JPH06247924A - New sulfonate, its production and mold remover composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a new sulfonate useful as an organic peracid precursor for oxygen-based mold removers and domestic bleaching agents such as for kitchens and clothing, each free from irritant odor and excellent in bleaching power and its sustainability. CONSTITUTION:The sulfonate of formula I [R<1> is H, <=10c alkyl, acyl or alkoxy; R<2> is 1-16C alkylene or (R<4>)p-O-R<5> (R<4> and R<5> are each 1-8C alkylene; (p) is O or 1); R<3> is 1-8C alkylene; A is 2-4C alkylene; M is alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium; (m) is O or 1; (n) is 0-100], e.g. 2-sulfoethyl phenoxyacetic acid ester sodium salt. The compound of the formula I can be obtained by reaction of an aromatic carbonyl compound of formula II (Y is OH, halogen or alkoxy) with a compound of formula III. A compound of formula IV (R<4> is alkylene; (p) is 0 or 1; R<5> is alkylene) as one of the compounds of the formula I can also easily obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel sulfonate useful as an organic peracid precursor in a household bleaching agent such as a fungicide, a kitchen bleaching agent and a clothing bleaching agent, and a process for producing the sulfonate. Further, the present invention relates to an oxygen-based fungicide composition which has no pungent odor and is excellent in bleaching power and durability of bleaching power.

[0002]

2. Description of the Related Art Cladospo cleans black stains on bathroom ceilings, tile joints, plastic walls and triangular corners of kitchens.
It is caused by the fungus-producing pigments of the genus rium and cannot be removed with a cleanser or a surfactant alone.Therefore, there is currently a spray-type fungicide that uses a chlorine bleach such as hypochlorite. It is on the market.

However, although the fungicide containing hypochlorite is excellent in bleaching performance, it is very dangerous to eyes and skin, and spray-like agents are not suitable for molds such as ceilings. Further, it has a problem that it has a strong chlorine-based odor and is resistant to use in a small bathroom, and when it is mistakenly used with an acidic detergent, it emits toxic gas.

In recent years, oxygen-based bleaching agents that do not have such a danger have been investigated. For example, JP-A-62-4794 discloses a composition in which hydrogen peroxide or sodium percarbonate, a bleaching activator and a peroxydisulfate are used in combination. The oxygen-based bleaching agent is generally used in combination with a bleaching activator, and as the bleaching activator, tetraacetyldiamine,
Tetraacetylglycoluril, pendant erythritol tetraacetate and the like can be mentioned.

However, since these bleach activators generate peracetic acid as a bleaching active species, they have a strong irritating odor and have many problems in practical use.

[0006] Further, JP-A-61-81498, JP-A-61-81499 and JP-A-63-15235.
In No. 7 publication,

[0007]

[Chemical 7]

(R ⁸ represents an alkyl group having 1 to about 14 carbon atoms, an aryl group or an alkanol group, R ⁹ represents a hydrogen atom or an alkyl group having 1 to about 10 carbon atoms, an aryl group or an alkanol group; ¹⁰ represents a group represented by an alkylene group having 1 to about 14 carbon atoms, an arylene group or an alkarylene group). ] The compound represented by the following is disclosed as an organic peracid precursor that can be used in a bleaching agent. However, in order to obtain a more excellent bleaching power, when the compound described in the above publication is used in a system in which hydrogen peroxide and the like and an organic peracid precursor are used at a high concentration, the organic peracid generated by perhydrolysis is phenol. Since it is consumed in the oxidation of sodium sulfonate, the expected effect cannot be obtained. Further, in the synthesis of the compound represented by the above formula, it is difficult to dehydrate an ester of a usual acid and an alcohol, which poses a problem in industrial implementation.

Further, Japanese Patent Application Laid-Open No. 1-311199 discloses the use of a phenol derivative as a leaving group of an organic peracid precursor. However, when sodium phenolsulfonate is used as a leaving group as described above. Due to the same reason as above, the expected effect cannot be obtained.

Further, Japanese Unexamined Patent Publication No. 1-311199 discloses the use of glucose as a leaving group.
In the industrially possible esterification reaction of acid and glucose,
The physical properties as a solid were poor, and the coloring was remarkable, and a substance desired by the present inventors could not be obtained.

In such a situation, the object of the present invention is to produce an organic peracid precursor which does not generate an unpleasant pungent odor under bleaching conditions and which is industrially inexpensive, and which can be easily synthesized. It is to provide a manufacturing method. A further object of the present invention is to provide an oxygen-based fungicide composition having no pungent odor, excellent bleaching power, and excellent bleaching power sustainability.

[0012]

Under these circumstances, the inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, the novel sulfonate represented by the following general formula (1) has no irritating odor and is excellent. The bleaching power and the persistence of the bleaching power are shown, and it was found that the bleaching power and the bleaching power are useful as an organic peracid precursor for oxygen-based bleaching agents such as mold scavengers, kitchen bleaching agents and clothing bleaching agents, and the present invention was completed. . That is, the present invention has the following general formula
The present invention provides a sulfonate represented by (1) and a method for producing the same.

