JP2002080218A - Method of producing fine particle zeolite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an efficient method of producing fine particle zeolite having fine average primary particle size being excellent in oil absorbing ability and cation exchanging ability, and also having fine average agglomerated particle size being excellent in dispersing ability by reacting an aluminum source and/or a silica source fed to a circulating line connecting to a reactor, and to provide fine particle zeolite obtained by the method and a detergent composition having excellent washing ability containing the fine particle zeolite. SOLUTION: This method of producing fine particle zeolite comprises reacting an aluminum source and/or silica source fed into a circulating line connecting to a reactor. This fine particle zeolite is made by the method and satisfies relationships of 0.6<=X<=1.5 and 20X/3-2.4<=Y<=15, provided X<=Y, where X represents average primary particle size in μm and Y represents average agglomerated particle size in μm. This detergent composition comprises the fine particle zeolite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing fine-particle zeolite, a fine-particle zeolite obtained by the production method, and a cleaning composition containing the same.

[0002]

2. Description of the Related Art Zeolite is used as a water softener in detergent builders due to its ion exchange ability.
It is known that the ion exchange capacity largely depends on the primary particle diameter of zeolite, and zeolite having a small primary particle diameter has an excellent ion exchange rate, and thus exhibits high washing performance.

[0003] Further, it is known that fine-particle zeolites also have advantages such as low deposition on clothing and reduced turbidity, and are useful as builders for detergents.

As a method for producing such a fine particle zeolite, for example, JP-A-60-127218 and JP-A-62-227
Japanese Patent Application Laid-Open No. 5016 discloses an example in which sodium aluminate and sodium silicate are mixed to synthesize zeolite, and the synthesis is completed under a specific charged composition and reaction conditions (temperature and time). When synthesizing a fine zeolite in this way, the raw material preparation composition and reaction conditions must be performed under limited restrictions, and a problem such as a decrease in productivity occurs.

On the other hand, attempts have been made to reduce the particle size from the viewpoint of the manufacturing process. For example, Japanese Patent Application Laid-Open
Japanese Patent No. 46494 discloses mechanical pulverization using various kinds of mixing devices. However, there is still room for improvement in terms of the performance and production efficiency of the fine particle zeolite.

[0006]

SUMMARY OF THE INVENTION The present invention provides an aluminum source and / or a silica source which is supplied into a circulation line of a reaction vessel having a circulation line to carry out a reaction. Efficient method for producing fine-particle zeolite composed of crystalline aluminosilicate having excellent cation exchange ability and having a small average aggregate particle size and excellent dispersibility, fine-particle zeolite obtained by the production method, and detergency containing the same An object of the present invention is to provide a cleaning composition having excellent cleaning properties.

[0007]

That is, the gist of the present invention is as follows.
(1) A method for producing a fine particle zeolite in which an aluminum source and / or a silica source is supplied to a circulation line of a reaction vessel having a circulation line to carry out a reaction, and (2) in the presence of a compound containing an alkaline earth metal. (3) a fine-particle zeolite obtainable by the fine-particle zeolite production method according to (1) or (2), and (4) an average primary particle diameter. X μm, when the average aggregate particle size is Y μm,
0.6 ≦ X ≦ 1.5, 20X / 3−2.4 ≦ Y ≦ 15,
However, fine-particle zeolite satisfying X ≦ Y, and (5)
A cleaning composition comprising the fine particle zeolite according to (3) or (4).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a fine particle zeolite of the present invention is characterized in that a reaction between an aluminum source and a silica source is carried out in a circulation line of a reactor having a circulation line. In particular, a preferred embodiment of the present invention is an embodiment in which the reaction between the aluminum source and the silica source is performed in the presence of a compound containing an alkaline earth metal. The method for producing fine particle zeolite of the present invention has few restrictions on the raw material charging composition, reaction conditions, and the like, and according to the production method, desired fine particle zeolite can be efficiently produced.

[0009] In the present specification, "cation exchange capacity" refers to both the cation exchange rate and the cation exchange capacity described later. The “aqueous liquid” refers to a liquid containing a certain component using water as a medium, such as an aqueous solution, suspension, or dispersion. Further, “line mixing” refers to a process of substantially uniformly mixing a plurality of components (raw materials and the like) in a line such as a raw material supply line described below.

The silica source and the aluminum source used in the present invention are not particularly limited, but those aqueous liquids are preferable from the viewpoint of the uniformity of the reaction and the dispersibility. For example, commercially available water glass is suitably used as the silica source.
If desired, a water source or a caustic alkali can be added to the water glass to provide a silica source whose molar ratio and concentration are adjusted. The aluminum source is not particularly limited, but aluminum hydroxide, aluminum sulfate, aluminum chloride, and alkali metal aluminates such as potassium aluminate or sodium aluminate are used. Sodium aluminate is preferably used in view of the height. These are used as an aluminum source after adjusting to an appropriate molar ratio and concentration using caustic alkali and water as required. For example, aluminum hydroxide and sodium hydroxide are mixed in water and then heated and dissolved to prepare a sodium aluminate solution, and this solution is added to water while stirring to form an aqueous liquid, which can be used as an aluminum source. Such a molar ratio and concentration adjustment can also be carried out by previously charging water into the reaction vessel and adding a high-concentration aqueous solution of alkali metal aluminate and caustic to the reaction vessel.

In the synthesis reaction of zeolite, it is preferable that a compound containing an alkaline earth metal coexist in the reaction system. By performing the zeolite synthesis reaction in the presence of the alkaline earth metal, the average primary particle diameter of the obtained fine particle zeolite can be further reduced. As the alkaline earth metal, Mg, Ca, Sr, Ba or the like is used. Of these, Mg and Ca are preferably used in view of simplicity of obtaining raw materials and cost. These may be used alone or in combination of two or more. These are added to the reaction system as alkaline earth metal hydroxides or alkaline earth metal salts such as carbonates, sulfates, chlorides and nitrates. Further, it is preferable to add as an aqueous liquid from the viewpoint of the uniformity of the reaction and the like, and it is particularly preferable to use a water-soluble salt thereof, and an aqueous chloride solution such as Ca and Mg is particularly preferably used. Alkaline earth metal hydroxides and alkaline earth metal salts may be present together when the silica source and the aluminum source are reacting. It is preferably added in advance, and more preferably added in advance to the silica source from the viewpoint of minimizing the average primary particle diameter. In that case,
It is preferable to add all of the compound containing an alkaline earth metal in advance, but a part of the compound may be added.

When the reaction between the aluminum source and the silica source is carried out in the presence of a compound containing an alkaline earth metal, the alkaline earth metal is incorporated into the structure of the zeolite during the synthesis of the zeolite and acts on the zeolite network. result,
Fine zeolites having an average primary particle diameter are generated. In particular, the silica source has a high affinity for the alkaline earth metal, and therefore it is more preferable that both coexist in advance. In addition, since alkaline earth metals can act during the synthesis of zeolite, alkaline earth metals are used in the initial stage of the reaction and / or
Alternatively, it is desirable to participate in the reaction during crystallization.

