JP4387787B2 - Solid detergent composition - Google Patents

Description

  The present invention relates to a solid detergent composition used for clothing, for example.

Numerous types of anionic surfactants used in clothing detergents have been developed and are blended in commercial detergents.
As anionic surfactants having excellent detergency, for example, α-sulfo fatty acid alkyl ester salts, α-olefin sulfonates, alkylbenzene sulfonates, and the like are known. In particular, α-sulfo fatty acid alkyl ester salts are known to have very excellent characteristics in detergency, hard water resistance, and biodegradability.

By the way, recent washing machines tend to have a large capacity, and a short-time washing mode is set during the washing time. Furthermore, there is a trend toward saving water, low-temperature washing, and shortening operation time in response to the environment / energy and economy.
These are all in the direction of reducing the work load of the washing machine, and as a result, the dissolution rate of the detergent particles is reduced and the cleaning power is deteriorated. The residual amount may increase.
Therefore, various proposals have been made to solve such problems.

For example, in the production of a powdered detergent containing sodium soap as the main organic cleaning active ingredient, the production of a powdered detergent in which sodium soap powder particles are impregnated or co-granulated with a finely divided easily water-soluble sodium salt A method is disclosed (for example, refer to Patent Document 1), and the formation of soap gel lumps is suppressed to improve solubility.
However, the easily water-soluble sodium salt has no effect of suppressing gel formation with respect to the sodium salt of a surfactant generally used in detergents other than sodium soap.

On the other hand, a granular detergent composition in which a pulverized product of a detergent component mixture is coated with a water-insoluble fine powder having an average particle size of 10 μm or less, an aluminosilicate fine powder, a hydrophobic fine powder, or the like is disclosed (for example, patents). References 2 and 3.)
JP 58-67799 A JP-A 61-272300 Japanese Patent Laid-Open No. 3-11497

  However, since the compositions described in Patent Documents 2 and 3 only use water-insoluble fine powder, the fine powder itself aggregates and sufficiently solves the problem relating to the solubility of the cleaning composition. It wasn't.

In addition, as a method of coating with a water-soluble salt, it has been proposed that spray-dried particles are coated with a water-soluble organic or inorganic builder to improve moisture absorption and solidification, but high bulk density detergent particles. There is no mention of.
A method for improving moisture absorption and solidification properties by coating detergent particles with a water-soluble salt has been proposed, but there are problems such as complicated processes, and further improvement is required.
In addition, sodium percarbonate particles coated with alkali metal sulfate, magnesium sulfate, and magnesium chloride are proposed to have excellent stability and solubility, and sodium percarbonate is coated with a coating containing an alkali metal citrate. There is a suggestion to do so. However, all of them are sprayed onto particles that are dissolved and dispersed in a solvent such as water and then dried, and the process of dissolving the coating substance in a solvent and the need for a drying process after coating are complicated. There was a problem of becoming.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a solid detergent composition having good detergency and improved solubility.
Furthermore, an object is to provide a solid detergent composition having good solubility even if it has a high bulk density.

The inventors of the present invention provide a detergent composition containing an α-sulfo fatty acid alkyl ester salt and an unsaturated linear fatty acid alkyl ester having one double bond in a hydrocarbon chain in a specific ratio. It was found that the solubility was improved and the solubility was improved.
That is, the solid detergent composition of the present invention contains 0.001 to 1.0% by mass of an unsaturated linear fatty acid alkyl ester having one double bond in the hydrocarbon chain, and a bulk density of 0.6 to characterized in that it is a 1.0 g / cm ^3.
The solid detergent composition of the present invention preferably further contains 2 to 60% by mass of carbonate and / or bicarbonate.
The solid detergent composition of the present invention preferably further contains 2 to 40% by mass of zeolite.

  According to the present invention, it is possible to provide a solid detergent composition having good detergency and improved solubility, particularly water solubility at low temperatures.