[0013]

[Chemical 8]

[In the formula, R ¹ represents a hydrogen atom or a linear or branched alkyl group, an acyl group or an alkoxy group having 10 or less carbon atoms, and R ² represents a linear or branched chain having 1 to 16 carbon atoms. alkylene group, or the formula _{^{- (R 4) p -O-}} R 5 - ( wherein R ⁴
And R ⁵ are the same or different and each represents a linear or branched alkylene group having 1 to 8 carbon atoms, p represents a group represented by 0 or 1, and R ³ represents 1 group. ~ 8 represents a linear or branched alkylene group, A represents an alkylene group having 2 to 4 carbon atoms, and n A's may be the same or different. M represents an alkali metal atom, an alkaline earth metal atom, ammonium, alkylammonium or alkanolammonium, m is a number of 0 or 1, and n is 0 to 0.
Indicates a number of 100. The present invention also provides a fungicide composition containing the following components (A) and (B) as essential components. (A) Hydrogen peroxide or peroxide that produces hydrogen peroxide in an aqueous solution 0.1 to 98% by weight (B) Organic peracid precursor represented by the following general formula (I) 0.002 to 50% by weight

[0015]

[Chemical 9]

(Wherein R ¹ , R ² , R ³ , M, n and p have the same meanings as described above).

In the sulfonate represented by the general formula (1) of the present invention (hereinafter abbreviated as sulfonate (1)), a linear or branched alkyl group having 10 or less carbon atoms represented by R ¹ , an acyl group, or Alkoxy groups include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Heptyl, octyl, nonyl, decyl, isopropyl,
alkyl groups such as tert-butyl, acetyl, propionyl, butyryl, acyl groups such as hexanoyl, methoxy,
Examples thereof include alkoxy groups such as ethoxy, propoxy and butoxy, and those having 4 or less carbon atoms are particularly preferable. Also, R ²
Examples of the linear or branched alkylene group having 1 to 16 carbon atoms represented by are methylene, ethylene, propylene, ethylethylene, trimethylene, tetramethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene, tridecamene. Examples thereof include groups such as methylene, tetradecamethylene, and hexadecamethylene, and those having 1 to 8 carbon atoms are particularly preferable. Examples of the linear or branched alkylene group having 1 to 8 carbon atoms represented by R ⁴ and R ⁵ include methylene, ethylene, propylene, ethylethylene,
Examples thereof include groups such as trimethylene, tetramethylene, hexamethylene, heptamethylene and octamethylene, and those having 1 to 4 carbon atoms are particularly preferable. The linear or branched alkylene group having 1 to 8 carbon atoms represented by R ³ includes methylene, ethylene, propylene, ethylethylene, trimethylene, tetramethylene, hexamethylene,
Examples include groups such as heptamethylene and octamethylene.
Examples of the alkylene group having 2 to 4 carbon atoms represented by A include ethylene, propylene, trimethylene and tetramethylene. Examples of the alkali metal atom represented by M include sodium and potassium, examples of the alkaline earth metal atom include magnesium and calcium, and examples of the alkylammonium include methylammonium and dimethylammonium. Examples of the alkanol ammonium include monoethanol ammonium and triethanol ammonium,
Alkali metal atoms are particularly preferred.

In the general formula (1) representing the sulfonate (1) of the present invention, n oxyalkylene groups (AO) are
It may be one kind of oxyalkylene group or a combination of different oxyalkylene groups. Specific examples include groups such as polyoxyethylene groups, polypropylene groups and polyoxyethylene-polyoxypropylene. Also n
Is a number from 0 to 100, preferably 0 to 20.

The sulfonate (1) of the present invention is produced, for example, by reacting the aromatic carbonyl compound represented by the general formula (2) with the compound represented by the general formula (3) according to the following reaction formula. can do.

[0020]

[Chemical 10]

(In the formula, R ¹ , R ² , R ³ , A, M, m and n have the same meanings as described above, and Y represents a hydroxy group, a halogen atom or an alkoxy group having 1 to 3 carbon atoms. ) In the above formula, examples of the halogen atom represented by Y include a chlorine atom, a bromine atom, an iodine atom, and the like, and the number of carbon atoms is 1 to 3.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and the like.

In this production method, the amount of the aromatic carbonyl compound represented by the general formula (2) is 0.5 to 3 times, preferably 0.8 to 3 times, the mole of the compound represented by the general formula (3).
Carry out the reaction using 1.5 molar times. A solvent is not always necessary for this reaction, but it can be used. As the solvent used here, any solvent may be used so long as it is inert to the raw materials and the reaction product, but an organic solvent having a high boiling point is preferable. Examples of such a high boiling point organic solvent include diglyme, triglyme, dimethylformamide, dimethylimidazolidinone and the like. The reaction temperature is 100 to 300 ° C, preferably 150
It is better to carry out at ℃ ~ 250 ℃.

The reaction in the above-mentioned production method proceeds sufficiently even without using a catalyst, but the reaction can be carried out more efficiently by using a catalyst usually used in the esterification reaction. As such a catalyst, an acidic catalyst,
Basic catalysts, oxide catalysts, etc. are used. Acidic catalysts include sulfuric acid, bases, paratoluene sulfonic acid, etc., basic catalysts include alkali metal hydroxides, alkali metal alcoholates, etc., and oxide catalysts. Examples thereof include magnesium oxide and tin oxide. The amount of these esterification reaction catalysts used is preferably about 0.1 to 5% by weight based on the entire reaction system.

