JP4515195B2 - Cleaning composition - Google Patents

Description

  The present invention relates to a cleaning composition for textile products, in particular, textile products such as carpets, chairs, sofas, automobile interiors, textile products for home interiors, and the like that cannot be washed by ordinary electric washing machines. More specifically, the present invention relates to a cleaning composition that uses a powdery soil occlusion agent as a soil carrier instead of water in cleaning that cannot use a large amount of water, such as an electric washing machine.

Recently, there has been an increase in the use of detergents for textile products that cannot be washed by an electric washing machine, especially for carpets and the like. Such a cleaning agent contains a surfactant, a soil storage agent, water and the like as main components. The surfactant separates the dirt from the fibers and, in combination with water, transfers the dirt to the dirt storage agent. Then, after the water has evaporated, the dirt storage agent is removed together with the dirt by cleaning with a brushing or electric washing machine. For example, a powdery cleaning composition in which ethanol and water containing a soil storage agent are highly blended is known (Patent Documents 1 and 2).
JP-A-1-215898 JP-A-1-215899

  However, these compositions of Patent Documents 1 and 2 have a problem of caking due to storage, and are still not sufficient in terms of storage stability and cleaning performance. An object of the present invention is to provide a cleaning composition having excellent cleaning performance and high caking resistance.

The present invention contains the following (A) surfactant-containing particles, the following (B) builder-containing particles, and (f) a soil storage agent having a soil storage capacity of 0.1 or more (hereinafter referred to as component (f)). Cleaning composition.
<(A) Surfactant-containing particles>
(A) a polyoxyalkylene alkyl ether sulfate having an addition mole number of alkylene oxide of 1 to 3 (hereinafter referred to as component (a)) 1 to 70% by mass, (b) a polyoxygenate having an addition mole number of alkylene oxide of 4 or more Oxyalkylene alkyl ether sulfate (hereinafter referred to as component (b)) 0 to 30% by mass, (c) alkyl sulfate (hereinafter referred to as component (c)) 10 to 95% by mass, (d) water-soluble inorganic salt and At least one selected from water-insoluble inorganic salts [hereinafter referred to as “component (d)”] 1 to 38% by mass, (e) water (moisture according to the superheat loss method described in JIS K 3362: 1998) [hereinafter referred to as component (e) In a sieving machine according to JIS K 3362: 1998, which contains 60 to 98% by weight of the surfactant equivalent according to JIS K 3362: 1998. Surfactant-containing particles having an average particle diameter determined from the particle size measured by Rufuruiwake method is 150～2000Myuemu.
<(B) Builder-containing particles>
Builder particles containing more than 50% by mass of a builder having at least one of metal chelating action, alkali buffering action, and solid particle dispersing action.

  The cleaning composition of the present invention is excellent in cleaning performance and powder characteristics such as caking resistance.

  In the cleaning composition of the present invention, the apparent density measured by the method described in JIS K 3362: 1998 is preferably 300 to 1200 g / L, and preferably 400 to 1100 g / L in terms of caking resistance, reduction of packaging materials, and productivity. L is more preferable, 600 to 1000 g / L is more preferable, and 700 to 980 g / L is particularly preferable.

  The cleaning composition of the present invention has an average particle size of 250 to 1800 μm determined from the particle size measured by a sieving method using a sieving machine described in JIS K 3362: 1998 in terms of solubility, fluidity and caking resistance. Preferably, 300-1500 micrometers is more preferable, and 300-1000 micrometers is still more preferable.

<(A) Surfactant-containing particles>
The cleaning composition of the present invention contains (A) surfactant-containing particles (hereinafter sometimes referred to as (A) particles) containing the components (a) to (e). In terms of cleaning performance and caking resistance, the content of (A) particles is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 40% by mass in the cleaning composition. .

  Moreover, in this invention, 50-100 mass% of all the surfactant mix | blended in a composition, Furthermore, 70-100 mass%, 70-90 mass% is contained in (A) particle | grains. preferable.

  In the cleaning composition of the present invention, the total amount of the component (a) and the component (b) and the mass ratio of the component (c) are (A) particles in terms of hard water resistance, caking resistance, and productivity. [(A) + (b)] / (c), preferably 70/30 to 5/95, more preferably 60/40 to 10/90, and still more preferably 50/50 to 15/85.

  The cleaning composition of the present invention is an alkylene oxide (hereinafter referred to as AO) in the particles (A), (a), (b), and (c) in terms of cleaning performance, caking resistance, and productivity. 0.05 to 2 is preferable, 0.1 to 1 is more preferable, and 0.2 to 0.8 is still more preferable.

  In the cleaning composition of the present invention, in terms of cleaning performance, powder physical properties, and productivity, the total amount of the component (a) and the component (c) and the mass ratio of the component (b) in (A) particles are: (A) + (c)] / (b), preferably 70/30 to 100/0, more preferably 80/20 to 100/0, and still more preferably 85/15 to 100/0.

  In the cleaning composition of the present invention, the total amount of the component (a), the component (b), and the component (c) is preferably 50 to 98% by mass in (A) particles in terms of cleaning performance and solubility. 60-96 mass% is more preferable, 70-94 mass% is still more preferable, and 80-92 mass% is especially preferable.

  In the cleaning composition of the present invention, in terms of productivity, caking resistance, and solubility, (A) particles are a powder containing component (d) under reduced pressure in a granulator having a stirring blade and a crushing blade. Surfactant-containing particles produced by granulating simultaneously with drying while adding paste containing (a) component, (b) component, (c) component, and (e) component to body material It is preferable.

  In view of cleaning performance and solubility, (A) the surfactant equivalent in the particles is preferably 65 to 98% by mass, more preferably 70 to 96% by mass, still more preferably 75 to 94% by mass, and more preferably 80 to 92 mass% is particularly preferred.

  From the viewpoint of caking resistance, reduction of packaging materials, and productivity, the apparent density of (A) particles is preferably 300 to 1200 g / L, more preferably 400 to 1100 g / L, still more preferably 600 to 1000 g / L, 700 to 980 g / L is particularly preferable.

  In terms of solubility, fluidity and caking resistance, the average particle size of the (A) particles is preferably 250 to 1800 μm, more preferably 300 to 1500 μm, and even more preferably 300 to 1000 μm.

<(A) component>
(A) particle | grains of this invention contain 1-70 mass% of polyoxyalkylene alkyl ether sulfates whose addition mole number of AO is 1-3 as (a) component. In terms of cleaning performance, hard water resistance, caking resistance, and productivity, 5 to 60% by mass is preferable, 10 to 50% by mass is more preferable, and 15 to 40% by mass is even more preferable.

Examples of the component (a) include compounds represented by the general formula (I).
_{^{[R 1 -O (AO) n}} -SO 3] p M (I)
[In the formula, R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, AO is an alkyleneoxy group having 2 to 4 carbon atoms, n is an integer of 1 to 3 indicating the number of added moles of AO, M is Cation, p represents the valence of M, and n AOs may be the same or different. ]

In the general formula (I), R ¹ is preferably an alkyl group having 10 to 18 carbon atoms, particularly a linear alkyl group. AO is preferably an alkyleneoxy group having 2 to 3, particularly 2 carbon atoms. 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.

