JP2005120159A - Powder detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition containing anionic surfactant granules which contains a polyoxyalkylene alkyl ether sulfate salt and is excellent in resistance to hard water and low-temperature solubility and is enhanced in powder characteristics such as caking resistance. <P>SOLUTION: The detergent composition comprises (a) specific anionic surfactant granules and (b) builder particles and has a surfactant equivalent, an apparent density and an average particle size each in a specific range. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a powder cleaning composition. Preferably, it is related with the powder cleaning composition for textiles used by melt | dissolving in water.

  An anionic surfactant having a sulfate group is because of its emulsification and dispersibility, so it is a detergent and various chemical additives such as clothes detergent, kitchen detergent, toothpaste foaming agent, powder shampoo, emulsion polymerization emulsifier. As a foaming agent for cement, a pharmaceutical / cosmetic emulsifier, etc., it is widely used from household use to industrial use.

  Anionic surfactants typified by alkyl sulfates obtained by sulfating / neutralizing higher alcohols are commercialized as powder products by drying their aqueous solutions. Has a problem with hard water resistance, and the cleaning performance is not sufficiently satisfactory, and there is a demand for improvement.

  On the other hand, the polyoxyalkylene alkyl ether sulfate obtained by adding an alkylene oxide to a higher alcohol and then sulfating / neutralizing has a lower Kraft point compared to an alkyl sulfate having an alkyl group with the same carbon number, and is low in temperature. Since it has excellent solubility and excellent hard water resistance, it is used as a main base for liquid detergents. However, due to the problem of poor caking resistance unique to polyoxyalkylene alkyl ether sulfates, it has been extremely difficult to blend in large amounts in a powder cleaning composition.

  For example, Patent Document 1 describes a method for producing an anionic activator granular material. In Example 3 of Patent Document 1, a solid slurry having a solid content concentration of 80% by mass of polyoxyethylene alkyl ether sulfate is dried. However, it was not possible to say that this granular material had a high water content of about 8% by mass, and had good fluidity with improved caking resistance. Further, although a detergent raw material containing a liquid surfactant, a water-soluble carrier, and a water-soluble structurant has been studied (Patent Document 2), the polyoxyalkylene alkyl ether sulfate contains only about 40% by mass at most. could not.

Therefore, a commercialized product containing a large amount of polyoxyalkylene alkyl ether sulfate has a liquid or pasty form, and a powdered product having excellent fluidity has not been industrialized yet.
Japanese Patent Laid-Open No. 5-331496 International Publication No. 00/31223 Pamphlet

  The object of the present invention is to contain an anionic surfactant granule containing polyoxyalkylene alkyl ether sulfate, which has excellent hard water resistance and low-temperature solubility, and improved powder characteristics such as caking resistance. An object of the present invention is to provide a cleaning composition.

The present invention provides (a) polyoxyalkylene alkyl ether containing 60% by mass or more of polyoxyalkylene alkyl ether sulfate having an average addition mole number of alkylene oxide of 0.05 to 2 and having added 4 mol or more of alkylene oxide. Anionic surfactant granulated product (hereinafter referred to as component (a)) having a sulfate content of 30% by mass or less based on the total amount of the anionic surfactant in component (a),
(B) Builder particles (hereinafter referred to as component (b)) containing 50% by mass or more of a builder having at least one of a metal chelating action, an alkali buffering action, and a solid particle dispersing action;
Containing
(I) 10-60 mass% equivalent to the surfactant described in JIS K 3362: 1998,
(II) JIS K 3362: The apparent density of all compositions measured by the method described in 1998 is 300 to 1200 g / L,
(III) The average particle size of all compositions determined from the particle size measured by the sieving method using a sieving machine described in JIS K 3362: 1998 is 150 to 2000 μm,
It is related with the cleaning composition which is.

  In the present invention, the polyoxyalkylene alkyl ether sulfate of component (a) is a mixture of polyoxyalkylene alkyl ether sulfate and alkyl sulfate when component (a) contains alkyl sulfate. The average added mole number of alkylene oxide for component (a) is the alkyl contained in the anionic surfactant granulated product when alkyl sulfate is included in component (a). It means the average number of moles of alkylene oxide added in a mixture of sulfate and polyoxyalkylene alkyl ether sulfate.

  The cleaning composition of the present invention is excellent in powder characteristics such as hard water resistance, low-temperature solubility, and caking resistance.

  In terms of low-temperature solubility, stability, and cleaning performance, the apparent density measured by the method described in JIS K 3362: 1998 is preferably 400 to 1100 g / L, more preferably 600 to 1000 g / L, and more preferably 700 to 980 g / L. Further preferred.

  In terms of low-temperature solubility and detergency, the average particle size determined from the particle size measured by the sieving method described in JIS K 3362: 1998 is preferably 250 to 1800 μm, more preferably 300 to 1500 μm, still more preferably. 300 to 1000 μm.