The compound containing an alkali metal such as caustic is optionally used for adjusting the molar ratio and concentration of the silica source and / or the aluminum source.
The compound may be used separately. When used separately, it can be used in the same manner as the compound containing an alkaline earth metal. As the alkali metal, Na and / or K are preferably used.

In the present specification, "to be added in advance" means that before the silica source and the aluminum source are supplied, a compound containing an alkaline earth metal in the silica source and / or the aluminum source is added in advance. An embodiment of mixing substantially uniformly, for example, by directly adding and mixing into a silica source and / or an aluminum source, and then mixing and reacting the silica source and the aluminum source, As another embodiment, it is not always necessary to directly add and mix a compound containing an alkaline earth metal in a silica source and / or an aluminum source, and to supply an alkaline earth metal during the supply of the silica source and / or the aluminum source. An embodiment in which a compound containing a metal is mixed, for example, a raw material supply line for a silica source and / or an aluminum source and a raw material supply line for a compound containing an alkaline earth metal Coupled in front of the ring line may be a method of performing the line mixing. Further, a method in which a compound containing an alkaline earth metal is directly charged into a reaction tank may be used.

The composition of the anhydrous zeolite of the present invention obtained by the method for producing the fine particle zeolite of the present invention has the general formula xM ₂ O.y SiO ₂ .Al ₂ O ₃ .z
MeO (where M represents an alkali metal, Me represents an alkaline earth metal, x = 0.2 to 2, y = 0.5 to 6, z =
0 to 0.1). More preferably, M in the above composition is Na and / or K, and Na is particularly preferred from the viewpoint of easy availability of raw materials and cost. Me is C
a and / or Mg are preferred. Also, x = 0.6-
1.3 is more preferred. y = 0.9-5 is more preferable. z is more preferably 0.005 or more from the viewpoint of the effect of minimizing the average primary particle diameter, and is preferably 0.1 or less from the viewpoint of cation exchange capacity, that is, cation exchange rate and cation exchange capacity, and 0.08 or less. More preferred.
Further, it is particularly preferably 0.01 to 0.03.

In order to obtain a zeolite having such a composition, the molar ratio of SiO ₂ / Al ₂ O ₃ is preferably 0.5 or more, more preferably 1.5 or more, from the viewpoint of stability of the crystal structure. More preferred. In addition, from the viewpoint of cation exchange capacity, it is preferably 6 or less, more preferably 4 or less, and 3 or less.
The following is more preferable, and the value of 2.5 is particularly preferable.

As the charged composition of the compound containing an alkaline earth metal, the alkaline earth metal (Me) is represented by an oxide, and the molar ratio of MeO / Al ₂ O ₃ is preferably 0 to 0.
0.1 from the viewpoint of the effect of miniaturization of the average primary particle diameter.
005 or more is more preferable, and 0.01 or more is particularly preferable. Further, from the viewpoint of cation exchange capacity, the value is preferably 0.1 or less, more preferably 0.08 or less, particularly preferably 0.05 or less, and still more preferably 0.03 or less.

As for the charged composition of the compound containing an alkali metal, an alkali metal (M) is represented by an oxide, and M ₂
The molar ratio of O / Al ₂ O ₃ is usually preferably from 0.2 to 8,
From the viewpoint of the crystallization rate, 0.2 or more is preferable, and 1.5 or more is more preferable. Also, from the viewpoint of yield, 8 or less is preferable, and 4 or less is more preferable. Further, the charged composition of the compound containing an alkali metal and water in the reaction system may be M ₂ O / H from the viewpoint of crystallization speed and miniaturization of the average primary particle diameter.
The molar ratio of ₂ O is preferably 0.03 or more, more preferably 0.04 or more. In addition, from the viewpoint of cation exchange ability, it is preferably 0.07 or less, more preferably 0.06 or less.

When an alkali metal and / or an alkaline earth metal is contained in a silica source and / or an aluminum source, a compound containing an alkali metal and / or a compound containing an alkaline earth metal is added to a silica source and / or an aluminum source. It may be added to the aluminum source or vice versa.

As the solid content concentration at the time of the reaction, the weight of all the elements of Si, M, Al and Me of the raw materials added so as to have the above molar ratio converted to oxides is regarded as the solid content, and the total water content is determined. When the concentration of the solid content relative to the slurry amount is defined as the solid content concentration during the reaction, the concentration is 1 from the viewpoint of productivity.
It is preferably at least 0% by weight, more preferably at least 15% by weight. Further, from the viewpoint of the fluidity of the slurry, the content is preferably 50% by weight or less, more preferably 40% by weight or less.

In the method for producing a fine particle zeolite of the present invention, a silica source and an aluminum source are used as main raw materials, and the raw materials are mixed and reacted in a circulation tank having a circulation system (circulation line) outside. At this time, as the other raw materials, preferably, a compound containing an alkaline earth metal is mixed in advance with a silica source and / or an aluminum source as described above and is supplied substantially uniformly or simultaneously, or a silica source and an aluminum source are mixed. Are mixed and supplied separately after the start of the reaction to mix and react the raw materials. If desired, a compound containing an alkali metal may be supplied in the same manner as a compound containing an alkaline earth metal, and the raw materials may be mixed and reacted. In the middle of the circulation line, a wet mixer (for example, a homomic line mill, a homomic line mixer, a homogenizer, a staticizer, or the like) is passed so that a slurry formed after each raw material is supplied to the circulation line can pass through. It is preferable to install a crusher, a disperser, a crusher, and the like such as a mixer, a gear pump, a turbine pump, and a vortex pump.

The silica source and the aluminum source may be supplied from the corresponding raw material tanks to the same or different portions in the circulation line, or one of the two may be directly charged into the reaction tank to circulate the circulation line. At the same time, the other may be supplied from the corresponding raw material tank into the circulation line. In addition, any of these may be supplied first or may be supplied simultaneously. Such a raw material tank is connected to any part of a circulation line via a raw material supply line, preferably a circulation line part connecting an outlet of the reaction tank and an inlet of the mixer, and is supplied from the raw material tank. The raw material will be supplied to the circulation line via the raw material supply line. Alternatively, when one raw material is directly charged into the reaction tank, the raw material is circulated from the reaction tank through the circulation line, so that the raw material is mixed with the other raw material supplied into the circulation line in the circulation line. . Raw materials are supplied and mixed in a circulating line connecting the outlet of the reaction tank and the inlet of the mixer, whereby the fine particle zeolite according to the present invention can be efficiently synthesized, which is preferable. In addition, so that the slurry becomes more uniform in the reaction tank, and so that the raw material supply in the raw material tank is performed smoothly, in the reaction tank and the raw material tank,
It is preferable to provide a stirrer having a stirring blade.

As a method for producing the fine particle zeolite of the present invention, the following method is specifically exemplified.

