WO2005111183A1 - METHOD FOR PRODUCING ANIONIC SURFACTANT CONTAINING α-SULFOFATTY ACID ALKYL ESTER, ANIONIC SURFACTANT AND DETERGENT COMPOSITION CONTAINING SAME - Google Patents

Abstract

Disclosed is a method for producing an α-sulfofatty acid alkyl ester comprising a step for obtaining a sulfonated product by sulfonating a fatty acid alkyl ester, an aromatic compound adding step wherein an aromatic compound is added to the sulfonated product, and an esterification step wherein an alcohol having 2 or more carbon atoms is added thereto for having the sulfonated product react with the alcohol. The esterification step is conducted after or concurrently with the aromatic compound adding step.

Description

 Method for producing anionic surfactant containing monosulfofatty acid alkyl ester salt, anionic surfactant and detergent composition containing the same

 Technical field

 The present invention relates to a method for producing an ionic surfactant containing an α-sulfofatty acid alkyl ester salt, an anionic surfactant, and a detergent composition containing the same.

 Priority is claimed on Japanese Patent Application No. 2004-149254, filed May 19, 2004, the content of which is incorporated herein by reference.

 Background art

 [0002] Neutralized salts of sulfonated fatty acid alkyl esters are also generally referred to as ex-sulfo fatty acid alkyl ester salts, which have good hard water resistance, good biodegradability, excellent detergency, and mild skin interface. Since it is an activator, it is a natural raw material that is renewable from the viewpoint of resources and is advantageous in terms of cost. It is also regarded as important in terms of global environmental protection.

 [0003] a Sulfo fatty acid alkyl ester salt is obtained by converting a fatty acid alkyl ester with SO.

 3 After sulfonation to obtain α-sulfofatty acid alkyl ester, it is obtained by neutralization with alkali.

The sulfonation mechanism of fatty acid alkyl esters is described in Smith and Stirton: JAOCS vol.44, P.405 (1967), Schmia, Baumann, Stein, Dolhaine: Proceeding of the world surfactants congrees Munchen, vol.2, P.105, Gelnhausen , Kurle (1984), and H. Yoshimura: Oil Chemistry (JJOCS), vol. 41, p. 10 (1992), illustrated by the following reaction scheme. [0004] [Formula 1] o

Ri_CH ₂ -C-0-R ² (fatty acid alkyl ester)

i so ₃

 o

 II

_{^{R 1 - CH 2 - CO- S0}} 2 - O- Ft 2 (SO - molecular adduct)

I so ₃

 o

 II

R - CH - C - O - S0 2 - O - R 2 (S0 3 bimolecular adduct)

S0 ₃ H

-S0 ₃

 o

 II

Ri-CH-COR ² (a-sulfo fatty acid alkyl ester)

S0 ₃ H

(Wherein R ¹ and R ² represent alkyl groups) [0005] That is, SO is first inserted into the alkoxy group portion of the ester, and the SO molecule

 3 3

 (Hereinafter referred to as “one-molecule adduct”). Next, SO

 3 introduced S

O bimolecular adducts (hereinafter referred to as “bimolecular adducts”) are produced.

 Three

 Finally, the SO inserted into the alkoxy group is eliminated, and the α-sulfofatty acid is removed.

 Three

 An alkyl ester is formed.

 In this reaction scheme, the reaction proceeds rapidly up to the step of producing the bimolecular adduct, but the reaction rate is very slow in the step of producing the α-sulfofatty acid alkyl ester from the bimolecular adduct.

 For this reason, in practice, excessive use of sulfone gas such as SO gas,

 Three

 After the reaction has progressed to the adduct formation stage, an aging step is provided to promote SO desorption.

 Three

 Is often done.

 Then, by neutralizing with an alkali after the aging step, a-sulfofatty acid alkyl ester salt is produced.

[0006] However, a odor may be a problem in the case of a detergent composition using an a-one surfactant containing a sulfo fatty acid alkyl ester salt as a main component. Therefore, the following means for reducing odor have been proposed.

[0007] For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 62-43499) discloses a detergent composition containing an oc-sulfofatty acid alkyl ester salt, zeolite, and formic acid or a salt thereof. I have.

 Patent Literature 2 (Japanese Patent Application Laid-Open No. 7-97080) discloses a washing method in which an oc-sulfofatty acid alkyl ester salt, a carbonate or bicarbonate, zeolite, acetic acid, and oxalic acid or a salt thereof are mixed. An agent composition is disclosed.

 Patent Document 3 (Japanese Patent Application Laid-Open No. 7-97081) discloses a detergent composition containing an oc-sulfofatty acid alkyl ester salt, wherein the Fe content is set to 200 ppm or less. Is disclosed.

 However, the methods of Patent Documents 1 to 3 cannot sufficiently reduce the odor.

[0008] On the other hand, the a-one surfactant containing the ex sulfo fatty acid alkyl ester salt thus obtained as a main component includes α-sulfofatty acid di-salt having the following structure (hereinafter referred to as “di-sulfo fatty acid di-salt”). "Salt" may be abbreviated).

[0009] [Formula 2]

0

 II

R ¹ -CH-C-0-Na

S0 ₃ Na

 (Nasul tree fatty acid disalt)

[0010] Since the α-sulfofatty acid disalt is hardly soluble in water and has poor surface activity, if the detergent contains a large amount thereof, there is a drawback that the washing power is reduced. .

 a Sulfofatty acid disalt is formed by neutralizing α-sulfofatty acid alkylsulfoester, and α-sulfofatty acid alkylsulfoester is inevitably formed when sulfonated fatty acid alkyl ester is used. Things.

[0011] Therefore, the following method has been proposed as a method for removing or reducing α-sulfofatty acid alkyl sulfester generated by sulfonation after sulfonation. [0012] That is, sulfonated, and添Ka卩alkyl alcohol sulfonation mixture before the neutralization step after the aging, alpha - transesterification between sulfo fatty acid alkyl sulfonate esters and alkyl alcohol, _alpha -A method of converting a sulfo fatty acid alkyl sulfo ester to an _α -sulfo fatty acid alkyl ester [for example, Patent Document 4 (JP-A-5-58428) and Patent Document 5 (JP-A-7-247259)].

 Examples of the alkyl alcohol used for transesterification include a short-chain alkyl alcohol having about 1 to 6 carbon atoms.