The progress of the reaction in the above production method can be confirmed by measuring the amount of water or alcohol distilled out of the system. In the obtained reaction mixture, in addition to the desired sulfonate (1) of the present invention, depending on the reaction molar ratio, an unreacted aromatic carbonyl compound represented by the general formula (2), a general formula (3) It contains the compound represented or the solvent or catalyst used. The reaction product thus obtained can be used as it is depending on the purpose of use, but can be made into a highly pure product by further purification described below.

General formula used in the above production method
Examples of the aromatic carbonyl compound represented by (2) include benzoic acid, phenylacetic acid, 3-phenylpropionic acid, and 4
-Phenylbutyric acid, 6-phenylcaproic acid, acetylbenzoic acid, propionylbenzoic acid, butyrylbenzoic acid, hexanoylbenzoic acid, methoxybenzoic acid, ethoxybenzoic acid, propoxybenzoic acid, butoxybenzoic acid, phenoxyacetic acid, 2-phenoxypropionic acid , 3-phenoxypropionic acid, 4-phenoxybutyric acid, 6-phenoxycaproic acid, benzyloxyacetic acid, 3-benzyloxypropionic acid, 4-benzyloxybutyric acid, 2-phenylethoxyacetic acid, 2- (2-phenylethoxy) propion Acid, 3- (2-phenylethoxy) propionic acid, 4
-(2-phenylethoxy) butyric acid, 6- (2-phenylethoxy) caproic acid, 3-phenylpropoxyacetic acid,
3- (3-phenylpropoxy) propionic acid, 4-
(3-phenylpropoxy) butyric acid, 6- (3-phenylpropoxy) caproic acid, 4-phenylbutoxyacetic acid,
3- (4-phenylbutoxy) propionic acid, 4- (4
-Phenylbutoxy) butyric acid, 6- (4-phenylbutoxy) caproic acid and other organic acids or mixed acids thereof, or acid halides of the above organic acids or mixtures thereof, or lower alcohol esters of the above organic acids or mixtures thereof Further, those having a substituent such as methyl, ethyl and t-butyl in the phenyl group of these compounds can be mentioned.

Further, the general formula used in the above production method
Of the compounds represented by (3), those in which n is other than 0 are
According to the following reaction formula, it is synthesized by reacting the hydroxyalkanesulfonate represented by the general formula (7) with the alkylene oxide represented by the general formula (8).

[0027]

[Chemical 11]

(Wherein R ³ , A and M have the same meanings as described above, and n'represents a number from 1 to 100.) That is, the hydroxyalkanesulfonate represented by the general formula (7) is treated with an alkali catalyst. Using an aqueous solution or dimethylformamide, dimethylimidazolidinone, etc. as a solvent,
The compound represented by the general formula (3 ′) is obtained by reacting with the alkylene oxide represented by the general formula (8). The reaction is carried out at a concentration such that the hydroxyalkanesulfonate represented by the general formula (7) is uniformly dissolved in water or an organic solvent, and the alkali catalyst is used in an amount of 0.1 to 5 mol relative to the hydroxyalkanesulfonate represented by the general formula (7). %, Preferably 0.2 to
The reaction is carried out using 1 mol%. For the alkylene oxide represented by the general formula (8), the desired addition mole number is calculated and the reaction is carried out. The temperature during the reaction is 50 to 150 ° C, preferably 90 to 120 ° C.
Done in. After the reaction, the purity of the target product may be increased by adding the reaction-terminated product to a solvent such as acetone and collecting the insoluble matter.

General formula used as a raw material for this reaction
Examples of the hydroxyalkane sulfonate represented by (7) include 2-hydroxyethanesulfonic acid, 2-hydroxypropane-1-sulfonic acid, 1-hydroxypropane-2-sulfonic acid, 3-hydroxypropanesulfonic acid, 1- Hydroxybutane-2-sulfonic acid, 4-
Hydroxyalkanesulfonic acid such as hydroxybutanesulfonic acid sodium salt, potassium salt, calcium salt,
Examples thereof include ammonium salt, methylammonium salt and triethanolammonium salt.

In the general formula (1), m = 1 and R ² is the formula-(R ⁴ ) _p -O-R ^5- (wherein R ⁴ , R ⁵ and p have the same meanings as described above). The sulfonate, which is a group represented by, can also be obtained by reacting an aromatic alcoholate or phenolate represented by the general formula (4) with a halide represented by the general formula (5) according to the following reaction formula. .

[0031]

[Chemical 12]

(Wherein R ¹ , R ³ , R ⁴ , R ⁵ , A, M, M ', n
And p have the same meaning as described above, and X represents a halogen atom. ) The aromatic alcoholate or phenolate represented by the general formula (4) and the halide represented by the general formula (5) are
The reaction is carried out using a Williamson synthesis or a phase transfer catalyst which is usually performed. The reaction is carried out using 0.5 to 3 mole times, preferably 0.8 to 1.5 mole times, of the halide represented by the general formula (5) per 1 mole of the aromatic alcoholate or phenolate represented by the general formula (4). . As the solvent, diglyme, triglyme, dimethylformamide, dimethylimidazolidinone or the like is used, and the reaction temperature is 50.
It is good to carry out at -150 ° C, preferably 70-100 ° C.

