides, acid fluorides and acid iodides of the following carboxylic acids. That is, acetic acid, n-propionic acid, n-butyric acid, n-hexanoic acid, n-heptanoic acid, i-
Heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid,
n-nonanoic acid, i-nonanoic acid, 3,5,5-trimethylhexanoic acid, n-decanoic acid, i-decanoic acid, n-undecanoic acid, i-undecanoic acid, lauric acid, myristic acid, palmitic acid, stearin Acid, isostearic acid,
Fatty acids typified by behenic acid, benzoic acid, methyl benzoic acid, aromatic carboxylic acids typified by octylbenzoic acid, chloroacetic acid, chlorobutyric acid, bromobutyric acid, chlorocaproic acid, bromocaproic acid, chloroundecanoic acid, etc. Carboxylic acid halides such as halogenated alkylcarboxylic acids represented by, phenylacetic acid, arylalkylcarboxylic acids represented by phenylpropionic acid, etc. can be used. , Acetic acid, n-propionic acid, n-butyric acid, n
-Hexanoic acid, n-heptanoic acid, i-heptanoic acid, n-
Octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, i
-Nonanoic acid, n-decanoic acid, i-decanoic acid, n-undecanoic acid, i-undecanoic acid, lauric acid, myristic acid, palmitic acid have good carboxylic acid halides, and also hydrophilic stains and hydrophobic stains. In order to obtain good effects and good water solubility, n-octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, i-nonanoic acid, n-decanoic acid, i-decanoic acid, n-undecanoic acid, i -Undecanoic acid, carboxylic acid halides of lauric acid, etc., having 8 to 16 carbon atoms
The straight-chain or branched fatty acid halide of is good. Particularly, in order to obtain lauroyloxybenzenesulfonate having a good balance of effects on hydrophilic stains and hydrophobic stains, lauric acid chloride is particularly preferable in terms of cost.

The amount of the carboxylic acid represented by the general formula (4) used in the present invention is 0.05 to 20 parts by weight based on 1 part by weight of the phenol sulfonate represented by the general formula (1). Good results are obtained. If the amount is less than 0.05 parts by weight, the reaction selectivity is poor, which is not preferable. In order to obtain higher reaction selectivity, 0.2 parts by weight or more is more preferable. Also,
Considering the productivity and the degree of freedom in blending the resulting base material, the most preferable amount is 0.2 to 10 parts by weight.

The reaction of the present invention can basically be carried out without using a solvent, but if necessary, for example, toluene, xylene, ethylbenzene, cumene, 1,2-dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene are used. , Tetrachloroethylene, carbon tetrachloride, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, cyclohexane and the like are represented by the general formula (1). 0.1 to 2 for phenol sulfonate
You may use 0 times the weight.

The carboxylic acid halide represented by the general formula (2) is usually used in an amount of 0.5 to 2.0 times the molar amount of the phenol sulfonate represented by the general formula (1). Preferably, a good reaction yield is obtained at a ratio such that the molar ratio calculated by the following formula is 0.5 to 1.2.

[0020]

[Equation 1]

Further, when the above molar ratio is 0.8 to 1.05,
A high reaction rate and high reaction selectivity of the carboxylic acid halide are obtained, which is particularly preferable. It should be noted that Na phenol sulfonate, which is one of the raw materials, is usually a mixture containing the p-form and the o-form as main components, and in general, the o-form is
Reactivity with carboxylic acid halide is significantly low. Therefore,
When using a raw material having a high content of o-phenol sulfonate, it is necessary to take measures such as carrying out a reaction for a long time.

The carboxylic acid halide represented by the general formula (2) is added dropwise to a slurry in which the phenol sulfonate represented by the general formula (1) is well dispersed in the carboxylic acid represented by the general formula (4). The carboxylic acid halide can be added dropwise at a temperature equal to or higher than the melting point of the carboxylic acid used. In order to suppress side reactions derived from carboxylic acid halides, the temperature during dropping is preferably 150 ° C or lower. A temperature of 120 ° C or lower gives more preferable results. The dropping time can be basically set within a range in which the above temperature can be maintained. Further, hydrogen halide such as HCl is produced as a byproduct when the carboxylic acid halide is dropped, so it is desirable to adjust the dropping time so that the hydrogen halide can be removed sufficiently. Specifically, in the case of a batch type reaction apparatus, it is 1 minute to 10 hours depending on the reaction scale, reaction tank, and type of stirring, but there is no particular limitation. It is also possible to use a continuous reactor in addition to the batch reactor.
In this case, temperature control of the carboxylic acid halide dropping zone,
Also, it is possible to divide the temperature management of the aging zone into a plurality of zones and control them arbitrarily, which gives good results. Aging is preferably carried out at a temperature above the melting point of the carboxylic acid used and below 150 ° C. From the viewpoint of terminating the reaction in a short time and suppressing side reactions, 60 to 120 ° C is more preferable. The aging time depends on the temperature, but at 150 ° C, for example, about 1 hour, 1
Appropriately about 1 to 4 hours at 00 ° C and about 1 to 6 hours at 80 ° C are suitable.

