JP5481721B2 - Method for producing granules containing α-sulfo fatty acid alkyl ester salt with improved solubility - Google Patents

Description

  The present invention relates to a method for producing granules containing an α-sulfo fatty acid alkyl ester salt with improved solubility without spray drying.

The α-sulfo fatty acid alkyl ester salt is widely used as a surfactant constituting a powder detergent for clothing. The α-sulfo fatty acid alkyl ester salt is referred to as an α-SF salt. When the alkyl moiety is a methyl group, it is particularly referred to as a MES (Methyl Ester Sulfonate) salt.
A high bulk density granule containing a surfactant is generally sprayed with an aqueous detergent slurry from a nozzle having a small pore size, and is made into fine droplets in a tower into which hot air is introduced and dried in a short time (so-called spraying). The spray-dried particles obtained by drying) and various detergent components can be produced by stirring and granulating, or kneading and pulverizing. As other methods, various detergent components can be produced by dry mixing and granulating with stirring, or kneading and pulverizing. In the former, the amount of energy used for spray drying is large, and therefore the load on the environment is large.
In order to reduce the load on the environment, the latter detergent component is preferably dry-mixed and stirred and granulated or kneaded and pulverized. However, granules containing α-SF salt are soluble in water. In order to produce granules containing α-SF salt, there are many kneading and pulverization processes in which uniform dispersibility of the granules in water is good in order to obtain good solubility. (See, for example, Patent Document 1). However, in the kneading and pulverization process, much adhesion to the pulverizer occurs, and the energy used in the process is still large (see, for example, Patent Document 2).
On the other hand, the stirring granulation process has the advantage of using less energy. In the coarse powder pulverization process performed after granulation, since the load on the pulverizer is light, adhesion to the pulverizer is not a big problem. However, there is a problem that the resulting granules have poor solubility in water (see, for example, Patent Document 3).

JP-A-8-253800 JP-A-8-283799 JP-A-6-128594

  Accordingly, an object of the present invention is to provide a method for producing α-SF salt-containing granules having good solubility in water while using agitation granulation means that uses less energy.

As a result of intensive studies by the present inventors, the non-ionic surfactant is included in the α-SF salt granule, and the total amount of sodium carbonate and sodium sulfate and the ratio of the two are set within a specific range, thereby achieving the above object. I found that I can achieve.
That is, this invention provides the manufacturing method of the alpha-sulfo fatty-acid alkylester salt containing granule characterized by including the following process 1 and 2.
Step 1:
(A) A paste containing an α-sulfo fatty acid alkyl ester salt and a nonionic surfactant, the α-sulfo fatty acid alkyl ester salt containing 60% by mass or more based on the total mass of the paste, and α- Sulfo fatty acid alkyl ester salt / nonionic surfactant (mass ratio) = 1 / 0.2 to 1 / 0.4, the paste being 15 to 30% by mass based on the granules obtained in step 2,
(B) Sodium carbonate and (c) Sodium sulfate are granulated with stirring.
(B) the total amount of sodium carbonate and (c) sodium sulfate is 50-80% by weight based on the granules obtained in step 2, and (b) sodium carbonate / (c) sodium sulfate (mass ratio) Process step 2 for obtaining a granulated product of 1 / 0.5 to 1 / 0.1:
The step of adding (d) A-type zeolite: 0.01 to 0.18 parts by mass (based on hydrate) to the granulated product obtained in Step 1 above: 1 part by mass, and mixing both.

  The present invention also provides a method for producing a granular detergent composition comprising spraying a nonionic surfactant onto granules containing an α-sulfo fatty acid alkyl ester salt produced by the above production method.

  ADVANTAGE OF THE INVENTION According to this invention, the alpha-SF salt containing granule with high solubility to water can be provided by the method of using little energy and therefore the load given to an environment small. According to the present invention, even if a pulverizer is not used, or even if a pulverizer is used, the pulverization can be performed with a light load. Since the granules obtained by the production method of the present invention have a high compressive strength against deformation, they are less likely to solidify during storage or transportation and are easy to handle.

Process 1
In step 1 of the present invention, the above-mentioned (a) α-SF salt-containing paste, (b) sodium carbonate, and (c) sodium sulfate are granulated with stirring to obtain a granulated product.
[Α-sulfo fatty acid alkyl ester salt]
In the present invention, as the α-sulfo fatty acid alkyl ester salt constituting the component (a), those represented by the following formula can be suitably used.

In the formula, R ¹ is a linear or branched, preferably linear alkyl or alkenyl group having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 14 to 18 carbon atoms. If the carbon number of R ¹ is less than 6 or more than 20, the detergency may be inferior.
R ² is a linear or branched, preferably linear alkyl or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 carbon atom.
M is an alkali metal, an ammonium or an amine, preferably an alkali metal, more preferably sodium or potassium.
Particularly preferred is a compound in which R ¹ is a linear or branched alkyl or alkenyl group having 12 to 16 carbon atoms, R ² is a methyl group, and M is sodium in the above formula.
In the present invention, the α-sulfo fatty acid alkyl ester salt may be used alone or as a mixture of two or more. A mixture is preferred.
The α-sulfo fatty acid alkyl ester salt used in the present invention can be produced by a known method, or a commercially available product can be used.

