JP3774663B2 - Fine particle zeolite - Google Patents

Description

【００８０】
【表２】

【００８１】
実施例１〜３より、本発明の微粒子ゼオライトの製造方法に従い結晶成長抑制化合物の存在下にゼオライトの合成反応を行うことで、平均一次粒子径が０．１μｍ以下の微粒子Ａ型ゼオライトが得られることが分かる。比較例４では、酸素原子を含む官能基を持つ有機化合物であるプロピレングリコールの存在下にゼオライトの合成反応を行っているが、該化合物の分子量は７６であり、平均一次粒子径が０．１μｍ以下の微粒子ゼオライトは得られていない。
【００８２】
また、適宜粉砕を行うことで実施例および比較例のゼオライトの平均凝集粒径は０．４μｍ以下となし得るが、粉砕前の平均一次粒子径が０．１μｍを超える比較例１、３および４のゼオライトでは、粉砕後に結晶性劣化が進行しており、また、平均一次粒子径分布の悪化も見られ、溶出Ａｌ量が増加し、かかるゼオライトを用いて得た洗浄剤組成物の洗浄率および／またはすすぎ性は低下することが分かる。一方、実施例１〜３では、粉砕を行っても結晶性劣化の進行は抑えられており（たとえば、結晶性劣化率）、平均一次粒子径分布等の実質的な変化は生じておらず、所望の平均凝集粒径を有する、カチオン交換能に優れた微粒子ゼオライトが得られており、該ゼオライトを用いて得た洗浄剤組成物の洗浄率およびすすぎ性は高いことが分かる。
【００８３】
【発明の効果】
本発明によれば、平均一次粒子径が０．１μｍ以下である、カチオン交換能に優れ、水性液において水中に溶出されるＡｌ量が少なく、しかも該水性液の水の濁りが少ない微粒子ゼオライトが得られる。また、該微粒子ゼオライトを含んでなる、洗浄性およびすすぎ性に非常に優れた洗浄剤組成物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fine particle zeolite, a method for producing the same, and a cleaning composition containing the fine particle zeolite.
[0002]
[Prior art]
Zeolite is a crystalline aluminosilicate, SiO_FourTetrahedra and AlO_FourDepending on the arrangement of tetrahedrons, it can be classified into various crystal structures such as A, X, and Y types. Zeolite has a uniform pore size depending on the crystal structure and expresses the function of a molecular sieve, so it is used for adsorbents and catalysts (supports). Further, since zeolite has a cation exchange ability, it is used as a builder for detergents or a wastewater treatment agent.
[0003]
The function of these zeolites is largely governed by the crystal structure and composition of the zeolite. For example, the cation exchange capacity increases as the Si / Al molar ratio of the zeolite decreases, and it can be said that the A-type zeolite having Si / Al = 1 is the most excellent theoretically. Therefore, type A zeolite having a high theoretical capacity for cation exchange is mainly used as a builder for detergents.
[0004]
Furthermore, as a builder for detergents, in particular, a zeolite having not only a calcium ion exchange capacity but also an excellent calcium ion exchange rate is required. This is because the cleaning performance is improved especially when a large amount of calcium ions in water at the initial stage of cleaning can be captured. Since the calcium ion exchange rate of zeolite is determined by the collision probability between the calcium exchange site of zeolite and calcium ion in water, it becomes higher as the primary particle diameter of zeolite is smaller.
[0005]
From this point of view, attempts have been made to produce fine A-type zeolite having a primary particle size. For example, Japanese Patent Application Laid-Open No. 54-81200 discloses that fine-particle A-type zeolite is produced by carrying out a reaction in the presence of an organic acid such as formic acid or acetic acid in a reaction mixture. However, in this production method, the primary particle size is at most 0.5 μm. On the other hand, Japanese Patent Application Laid-Open No. 1-153514 discloses a method for producing a fine particle A-type zeolite having a maximum particle size of 0.4 μm or less by generating zeolite nuclei at a temperature of 40 ° C. or less. However, the primary particle size of the A-type zeolite produced in this production method is limited to 0.2 μm.
[0006]
On the other hand, the biggest drawback of the zeolite builder is the turbidity of washing water due to the water insolubility of the zeolite. On the other hand, attempts have been made to reduce the turbidity of zeolite by reducing the agglomerated particle size of zeolite to a wavelength of visible light (0.4 μm) or less (Okumura, Clay Science, 27, 21 (1987)). . That is, the turbidity of washing water is reduced as the aggregated particle size becomes smaller, and when the aggregated particle size becomes 0.4 μm or less, the washing water (zeolite concentration: 0.013% by weight) becomes almost transparent. However, the A-type zeolite with a reduced aggregate particle size down to the submicron size as described above can be re-agglomerated to form a large aggregate when powdered, or it can be separated into solid and liquid by filtration and concentration. Since it is very difficult, it is actually blended into the detergent raw material in a slurry state. At this time, the presence of Al ions (unreacted zeolite raw material or zeolite eluate) in the slurry causes a reduction in cleaning performance, so the Al ion concentration in the slurry must be kept low.