  In the cleaning composition of the present invention, the pH of 0.05% by mass measured at 20 ° C. described in JIS K3362: 1998 is preferably 8-12, more preferably 9-11.5 in terms of cleaning performance and damage. 9.5 to 11 are more preferable, and 10 to 11 are particularly preferable.

  The equilibrium relative humidity at 40 ° C. of the cleaning composition of the present invention is preferably 15 to 35%, more preferably 18 to 32%, and still more preferably 20 to 30% in terms of storage stability. Equilibrium relative humidity is measured in a 2.4 liter moisture-proof container (a) 600g component and polymer thin film humidity sensor (preferably a combination of T & D Thermo Recorder Ondotori RH TR-72S and TR-3110 temperature and humidity sensor ) And seal. This is maintained at 40 ° C. and stored for 24 hours. Humidity readings are read every 30 minutes, and the value at which there is no change is the equilibrium relative humidity.

<(A) component>
The cleaning composition of the present invention contains, as component (a), 60% by mass or more of polyoxyalkylene alkyl ether sulfate having an average addition mole number of alkylene oxide of 0.05 to 2, and 4 moles of alkylene oxide. It contains an anionic surfactant granulated product in which the content of the added polyoxyalkylene alkyl ether sulfate is 30% by mass or less based on the whole anionic surfactant in the component (a). In terms of cleaning performance, hard water resistance, low temperature solubility, and caking resistance, 1 to 90% by mass is preferable, 5 to 80% by mass is more preferable, and 10 to 70% by mass is further preferable. -60 mass% is particularly preferred.

  In terms of hard water resistance, low-temperature solubility, and caking resistance, the polyoxyalkylene alkyl ether sulfate having an average addition mole number of alkylene oxide in the component (a) of the present invention of 0.05 to 2 is 60 to 99 mass% is preferable, 70-98 mass% is more preferable, 80-95 mass% is still more preferable.

  In the polyoxyalkylene alkyl ether sulfate contained in the component (a) of the present invention, the average added mole number of alkylene oxide is an important factor, and excellent powder characteristics are obtained. From the viewpoint of improving the average number of moles of alkylene oxide added, it is 0.05 to 2, preferably 0.1 to 1, and more preferably 0.2 to 0.8. Here, the average number of added moles is a molar average measured by HPLC-MS (high performance liquid chromatography-mass spectrometer).

  Furthermore, when there are many compounds in which a large amount of alkylene oxide has been added, even if the average number of added moles is in the range of 0.05 to 2, fluidity cannot be maintained. Specifically, it is necessary that the content of the polyoxyalkylene alkyl ether sulfate added with 4 mol or more of alkylene oxide is 0 to 30% by mass with respect to the entire anionic surfactant in the component (a). Preferably it is 0-20 mass%, More preferably, it is 0-15 mass%.

  In addition, the carbon number of the alkyl group in the polyoxyalkylene alkyl ether sulfate is 8 to 20 in terms of ease of handling during production, performance such as caking resistance when powdered, powder solubility, and the like. Is preferable, and 10 to 18 is more preferable.

Examples of the polyoxyalkylene alkyl ether sulfate according to the present invention include compounds represented by the general formula (I).
_{^{[R 1 -O (AO) n}} -SO 3] p M (I)
[Wherein, R ¹ is a linear alkyl group having 8 to 20 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an average added mole number of alkylene oxide, a number of 0.05 to 2, M is a cation, p is the valence of M, and n AOs may be the same or different. ]

In general formula (I), R ¹ is preferably an alkyl group having 10 to 18 carbon atoms. AO is preferably an oxyalkylene group having 2 to 3, particularly 2 carbon atoms. n is preferably a number from 0.1 to 1, particularly from 0.2 to 0.8. M is preferably an alkali metal atom such as Na or K, an alkaline earth metal atom such as Ca or Mg, or an alkanol-substituted or unsubstituted ammonium group, and more preferably an alkali metal atom, particularly Na. p is preferably 1 or 2, and more preferably 1.

  The polyoxyalkylene alkyl ether sulfate according to the present invention is not particularly limited in the addition distribution of alkylene oxide, and may be an addition distribution obtained by a known method such as broad and narrow distribution. However, if pursuing both the washing performance and the caking property, the content of the alkyl sulfate is 30 to 95% by mass in the polyoxyalkylene alkyl ether sulfate having an average addition mole number of alkylene oxide of 0.05 to 2. Is preferable, and 50-90 mass% is still more preferable.

  The component (a) of the present invention preferably further contains water (water by the superheat loss method described in JIS K 3362: 1998) in terms of productivity, solubility, and caking resistance. It is more preferable to contain 0.1-10 mass%, 0.5-5 mass% is still more preferable, and 0.5-2 mass% is especially preferable.