<(B) component>
The (A) particles of the present invention contain 0 to 30% by mass of polyoxyalkylene alkyl ether sulfate having 4 or more added moles of AO as the component (b). In terms of washing performance, hard water resistance, caking resistance, and productivity, 0 to 20% by mass is preferable, 0 to 15% by mass is more preferable, and 0 to 10% by mass is even more preferable.

Examples of the component (b) include compounds represented by general formula (II).
_{^{[R 1 -O (AO) n}} '-SO 3] p M (II)
[Wherein, R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, AO is an alkyleneoxy group having 2 to 4 carbon atoms, n ′ is an integer of 4 or more indicating the number of added moles of AO, M is Cation, p represents the valence of M, and n ′ AO may be the same or different. ]

In general formula (II), R ¹ is preferably an alkyl group having 10 to 18 carbon atoms. AO is preferably an alkyleneoxy group having 2 to 3, particularly 2 carbon atoms. 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.

<(C) component>
(A) particle | grains of this invention contain 10-95 mass% of alkyl sulfates as (c) component. 20-90 mass% is preferable at the point of washing | cleaning performance, hard water resistance, caking resistance, and productivity, 30-85 mass% is more preferable, and 40-80 mass% is still more preferable.

(C) As a component, the compound represented by general formula (III) is mentioned, for example.
_{^{[R 1 -O-SO 3]}} p M (III)
[Wherein, R ¹ represents a linear or branched alkyl group having 8 to 20 carbon atoms, M represents a cation, and p represents a valence of M. ]

In the general formula (III), R ¹ is preferably an alkyl group having 10 to 18 carbon atoms, particularly a linear alkyl group. 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.

<(D) component>
The (A) particles of the present invention contain 1 to 38% by mass of at least one selected from a water-soluble inorganic salt and a water-insoluble inorganic salt as the component (d). 3-30 mass% is preferable at the point of washing | cleaning performance, caking resistance, and productivity, 5-25 mass% is more preferable, and 8-20 mass% is still more preferable. In particular, it is preferable to contain a water-insoluble inorganic salt in terms of productivity and solubility. Here, the inorganic salt being water-soluble means that the solubility in water at 20 ° C. is 1 g / dm ³ or more, and the water insolubility is that the solubility in water at 20 ° C. is less than 1 g / dm ^3. It means that.

  Water-soluble inorganic salts include water-soluble inorganic salts such as carbonates, hydrogen carbonates, sulfates, sulfites, hydrogen sulfates, hydrochlorides, or alkali metal salts such as phosphates or phosphates, ammonium salts, or amine salts. Can be mentioned. Especially, it is preferable to contain carbonate and a sulfate, and it is more preferable to contain a sulfate. From the viewpoint of caking resistance and productivity, the (A) particles preferably contain 0.1 to 30% by mass of a water-soluble inorganic salt, more preferably 0.2 to 20% by mass, and 0.5 to 10%. Mass% is particularly preferred.

  Water-insoluble inorganic salts include crystalline aluminosilicate, amorphous aluminosilicate, silicon dioxide, hydrated silicate compound, talc, pyrophyllite, smectite (saponite, hectorite, soconite, stevensite, montmorillonite, beidellite, Nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald mica, muscovite, paragonite, celadonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, sudite, donbasite, etc.) , Brittle mica (Clintnite, Margarite, etc.), Sulite, Serpentine mineral (Antigolite, Lizardite, Chrysotile, Amesite, Clonsteadite, Burcherin, Greenerite, Garnierite, etc.), Kaolin mineral (Kaolinite, Di Kite, nacrite, it can be used clay minerals such as halloysite, etc.) and the like. For reasons such as not promoting the generation of undissolved residues, it is preferable to contain crystalline aluminosilicate and amorphous aluminosilicate, and more preferably to contain crystalline aluminosilicate. Moreover, 0.1-10 micrometers is preferable and, as for the average particle diameter of this aluminosilicate, 0.5-5 micrometers is more preferable. Suitable as the crystalline aluminosilicate is A-type zeolite (for example, trade name: “Toyo Builder”; manufactured by Tosoh Corporation, trade name: “synthetic zeolite”; manufactured by Nippon Builder Co., Ltd., trade name: “ VALFOR100 ”; PQ CHEMICALS (Thailand) Ltd., trade name:“ ZEOBUILDER ”; ZEOBILDER Ltd, trade name:“ VEGOBOND A ”; OMAN CHEMICAL INDUSTRIES Ltd; It is also preferable in terms of sealing ability and economy. In addition, there are P type (for example, trade name “Ducil A24”, “ZSE064”, etc .; manufactured by Crosfield) and X type (for example, trade name: “WessalithXD”; manufactured by Degussa). The hybrid zeolite described in WO 98/42622 is also mentioned as a suitable crystalline aluminosilicate. Amorphous aluminosilicate and amorphous silica can also be used. For example, Japanese Patent Application Laid-Open No. 62-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (particularly, the initial temperature is preferably in the range of 15 to 60 ° C.), Japanese Patent Application Laid-Open No. 62-191419. Amorphous aluminosilicate described in the second page, lower right column, line 20 to page 5, lower left column, line 11; JP-A-9-132794, column 17, line 46 to column 18, line 38; JP-A-7-10526, column 3, line 3 to column 5, line 9, JP-A-6-227811, column 2, line 15 to column 5, line 2, JP-A-8-119622 The amorphous aluminosilicate etc. which are described in 2nd column 18th line-3rd column 47th line can be mentioned. For example, “Toxeal NR” (manufactured by Tokuyama Soda Co., Ltd.), “Flowlite” (same as above), “TIXOLEX25” (manufactured by Han France Chemicals), “Silo Pure” (manufactured by Fuji Divison Co., Ltd.) Can be used. In particular, those described in JP-A-6-179899, column 12, line 12 to column 13, line 1, column 17, line 34 to column 19, line 17 are suitable.

  From the viewpoint of caking resistance and productivity, the (A) particles preferably contain 0.5 to 30% by mass of a water-insoluble inorganic salt, more preferably 1 to 25% by mass, and particularly preferably 5 to 20% by mass. preferable.

In terms of cleaning performance and hard water resistance, the component (d) preferably contains an inorganic salt having a calcium capture amount of 200 to 600 CaCO ₃ mg / g. The content of the inorganic salt is preferably 1 to 38% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 25% by mass in the particles (A) in terms of washing performance and hard water resistance. -20% by weight is particularly preferred. The calcium capture amount is determined by the method described in JP-A-3-277696, page 3, lower right column, line 6 to page 4, upper left column, line 6 (however, an anionic surfactant is read as an inorganic salt). .

<(E) component>
The (A) particle | grains of this invention contain 0.1-5 mass% of water (the water | moisture content by the overheating weight loss method of JISK3362: 1998) as (e) component. In terms of cleaning performance, caking resistance, and productivity, 0.2 to 4% by mass is preferable, 0.5 to 3% by mass is more preferable, and 0.5 to 2% by mass is still more preferable.

<Other ingredients>
The particles (A) of the present invention are composed of (a) component, (b) component, surfactants other than (c) component, builders other than (d) component, and anti-staining agent (carboxy). Methylcellulose, etc.), softeners, fluorescent brighteners, foam suppressors (silicone, etc.), enzymes, enzyme stabilizers, colorants, fragrances and the like.