[0007]
In general, the agglomerated particle size of the A-type zeolite is reduced by a technique such as strong stirring or pulverization. For example, as disclosed in JP-A-9-67117, the aggregate particle size and the primary particle size are reduced to a submicron size by mechanical grinding. However, when pulverizing A-type zeolite with a large primary particle size, the cation exchange capacity (cation exchange capacity and cation exchange rate) is reduced due to the deterioration of crystallinity and primary particle size distribution accompanying the collapse of the primary crystals of A-type zeolite. It will decline. Also, due to the mechanochemical reaction on the surface of the zeolite particles, the zeolite constituent elements (Al, Si, Na) ions easily elute into the water (especially Al) in the aqueous zeolite solution after pulverization. When used in a cleaning composition, there also arises a problem that the cleaning performance of the composition is lowered.
[0008]
In order to suppress the occurrence of such problems associated with the micronization step of the aggregated particle size, it is necessary to avoid the collapse of the zeolite primary crystals due to the micronization step. For this purpose, it is desirable that the primary particle size of the A-type zeolite before pulverization is equal to or less than the aggregate particle size after pulverization. Specifically, normally, when the average agglomerated particle size is reduced to 0.4 μm or less, the average primary particle size shows 0.1 μm or less, thereby suppressing the occurrence of the above problem and washing water. In order to pulverize the A-type zeolite until the average agglomerated particle size (0.4 μm or less) becomes substantially transparent (zeolite concentration: 0.013% by weight), the average primary of the A-type zeolite before pulverization It is considered that the particle diameter is desirably 0.1 μm or less. Further, it is considered that a zeolite having such an average primary particle size can exhibit a desired average aggregate particle size without undergoing a pulverization treatment. However, as described above, there has been no example of synthesizing fine particle A-type zeolite having an average primary particle size of 0.1 μm or less without performing pulverization after the synthesis reaction of zeolite.
[0009]
[Problems to be solved by the invention]
The present invention has an average primary particle size of 0.1 μm or less (coefficient of variation of 90% or less), excellent cation exchange capacity, a small amount of Al eluted in water in an aqueous liquid, and turbidity of water in the aqueous liquid A fine particle A-type zeolite with a small amount of particles, a method for producing the fine particle A-type zeolite, and a cleaning composition containing the fine particle A-type zeolite (hereinafter referred to as a fine particle zeolite) and having excellent cleaning properties and rinsing properties. With the goal.
[0010]
[Means for Solving the Problems]
  The gist of the present invention is as follows.
(1) Average primary particle size is0.08Fine particle type A that is μm or less (coefficient of variation of 90% or less), and the ratio of the peak area above the background to the total peak area in the range of 2θ = 20 to 40 ° of the powder X-ray diffraction spectrum is 30% or more Zeolite,
(2) In producing zeolite by reacting a silica source and an aluminum source,Preparation composition of compound containing alkali metal and water in reaction system (M ₂ O / H ₂ O: M represents an alkali metal) in a molar ratio of 0.02 to 0.2, andThe method for producing a fine particle A-type zeolite according to (1), wherein the reaction is performed in the presence of an organic compound having a functional group containing an oxygen atom and having a molecular weight of 100 or more, and
(3) A detergent composition comprising the surfactant and the fine particle zeolite described in (1) above.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The fine particle zeolite of the present invention can be obtained by reacting a silica source and an aluminum source in the presence of an organic compound having a functional group containing an oxygen atom and having a molecular weight of 100 or more. By carrying out the zeolite synthesis reaction in this way, it is possible to suppress the crystal growth of the zeolite and to produce a fine particle A-type zeolite having an average primary particle size of 0.1 μm or less. The fine particle zeolite thus obtained was further miniaturized by mechanical grinding or the like as required until the washing water (zeolite concentration: 0.013% by weight) had an average aggregate particle size (0.4 μm or less) that became substantially transparent. Even so, crystallinity deterioration, deterioration of the average primary particle size distribution and elution of Al (Al ions) can be suppressed.
[0012]
That is, the fine particle zeolite of the present invention is an A-type zeolite having an average primary particle size of 0.1 μm or less (coefficient of variation of 90% or less), the zeolite is excellent in cation exchange capacity, and in the aqueous solution of the zeolite, Al ions from zeolite are not substantially eluted into water, and the aqueous liquid is less turbid.
[0013]
In the present specification, the “aqueous liquid” refers to a liquid containing a certain component using water as a medium, such as an aqueous solution, a suspension, or a dispersion.
[0014]
The average primary particle diameter of the fine particle zeolite of the present invention is 0.1 μm or less, preferably 0.08 μm or less, more preferably 0.05 μm or less. As described above, when the average agglomerated particle size is reduced by pulverization from the viewpoint of improving the turbidity of washing water, various problems such as crystallinity deterioration of zeolite occur. The degree of occurrence of such problems depends on the average primary particle size of the zeolite before pulverization, and the larger the average primary particle size, the more serious the problem. In general, in an A-type zeolite having an average primary particle size larger than 0.1 μm, the primary crystal itself is collapsed by pulverization, and a large amount of ions of constituent elements are eluted as described above, and the crystallinity is severely deteriorated. Since the average primary particle diameter of the fine particle zeolite of the present invention is within the above range, the occurrence of such a problem associated with pulverization is substantially completely suppressed. The average primary particle size can be determined by the method described in Examples described later.