  The component (a) of the present invention preferably further contains a water-soluble inorganic salt. Examples of the water-soluble inorganic salt include sodium chloride, sodium sulfate, sodium carbonate and the like. The content of the water-soluble inorganic salt in the anionic surfactant granulated product of the present invention is not particularly limited as long as the object of the present invention is not hindered, but is usually polyoxyalkylene alkyl ether sulfate. 10 mass parts or less, preferably 2 mass parts or less with respect to 100 mass parts of the salt is desirable in terms of keeping the solid content of the polyoxyalkylene alkyl ether sulfate high.

  The component (a) of the present invention can contain other additives as necessary. Other additives include, for example, alkalizing agents such as silicates and carbonates, divalent metal ion scavengers such as citrate and zeolite, anti-contamination agents such as polyvinylpyrrolidone and carboxymethylcellulose, and other caking Examples thereof include an inhibitor and an antioxidant. Such other additives can be used as long as the object of the present invention is not impaired.

  The component (a) of the present invention may also contain water, unreacted alcohol and the like.

  The component (a) of the present invention is obtained by drying and granulating a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste obtained by the method shown in the following Step 1 by a known method as shown in Step 2. Can be obtained.

Step 1: Step of Preparing Polyoxyalkylene Alkyl Ether Sulfate-Containing Aqueous Solution or Paste To prepare a polyoxyalkylene alkyl ether sulfate-containing aqueous solution, the following methods (1) to (3) are exemplified.
(1) An alkylene oxide adduct of a higher alcohol obtained by adding an alkylene oxide to an alcohol having 8 to 20 carbon atoms (hereinafter referred to as a higher alcohol) so as to have an average addition mole number of 0.05 to 2 is sulfated and neutralized. Method.
(2) A method in which a higher alcohol and an alkylene oxide adduct of a higher alcohol are mixed so that the average number of added moles of alkylene oxide in the mixture is 0.05 to 2, and then sulfated and neutralized.
(3) A method in which a higher alcohol and an alkylene oxide adduct of a higher alcohol are separately sulfated and neutralized, and mixed so that the average number of moles of alkylene oxide added to the mixture is 0.05-2.

  Sulfation and neutralization can be performed by known methods. The sulfating agent used for sulfation is preferably sulfur trioxide or chlorosulfonic acid. When using sulfur trioxide gas, it is usually diluted with an inert gas, preferably dry air or nitrogen, and a sulfur trioxide gas concentration of 1 to 8% by volume, preferably 1.5 to 5% by volume of gas. Used as a mixture. Examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, sodium carbonate and the like.

  The unreacted component contained in the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste of the present invention is not preferable because it causes a decrease in purity and the caking property of the powder. Is acceptable, and more preferably 2% by mass or less. Here, the unreacted component includes alcohol, alkoxylate that has not been sulfated, and a small amount of hydrocarbon and wax by-produced from the reaction.

  The effective component of the neutralized product obtained by the above method is preferably 30% by mass or less, and if it exceeds 30% by mass, the viscosity increases and the handleability deteriorates. Moreover, since it becomes paste-form in 60-80 mass% of active ingredients, and shows fluidity | liquidity, preparing this comparatively high concentration paste at the time of neutralization reduces the energy load at the time of drying, and more preferable.

  In the present invention, a water-soluble inorganic salt may be present in the product. Representative examples of the water-soluble inorganic salt include sodium chloride, sodium sulfate, sodium carbonate and the like. These water-soluble inorganic salts may be added as they are, but may be by-produced by reaction. For example, when NaClO (sodium hypochlorite) is added to a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste for the purpose of improving the hue, NaCl (sodium chloride) is by-produced. Although use is limited, sodium hypochlorite can be added in this way, and sodium chloride can also be by-produced as an inorganic salt.

  The obtained polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste is subjected to the next step 2.

Step 2: Drying and granulating step Step 2 is a step of drying and granulating the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste prepared in Step 1 under various conditions. Sometimes it happens.

  As a drying means, drying under vacuum is preferable in order to suppress degradation in quality such as hydrolysis due to heating of the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste. Furthermore, in view of the foaming property peculiar to polyoxyalkylene alkyl ether sulfate and pulverization at the end of drying, a continuous or batch-type vacuum dryer having a stirring blade and a crusher or a drying process capable of obtaining the same effect is preferable. Examples of the continuous dryer include rotating thin film evaporators such as Contro, Cebucon [trade name, manufactured by Hitachi, Ltd., trade name], Smith thin film evaporator [manufactured by Shinko Pantech Co., Ltd.], and the like. . In the case of these continuous dryers, a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste can be continuously charged into a rotary thin film evaporator under reduced pressure to obtain a dried product. Examples of the batch dryer include a mixer vacuum dryer (SV mixer) manufactured by Shinko Pantech Co., Ltd., a microwave granulator / dryer manufactured by Fukae Powtech Co., Ltd., and Tanabe Wiltech Co., Ltd. And the like. Among these, a microwave granulator / dryer which is easy to perform step 1 in the same tank and can be dried and granulated in step 2 is particularly preferable because the load on the equipment is small.