[Nonionic surfactant]
In the present invention, the nonionic surfactant constituting the component (a) can be used without particular limitation as long as it is generally used for producing granular detergents. In particular,
(1) a polyoxyalkylene alkyl ether having an alkyl group having 10 to 20 carbon atoms and a polyoxyalkylene (alkylene having 2 to 4 carbon atoms) having an addition mole number of 5 to 50;
(2) an alkyl polyglucoside having an alkyl group having 8 to 18 carbon atoms and having an average addition mole number of glucose units of 1 to 10,
(3) an alkyl glyceryl ether having an alkyl group having 8 to 18 carbon atoms and having an average addition mole number of glycerin units of 1 to 3,
(4) C10-20 fatty acid diethanolamide,
(5) Methoxypolyoxyethylene alkanoate having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide of 1 to 30 is included.
Of these, polyoxyalkylene alkyl ethers (1) are preferable, polyoxyethylene alkyl ethers are particularly preferable, and polyoxyethylene having an average carbon chain length of 10 to 18 and an average EO addition mole number of 5 to 25 is particularly preferable. Alkyl ethers are preferred.

[(A) α-SF salt-containing paste]
An α-SF salt-containing paste containing an α-SF salt and a nonionic surfactant is prepared by, for example, sulfonating and esterifying a fatty acid alkyl ester by a conventional method (hereinafter referred to as α-sulfo fatty acid alkyl ester). Manufactured by adding a nonionic surfactant to an α-SF acid together with an aqueous alkali solution when neutralizing with an alkali agent such as NaOH to form an α-SF salt. can do. The α-SF acid or α-SF salt may be bleached before and after neutralization.

  After neutralization, if necessary, it is concentrated to remove water contained in the neutralized product and alcohol used for esterification, and the amount of α-SF salt is 60% by mass or more, preferably based on the total mass of the paste. 60 to 80% by mass, more preferably 60 to 75% by mass. If it is less than 60% by mass, the moisture in the paste becomes high, so the moisture in the resulting granulated product also becomes high, and the compressive strength against deformation of the resulting granulated product becomes low. If it exceeds 80% by mass, the viscosity of the paste increases and handling becomes difficult. The amount of α-SF salt in the paste can be measured by a high performance liquid chromatograph. Concentration can be performed using, for example, a recycle flash evaporator.

  At this time, the amount of the nonionic surfactant contained in the granule is 1 / 0.2 to 1 / 0.4 (mass ratio) with respect to the α-SF salt contained in the granule. It is preferably ~ 1 / 0.35. When the amount is less than 0.2 with respect to the α-SF salt, the viscosity of the paste containing the α-SF salt becomes high and handling becomes difficult. If it exceeds 0.4 with respect to the α-SF salt, nonionic oozes out frequently when granulated, and the compressive strength against deformation becomes low.

The amount of water contained in the paste is preferably 5 to 15% by mass, more preferably 7 to 13% by mass. When the amount of moisture is in such a range, moisture in the granulated product can be kept low, and the paste viscosity can be lowered to allow good handling. The water content in the paste can be measured with a Karl Fischer moisture meter.
The α-SF salt-containing paste is used in an amount of 15 to 30% by mass, preferably 17 to 28% by mass, more preferably 17 to 26% by mass, based on the granules obtained in Step 2. If it is less than 15% by mass, the amount of builder in the resulting granule becomes relatively large, and as a result, the solubility of the granule in water decreases. If it exceeds 30% by mass, the particles may be agglomerated due to gelation of the α-SF salt when dissolved in water, and the solubility may be lowered.

[(B) Sodium carbonate and (c) Sodium sulfate]
Sodium carbonate used in the present invention acts as an alkaline agent for washing, and sodium sulfate acts as a solubility improver. Sodium carbonate and sodium sulfate are the core of the granulated product. For this reason, it is preferable that these average particle diameters are 100-400 micrometers. The bulk density and particle shape are not particularly limited. In addition, the average particle diameter of sodium carbonate and sodium sulfate can be measured with a sieve (see [Method for measuring average particle diameter with sieve] described later) or a laser diffraction / scattering particle size distribution analyzer.
The total amount of sodium carbonate and sodium sulfate is 50 to 80% by mass, preferably 55 to 75% by mass, and more preferably 60 to 72% by mass with respect to the total amount of the granulated product obtained in Step 2. If it is less than 50%, the number of particles serving as the core of the granulated product is reduced, and the particle size distribution of the granulated product becomes very broad. As a result, water solubility and solidification deteriorate. If it exceeds 80% by mass, the solubility of the granules in water decreases.
Sodium carbonate and sodium sulfate are sodium carbonate / sodium sulfate (mass ratio) = 1 / 0.5 to 1 / 0.1, preferably 1 / 0.13 to 1 / 0.47, more preferably 1/0. .15 to 1 / 0.45. When the amount of sodium sulfate relative to sodium carbonate is more than 0.5, the compressive strength of the granules is lowered. If the amount of sodium sulfate relative to sodium carbonate is less than 0.1, the solubility of the granules in water decreases.

In step 1 of the present invention, the above-mentioned (a) α-SF salt-containing paste, (b) sodium carbonate, and (c) sodium sulfate are granulated with stirring to obtain a granulated product.
In step 1, a builder (eg, zeolite, potassium carbonate), an anionic surfactant, a fluorescent agent, and the like may be added as optional components. In this case, the blending time can be set according to the form of each optional component. For example, when the optional component is a powder, it may be added together with (b) sodium carbonate and (c) sodium sulfate. When adding zeolite, type A is preferred. However, the total of the amount of zeolite added in step 1 and the amount of A-type zeolite added in step 2 should not exceed the range specified in the present invention. When the shape of the optional component is a liquid, it is preferably blended after the addition of (b) sodium carbonate, (c) sodium sulfate and other powders.