  As surfactant, it is 1 type of (a) component, (b) component, anionic surfactant other than (c) component, nonionic surfactant, amphoteric surfactant, cationic surfactant Alternatively, two or more combinations can be mentioned, but preferably an anionic surfactant other than the component (a), the component (b), and the component (c) is used in combination with a nonionic surfactant. It is. Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose.

  Examples of the anionic surfactant other than the component (a), the component (b), and the component (c) include alkylbenzene sulfonate, paraffin sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α- Sulfo fatty acid alkyl ester salts or fatty acid salts are preferred. 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 (8 to 20 carbon atoms) ether, alkyl (8 to 20 carbon atoms) polyglycoside, polyoxyalkylene alkyl (8 to 20 carbon atoms) phenyl ether, polyoxyalkylene. Sorbitan fatty acid (carbon number 8 to 22) ester, polyoxyalkylene glycol fatty acid (carbon number 8 to 22) ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, as the nonionic surfactant, polyoxyalkylene alkyl ether obtained by adding an average of 4 to 20 moles of AO such as ethylene oxide (hereinafter referred to as EO) or propylene oxide to an alcohol having 10 to 18 carbon atoms. preferable. 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.

  As the organic builder, aminocarboxylate, hydroxyaminocarboxylate, hydroxycarboxylate, cyclocarboxylate, ether carboxylate, and organic carboxylic acid (salt) polymer are preferable, and organic carboxylic acid (salt) polymer is preferable. Are more preferable.

  (A) From the viewpoint of particle fluidity and caking resistance, (A) particle surface modification may be performed. 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 (A) particles of the present invention in terms of storage stability. Moreover, 1 mass% or more in (A) particle | grains 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.

<Manufacturing method>
The particles (A) of the present invention are produced in a powder raw material containing the component (d) under reduced pressure in a granulator having a stirring blade and a crushing blade in terms of productivity, caking resistance, and solubility. ), (B) component, (c) component, (e) It is preferable to produce by granulating simultaneously with drying while adding a paste containing the component.

  In order to prepare a paste containing the component (a), the component (b), the component (c), and the component (e), the following methods (1) to (3) are exemplified.

(1) A method of sulfating and neutralizing an AO adduct of a higher alcohol obtained by adding AO 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.

(2) A method in which a higher alcohol and an AO adduct of a higher alcohol are mixed so that the AO average addition mole number of the mixture is 0.05 to 2, and then sulfated and neutralized.

(3) A method in which a higher alcohol and a higher alcohol AO adduct are separately sulfated and neutralized in advance so as to have an AO average addition mole number of the mixture of 0.05 to 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 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.

  The powder raw material containing the component (d) used in the present invention preferably contains a surfactant in addition to the component (d), and a part of the granular material obtained by the production method of the present invention, More preferably, it is used as a powder raw material. Furthermore, you may grind | pulverize a granular material.

  The particle size of the powder raw material is preferably 300 μm or less, more preferably 200 μm or less, from the viewpoints of drying speed, particle size control of the final granulated product, and handling properties.

  Examples of the pulverizer preferably used in the present invention include, for example, an atomizer (manufactured by Fuji Powder Co., Ltd.), Fitzmill (manufactured by Dalton Co., Ltd.), Pulverizer (manufactured by Dalton Co., Ltd.), )), Comil (manufactured by Quadro) and the like.

  The method for producing (A) particles of the present invention is a method of granulating simultaneously with drying while adding an anionic surfactant paste to a powder raw material under reduced pressure in a granulator having a stirring blade and a crushing blade. It is.

  In the present invention, the temperature of the granular material is preferably in the range of 40 to 75 ° C., more preferably 45 to 70 ° C., and the temperature change during drying is within ± 5 ° C., more preferably within ± 2 ° C., particularly It is preferable to perform granulation simultaneously with drying while controlling the temperature to be within ± 1 ° C. As a method for controlling the temperature change in this way, (1) the addition rate of the anionic surfactant paste, (2) pressure in the granulator, (3) jacket temperature in the granulator, (4) granulation Examples thereof include introduction of air and / or inert gas into the machine, and (5) appropriate adjustment of the fluid number of the blades of the granulator. Hereinafter, each method will be described in detail.

(1) Anionic surfactant paste addition amount The drying rate of the anionic surfactant paste is preferably controlled so that the temperature of the granular material is within the above range. The addition amount of the anionic surfactant paste is preferably such that the mass ratio of the anionic surfactant paste to the powder raw material is 1/10 to 10/1, more preferably 1/4 to 4/1.

(2) Pressure in the granulator The pressure in the granulator is preferably 0.67 to 40 kPa from the viewpoint of lowering the operation product temperature and suppressing the decomposition of the paste and the granulated product, and further the burden on the vacuum pump. From the viewpoint of the airtightness of the granulator and the granulator, 4.0 to 40 kPa is preferable, and 4.0 to 8.0 kPa is particularly preferable.

(3) Jacket temperature in the granulator The heating source of the granulator includes a warm water jacket, electric tracing, etc., but a warm water jacket is preferred, and the jacket temperature is preferably 100 ° C. or less, and is more sensitive to heat. From the viewpoint of application to other raw materials, 90 ° C. or lower is more preferable.

(4) Introduction of air and / or inert gas into the granulator In the present invention, during the addition of the anionic surfactant paste, the air and / or the granulator is more effectively dried. Alternatively, an inert gas may be introduced. The introduction amount is preferably 2 to 30 L / min, more preferably 3 to 10 L / min.

(5) Froude number of granulator blades In the present invention, from the viewpoint of promoting consolidation and sufficiently forming an adhesion layer to narrow the particle size distribution, the blades of the granulator defined by the following formula The fluid number is preferably 1 to 5, more preferably 1.5 to 4.
Fr = V / [(R × g) ^0.5 ]
(Where Fr is the fluid number, V is the peripheral speed [m / sec] of the tip of the stirring blade, R is the rotational radius [m] of the stirring blade, and g is the acceleration of gravity [m / sec. ² ]. Show.)

  The granulator used in the present invention is preferably equipped with a stirring blade and a crushing blade and forms a clearance between the stirring blade and the wall surface when the stirring blade rotates. The average clearance is preferably 1 to 30 mm, more preferably 3 to 10 mm. When the average clearance is 1 mm or more, the pressure density of the adhesion layer is moderate, and the granulator does not become overpowered. Further, if the average clearance is 30 mm or less, the consolidation efficiency is good, the particle size distribution is not broad, and the productivity is good.

  Examples of the granulator preferably used in the present invention include, for example, a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), a high speed mixer (manufactured by Fukae Powtech Co., Ltd.), a vertical granulator [(stock) ) Powrec], Redige mixer [Matsuzaka Giken Co., Ltd.], Pro-share mixer [Pacific Kiko Co., Ltd.], etc., particularly preferred Redige mixer [Matsuzaka Giken Co., Ltd.], high Speed mixer [Fukae Powtech Co., Ltd.], Pro-share mixer [Pacific Kiko Co., Ltd.]. Continuous type readyge mixer (medium speed mixer: relatively long residence time) as a continuous type, CB recycler (manufactured by Loedige) as a high speed mixer (relatively short residence time), turbulizer (Hosokawa Micron Co., Ltd.) Product), Shugi mixer (manufactured by POWREC Co., Ltd.), flow jet mixer (manufactured by Powder Research Co., Ltd.) and the like.