 [0013] When transesterification is performed, unreacted lower alcohol added to transesterification or lower alkyl sulfate by-produced by transesterification remains in the obtained reaction product. In order to reduce the odor by removing the lower alcohol and the lower alkyl sulfate, Patent Document 5 discloses that the reaction solution after the sulfonation is applied to the lower alcohol or the lower alkyl sulfate by using a device such as a thin film evaporator. The step of removing is indispensable. Therefore, there is a problem that this process complicates the process and requires additional equipment.

 Although not from the viewpoint of odor reduction, there are the following proposals for the reduction of alkyl sulfate.

 In Patent Document 6 (Japanese Patent Application Laid-Open No. 58-157762), the reaction solution after the sulfonation reaction is aged under reduced pressure to remove excess SO, and thereby the alkyl product as a by-product is removed.

 Three

 Methods for suppressing the formation of sulfate and sulfate are described.

 In Patent Document 7 (JP-A-59-25368), when an a-sulfofatty acid ester is bleached using a bleaching agent in the presence of a lower alcohol, an alkyl sulfate is formed, and the a-sulfofatty acid alkyl ester salt is produced. It is described that the hygroscopicity of an a-one surfactant containing is reduced. To solve the problem, surplus SO is removed by adding alkylbenzene to the a-sulfo fatty acid ester prior to the bleaching process.

 3 It is described that the removal can reduce the by-product of alkyl sulfate.

 Patent Document 1: JP-A-62-43499

 Patent Document 2: JP-A-07- 197080

Patent Document 3: JP-A-07-97081 Patent Document 4: JP-A-5-58428

 Patent Document 5: JP-A-07-247259

 Patent Document 6: JP-A-58-157762

 Patent Document 7: JP-A-59-25368

 Disclosure of the invention

 Problems to be solved by the invention

[0015] Meanwhile, according to the study of the present inventors, it has been found that an a-surfactant containing an a-sulfofatty acid alkyl ester salt as a main component obtained by the methods of Patent Documents 5 to 7 is stored for a long time. However, odor degradation may be large especially at high temperatures of about 60 to 80 ° C.

 The odor stability under the temperature condition of about 60 to 80 ° C is required from the following viewpoints. That is, the temperature condition is a condition under which the OC sulfo fatty acid alkyl ester salt can be handled as a paste containing water. In addition, the surface conditions of overseas transportation and storage conditions must be considered, unless sufficient care is taken.

[0016] Therefore, it is possible to provide an a-on surfactant containing an α-sulfofatty acid alkyl ester salt which has improved odor, good long-term storage stability, and hardly causes odor deterioration even under high-temperature storage conditions. Desired.

[0017] The present invention has been made in view of the above circumstances, and has an improved odor, good long-term storage stability, and is particularly resistant to odor deterioration even under high-temperature storage conditions. An object of the present invention is to provide an anionic surfactant containing a salt and a detergent composition containing the same.

 Means for solving the problem

In order to solve the above problems, the present invention provides the following means.

 In the first invention, a 50 to 95% by mass of a sulfo fatty acid alkyl ester salt, 3% by mass or less of methyl sulfate, 0.5 to 8% by mass of an alkyl sulfate having 2 or more carbon atoms, and an aromatic sulfonide salt 0.1 -20% by mass.

The second invention comprises a step of sulfonating the fatty acid alkyl ester to obtain a sulfonated product, an aromatic compound adding step of adding an aromatic compound to the sulfonated product, A method for producing a surfactant comprising a step of adding an alcohol having 2 or more carbon atoms to the sulfonated product and reacting the alcohol with the alcohol after or simultaneously with the compound-added kneading process. It is.

 According to a third aspect of the present invention, in the method for producing an a-one surfactant according to the second aspect, the amount of the aromatic compound is 0.5 to 20 parts by mass with respect to 100 parts by mass of the sulfonide. A method for producing an ionic surfactant, characterized in that the amount of alcohol added with several or more alcohols is 1 to 15 parts by mass with respect to 100 parts by mass of a sulfonated product.

 A fourth invention is an anion surfactant obtained by the method for producing an aion surfactant of the second or third invention.

 A fifth aspect of the present invention is a cleaning composition comprising the auronic surfactant of the first or fourth aspect.

 In the present invention, the term “a-one surfactant” refers to an alkyl sulfate or an aromatic sulfonide formed mainly in an a-sulfofatty acid alkyl ester salt as an activator component, for example, in other production processes. A composition containing a salt or the like. The invention's effect

 In the present invention, an anionic surfactant containing an α-sulfofatty acid alkyl ester salt, which has an improved odor, good long-term storage stability, and hardly causes odor deterioration even under high-temperature storage conditions, and A detergent composition comprising: BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, for convenience, a method for producing an a-on surfactant, an a-on surfactant, and a detergent composition will be described in this order.

 [Method for producing anionic surfactant]

 The process for producing an a-surfactant containing a sulfo fatty acid alkyl ester salt of the present invention comprises the steps of sulfonating a fatty acid alkyl ester to obtain a sulfonated product, and adding an aromatic compound to the sulfonated product. An aromatic compound-adding step, and after or simultaneously with the aromatic compound-added kneading step, adding an alcohol having 2 or more carbon atoms to the sulfonated product, and reacting with the alcohol. I do.

[0021] As a result, a sulfo fatty acid alkyl ester salt and an alkyl An aeon surfactant containing a fate or an aromatic sulfonide salt is obtained. Then, even when the raw material is, for example, a fatty acid alkyl ester or a methyl ester, methyl sulfate is significantly reduced.

 In the production method of the present invention, preferably, the following steps (A) to (D) are sequentially performed to obtain an a-surfactant containing an a-sulfo fatty acid alkyl ester salt.

 (A) a sulfonation step of sulfonating a fatty acid alkyl ester to obtain a sulfonate; (B) an aromatic compound addition step of adding an aromatic compound to the sulfonide and heating to ripen it; and (C) an alkyl having 2 or more carbon atoms in the sulfonate. Esterification step of esterification with alcohol (D) Neutralization step of obtaining α-sulfo fatty acid alkyl ester salt from α-sulfo fatty acid alkyl ester by neutralization with alkali

 In the step (工程), the sulfonation reaction may be performed by bringing the raw material fatty acid alkyl ester into contact with at least a substance that promotes sulfonation, such as a sulfonated gas.