The aromatic alcoholate or phenolate represented by the general formula (4) used herein is an alcohol having an aromatic group such as benzyl alcohol, 2-phenylethanol, 3-phenylpropanol, 4-phenylbutanol or the like. Mention may be made of alcoholates or phenolates of phenol and alkyl metals.

The halide represented by the general formula (5) may be obtained by any method, and can be synthesized, for example, according to the following reaction formula.

[0035]

[Chemical 13]

(In the formula, R ³ , R ⁵ , A, M, X and n have the same meanings as described above, and L represents a hydroxy group, a halogen atom or an alkoxy group having 1 to 3 carbon atoms). By reacting the compound represented by the general formula (3) with a compound having a halogen group represented by the general formula (9) represented by chloroacetyl chloride and 3-chloropropionyl chloride, the compound represented by the general formula (5) The represented halide can be obtained. In the reaction, the compound represented by the general formula (3) is dissolved in a solvent such as dimethylformamide and dimethylimidazolidinone, and then the compound represented by the general formula (9)
The method of dropping the compound represented by General formula
The compound represented by (9) is used in an amount of 0.8 to 2.0 times, preferably 0.9 to 1.2 times the amount of the compound represented by the general formula (3), and the dropping temperature is 20 to 40 ° C. Is 0.3
~ 4.0 hours, preferably 0.5-1.5 hours. After dropping
The aging reaction is carried out at 40 to 100 ° C, preferably 50 to 80 ° C for 2 to 10 hours. After this, under reduced pressure at a temperature of 50-150 ℃,
General formula unreacted with the compound represented by general formula (10) as a by-product
The compound represented by (9) is removed. The reaction mixture thus obtained is added to a solvent such as acetone and the insoluble matter is recovered, whereby the halide represented by the general formula (5) can be obtained.

As a method for purifying the sulfonate (1) of the present invention obtained by the method as described above, removal of the reaction solvent may be carried out by filtration or distillation under reduced pressure, and removal of the unreacted raw materials and the catalyst may be carried out. Examples thereof include crystallization, reprecipitation, dialysis and the like.

Next, the fungicide composition of the present invention will be described.

Among the components (A) of the fungicide composition of the present invention, peroxides that generate hydrogen peroxide in an aqueous solution include sodium percarbonate, sodium tripolyphosphate / hydrogen peroxide adduct, and pyrophosphoric acid. Sodium / hydrogen peroxide adduct, urea / hydrogen peroxide adduct, or 4Na ₂ SO ₄・ 2H ₂ O ₂
-NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium persilicate, sodium peroxide, calcium peroxide and the like are exemplified. Among these, sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferable.

The component (A) is incorporated in the fungicide composition of the present invention in an amount of 0.1 to 98% by weight. When hydrogen peroxide is used as the component (A), the desirable blending amount in the composition is
0.1 to 30% by weight, more preferably 0.5 to 6% by weight, and when a peroxide that generates hydrogen peroxide in an aqueous solution is used as the component (A), the content in the composition is
It is 0.1 to 98% by weight, more preferably 0.5 to 30% by weight.

In the fungicide composition of the present invention, the component (B), the organic peracid precursor represented by the general formula (I), is added in an amount of 0.002 to 50% by weight.

Further, the hydrogen peroxide of the component (A) or the peroxide which produces hydrogen peroxide in the aqueous solution and the organic peracid precursor of the component (B) have a weight ratio (A ) /
(B) = 50/1 to 1/10, preferably 20/1 to 1/5. If the weight ratio of both exceeds 50/1, the concentration of organic peracid generated with respect to hydrogen peroxide becomes relatively low, so the bleaching power improving effect may decrease, which is not very desirable. Is less than 1/10, an excessive amount of unreacted organic peracid precursor remains in the system, which is economically disadvantageous.

Further, it is preferable that the fungicide composition of the present invention contains the respective components so that the effective oxygen concentration during use is 0.01 to 5%. If the effective oxygen concentration is less than 0.01%,
It is not preferable because the bleaching power is low, and even if the effective oxygen concentration exceeds 5%, no further effect is obtained, which is economically disadvantageous.

By further adding a surfactant to the fungicide composition of the present invention, penetration into dirt can be promoted and high bleaching power can be obtained. Surfactant (C)
The weight ratio of the component (A) to the total amount of the component (B) is [(A) + (B)] / (C) = 99.9 / 0.1 to 50/50,
In particular, the range of 70/30 to 90/100 is preferable. If this weight ratio is less than 99.9 / 0.1, the permeability to dirt cannot be sufficiently promoted, and if it exceeds 50/50, the stability of the organic peracid generated will be low and a sufficient cleaning effect will be obtained. I can't. Surfactant (C) is used in an amount of 0.01 to 20% by weight, particularly 0.1 to 20% by weight in the fungicide composition obtained by blending the surfactant.
It is desirable to add 10% by weight. Also in this case, the compounding amounts of the component (A) and the component (B) in the entire composition are in the same range as described above.