[0015]
The particle size distribution of zeolite having an average primary particle size in the above range can be evaluated by a coefficient of variation. Such a coefficient of variation can be obtained by a method described in Examples described later. The uniformity of the particle size distribution of the fine particle zeolite of the present invention is high, and the variation coefficient of the average primary particle size is 90% or less, preferably 70% or less, more preferably 50% or less, and further preferably 35% or less. That is, the fine particle zeolite of the present invention comprises a zeolite having a uniform average particle size distribution having a desired average primary particle size of 0.1 μm or less, which contributes to the development of excellent cation exchange ability. In the case of A-type zeolite having a large average primary particle size of 1 μm or more, the state of collapse of the primary crystal accompanying the pulverization can be grasped by a scanning electron microscope. On the other hand, in the fine particle zeolite of the present invention, the collapse of primary crystals accompanying pulverization is substantially completely suppressed, and in the pulverization, aggregates of primary particles are simply deagglomerated. Therefore, the variation of the coefficient of variation due to pulverization does not substantially occur.
[0016]
The fine particle zeolite of the present invention is an A-type zeolite, and can exhibit a powder X-ray diffraction pattern substantially the same as a known A-type zeolite (Joint Committee on Powder Diffraction Standards No. 38-241). In addition, it should just be substantially the same, and the peak of a crystalline substance and the halo peak attributed to an amorphous substance may be contained. In addition, the powder X-ray diffraction peak intensity (I) assigned to the (410) plane of a commercially available A-type zeolite having an average primary particle diameter of 1 μm or more (for example, Toyo Builder, manufactured by Tosoh Corp.)₄₁₀I) of the fine particle zeolite of the present invention₄₁₀The ratio (powder X-ray diffraction intensity ratio) is preferably 10% or more, more preferably 20% or more, from the viewpoint of improving the cation exchange capacity.
[0017]
The crystallinity of the fine particle zeolite of the present invention is determined by the ratio of the peak area above the background to the total peak area in the range of 2θ = 20 to 40 ° (A_r). A_rSpecifically, the calculation of can be performed by the method shown in the examples described later. The fine particle zeolite of the present invention is A_rIs 30% or more, preferably 33% or more. Within such a range, the ratio of the amorphous portion in the primary crystal structure is small, and an excellent cation exchange ability can be exhibited, and the deterioration of the cleaning performance due to elution of Al ions can be suppressed.
[0018]
On the other hand, A_rShows the crystallinity of zeolite, A_rAnd the degree of crystallinity deterioration accompanying pulverization can be expressed and evaluated as a crystallinity deterioration rate. Such a crystallinity deterioration rate can be determined by the method described in Examples described later. In the fine particle zeolite of the present invention, the crystallinity deterioration rate is preferably 50% or less, more preferably 40%, from the viewpoint of maintaining the primary crystallinity, and further reducing the cation exchange capacity and suppressing the elution of Al ions. Hereinafter, it is more preferably 35% or less.
[0019]
The average agglomerated particle size of the fine particle zeolite of the present invention is preferably 0.4 μm or less, more preferably 0.3 μm or less. The average agglomerated particle size can be determined by the method described in the examples below. The degree of turbidity due to the fine particle zeolite of the present invention can be determined as turbidity by the method described in the examples below. However, if the average agglomerated particle size is within the above range, the turbidity is preferably 30% or less, more preferably May be 20% or less. If the average agglomerated particle size and turbidity are within the above ranges, when the zeolite is used in a detergent composition such as a powder detergent for clothing or a liquid detergent for clothing, washing water or initial rinsing water is used. This is preferable because the turbidity is significantly improved and becomes substantially transparent, and there is no problem of zeolite remaining on the fiber surface and falling off.
[0020]
If the average agglomerated particle size of the fine particle zeolite as the primary product obtained by the method for producing the fine particle zeolite of the present invention described later does not become 0.4 μm or less, it may be further pulverized as described later if desired. As described above, the fine particle zeolite of the present invention has an average primary particle size of 0.1 μm or less, so even if the average agglomerated particle size is appropriately reduced to 0.4 μm or less, the primary crystallinity is hardly lowered. Therefore, there is substantially no problem of a decrease in cation exchange capacity or a large amount of Al elution. In the present invention, when the fine particle zeolite of the present invention is used as a detergent builder, it is preferable to appropriately pulverize the fine particle zeolite obtained as a primary product from the viewpoint of further improving the transparency of washing water.
[0021]
In addition, the ratio of the amount of Al eluted in water in the aqueous solution of the fine particle zeolite of the present invention is preferably less than 4% by weight, more preferably 3.5% by weight or less of the total amount of Al contained in the fine particle zeolite, Preferably it is 3.2 weight% or less. If the ratio of the amount of Al to be eluted is within the above range, for example, when the fine particle zeolite is blended in a cleaning composition, the quality (cleaning performance, storage stability, etc.) of the cleaning composition is deteriorated. Suppressed and preferred. Further, even if the average agglomerated particle size is appropriately pulverized so as to be within a desired range, the primary crystallinity is hardly lowered and the Al elution amount is also small. In addition, the ratio of the amount of eluted Al can be calculated | required by the method as described in the below-mentioned Example.