 Then, in the production method of the present invention, it is particularly preferable to carry out the (Α ') aging step after obtaining the sulfonated product by the sulfonated reaction.

 (Α) When the sulfonidation process is performed, a sulfonated product generally containing a one-molecule adduct and a bimolecular adduct is obtained. However, when the (Α ′) aging process is performed, the by-produced bimolecular adduct power is also reduced to SO. Detached

 By doing so, the purity of the α-sulfofatty acid alkyl ester can be increased.

 (Α ′) The aging step can be inserted between (1) the above-mentioned steps (Α) and (Β); and (2) between the steps (Β) and (C).

 Among them, from the viewpoint of suppressing by-products and odor, preferably, (1) the above (Α) step,

(Β) process.

 [0024] The order of the (Β) aromatic addition step and the (C) esterification step may be the same, but the step (C) may be carried out after the step (Β). It is preferable from the viewpoint of adjusting the amount of alkyl sulfate having 2 or more carbon atoms.

Hereinafter, each step will be described in detail.

 (Α) Sulfonidation process, (Α ') Aging process

(Ii) In the sulfonation step, the sulfonation reaction is carried out by bringing the fatty acid alkyl ester as a raw material into contact with at least a substance that promotes sulfonation such as a sulfonation gas. It is particularly preferable that after the sulfonated product (reaction liquid containing α-sulfofatty acid ester as a main component) obtained by the sulfonidation reaction, a (Α ′) aging step is performed. The term “sulfonated compound” as used herein refers to the entire reaction solution after the sulfonation reaction.

 In this example, the case where the step (Α) and the step (Α ′) are performed continuously will be described.

[0026] In the sulfonation reaction step, a substance that promotes sulfonation is preferably a sulfonated gas.

 Examples of the sulfonide gas include SO gas and fuming sulfuric acid.

 3 3 gas is used.

 SO gas is usually a concentration of 1-40% by volume of dehumidified air or an inert gas such as nitrogen.

Three

 Used after dilution. If it is less than 1% by volume, the volume of the sulfonated gas becomes large, and the capacity of the device becomes large, which is inconvenient. If it exceeds 40% by volume, the reaction becomes excessive, and by-products are easily formed, and the color tone may deteriorate.

 In particular, in order to suppress color tone deterioration, it is preferable to dilute to 1 to 30% by volume. SO is

 3 It is used in a ratio of 1.0 to 2.0 moles, preferably 1.1 to 1.5 moles, with respect to 1.0 mole of the fatty acid alkyl ester to be sulfonated. If the molar ratio is less than 1.0, the sulfonation reaction does not proceed sufficiently, and if the molar ratio exceeds 2.0, the sulfonation reaction becomes more intense and the coloring due to local heat becomes remarkable, resulting in a light-colored product. May not be desirable in terms of obtaining

 [0027] The fatty acid alkyl ester is typically a compound represented by the following general formula (I).

[0028] R'CH COOR ² ··· (I) (wherein, R ¹ is a linear or branched alkyl group having 6 to 24 carbon atoms or

 2

Represents an alkenyl group, and R ² represents a linear or branched alkyl group having 1 to 6 carbon atoms. In general, fatty acid methyl esters are often used.

[0029] The fatty acid alkyl ester is preferably a saturated fatty acid alkyl ester.

Examples of the saturated fatty acid alkyl esters include animal fats and oils derived from power such as beef tallow and fish oil lanolin; vegetable fats and oils derived from coconut oil, palm oil, soybean oil, etc .; There is no particular limitation on the deviation of the synthetic fatty acid alkyl ester or the like that can be induced.

 Specifically, methyl, ethyl or propyl laurate; methyl, ethyl or propyl myristate; methyl, ethyl or propyl palmitate; methyl, ethyl or propyl stearate; methyl, ethyl or propyl hardened tallow fatty acid; Methyl, ethyl or propyl; coconut oil fatty acid methyl, ethyl or propyl; palm oil fatty acid methyl, ethyl or propyl; palm kernel oil fatty acid methyl, ethyl or propyl.

 These can be used alone or in combination of two or more.

 The iodine value is preferably 0.5 or less, more preferably 0.1 or less.

[0030] In the (A) sulfonidation step, the reaction temperature may be a temperature at which the fatty acid alkyl ester has fluidity.

 In general, the temperature range is not less than the melting point of the fatty acid alkyl ester and is 100 ° C higher than the melting point, and preferably the temperature range is not less than the melting point and 70 ° C higher than the melting point.

The sulfonation method may be any one of a thin film type sulfonation method, a batch type sulfonation method and the like. As the sulfonation reaction method, a tank-type reaction, a film reaction, a tube-type gas-liquid multiphase reaction and the like are used.

[0032] (A) The reaction time of the sulfonidation step varies depending on the sulfonidation method employed, but is generally about 5 to 120 seconds for the thin film type sulfonation method and about 10 to 240 minutes for the batch type sulfonation method. .

 [0033] The (A) sulfonation step is preferably performed in the presence of a coloring inhibitor.

 As the coloring inhibitor, various agents that have been proposed in the past can be used. For details of effective coloring inhibitors, refer to Japanese Patent Application Nos. 08-024433, 08-3360, 08-340149, 08-340148, 08-340147 and 08-340147. It is disclosed in Japanese Patent Application No. 08-342244, Japanese Patent Application Laid-Open No. 09-216861, Japanese Patent Application Laid-Open No. 09-216862, Japanese Patent Application Laid-Open No. 09-216863, and the like.

Among these, it is preferable to use an inorganic sulfate having a monovalent metal ion described in JP-A-09-216863 and having an average particle size of 250 / zm or less. Inorganic sulfate wears Many are inexpensive and have high color suppression effects, and are components to be added to detergents, so there is no need to remove them from _α- sulfo fatty acid alkyl ester salts.

 [0034] The inorganic sulfate is not particularly limited as long as it is a powdered anhydrous salt having a monovalent metal ion, and examples thereof include sodium sulfate, potassium sulfate, and lithium sulfate.

 As the inorganic sulfate, those having an average particle size of 250 μm or less, preferably 50 μm or less are used. During the reaction, the inorganic sulfate hardly dissolves in the reaction solution to the extent that its surface is slightly dissolved, and is dispersed in the reaction solution.