As the surfactant used in the present invention,
Nonionic surfactants such as alkyl glycosides, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, oxyethyleneoxypropylene block polymers (Pluronic), fatty acid monoglycerides, and amine oxides; Anionic surfactants such as soaps, alkyl sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate ester salts, sulfosuccinic acid diester salts; mono- or dialkyl amines and their polyoxyethylene adducts, mono- or di-long chain alkyl primary salts Cationic surfactants such as quaternary ammonium salts; amphoteric surfactants such as carbobetaine, sulfobetaine and hydroxysulfobetaine. Of these, anionic surfactants such as alkylbenzene sulfonates and soaps are particularly excellent in terms of detergency.

The fungicidal composition of the present invention can further enhance the effect by further containing a buffering agent for adjusting the pH. The pH of the stock solution of the composition is preferably 5 to 13, and more preferably 9 to 11. If the pH in the system is less than pH 5, the reactivity of the components (A) and (B) will decrease, so the production rate of the organic peracid as the active ingredient will decrease, and if it exceeds pH 13, it will be produced. The stability of the organic peracid decreases.

Examples of the buffer include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, ammonium hydroxide, amine derivatives such as mono-, di- and triethanolamines, alkali metals such as sodium carbonate and potassium carbonate. The above-mentioned carbonates, carbonates such as ammonium carbonate, alkali metal silicates such as sodium silicate and potassium silicate, and silicates such as ammonium silicate can be used. Furthermore, if necessary, alkali metal sulfates such as sodium sulfate, potassium sulfate and lithium sulfate, or ammonium sulfate, alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate and lithium bicarbonate, ammonium bicarbonate and the like can be used.

In addition, if necessary, solubilizers such as sodium p-toluenesulfonate, sodium xylenesulfonate, sodium alkenylsuccinate and urea, penetrants, suspending agents such as clay, abrasives, chelating agents, pigments,
Dyes, fragrances, etc. can be added.

The preferable blending amount in the composition of the above optional components which can be blended in the present invention is as follows. Buffering agent 0.1 to 30% by weight Solubilizing agent 0.1 to 10% by weight Thickening agent 0.1 to 5% by weight Abrasive agent 0.1 to 20% by weight Chelating agent 0.1 to 10% by weight Pigment, dye, fragrance, etc. When the composition is in liquid form, it is prepared by adding (D) water to the above essential and optional components. The blending amount of water is not limited.

The mold-removing agent composition of the present invention may be used in the form of a single agent containing both the component (A) and the component (B),
The component (A) and the component (B) can be used in any two-part form, but it is preferable to use a one-part formulation for the convenience of use. In this case, the component (A) is used. Since it is difficult to use liquid hydrogen peroxide as the storage stability, it is preferable to use a powdery peroxide that produces hydrogen peroxide in an aqueous solution. In this fungicide composition, the water of the component (D) is substantially 0%. Therefore, the user dissolves the powdery or solid product of the present invention with water before use, and then sprays or sprays it on the target surface for bleaching treatment.

As a form other than the one-pack type, a peroxide (A) which produces hydrogen peroxide in hydrogen peroxide or an aqueous solution and an organic peracid precursor (B) are separately packaged and used. It can be a composition of dosage form. Arbitrary components and water can be mixed in each package. In the case of a two-pack composition, the user mixes the individual sachets (add water if necessary) immediately before use to form a solution, slurry or paste, and immediately sprays or sprays on the target surface to bleach. Perform processing.

[0052]

INDUSTRIAL APPLICABILITY The novel sulfonate (1) of the present invention is excellent in that it reacts with hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution to produce an organic peracid and has no irritating odor. Since it exhibits bleaching power, it is an excellent organic peracid precursor for oxygen-based bleaching agents, and a bleaching agent composition containing it is a household bleaching agent such as mold scavenger, kitchen bleaching agent, clothing bleaching agent, etc. It is particularly useful as an agent.

Further, according to the present invention, there is no irritating odor, a high bleaching power is exhibited, the bleaching power at the time of use is maintained for at least about 30 minutes, and a high bleaching oxygen type fungus having a good permeability to stains is obtained. An agent composition can be obtained.

[0054]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1 A 1-liter four-necked flask equipped with a reflux condenser equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a water separator,
228 g (1.5 mol) of phenoxyacetic acid and 148 g (1.0 mol) of sodium isethionate were charged and heated from the outside with stirring under a nitrogen atmosphere, and the reaction was carried out at a reaction temperature of 250 ° C. for 8 hours. The amount of distilled water during the reaction was 17 ml, and when cooled after the reaction, 358 g of a yellow solid was obtained. Then
Acetone (500 ml) was added to the reaction product, and the mixture was refluxed with acetone.
Stirring was performed. The phenoxyacetic acid used in excess was removed by separating the solid and liquid by filtration. This washing operation 3
After repeating this operation twice, acetone was removed by drying under reduced pressure to obtain 242 g of 2-sulfoethylphenoxyacetic acid ester sodium salt (I) as a white solid (yield 85.9% based on sodium isethionate). The results of ¹³ C-NMR analysis are shown below.