[0022]
The fine particle zeolite of the present invention is excellent in cation exchange ability. Here, cation exchange capacity refers to both cation exchange rate and cation exchange capacity, more specifically, cation exchange rate refers to the amount of Ca ion exchanged per gram of zeolite in 1 minute, while cation exchange. The capacity refers to the amount of Ca ion exchanged per gram of zeolite in 10 minutes. They are determined by the method described in the examples described later.
[0023]
The cation exchange rate (CER) is preferably 180 mg CaCO._Three/ G or more, more preferably 200 mg CaCO_Three/ G or more, more preferably 220 mg CaCO_Three/ G or more. On the other hand, the cation exchange capacity (CEC) is preferably 200 mg CaCO._Three/ G or more, more preferably 210 mg CaCO_Three/ G or more, more preferably 220 mg CaCO_Three/ G or more. If the cation exchange capacity of the fine particle zeolite of the present invention is within such a range, it is preferable to use the zeolite in a cleaning composition because the cleaning performance of the composition is remarkably improved. Even if the average agglomerated particle size is appropriately pulverized so as to be within the desired range, there is little deterioration in crystallinity and particle size distribution, and therefore no substantial change in cation exchange capacity occurs.
[0024]
The composition of the fine particle zeolite of the present invention is represented by the general formula xM₂O · ySiO₂・ Al₂O_ThreeWhen represented by zMeO (where M is an alkali metal atom and Me is an alkaline earth metal atom), x = 0.2 to 4, y = 0.5 to 6, and z = 0 to 0.2 are preferable. More preferably, x = 0.8 to 2, y = 1 to 3, and z = 0.001 to 0.1. In addition, elements other than those listed in the above composition formula may be included as long as the cation exchange capacity is not lowered. The alkali metal atom belongs to group IA of the periodic table and is not particularly limited, but sodium is particularly preferable. The fine particle zeolite of the present invention may contain two or more of such alkali metal atoms. The alkaline earth metal atom belongs to group IIA of the periodic table and is not particularly limited, but calcium or magnesium is particularly preferable. Two or more of these alkaline earth metal atoms may also be contained.
[0025]
Next, a method for producing the fine particle zeolite of the present invention will be described. The production method involves reacting a silica source and an aluminum source in the presence of an organic compound having a functional group containing an oxygen atom and having a molecular weight of 100 or more (hereinafter referred to as a crystal growth inhibiting compound). One major feature is to do. By carrying out the reaction in the presence of such a crystal growth inhibiting compound, the fluidity of the reaction mixture (slurry) composed of the silica source and the aluminum source is increased, the reaction efficiency is improved, and the crystal growth of the zeolite is suppressed and the average primary is suppressed. A zeolite having a small particle size and a uniform particle size distribution is produced.
[0026]
Regarding the mechanism of zeolite crystal growth inhibition by coexistence of the above-mentioned crystal growth inhibiting compound, silanol (Si-OH) groups on the surface of the zeolite core interact with oxygen atoms of the functional group in a hydrogen bond, and the surface of the zeolite nucleus is stable. As a result, the crystal growth (Ostwald growth) is suppressed, and the steric hindrance of the crystal growth inhibiting compound adsorbed (interacted) on the zeolite nuclei causes steric repulsion between the zeolitic nuclei. Since crystal growth due to collision is hindered, it is considered that fine zeolite with a small average primary particle size is generated.
[0027]
The silica source and the aluminum source used in the method for producing the fine particle zeolite of the present invention are not particularly limited. For example, commercially available water glass can be used as the silica source, and quartzite, quartz sand, cristobalite stone can be used. , Kaolin, cullet, or the like may be used, and these may be appropriately diluted with water or an aqueous alkali metal hydroxide solution. The aluminum source may be an aluminum-containing compound such as aluminum hydroxide, aluminum sulfate, or aluminum chloride, but an alkali metal aluminate, particularly sodium aluminate powder or an aqueous liquid is preferably used. Commercially available products may be used, and an aqueous solution obtained by heating and dissolving aluminum hydroxide and alkali metal hydroxide in water may be used as the aqueous sodium aluminate solution.
[0028]
The molecular weight of the crystal growth inhibiting compound is 100 or more, preferably 200 or more, more preferably 400 or more. If the molecular weight of the crystal growth inhibiting compound is less than 100, the steric hindrance of the crystal growth inhibiting compound adsorbed (interacted) on the surface of the zeolite core is small, and the progress of crystal growth due to collision between the zeolite nuclei cannot be effectively suppressed, A desired crystal growth suppressing effect cannot be obtained. Further, the molecular weight of the crystal growth inhibiting compound is preferably 60,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less. If the molecular weight is within such a range, the crystal growth inhibiting compound is sufficiently dissolved in the reaction solution composed of the silica source and the aluminum source, and the amount adsorbed on the zeolite nucleus (the crystal growth inhibiting compound interacting with the zeolite nucleus) Amount) is increased, and the crystal growth suppressing effect is sufficiently exhibited. That is, the molecular weight of the crystal growth inhibiting compound is preferably from 100 to 60,000, more preferably from 200 to 30,000, and still more preferably from 400 to 10,000. The molecular weight is determined by functional group quantitative analysis such as analysis of hydroxyl value, acid value, etc. when the crystal growth inhibiting compound has a hydroxyl group, a carboxylic acid group or the like at one or both ends of the compound. You can ask for it. For example, in the case of a polymer compound having a molecular weight of 1000 or more, the molecular weight is a weight average molecular weight and can be measured by GPC (gel permeation chromatography) according to a known method.