  As drying conditions at this time, drying at a degree of vacuum at which the temperature of the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste becomes 80 ° C. or lower reduces heat history and suppresses degradation of quality such as decomposition. To preferred.

  As a more specific drying method, a method in which the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste obtained in Step 1 is dried by any of the following methods (4) to (6) can be mentioned.

(4) A stirring blade and / or a crusher for a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste, or a mixture of a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste and an alkyl sulfate-containing aqueous solution, paste or powder. The batch type vacuum dryer which has this and puts it in a lump, and dries under reduced pressure.
(5) In a batch-type vacuum dryer having a stirring blade and / or a pulverizer, an anionic surfactant granulated material is charged in advance to such an extent that an effect of stirring and pulverization can be obtained, and then the powder in the machine under reduced pressure. A method of drying by supplying an aqueous solution or paste containing a polyoxyalkylene alkyl ether sulfate at a supply rate such that the body maintains a powder state. The anionic surfactant granulated product prepared in advance at this time may be used in combination with the anionic surfactant granulated product obtained in the present invention or an alkyl sulfate powder, or only an alkyl sulfate powder. Good.
(6) A method in which a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste is continuously charged into a rotary thin film evaporator under reduced pressure and dried.

  On the other hand, an aqueous solution having a polyoxyalkylene alkyl ether sulfate content of 30% by mass or less has a relatively low viscosity and fluidity, and a dryer using a spray dryer or the like can also be used. However, a polyoxyalkylene alkyl ether sulfate content of 30% by mass or more and 60% by mass or less is not preferable because the viscosity is remarkably increased and the spray device is blocked.

  The component (a) in the present invention can be granulated and used as necessary, but the granulator that can be used at that time is not particularly limited. For example, a stirring rolling granulator (Fukae Pautech Co., Ltd., Tanabe) Can be used, and can be granulated by adding water, an aqueous solution containing polyoxyalkylene alkyl ether sulfate as a binder, and can obtain a granulated product with an appropriate particle size by sieving. it can. The size and shape of the granulated product at this time are not particularly limited, but in order to improve the solubility in water, the particle size is preferably 150 to 3000 μm, more preferably 150 to 2000 μm, and further preferably 150 to 1500 μm.

  The apparent density of component (a) is measured by the method described in JIS K 3362: 1998, and is preferably 300 to 1200 g / L, more preferably 400 to 900 g / L in terms of low-temperature solubility, stability, and detergency. L, particularly preferably 500 to 800 g / L.

  Extrusion granulation can also be performed. There is no restriction | limiting in particular as a needle machine which can be used in this case, An extrusion granulator (made by Dalton Co., Ltd.) etc. can be used, and it can granulate using the same binder as the above. Although there is no restriction | limiting in the magnitude | size of an extrusion granulated material, the thing of 0.5-1.0 mm in diameter and 3-5 mm in length is preferable from a viewpoint of handling.

  Furthermore, the granulation which combined this extrusion granulation and crushing granulation or extrusion granulation, crushing granulation, and stirring rolling granulation can also be performed. That is, a cylindrical granulated product obtained by an extrusion granulator is crushed by a crushing granulator and then obtained by sieving, or by using an extrusion granulator. After the obtained cylindrical granulated material is crushed by a crushing granulator, it is charged into a stirring tumbling granulator, further granulated by adding a predetermined amount of water, and sieving to obtain a predetermined particle size. The granulated product of component (a) can be obtained by a method of obtaining a granulated product having

  In addition, the granulated product of component (a) obtained by these methods may be coated with an inorganic powder such as mirabilite or zeolite or an alkyl sulfate powder as necessary to further improve the powder physical properties. It is also preferable to improve.

<(B) component>
The cleaning composition of the present invention contains, as component (b), builder particles containing 50% by mass or more of a builder having at least one of a metal chelate action, an alkali buffer action, and a solid particle dispersion action. In terms of cleaning performance, hard water resistance, low-temperature solubility, and caking resistance, 1 to 80% by mass is preferable, 5 to 70% by mass is more preferable, 10 to 60% by mass is further preferable, and 20 ˜50 mass% is particularly preferred.

  In terms of low-temperature solubility and caking resistance, the builder in component (b) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. .

  Examples of the builder of the component (b) include detergents and washing encyclopedias, Asakura Shoten Co., Ltd., November 25, 1990, first edition, first edition, Haruhiko Okuyama, Motomi Minagawa, pages 56-74. .