The solid detergent composition of the present invention contains 2 to 50% by mass of α-sulfo fatty acid alkyl ester salt and 0.001 to 1.0% by mass of unsaturated fatty acid alkyl ester.
The α-sulfo fatty acid alkyl ester salt has very excellent characteristics in detergency, hard water resistance, and biodegradability. In the present invention, by using an α-sulfo fatty acid alkyl ester salt having such properties, it is possible to improve the solubility while exhibiting good detergency in the solid detergent composition.
Here, the solid cleaning composition of the present invention (hereinafter referred to as “cleaning composition”) preferably contains the following components (a) to (d).
(A) α-sulfo fatty acid alkyl ester salt.
(B) Carbonate and / or bicarbonate.
(C) Zeolite.
(D) Unsaturated fatty acid alkyl ester.

  As the (a) α-sulfo fatty acid alkyl ester salt (hereinafter sometimes simply referred to as “component (a)”) in the present invention, a compound represented by the following general formula (I) can be preferably used.

(Wherein, R ¹ represents a linear or branched alkyl group or alkenyl group, R ² represents a linear or branched alkyl group, and M represents a water-soluble salt such as an alkali metal or alkaline earth metal. The counter ion to be formed is shown.)
Here, the carbon number of R ¹ is preferably 6 to 20, more preferably 10 to 18, and the carbon number of R ² is preferably 1 to 6, and more preferably 1 to 4.

The (a) α-sulfo fatty acid alkyl ester salt can be obtained, for example, using a corresponding fatty acid alkyl ester represented by the following general formula (II) as a raw material.
R ¹ —CH ₂ —COO—R ² (II)
(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group, and R ² represents a linear or branched alkyl group.)
As the fatty acid alkyl ester, a saturated fatty acid alkyl ester is preferably used.
Fatty acid alkyl esters are animal fats derived from beef tallow, fish oil lanolin, etc .; vegetable fats derived from coconut oil, palm oil, soybean oil, etc .; synthetic fatty acid alkyls derived from the oxo method of α-olefins Any of ester etc. may be sufficient and it does not specifically limit.
Specifically, methyl dodecanoate, ethyl or propyl; tetradecanoate methyl, ethyl or propyl; methyl palmitate, ethyl or propyl; stearate methyl, ethyl or propyl; hydrogenated beef tallow fatty acid methyl, ethyl or propyl; hydrogenated fish oil 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, and the like. A mixture of more than one species can be used. The iodine value of the fatty acid alkyl ester is preferably 0.5 or less, more preferably 0.1 or less.

The component (a) can be obtained by sulfonating a fatty acid alkyl ester to obtain an α-sulfo fatty acid alkyl ester, followed by neutralization. More specifically, for example, the component (a) can be obtained by the following production method.
First, the raw material fatty acid alkyl ester is brought into contact with a sulfonated gas.
Examples of the sulfonated gas include SO ₃ gas and fuming sulfuric acid, but SO ₃ gas is preferred. More preferably, a sulfonated gas diluted with an inert gas such as dehumidified air or nitrogen so that the SO ₃ concentration is 1 to 40% by volume is used. If it is less than 1% by volume, the volume of the sulfonated gas becomes large, and the capacity of the apparatus becomes large, which is disadvantageous. If it exceeds 40% by volume, the reaction becomes excessive and by-products are likely to be generated, and the color tone of the α-sulfo fatty acid alkyl ester may be deteriorated. In particular, in order to suppress color tone deterioration of the α-sulfo fatty acid alkyl ester, it is preferably diluted to 1 to 30% by volume.
The sulfonated gas such as SO ₃ is preferably 1.0 to 2.0 times mol, more preferably 1.0 to 1.7 times mol, particularly preferably 1.05 to 1 mol with respect to the fatty acid alkyl ester of the raw material. .5 moles are used. If the amount is less than 1.0 times mol, the sulfonation reaction may not proceed sufficiently. If the amount exceeds 2.0 times mol, the sulfonation reaction becomes more radical, which may cause by-products or coloring.