  The granulator used in the present invention is preferably equipped with a jacket for adjusting the internal temperature (article temperature) or equipped with a nozzle for performing a gas blowing operation. Specific examples of such a more preferred granulator include those described in JP-A-10-296064, JP-A-10-296065, and Japanese Patent No. 3165700.

  In the present invention, by using a granulator having a stirring blade and a crushing blade, even if the anionic surfactant paste is granulated and adhered to the wall of the granulator, the overpower of the granulator (overload) ), A granulated product having a high density can be produced without causing a decrease in granulation properties (generation of coarse particles). This phenomenon is considered as follows. The anionic surfactant paste added to the granulator has a deposit with a high pressure density due to contact with the stirring blade on the stirring blade side, and a deposit with a lower pressure density as it becomes the wall of the granulator It has become. Therefore, the anionic surfactant paste can be taken into the adhesion layer due to the stirring effect, and the granulator is not overpowered. The anionic surfactant paste taken into the adhering layer and the stirring blade is consolidated and spheroidized by the rolling operation, and is released from the adhering layer. Further, the spheroidized spheroidizing proceeds by the rolling action in the granulating part or mixing part in the granulator. That is, in the granulator, it is considered that the compaction / rolling granulation can be favorably performed by the compaction effect in the adhesion layer portion and the rolling operation in the granulation portion or the mixing portion. In order to perform such compaction / rolling granulation, it is important that a clearance is formed between the wall of the granulator and the stirring blade when the stirring blade rotates.

  In the present invention, since granulation is performed simultaneously with drying, it is preferable to carry out while blowing gas. This is to suppress the particulate matter from becoming a large lump by evaporating moisture and cooling the obtained particulate matter using gas. Examples of such gas include nitrogen gas and air.

  Further, in the present invention, after the addition of the anionic surfactant paste, fine powder may remain, so that it has a step of rotating only the stirring blade without substantially rotating the crushing blade, It is preferable from the viewpoint of taking in fine powder.

  In addition, the particles (A) obtained by the production method of the present invention may be made of crystalline aluminosilicates such as A-type, P-type, X-type, and Y-type zeolite, for example, in order to further improve caking properties. In order to coat the particle surface with an inorganic powder such as salt or sodium sulfate or an alkyl sulfate powder, these may be added.

  The particles (A) obtained by the production method of the present invention may be colored with a known colorant such as a pigment or dye in order to improve the appearance of the granulated product itself. The coloring method is not particularly limited. For example, an aqueous solution containing a dye or a pigment described in JP-A-2-258882 is sprayed on the surface of the granular anionic surfactant to color, or JP-A-11-158493. For example, a method of blending an appropriate amount of a dye or pigment described in Japanese Patent Publication (A) in a paste and coloring the particles (A) may be used. The colorant to be used is not particularly limited, but those having high solubility or dispersibility are preferable. For example, Bengala, Ultramarine Blue, Lionol Green, Red 226, Red 405, Blue 1 and the like are preferable.

<(B) Builder-containing particles>
The cleaning composition of the present invention comprises builder particles (hereinafter also referred to as (B) particles) containing more than 50% by mass of a builder having at least one of a metal chelating action, an alkali buffering action, and a solid particle dispersing action. contains. In terms of cleaning performance, hard water resistance, low-temperature solubility, and caking resistance, the content of (B) particles is preferably 1 to 80% by mass, more preferably 5 to 70% by mass in the cleaning composition. -60 mass% is still more preferable, and 20-50 mass% is especially preferable.

  In the present invention, 20 to 80% by mass, and further 25 to 75% by mass, of the total amount of the builder having at least one of metal chelating effect, alkali buffering effect, and solid particle dispersing effect, which is blended in the composition. In particular, it is preferable that 20 to 70% by mass is contained in the (B) particles.

  In terms of low-temperature solubility and caking resistance, the builder in the particles (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. .

  (B) Examples of particle builders include detergents and cleaning encyclopedias, Asakura Shoten Co., Ltd., November 25, 1990, first edition, first edition, Haruhiko Okuyama, edited by Motoki 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, the inorganic builder is preferably zeolite, carbonate, or silicate, and the organic builder is preferably an organic carboxylic acid (salt) polymer.

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

  Among the builders, the builder having a metal chelate action is preferably used in the cleaning composition so as to be 0.5 to 30% by mass in terms of cleaning performance, more preferably 10 to 20% by mass. .

  The builder having a metal chelating action is not particularly limited, but is a copolymer of ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, citric acid, malic acid, tartaric acid, polyacrylic acid, methacrylic acid, acrylic acid and maleic anhydride , A copolymer of maleic anhydride and methyl vinyl ether, a copolymer of maleic anhydride and olefin, a copolymer of acrylic acid and methacrylic acid, a condensate of maleic anhydride and tartaric acid, and zeolite, tripolyphosphoric acid, Examples thereof include condensed phosphoric acid such as pyrophosphoric acid, and water-soluble salts thereof. The weight average molecular weight of the acrylic acid or methacrylic acid polymer, the copolymer of acrylic acid and methacrylic acid or their water-soluble salt is preferably in the range of 1500 to 100,000, particularly 3000 to 20000. Examples of the salt include sodium salt, potassium salt, monoethanolamine salt, diethanolamine salt, and triethanolamine salt. As the chelating agent for the component (d), citric acid, ethylenediaminetetraacetate, and a copolymer of acrylic acid and methacrylic acid are particularly preferable.

  Among the builders, a builder having an alkaline buffering action is preferably used in the cleaning composition so as to be 1 to 85% by mass in terms of cleaning performance and prevention of calcium insoluble salt adhesion, and more preferably 6 -50 mass%.

Although it does not specifically limit as an alkali agent, For example, carbonate or hydrogen carbonate, such as sodium carbonate, sodium hydrogencarbonate, ammonium carbonate, guanidine carbonate, 1 sodium silicate, 2 sodium silicate, 3 sodium silicate, Preferred examples include silicates such as sodium orthosilicate, sodium metasilicate and potassium silicate, and borates such as sodium borate and potassium borate. These alkaline agents can be used alone or in combination of two or more. In addition, when using sodium silicate, since this compound has a metal corrosion prevention effect | action, it is preferable to use this together with other alkaline agents, 35-85 mass% of other alkaline agents, sodium silicate (SiO2) Most preferably, ₂ / Na ₂ O molar ratio is 1/1 to 4/1, preferably 2/1 to 2.5 / 1. It is preferable to adjust the amount of the alkaline agent so that the aqueous cleaning composition solution having a concentration of 0.05% by mass at 20 ° C. has a pH of 9.0 to 11.0.

  Among the builders, a builder having a solid particle dispersing action is preferably used in the cleaning composition in an amount of 0.1 to 20% by mass in terms of cleaning performance and calcium insoluble salt adhesion prevention, and more preferably. Is 0.5 to 10% by mass.

  The builder having a solid particle dispersing action is not particularly limited. For example, a copolymer of acrylic acid and maleic anhydride, a copolymer of maleic anhydride and methyl vinyl ether, and a copolymer of maleic anhydride and olefin. A copolymer of acrylic acid and methacrylic acid, a condensate of maleic anhydride and tartaric acid, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose and the like.