[0023]

The mechanism of improving the reactivity and suppressing side reactions by the carboxylic acid represented by the general formula (4) used in the present invention is not clear yet, but it is represented by the general formula (2) to be acted on. The carboxylic acid halide reacts with the carboxylic acid represented by the general formula (4) to form a carboxylic acid anhydride having the same esterification ability as the carboxylic acid halide, and the carboxylic acid halide is effectively consumed. It is speculated that side reactions due to acid halides are effectively suppressed. Carboxylic anhydrides have a slightly lower esterification reactivity than the carboxylic acid halides used as raw materials,
It has a sufficiently high reactivity to the phenol sulfonate represented by the general formula (1). In the present invention, a transesterification reaction involving the carboxylic acid represented by the general formula (4) occurs during the esterification reaction. This transesterification reaction may be a problem, but when the carboxylic acid halide of the target acyl group is industrially difficult to obtain,
It is also possible to prepare a target acyloxybenzene sulfonate by combining a carboxylic acid having a target acyl group which is easily available and an inexpensive or easily available carboxylic acid halide. However, unless there is a particular problem, it is usually preferable to select a carboxylic acid halide and a carboxylic acid having the same acyl group with favorable results. The reaction-completed product contains the carboxylic acid used and the carboxylic acid derived from the carboxylic acid halide. However, for example, in the case of blending into a laundry detergent or the like, these carboxylic acids act as one of the cleaning components due to the alkaline agent in the detergent, and also effectively act to eliminate bubbles during rinsing. Therefore, the reaction-completed product in the present invention can be directly supplied to the detergent as it is, or directly to the granulation operation if necessary.

[0024]

The present invention will be described below with reference to reference examples and examples, but the present invention is not limited to these examples.

Reference Example [Sulfonation of Phenol] 200.0 g of phenol (purity: 99.5%) was charged into a four-necked flask equipped with a stir bar, a thermometer, a nitrogen gas blowing tube, and a dropping funnel for 98% sulfuric acid. After raising the temperature to 0 ° C, 222.2 g of 98% sulfuric acid was added dropwise while cooling so as to maintain 60 to 70 ° C. Then, by aging at 100 ° C. for 1 hour, 422.2 g of an intermediate phenolsulfonic acid having a pink color was obtained. The acid value is 350.
It was 8 (mg KOH / g). [Neutralization] To 296.0 g of a 30% NaOH aqueous solution, 355.0 g of the above phenolsulfonic acid was added dropwise over about 30 minutes to adjust the pH
The (stock solution) was adjusted to about 6. [Dehydration] Lauric acid was added to 200.0 g of the neutralized slurry.
120.6 g was charged, the temperature was raised to 170 ° C. over about 2 hours under a reduced pressure of 50 Torr, and dehydration was performed at 170 ° C. for another 2 hours. At this time, the composition was Na p-phenol sulfonate.
54.8%, o-phenolsulfonic acid Na 4.2%, phenolsulfonic acid di-Na salt 0.4%, Na ₂ SO ₄ 3.1%,
The water content was 0.02% and lauric acid was 37.4%.

Example 1 In a four-necked flask equipped with a stirring rod, a thermometer, a nitrogen gas blowing tube, a dropping funnel for carboxylic acid halide, and a Dimroth condenser equipped with a drying tube filled with granular calcium chloride, Phenolsulfonic acid Na salt (p-form content 99.5
%, Water content 0.02%, can be prepared by recrystallizing the neutralized product obtained in Reference Example several times in water or ethanol and drying, etc.) 120.0 g, lauric acid (Lunack L manufactured by Kao Corporation)
-98) 60.0 g was weighed and heated to 60 ° C. in an oil bath whose temperature could be adjusted while stirring. After reaching 60 ° C., 134.6 g of lauric chloride was added dropwise over about 20 minutes. Nitrogen gas was circulated at a supply rate of about 500 ml / min upon completion of dropping. After the completion of the dropping, the mixture was digested at 60 ° C for 1 hour and then 80
The temperature was raised to 80 ° C and aging was carried out at 80 ° C for 4 hours. The pressure was reduced to 200 Torr while maintaining the temperature at 80 ° C., and hydrochloric acid was removed over 1 hour. At this time, at 80 ° C., the reaction product is slurry-like. As a result of quantification by liquid chromatography analysis, the target substance, Na p-lauroyloxybenzenesulfonate was obtained in a yield of 98.0%. At this time, there were almost no side reactions other than hydrolysis of lauric chloride.
(Less than 0.5%). The product hue is APHA 2
It was 0.

The reaction products were analyzed by liquid chromatography using the following columns, eluents and detectors. Column: Merck Recloth Fur 100 RP-18 (5 μm),
250mm × 4mmφ Eluent: Gradient method using the following solutions A and B Solution A: 0.1M NaClO ₄ in CH ₃ CN / water = 30/70 (vol / vol) Solution B: CH ₃ CN 100% Detector : UV 260nm hue is 5% solid content, acetonitrile / water = 50/50 (vo
(l / vol) solution and compared with APHA standards.