Here, it is preferable to carry out the reaction by dispersing a coloring inhibitor in the raw material liquid phase. As the coloring inhibitor, for example, an organic acid salt, an inorganic sulfate, or the like can be used, and an inorganic sulfate is preferably used. Among organic acid salts and inorganic sulfates, monovalent metal salts are preferably used.
Examples of the organic acid salt include sodium formate, potassium formate, and sodium acetate. The inorganic sulfate is preferably a monovalent metal salt and a powdery anhydrous salt, and examples thereof include sodium sulfate, potassium sulfate, and lithium sulfate. Inorganic sulfate has a high coloration suppressing effect and is inexpensive, and since it is a component blended in the detergent, it is not necessary to remove it from the α-sulfo fatty acid alkyl ester salt in the case of detergent use.
Further, the average particle size of the coloring inhibitor is preferably 250 μm or less, and more preferably 100 μm or less. For example, during the reaction, inorganic sulfate is hardly dissolved in the raw material liquid phase to the extent that its surface is slightly dissolved, and is dispersed in the raw material liquid phase. Therefore, by using the inorganic sulfate having a small particle diameter as described above, the contact area with the raw material liquid phase is increased, the dispersibility is improved, and the effect can be further enhanced.
The addition amount of the coloring inhibitor is preferably 0 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 3 to 20% by mass with respect to the fatty acid alkyl ester as a raw material. This is because when the amount exceeds 30% by mass, the effect of suppressing coloring is saturated.

As the sulfonation method of the fatty acid alkyl ester, any of a thin film type sulfonation method and a tank type sulfonation method can be adopted. From the viewpoint of uniformly dispersing the coloring inhibitor and sufficiently exerting the coloring suppressing effect, the tank type is preferable.
When the fatty acid alkyl ester is brought into contact with the sulfonated gas, as shown by the following general formula, SO ₃ is first inserted into the alkoxy group part of the ester, and an SO ₃ monomolecular adduct (hereinafter referred to as “single molecule adduct”). Generated). Next, SO ₃ is further introduced into the α-position of the single molecule adduct, and an SO ₃ bimolecular adduct (hereinafter referred to as “bimolecular adduct”) is generated. Thereafter, SO ₃ inserted into the alkoxy group moiety is eliminated to produce α-sulfo fatty acid alkyl ester.

Next, the reaction product is aged to complete the sulfonation to obtain a sulfonated product. By aging, the elimination of SO ₃ from the bimolecular adduct is promoted. The aging temperature is preferably 70 to 100 ° C. If it is lower than 70 ° C., the reaction does not proceed rapidly, and if it exceeds 100 ° C., the coloring may be remarkable. The aging reaction time is preferably 1 to 120 minutes. In addition, ripening can also be abbreviate | omitted if sufficient reaction rate is obtained as a result of contacting fatty-acid alkylester with sulfonated gas.

Next, by performing an esterification step of adding a lower alcohol, by-products can be suppressed, and the purity of the α-sulfo fatty acid alkyl ester salt obtained in the neutralization step described later can be improved. This esterification step is provided as necessary.
The lower alcohol used in the esterification step preferably has a carbon number equal to the carbon number of the alcohol residue of the starting fatty acid alkyl ester. For example, a fatty acid alkyl esters, if the number of carbon atoms in the alcohol residue R ² represented by the above general formula (II) was used as 1 to 6 carbon atoms in the lower alcohol used in the esterification step 1-6 is preferred However, there is no particular limitation.
The lower alcohol is preferably used in an amount of 0.5 to 5.0 times mol, more preferably 0.8 to 2.0 times mol for the bimolecular adduct in the reaction solution. The reaction temperature is preferably 50 to 100 ° C, more preferably 50 to 90 ° C, and the reaction time is preferably 5 to 120 minutes.