 Therefore, by using such an inorganic sulfate having a small particle size, the dispersibility can be improved with a large contact area, and the effect can be further enhanced.

 The coloring inhibitors can be used alone or in combination of two or more.

 The addition amount of the coloring inhibitor is 0.1 to 20% by mass, and preferably 2 to 10% by mass, based on the fatty acid alkyl ester as the raw material. If the amount is less than 0.1% by mass, the effect of addition may not be obtained.

 Next, after the (A) sulfonidation step is completed, (Α ′) aging step is performed.

 (Α ') The temperature of the aging step is 70 ~: LOO ° C is appropriate. If the temperature is lower than 70 ° C, the elimination reaction does not proceed rapidly. If the temperature is higher than 100 ° C, coloring may be remarkable. The time required for the aging step is usually in the range of 1 to 120 minutes.

(B) Step of adding aromatic compound

 The step (B) of adding an aromatic compound is a step of adding an aromatic compound to the sulfonide obtained at least through the step (A).

 When the aromatic compound is added, the excess SO I aromatic compound remaining in the sulfonated product

 Three

 Reacts with the product and turns it into an aromatic sulfonid. As a result, surplus SO amount is reduced

 3 You can.

 As a result, in the subsequent steps, for example, methanol present in the system reacts with so

 Therefore, it can be assumed that the formation of by-products such as methyl sulfate can be suppressed, which contributes to the reduction of odor.

In the present invention, the esterification step using methanol is not performed, but when fatty acid methyl ester is used as a raw material, a very small amount of methanol may be left in the system. May exist. Even in such a case, by performing the step (B), the excess SO can be reduced after the (A) sulfonation reaction step, and the production of methyl sulfate can be suppressed.

 Three

 In addition, the aromatic sulfonide has a low SO content and a low methyl sulfate content.

 Three

 It is presumed that, together with the alkyl sulfate having 2 or more carbon atoms described below, the odor masking action is also exerted.

[0037] In the present invention, the aromatic compound means an aromatic compound that causes a sulfonation reaction, that is, an aromatic compound having an aromatic cyclic structure such as a benzene ring, a naphthalene ring, and an anthracene ring. There is no particular limitation. Preferably, at least one alkyl group is bonded to the aromatic ring.

 The alkyl group may be linear or branched and has 1 to 24, preferably 3 to 16 carbon atoms.

 [0038] Among them, those having one or two or more benzene rings are preferable, and those having one benzene ring are particularly preferable.

 Preferably, the aromatic compound is represented by the following general formula (Π).

[0039] [Formula 3]

In the formula, R to R represent H or a linear or branched alkyl group having 1 to 24 carbon atoms.

 1 6

 In the compound represented by the general formula (Π), preferably, R to R are H, and R is 1 to 2 carbon atoms.

 1 5 6

 4 (preferably 3 to 16) linear or branched alkyl groups.

[0040] Specific preferred examples include tamen and linear alkylbenzene.

 One or more aromatic compounds can be used.

 In addition, a disulfide compound (an aromatic sulfonide salt) obtained by neutralizing a sulfonated aromatic compound is used as a surfactant in a detergent composition such as a linear alkylbenzene sulfonate. Used! / It is intended to be used for cleaning effect!

[0041] The amount of the aromatic compound added is 0.5 to 20 parts by mass based on 100 parts by mass of the sulfonide. It is preferably 0.7 to 15 parts by mass, and more preferably 1 to LO parts by mass. If the amount is less than 0.5 part by mass, a sufficient effect cannot be obtained, and if it exceeds 20 parts by mass, a large amount of the aromatic compound remains unreacted and may not be preferable.

 Here, 100 parts by mass of the sulfonide is based on 100 parts by mass of the reaction solution immediately after the sulfonation reaction.

 [0042] In the step (B), after the addition of the aromatic compound, the reaction is carried out by heating to a predetermined temperature.

 The reaction temperature is preferably 40 to 90 ° C! / ,.

 If the temperature is less than 0 ° C, a mixture containing sulfofatty acid alkyl ester solidifies, making it difficult to handle.On the other hand, if the temperature exceeds 90 ° C, color deterioration may be promoted, which may be undesirable. is there.

 The reaction time holds the time required for the aromatic compound to react sufficiently with the excess SO.

 Three

 It is preferable that the time is about 1 to 120 minutes. If the time is less than 1 minute, the added aromatic compound may not sufficiently react with excess SO in the system, and the effect may not be obtained. 1

 Three

 If the time exceeds 20 minutes, the effect is saturated and the color tone is deteriorated, which is not preferable in some cases.

(C) Esterification step

 Next, an esterification step is performed.

 By performing the esterification process, by-products such as a bimolecular adduct can be suppressed, and the purity of the α-sulfofatty acid alkyl ester salt can be improved.

 By using an alcohol having 2 or more carbon atoms, the effect of the above-mentioned step is improved.

 This is because the generation of methyl sulfate in the esterification process can be reduced! In addition to the effect, the alkyl sulfate having 2 or more carbon atoms synergizes with the aromatic sulfonide to exert a masking effect, and Is assumed.

[0044] In the alkyl alcohol having 2 or more carbon atoms, the alkyl group may be either linear or branched. Preferably, it is an alcohol having 2 to 4 carbon atoms. Particularly preferred are ethyl alcohol and isopropyl alcohol. The alkyl alcohol having 2 or more carbon atoms can be used alone or in combination of two or more.

 The added amount of the alkyl alcohol having 2 or more carbon atoms is preferably 1 to 15 parts by mass, more preferably 1.5 to 10 parts by mass, and particularly preferably 2 to 6 parts by mass based on 100 parts by mass of the sulfonated product. Here, “100 parts by mass of the sulfonated product” is the same as the standard for the amount of the aromatic compound added in the above step (B).

 The reaction temperature is 50 to 100 ° C, preferably 50 to 90 ° C, and the reaction time is 5 to 120 minutes. The esterification step does not include the bleaching step performed in the presence of alcohol, and is distinguished therefrom.

(D) Neutralization step

 In the neutralization step, for example, an aqueous solution of an alkali metal, an alkaline earth metal, ammonia, or ethanolamine is used as the alkali. As a result, a paste of an ionic surfactant containing a monosulfo fatty acid alkyl ester salt is obtained.