Example 2 Using the same equipment as in Example 1, weigh 200.0 g of the dried crude Na phenolsulfonate obtained in Reference Example,
The mixture was heated to 120 ° C. in an oil bath whose temperature could be adjusted while stirring. After reaching 120 ° C, lauric chloride 132.2
g was added dropwise after about 30 minutes. Nitrogen gas was circulated at a supply rate of about 500 ml / min upon completion of dropping. After completion of dropping
It was digested by digestion at 120 ° C. for 3 hours. The pressure was reduced to 200 Torr while cooling to 80 ° C., and hydrochloric acid was removed over 1 hour.
At this time, at 120 ° C. and 80 ° C., this reaction product was in the form of slurry as in Example 1. As a result of quantifying the reaction product by liquid chromatography, the target substances p- and o-
Na lauroyloxybenzene sulfonate, total 96.7%
It was obtained in a yield of. At this time, it was confirmed that side reactions other than hydrolysis were less than 0.5% of Na against phenolsulfonate. The product hue was APHA 30.

Example 3 Using the same equipment as in Example 1, cresol sulfonate Na (content (total of all isomers) 98.5%, water content 0.01%) 1
40.0 g and 140.0 g of lauric acid were weighed and heated to 60 ° C. in an oil bath whose temperature could be adjusted while stirring. After reaching 60 ° C., 145.1 g of lauric chloride was added dropwise over about 20 minutes. Hereinafter, the reaction was performed under the same reaction conditions as in Example 2. As a result, the target ester of cresolsulfonic acid Na salt with lauric acid was obtained in a yield of 98.5%. The hue was APHA 50.

Effects of carboxylic acid species Examples 4 to 9 Under the same equipment and conditions as in Example 2, p-phenolsulfonic acid Na (the same as in Example 1), n-nonanoic acid chloride and n-nonanoic acid were used. 3,3,5-trimethylhexanoic acid chloride and 3,5,5-trimethylhexanoic acid, n-decanoic acid chloride and n-decanoic acid, myristic acid chloride and myristic acid, palmitic acid chloride and palmitic acid, stearic acid chloride And stearic acid were used to confirm the reactivity. The results are summarized in Table 1.

[0031]

[Table 1]

Effect of Addition Amount of Carboxylic Acid Comparative Examples 1-2 and Examples 10-14 Lauric acid was added to the dried Na Na phenolsulfonate (the same as in Example 1) at the addition amount shown in Table 2, The reaction was carried out in the same manner as in Example 1, and the yield was calculated by liquid chromatography analysis. The results are summarized in Table 2.

[0033]

[Table 2]

A carboxyl group different from the acyl group of the carboxylic acid halide
Effect of Rubonic Acid Species Examples 15-18 Under the same reaction conditions as in Example 1, only carboxylic acid was changed to lauric acid (versus 50% by weight of phenolsulfonic acid salt).
-Decanoic acid, n-nonanoic acid, n-hexanoic acid, and acetic acid were used and reacted with 50 mol% of phenolsulfonic acid salt. The results are summarized in Table 3.

[0035]

[Table 3]

Effect of Counterion Examples 19 to 21 Reactions were carried out under the same conditions as in Example 1 except that the counterion of phenolsulfonic acid was changed as shown in Table 4. The results are summarized in Table 4.

[0037]

[Table 4]

Claims (4)

[Claims] 1. A substantially anhydrous general formula (1): (In the formula, R ¹ represents a linear or branched lower alkyl group having 1 to 4 carbon atoms. N: represents a number of 0 to 2, and in the case of n = 2, two R ^1's may be the same. M: an alkali metal, an alkaline earth metal or ammonium).
General formula (2) (In the formula, R ² is a linear or branched alkyl having 1 to 21 carbon atoms, which may be substituted with a halogen or a phenyl group, and an ester group, an amide group, an ether group or a phenylene group may be inserted. Group or an alkenyl group, or a phenyl group which is unsubstituted or substituted with a halogen or an alkyl group. X: represents a halogen atom selected from F, Cl, Br or I.). A carboxylic acid halide is reacted to give a compound of the general formula (3): (In the formula, R ¹ , R ² , n and M have the above-mentioned meanings.) In the production of the acyloxybenzenesulfonate represented by the general formula (4): (In the formula, R ³ is a linear or branched alkyl group having 1 to 21 carbon atoms, which may be substituted with a halogen or a phenyl group, and in which an ester group, an amide group, an ether group or a phenylene group may be inserted. Group or an alkenyl group, or represents a phenyl group which is unsubstituted or substituted with a halogen or an alkyl group.) Acyloxybenzene sulfone Method for producing acid salt. 2. The carboxylic acid represented by the general formula (4) is
The method for producing an acyloxybenzene sulfonate according to claim 1, which is a linear or branched fatty acid having 8 to 16 carbon atoms. 3. The carboxylic acid represented by the general formula (4) is
The method for producing an acyloxybenzene sulfonate according to claim 1, which has a carboxylic acid residue of the carboxylic acid halide represented by the general formula (2). 4. A carboxylic acid represented by the general formula (4):
The method for producing an acyloxybenzene sulfonate according to claim 1, wherein 0.05 to 20 parts by weight is used for 1 part by weight of the phenol sulfonate represented by the general formula (1).