Then, (a) alpha-sulfo fatty acid alkyl ester salt can be obtained by performing the neutralization process which neutralizes the reaction liquid containing alpha-sulfo fatty acid alkyl ester.
As a neutralization method, it can carry out by the method of adding an alkali. Here, a method using an alkali as an aqueous solution is possible, and according to this method, a paste of (a) α-sulfo fatty acid alkyl ester salt can be obtained.

When alkali is used as an aqueous solution, examples of the alkali include alkali metal, alkaline earth metal, ammonia, and ethanolamine.
Since the ester bond of the α-sulfo fatty acid alkyl ester salt is likely to be cleaved under strong alkaline conditions, the neutralization step is carried out when the pH of the reaction mixture containing the sulfonated product and the alkali is acidic or weakly alkaline. It is preferable to carry out in the range (pH 4-9). More preferably, after premixing a neutralized product and a sulfonated product obtained in advance, neutralization with an alkali from the acidic side results in cleavage of the ester bond and α-sulfo fatty acid dialkali salt (di salt; the above general formula ( In I), by-product of R ² as M) can be suppressed. Since di-salts do not contribute to cleaning performance, it is desirable to suppress by-products.
The concentration of the aqueous alkali solution is preferably about 2 to 50% by mass. The concentration of the α-sulfo fatty acid alkyl ester salt in the reaction mixture is preferably about 10 to 80% by mass. The neutralization temperature is preferably 30 to 140 ° C., and the neutralization time is preferably 10 to 60 minutes.

  If necessary, a treatment for making the color tone of the (a) α-sulfo fatty acid alkyl ester salt close to white can be performed before or after the neutralization step. Examples of the treatment for making the color tone close to white include a bleaching treatment using a bleaching agent such as hydrogen peroxide. Such treatment is preferably performed after the neutralization step. Thereafter, if necessary, the (a) α-sulfo fatty acid alkyl ester salt is converted into a flake shape, noodle shape, powder shape, particle shape, or the like from the paste of the (a) α-sulfo fatty acid alkyl ester salt by a conventional method. Can be molded.

The neutralization step can be carried out by a method in which a solid alkali is added to a sulfonated product or a reaction product that has undergone an esterification step to obtain a reaction mixed powder in addition to a method using an aqueous alkali solution. At this time, it is preferable to use an alkali composed of carbonate and / or bicarbonate as the solid alkali.
In particular, neutralization with solid carbonate (for example, concentrated soda ash) is preferable because it is less expensive than using other alkalis. Moreover, when neutralizing with solid carbonate, the water | moisture content in a reaction mixture will decrease and it will not become strong alkalinity. Moreover, since the heat of neutralization at the time of neutralization is lower than the case of a metal hydroxide, it is advantageous.
Examples of the carbonate and bicarbonate include alkali metal carbonates such as sodium carbonate and potassium carbonate; ammonium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; ammonium bicarbonate and the like An anhydrous salt, a hydrated salt, or a mixture thereof can be used.

The concentration of the α-sulfo fatty acid alkyl ester salt in the reaction mixture powder is preferably 10 to 95% by mass. The neutralization temperature is preferably 10 ° C. to 80 ° C., and the neutralization time is preferably 10 to 180 minutes.
The (a) α-sulfo fatty acid alkyl ester salt neutralized with a solid alkali can be bleached using a bleaching agent such as hydrogen peroxide as necessary.

In (a) α-sulfo fatty acid ester salt obtained by these methods, α-sulfo fatty acid dialkali salt (di-salt) is usually contained as a by-product, usually 0.1 to 40% by mass, This does not impair the cleaning effect. Therefore, in the following, (a) α-sulfo fatty acid ester salt shall mean a di-salt-containing product.
(A) α-sulfo fatty acid alkyl ester salt paste or (a) α-sulfo fatty acid alkyl ester salt obtained by neutralization with solid alkali is then mixed with other components to form a detergent composition. .

  The content rate of (a) component in the solid cleaning composition of this invention is 2-50 mass%, Preferably it is 5-30 mass%. If it is less than 2% by mass, sufficient detergency of the component (a) cannot be obtained.