First Production Method Water is charged into a reaction tank, and an aluminum source and a silica source are supplied from a corresponding raw material tank to a circulation line via a raw material supply line while circulating the water through a circulation line. The compound containing an alkali metal is previously added to a silica source and / or an aluminum source, supplied simultaneously with a silica source and / or an aluminum source from a corresponding raw material tank to a circulation line, or directly charged into a reaction tank. It is preferable to keep it. It is preferable that the compound containing an alkaline earth metal is partially or entirely added to the silica source in advance, but may be added to the aluminum source in advance. Also, the silica source and / or the aluminum source may be supplied simultaneously to the circulation line from the corresponding raw material tank, or the raw material supply line for the silica source and / or the aluminum source and the alkaline earth metal may be contained before the circulation line. The compound raw material supply line may be combined with the compound raw material supply line, and may be added and supplied in advance by line mixing. Further, it may be directly charged into the reaction tank.

Second Production Method An aluminum source is charged into a reaction tank, and while the aluminum source is circulated in a circulation line, a silica source and water are simultaneously supplied from a corresponding raw material tank to a circulation line via a raw material supply line. Supply. The compound containing an alkali metal is previously added to the silica source and / or water, or the silica source and / or
Alternatively, it is preferable to supply water to the circulation line simultaneously from the corresponding raw material tank together with water, or to directly feed the reaction tank and add it to the aluminum source in advance, or supply the aluminum source to the reaction tank at the same time. It is preferable that the compound containing the alkaline earth metal is previously or partially added to the silica source in advance, but it may be supplied from the corresponding raw material tank to the circulation line at the same time, or before the circulation line. The raw material supply line for the silica source and the raw material supply line for the compound containing an alkaline earth metal may be combined and added in advance by line mixing before supplying. Alternatively, it may be directly charged into the reaction tank and added to the aluminum source in advance, or may be supplied to the reaction tank simultaneously with the aluminum source. Furthermore, it may be supplied together with water.

Third Production Method A silica source is charged into a reaction vessel, and while the silica source is circulated in a circulation line, an aluminum source and water are simultaneously supplied from a corresponding raw material tank to a circulation line via a raw material supply line. Supply. The compound containing an alkali metal is previously added to the aluminum source and / or water, or the aluminum source and / or
Alternatively, it is preferable to simultaneously supply water to the circulation line from the corresponding raw material tank, or directly feed into the reaction tank and add it to the silica source in advance, or charge simultaneously with the silica source into the reaction tank. It is preferable to add a part or all of the compound containing an alkaline earth metal to the silica source in advance, but it is preferable that the compound is directly added to the reaction tank and added to the silica source in advance, or simultaneously with the reaction tank. May be supplied. Also, the aluminum source and the corresponding raw material tank may be added to the circulation line in advance or supplied simultaneously with the aluminum source, or the raw material supply line of the aluminum source and the compound containing an alkaline earth metal may be provided before the circulation line. May be combined with the raw material supply line and added in advance by line mixing before supplying. Furthermore, it may be supplied together with water.

The above-described first to third production methods are preferred embodiments particularly when the main reaction is carried out in a reaction tank.

The mixing ratio between the aluminum source and the silica source in the circulation line can be adjusted by the circulation flow rate and the supply flow rate of each raw material. Such a mixing ratio, from the viewpoint of oil absorption capacity, Si
The molar ratio of O ₂ / Al ₂ O ₃ is preferably 0.1 or more,
0.5 or more is more preferable, and 1 or more is particularly preferable. Further, from the viewpoint of the fluidity of the slurry, 3 or less is preferable,
2.5 or less is more preferable, and 2 or less is particularly preferable.

As in the second production method and the third production method, a silica source or an aluminum source is charged into a reaction tank, and another raw material is supplied into the circulation line while circulating the raw material in the circulation line. If the reaction is carried out in such a manner, the product ratio increases during the reaction, so that the mixing ratio may change over time. In such a case, the mixing ratios of raw materials at the time of starting to supply the other raw materials at a molar ratio of SiO ₂ / Al ₂ O _3, preferably 0.1 to 3, more preferably 0.5
2.5, particularly preferably the raw material concentration to be 1-2,
By adjusting the circulation flow rate and the like, desired fine particle zeolite can be obtained according to the production method of the present invention. The molar ratio is calculated by the following equation: molar ratio = (Qs × Cs) / (Qa × Ca) [wherein Qa represents the flow rate (kg / min) of the aluminum source, C
a is the molar concentration (mo) of Al ₂ O ₃ contained in the aluminum source.
1 / kg) and Qs is the flow rate (kg / min) of the silica source.
And Cs represents the molar concentration (mol / kg) of SiO ₂ contained in the silica source].

The reaction temperature is preferably 25 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C., and even more preferably 5 ° C.
It is 0-70 ° C, particularly preferably 50-60 ° C, most preferably 50-55 ° C. From the viewpoint of the reaction rate, the temperature is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. In addition, from the viewpoint of energy load and pressure resistance of the reaction vessel, the temperature is preferably 100 ° C or lower, more preferably 80 ° C or lower, further preferably 70 ° C or lower, particularly preferably 60 ° C or lower, and most preferably 55 ° C or lower.

In the initial stage of the reaction, the resulting slurry thickens due to a rapid gel formation reaction. Therefore, it is preferable to vigorously stir to promote the reaction of the slurry.

The reaction time is not particularly limited, but is preferably 1 to 180 minutes, more preferably 2 to 60 minutes, more preferably 2 to 60 minutes after completion of addition of all the charged components, from the viewpoint of productivity and stability of the reaction. Is 4-20 minutes.

More specifically, crystallization of zeolite proceeds after the reaction is completed by stopping the circulation of the slurry in the circulation line or by aging the slurry while maintaining the circulation. The aging temperature is not particularly limited, but is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher from the viewpoint of the crystallization rate. Further, the temperature is preferably 100 ° C. or less from the viewpoint of energy load and pressure resistance of the reaction vessel. The aging time is not particularly limited, but is usually preferably 1 to 300 minutes from the viewpoint of productivity. At that time, it is preferable to ripen until the strongest peak intensity of the X-ray diffraction pattern becomes maximum or the cation exchange capacity becomes maximum.

After the aging is completed, the slurry is washed by filtration or
Alternatively, the crystallization is terminated by neutralization with an acid. When performing filtration washing, the pH of the washing solution is preferably 1
It is better to perform until 2 or less. When neutralizing, there is no particular limitation, sulfuric acid, hydrochloric acid, nitric acid, carbon dioxide,
Oxalic acid, citric acid, tartaric acid, fumaric acid, succinic acid and the like can be used, but sulfuric acid and carbon dioxide are preferred from the viewpoint of apparatus corrosion and cost. The pH of the slurry is preferably adjusted to 7 to 12. After completion of the crystallization, drying is carried out if necessary, to obtain the fine particle zeolite of the present invention.