 Here, the aromatic sulfonidious compound obtained in the step (B) is also neutralized here to obtain an aromatic sulfonidious salt.

In the neutralization step, the α-sulfofatty acid alkyl ester salt is strongly alkaline and may easily break the ester bond. Therefore, ρΗ of the neutralized solution of the sulfonide and the alkali is acidic or acidic. It is preferable to adjust to a weak alkaline range (ρΗ4-9, more preferably ρΗ5-8).

 More preferably, in order to avoid cleavage of the ester bond under alkaline conditions, after premixing the neutralized product obtained in advance and the reaction product before neutralization, neutralization with an alkali from the acidic side produces by-products of disalts. Can be suppressed.

 The concentration of the aqueous alkali solution is 2 to 50% by mass, the neutralization temperature is 30 to 140 ° C, and the neutralization time is 10 to 60 minutes.

 [0047] The (D) neutralization step can also be performed by reacting with a solid carbonate or bicarbonate.

In particular, neutralization with solid carbonate (rich soda ash) is cheaper than other bases and is preferred. In addition, when neutralization is performed with solid carbonate, the water content in the reaction mixture decreases, It does not become Lucari. Further, since the heat of neutralization at the time of neutralization is lower than that of the metal hydroxide, it is advantageous.

 Examples of the carbonate or bicarbonate include sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, etc. A mixture or the like can be used.

[0048] Other steps

 If necessary, before or after the (D) neutralization step, a treatment for improving the color tone to a color closer to white can be performed.

 The treatment for improving color tone includes, for example, a bleaching treatment using a bleaching agent such as hydrogen peroxide, and is preferably performed after the neutralization step.

 Then, if necessary, it is formed into a flake, noodle, powder, particle, or the like from the aeon surfactant paste by an ordinary method, if necessary.

[0049] As described above, in the method for producing an aeon surfactant of the present invention, the synergistic effect of (B) the step of adding an aromatic compound, and (C) the step of esterification with an alcohol having 2 or more carbon atoms. Thus, it is possible to provide an a-on surfactant containing an α-sulfofatty acid alkyl ester salt which has improved odor, good long-term storage stability, and hardly causes odor deterioration even under high-temperature storage conditions. . The same effect can be obtained in a detergent composition using the same.

 In addition, since the bimolecular adduct can be reduced by performing (C) the esterification step, and can be produced without performing the operation of removing the alkyl sulfate, the reduction of the bimolecular adduct and the reduction of the odor can be achieved. It is possible to provide a technology that can be realized by a simple process and a simple apparatus.

The major feature of the production method of the present invention is that, by performing both (Β) an aromatic compound addition step and (C) an esterification step produced by using an alcohol having 2 or more carbon atoms, the above-mentioned Patent Document As described in 5, conventional sulphate is believed to be the cause of odor, and even in the case of alkyl sulphate, it should be removed in an amount as small as possible in terms of odor reduction. In the case of alkyl sulfates having 2 or more carbon atoms, the odor is not deteriorated even if it is present in the product. Long term stability (especially long term stability under high temperature storage) ) Has been found to be preferable.

 Although the mechanism of this action is not clear, in the production method of the present invention, for example, even when fatty acid methyl ester is used as a raw material, an aromatic sulfonide salt having a relatively small content of methyl sulfate and a C 2 -C 2 As described above, since an ionic surfactant containing an alkyl sulfate can be obtained, it is possible to suppress the generation of a substance causing an odor component due to methyl sulfate, which is generated by long-term storage at a high temperature, and to reduce aromatic sulfonide salt and carbon. It is presumed that the odor masking is not synergistic with the alkyl sulfate in synergy with the number 2 or more!

 [A-Surfactant Containing a Sulfofatty Acid Alkyl Ester Salt] First Embodiment The first embodiment is that a-sulfofatty acid alkyl ester salt is 50 to 95% by mass, methyl sulfate is 3% by mass or less, carbon number An ionic surfactant comprising 0.5 to 8% by mass of two or more alkyl sulfates and 0.1 to 20% by mass of an aromatic sulfonide salt.

 With this configuration, an aeon surfactant having an improved odor can be obtained. In addition, the effect that the long-term storage stability is good and the odor deterioration hardly occurs even under high-temperature storage conditions can be obtained.

[0052] 50 to 95 mass content of a-sulfofatty acid alkyl ester salt _^0/0, preferably by a 60-70 wt%, § - favorable characteristics as an on surfactant paste obtained, et al are also 80 When the content is set to 95% by mass, favorable characteristics as a powdered a-on surfactant can be obtained.

 By reducing the content of methyl sulfate to 3% by mass or less, preferably 2% by mass or less, the effect of improving odor can be enhanced. Since less methyl sulfate is preferred, there is no technical significance in defining the lower limit. However, in the present invention, the effect is obtained even if methyl sulfate is present, for example, 3% by mass or more. be able to. For example, when a methyl ester is used as a fatty acid alkyl ester as a raw material, an effect can be obtained even in the case of a force that naturally produces methyl sulfate.

[0053] The content of the alkyl sulfate having 2 or more carbon atoms is 0.5 to 8% by mass, preferably 1 to 8% by mass.

By adjusting the content to 5% by mass, the effect of improving odor can be enhanced. Also, long-term storage It has good qualitative properties and has an effect that odor deterioration hardly occurs particularly under high-temperature storage conditions. A sufficient effect can be obtained by setting the lower limit or more. If it exceeds the upper limit, the physical properties of the ionic surfactant may not be favorable.

 By setting the content of the aromatic sulfonate salt to 0.1 to 20% by mass, preferably 0.5 to 15% by mass, the effect of improving odor can be enhanced. In addition, long-term storage stability is good, and odor deterioration hardly occurs even under high-temperature storage conditions! A sufficient effect can be obtained by setting the lower limit or more. If the value exceeds the upper limit, the effect may not be obtained any more.

[0054] The method for producing such a surfactant surfactant is not particularly limited. For example, an operation of reducing methyl sulfate for a reaction product containing a large amount of an α-sulfofatty acid alkyl ester salt, an aromatic sulfonate, or the like. It can be obtained by adjusting the composition by performing an operation of adding a dandelion salt or an alkyl sulfate having 2 or more carbon atoms or the like, but it is convenient to produce it by the production method of the present invention.