  (B) Carbonates and / or bicarbonates (hereinafter sometimes simply referred to as “component (b)”) include alkali carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates; An alkali metal hydrogen carbonate such as sodium; an alkaline earth metal hydrogen carbonate is preferably used. These may be used alone or in combination of two or more.

  When the cleaning composition of the present invention contains the carbonate and / or bicarbonate of the component (b), the content is 2 to 60% by mass, preferably 8 to 40% by mass. If it is less than 2% by mass, the effect of contributing to the cleaning performance is small. On the other hand, if it exceeds 60% by mass, no further effect can be expected.

(C) Zeolite (hereinafter sometimes simply referred to as “component (c)”) is a crystalline aluminosilicate, and examples include A-type zeolite, P-type zeolite, X-type zeolite, etc. A type and X type are preferable. (C) The particle size of the zeolite is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm in terms of mass average particle size.
When the cleaning composition of the present invention contains the component (c) zeolite, the content is 2 to 40% by mass, preferably 10 to 30% by mass. If it is less than 2% by mass, the effect of contributing to the cleaning performance is small. On the other hand, if it exceeds 40% by mass, no further effect can be expected.

(D) The unsaturated fatty acid alkyl ester (hereinafter sometimes simply referred to as “component (d)”) can be generally represented by the following general formula (III).
R ³ —COO—R ⁴ (III)
(In the formula, R ³ represents an alkenyl group, and R ⁴ represents a linear or branched alkyl group.)
Here, the carbon number of R ³ is preferably 7 to 25, and more preferably 11 to 19. R ⁴ preferably has 1 to 6 carbon atoms, more preferably 1 to ⁴ carbon atoms.
(D) Specifically, as a component, methyl myristate, ethyl or propyl having one double bond; methyl permitoleate, ethyl or propyl; methyl oleate, ethyl or propyl; methyl or ethyl elaidate; Examples include methyl and ethyl vaccenate; methyl or ethyl erucate and the like. Docosahexaenoic acid having 2 double bonds, methyl linoleate, ethyl or propyl; 3 double bonds, methyl α- or γ-linolenate, ethyl or propyl; 4 or more double bonds Examples include methyl, ethyl or propyl. Among these, unsaturated linear fatty acid ester having one double bond is preferable.
The component (d) can be used alone or as a mixture of two or more in the cleaning composition of the present invention.

  The content rate of (d) component in the cleaning composition of this invention is 0.001-1.0 mass%, Preferably it is 0.01-0.1 mass%. If the content is less than 0.001% by mass, the effect of improving the solubility of the detergent composition containing the α-sulfo fatty acid alkyl ester salt cannot be obtained, while exceeding 1.0% by mass. However, no further effect can be expected.

In addition, the following components can be used in the cleaning composition of the present invention as necessary.
(1) Surfactant: straight chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16, and a linear or branched alkyl group having an average carbon number of 10 to 20, having an average of 0 per molecule Alkyl ethoxy sulfate added with 5 to 10 mol of ethylene oxide, alkyl sulfate having an alkyl group having an average carbon number of 10 to 20, olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule, average An anionic surfactant such as a fatty acid salt having 10 to 20 carbon atoms; a polyoxyethylene alkyl ether having an alkyl group having an average carbon number of 10 to 20 and having 1 to 20 moles of ethylene oxide added thereto, a higher fatty acid alkanolamide or Nonionic surfactants such as alkylene oxide adducts (nonionic surfactants); other betaine type amphoteric Surface active agents, sulfonate-type amphoteric surfactants, phosphate ester surfactants, such as cationic surfactants. In the section of (1) surfactant, “alkyl” is a concept including alkenyl containing an unsaturated bond.
(2) Divalent metal ion scavenger: orthophosphate, pyrophosphate, tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetate, citrate, isocitrate, polyacrylate, polyacetal carboxylate, etc. .
(3) Alkaline agents and inorganic salts: silicates, carbonates, sesquicarbonates, sulfates and the like.
(4) Anti-staining agent: polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose and the like.
(5) Bleach, fluorescent dye, enzyme, etc .: sodium percarbonate, sodium perborate, sodium sulfate, sodium chloride hydrogen peroxide adduct, etc. as bleach. In addition, commercially available fluorescent dyes as brighteners; fragrances; enzymes such as proteases, cellulases, amylases, lipases; and amino acids such as alanine, ketones, ketoesters, etc., as needed Can be blended.
(6) Other components of the solid detergent other than those described above can be used as necessary.