In a particularly preferred embodiment of the method for producing a fine particle zeolite of the present invention, as described above, an aluminum source and a silica source are supplied into the circulation line of a reaction vessel having a circulation line to contain an alkaline earth metal. In this embodiment, the reaction is performed in the presence of a compound. The compound containing an alkaline earth metal is allowed to be present in the reaction system as described above, for example, by previously adding it to an aluminum source and / or a silica source, and more preferably by previously adding it to a silica source. Can be. As the alkaline earth metal, Ca and / or Mg are preferable as described above.
As the preparation composition of the compound containing an alkaline earth metal, alkaline earth metal (Me) is represented by an oxide, and MeO
/ Al ₂ O ₃ molar ratio of preferably 0.005 to 0.1
From the viewpoint of the effect of miniaturizing the average primary particle diameter.
5 or more is preferable, and 0.01 or more is more preferable. In addition, from the viewpoint of cation exchange capacity, 0.1 or less is preferable, and 0.1 or less.
08 or less, more preferably 0.05 or less, and even more preferably 0.03 or less. Further, a compound containing an alkali metal can be used in the same manner.
The charged composition is the same as described above.

By reacting the aluminum source and the silica source according to this embodiment, the desired fine particle zeolite of the present invention can be efficiently obtained even in a reaction having a particularly high solid content during the reaction. Further, such an embodiment is particularly preferable from the viewpoint of improving the cation exchange ability and the oil absorption ability. This embodiment is particularly effective when the solid concentration at the time of the reaction is 25% by weight or more, and the desired fine particle zeolite of the present invention can be efficiently obtained even at a high concentration of 30% by weight or more.

The crystalline form of the fine particle zeolite of the present invention obtained by the method for producing the fine particle zeolite of the present invention has a known crystal form, and examples thereof include A type, X type, Y type, and P type. . The crystal form is not particularly limited, but is preferably X-type or A-type from the viewpoint of cation exchange ability,
A-type zeolites are more preferred. These generated crystal phases may be a single phase or a mixed phase.

The average primary particle diameter can be determined from the average value of the tangential tangent diameter (Ferret diameter) by a scanning electron microscope (SEM), and is preferably 1.5 μm or less from the viewpoint of the cation exchange rate, and is preferably 1.3 μm. The following is more preferred. Further, if the average primary particle size is too small, the crystallinity is reduced, or the average aggregate particle size is increased from the point of 0.2 μm
Or more, more preferably 0.5 μm or more.

On the other hand, the average agglomerated particle size is measured by a laser diffraction / scattering type particle size distribution analyzer or the like. The average agglomerated particle size is defined as the dispersibility of the fine zeolite and the deposition property on clothes when blended in a detergent. In view of the above, 13 μm or less is preferable, 9 μm or less is more preferable, 7 μm or less is further preferable, 2 to 7 μm is particularly preferable, and 1 to 5 μm is most preferable.

When the average primary particle diameter is X μm and the average aggregate particle diameter is Y μm, 0.6 ≦ X ≦ 1.5, preferably 0.7 ≦ X ≦ 1.2, more preferably 0.8. ≦ X ≦
1.0 and 20X / 3−2.4 ≦ Y ≦ 1
5, preferably Y satisfies 12 or less, more preferably 10 or less in the above relational expression, and those satisfying X ≦ Y are preferable because they generally have excellent oil absorbing ability. When X and Y satisfy the above-mentioned relationship in the obtained zeolite particles, the average primary particle size is small, and the average aggregate particle size tends to be appropriately developed. It is presumed that “formation” and “exposure of the primary particle surface” occur simultaneously, and that an improvement in the oil absorption capacity is exhibited.

Further, in the present invention, the average primary particle size is defined as Xμ
Assuming that m and the average agglomerated particle size are Y μm, a value (X × Y) obtained by multiplying the product is defined as a dispersion parameter. When this value is preferably 7 or less, more preferably 0.1 to 5,
It has a cation exchange rate of at least 150 mg CaCO ₃ / g and is suitable as the fine particle zeolite of the present invention.

The oil-absorbing capacity indicates the amount of linseed oil absorbed as described in detail in Examples, and this value is preferably 50 mL.
/ 100 g or more, more preferably 70 mL / 100 g or more, and particularly preferably 80 to 130 mL / 100 g. Within this range, it is preferable from the viewpoint of the redispersibility of the fine particle zeolite.

The cation exchange rate of the fine particle zeolite of the present invention means the exchange capacity of Ca ions per minute of the fine particle zeolite.
0 mgCaCO ₃ / g or more.
More preferably, it is 0 mgCaCO ₃ / g or more.
On the other hand, the cation exchange capacity, means Ca ion exchange capacity per 10 minutes particulate zeolite of the present invention, preferably from the viewpoint of cleaning performance that this value is 150mgCaCO ₃ / g or more, 180mgCaCO ₃ / g or more And more preferably 200 mgCaCO ₃ / g
It is particularly preferable that the above is satisfied.

The fine-particle zeolite of the present invention has a small average primary particle diameter, is excellent in cation exchange ability and oil absorption ability, and has a small average aggregate particle diameter and is excellent in dispersibility. Therefore, it is preferably used as a filler for papermaking, a resin filler, a water treatment agent, a builder for detergents, an oxygen-nitrogen separator, a soil improvement agent for horticulture, an abrasive, etc., and is particularly preferably used as a builder for detergents. .

Next, a detergent composition using the fine particle zeolite of the present invention as a builder for a detergent will be described. The content of the fine particle zeolite in the detergent composition is not particularly limited, but is preferably 1% by weight or more, more preferably 3% by weight or more, and particularly preferably 10% by weight or more from the viewpoint of exhibiting sufficient cleaning performance. . In addition, from the viewpoint of smearing of the cleaning liquid and persistence on clothing, it is preferably 80% by weight or less, more preferably 70% by weight or less, and 60% by weight.
The following are particularly preferred.

The detergent composition may further contain a surfactant. The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.

Specifically, as the nonionic surfactant, a known nonionic surfactant described in Japanese Patent Office Publication “Chapter 3-1 of Collection of Well-known and Conventional Techniques (Powder Detergent for Clothing)” can be used. Can be.

In particular, it is preferable to use a nonionic surfactant of the polyoxyethylene oxide and / or polypropylene oxide type.
It is preferable to use a polyoxyethylene alkyl ether obtained by adding an average of 5 to 15 moles of ethylene oxide to 16 primary or secondary alcohols.

Other nonionic surfactants include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, sucrose fatty acid esters, fatty acid glycerin monoesters, higher fatty acid alkanolamides, and polyoxyethylene higher fatty acid alkanols. Amides, amine oxides, alkyl glycosides, alkyl glyceryl ethers, N-alkyl gluconamides and the like can also be used.

As the anionic surfactant, for example, Japanese Patent Office Publication “Known and Commonly Used Techniques (Powder Detergent for Clothing)”
The known anionic surfactants described in 1 of Chapter 3 can be used.