  Among them, zeolite, amorphous aluminosilicate, crystalline silicate, sodium tripolyphosphate, sodium pyrophosphate, carbonate, silicate are preferable as the inorganic builder, and aminocarboxylate, hydroxy is preferable as the organic builder. Amino carboxylate, hydroxycarboxylate, cyclocarboxylate, ether carboxylate, and organic carboxylic acid (salt) polymer are preferred. In particular, zeolite, carbonate and silicate are preferable as the inorganic builder, and organic carboxylic acid (salt) polymer is preferable as the organic builder.

  In view of low-temperature solubility and caking resistance, the component (b) has an apparent density measured by the method described in JIS K 3362: 1998 of preferably 300 to 1000 g / L, more preferably 400 to 1000 g / L, and 600 to 950 g / L is more preferable, and 700 to 950 g / L is particularly preferable. Moreover, the average particle diameter calculated | required from the particle size measured by the screening method by the screening machine of JISK3362: 1998 is preferable 150-1000 micrometers, 150-750 micrometers is more preferable, 150-700 micrometers is still more preferable, 180-600 micrometers is preferable. Particularly preferred.

  The component (b) can be obtained by making a builder component into a slurry and spray-drying it, or by granulating using a binder component.

<Equivalent to surfactant described in JIS K 3362: 1998>
In the powder detergent composition of the present invention, the amount corresponding to the surfactant described in JIS K 3362: 1998 is 10 to 60% by mass. 15-50 mass% is preferable and 20-40 mass% is more preferable at the point of productivity, solubility, and caking resistance.

  The component corresponding to the surfactant may be the component (a) alone, or in addition to the component (a), an anionic surfactant other than the component (a), a nonionic surfactant, an amphoteric surfactant, One or more ionic surfactants can be used in combination. Preferably, in addition to component (a), an anionic surfactant other than component (a) and a nonionic surfactant are used. It is to be used in combination.

  As the anionic surfactant other than the component (a), alkylbenzene sulfonate, paraffin sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt or fatty acid salt are preferable. . In the present invention, a linear alkylbenzene sulfonate having an alkyl chain having 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms is preferable, and an alkali metal salt or an amine is preferable as the counter ion. Or potassium, monoethanolamine, and diethanolamine are preferable.

  Nonionic surfactants include polyoxyalkylene alkyl (carbon number 8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (carbon number 8-20) phenyl ether, polyoxyalkylene sorbitan fatty acid (carbon number 8-8). 22) Ester, polyoxyalkylene glycol fatty acid (carbon number 8 to 22) ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, the nonionic surfactant is preferably a polyoxyalkylene alkyl ether obtained by adding an average of 4 to 20 moles of an alkylene oxide such as ethylene oxide or propylene oxide to an alcohol having 10 to 18 carbon atoms. The nonionic surfactant preferably has an HLB value (calculated by the Griffin method) of 10.5 to 15.0, more preferably 11.0 to 14.5.

  Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose.

<Other ingredients>
The cleaning composition of the present invention comprises a bleaching agent (percarbonate, perborate, bleach activator, etc.), a recontamination inhibitor (carboxymethylcellulose, etc.), a softening agent known in the field of garment cleaning agents. , Reducing agents (sulfites, etc.), fluorescent brighteners, foam inhibitors (silicones, etc.), enzymes, colorants, fragrances, and the like can be included.

  In addition, surface modification may be performed from the viewpoint of fluidity of the detergent particles and caking resistance. Examples of the surface modifier include aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, silicate compounds such as crystalline silicate compounds, metal soap, powder surfactants, etc. Fine powder, carboxymethyl cellulose, polyethylene glycol, polyacrylic acid soda, water-soluble polymers such as polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, and fatty acids. Aluminosilicates and crystalline silicates are more preferable, and aluminosilicates are more preferable.

  The content of the surface modifier is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less in the cleaning agent of the present invention from the viewpoint of storage stability. Moreover, 1 mass% or more in the high bulk density cleaning agent of this invention is preferable at the point of surface modification, 3 mass% or more is more preferable, and 5 mass% or more is still more preferable.

  In the following examples, what is not specified in% is% by mass.

Synthesis example 1
In a thin film flow reactor with an inner diameter of 14 mmφ and a length of 4 m, together with 2.0% by volume of sulfur trioxide gas, the distribution is 12 to 16 carbon atoms of alkyl group and C12 / C14 / C16 = 67% / 28%. / 5% higher alcohol (molecular weight: 199) was continuously charged at 60 ° C. for reaction. The flow rate was adjusted so that the reaction molar ratio of sulfur trioxide gas to higher alcohol was 1.01. The obtained sulfate was neutralized with a 32.2% aqueous sodium hydroxide solution, 75% phosphoric acid (buffer) was added, and then the pH was adjusted to 10 with a 32.1% aqueous sodium hydroxide solution. The active ingredient of the obtained alkyl sulfate sodium salt paste was 73%.