  The stirring granulator which can be used in this step preferably has a structure having one or more stirring shafts equipped with stirring blades in the center of the device and a chopper on the inner wall surface of the device. The average clearance between the stirring blade and the inner wall of the apparatus is preferably 1 to 30 mm. Either continuous type or batch type may be used. Examples include a turbulizer (Hosokawa Micron Co., Ltd.), a Redige mixer (Matsubo Co., Ltd.), a pro-share mixer (Daihei Kiko Co., Ltd.), a high speed mixer (Fukae Powtech Co., Ltd.), and the like.

Agitation granulation is performed by simultaneously or sequentially adding the above components to an agitation granulator. Rather than simultaneously charging, it is preferable to divide into (a) α-SF salt-containing paste that is in the form of paste and (b) sodium carbonate and (c) sodium sulfate that are powdered, and sequentially add them. It is better to put the powder first and the paste later. More particularly, it is preferable to add the (a) α-SF salt-containing paste while fluidizing the powders (b) and (c) by rotating the main shaft of the stirring granulator alone or together with the chopper.
When using a batch type agitation granulator, the higher the filling ratio of the components (a) to (c), the higher the agitation granulation capability, which is preferable. However, if the filling rate is too high, a large number of coarse particles aggregated with each other are generated, making granulation difficult. The filling rate is preferably 10 to 60% by volume, more preferably 15 to 50% by volume. For example, in the case of an agitation granulator having an internal volume of 300 L, the total apparent volume of the components (b) and (c) and other powders added if necessary is preferably about 30 to 180 L.
The number of rotations of the stirring shaft is preferably adjusted so that the fluid number defined by the following formula 1 is 1 to 4 when granulating, and more preferably 1.2 to 3. If the Froude number is less than 1, consolidation is not promoted, which is not preferable. If it exceeds 4, the particle size distribution becomes wide, which is not preferable.
Fr = V / (R × g) ^0.5 Formula 1
V: peripheral speed at the tip of the stirring blade [m / s]
R: Rotating radius of stirring blade [m]
g: Gravity acceleration [m / s ² ]
The chopper may not be used when aggregation of particles does not cause a problem, but it is generally preferable to use the chopper at 2000 to 7000 rpm.
The granulation time is preferably 0.5 to 15 minutes, more preferably 0.5 to 10 minutes, from the viewpoints of aggregation / dispersion of particles, heat generation due to power during granulation, and production capacity.

The addition rate of the α-SF salt-containing paste is determined from the mixed state and the particle size of the granules to be obtained, but it is preferable to add at 0.5 to 10 kg / min.
(A) It is preferable that the temperature of (alpha) -SF salt containing paste is 55-80 degreeC. It is preferable that the temperature of (b) and (c) component is 5-40 degreeC. In the case where coarse particles with agglomerated particles become a problem, it is possible to suppress aggregation by attaching a jacket to the outside of the agitation granulator and cooling it by flowing a coolant such as cooling water at 0 to 20 ° C.

Process 2
In Step 2 of the present invention, the granulated product obtained in Step 1 and A-type zeolite are mixed to obtain α-SF salt-containing granules.
[(D) A-type zeolite]
Type A zeolite acts as a builder. In general, A-type, P-type and X-type zeolites can be used, but in the present invention, A-type zeolite is used. Type A zeolite is inexpensive and has a high contribution to cleaning performance, and is excellent in fluidity and solidification of granules obtained by use. The average particle size of the primary particles of the A-type zeolite is preferably 1 to 10 μm. The average particle size of the A-type zeolite can be measured with a laser diffraction / scattering particle size distribution analyzer.
The amount of A-type zeolite is 0.01 to 0.18 parts by mass, preferably 0.05 to 0.12 parts by mass (based on hydrate) with respect to 1 part by mass of the granulated product obtained in step 1. Is used. If it is less than 0.01 part by mass, the coalescence of the granules is remarkable and becomes a lump. If the amount exceeds 0.18 parts by mass, the amount of the zeolite alone increases, so the solubility of the granules in water decreases.
As the stirring granulator that can be used in this step, the same apparatus as described in step 1 can be used. The conditions for stirring granulation in step 2 are the same as those described for step 1. The temperature of the granules obtained after step 2 is usually 25-50 ° C. When the temperature exceeds 50 ° C., many coarse particles may be generated due to aggregation of particles.

The amount of the α-SF salt in the granule obtained by the production method of the present invention is preferably 10 to 18% by mass, and more preferably 10 to 16% by mass. If it is less than 10% by mass, the range of utilization becomes narrow, the amount of inorganic builder compounding of other components is relatively increased, and the solubility of the granules in water decreases. When it exceeds 18 mass%, when it melt | dissolves in water, aggregation of the particle | grains by gelatinization of (alpha) -SF salt will generate | occur | produce frequently and the solubility to the water of a granule may fall.
The average particle size of the granules obtained by the production method of the present invention is about 200 to 800 μm, and the bulk density is about 0.5 to 1.0 g / cm ³ . The average particle size of the granules can be measured with a sieve (see [Method for measuring average particle size with sieve] described later) or a laser diffraction / scattering particle size distribution measuring apparatus. The bulk density can be measured according to JISK3362.
The water content of the granules obtained by the production method of the present invention is 1.0 to 3.0% by mass. This moisture content does not include moisture brought in from zeolite. If it is less than 1.0% by mass, there is a concern of dust generation. Moreover, when it exceeds 3.0 mass%, compressive strength may fall. The moisture content of the granules can be measured with a Kett moisture meter (trade name, manufactured by Ketto Scientific Laboratory; infrared moisture meter). The measurement conditions are 110 ° C. and 20 minutes.