Specifically, alkyl benzene sulfonates, alkyl sulfates, alkenyl sulfates, polyoxyethylene alkyl ether sulfates having a linear or branched alkyl or alkenyl group having an average carbon number of 8 to 22 ( Average number of moles of ethylene oxide added:
0.5 to 6), one or more anionic surfactants selected from monoalkyl phosphates and fatty acid salts, and among them, alkylbenzene sulfonate and alkyl sulfate are particularly preferable.

Counter ions of these anionic surfactants include sodium ion, potassium ion, magnesium ion, calcium ion, cations obtained by protonating amines such as ethanolamines, quaternary ammonium salts, and quaternary ammonium salts thereof. Selected from the group consisting of mixtures.
When the above-mentioned anionic surfactant is used, a method of adding an alkali separately after blending in an acid form may be used.

As the cationic surfactant, for example, a known cationic surfactant described in Japanese Patent Office Publication “Chapter 3-1 of Collection of Well-known and Conventional Techniques (Powder Detergent for Clothing)” can be used. For example, a quaternary ammonium salt such as a benzalkonium type is suitably blended.

As the zwitterionic surfactant, for example, a known zwitterionic surfactant described in Japanese Patent Office Publication “Chapter 3-1 of Collection of Well-known and Conventional Techniques (Powder Detergent for Clothing)” can be used. For example, an alkyl betaine type is preferably used.

The above surfactants can be used alone or in combination of two or more. Further, the surfactant may be selected from the same type as in the case of selecting a plurality of anionic surfactants, or may be selected from anionic surfactants and nonionic surfactants As such, a plurality of various types may be selected.

The surfactant content in the detergent composition of the present invention is not particularly limited, but is preferably 1% by weight or more, more preferably 5% by weight or more, from the viewpoint of detergency.
% By weight or more is particularly preferred. Further, from the viewpoint of rinsing properties, it is preferably at most 80% by weight, more preferably at most 60% by weight, particularly preferably at most 50% by weight.

The detergent composition containing the fine-particle zeolite of the present invention may appropriately contain various additives which are usually contained in detergents for clothes. Their content can be adjusted appropriately as long as the desired effect of the cleaning composition of the present invention is not impaired.

The additive is not particularly limited as long as it is generally used in detergents. For example, commercially available zeolite (having an average primary particle size of 1.
Inorganic chelating agents such as amorphous aluminosilicate, crystalline silicate, amorphous silicate, sodium tripolyphosphate and sodium metasilicate, organic chelating agents such as aminopolyacetate and polyacrylate, carboxyl Anti-resoiling agents such as methylcellulose, water-soluble organic solvents such as polyethylene glycol and glycerin, alkaline agents such as sodium carbonate and potassium carbonate, enzymes such as protease, lipase, cellulase, amylase, sodium percarbonate, sodium perborate, etc. Bleach, bleach activator, sodium salts such as sodium sulfate and sodium chloride, antioxidants, clay minerals, fluorescent dyes, bluing agents,
Fragrance and the like.

The cleaning composition of the present invention can be obtained by mixing and stirring the above-mentioned components according to a known method, and optionally granulating the mixture. Such a composition comprises:
Since it contains the fine particle zeolite of the present invention, it has very excellent detergency. The detergency can be evaluated according to the test examples described below.

[0060]

The physical properties measured in the examples and comparative examples were measured by the following methods. "%" Means "% by weight"
Represents In each table, the units of the cation exchange rate and the cation exchange capacity are simply indicated as “mg / g”. In Examples and Comparative Examples, sodium aluminate was used as an aqueous solution of sodium aluminate unless otherwise specified.

(1) Cation exchange rate A sample was precisely weighed in an amount of 0.04 g in terms of anhydride, and an aqueous solution of calcium chloride in a 100 mL beaker (calcium concentration was Ca
100 ppm in terms of CO ₃ )
After stirring at 1 ° C. for 1 minute, the mixture was filtered through a 0.2 μm membrane filter. Take 10 mL of the filtrate and measure the amount of Ca in the filtrate by EDTA titration.
Ca amount ion-exchanged per g (CaCO ₃ amount conversion)
Was determined as a cation exchange rate (mgCaCO ₃ / g).

(2) Cation exchange capacity A sample was precisely weighed in an amount of 0.04 g in terms of anhydride, and an aqueous solution of calcium chloride in a 100 mL beaker (calcium concentration was Ca
100 ppm in terms of CO ₃ )
After stirring at 10 ° C. for 10 minutes, the mixture was filtered with a 0.2 μm membrane filter. An amount of Ca in the filtrate was measured by EDTA titration by taking 10 mL of the filtrate, and the amount of Ca ion-exchanged per gram of the sample in 10 minutes (in terms of the amount of CaCO ₃ ) was determined as the cation exchange capacity (mg CaCO ₃ / g). .

(3) Average primary particle size Electrolytic emission high-resolution scanning electron microscope (FE-SEM,
Based on a scanning electron micrograph taken by Hitachi S-400, a digitizer (Graftik,
The average primary particle size (μm; average value of 50 or more particles) was measured with a digitizer KW3300).

(4) Average agglomerated particle size Laser diffraction / scattering type particle size distribution device (LA manufactured by Horiba, Ltd.)
Using -700), the particle size distribution after dispersing the sample in ultrasonic waves for 1 minute using ion-exchanged water as a dispersion medium was measured, and the obtained median diameter was defined as the average aggregated particle diameter (μm).

(5) Oil Absorbing Capacity The oil absorbing capacity (mL / 100 g) was determined as the amount of linseed oil to be absorbed based on the method described in JIS K 5101.

(6) Crystal form X-ray diffractometer (Model RAD-20, manufactured by Rigaku Corporation)
0), the X-ray diffraction pattern was measured under the conditions of a light source CuKα ray, a tube voltage of 40 kV, and a tube current of 120 mA, and JC was measured.
PDS (Joint Committee on Pow)
der Diffraction Standard
qualitatively based on the X-ray crystal diffraction pattern presented in s).

Hereinafter, the apparatus for producing zeolite used in the examples will be described based on the outline of the apparatus shown in FIGS. As shown in each figure, the synthesis of the fine particle zeolite was performed using an apparatus having a reaction vessel equipped with a stirrer provided with an external circulation line having a mixer in the middle. The temperature of the raw material tank, the raw material supply line, the circulation line, and the reaction tank in each drawing can be appropriately adjusted, but the description of the apparatus for adjusting the temperature is omitted.