The solid detergent composition comprises the above components (a), (d) and, if necessary, the component (b), the component (c), the other components (1) to (6), etc. Manufactured by known granulation methods such as stirring granulation method, kneading / crushing granulation method, paste granulation method, wet granulation / drying method, fluidized bed granulation method, extrusion granulation method, rolling granulation method can do.
Moreover, when manufacturing molded articles, such as a tablet form, a briquette form, and a sheet form, what is necessary is just to shape | mold this detergent particle | grain by well-known shaping | molding methods, such as a tableting method and a roll press method.
The cleaning composition of the present invention can be formulated into various dosage forms and uses by blending the above-described components. For example, the average particle size is 300 to 700 μm, and the bulk density is 0.6 to 1.0 g / cm. ³ granular detergent composition for clothing or fiber.
When the kneading and crushing granulation method is used, first, for example, (a) the α-sulfo fatty acid alkyl ester salt obtained by the above method is mixed with the component (d), and then concentrated by evaporation (b) The solid detergent composition of the present invention can be obtained by kneading together with spray-dried particles containing the component (c) and component (c) and then pulverizing.
In obtaining the cleaning composition of the present invention, (d) the unsaturated fatty acid alkyl ester may be preliminarily mixed with the fatty acid alkyl ester used as the raw material of the component (a), or in order to obtain the component (a). It may be added to the reaction product containing the α-sulfo fatty acid alkyl ester that has been sulfonated, or may be added to the component (a) obtained through the neutralization step.

  As described above, the cleaning composition of the present invention has improved solubility, particularly solubility at low temperatures. Therefore, even if the washing machine is operated in a short-time washing mode or the like, it does not cause problems such as deterioration of washing power and residual clothes of detergent particles. Since it exhibits solubility, it is extremely superior in terms of environment, energy and economy.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example. Note that “%” in each composition in the table below represents mass% unless otherwise specified.
<Raw material>
The raw materials used in this example are shown below together with abbreviations described in the table described later.
α-sulfo fatty acid alkyl ester salt (α-SF): α-sulfo fatty acid methyl ester sodium salt paste having a fatty acid residue of 14: 16 = 20: 80 (mass ratio).
Unsaturated fatty acid alkyl ester (methyl myristoleate): ICN Pharmaceuticals, Inc. (methyl myristoleate).
LAS: linear alkylbenzenesulfonic acid sodium salt having an alkyl group having 10 to 14 carbon atoms (AI (active ingredient) = 70%, the remainder being unreacted alkylbenzene, sodium sulfate, water, etc.).
Soap: Fatty acid sodium (AI = 67%) of carbon number 16: 18: TMD (ester mixture of carbon number 10-20 = 1: 3: 1).
Nonionic activator: alcohol ethoxylate (AI = 90%, balance is unreacted alcohol, polyethylene glycol (PEG), water, etc.) obtained by adding an average of 13 moles of ethylene oxide to an alcohol having 12 to 13 carbon atoms.
Potassium carbonate: Food grade manufactured by Asahi Glass Co., Ltd.
Sodium carbonate: Asahi Glass Co., Ltd., food grade.
Sodium sulfite: manufactured by Shinshu Chemical Co., Ltd., anhydrous sodium sulfite.
Polymer: A copolymer of maleic acid and acrylic acid (manufactured by Nippon Shokubai Co., Ltd., “AQUALIC” TL-400).
Fluorescent agent: “Chino Pearl CBS-X” manufactured by Ciba Specialty Chemicals.
Other ingredients: enzymes, fragrances, pigments.