Granules obtained by the production method of the present invention can be used as they are, or can be used in a powder mixture with granules containing other detergent components. Furthermore, it can also be made into a granular detergent composition together with an anionic surfactant, a nonionic surfactant, a builder, an enzyme, a pigment | dye, a fragrance | flavor, etc.
Examples of the anionic surfactant include linear alkylbenzene sulfonic acid and soap. As the nonionic surfactant, the same ones as described above can be used. Examples of the builder include zeolite, sodium tripolyphosphate, polyacrylic acid, acrylic acid-maleic acid copolymer, and the like.
The granular detergent composition of the present invention can be produced by spraying a nonionic surfactant onto the α-SF salt-containing granules obtained by the above method. In this case, it is preferable to spray 0.1-2.0 mass% nonionic surfactant with respect to the granule obtained at the process 2. FIG. The total amount of the nonionic surfactant contained in the granule and the nonionic surfactant sprayed on the granule is preferably 2 to 11% by mass based on the total amount of the granular detergent composition, and 3 to 8 mass. % Is more preferred. It is preferable that the total amount of the nonionic surfactant is in such a range because there is a dust generation suppressing effect and it is difficult to solidify.
The granular detergent composition of the present invention is also obtained by mixing the α-SF salt-containing granules obtained by the above-described method with a builder, spraying a nonionic surfactant and a pigment sequentially thereto, and finally adding an enzyme. It can also be manufactured.

〔material〕
<Ingredients used for production of α-SF salt-containing paste>
・ Methyl myristate (product name: Pastel M-14, manufactured by Lion Corporation)
・ Methyl palmitate (product name: Pastel M-16, manufactured by Lion Corporation)
・ Methyl stearate (product name: Pastel M-180, manufactured by Lion Corporation)
-Methanol (Methanol manufactured by Sumitomo Chemical Co., Ltd .: industrial grade moisture 500 ppm or less)
・ 35% hydrogen peroxide (35% industrial hydrogen peroxide manufactured by Mitsubishi Gas Chemical Co., Inc .: industrial grade)
-LAS-H: linear alkyl (C10-C14) benzenesulfonic acid (Laipon LH-200 (manufactured by Lion Corporation) LAS-H (pure content 96%)).
Nonionic surfactant: An average of 15 moles of ethylene oxide adduct of ECOROL 26 (alcohol having an alkyl group having 12 to 16 carbon atoms manufactured by ECOGREEN) (pure content: 90%).
・ NaOH (Caustic soda manufactured by Daiso Corporation: Industrial grade)

<Ingredients used for production of α-SF salt-containing granules>
・ Sodium carbonate: granular ash (Asahi Glass Co., Ltd., average particle size of 320 μm (measured with a sieve (refer to [Method for measuring average particle size by sieve] described later)), bulk density of 1.07 g / cm ³ )
Sodium sulfate: manufactured by Nippon Kagaku Kogyo Co., Ltd., neutral anhydrous sodium sulfate, average particle size of 300 μm (measured with a sieve (see “Measurement method of average particle size by sieve” described later)), bulk density of 1.53 g / cm ³ )
A-type zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd., pure content 80%, average particle size 4 μm (measured with a laser diffraction / scattering particle size measuring device), bulk density 0.45 g / cm ³ )
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd., average particle size 490 μm, bulk density 1.30 g / cm ³ ) crushed (average particle size 50 μm, bulk density 0.77 g / cm ³ )

<Ingredients used for production of anionic surfactant-containing particles and granular detergent composition in formulation example>
Sodium carbonate: grain ash (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ )
Maleic acid-acrylic acid copolymer: acrylic acid / maleic acid copolymer Na salt, Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
-Lauric acid: manufactured by NOF Corporation, NAA-122, melting point 43 ° C
A-type zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd., pure content 80%, bulk density 0.45 g / cm ³ )
LAS-K (potassium salt): Linear alkyl (C10-14) benzenesulfonic acid (Lypon LH-200 (manufactured by Lion Corporation)) LAS-H (96% pure) during preparation of spray drying slurry Neutralize with 48% aqueous potassium hydroxide). The compounding quantity in Table 4 shows the mass% as LAS-K.

Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: carbon number C12: 11.7%, carbon number C14: 0.4 %, Carbon number C16: 29.2%, carbon number C18F0 ^* (stearic acid): 0.7%, C18F1 ^* (oleic acid): 56.8%, carbon number 18F2 ^* (linoleic acid): 1.2% Molecular weight: 289). * F0, F1, and F2 are the number of double bonds in the fatty acid.
Nonionic surfactant: Ethanol oxide average 15-mole adduct of ECOROL 26 (alcohol having an alkyl group of 12 to 16 carbon atoms manufactured by ECOGREEN) (pure content 90%)
・ Sodium sulfite / potassium carbonate: pulverized potassium carbonate (powder) (Asahi Glass Co., Ltd. average particle size 490 μm, bulk density 1.30 g / cm ³ ) (average particle size 50 μm, bulk density 0.77 g / cm ³ )
Sodium sulfate: manufactured by Nippon Chemical Industry Co., Ltd., neutral anhydrous sodium sulfate (bulk density 1.53 g / cm ³ )
Enzyme: Sabinase 12TW (Novozymes Japan) / LIPEX100T (Novozymes Japan) / Stainzyme 12T (Novozymes Japan) / Cell Clean 4500T (Novozymes Japan) (Made by Co., Ltd.) = 4/2/2/2 (mass ratio) mixture, average particle size 700 μm, bulk density 0.85 g / cm ³
-Dye: Ultramarine (Daiichi Seika Kogyo Co., Ltd., Ultramarine Blue)
Fragrance: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]
-Fluorescent agent: Chinopearl CBS-X (Ciba Specialty Chemicals) / Chinopearl AMS-GX (Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture

Production Example 1 (A) Production of paste A containing α-SF salt
1.1 Production of α-sulfo fatty acid alkyl ester <Raw material>
As fatty acid alkyl ester, α-SF salt-containing paste A is a mixture of methyl myristate and methyl palmitate in a mass ratio of 18/82, and α-SF salt-containing paste B and C are methyl palmitate (lion Co., Ltd., trade name: Pastel M-16) and methyl stearate (Lion Corporation, trade name: Pastel M-180) are mixed at a mass ratio of 80:20 to produce a hydrogenation catalyst (commercial product). No. SO-850 (manufactured by Sakai Chemical Industry Co., Ltd.) was added in an amount of 0.1% by mass to the fatty acid methyl ester mixture, and hydrogenated at 170 ° C. for 1 hour, so that the iodine value was α The -SF salt-containing paste A was 0.2, and the α-SF salt-containing pastes B and C were 0.03. The iodine value is a value obtained by converting the amount of halogen that reacts with 100 grams of fatty acid alkyl ester into the number of grams of iodine, and was measured according to the standard fat analysis method 2.3.4.1-1996.
After the hydrogenation treatment, the catalyst was removed by filtration. As the sulfonation gas, SO ₃ gas produced by catalytic oxidation of SO ₂ using dry air (dew point −55 ° C.) was used. As the catalyst, vanadium pentoxide (manufactured by Monsanto) was used. As a coloring inhibitor, sodium sulfate (manufactured by Shikoku Kasei Co., Ltd .; particle size 40-50 μm) was used.

<Sulfonation>
Using a flow-down type thin film reactor, the fatty acid methyl ester is sulfonated with the SO ₃ gas under the conditions of a reaction molar ratio (SO ₃ / saturated fatty acid ester) = 1.18 and a reaction temperature of 80 ° C. I got a thing.
<Aging>
The resulting sulfonated product was aged. Aging is performed by continuously connecting three loop-type aging tubes with a double tube jacket having an average residence time of 20 minutes, and introducing the sulfonation product at an average residence time of 60 minutes. This was carried out by flowing and agitating the sulfonated product at a linear velocity of 0.16 m / s at an aging pipe setting temperature of 80 ° C.). In this way, α-SF acid was obtained.
<Bleaching>
20 parts by mass of methanol was added to 100 parts by mass of the obtained α-SF acid to obtain a mixture. This mixture and 5.7 parts by mass of 35% hydrogen peroxide were introduced into a continuous loop reactor equipped with a mixing mixer and a heat exchanger for bleaching (obtained an α-sulfo fatty acid methyl ester bleached product). .

1.2 Production of α-SF salt-containing paste Next, a 48% NaOH aqueous solution and a nonionic interface were prepared so that the paste obtained after neutralization and concentration had the same composition as the α-SF salt-containing paste A shown in Table 1. An activator, water, methanol, and the α-SF acid (α-sulfo fatty acid methyl ester bleached product) are introduced into a loop-type continuous neutralization apparatus, and the pH is adjusted to 7 to adjust the α-SF acid. Was neutralized to obtain an α-SF salt-containing composition. In addition, the apparatus shown in FIG. 1 was used as a loop type continuous neutralization apparatus. The loop-type continuous neutralization apparatus includes a mixing tank, a neutralization mixer, a recycle pump, an extraction pump, and a heat exchanger.
The α-SF salt-containing composition A obtained above was subjected to recycle flash evaporation with the apparatus shown in FIG. 2 to remove and concentrate the lower alcohol to obtain an α-SF salt-containing paste A. Note that the recycling flash evaporator includes a heater (for example, a plate-type heat exchanger), a pressure control valve (for example, a globe valve (3 / 8B) manufactured by KITZ), a flash can (capacity 30 L), and a circulation pump (for example, Daito Kogyo HP- 4TJV2B-38 (5L / min)) and a condenser (for example, a shell and tube heat exchanger). The conditions for the recycle flash evaporation are as follows: the heating tube temperature in the heater is 120 to 130 ° C., the heater internal pressure is 0.2 MPa or less, and the circulation pressure is 0.6 MPa or less. Concentrate flash at normal pressure until mass%.

Production Example 2 (A) Production of α-SF salt-containing paste B In Production Example 1, the raw material fatty acid methyl ester was changed to an 80/20 mixture (mass ratio) of methyl palmitate and methyl stearate, and aged α- Α-SF salt-containing paste B concentrated in the same manner as in Production Example 1 except that SF acid was mixed with LAS-H (therefore, the obtained α-SF salt-containing composition also contains LAS-Na). Got.

Production Example 3 (A) Production of α-SF salt-containing paste C In Production Example 1, the raw material fatty acid methyl ester was changed to an 80/20 mixture (mass ratio) of methyl palmitate and methyl stearate, and the water content was 25 to 26. A concentrated α-SF salt-containing paste C was obtained in the same manner as in Production Example 1 except that atmospheric pressure flash concentration was performed until the mass was reached.
Table 1 shows the compositions of the α-SF salt-containing pastes obtained in Production Examples 1 to 3.