[0056]

[Chemical 14]

[0057] Example 2 In a 1 liter flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a reflux condenser equipped with a water separator, 183 g (1.5 mol) of benzoic acid and 148 g of sodium isethionate were added.
(1.0 mol) was charged, and 0.17 g of SnO 2 was added as a catalyst,
Externally heat the reaction temperature while stirring under a nitrogen atmosphere.
The reaction was carried out at 220 ° C for 8 hours. The amount of distilled water during the reaction was 17 ml, and when cooled after the reaction, 310 g of a pale yellow solid was obtained. Next, 500 ml of acetone was added to the reaction product, and the mixture was stirred under reflux of acetone. By separating the solid-liquid by filtration, excess benzoic acid was removed. After repeating this operation 3 times, acetone was removed by drying under reduced pressure to obtain 231 g of white 2-sulfoethylbenzoic acid ester sodium salt (II) (yield 91.6% based on sodium isethionate). The results of ¹³ C-NMR analysis are shown below.

[0058]

[Chemical 15]

[0059] Example 3 In a 1 liter flask equipped with a stirrer, thermometer, nitrogen sparge tube and reflux condenser with water separator, 4-t.
-Butylphenol 150 g (1.0 mol) and xylene 300 ml as a solvent were charged, heated to 60 ° C, and then stirred vigorously.
83.4 g of 48% NaOH aqueous solution (1.0 mol as NaOH) was added dropwise over 1 hour. Then, the temperature was raised and dehydration was performed at 120 ° C. for 2 hours. The water content in the system was confirmed to be 0.5% or less by Karl Fischer water content measurement, cooled to 70 ° C., and 184 g (1.1 mol) of ethyl bromide acetate was added dropwise over 2 hours. Then, the reaction was carried out at the same temperature for 2 hours. Then, the reaction product was distilled to obtain 182 g of ethyl 4-t-butylphenoxyacetate having a gas chromatography purity of 98.0%. 180 g of ethyl 4-t-butylphenoxyacetate obtained (0.
76 mol) and 350 ml of 10% NaOH (0.88 mol as NaOH) were charged into a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen blowing tube, and hydrolyzed for 2 hours on a 70 ° C water bath. After hydrolysis, the mixture was cooled to room temperature and adjusted to pH <1 with 36% HCl on a water bath. The solid precipitated in the process of adjusting pH <1 was extracted with 500 ml of ethyl ether. This extraction operation was repeated 3 times. The obtained ethyl ether layer was washed with a saturated Na ₂ CO ₃ aqueous solution and water, and after removing ethyl ether with a rotary evaporator, it was dried under reduced pressure.
41 g of 4-t-butylphenoxyacetic acid was obtained. As a result of treating this product with diazomethane and examining the gas chromatography purity, it was 96.8%.

125 g (0.6 mol) of 4-t-butylphenoxyacetic acid synthesized by the above method and 74 g (0.5 mol) of sodium isethionate were added to a reflux condenser equipped with a stirrer, a thermometer, a nitrogen blowing tube and a water separator. The mixture was charged into a 500 ml flask equipped with a reactor and heated from the outside with stirring under a nitrogen atmosphere, and the reaction was carried out at a reaction temperature of 230 ° C. for 8 hours. When cooled after the reaction, 188 g of a yellow solid was obtained. Next, 250 ml of acetone was added to the reaction product, and the mixture was refluxed with acetone.
Stirring was performed. By separating the solid-liquid by filtration, excess 4-t-butylphenoxyacetic acid used was removed. After repeating this operation 3 times, the acetone was removed by drying under reduced pressure to obtain 146 g of white solid 2-sulfoethyl 4-t-butylphenoxyacetic acid ester sodium salt (III) (86% yield based on sodium isethionate). Obtained. ¹³ C-
The results of NMR analysis are shown below.

[0061]

[Chemical 16]

[0062] Example 4 In a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen blowing tube, 157 g (1 mol) of ammonium 3-hydroxypropanesulfonate and 500 ml of dimethylformamide were added.
Was charged, and the temperature was raised to 80 ° C. with stirring under a nitrogen atmosphere. 171 g of phenoxyacetyl chloride at this temperature
(1 mol) was added dropwise. After continuing stirring at the same temperature for 3 hours, the temperature was raised to 120 ° C. and dimethylformamide was distilled off under reduced pressure to obtain a slurry mixture. Next, this mixture was mixed with 1000 ml of acetone to deposit a white precipitate. The white precipitate was separated by filtration and further washed with 500 ml of acetone.
Washed twice. Then, acetone was removed by drying under reduced pressure to obtain 267 g of 3-sulfopropylphenoxyacetic acid ester ammonium salt (IV) as a white solid. ¹³ CN
The results of MR analysis are shown below.

[0063]

[Chemical 17]