 Then, the content of the aromatic sulfonide salt can be changed by adjusting the reaction conditions in the step (ii) in the production method of the present invention.

 The content of the alkyl sulfate having 2 or more carbon atoms can be changed by adjusting the reaction conditions in the step (C) in the production method of the present invention.

 Further, the content of methyl sulfate can be adjusted by not performing the transesterification reaction using methanol.

[0055] In the present embodiment, with respect to the α-sulfofatty acid alkyl ester salt, the alkyl sulfate having 2 or more carbon atoms, and the aromatic sulfonate salt, the preferred embodiments are the preferred raw materials and the additives described in the above-mentioned production method of the present invention. This is the same as that obtained by using an agent.

 [0056] Second form

 A second embodiment is an iron surfactant obtained by the method for producing an iron surfactant of the present invention. In this embodiment, the same effect as in the first embodiment can be obtained.

Also in the second embodiment, the effect can be further improved if the conditions for the amounts of the components of the first embodiment are satisfied. [0057] [Cleaning composition]

 The ar-one surfactant containing the sulfosulfo fatty acid alkyl ester salt of the present invention can be made into a detergent composition by a conventional method. The detergent composition is suitable for clothing and the like.

 The detergent composition may contain ordinary detergent components such as a chelate builder, an alkali agent, a re-staining inhibitor, a bleaching agent, a fluorescent agent, an enzyme, and other surfactants.

 Examples of materials that can be blended include the following. Needless to say, detergent-use components other than those exemplified below can be used as needed.

[0058] Surfactant 'a-ionic surfactant: a straight-chain alkylbenzene sulfonate having an alkyl group having an average of 10 to 16 carbon atoms, a linear or branched alkyl group having an average of 10 to 20 carbon atoms. Alkyl ethoxy sulphate with an average of 0.5 to 10 moles of ethylene oxide added per molecule, alkyl sulphate with an alkyl group with an average of 10 to 20 carbon atoms, and an average of 10 to 20 carbon atoms Olefin sulfonic acid salts in one molecule, fatty acid salts having an average carbon number of 10 to 20 and the like can be mentioned.

 'Nonionic surfactants: polyoxyethylene alkyl ethers having an alkyl group having an average number of carbon atoms of 10 to 20 and added with 1 to 20 moles of ethylene oxide, higher fatty acid alcohol amides or alkylene oxide adducts thereof And the like.

 • Other surfactants: include betaine-type amphoteric surfactants, sulfonic acid-type amphoteric surfactants, phosphate ester-based surfactants, and cationic surfactants.

 Here, the term “alkyl” is a concept including an alkyl containing an unsaturated bond.

[0059] Chelate vinoreda

 Chelate builders are divalent metal ion scavengers.

 Specifically, zeolites, orthophosphates, pyrophosphates, tripolyphosphates, nitrite triacetates, ethylenediaminetetraacetates, citrates, isoquates, polyacrylates, polyacetal carboxylates And the like.

[0060] Alkaline agent

 Cay salts, carbonates, sesquicarbonates and the like.

[0061] Recontamination inhibitor Examples include polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose and the like.

[0062] Additives such as bleach, optical brightener, and enzyme

 Examples of the bleaching agent include sodium percarbonate, sodium perborate, sodium sulfate, sodium chloride and sodium hydrogen peroxide.

 As the fluorescent whitening agent, a commercially available fluorescent dye can be blended.

 Examples of the enzyme include protease, cellulase, amylase, lipase and the like.

 Other additives include fragrances and the like. In addition, a bluing agent and the like can be added as necessary.

 Example

 Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

 In the examples, “%” indicates “% by mass”.

An α-sulfofatty acid alkyl ester salt-containing surfactant was prepared by the following method under the conditions shown in Tables 1 to 4, and the change in odor with time was tested by the following evaluation method.

 [Examples 1 to 9]

 The raw material fatty acid methyl ester is Endogor ME PA MY (product name, C16 [methyl ester of fatty acid having 16 carbon atoms]: C18 [methyl ester of fatty acid having 18 carbon atoms] = 45:55 [mass ratio]) manufactured by Cognis. An iodine value reduced to 0.02 by the addition treatment was used.

 The sulfonidation reaction was carried out in a tank reactor (made of SUS316L having a capacity of 200 L and equipped with a jacket cooling and stirrer) as follows.

First, 92 kg of the above-mentioned raw material fatty acid methyl ester was charged into a reaction vessel, and 5% by weight of fine powdered mirabilite as a coloring inhibitor was added to the fatty acid methyl ester while stirring well. While continuing to stir, control the reaction temperature to 80 ° C and dilute to 8% by volume with nitrogen gas. SO gas (sulfonated gas) 112m ³ (1.2 times that of raw material methyl ester) Mol) was blown at a constant speed over 1 hour with a ring sparger to carry out a sulfonidation reaction.

 The aging process was performed for 40 minutes while maintaining the temperature at 80 ° C.

Then, a predetermined amount of a linear alkyl benzene having an alkyl group having 10 to 14 carbon atoms as an aromatic compound shown in the table was added, and the mixture was stirred at 30 ° C. for 30 minutes to carry out a reaction.

 The addition amount of the aromatic compound is shown by the addition amount (parts by mass) relative to 100 parts by mass of the sulfonate.

 After the reaction, a predetermined amount of alkyl alcohol having 2 or more carbon atoms shown in the table was added, and an esterification reaction was performed at 80 ° C. for 120 minutes to produce methyl monosulfo fatty acid. The amount of alcohol added to the esterification reaction is indicated by the amount added (parts by mass) to 100 parts by mass of the sulfonated product.

 [0069] Next, the esterified reaction solution was continuously neutralized with an aqueous sodium hydroxide solution (by the neutralization method described in JP-A-2001-64248), and the pH was 5 to 7; Neutralized product with 50% to 70% by mass of alkyl ester salt was obtained. The neutralization temperature was controlled at 70 to 80 ° C, and the residence time of the neutralized product was 15 to 30 minutes.

 The neutralization method described in Japanese Patent Application Laid-Open No. 2001-64248 refers to a method in which a reaction solution before neutralization is supplied to a loop formed with a line force capable of circulating the reaction solution, and circulated. This is a method of gradually neutralizing while supplying. In the loop, the mixture of the reaction solution before neutralization and the neutralized product begins to circulate as the alkali is supplied and circulated, initially circulating the reaction solution before neutralization. Then, alkali is gradually supplied to the mixture. By such an operation, neutralization can be performed under mild conditions.