[0029]
The functional group of the crystal growth inhibiting compound is not particularly limited as long as it contains an oxygen atom. For example, it is preferably an OR group, COOR group, SO_ThreeR group, PO_FourR group, CO group, CONH group, etc. are mentioned. Among these, an OR group and / or a COOR group is more preferable. R is at least one selected from a saturated or unsaturated organic group having 1 to 22 carbon atoms, a hydrogen atom, and an alkali metal atom. Examples of the saturated or unsaturated organic group having 1 to 22 carbon atoms include an ethyl group, a vinyl group, a phenyl group, a hexyl group, and a dodecyl group. Examples of the alkali metal atom include sodium and potassium. Can be mentioned. These functional groups may constitute a main chain or may constitute a side chain. The number of functional groups per molecule of the crystal growth inhibiting compound is not particularly limited, but the number of functional groups per molecule is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. If the number of functional groups per molecule is within such a range, the number of interaction points between the zeolite nucleus and the crystal growth inhibiting compound is sufficient, and the crystal growth inhibiting effect of zeolite is high, which is preferable. The number of functional groups per molecule of the crystal growth inhibiting compound is preferably 1000 or less, more preferably 500 or less, and even more preferably 200 or less. If the number of functional groups per molecule of the crystal growth inhibiting compound is within such a range, the molecular weight of the crystal growth inhibiting compound is appropriate, and it can be sufficiently dissolved in the reaction solution to exhibit a good crystal growth inhibiting effect. Therefore, it is preferable.
[0030]
Specific examples of the crystal growth inhibiting compound include nonionic surfactants such as polyoxyethylene lauryl ether and water-soluble polymers such as polyethylene glycol, polyvinyl alcohol, acrylic acid polymers, carboxymethyl cellulose, and hexametaphosphoric acid. However, it is not limited to these. The crystal growth inhibiting compounds may be used alone or as a mixture of two or more.
[0031]
As the preparation composition for producing the fine particle zeolite of the present invention, SiO₂/ Al₂O_Three The molar ratio is preferably 0.5 or more, more preferably 1 or more, and further preferably 1.5 or more. SiO₂/ Al₂O_Three If the molar ratio is within such a range, the crystal structure of the zeolite is stabilized, the decrease in crystallinity is suppressed, and the progress of crystallization is promoted. In addition, SiO₂/ Al₂O_Three Is preferably 4 or less, more preferably 3 or less, and even more preferably 2.5 or less. SiO₂/ Al₂O_Three If the molar ratio is within such a range, the reaction proceeds satisfactorily and a sufficient cation exchange capacity is obtained, which is preferable. Moreover, as preparation composition of the compound containing an alkali metal, an alkali metal (M) is represented by an oxide, M₂O / Al₂O_Three Is preferably 0.08 or more, more preferably 0.8 or more, and further preferably 1.4 or more. M₂O / Al₂O_Three If the molar ratio is within such a range, the progress of crystallization is favorable. M₂O / Al₂O_Three The molar ratio is preferably 20 or less, more preferably 5 or less, and still more preferably 3 or less. M₂O / Al₂O_Three If the molar ratio is within such a range, productivity is good and preferable. Furthermore, as the charged composition of the compound containing alkali metal and water in the reaction system, M₂O / H₂The molar ratio of O is preferably 0.02 or more, more preferably 0.05 or more, and further preferably 0.07 or more. M₂O / H₂If the molar ratio of O is within such a range, it is preferable because the average primary particle diameter of the fine-particle zeolite produced with an appropriate crystallization rate is favorably improved. M₂O / H₂The molar ratio of O is preferably 0.2 or less, more preferably 0.15 or less, and even more preferably 0.1 or less. M₂O / H₂If the molar ratio of O is within such a range, it is preferable because the reaction proceeds appropriately and sufficient cation exchange ability is obtained. Moreover, as preparation composition of the compound containing an alkaline-earth metal, an alkaline-earth metal (Me) is represented by an oxide, and MeO / Al₂O_Three The molar ratio is preferably 0 to 0.1, preferably 0.005 or more, and more preferably 0.01 or more from the viewpoint of the effect of reducing the average primary particle size and improving the thermal stability. Further, from the viewpoint of improving the cation exchange capacity, 0.1 or less is preferable, 0.08 or less is more preferable, and 0.05 or less is more preferable. In addition, the charge composition of aluminum in the reaction system is Al₂O_Three / H₂The molar ratio of O is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more. Al₂O_Three / H₂When the molar ratio of O is within such a range, productivity is good, and miniaturization of the average primary particle diameter is promoted, which is preferable. Al₂O_Three / H₂The molar ratio of O is preferably 0.25 or less, more preferably 0.2 or less, and even more preferably 0.1 or less. Al₂O_Three / H₂If the molar ratio of O is within such a range, it is preferable because the fluidity of the slurry is well expressed and the reaction proceeds efficiently. Further, the weight of each raw material used in the present invention constituting the fine particle zeolite converted to oxides was regarded as the solid content, and the solid content in the entire hydrous slurry was defined as the solid content concentration during the reaction. In this case, the solid content concentration is preferably 10% by weight or more, more preferably 20% by weight or more, and further preferably 30% by weight or more from the viewpoint of productivity. Moreover, from a viewpoint of the fluidity | liquidity of a slurry, 70 weight% or less is preferable, 60 weight% or less is more preferable, and 50 weight% or less is further more preferable.