  The cleaning composition of the present invention contains the enzyme-containing particles (B1) [hereinafter referred to as (B1) particles] as part of the (B) particles, so that the cleaning performance, hard water resistance, and low-temperature solubility are included. In terms of anti-caking property, the content of (B1) particles is more preferably 0.05 to 10% by mass, further preferably 0.1 to 8% by mass, and 0.5 to 5% in the cleaning composition. Mass% is particularly preferred.

  (B1) Examples of the enzyme contained in the particles include amylase, protease, cellulase, lipase, pullulanase, isopullulanase, and isoamylase. Among these, amylase, protease, cellulase, and lipase are preferable.

  As the amylase, any amylase conventionally used as an enzyme for detergents can be used. Suitable amylase is an enzyme obtained from Bacillus licheniformis or Bacillus subtilis, and is commercially available from Novo Industries. Examples include “Termamyl” (registered trademark) and “Maxamyl” (registered trademark) commercially available from Gist.

  When amylase is used as the enzyme, the amount of amylase per 1 g of the cleaning composition is preferably 0.05 to 500 units, particularly preferably 100 to 500 units. If the amount of the amylase is 0.05 units or more, the finish of the tableware with starchy stains within a predetermined time is sufficient, and if it is 500 units or less, it is economically advantageous.

Here, one unit of amylase activity is a value determined by measurement under the following conditions.
0.1 ml of enzyme solution is added to 0.9 ml of a substrate solution in which soluble starch (final concentration in the reaction system is 0.5% by mass) is dissolved in various buffers, and reacted at 50 ° C. for 15 minutes. . After the reaction, the reducing sugar is quantified by the following (DNS) method. That is, 1.0 ml of a DNS reagent is added to 1.0 ml of a reaction solution, heated and colored at 100 ° C. for 5 minutes, and after cooling, 4.0 ml of deionized water is added for dilution, followed by colorimetric determination at a wavelength of 535 nm. The enzyme titer was defined as 1 unit (IU) of the amount of enzyme generated in reducing sugar corresponding to 1 μmol of glucose per minute.

  As the protease, any protease widely used as a detergent enzyme can be used. Suitable proteases include, for example, subtilisin obtained from specific strains of B. subtilis and B. licheniformis. Such proteases include “Maxatase” (registered trademark) sold by Gist, “Alcalase” (registered trademark), “Esperase” (registered trademark), and “Sabinase” (registered trademark) of Novo Industry. Etc. are exemplified.

  When protease is used as the enzyme, the amount of protease per kg of the cleaning composition is preferably 0.05 to 100 anson units, particularly 1 to 60 anson units. If the amount of the protease is 0.05 anson units or more, the finish of the tableware with protein stains within a predetermined time is sufficient, and if it is 100 anson units or less, it is economically advantageous.

  Here, the quantification of protease activity is performed by a modified Anson-hemoglobin method, that is, by denatured denatured hemoglobin with protease under standard conditions. Undegraded hemoglobin is precipitated with trichloroacetic acid (TCA) and then the amount of TCA soluble product is colorimetrically determined at 750 nm with a foreign thiocarto phenol reagent.

  One anson unit (AU) is an enzyme that gives a TCA-soluble component that shows the same coloration as 1 m equivalent of tyrosine is colored by a phenol reagent in 1 minute in the hemoglobin hydrolysis under standard conditions. The amount of activity [ML Anson, Journal of General Physiology, 22 (1939), P79-89].

  When cellulase is used as the enzyme, the amount of cellulase per kg of the cleaning composition is preferably 50 to 2000000 units, particularly preferably 100 to 100000 units. If the amount of the cellulase is 50 units or more, the detergency against dirt having dietary fibers such as curry dirt is sufficient, and if it is 2000000 units or less, it is economically advantageous.

  Here, 1 unit of cellulase refers to an enzyme activity that produces 1 μmol of glucose from cellulose in 1 hour at an optimal temperature and an optimal pH.

  Moreover, when using lipase as an enzyme, it is preferable that the quantity of lipase per 1 kg of cleaning compositions will be 1000-100,000 lipase units (LU). If the amount of the lipase is 10,000 LU or more, the effect of improving the detergency is excellent, and if it is 1000000 LU or less, it is economically advantageous.

  Here, one unit of lipase activity (1 LU) refers to an enzyme activity that liberates 1 μM fatty acid per minute from olive oil used as a substrate. Specifically, 4 ml of olive oil emulsion and 4 ml of 0.1 M phosphate buffer (pH 7.0) are accurately placed in a 50 ml conical flask with a stopper, mixed well, and preheated in a constant temperature bath at 37 ° C. for 10 minutes. Add exactly 1 ml of the sample solution to this, mix well, and after 20 minutes, add the acetone / ethanol mixture. Then, titrate with 0.05N sodium hydroxide reagent using 5 drops of phenolphthalein solution as an indicator. Separately, 5 ml of olive oil emulsion and 4 ml of 0.1 M phosphate buffer (pH 7.0) are accurately taken in a 50 ml conical flask with a stopper, and heated at 37 ° C. for 30 minutes. Then, 20 ml of an acetone / ethanol mixture is poured, and then 1 ml of the sample solution. Is added exactly and titrated with 0.05N sodium hydroxide reagent using 5 drops of phenolphthalein reagent as an indicator to make a control solution. The lipase activity is determined by the following formula.

  As other suitable enzymes, pullulanase having an amylopectin-6-glucanohydrase activity obtained from bacteria belonging to the genus Klebsiella, bacteria belonging to the genus Bacillus, bacteria belonging to the genus Aspergillus, bacteria belonging to the genus Pseudomonas, etc. Examples thereof include starch debranching enzymes such as pullulanase and isoamylase.

Examples of commercially available pullulanase include “Sprentase” (registered trademark, Amano Pharmaceutical Co., Ltd.), “Promozyme 200L” (registered trademark, Novo Industry Co., Ltd.), etc., and “isoamylase” ( Reagents, Seikagaku Corporation). These starch debranching enzymes are generally supplied in the form of granules, and the enzyme activity is about 10 ⁵ to 10 ⁶ units / liter.

<Component (f)>
The cleaning composition of the present invention contains a soil storage agent as the component (f). In the present invention, the soil storage agent is the soil storage capacity described in Japanese Patent No. 2551965 (Japanese Patent Laid-Open No. 1-215898) (however, in the measurement method, porous silica is read as a sample that becomes a soil storage agent). It means 0.1 or more, preferably 0.3 or more. In terms of cleaning performance, hard water resistance, low temperature solubility, and caking resistance, the content of the component (f) is preferably 1 to 80% by mass, more preferably 5 to 70% by mass in the cleaning composition. -60 mass% is still more preferable, and 20-50 mass% is especially preferable.

  As the component (f), (f1) powdered synthetic resin foam (for example, those described in US Pat. No. 3,598,844), (f2) acid clay, (f3) talc, (f4) sawdust (for example, US Pat. 3418243), (f5) bleached wood flour (for example described in Swiss Patent No. 461685), (f6) hollow silica (for example described in JP-A 61-130400), ( f7) particulate polymer material (for example, described in JP-B-50-33882), (f8) mixture of silica particles and organic fibers (for example, described in JP-B-60-8280), (f9) zeolite Examples thereof include a mixture of powder and cellulose powder (for example, those described in US Pat. No. 4,493,781), (f10) porous silica, and the like. Among these, (f10) porous silica is preferable in terms of washing performance and caking resistance. In particular, porous silica described in JP-A-1-215898 and JP-A-1-215899 is preferable.