The apparatus shown in FIG. 1 has an 80 L stainless steel reaction tank 3 in which an external circulation line 6 having a mixer 5 is installed, and a liquid feed pump 9 (manufactured by Daido Metal Co., Ltd., WP The liquid can be sent using a pump (WP2SS042C0 type). Immediately before the entrance of the mixer 5 (line mill; LM-S type, manufactured by Tokushu Kika Kogyo Co., Ltd.), the raw materials are supplied from the raw material tank 1 and the raw material tank 2 (both of which are 80 L stainless steel tanks) via raw material supply lines 7 and 8 Can be supplied. Further, the raw materials can be independently supplied from the raw material tank 1 and the raw material tank 2 into the circulation line 6. The reactor 3 has a diameter of 210
A stirrer 4 having a stirring blade having a diameter of 1 mm (in operation, used at a rotation speed of 100 rpm) was installed. The same stirrer as the stirrer was installed in each of the raw material tank 1 and the raw material tank 2, but is not shown in FIG.

In the apparatus shown in FIG. 2, before the raw materials supplied from the raw material tanks 10 and 11 through the raw material supply lines 7 and 8 are supplied into the circulation line 6, the raw material supply lines 7 and 8 are previously prepared. Line mixing can be performed at the confluence of the two, and only one of the raw material tanks can be used. The liquid in the circulation line 6 is supplied by a liquid feed pump 9
(Made by Daido Metal Co., Ltd., WP pump, WP3WL1
(40C0 type). Raw material tank 10 and raw material tank 1
1 is a 200 L stainless steel tank, and the reaction tank 12 has an inner diameter of 750.
A 350 L stainless steel tank and a mixer 14 were a line mixer (2S6 type, manufactured by Tokushu Kika Kogyo Co., Ltd.). A stirrer having a stirring blade having a diameter of 210 mm (the number of rotations is 100 rpm in practice) is provided in the raw material tank 10 and the raw material tank 11.
m) and a stirrer 13 having one pitched paddle and one anchor paddle each having a diameter of 500 mm (in practice, used at a rotation speed of 100 rpm). In FIG. 2, the description of the stirrers for the raw material tanks 10 and 11 is omitted.

The apparatus shown in FIG. 3 has a 200 L stainless steel reaction tank 16 in which an external circulation line 19 having a mixer 18 is installed, and a liquid feed pump 21 (manufactured by Daido Metal Co., Ltd., WP Pump, WP2SS040
(C0 type). Mixer 18 (line mixer;
Raw material tank 1 just before the entrance (2S6 type, manufactured by Tokushu Kika Kogyo Co., Ltd.)
5 (200L stainless steel tank) to raw material supply line 20
The raw material can be supplied via the. Further, a stirrer 17 having a Max Blend type stirring blade having a diameter of 340 mm (in operation, used at a rotation speed of 100 rpm) was installed in the reaction tank 16. The raw material tank 15 has a diameter of 210 mm.
Stirrer with stirring blades
00 rpm), but the description is omitted in FIG.

The apparatus shown in FIG. 4 has a 350 L stainless steel reaction tank 23 provided with an external circulation line 26 having a mixer 25, and a liquid feed pump 28 (manufactured by Daido Metal Co., Ltd., WP Pump, WP3WL140
(C0 type). Raw materials can be supplied from a raw material tank 22 (200 L stainless steel tank) via a raw material supply line 27 immediately before the entrance of the mixer 25 (line mixer; 2S6 type, manufactured by Tokushu Kika Kogyo Co., Ltd.). A stirrer 24 having one pitched paddle and one anchor paddle having a diameter of 500 mm (the number of rotations is
00 rpm). In addition, a stirrer having a stirring blade with a diameter of 210 mm (used at a rotation speed of 100 rpm in the embodiment) was installed in the raw material tank 22, but the description is omitted in FIG.

According to the apparatus shown in FIGS. 1 to 4, the liquid sent from the reaction tank to the circulation line is returned to the reaction tank again. In the apparatus shown in FIG. 3, as can be seen from the figure, the liquid is returned into the reaction tank from the side of the reaction tank, and the liquid diffuses into the liquid existing in the reaction tank. On the other hand, in the other devices shown in FIGS. 1, 2 and 4, the liquid sent from the reaction tank is returned from the upper surface of the reaction tank through the circulation line and diffuses into the liquid existing in the reaction tank. Become.

Example 1 The apparatus shown in FIG. 1 was used. No. 3 water glass (Na ₂ O:
_{9.68%, SiO 2: 29.83%} ) were placed in a raw material tank 1, a 48% aqueous solution of sodium and sodium aluminate hydroxide _{(Na 2 O: 21.01%,} Al 2 O 3: 28.1
8%) in the raw material tank 2, and further, a 35% calcium chloride solution and ion-exchanged water were charged in the reaction tank 3, and the temperature was raised to 50 ° C. while stirring until the mixture became uniform. While the stirrer 4 is operated, the rotation speed of the mixer 5 is set to 1800 rpm while the calcium chloride solution in the reaction tank 3 is previously sent to the circulation line 6 by the liquid sending pump 9, and the raw material tank 1 and the raw material tank 2
(Aqueous glass) and an aluminum source (a sodium aluminate solution comprising a 48% aqueous sodium hydroxide solution and sodium aluminate) were simultaneously fed into the circulation line 6 via the raw material supply lines 7 and 8 for 2.2 minutes. The reaction was carried out. After completion of the reaction, circulation of the slurry was stopped, the temperature was raised to 80 ° C., and aging was performed for 1.5 hours. The pH of the filtrate obtained was 11.4.
The mixture was filtered and washed until it became water. Then, it dried and obtained the zeolite powder. Table 1 shows the charging conditions and reaction conditions, and Table 2 shows the composition and physical properties of the obtained zeolite. In addition,
The molar ratio of Na ₂ O / H ₂ O was 0.04.

Example 2 The apparatus shown in FIG. 2 was used. No. 3 water glass into raw material tank 10
And a 35% calcium chloride solution and ion-exchanged water are placed in the raw material tank 11, a 48% aqueous sodium hydroxide solution and sodium aluminate are placed in the reaction tank 12, and the temperature is raised to 50 ° C. while stirring until uniform. . While the stirrer 13 is moved, the aluminum source (a sodium aluminate solution composed of a 48% aqueous sodium hydroxide solution and sodium aluminate) of the reaction tank 12 is previously fed to the circulation line 6 by the feed pump 9 while the mixer is being used. 14 rpm 3600
The raw material tank 10 and the raw material tank 11 were supplied with the silica source (water glass) and the calcium chloride solution simultaneously via the raw material supply lines 7 and 8 into the circulation line 6 over 4 minutes to carry out the reaction. After completion of the reaction, the temperature was raised to 80 ° C. while circulating the slurry obtained in the circulation line 6 and aging was performed for 1.5 hours while maintaining the temperature at 80 ° C. The pH of the filtrate obtained was 11.4.
The mixture was filtered and washed until it became water. Thereafter, drying was performed to obtain a zeolite powder. Table 1 shows the charging conditions and reaction conditions, and Table 2 shows the composition and physical properties of the obtained zeolite. Note that N
The molar ratio of a ₂ O / H ₂ O was 0.06.