[0032]
On the other hand, the amount of the crystal growth inhibiting compound charged is preferably 1% by weight or more in the reaction solution composed of the silica source and the aluminum source, from the viewpoint of expressing the crystal growth inhibiting effect, and preferably 5% by weight or more. The amount is more preferably 10% by weight or more. From the viewpoint of productivity, an amount of 80% by weight or less is preferable, an amount of 60% by weight or less is more preferable, and an amount of 50% by weight or less is more preferable.
[0033]
The fine particle zeolite of the present invention is produced, for example, by taking a silica source, an aluminum source, and a crystal growth inhibiting compound in separate containers, and then mixing and reacting them appropriately according to a known method. In that case, you may add another component in the range which does not prevent manufacture of the fine-particle zeolite of this invention if desired. Examples of such components include calcium chloride and magnesium chloride. In addition, from the viewpoint of performing the reaction uniformly and efficiently, it is preferable that the silica source, the aluminum source, and the crystal growth inhibiting compound are each subjected to the reaction as an aqueous liquid thereof.
[0034]
The order of mixing the silica source, the aluminum source, and the crystal growth inhibiting compound is not particularly limited, and the silica source may be mixed in a mixed solution of the aluminum source and the crystal growth inhibiting compound, while the silica source and the crystal are mixed. You may mix an aluminum source with the liquid mixture with a growth inhibitory compound. Further, a silica source and an aluminum source may be simultaneously supplied to and mixed with the crystal growth inhibiting compound, and the crystal growth inhibiting compound is previously mixed with the silica source and / or the aluminum source, and then the silica source and the aluminum source are mixed. The source may be mixed.
[0035]
The mixing method is not particularly limited. For example, the silica source, the aluminum source, and the crystal growth inhibiting compound may be mixed in the specific circulation line while being circulated in the specific circulation line. You may mix (batch type mixing) in a tank. The reaction time is not particularly limited by the reaction temperature, but from the viewpoint of the uniformity of the reaction, it is preferably 30 seconds or longer after the addition of all charged components, more preferably 1 minute or more, and further preferably 5 minutes or more. preferable. Moreover, 120 minutes or less are preferable from a viewpoint of productivity, 60 minutes or less are more preferable, and 30 minutes or less are further more preferable.
[0036]
The reaction temperature is preferably 10 ° C or higher, more preferably 20 ° C or higher, and further preferably 40 ° C or higher. Within such a range, the fluidity of the reaction solution is good, and a uniform reaction can be performed, which is preferable. The reaction temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower. Within such a range, the energy load is suitable and the industrial economy is excellent, which is preferable.
[0037]
Crystallization can be carried out after the reaction by aging the reaction mixture at a temperature above the reaction temperature under stirring. The aging temperature is not particularly limited, but is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher from the viewpoint of crystallization speed. Moreover, 120 degrees C or less is preferable from a viewpoint of an energy load or the pressure | voltage resistance of a reaction container, 100 degrees C or less is more preferable, and 90 degrees C or less is further more preferable. The aging time varies depending on the aging temperature, but is preferably 1 minute or longer, more preferably 10 minutes or longer, and further preferably 30 minutes or longer from the viewpoint of obtaining sufficient crystallization. In addition, from the viewpoint of reduction in cation exchange ability due to sodalite by-product and productivity, it is preferably 300 minutes or less, more preferably 180 minutes or less, and even more preferably 120 minutes or less.
[0038]
After completion of the aging, the slurry is cooled, diluted or filtered and washed or neutralized by adding an acid agent to finish crystallization. In the case of washing by filtration, the washing is preferably carried out until the pH of the washing solution is preferably 12 or less. In the case of neutralization, the acid agent used for neutralization is not particularly limited, and sulfuric acid, hydrochloric acid, nitric acid, carbon dioxide, oxalic acid, citric acid, tartaric acid, fumaric acid, succinic acid, and the like can be used. However, sulfuric acid and carbon dioxide are preferable from the viewpoint of preventing corrosion of the apparatus and cost. The slurry pH is preferably adjusted to 8-12. After the completion of crystallization, a slurry fine particle zeolite of the present invention is obtained. Further, this slurry may be appropriately filtered or centrifuged to separate the zeolite precipitate, washed and dried to obtain a cake or powder.
[0039]
Next, the fine-particle zeolite obtained as the primary product may be pulverized, if desired, from the viewpoint of adjusting so as to exhibit a desired average agglomerated particle size. Such pulverization may be performed by directly wet pulverizing the fine particle zeolite slurry, or may be performed by redispersing the obtained fine particle zeolite in a solvent and then wet pulverizing, or in a powder form. The fine particle zeolite may be dry pulverized. Each pulverization method may be a known method.