[Example 1]
Process 1
(B) Sodium carbonate, (c) Sodium sulfate and A-type zeolite were charged into a stirring granulator. As the agitation granulator, a Roedige mixer (M20 type, manufactured by Matsubo Co., Ltd.) having a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm was used. The total of the input amounts was such that the apparent volume of the powder raw material blended in Step 1 and Step 2 was 4 L (filling rate 25% by volume).
Next, the spindle rotation speed was set to 175 rpm, and stirring was performed for 30 seconds with the chopper stopped (fluid number 2.4). Thereafter, while maintaining the main shaft rotation speed at 175 rpm, the chopper rotation speed was 4000 rpm, and 9 to 11 ° C. cold water was passed through the jacket at 7 kg / min, while (a) the α-SF salt-containing paste B (70 ° C.) was about The mixture was added at a rate of 1.7 kg / min and stirred under the same conditions for 30 seconds after the paste was charged to obtain a granulated product.
Process 2
After the addition of the α-SF salt-containing paste, (d) A-type zeolite was charged while the stirring granulator was operated under the same operating conditions. After completion of the A-type zeolite addition, the mixture was further stirred for 30 seconds under the same conditions to obtain α-SF salt-containing granules (35 ° C.).

[Example 2]
In Example 1, in addition to sodium carbonate, sodium sulfate and A-type zeolite, potassium carbonate was added to the agitation granulator in Step 1, and instead of α-SF salt-containing paste B, α-SF salt-containing paste A ( 70 ° C.) and α-SF salt-containing granules (37 ° C.) were obtained in the same manner as in Example 1 except that the amount of each component used was changed as shown in Table 2.

[Examples 3-4 and 6-7]
In Example 1, (alpha) -SF salt containing granule (35-36 degreeC) was obtained like Example 1 except having changed the quantity of each component used as described in Table 2.

Example 5
In Step 1 of Example 1, the nonionic surfactant (70 ° C.) was added after the α-SF salt-containing paste was added, and the amount of each component used was changed as shown in Table 2. Except for the above, α-SF salt-containing granules (35 to 37 ° C.) were obtained in the same manner as in Example 1.

[Comparative Examples 1 to 5 and 8]
In Example 1, (alpha) -SF salt containing granule (35-38 degreeC) was obtained like Example 1 except having changed the quantity of each component used as described in Table 2.

[Comparative Example 6]
In Example 1, in addition to sodium carbonate, sodium sulfate and A-type zeolite, potassium carbonate was added to the agitation granulator in Step 1, and α-SF salt-containing paste A was used instead of α-SF salt-containing paste B. An α-SF salt-containing granule (40 ° C.) was obtained in the same manner as in Example 1 except that it was used and the amount of each component used was changed as shown in Table 2.

[Comparative Example 7]
In Example 1, in place of the α-SF salt-containing paste B, α-SF salt-containing paste C (70 ° C.) was used, and the amount of each component used was changed as described in Table 2. Α-SF salt-containing granules (35 ° C.) were obtained in the same manner as in Example 1.

〔Evaluation method〕
Moisture of α-SF salt-containing granules obtained in Examples and Comparative Examples, α-SF salt mass% in granules, average particle diameter, particle cohesiveness, solubility and solidification (compressive strength (deformation of molded body by load) (deformation) The compressive strength) was evaluated by the method described below. The results are shown in Table 2.
[Method of measuring moisture content of α-SF salt-containing granules]
The moisture content of the granules was measured with a Kett moisture meter (trade name, manufactured by Ketto Scientific Laboratory; infrared moisture meter). The measurement conditions were 110 ° C. and 20 minutes.
[Method for measuring α-SF salt concentration]
Standard α-SF salt products (0.02, 0.05, 0.1 g) were accurately weighed into a 200 mL volumetric flask, and methanol was added and dissolved using ultrasonic waves. After dissolution, the mixture was cooled to about 25 ° C., and methanol was accurately added up to the marked line to obtain a standard solution.
About 2 mL of this standard solution was filtered using a 0.45 μm chromatographic disk and then subjected to high performance liquid chromatography under the following measurement conditions to prepare a calibration curve from the peak area.
(High-performance liquid chromatography measurement conditions)
・ Device (liquid feed pump): LC-6A (manufactured by Shimadzu Corporation)
Column: Nucleosil AX (manufactured by GL Sciences)
Column temperature: 40 ° C.
・ Detector: Differential refractive index detector RID-6A (manufactured by Shimadzu Corporation)
-Mobile phase: 0.75% sodium perchlorate, 0.2% monochloroacetic acid in methanol-Flow rate: 1.0 mL / min.
・ Injection volume: 100 μL
Next, 1.5 g of α-SF salt-containing paste was accurately weighed into a 200 mL volumetric flask, and about 50 mL of water and about 50 mL of methanol were added and dissolved using ultrasonic waves. After dissolution, the mixture was cooled to about 25 ° C., and methanol was accurately added up to the marked line to make a test solution.
About 2 mL of the test solution was filtered using a 0.45 μm chromatographic disk, analyzed by high performance liquid chromatography under the same measurement conditions as described above, and the α-SF salt in the sample solution using the calibration curve prepared above. The concentration was determined.