<Other ingredients>
In the cleaning composition of the present invention, in addition to the above essential components, known additives can be blended as required within a range not impairing the intended performance. Examples of such additives include carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphate / hydrogen peroxide adduct, urea / peroxide. Compounds that release hydrogen peroxide in aqueous solutions such as hydrogen oxide adducts; glucose pentaacetate, triacetin, N, N, N ′, N′-tetraacetylethylenediamine, tetraacetylglycolyluril, the following general formula (1) to (4) A compound that reacts with hydrogen peroxide in an aqueous solution such as the compound represented by (4) to generate an organic peracid; a hydrotrope such as ethanol, propylene glycol, or glycerin; a fragrance, a dye, an antiseptic / antifungal agent, etc. Can be mentioned.

[In the formula, R ¹¹ is preferably an alkyl group having 4 to 13 carbon atoms (more preferably 10 to 13), R ¹² is preferably an alkyl group having 5 to 13 carbon atoms (more preferably 7 to 11), and M is A hydrogen atom or an alkali metal, an alkaline earth metal, ammonium or alkanolamine is shown. ]

[In the formula, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ are a methyl group, an ethyl group, and a hydroxyethyl group, respectively, and R ¹⁸ is an alkylene group having 2 to 10 carbon atoms. And X ⁻ represents an anion (preferably a halogen ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, a phosphate ion, or a sulfate ion). ]

<How to use>
Specifically, the cleaning composition of the present invention can be used by the following methods (1) to (3).
[Method (1)]
The cleaning composition of the present invention is dissolved / dispersed in water or the like in advance, applied to the object to be cleaned, brushed (transfers the dirt from the object to be cleaned to the solution), and then dried (to remove the dirt in the solution). A method of removing the soil storage agent from the object to be cleaned together with the soil using an electric vacuum cleaner or the like.

[Method (2)]
The object to be cleaned is moistened with water or the like, the cleaning composition of the present invention is applied to the object to be cleaned, brushed, etc., then dried, and the dirt occlusion agent is removed from the object to be cleaned together with dirt by a vacuum cleaner or the like How to remove.

[Method (3)]
The cleaning composition of the present invention is applied to an object to be cleaned, the object to be cleaned is moistened with water, brushed, etc., then dried, and the dirt occlusion agent is removed from the object to be cleaned together with dirt by an electric vacuum cleaner or the like. How to remove.

  Method (1) is preferable in that it can be applied and washed uniformly. Moreover, it is preferable to use alcohol, such as ethanol, with water from the point of shortening drying time.

<Surfactant-containing particles 1>
Adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, the alkyl (carbon number: 12-16) sodium sulfate salt (hereinafter, the alkyl sulfate is expressed as AS) Paste) (73% by mass of active ingredient) and polyoxyethylene (EO average added mole number 3.7) alkyl (carbon number 12 to 16) sodium sulfate (hereinafter, polyoxyalkylene alkyl sulfate is expressed as ES) ) Containing aqueous solution (25% by mass of active ingredient) and a paste obtained by mixing the active ingredient so that the mass ratio of AS: ES = 96: 4 is a vacuum dryer having a dryer capacity of 2500 L [Fukae Pautech Co., Ltd. , FDM-1200JE type] at an average addition rate of 150 kg / Hr, agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min, flatness between stirring blade and wall surface Clearance: granulating conditions 5.5 mm, dried and subjected to granulation at the same time, to obtain a granulated product 600 kg. Further, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having an average particle size of 120 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. While adjusting to dry conditions such that the paste contains alkyl (carbon number 12 to 16) sodium sulfate (AS) -containing paste (active ingredient 73 mass%) and polyoxyethylene (EO average added mole number 3.7) alkyl ( C12-16) Sodium sulfate (ES) -containing aqueous solution (active ingredient 25% by mass) is averaged in a dryer with a paste mixed so that the active ingredient mass ratio is AS: ES = 96: 4 Dropped at an addition rate of 150 kg / Hr, granulated simultaneously with drying under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. There was obtained granulated product polyoxyethylene alkyl sulfate sodium salt 0.1. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 3% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 950 μm and an apparent density of 650 g / L by vibration sieving. Activator-containing particles 1 were obtained.

<Surfactant-containing particles 2>
While adjusting the drying conditions so that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the operation product temperature is 70 ± 1 ° C., the paste containing alkyl (12 to 16 carbon atoms) sodium sulfate (AS) (active ingredient 73 mass) %) And polyoxyethylene (EO average addition mole number 3.8) alkyl (carbon number 12 to 16) sodium sulfate (ES) -containing aqueous solution (active ingredient 25 mass%), the mass ratio of the active ingredient is AS : The paste mixed so that ES = 50: 50 was dropped into a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) with an internal volume of 2500 L at an average addition rate of 150 kg / Hr, and the agitator was rotated. Number: 55 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blades and wall surface: granulation at the same time as drying under granulation conditions of 5.5 mm, 600 kg To obtain a granulated product. Further, a part of the granulated material was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated material to obtain a powder raw material having an average particle size of 100 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. While adjusting to the drying conditions, the alkyl (carbon number 12 to 16) sodium sulfate (AS) -containing paste (active ingredient 73 mass%) and polyoxyethylene (EO average added mole number 3.8) alkyl ( C12-16) Sodium sulfate (ES) -containing aqueous solution (active ingredient 25% by mass) is averaged in a dryer with a paste mixed so that the active ingredient has a mass ratio of AS: ES = 50: 50 Dropped at an addition rate of 150 kg / Hr and granulated simultaneously with drying under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. Number to obtain a granulated product polyoxyethylene alkyl sulfate sodium salt 1.9. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 40% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 920 μm and an apparent density of 680 g / L by vibration sieving. Activator-containing particles 2 were obtained.

<Surfactant-containing particle 3>
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 paste containing alkyl (carbon number 12-18) sodium sulfate (AS) (active ingredient 73 mass) %) And polyoxyethylene (EO average added mole number 2.1) alkyl (carbon number 12 to 18) sodium sulfate (ES) -containing aqueous solution (active ingredient 25 mass%), the mass ratio of the active ingredient is AS : The paste mixed so that ES = 10: 90 was dropped into a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) with an internal volume of 2500 L at an average addition rate of 150 kg / Hr, and the agitator was rotated. Number: 55 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blades and wall surface: granulation at the same time as drying under granulation conditions of 5.5 mm, 600 kg To obtain a granulated product. Further, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having an average particle size of 120 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. While adjusting to the drying conditions, the alkyl (carbon number 12-18) sodium sulfate (AS) -containing paste (active ingredient 73% by mass) and polyoxyethylene (EO average added mole number 2.1) alkyl ( C12-18) Sodium sulfate (ES) -containing aqueous solution (active ingredient 25% by mass) is averaged in a dryer with a paste mixed so that the mass ratio of the active ingredient is AS: ES = 10: 90 Dropped at an addition rate of 150 kg / Hr and granulated simultaneously with drying under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. Number to obtain a granulated product polyoxyethylene alkyl sulfate sodium salt 2.0. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 7% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite was added to the obtained granulated product, and the zeolite was uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 960 μm and an apparent density of 710 g / L by vibration sieving. Activator-containing particles 3 were obtained.