Synthesis example 2
Ethoxy obtained by adding an average of 1.0 mole of ethylene oxide to a higher alcohol having an alkyl group having 12 to 16 carbon atoms and a C12 / C14 / C16 = 67% / 28% / 5% distribution using a potassium hydroxide catalyst. The reaction was carried out in the same manner as in Synthesis Example 1 except that the rate (average molecular weight 242) was used in place of the higher alcohol and a 4.0% aqueous sodium hydroxide solution was used. The active ingredient in the obtained aqueous sodium polyoxyethylene alkylsulfate salt was 25.4%.

Synthesis example 3
A higher alcohol whose alkyl group has 12 and 14 carbon atoms and whose distribution is C12 / C14 = 75% / 25% is used with a Kyoward 2030 catalyst (manufactured by Kyowa Chemical Industry Co., Ltd.), and an average of ethylene oxide is 2. The reaction was carried out in the same manner as in Synthesis Example 1 except that 0 mole added ethoxylate (average molecular weight 280) was used instead of the higher alcohol and a 3.6% sodium hydroxide aqueous solution was used. The effective component of the obtained sodium polyoxyethylene alkylsulfate aqueous solution having a narrow distribution (narrow distribution range of added moles) was 25.2%.

Synthesis example 4
Catalyst for alkylene oxide addition reaction synthesized by the method described in Example 1 of JP-A-2001-327866 into a higher alcohol having an alkyl group of 12,14 and a distribution of C12 / C14 = 75% / 25% The same as in Synthesis Example 1 except that ethoxylate (average molecular weight 280) obtained by adding 2.0 mol of ethylene oxide on average in place of higher alcohol was used instead of higher alcohol and 3.6% aqueous sodium hydroxide solution was used. To react. The active ingredient of the obtained sodium polyoxyethylene alkyl sulfate aqueous solution having a narrow distribution was 25.1%.

Synthesis example 5
An alkyl group having 12 to 16 carbon atoms and a distribution of C12 / C14 / C16 = 67% / 28% / 5% and an average of 1.0 ethylene oxide using a potassium hydroxide catalyst in the higher alcohol. Synthetic examples, except that a raw material (average molecular weight 209) blended with a mole-added ethoxylate at a ratio of 75%: 25% is used in place of the higher alcohol and a 30.1% aqueous sodium hydroxide solution is used. The reaction was carried out in the same manner as in 1. The active ingredient of the obtained polyoxyethylene alkyl sulfate sodium salt paste was 72%.

Synthesis Example 6
An ethoxylate obtained by adding an average of 1.0 mole of ethylene oxide to a higher alcohol having 12 to 16 carbon atoms and a distribution of C12 / C14 / C16 = 67% / 28% / 5% using a potassium hydroxide catalyst. (Molecular weight 242) was used in the same manner as in Synthesis Example 1 except that it was used in place of the higher alcohol and a 28.9% aqueous sodium hydroxide solution was used. The active ingredient of the obtained polyoxyethylene alkyl sulfate sodium salt paste was 73%.

Anionic surfactant granulated product example 1 [(a) component; 1]
While adjusting the drying conditions such that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the operation product temperature is 70 ± 1 ° C., the alkyl sulfate sodium salt (AS) -containing paste obtained in Synthesis Example 1 and Synthesis Example 2 A paste obtained by mixing the obtained polyoxyethylene alkyl sulfate sodium salt (ES) -containing aqueous solution so that the mass ratio of the active ingredient is AS: ES = 85: 15 is a vacuum dryer having a dryer internal volume of 2500 L [Fukae POWTECH Co., Ltd., FDM-1200JE] was added dropwise at an average addition rate of 150 kg / Hr, agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blade and wall surface: Under the granulation conditions of 5.5 mm, granulation was performed simultaneously with drying to obtain 600 kg of granulated material. Further, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) to obtain a powder raw material having an average particle size of 120 μm.

  200 kg of the above powdered alkyl sulfate sodium salt [average molecular weight: 310, average particle size: 120 μm] is placed in a 2500 L vacuum dryer (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature 85 C., pressure: 4.0 kPa, adjusted to dry conditions such that the product temperature is 70. +-. 1.degree. C. A paste prepared by mixing a polyoxyethylene alkyl sulfate sodium salt (ES) -containing aqueous solution with an active ingredient mass ratio of AS: ES = 85: 15 was dropped into the dryer at an average addition rate of 150 kg / Hr. , Granulation was performed simultaneously with drying under conditions of agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min, and ethylene oxide averaged Moles of 0.25 polyoxyethylene alkyl sulfate sodium salt [average molecular weight: 310] was obtained granulated product. Thereafter, zeolite was added to 8% by mass in the obtained granulated product, and the zeolite was uniformly coated on the granular anionic surfactant, and the average particle size was 1100 μm and the apparent density was 680 g / L by vibration sieving. A granular anionic surfactant granulated product was obtained.