[0064] Example 5 In a 5 liter autoclave, 148 g (1 mol) of sodium isethionate and dimethyl sulfoxide as a solvent were used.
Charge 1332g and NaOH 0.2g as catalyst, reaction temperature 90 ℃
Slowly inject 440 g (10 mol) of ethylene oxide,
The reaction temperature was raised to 100 ° C. When there was no decrease in pressure, cooling was performed to obtain 1870 g of a reaction mixture. 1870 g of this reaction mixture was mixed into 10 liters of acetone, and a white precipitate was deposited. The white precipitate is filtered off by filtration,
The white precipitate was washed with 10 liters of acetone. The white precipitate was dried under reduced pressure at 60 ° C. to obtain 571 g of white powder.
The hydroxyl value of this white powder was 97.6 mgKOH / g, and the average number of moles of ethylene oxide added was 9.7
Met. 115 g of this white powder (ethylene oxide 9.7
(Mole addition, 0.2 mole equivalent) was dissolved in 1000 ml of dimethylimidazolidinone, the temperature was raised to 80 ° C., and 38 g (0.3 mole) of 3-chloropropionyl chloride was gradually added dropwise.
Hydrochloric acid generated at this time was removed by blowing nitrogen into the reaction system. After 3-chloropropionyl chloride was added dropwise, an aging reaction was carried out at the same temperature for 5 hours. Used in excess 3
-Chloropropionyl chloride and the solvent were distilled off under reduced pressure to obtain 208 g of a slurry-like mixture. This slurry-like mixture was mixed in 1000 ml of acetone to precipitate white crystals. White crystals were separated by filtration and acetone 1000
Wash with ml and dry under reduced pressure at 60 ° C.
-Chloropropionyloxypolyoxyethylene (9.7)
Sodium ethyl sulfonate was obtained as a white powder. The chlorine content of this product was 5.3%, which was in agreement with the theoretical value. In addition, absorption of carbonyl derived from ester was observed at 1760 cm ^-1 by IR measurement.

Next, 11 g (0.1 mol) of benzyl alcohol, 500 ml of dimethylimidazolidinone, and 8.3% of 48% NaOH.
g, and dehydrate under reduced pressure at 150 ° C with strong stirring.
Cooled to 80 ℃, 67g of white powder (0.1 mol equivalent)
Was added. React at 80 ℃ for 10 hours, and filter by NaCl
Separated. Dimethyl imidazolidinone was distilled off from the obtained filtrate under reduced pressure to obtain a slurry-like reaction product. This slurry was mixed with 1000 ml of acetone to deposit a white precipitate. The obtained white precipitate was further washed with 1000 ml of acetone and dried under reduced pressure at 60 ° C. to obtain 69 g of sodium benzyloxypropionyloxypolyoxyethylene (9.7) ethylsulfonate (V) represented by the following formula as a white powder. It was

[0066]

[Chemical 18]

The ester value of this product is 76 mgKOH / g,
In agreement with the theoretical value. Further, from the measurement of IR, absorption derived from ester 1762Cm ^-1, absorption attributed width wider sulfonic acid 1200 cm ^-1, the absorption derived from sharp ether 1,120 cm ^-1 were observed.

Comparative Example In a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen blowing tube, 57 g of disodium phenolsulfonate was added.
(0.25 mol) and 500 ml of dimethylformamide were charged, and the temperature was raised to 70 ° C. with stirring under a nitrogen atmosphere. At this temperature, 50 g (0.29 mol) of phenoxyacetyl chloride was added dropwise. After stirring for 3 hours at the same temperature,
The pressure was reduced to Torr, and excess phenoxyacetyl chloride and dimethylformamide were distilled off to obtain a slurry mixture. This mixture was mixed with 1000 ml of acetone to precipitate a white precipitate. A white precipitate was separated by filtration and washed three times with 500 ml of acetone to obtain 62 g of p-sulfophenylphenoxyacetic acid ester sodium salt (VI). The results of ¹³ C-NMR analysis are shown below.

[0069]

[Chemical 19]

[0070] Example 6 Sulfonate (I) of each of the present invention obtained in Examples 1 to 5
To (V), or tetraacetylethylenediamine conventionally used as an organic peracid precursor, or 10% by weight of p-sulfophenylphenoxyacetic acid ester sodium salt (VI) obtained in Comparative Example, and 3% by weight of hydrogen peroxide. % Bleaching agent aqueous solution (effective oxygen concentration of about 1.41%) was prepared and subjected to the mold bleaching power test and odor test by the following methods. The results are shown in Table 1.

<Mold bleaching test> Cladosporium herbarum was inoculated at 30 ° C, 14 ° C.
A plastic plate (made of ABS resin) that had been cultured for a day was used as a model mold plate, which was placed horizontally, and a bleach solution was added to it.
After 40 μl of the solution had been dropped, the mixture was allowed to stand for 30 minutes, washed with water and air-dried, and then the lightness (L value) was measured using a colorimeter 1001DP manufactured by NEC Corporation. The L value of the plastic plate was 92.4, and the L value of the model mold plate was 65 to 75. The higher the value, the better the bleaching power against mold.

<Odor Test> The odor of the aqueous bleach solution solution was sensory-evaluated by 10 panelists according to the following criteria. ◯: No irritating odor or offensive odor ×: Irritating or offensive odor

[0073]

[Table 1]

Example 7 A fungicide composition having the composition shown in Table 2 was prepared, and Example 6 was prepared.
The bleaching power and odor of fungi were evaluated in the same manner as in. The results are shown in Table 2.