[0040]
For example, when the fine particle zeolite of the present invention is blended with the cleaning composition of the present invention described later, the zeolite may be blended in a slurry state, and in such a case, wet grinding is performed from the viewpoint of simplifying the production process. It is preferred to do so. The pulverization method at that time is not particularly limited, and for example, a pulverizer described in Chemical Engineering Handbook (Maruzen, 1988), 5th edition, pages 826-838 may be used. In addition to water, examples of the dispersion medium used for wet pulverization include alcohol solvents such as ethanol, surfactants such as polyoxyethylene alkyl ether, and polymer dispersants. The said dispersing agent can be used individually or as a 2 or more types of liquid mixture. When wet pulverization is performed, the zeolite concentration in the slurry is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more from the viewpoint of productivity. In addition, the zeolite concentration in the slurry is preferably 60% by weight or less, more preferably 55% by weight or less, and more preferably 50% by weight from the viewpoint of handling properties of the zeolite slurry during wet pulverization and prevention of reaggregation of finely divided zeolite after pulverization. The following is more preferable.
[0041]
The fine particle zeolite of the present invention is suitably used for, for example, detergent builders, water treatment agents, paper making fillers, resin fillers, oxygen-nitrogen separating agents, adsorbents, catalyst carriers, horticultural soil improvers, abrasives, and the like. However, it is particularly preferably used as a detergent builder.
[0042]
Next, the cleaning composition of the present invention will be described. Such a detergent composition contains a surfactant and the fine particle zeolite of the present invention, and exhibits excellent cleaning performance due to the high cation exchange ability, low Al ion elution, and low turbidity of the zeolite, There is almost no turbidity of the rinsing water, and the amount of water and time required for rinsing can be greatly reduced.
[0043]
The content of the fine particle zeolite in the cleaning composition of the present invention is not particularly limited, but is preferably 1% by weight or more, more preferably 3% by weight or more, and more preferably 5% by weight or more from the viewpoint of developing sufficient cleaning performance. Further preferred. Further, from the viewpoint of stable production of the cleaning composition, it is preferably 60% by weight or less, more preferably 50% by weight or less, and further preferably 40% by weight or less. That is, the content of the fine particle zeolite in the cleaning composition is preferably 1 to 60% by weight, more preferably 3 to 50% by weight, and further preferably 5 to 40% by weight. Moreover, you may mix | blend another well-known zeolite with the fine particle zeolite of this invention in the cleaning composition of this invention. Other zeolites may be commercially available zeolites, and the crystal structure of such zeolites may be P-type, X-type, etc. in addition to A-type, or a mixture of two or more thereof. The average primary particle size and average aggregate particle size of other zeolites are not particularly limited, but from the viewpoint of the cation exchange rate, the average primary particle size is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 2 μm or less. Further, from the viewpoint of dispersibility in water, the average aggregate particle size is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. From the viewpoint of ensuring the desired effect of the cleaning composition of the present invention, the content of the fine particle zeolite of the present invention in the total zeolite used in the composition is preferably 10% by weight or more, preferably 20% by weight. The above is more preferable, and 50% by weight or more is more preferable.
[0044]
The surfactant to be blended in the cleaning composition of the present invention is not particularly limited, and examples thereof include nonionic, anionic, cationic and zwitterionic surfactants.
[0045]
Specifically, as the nonionic surfactant, a publicly known nonionic surfactant described in “Patents of Chapter 3 of Known and Conventional Techniques (Powder Detergent for Clothing)” of the Japan Patent Office can be used. Other nonionic surfactants include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, sucrose fatty acid esters, glycerin fatty acid monoesters, higher fatty acid alkanolamides, polyoxyethylene higher fatty acid alkanolamides. Amine oxides, alkyl glycosides, alkyl glyceryl ethers, N-alkyl gluconamides and the like can also be used.
[0046]
As the anionic surfactant, for example, a known anionic surfactant described in “Chapter 3 of the well-known / conventional technology collection (powder detergent for clothing)” of the Japan Patent Office can be used. The counter ion of the anionic surfactant is selected from the group consisting of sodium ions, potassium ions, magnesium ions, calcium ions, cations obtained by protonating amines such as ethanolamines, quaternary ammonium salts and mixtures thereof. Selected.
[0047]
As the cationic surfactant, for example, a known cationic surfactant described in “Patents of Chapter 3 of the well-known / conventional technology collection (powder detergent for clothing)” published by the Japan Patent Office can be used.
[0048]
As the zwitterionic surfactant, for example, a known zwitterionic surfactant described in “Patents of Chapter 3 of the well-known and commonly used technology collection (powder detergent for clothing)” of the Japan Patent Office can be used.
[0049]
The above surfactants can be used alone or in admixture of two or more. Further, the surfactant may be selected from the same type or may be selected from a plurality of types.
[0050]
The content of the surfactant in the cleaning composition of the present invention is not particularly limited, but is preferably 1% by weight or more, more preferably 5% by weight or more, and further preferably 10% by weight or more from the viewpoint of cleaning properties. Further, from the viewpoint of productivity of the cleaning composition, it is preferably 90% by weight or less, more preferably 70% by weight or less, and further preferably 60% by weight or less. That is, the content of the surfactant in the cleaning composition is preferably 1 to 90% by weight, more preferably 5 to 70% by weight, and still more preferably 10 to 60% by weight.