<Surfactant-containing particles 4>
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, higher alcohols (12 to 16 carbon atoms) and higher alcohols (12 to 16 carbon atoms) Polyoxyethylene (EO average added mole number of 0.00) obtained by neutralizing a sulfated mixture of ethoxylate added with an average of 2.5 moles of EO at a mass ratio of 75/25 with an aqueous sodium hydroxide solution. 25) Alkyl (carbon number 12 to 16) sodium sulfate salt-containing paste (active ingredient 72% by mass) in a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) with an inner volume of 2500 L on average 150 kg / Hr Dropping at an addition rate, agitation speed: 55 r / min, chopper speed: 2000 r / min, average clearance between stirring blade and wall: 5.5 mm It performs granulation simultaneously with 燥 to obtain granules of 600 kg. Further, a part of the granulated material was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated material to obtain a powder raw material having an average particle size of 100 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. 75/25 mass of higher alcohol (carbon number 12-16) and ethoxylate obtained by adding 2.5 mol of EO to higher alcohol (carbon number 12-16) on average while adjusting to dry conditions Polyoxyethylene (EO average addition mole number 0.6) alkyl (carbon number 12 to 16) sodium sulfate-containing paste (active ingredient) obtained by neutralizing the sulfate of the mixture blended at a ratio with an aqueous sodium hydroxide solution 72% by mass) was dropped into the dryer at an average addition rate of 150 kg / Hr and dried under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. Sometimes it performs granulation to obtain granules of polyoxyethylene alkyl sodium sulfate EO average addition mole number of 0.6. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 4% by mass. Moreover, sodium sulfate was 15 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 1160 μm and an apparent density of 670 g / L by vibration sieving. Activator-containing particles 4 were obtained.

<Surfactant-containing particles 5>
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, higher alcohol (carbon number 14-18) and higher alcohol (carbon number 14-18) Polyoxyethylene (EO average added mole number of 0.00) obtained by neutralizing a sulfoxide of a mixture of ethoxylate added with 2.8 moles of EO in an average ratio of 75/25 with a sodium hydroxide aqueous solution. 7) Alkyl (carbon number 14-18) sodium sulfate salt-containing paste (active ingredient 72% by mass) in a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) with an inner volume of 2500 L on average 150 kg / Hr Dropping was carried out at an addition rate, and the agitator rotation speed was 55 r / min, the chopper rotation speed was 2000 r / min, and the average clearance between the stirring blade and the wall surface was 5.5 mm. Simultaneously performs granulation to obtain granules of 600 kg. Furthermore, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having an average particle size of 80 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. 75/25 mass of higher alcohol (carbon number 14-18) and ethoxylate obtained by adding 2.8 mol of EO on average to higher alcohol (carbon number 14-18) Polyoxyethylene (EO average added mole number 0.7) alkyl (carbon number 14-18) sodium sulfate-containing paste (active ingredient) obtained by neutralizing the sulfate of the mixture blended at a ratio with an aqueous sodium hydroxide solution 72% by mass) was dropped into the dryer at an average addition rate of 150 kg / Hr and dried under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. Sometimes it performs granulation to obtain granules of polyoxyethylene alkyl sodium sulfate EO average addition mole number of 0.7. The water content was 7% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 1% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite was added to the obtained granulated product, and the zeolite was uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 980 μm and an apparent density of 650 g / L by vibration sieving. Activator-containing particles 5 were obtained.

<Surfactant-containing particle 6>
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, higher alcohol (carbon number 14-18) and higher alcohol (carbon number 14-18) Polyoxyethylene (EO average added mole number of 0.00) obtained by neutralizing a sulfate of a mixture of ethoxylate added with an average of 2.5 moles of EO at a mass ratio of 85/15 with an aqueous sodium hydroxide solution. 4) Alkyl (carbon number 14 to 18) sodium sulfate salt-containing paste (active ingredient 72 mass%) was averaged at 150 kg / Hr in a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) with a capacity of 2500 L in the dryer. Dropping was carried out at an addition rate, and the agitator rotation speed was 55 r / min, the chopper rotation speed was 2000 r / min, and the average clearance between the stirring blade and the wall surface was 5.5 mm. Simultaneously performs granulation to obtain granules of 600 kg. Furthermore, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having an average particle size of 80 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. 75/25 mass of higher alcohol (carbon number 14-18) and ethoxylate obtained by adding 2.5 mol of EO on average to higher alcohol (carbon number 14-18) Polyoxyethylene (EO average added mole number 0.5) alkyl (carbon number 14 to 18) sodium sulfate-containing paste (active ingredient) obtained by neutralizing the sulfate of the mixture blended at a ratio with an aqueous sodium hydroxide solution 72% by mass) was dropped into the dryer at an average addition rate of 150 kg / Hr and dried under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. Sometimes it performs granulation to obtain granules of polyoxyethylene alkyl sodium sulfate EO average addition mole number of 0.4. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 3% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite was added to the obtained granulated product, and the zeolite was uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 990 μm and an apparent density of 660 g / L by vibration sieving. Activator-containing particles 6 were obtained.

<Surfactant-containing particle 7>
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, higher alcohol (carbon number 14-18) and higher alcohol (carbon number 14-18) Polyoxyethylene (EO average added mole number of 0.00) obtained by neutralizing a sulfate of a mixture of ethoxylate added with 2.3 moles of EO in an average ratio of 75/25 with a sodium hydroxide aqueous solution. 6) Alkyl (carbon number 14-18) sodium sulfate salt-containing paste (active ingredient 72% by mass) in a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) with an internal volume of 2500 L of average 150 kg / Hr Dropping was carried out at an addition rate, and the agitator rotation speed was 55 r / min, the chopper rotation speed was 2000 r / min, and the average clearance between the stirring blade and the wall surface was 5.5 mm. Simultaneously performs granulation to obtain granules of 600 kg. Furthermore, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having an average particle size of 80 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. 75/25 mass of higher alcohol (carbon number 14-18) and ethoxylate obtained by adding 2.3 mol of EO to higher alcohol (carbon number 14-18) on average while adjusting to dry conditions such that Polyoxyethylene (EO average added mole number 0.6) alkyl (carbon number 14 to 18) sodium sulfate-containing paste (active ingredient) obtained by neutralizing the sulfate of the mixture blended at a ratio with an aqueous sodium hydroxide solution 72% by mass) was dropped into the dryer at an average addition rate of 150 kg / Hr and dried under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. Sometimes it performs granulation to obtain granules of polyoxyethylene alkyl sodium sulfate EO average addition mole number of 0.6. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 3% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite was added to the obtained granulated product, and the zeolite was uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 1080 μm and an apparent density of 690 g / L by vibration sieving. Activator-containing particles 7 were obtained.

<Surfactant-containing particles 8>
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, higher alcohol (carbon number 14-18) and higher alcohol (carbon number 14-18) Polyoxyethylene (EO average added mole number of 0.00) obtained by neutralizing a sulfate of a mixture of ethoxylate added with an average of 2.2 mole of EO at a mass ratio of 60/40 with a sodium hydroxide aqueous solution. 9) Alkyl (carbon number 14-18) sodium sulfate salt-containing paste (active ingredient 72% by mass) was averaged at 150 kg / Hr in a vacuum dryer [FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.] with a dryer capacity of 2500 L. Dropping was carried out at an addition rate, and the agitator rotation speed was 55 r / min, the chopper rotation speed was 2000 r / min, and the average clearance between the stirring blade and the wall surface was 5.5 mm. Simultaneously performs granulation to obtain granules of 600 kg. Furthermore, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having an average particle size of 80 μm.