Example 3 The apparatus shown in FIG. 2 was used. A 48% aqueous solution of sodium hydroxide and sodium aluminate are placed in the raw material tank 10, and 35%
% Calcium chloride solution and ion-exchanged water were placed in the raw material tank 11, and No. 3 water glass was placed in the reaction tank 12, and the temperature was raised to 50 ° C. with stirring until they became uniform. While the stirrer 13 is being moved, the silica source (water glass) of the reaction tank 12 is previously sent to the circulation line 6 by the feed pump 9 while the rotation speed of the mixer 14 is set to 3600 rpm, and the raw material tank 10 and the raw material tank 11 are rotated. (A sodium aluminate solution composed of a 48% aqueous sodium hydroxide solution and sodium aluminate) and a calcium chloride solution were simultaneously introduced into a circulation line 6 via raw material supply lines 7 and 8, respectively.
The reaction was carried out by supplying for minutes. After completion of the reaction, the slurry obtained in the circulation line 6 is continuously circulated at 80 ° C.
And aged for 1.5 hours while maintaining the temperature at 80 ° C. The obtained slurry was filtered and washed with water until the pH of the filtrate became 11.4. Thereafter, drying was performed to obtain a zeolite powder. Table 1 shows the charging conditions and reaction conditions, and Table 2 shows the composition and physical properties of the obtained zeolite. In addition, Na ₂ O
The molar ratio of / H ₂ O was 0.06.

Example 4 In Example 3, a zeolite was synthesized without using calcium chloride. Table 2 shows the composition and physical properties of the obtained zeolite.

Example 5 The apparatus shown in FIG. 3 was used. No. 3 water glass into raw material tank 15
And stirred. Next, a calcium chloride solution obtained by previously mixing a 35% calcium chloride solution and ion-exchanged water was added to the raw material tank 15 over 1 minute, and then the temperature was raised to 50 ° C. Next, while moving the stirrer 17, sodium aluminate and a 48% aqueous sodium hydroxide solution were added to the reaction tank 16, and the temperature was raised to 50 ° C. After the temperature is raised, an aluminum source (sodium aluminate and 48%
While circulating a sodium aluminate solution comprising an aqueous sodium hydroxide solution), the rotation speed of the
At 0 rpm, the silica source (water glass solution composed of No. 3 water glass and calcium chloride solution) in the raw material tank 15 was supplied to the circulation line 19 via the raw material supply line 20 over a period of 3.5 minutes to carry out the reaction. . After the completion of the reaction, the slurry obtained at the circulation line 19 is continuously circulated at 80 ° C.
, And aged for 2 hours while maintaining the temperature at 80 ° C.
The obtained slurry was filtered and washed with water until the pH of the filtrate became 11.4. Thereafter, drying was performed to obtain a zeolite powder. Table 1 shows the charging conditions and reaction conditions, and Table 2 shows the composition and physical properties of the obtained zeolite. In addition, Na ₂ O / H ₂
The molar ratio of O was 0.06.

Example 6 The apparatus shown in FIG. 4 was used. No. 3 water glass in raw material tank 22
And stirred. Subsequently, a 48% aqueous sodium hydroxide solution is put into the raw material tank 22, and a calcium chloride solution obtained by previously mixing a 35% calcium chloride solution and ion-exchanged water is added over 1 minute, and the temperature is raised to 50 ° C. did. Next, while moving the stirrer 24, sodium aluminate was charged into the reaction tank 23, and the temperature was raised to 50 ° C. After the temperature is raised, the rotation speed of the mixer 25 is increased to 240 while circulating the aluminum source (sodium aluminate) with the liquid sending pump 28 through the circulation line 26.
0 rpm, and the silica source (3 water glass,
A 48% aqueous sodium hydroxide solution and a calcium chloride solution (a water glass solution) were supplied to the circulation line 26 via the raw material supply line 27 over 8 minutes to carry out the reaction. After the completion of the reaction, the temperature was raised to 80 ° C. while circulating the slurry obtained in the circulation line 26, and aging was performed for 1 hour while maintaining the temperature at 80 ° C. The obtained slurry was filtered and washed with water until the pH of the filtrate reached 11.4. Thereafter, drying was performed to obtain a zeolite powder. Table 1 shows the charging conditions and reaction conditions, and Table 2 shows the composition and physical properties of the obtained zeolite. The molar ratio of Na ₂ O / H ₂ O was 0.06
Met.

COMPARATIVE EXAMPLE 1 In Example 2, the circulation line 6 and the mixer 14 were removed from the reaction tank 12, and the aluminum source and the calcium chloride solution were directly charged into the reaction tank 12, and the zeolite was circulated without being circulated in the circulation line 6. Was synthesized. Table 2 shows the composition and physical properties of the obtained zeolite.

Comparative Example 2 In Example 2, an aluminum source and a calcium chloride solution were directly charged into the reaction tank 12 and zeolites were synthesized while circulating in the circulation line 6. Table 2 shows the composition and physical properties of the obtained zeolite.

[0081]

[Table 1]

[0082]

[Table 2]

In comparison with Comparative Examples 1 and 2, Example 1
From # 6, it can be seen that the method for producing a fine particle zeolite of the present invention can provide an A-type zeolite having a fine average primary particle diameter, excellent oil absorbing ability and cation exchange ability, and a fine average agglomerated particle size. Further, from the comparison between Example 4 and Examples 1 to 3 and 5 to 6, performing the synthesis reaction of zeolite in the presence of the compound containing an alkaline earth metal further improved the cation exchange ability and the oil absorption ability. Examples 5 and 6 show that it is preferable to add a compound containing an alkaline earth metal to the silica source in advance from the viewpoint of miniaturization of the average primary particle diameter.

On the other hand, when the circulation line and the mixer were removed, all the raw materials were put into the reaction tank, and the reaction was performed only in the reaction tank without circulation (Comparative Example 1), the average primary particle diameter became large. The cation exchange capacity decreases, and the average aggregate particle size also increases. Even if all the raw materials are put into the reaction tank and circulated to carry out the reaction, if the raw materials are not supplied into the circulation line (Comparative Example 2), the product is insufficiently disintegrated and The diameter increases and the cation exchange capacity also decreases.
A decrease in the cation exchange capacity is not preferable as a detergent builder.

Test Example A comparison of the effects of the fine-particle zeolite obtained in Example 6 and the zeolite obtained in Comparative Example 1 on the detergency of the detergent composition when they were used was as follows. The method was performed as described in the above section.

Preparation of artificially stained cloth An artificially stained cloth was prepared by adhering an artificially stained liquid having the following composition to the cloth.
did. The adhesion of the artificially contaminated liquid to the cloth is described in JP-A-7-2703.
A gravure roll coater manufactured according to No. 95
This was performed by printing an artificially contaminated liquid on a cloth. Artificial pollution
The process of attaching the dye liquor to the cloth to produce an artificially stained cloth
Via roll cell capacity 58cm^Three/ Cm ^Two, Coating speed
1.0 m / min, drying temperature 100 ° C, drying time 1 minute
went. The cloth used is cotton cloth 2003 (manufactured by Tanito Shoten).
did.