<Manufacture of α-SF>
The sulfonation reaction was carried out in a tank reactor (200 L capacity, manufactured by SUS316L with jacket cooling / stirring device).
First, 80 kg of raw material fatty acid methyl ester (manufactured by Lion Oleochemical Co., Ltd., carbon number 14: 16 = 20: 80 (mass ratio)) is charged into a reaction tank, and finely powdered salt cake is used as a color inhibitor while stirring well. 5% was added to the ester.
While continuing stirring, ring the SO ₃ gas (sulfonated gas) 102m ³ (1.2 times mol with respect to the raw material fatty acid methyl ester) diluted to 8% by volume with nitrogen gas by controlling the heat removal. The sulfonation reaction was carried out by blowing with a sparger at a constant speed over 1 hour. Further, aging was performed for 30 minutes while maintaining at 80 ° C. to obtain a sulfonated product.
Next, 4.5 kg of methanol as a lower alcohol was added to the tank reactor to carry out an esterification reaction. The esterification reaction rate was 80 ° C., and the aging time was 30 minutes.
Subsequently, the esterified sulfonated product was continuously fed at 117 kg / hr, and a 34% by mass aqueous sodium hydroxide solution was quantitatively fed at a rate of 46.6 kg / hr to continuously neutralize (JP-A No. 2001-64248 publication). The neutralization temperature was controlled at 70 ° C., and the residence time of the neutralized product was 20 minutes. The pH of the obtained neutralized product was 6.5.
Next, 82 kg of this neutralized product was charged into a 200-L jacketed stirring tank, and 3.3 kg of 35% hydrogen peroxide water (1.0 mass% pure with respect to AI (active ingredient)) was thoroughly mixed. And the bleaching reaction was carried out. The bleaching temperature was adjusted to 80 ° C. with a jacket, and the bleaching time was 7 hours.
The α-sulfo fatty acid alkyl ester sodium salt thus obtained has an active ingredient (AI) = 67% by mass, α-sulfo fatty acid alkyl ester salt / di-salt = 96/4 (mass ratio), sodium sulfate = 1.5 mass. %, Methyl sulfate = 5.5% by mass, and moisture = 26% by mass.

Examples 1-14 and Comparative Examples 1-6
<Production of granular detergent composition>
1. Activator concentration Part of nonionic surfactant (25% by mass with respect to α-SF) and unsaturated fatty acid alkyl ester are added to α-sulfo fatty acid alkyl ester sodium salt paste, and a flash concentrator (heating tube SFC- 300 (heat transfer area 0.5 m ² ), manufactured by Sakuma Seisakusho Co., Ltd., and heated to a temperature of 130 ° C. (uses pressurized steam as the heating medium). The mixture was concentrated to obtain a mixed concentrate of α-sulfo fatty acid alkyl ester sodium salt and nonionic surfactant.

2. Spray drying After dissolving or dispersing nonionic surfactant and optional components except some zeolite in tap water (Edogawa-ku, Tokyo) to prepare slurry (solid content concentration 60 mass%), this slurry is sprayed as follows Spray drying was performed under dry conditions to obtain dry particles.
[Slurry preparation conditions]
Solid content concentration: 60%, temperature: 60 ° C.
[Spray drying conditions]
Spray drying apparatus: countercurrent type, tower diameter 2.0 m, effective length 5.0 m, atomization method: pressurized nozzle method, spray pressure: 30 kg / cm ² , hot air inlet temperature: 260 ° C., hot air outlet temperature: 90 C, discharge method: Zeolite (1.5% by weight vs. dry particles) is introduced into the tower bottom together with cold air, discharged after cooling and fluidity improvement.
[Physical properties of spray-dried particles]
Mass average particle size: about 400 μm, bulk density: 300 g / L, angle of repose: 40 °, moisture: 4.5% by mass.