[Measurement method of average particle diameter by sieve]
Classification operation was performed using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening and a sieve with a large opening are stacked in the order of the sieve, and a sample of 100 g / time is put on the top of the top 1680 μm sieve. ) Made by Iida Seisakusho, Tapping: 156 times / minute, Rolling: 290 times / minute), and vibrated for 10 minutes under an atmospheric condition of a temperature of 25 ° C. and a relative humidity of 40%. Operation which collect | recovers the remaining sample for every sieve mesh was performed.
By repeating this operation, 1410 to 1680 μm (1410 μm.on), 1190 to 1410 μm (1190 μm.on), 1000 to 1190 μm (1000 μm.on), 1000 to 710 μm (710 μm.on) 500 to 710 μm (500 μm.on) ), 350 to 500 μm (350 μm.on), 250 to 350 μm (250 μm.on), 149 to 250 μm (149 μm.on), dish to 149 μm (149 μm.pass), and classified samples with respective particle sizes, and weight frequency ( %) Was calculated.
Next, the opening of the first sieve with a calculated weight frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, and the cumulative weight frequency from the tray to the sieve of a μm is calculated as c %, And the weight frequency on a μm sieve was d%, and the average particle diameter (weight 50%) was determined by the following formula.

Average particle diameter (weight 50% diameter) =
10 (50- (cd / (log b-log a) x log b)) / (d / (log b-log a))

[Particle Aggregation Evaluation Method]
The α-SF salt-containing granules immediately after production were passed through a sieve having a mesh opening size of 1.7 mm, and the mass of the material remaining on the sieve was measured. By calculating the ratio of the α-SF salt-containing granules remaining on the sieve from the mass of the α-SF salt-containing granules that passed through the sieve relative to the mass of the α-SF salt-containing granules before passing through the sieve, Evaluated.
Evaluation criteria ◎: 0% to 15%
○: Over 15% to 30%
Δ: over 30% to 50%
X: Over 50% to 100%

[Solubility Evaluation Method]
Two acrylic shirts, two nylon slips and two cotton shirts were used as the cloth to be washed, and five skin shirts were used as the weight balance cloth to make the total weight 1.5 kg. These were put into a two-tank washing machine CW-225 (W) manufactured by Mitsubishi Electric Corporation. The three types of cloth to be washed were made to be able to see all the cloths when viewed from above. 30 g of α-SF salt-containing granules of Examples or Comparative Examples and 30 liters of tap water at 20 ° C. were added and washed for 5 minutes at a bath ratio of 1:20.
After the washing was finished, the cloth to be washed was dehydrated for 1 minute, and the adhesion amount of the α-SF salt-containing granules to the cloth to be washed was visually evaluated according to the following evaluation criteria.
Evaluation criteria ○: No or almost no deposits are found Δ: Very little deposits are found ×: Many deposits are found

[Method for evaluating solidification (method for evaluating the compressive strength of a molded article by load)]
The α-SF salt-containing granules of Examples or Comparative Examples heated to 35 ° C. up to a height of 5 cm were placed in a cylinder having a diameter of 5 cm and a height of 10 cm heated to 35 ° C. A cylinder having a diameter of 4.9 cm and a weight of 3 kgf was put into the cylinder from above, and the granules were loaded and allowed to stand for 3 minutes to obtain a cylindrical granule molded body. The obtained molded body was allowed to stand on an electronic balance, the pressure arm attached with a horizontal plate was lowered at a speed of 3 cm / min, a load was gradually applied to the molded body, and the maximum amount of time required to collapse. The load (kg) was measured.
The maximum load (kg) applied until the molded body collapsed was evaluated based on the following evaluation criteria.
Evaluation criteria ○: Maximum load applied until the molded body collapses: less than 3 kg Δ: Maximum load applied until the molded body collapses: 3 kg to less than 5 kg ×: Maximum load applied until the molded body collapses : 5kg or more

[Prescription example]
From the α-SF salt-containing granules of Example 1, granular detergent compositions shown in Table 3 were prepared by the following method.

Surface coated sodium carbonate was prepared as follows:
Sodium carbonate was charged into a stirring granulator (Laedge mixer (Matsubo Co., Ltd., M20 type)) (filling rate: 30% by volume), and the spindle rotation speed was 200 rpm, and the chopper was stirred and stopped. Ten seconds after the start of stirring, a maleic acid-acrylic acid copolymer was added over 30 seconds, and the sodium carbonate surface was coated with the copolymer.
Lauric acid was added over 30 seconds with stirring under the same conditions, and the copolymer was further coated with lauric acid.
The composition of the surface-coated sodium carbonate is 85% by weight of sodium carbonate, 3% by weight of maleic acid-acrylic acid copolymer, 7% by weight of lauric acid, and the balance is water.

Anionic surfactant-containing particles were produced as follows:
[Preparation of spray-dried particles]
The components shown in the spray-dried particle composition of Table 4 were charged into a reactor having a stirrer and a jacket, dissolved and dispersed in water (stirrer jacket temperature 75 ° C.), and a slurry having a solid content concentration of about 60% by mass was prepared. .
Subsequently, this slurry was spray-dried under the following conditions using a countercurrent drying tower to obtain spray-dried particles. Further, A-type zeolite (2) was introduced as a spray-dried particle coat coating agent from the lower part of the spray-drying tower so as to have a blending ratio shown in Table 4.
Spray drying apparatus: countercurrent type, tower diameter 2.0 m, effective length 5.0 m.
・ Atomization method: Pressure nozzle method.
- Spray pressure: 30kg / cm ^2.
-Hot air inlet temperature: 300 degreeC.
-Hot air outlet temperature: 100 ° C.
The average particle diameter of the obtained spray-dried particles was about 300 μm, the bulk density was 0.3 g / cm ³ , and the water content was 5% by mass. The average particle size of the spray-dried particles was measured by the method described above in [Method for measuring average particle size using sieve]. The water content (mass%) in the spray-dried particles was measured with a Kett moisture meter (trade name, manufactured by Ketto Scientific Laboratory; infrared moisture meter). The measurement conditions were 170 ° C. and 20 minutes.