[0070] Next, this neutralized product was charged into a 200 L stirred tank equipped with a jacket, and 1 to 2% by mass of a pure content with respect to the α-sulfofatty acid alkyl ester salt was sufficiently added using 35% hydrogen peroxide solution. The mixture was added with mixing, and a bleaching reaction was carried out at a bleaching temperature of 80 ° C. and a bleaching time of 6 to 24 hours to obtain an ionic surfactant paste containing a sulfofatty acid alkyl ester salt. In Examples 1 to 8, an odor test was performed at this stage. [0071] In Example 9, after that, a sulfone fatty acid alkyl ester salt-containing a-one surfactant paste was rotated at a rotational speed of 1060 rpm and a blade tip speed of about 11 lmZsec. , Heat transfer surface: 0.5m ² , inner diameter: 205mm, clearance between heat transfer surface and blade tip: 2-4mm, introduced by Shinko Pantech Co., Ltd. at 50-90kgZhr, and inner wall heating temperature 120- Concentration was performed at 140 ° C and a degree of vacuum of 0.007 to 0.014 MPa, and the concentrated product was cooled to 20 to 30 ° C using a drum flaker (manufactured by Kusunoki Kikai Seisakusho). Fitzmill (product name, manufactured by Hosokawa Micron Co., Ltd., DKA-3 type, first stage screen diameter 8mm φ, second stage screen diameter: 3.5mm φ, blade rotation speed first stage: 4700rpm, second stage: 2820rpm) and pulverized with high concentration oc-sulfo fatty acid alkyl ester salt-containing surfactant powder Got.

 The obtained pastes of Examples 1 to 8 and the powder of Example 9 were evaluated by performing an odor test as follows.

 <Operating change test method of odor over time>

 One month after storage in a constant temperature room at 80 ° C, five panelists conducted a sensory evaluation on the odor of each sample, and evaluated it according to the following criteria.

 ◎: almost odorless

 〇: Slight odor, but practically problematic

 △: A considerable odor is felt

 X: Strong odor

[Example 10-: L 1]

 Except that cumene was used as the aromatic compound, an ionic surfactant paste containing a sulfo fatty acid alkyl ester salt was obtained in the same manner as in Examples 1 to 8, and an odor test was similarly performed. .

[Examples 12 to 13]

In Examples 12 and 13, as raw material fatty acid methyl esters, C14 (methyl ester of fatty acid having 14 carbon atoms): C16 (methyl ester of fatty acid having 16 carbon atoms) = 2: 8 (mass ratio) (lion ratio) Manufactured by Reo Chemical Co., Ltd., iodine value: 0.02; C16 (methyl ester of fatty acid having 16 carbon atoms): C18 (methyl ester of fatty acid having 18 carbon atoms) = 6: 4 (mass Ratio) An ionic surfactant containing an OC sulfo fatty acid alkyl ester salt in the same manner as in Examples 1 to 8 except that (Iodine value: 0.02, manufactured by Lion Leo Chemical Co., Ltd.) was used. And an odor test was conducted in the same manner.

[Comparative Example 1]

 An a-one surfactant paste containing a sulfo fatty acid alkyl ester salt was obtained in the same manner as in Examples 1 to 8 except that the aromatic compound was not added and methanol was used in the esterification reaction, and similarly, An odor test was performed.

[Comparative Example 2]

 Except that the esterification process was not performed, the α-sulfofatty acid alkyl ester salt was prepared in the same manner as in Examples 1 to 8 under the conditions of the aromatic compound addition process and the esterification process shown in the table. A -on surfactant paste was obtained and similarly odor tested.

[Comparative Example 3]

 After the esterification step, distilling was performed under the conditions of 50 Torr and 180 ° C. to distill off methyl sulfate, and the same procedure as in Comparative Example 1 was carried out, except that the ionic surfactant containing the a-sulfofatty acid alkyl ester salt was used. The paste was obtained, and an odor test was performed in the same manner.

[Comparative Example 4]

 Under the conditions shown in the table, except that no aromatic compound was added, an ionic surfactant paste containing an α-sulfofatty acid alkyl ester salt was obtained in the same manner as in Examples 1 to 8, and an odor was similarly obtained. The test was performed.

[0079] The experimental conditions, the composition of the resulting anionic surfactant, and the results of the odor evaluation are summarized in a table.

 In addition, components other than the main components shown in the table are disalts, sodium sulfate, fatty acid alkyl esters, alkylbenzenes or turmeric, moisture, and the like.

 “Α-SF′Na” is “α-sulfofatty acid methyl ester sodium salt”, and “LAS-NaJ” is “straight chain alkylbenzene sodium having an alkyl group having 10 to 14 carbon atoms (aromatic sulfonamide) Salt) ”.

Regarding the raw materials used, for example, “C16ZC18 = 45Z55 methyl ester” refers to a methyl ester of a fatty acid having 16 carbon atoms and a methyl ester of a fatty acid having 18 carbon atoms. Represents a mixture with a mass ratio of 45:55. Other than this, it follows this notation.

[0080] [Table 1]

 [0081] [Table 2]

[0082] [Table 3]

[Table 4]

[Examples 14 to 17, Comparative Examples 5 to 6]

 Using the surfactants containing the sodium salt of the OC-sulfo fatty acid alkyl ester sodium salt of each of Examples and Comparative Examples, a granular detergent composition was produced by the following method, and the odor change was tested. Table 5 shows the composition and evaluation results.

[0085] Activator concentration

To a paste of α-sulfofatty acid alkyl ester sodium salt-containing surfactant, a part of Noun surfactant (25% by mass based on pure a-sulfofatty acid ester sodium salt) is added and flash concentrated. Water (heating tube product name SFC-300 (heat transfer area 0.5 m ² ) manufactured by Sakuma Seisakusho Co., Ltd.) at a heating tube temperature of 130 ° C (using pressurized steam as a heating medium). Recycle flash concentration was carried out to 10% to obtain a mixed concentrate of oc sulfo fatty acid alkyl ester sodium salt and Noon surfactant.