Anionic surfactant granulated examples 2 to 11 [component (a); 2 to 11]
Alkyl sulfate sodium salt (AS) -containing paste having the alkyl composition shown in Table 1 and polyoxyethylene alkyl sulfate sodium salt (ES) containing the alkyl composition shown in Table 1 and an average of 1.0 mol of ethylene oxide added Polyethylene having an average added mole number of ethylene oxide shown in Table 1 is the same as in Example 1 except that a mixed solution in which an aqueous solution is mixed so that the mass ratio of the active ingredient is the ratio shown in Table 1 is used. An anionic surfactant granulated product composed of sodium oxyethylene alkyl sulfate was obtained. In addition, the average particle diameter of these (a) components was 150-1500 micrometers, and the apparent density was 500-800 g / L.

* 1: Average addition mole number of the mixture of AS and ES * 2: Mass percentage of polyoxyalkylene alkyl ether sulfate added with 4 moles or more of ethylene oxide with respect to the anionic surfactant in component (a) * 3: (A) Percentage by mass in component

Builder particle example 1 [component (b); 1]
α-sulfo fatty acid methyl ester sodium [SFE-Na] (from palm oil) 10 parts by mass, polyethylene glycol (molecular weight 8500) 1 part by mass, 4A zeolite 12 parts by mass, acrylic acid-maleic acid copolymer (weight average molecular weight 70000) 3 parts by weight, fatty acid sodium (derived from beef tallow) 8 parts by weight, No. 1 sodium silicate 1 part by weight, sodium carbonate 16 parts by weight, sodium sulfate 5 parts by weight, sodium sulfite 1 part by weight, fluorescent dye 0.3 part by weight and water A spray-dried composition consisting of 3.2 parts was obtained by preparing a slurry having a solid content of 50% by mass and spray-drying. This was mixed with 3 parts by mass of crystalline silicate and 10 parts by mass of sodium carbonate in a ribbon mixer. The obtained mixture was extruded into a cylindrical shape having a diameter of 10 mm by using a pre-extrusion type biaxial extrusion granulator (pellet double: manufactured by Fuji Powder Co., Ltd., jacket cooling) to be consolidated. The obtained pellet-like material (48 ° C.) was pulverized and granulated with a flash mill (manufactured by Fuji Powder Co., Ltd., jacket cooling) together with 4 parts by mass of 4A zeolite to perform surface coating. After removing the coarse product from this granulated product, it was transferred to a V blender, and 4 parts by mass of 4A zeolite was mixed to obtain builder particles 1. The acrylic acid-maleic acid copolymer was a sodium salt (70 mol% neutralized), and the monomer ratio was acrylic acid / maleic acid = 3/7 (molar ratio) (the same applies hereinafter). Whitetex SA (manufactured by Sumitomo Chemical Co., Ltd.) was used as the fluorescent dye (the same applies hereinafter). As zeolite, 4A-type zeolite (manufactured by Tosoh Corporation) was used (the same applies hereinafter).

Builder particle example 2 [component (b); 2]
Water was added to a mixing tank having a stirring blade, and after the water temperature reached 55 ° C., an aqueous solution of 40% by mass of acrylic acid-maleic acid copolymer (weight average molecular weight 70000) was added. After stirring for 15 minutes, sodium carbonate, sodium sulfate, sodium sulfite, and fluorescent dye were added. This was stirred for an additional 15 minutes before adding the zeolite. This was stirred for 30 minutes to obtain a slurry. The final temperature of this slurry was 60 ° C.

The slurry was supplied to a spray drying tower, and builder particles 2 were prepared by spraying from the top of the tower at a spraying pressure of 25 kg / cm ² . The composition of the obtained builder particles is as follows.

  Acrylic acid-maleic acid copolymer 6 mass%, sodium carbonate 26 mass%, sodium sulfate 10 mass%, sodium sulfite 1.5 mass%, fluorescent dye 0.5 mass%, zeolite 52 mass%, water 4 mass%.

Builder particle example 3 [component (b); 3]
Sodium alkylbenzene sulfonate [LAS-Na] (C12-14) 10 parts by mass, polyethylene glycol (molecular weight 8500) 1 part by mass, 4A zeolite 12 parts by mass, acrylic acid-maleic acid copolymer (weight average molecular weight 70000) 3 1 part by weight, 1 part by weight sodium silicate, 16 parts by weight sodium carbonate, 5 parts by weight sodium sulfate, 1 part by weight sodium sulfite, 0.3 part by weight fluorescent dye and 3 water A 2 parts spray-dried composition was obtained by preparing a 50 wt% solids slurry and spray drying. This was transferred to a V blender, and 4 parts by mass of 4A zeolite was mixed to obtain builder particles 3.