[Preparation of dough]
The obtained spray-dried particles and the blending ingredients shown in Table 4 were put into a continuous kneader (Kurimoto Steel Works, KRC-S4 type) and kneaded [conditions: kneader rotation speed 135 rpm, Jacket temperature: jacket inlet 5 ° C., outlet 25 ° C. (cooled by passing water through the jacket)], and a dough-like material was prepared. The temperature of the resulting dough was 55 ± 15 ° C.
[Dough-like granulation]
Next, the obtained dough-like material was put into a pelleter double (Fuji Paudal Co., Ltd., product name: EXD-100 type), and extruded from a die having a hole diameter of about 10 mm and a thickness of 10 mm, and simultaneously cut. A pellet-shaped formed body [diameter of about 10 mm, length of 70 mm or less (substantially 5 mm or more)] was obtained [the cutter peripheral speed of the pelleter (cutter) was 5 m / s].

[Crushing]
To this pellet-like molded product, A-type zeolite (3) as a grinding aid was added, and Fitzmill (made by Hosokawa Micron Co., Ltd., DKA-6 type) arranged in three stages in the presence of air blowing was used. The powder was obtained by grinding. The grinding conditions were as follows. The temperature of the obtained powder was 30 ± 10 ° C.
-Air temperature: 15 ± 3 degreeC.
-Air flow rate (ratio of gas / solid): 2.8 ± 0.25 m ³ / kg.
-Screen diameter: 6 mm for the first stage, 4 mm for the second stage, and 2 mm for the third stage.
-Crusher rotation speed: 4700 rpm (circumferential speed about 60 m / s).
Processing speed: 244 kg / hr.

[Preparation method of formulation example]
Α-SF salt of Example 1 on a horizontal cylindrical rolling drum (with a baffle plate having a diameter of 0.70 m, a length of 1.40 m, an inclination angle of 3 °, a thickness of 1 mm, a height of 50 mm, and a length of 350 mm) The containing granules, surface-coated sodium carbonate, anionic surfactant-containing particles and A-type zeolite were added according to the ratios in Table 3, mixed and sprayed with a nonionic surfactant at the same time. The nonionic surfactant was sprayed at a spraying pressure of 0.5 to 1.5 MPa using a pressure cone nozzle K series (manufactured by Ikeuchi Co., Ltd.). Then, after spraying a dye (20% by mass aqueous solution) and a fragrance, an enzyme was added to obtain a granular detergent composition of the formulation example. The moisture was measured with a Kett moisture meter (trade name, manufactured by Kett Scientific Laboratory; infrared moisture meter). The measurement conditions were 130 ° C. and 20 minutes.

It is a schematic block diagram of the loop type continuous neutralization apparatus which can be used in the Example of this invention. It is a schematic block diagram of the recycle flash evaporator which can be used in the Example of this invention.

Claims (7)

The manufacturing method of the granule for detergent containing the alpha-sulfo fatty-acid alkylester salt which has the C14-C18 alkyl group characterized by including the following processes 1 and 2:
Step 1:
(A) A paste containing an α-sulfo fatty acid alkyl ester salt having an alkyl group having 14 to 18 carbon atoms and a nonionic surfactant, wherein the α-sulfo fatty acid alkyl ester salt is added to the total mass of the paste. containing 60 wt% to 80 wt% Te, and the α- sulfofatty acid alkyl ester salt / nonionic surfactant (mass ratio) is a = 1 / 0.2 to 1 / 0.4 of the paste, step 2 15 to 30% by mass based on the granules obtained in
(B) Sodium carbonate and (c) Sodium sulfate are granulated with stirring.
(B) the total amount of sodium carbonate and (c) sodium sulfate is 50-80% by weight based on the granules obtained in step 2, and (b) sodium carbonate / (c) sodium sulfate (mass ratio) Process step 2 for obtaining a granulated product of 1 / 0.5 to 1 / 0.1:
(D) A type zeolite: 0.01-0.18 mass part (hydrate reference | standard) is added with respect to 1 mass part of granulated materials obtained at the said process 1, and both are mixed. The production method according to claim 1 , wherein the water content in the obtained granules is 1.0 to 3.0% by mass ( however, this water content does not include water brought in from zeolite ). The production method according to claim 1 or 2, wherein an amount of the α-sulfo fatty acid alkyl ester salt having an alkyl group having 14 to 18 carbon atoms in the granule is 10 to 18% by mass. The production method according to claim 3, wherein the amount of the α-sulfo fatty acid alkyl ester salt having an alkyl group having 14 to 18 carbon atoms in the granule is 10 to 16% by mass. The production method according to any one of claims 1 to 4 , wherein an amount of the nonionic surfactant contained in the granule is 2 to 11% by mass.   The manufacturing method of any one of Claims 1-5 in which the said granule does not contain potassium carbonate. Sprayed detergent granules containing α- sulfofatty acid alkyl ester salts having any one alkyl group having a carbon number of 14 to 18 produced by the method according to claims 1-6, a nonionic surfactant A process for producing a granular detergent composition comprising:

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