3. Next, continuous kneader (manufactured by Kurimoto Iron Works) with nonionic surfactant (water content 10% by mass) and a small amount of tap water (Edogawa-ku, Tokyo) together with the obtained active agent concentrate and spray-dried particles. , KRC-S4 type) and continuously kneaded at a temperature of 50 to 65 ° C. and a throughput of 178 kg / hr to obtain a dough-like product. Warm water or cold water or an ethylene glycol aqueous solution was passed through the kneader jacket at 3 to 7 L / min so as to maintain the kneading temperature.
Then, after extruding at a temperature of 45 to 60 ° C. with a pelleter (made by Fuji Powder, die hole diameter 10 mm (10 mmφ)), a pellet type solid detergent of 5 to 30 mm was formed with a rotary cutter.
Next, Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKASO-6 type) is arranged in three stages in series (the screen diameter and rotation speed are the first stage: 12 mm, 1880 rpm, the second stage; 6 mm, 4700 rpm, the third stage. 3 mm, 4700 rpm), the obtained solid detergent and zeolite as a grinding aid (4.3 mass% solid detergent) were introduced together with cold air at 15 ° C. and ground at a throughput of 186 kg / hr. The temperature of the obtained pulverized particles was 20 to 30 ° C.
Finally, zeolite (2.0% by mass vs. pulverization) in a rolling drum (diameter 0.6m, length 0.48m, thickness 1mm x width 12cm x length 48cm with 4 baffle plates, rotation speed 20rpm) The resulting detergent particles are coated to add nonionic surfactant (0.5% by mass to pulverized particles for dust generation prevention), enzyme (1.0% by mass to pulverized particles), perfume ( 0.1 mass% to pulverized particles) and a dye (0.01 mass% to pulverized particles) were added to obtain a granular detergent composition having a high bulk density.
The cleaning composition thus obtained had a mass average particle size of 600 μm and a bulk density of 0.80 g / cm ³ .

<Solubility evaluation>
Two tank washing machine (Mitsubishi Electric Co., Ltd., “CW-C30A1-H”) is filled with 30 L of tap water at 5 ° C., bath ratio of 7 cotton shirts, 2 polyester shirts and 2 acrylic shirts. Adjusted to 20 times, they were folded and floated on the water surface. The granular detergent composition 30g was put on the center, and the cloth was immersed for 2 minutes and then stirred for 5 minutes with a weak water flow. After draining, the cloth was dehydrated for 1 minute, the undissolved residue on the cloth and in the washing machine was picked up, and the undissolved amount was visually evaluated according to the following evaluation criteria.

<Evaluation criteria>
A: There is almost no undissolved residue.
○: Some undissolved residue is seen.
Δ: Some undissolved residue is seen.
X: Remarkably much undissolved residue is observed.
Considering usability at home, the cleaning composition is preferably evaluated as “◯” or more.
The composition and solubility of each composition in Examples and Comparative Examples are shown in Tables 1-3.

As is clear from the table above, the detergent compositions obtained in the examples had good results with a solubility in tap water of 5 ° C. being better than ○. However, in Comparative Examples 1 to 6 that did not contain the unsaturated fatty acid alkyl ester or the content was less than 0.001%, the solubility was insufficient.

Claims (3)

It contains 2 to 50% by mass of an α-sulfo fatty acid alkyl ester salt and 0.001 to 1.0 % by mass of an unsaturated linear fatty acid alkyl ester having one double bond in the hydrocarbon chain, and a bulk density of 0.001 . solid detergent composition which is a 6~1.0g / cm ^3.   The solid detergent composition according to claim 1, further comprising 2 to 60% by mass of carbonate and / or bicarbonate.   The solid detergent composition according to claim 1 or 2, further comprising 2 to 40% by mass of zeolite.