 [0086] Spray drying

 The non-ionic surfactant and optional components except for some zeolites are dissolved or dispersed in tap water (Edogawa-ku, Tokyo), and a slurry (solid content: 60% by mass) is prepared under the following conditions. Spray drying was performed under the following spray drying conditions to obtain dried particles.

 [0087] <Slurry preparation conditions> Solid content: 60%, temperature: 60 ° C, Impurities: There is an operation of re-dissolving waste powder in water and partially adding this to the slurry. A small amount of components was mixed.

[Spray drying conditions] · Spray drying equipment: countercurrent type, tower diameter 2.0 m, effective length 5.0 m, atomization method: pressurized nozzle method, spray pressure: 30 kgZcm ² , hot air inlet temperature: 260 ° C, hot air outlet temperature: 90 ° C, discharge method: Zeolite (1.5% by mass vs. dry particles) is introduced at the bottom of the tower together with cold air And then discharged after cooling + improving flowability.

[0089] Kneading and crushing granulation

 Next, together with the obtained activator concentrate and the spray-dried particles, a non-ionic surfactant (10% by mass of water) and a small amount of tap water (Edogawa-ku, Tokyo) are continuously kneaded (KRC, manufactured by Kurimoto Iron Works, Ltd.). (S4 type) and continuously kneaded at a temperature of 50 to 65 ° C. to obtain a dough. Kneader jacket Warm or cold water or an aqueous solution of ethylene glycol was flowed so as to maintain the above-mentioned kneading temperature.

 Then, after extruding at a temperature of 45 to 60 ° C. with a pelletizer (made by Fuji Padal, die hole diameter: 10 mmφ), a pellet type solid detergent of 5 to 30 mm was formed with a rotary cutter. Next, a Fitzmill (product name, manufactured by Hosokawa Micron Corporation, DKASO-6 type) was arranged in three stages in series. , Third stage; 3 mm, 4700 rpm), the obtained solid detergent and zeolite as a grinding aid (4.3% by mass relative to the solid detergent) were introduced together with cold air at 15 ° C, and pulverized. At this time, the temperature of the ground product was 20 to 30 ° C.

 Finally, zeolite (2.0 mass% vs. crushing) was placed in a rolling drum (0.6 m in diameter, 0.48 m in length, with 4 baffles of thickness Imm x 12 cm x width 48 cm, rotation speed 20 rpm). Particles) and coat the resulting detergent particles with a non-ionic surfactant (0.5% by mass vs. crushed particles: added to prevent dusting), enzyme (1.0% by mass vs. crushed particles) , A fragrance (0.1% by mass to ground particles) and a pigment (0.01% by mass to ground particles) were added to obtain a high bulk density granular detergent composition.

 The odor test of the obtained detergent composition was performed by the following test method.

<Time-dependent change test method of odor>

 One month after storage in a constant temperature room at 80 ° C, five panelists conducted a sensory evaluation on the odor of each sample, and evaluated it according to the following criteria.

 ◎: almost odorless

 〇: Somewhat smell

 △: A considerable odor is felt

 X: Strong odor

[0091] The abbreviations in the table are described below. Description of abbreviations in the table> α-SF-Na: a sulfo fatty acid methyl ester sodium salt LAS 'Na: linear alkyl benzene sulfonic acid sodium salt having an alkyl group having 10 to 14 carbon atoms (activator concentration = 70%, The remainder is unreacted alkylbenzene, sodium sulfate, water, etc.).

Stone: Fatty acid with 16 carbon atoms: Fatty acid with 18 carbon atoms: TMD (mixture of fatty acid ester system with 10 to 20 carbon atoms) = 1: 3: 1 (mass ratio) Mixture strength Sodium fatty acid derived from fatty acids (Activator concentration = 67%).

Nonionic activator: alcohol ethoxylate obtained by adding an average of 13 moles of ethylene oxide to an alcohol having 12 to 13 carbon atoms (activator concentration = 90%, the remainder is unreacted alcohol, PEG (polyethylene glycol), water, etc.).

Potassium carbonate: Asahi Glass Co., Ltd., food grade.

Sodium carbonate: Asahi Glass Co., Ltd., food grade.

Sodium sulfite: Anhydrous sulfite, manufactured by Shinshu Chemical Co., Ltd.

 Type A zeolite: manufactured by Mizusawa Chemical Co., Ltd., product name: Shilton B (fine powder, active ingredient = 80%). Hydrogen peroxide: manufactured by Mitsubishi Gas Chemical Co., Ltd. (active ingredient = 35%) Polymer: a copolymer of maleic acid and atalylic acid (Nippon Shokubai Co., Ltd., product name Aqualic TL 400).

Fluorescent agent: Chino Pearl CBS—X, manufactured by Ciba Specialty Chemicals.

Other components: Bleaching components such as enzymes, fragrances, dyes, and organic peracid precursors.

[Table 5]

[0093] As is clear from the above examples, in the examples according to the present invention, the effect of reducing the odor in high-temperature and long-term storage was confirmed.

 Industrial applicability

[0094] The present invention can be applied to the production of an anionic surfactant containing an α-sulfofatty acid alkyl ester salt and a detergent composition containing the same.

Claims

The scope of the claims [1] a sulfofatty acid alkyl ester salt 50-95 wt _^0/0, methylsulfate 3 wt% or less, more alkyl sulfates 0.5 to 8 wt% carbon, aromatic sulfonated Monoshio 0. 1 An a-on surfactant characterized by being 20% by mass.  [2] a step of sulfonating the fatty acid alkyl ester to obtain a sulfonated product, a step of adding an aromatic compound to the sulfonated product, and a step of adding carbon to the sulfonated product after or simultaneously with the aromatic compound adding step. A method for producing an a-ion surfactant, comprising a step of adding an alcohol of several or more and reacting the alcohol with the alcohol.  [3] The method for producing an anionic surfactant according to claim 2, wherein the amount of the aromatic compound to be added is 0.5 to 20 parts by mass relative to 100 parts by mass of the sulfonated product, and the amount of the aromatic compound is 2 or more. A method for producing an anionic surfactant, characterized in that the amount of alcohol added to alcohol is 1 to 15 parts by mass with respect to 100 parts by mass of a sulfonated product.  [4] A carbon surfactant obtained by the method for producing a carbon surfactant according to claim 2 or 3.  [5] A cleaning composition comprising the anionic surfactant according to claim 1.