(Composition of artificial contaminant) The composition of the artificial contaminant was 0.44% lauric acid, 3.09% myristic acid,
2.31% pentadecanoic acid, 6.18% palmitic acid,
Heptadecanoic acid 0.44%, stearic acid 1.57%,
Oleic acid 7.75%, trioleic acid 13.06%,
2.18% n-hexadecyl palmitate, 6.53% squalene, egg yolk lecithin liquid crystal (manufactured by Wako Pure Chemical Industries, Ltd.)
94%, 8.11% of Kanuma red clay for horticulture, 0.01% of carbon black (manufactured by Asahi Carbon Co., Ltd.), and the remainder was tap water.

Cleaning Conditions and Evaluation Method (Composition of Detergent Composition) The composition of the detergent composition was 25% fine zeolite of Example 6 or Comparative Example 1, and LAS-
Na [LAS precursor (Neopelex FS, Kao Corporation)
Prepared by mixing a 48% aqueous sodium hydroxide solution as a neutralizing agent], 15% polyoxyethylene alkyl ether [Emulgen 108K
M, number of moles of ethylene oxide (EO) added: 8.5,
8%, sodium carbonate (dense ash, manufactured by Central Glass Co., Ltd.) 15%, sodium sulfate (anhydrous neutral bowl glass, manufactured by Shikoku Chemicals Co., Ltd.) 17%, sodium sulfite (sodium sulfite, Mitsui Toatsu Co., Ltd. 1%, sodium polyacrylate (weight average molecular weight 10,000, Kao Co., Ltd.) 4%, and crystalline silicate (SKS6,
Clariant Tokuyama Co., Ltd.) 15%.

Clothing (underwear and Y-shirt 7: 3 ratio) 2.
2 kg was prepared. Next, the 10 cm × 10
10 cm of artificially stained cloth was sewn on three pieces of cotton cloth of 35 cm × 30 cm (hereinafter referred to as “contaminated cloth”). Matsushita Electric Industrial washing machine "Aizumago (registered trademark) N
A-F70AP "was uniformly charged with clothing and a contaminated bed cloth, and 20 g of the above detergent composition was added to a washing machine for washing. The washing conditions are as follows. Cleaning course: standard course, detergent composition concentration 0.067
%, Water hardness 4 ° DH, water temperature 10 ° C, bath ratio 20L / k
g.

The detergency was measured by measuring the reflectance at 550 nm of the original cloth before and after the cleaning and the artificially contaminated cloth before and after the cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation). (%) = (Reflectance after cleaning-reflectance before cleaning) /
(Reflectance of original cloth−Reflectance before washing) × 100 The average value of the measured values of 10 sheets was obtained and evaluated based on the washing rate.

As a result, the cleaning rate of the cleaning composition containing the fine particle zeolite of Example 6 was 48%. On the other hand, the cleaning rate of the cleaning composition containing zeolite of Comparative Example 1 was as low as 27%, and it was revealed that the cleaning composition containing fine zeolite of Example 6 was superior in cleaning power. . From these results, it can be seen that the fine particle zeolite obtained by the method for producing fine particle zeolite of the present invention, when used in a detergent composition, significantly improves the detergency of the composition.

[0092]

EFFECT OF THE INVENTION According to the method for producing fine zeolite of the present invention, a crystalline aluminosilicate having a fine average primary particle diameter, excellent oil absorption ability and cation exchange ability, and a fine average aggregate particle diameter and excellent dispersibility is obtained. A fine particle zeolite can be obtained efficiently. In addition, a detergent composition containing such fine-particle zeolite and having excellent detergency can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one example of an apparatus for producing fine-particle zeolite according to the present invention.

FIG. 2 is a schematic view showing one example of an apparatus for producing fine particle zeolite according to the present invention.

FIG. 3 is a schematic view showing one example of an apparatus for producing fine-particle zeolite according to the present invention.

FIG. 4 is a schematic view showing one example of an apparatus for producing fine particle zeolite according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 raw material tank 2 raw material tank 3 reaction tank 4 stirrer 5 mixer 6 circulation line 7 raw material supply line 8 raw material supply line 9 liquid feed pump 10 raw material tank 11 raw material tank 12 reaction tank 13 stirrer 14 mixer 15 raw material tank 16 reaction tank 17 Stirrer 18 Mixer 19 Circulation line 20 Raw material supply line 21 Liquid feed pump 22 Raw material tank 23 Reaction tank 24 Stirrer 25 Mixer 26 Circulation line 27 Raw material supply line 28 Liquid feed pump

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Jin Takatani 1334 Minato, Wakayama, Kao Corporation Research Institute (72) Inventor Kazuo Oki 1334 Minato, Wakayama City Kao Corporation Research Institute F Term (reference) 4G073 BA57 BA63 BD21 FA07 FA20 FB01 FB02 FB04 FC05 FC13 FD02 FD23 GA21 GA37 UA07 4H003 AB19 AC08 DA01 EA12 EA16 EA24 EA28 EB30 FA04

Claims (10)

[Claims] 1. A method for producing a fine particle zeolite in which an aluminum source and / or a silica source is supplied into a circulation line of a reaction vessel having a circulation line to carry out a reaction. 2. The method according to claim 1, wherein the supply of the aluminum source and / or the silica source is carried out through a circulation line connecting an outlet of the reaction vessel and an inlet of the mixer. 3. The method according to claim 1, wherein an aluminum source is charged into the reaction tank and circulated in a circulation line, and a silica source is supplied into the circulation line. 4. The production method according to claim 1, wherein a silica source is charged into the reaction tank and circulated in a circulation line, and an aluminum source is supplied into the circulation line. 5. An aluminum source and a silica source in a circulation line.
Is SiO 2 _Two/ Al_TwoO_Three0.1 to molar ratio of
The mixture according to any one of claims 1 to 4, wherein the mixture is mixed so as to be 3.
Production method. 6. The method for producing a fine particle zeolite according to claim 1, wherein the reaction is performed in the presence of a compound containing an alkaline earth metal. 7. An alkaline earth metal is Ca and / or Mg, and a compound containing an alkaline earth metal is Me
O / Al ₂ O ₃ (Me is Ca and / or Mg) method for producing a particulate zeolite according to claim 6, wherein the molar ratio used an amount containing 0.005 to 0.1 of. 8. A fine-particle zeolite obtainable by the method for producing a fine-particle zeolite according to claim 1. 9. When the average primary particle diameter is X μm and the average aggregate particle diameter is Y μm, 0.6 ≦ X ≦ 1.5, 20X / 3−
2.4.ltoreq.Y.ltoreq.15, provided that X.ltoreq.Y. 10. A cleaning composition comprising the fine particle zeolite according to claim 8 or 9.