Builder particle example 4 [component (b); 4]
100 parts by weight of Builder Particle Example 2 is charged into a high speed mixer (made by Fukae Kogyo Co., Ltd.) together with 10 parts by weight of crystalline silicate, and pulverized while spraying 3 parts by weight of a nonionic surfactant. Done the grain. After granulation, 5 parts by mass of zeolite was added and stirred to coat the surface of the granulated particles, then transferred to a V blender, and 5 parts by mass of zeolite was mixed to prepare Builder Particle Example 4.

表中、漂白剤はＮ，Ｎ，Ｎ’，Ｎ’−テトラアセチルエチレンジアミン、漂白活性化剤は硼酸ナトリウム・過酸化水素付加物である。 Cleaning composition examples 1-11
The cleaning composition shown in Table 2 was prepared. These detergency, caking resistance, and low-temperature solubility were all good.

In the table, the bleaching agent is N, N, N ′, N′-tetraacetylethylenediamine, and the bleaching activator is sodium borate / hydrogen peroxide adduct.

Claims (6)

(A) Polyoxyalkylene alkyl ether sulfate containing 60% by mass or more of polyoxyalkylene alkyl ether sulfate having an average addition mole number of alkylene oxide of 0.05 to 2 and containing 4 mol or more of alkylene oxide An anionic surfactant granulated product whose amount is 30% by mass or less based on the whole anionic surfactant in the component (a),
(B) Builder particles containing 50% by mass or more of a builder having at least one of metal chelate action, alkali buffer action, and solid particle dispersion action,
Containing
(I) 10-60 mass% equivalent to the surfactant described in JIS K 3362: 1998,
(II) JIS K 3362: The apparent density of all compositions measured by the method described in 1998 is 300 to 1200 g / L,
(III) The average particle size of all compositions determined from the particle size measured by the sieving method using a sieving machine described in JIS K 3362: 1998 is 150 to 2000 μm,
A detergent composition.   (A) Polyoxyalkylene alkyl ether sulfate having 1 to 3 mol of alkylene oxide added in polyoxyalkylene alkyl ether sulfate having an average addition mole number of alkylene oxide of 0.05 to 2 as component (a) 5 to 70% by mass The cleaning composition according to claim 1, wherein the alkyl sulfate is 30 to 95% by mass.   The component (a) is a polyoxyalkylene alkyl ether sulfate salt having an average addition mole number of alkylene oxide of 0.05 to 2, 60 to 98% by mass, water-insoluble inorganic powder 0.5 to 30% by mass, water-soluble inorganic The detergent composition according to claim 1, which has a salt content of 0.1 to 30% by mass and a moisture content of 0.1 to 5% by mass as measured by a heat loss method described in JIS K 3362: 1998. (A) The average particle diameter calculated | required from the particle size measured by the sieving method by the sieving machine of the apparent density of 300-1200 g / L and JIS K 3362: 1998 as which component (a) is measured by the method of JIS K 3362: 1998 is 150. The cleaning composition according to any one of claims 1 to 3, which is -2000 µm. (A) An anionic interface obtained by drying and granulating the component after obtaining a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste by any of the following methods (1) to (3) The cleaning composition according to any one of claims 1 to 4, which is an activator granulated product.
(1) An alkylene oxide adduct of a higher alcohol obtained by adding an alkylene oxide to an alcohol having 8 to 20 carbon atoms (hereinafter referred to as a higher alcohol) so as to have an average addition mole number of 0.05 to 2 is sulfated and neutralized. Method.
(2) A method in which a higher alcohol and an alkylene oxide adduct of a higher alcohol are mixed so that the average number of added moles of alkylene oxide in the mixture is 0.05 to 2, and then sulfated and neutralized.
(3) A method in which a higher alcohol and an alkylene oxide adduct of a higher alcohol are separately sulfated and neutralized, and mixed so that the average number of moles of alkylene oxide added to the mixture is 0.05-2. The component (a) is a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste obtained by the method according to any one of (1) to (3) according to claim 5, and the following (4) to (6): The detergent composition according to any one of claims 1 to 5, which is an anionic surfactant granulated product obtained by drying by any of the above methods to obtain a dried product, or further granulating the dried product. .
(4) A stirring blade and / or a crusher for a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste, or a mixture of a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste and an alkyl sulfate-containing aqueous solution, paste or powder. The batch type vacuum dryer which has this and puts it in a lump, and dries under reduced pressure.
(5) In a batch-type vacuum dryer having a stirring blade and / or a pulverizer, an anionic surfactant granulated material is charged in advance to such an extent that an effect of stirring and pulverization can be obtained, and then the powder in the machine under reduced pressure. A method of drying by supplying an aqueous solution or paste containing a polyoxyalkylene alkyl ether sulfate at a supply rate such that the body maintains a powder state.
(6) A method in which a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste is continuously charged into a rotary thin film evaporator under reduced pressure and dried.