[0075]

[Table 2]

[0076] Note) * 1 AS: alkyl (C ₁₂ ~C ₁₄₎ sulfuric acid soda * 2 di Quest 2010: Monsanto Co., Ltd. of 1-hydroxy-1,1-diphosphonic acid [Results] comparative product No.10 smell It is not good and cannot be used. Further, the organic peracid precursor (VI) used in Comparative Product No. 11 had a leaving group of sodium phenolsulfonate, and the bleaching performance was not good. The products Nos. 1 to 9 of the present invention have excellent bleaching performance without irritating odor, and moreover, the bleaching power has good sustainability. Further, the products of the present invention Nos. 5 to 9 containing a surfactant have an improved bleaching effect because the penetration power to stains is improved.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location D06L 3/00 7199-3B 3/02 7199-3B (72) Inventor Yumoto Politics 4954 Hanawa-cho, Haga-gun, Tochigi Prefecture Kao Castle Dormitory D-311 (72) Inventor Kozo Ohira 2-4-39 Tenjin Utsunomiya City, Tochigi Prefecture Wing States 1003

Claims (6)

[Claims] 1. A sulfonate represented by the following general formula (1): [Chemical 1] [In the formula, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 10 or less carbon atoms, an acyl group or an alkoxy group, and R ² represents a linear or branched alkylene group having 1 to 16 carbon atoms, or the formula _{^{- (R 4) p -O-}} R 5 - ( wherein R ⁴ and R ⁵ are the same or different, represents a linear or branched alkylene group having 1 to 8 carbon atoms, p is 0 or 1 R ³ represents a straight-chain or branched-chain alkylene group having 1 to 8 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n A May be the same or different. M represents an alkali metal atom, an alkaline earth metal atom, ammonium, alkylammonium or alkanolammonium, m represents a number of 0 or 1 and n represents a number of 0 to 100. ] 2. In the general formula (1), R ¹ is a hydrogen atom or a linear or branched alkyl group having 4 or less carbon atoms, an acyl group or an alkoxy group, and R ² is a straight chain having 1 to 8 carbon atoms. chain or branched alkylene group, or the formula - (R ⁴⁾ _p -O-
R ⁵ − (wherein R ⁴ and R ⁵ are the same or different and have 1 to
4 represents a linear or branched alkylene group, and p is 0
Or a group represented by 1), M is an alkali metal atom, and n is a number from 0 to 20. 3. The following general formula (2): [In the formula, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 10 or less carbon atoms, an acyl group or an alkoxy group, and R ² represents a linear or branched alkylene group having 1 to 16 carbon atoms, or the formula _{^{- (R 4) p -O-}} R 5 - ( wherein R ⁴ and R ⁵ are the same or different, represents a linear or branched alkylene group having 1 to 8 carbon atoms, p is 0 or 1 Represents the number of), m is 0 or 1, Y is a hydroxy group,
A halogen atom or an alkoxy group having 1 to 3 carbon atoms is shown. Aromatic carbonyl compounds represented by] the following general formula _{(3) HO- (AO) n} -R 3 -SO 3 M (3) wherein, R ³ is a straight-chain or branched having 1 to 8 carbon atoms Represents an alkylene group in a chain, A represents an alkylene group having 2 to 4 carbon atoms, and n A's may be the same or different. M is an alkali metal atom, an alkaline earth metal atom, ammonium,
It represents alkylammonium or alkanolammonium, and n represents a number from 0 to 100. ] The compound represented by these is reacted, The manufacturing method of the sulfonate of Claim 1 characterized by the above-mentioned. 4. The following general formula (4): [In the formula, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 10 or less carbon atoms, an acyl group or an alkoxy group, and R ⁴ represents a linear or branched alkylene group having 1 to 8 carbon atoms. In the formula, M ′ represents an alkali metal atom, and p represents a number of 0 or 1. ] To the aromatic alcoholate or phenolate represented by the following general formula (5) [In the formula, R ³ represents a linear or branched alkylene group having 1 to 8 carbon atoms, R ⁵ represents a linear or branched alkylene group having 1 to 8 carbon atoms, and A represents 2 to 2 carbon atoms. 4 alkylene groups are shown, and n A's may be the same or different.
X represents a halogen atom, M represents an alkali metal atom, an alkaline earth metal atom, ammonium, an alkylammonium or an alkanolammonium, and n is 0 to 100.
Indicates the number of. ] The manufacturing method of the sulfonate represented by following General formula (1 ') characterized by reacting the halide represented by this. [Chemical 5] (In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , A, M, n and p have the same meanings as described above.) 5. A fungicide composition containing the following components (A) and (B) as essential components. (A) Hydrogen peroxide or a peroxide that produces hydrogen peroxide in an aqueous solution 0.1 to 98% by weight (B) Organic peracid precursor represented by the following general formula (I) 0.002 to 50% by weight 6] [In the formula, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 10 or less carbon atoms, an acyl group or an alkoxy group, and R ² represents a linear or branched alkylene group having 1 to 16 carbon atoms, or the formula _{^{- (R 4) p -O-}} R 5 - ( wherein R ⁴ and R ⁵ are the same or different, represents a linear or branched alkylene group having 1 to 8 carbon atoms, p is 0 or 1 R ³ represents a straight-chain or branched-chain alkylene group having 1 to 8 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n A May be the same or different. M represents an alkali metal atom, an alkaline earth metal atom, ammonium, alkylammonium or alkanolammonium, m represents a number of 0 or 1 and n represents a number of 0 to 100. ] 6. A composition further comprising (C) a surfactant and (D) water, wherein the weight ratio of the (C) component to the total amount of the (A) component and the (B) component is [(A) + ( B)] / (C) = 99.9
The mold-removing agent composition according to claim 5, which has a ratio of /0.1 to 50/50.