  Next, 200 kg of the above powder raw material is put into a vacuum dryer having a capacity of 2500 L (FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.), jacket temperature is 85 ° C., pressure is 4.0 kPa, and product temperature is 70 ± 1 ° C. 75/25 mass of higher alcohol (carbon number 14-18) and ethoxylate obtained by adding 2.2 mol of average EO to higher alcohol (carbon number 14-18) Polyoxyethylene (EO average added mole number 0.9) alkyl (carbon number 14-18) sodium sulfate-containing paste (active ingredient) obtained by neutralizing the sulfate of the mixture blended at a ratio with an aqueous sodium hydroxide solution 72% by mass) was dropped into the dryer at an average addition rate of 150 kg / Hr and dried under the conditions of agitator rotation speed: 55 r / min and chopper rotation speed: 2000 r / min. Sometimes it performs granulation to obtain granules of polyoxyethylene alkyl sodium sulfate EO average addition mole number of 0.9. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 3% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granular anionic surfactant, and an interface having an average particle size of 1120 μm and an apparent density of 750 g / L by vibration sieving. Activator-containing particles 8 were obtained.

<Builder-containing particles 1>
Pre-feed granule (Made by Tokuyama Siltech Co., Ltd.)

<Builder-containing particles 2>
Builder particles were prepared by supplying the aqueous slurry to a spray drying tower and 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. Sodium carbonate 30% by mass, sodium sulfate 15% by mass, sodium sulfite 1% by mass, zeolite 50% by mass, water 4% by mass.

<Builder-containing particles 3>
85 parts by weight of anhydrous sodium carbonate (light ash made by Tokuyama Co., Ltd.) and 10 parts by weight of polyethylene glycol having a molecular weight of 4000 are put into a readyge mixer (Matsuzaka Giken Co., Ltd., capacity 130L, with jacket) to a total of 30 kg. The main shaft (rotation speed: 60 rpm, peripheral speed: 1.6 m / s) was stirred for 5 minutes. Warm water at 80 ° C. was passed through the jacket at 10 L / min.

<Dirt storage 1>
Table 1 of JP-A-1-215898, porous silica used in the product 2 of the present invention (dirt storage capacity 0.5)

<Dirt storage agent 2>
Table 1 of JP-A-1-215898, porous silica used in product 3 of the present invention (dirt storage capacity 1.0)

<Dirt storage 3>
Table 1 of JP-A-1-215898, porous silica used in product 4 of the present invention (dirt storage capacity 1.0)

<Example>
A powder cleaning composition shown in Table 1 was prepared using the above components and the components in Table 1, and the following evaluations were performed. The results are shown in Table 1.

[Cleaning performance evaluation]
As model stain test pieces, rapeseed oil stain test cloth (2g of rapeseed oil colored with Sudan III applied to 10cm x 10cm acrylic pile carpet), coffee stain test cloth (instant coffee 10g, powdered milk 20g, sugar 30g) A solution consisting of 500 g of water was boiled for 10 minutes, and after cooling, 5 g of this solution was applied to a 10 cm × 10 cm acrylic pile carpet and dried. Each model soil test piece was sprayed with 3 g of each cleaning composition, 3 g of water, and 0.5 g of ethanol, each of which was rubbed with a brush for 1-2 minutes and dried for 10-15 minutes (room temperature standing) Then, it was removed by suction with a vacuum cleaner, and the cleaning effect was evaluated. Evaluation was carried out by 10 persons according to the following criteria, and the average value is shown in Table 1.

<Evaluation point of cleaning effect>
1: No cleaning effect (same as before cleaning)
2: Slightly soiled 3: Slightly soiled 4: Slightly soiled 5: Slightly soiled

[Evaluation of caking resistance]
Using a two-type filter paper defined by JIS P 3801 (for example, “Qualitative No. 2 filter paper” manufactured by Toyo Filter Paper Co., Ltd.), a container having an open top of length × width × height = 10 cm × 6 cm × 4 cm is made. 100 g of a sample is put in this box, and a total mass of 15 g + 250 g of an acrylic resin plate and a lead plate (or iron plate) is placed thereon. This is left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 80%, and the caking state is determined after 7 days. The determination is performed by obtaining the passage rate as follows. Higher pass rate means higher caking resistance. The pass rate is determined by gently opening the sample after storage on a sieve (aperture 4760 μm defined in JIS Z 8801), measuring the mass of the passed powder, and passing rate relative to the sample after storage (sample used for the test). Asking.

Claims (8)

The following (A) surfactant-containing particles, (B) builder-containing particles, and (f) a soil occlusion agent having a soil occlusion capacity of 0.1 or more selected from porous silica ,
(F) Contaminant is used in a cleaning method for removing a soil storage agent from an object to be cleaned by a vacuum cleaner.
Cleaning composition.
<(A) Surfactant-containing particles>
(A) 1 to 70% by mass of polyoxyalkylene alkyl ether sulfate having 1 to 3 added moles of alkylene oxide, and (b) 0 to 30 polyoxyalkylene alkyl ether sulfate having 4 or more added moles of alkylene oxide. Mass%, (c) 10 to 95 mass% of alkyl sulfate, (d) at least one selected from water-soluble inorganic salts and water-insoluble inorganic salts, 1 to 38 mass%, (e) water (described in JIS K 3362: 1998) The water content is 0.1 to 5% by mass based on the superheat loss method, and is measured by a sieving method using a sieving machine described in JIS K 3362: 1998 and a sizing machine described in JIS K 3362: 1998. Surfactant-containing particles having an average particle size determined from the particle size of 150 to 2000 μm.
<(B) Builder-containing particles>
Builder particles containing more than 50% by mass of a builder having at least one of metal chelating action, alkali buffering action, and solid particle dispersing action. (A) In the particles, the total amount of (a) and (b) and the mass ratio of (c) is [(a) + (b)] / (c), and is 70/30 to 5/95. Item 2. A cleaning composition according to Item 1 . The cleaning composition according to claim 1 or 2, wherein the average added mole number of alkylene oxides in (A), (a), (b), and (c) is 0.05 to 2 . (A) In the particles, the total amount of (a) and (c) and the mass ratio of (b) is [(a) + (c)] / (b) and is 70/30 to 100/0. Item 4. The cleaning composition according to any one of Items 1 to 3 . (A) The cleaning composition according to any one of claims 1 to 4 , comprising an inorganic salt having a calcium capture amount of 200 to 600 CaCO ₃ mg / g as at least a part of (d) in the particles. (A) The cleaning composition according to any one of claims 1 to 5 , wherein the total amount of (a), (b) and (c) in the particles is 50 to 98 mass%. (A) A paste containing (a), (b), (c) and (e) in a powder raw material containing (d) under reduced pressure in a granulator having a stirring blade and a crushing blade The composition for cleaning according to any one of claims 1 to 6 , which is a surfactant-containing particle obtained by granulating simultaneously with drying while adding. The cleaning composition according to any one of claims 1 to 7, which is in a powder form .