[0051]
In addition to the surfactant and the fine particle zeolite of the present invention, various additives that are usually blended in a detergent for clothing can be appropriately blended in the detergent composition of the present invention. Their content can be appropriately adjusted as long as the desired effect of the cleaning composition of the present invention is not impaired.
[0052]
Examples of the additive include other inorganic builders, organic builders, enzymes, anti-staining agents, fluorescent dyes, viscosity modifiers, solvents, bleaches, dispersants, and fragrances. Examples of the inorganic builder include silicates, carbonates, sulfates, sulfites, condensed phosphates, sodium chloride and the like in addition to zeolite, and alkali metal salts are preferable as the salts. Examples of the organic builder include organic alkali agents such as alkanolamines such as triethanolamine, diethanolamine, and monoethanolamine. Also, organic cation exchange agents such as aminopolyacetates such as ethylenediaminetetraacetate, oxycarboxylates such as citric acid, polycarboxylates such as polyacrylic acid and acrylic acid-maleic acid copolymer, As such, alkali metal salts and ammonium salts are suitable. Examples of the enzyme include cellulase, amylase, cannase, lipase, protease and the like. Examples of the recontamination inhibitor include polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, and carboxymethyl cellulose. Examples of the viscosity modifier and the solvent include lower alcohols such as isopropanol, glycols such as ethylene glycol, and glycerin. Examples of the bleaching agent include inorganic peroxygen bleaches such as sodium percarbonate and sodium perborate, or mixtures of these inorganic peroxygen bleaches and bleach activators. Examples of the bleach activator include organic compounds having a reactive acyl group that forms an organic peracid. Specifically, sodium lauroyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, lauroyloxybenzoate Acid, decanoyloxybenzoic acid, and the like. In addition, bleach activating catalysts such as manganese, cobalt, and iron complexes can be blended as a bleach activating agent.
[0053]
Such a cleaning composition of the present invention can be obtained by mixing and stirring the above-mentioned components according to a known method, and granulating as desired. Since such a composition contains the fine particle zeolite of the present invention, it is very excellent in cleaning properties and rinsing properties. In addition, detergency and rinseability can be evaluated according to the method described in the below-mentioned Example.
[0054]
【Example】
The measured physical properties of each sample in Examples and Comparative Examples were measured by the following methods. “%” Represents “% by weight” unless there are special circumstances. In the table, the unit of cation exchange capacity is simply expressed as “mg / g”.
[0055]
(1) Average primary particle size
Zeolite particles with a digitizer (Graphtech, Digitizer KW3300) based on a scanning electron micrograph of a sample (zeolite) taken with a high resolution scanning electron microscope (FE-SEM, Hitachi S-4000) The primary particle diameter (number of particles of 100 or more) is measured. Using all the measured values as a population, the number average value [average primary particle size (μm)] and coefficient of variation (%) are determined. The coefficient of variation (%) is obtained by the following equation.
Coefficient of variation (%) = standard deviation (μm) / average primary particle diameter (μm) × 100
[0056]
(2) Powder X-ray diffraction
Using a powder X-ray diffractometer (RINT2500VPC manufactured by Rigaku Corporation; light source CuKα ray, tube voltage 40 kV, tube current 120 mA), scanning interval 0.01 °, scanning speed 10 ° / min, divergent in the range 2θ = 5-40 ° A sample is measured at room temperature (20 ° C.) under the conditions of a vertical restriction slit 10 mm, a diverging slit 1 °, a light receiving slit 0.3 mm, and a scattering slit automatically. A background curve is drawn by approximation of a cubic equation with background points at 2θ = 20 °, 28.5 °, 37 °, and 40 °, and the diffraction curve and the background curve in the range of 2θ = 20-40 ° are drawn. The peak area (A_peak) Total peak area in the range of 2θ = 20-40 ° (A_all) Peak area above background (A_peak) Ratio (A_r) From the peak area and the total peak area:
A_r(%) = A_peak/ A_all× 100
Ask for. The total peak area is an area between a diffraction curve and a straight line with zero intensity in the range of 2θ = 20 to 40 °. In addition, the crystallinity deterioration rate due to grinding is expressed by the following formula:
Crystalline deterioration rate (%)
= [1- (Zeolite A after grinding)_r) / (Zeolite A before grinding)_r)] X 100
Ask for.
[0057]
Further, the powder X-ray diffraction intensity ratio (%) is obtained by measuring the powder X-ray diffraction peak intensity (I) of the interplanar spacing d = 0.3 nm attributed to the (410) plane of the A-type zeolite obtained for the zeolite to be measured.₄₁₀) Commercially available A-type zeolite having an average primary particle diameter of 1 μm or more (Toyo Builder, Tosoh Corporation, I₄₁₀= 32837 cps) I₄₁₀As a percentage of
[0058]
(3) Average agglomerated particle size
Using a laser scattering particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.), a sample in a slurry state using water as a dispersion medium with a refractive index of 1.2, an ultrasonic intensity of 7, an ultrasonic irradiation time of 1 minute, and a stirring speed of 4 Measure the particle size distribution. The obtained median diameter (volume basis) is defined as the average aggregate particle diameter (μm).
[0059]
(4) Cation exchange capacity
CaCl₂ Aqueous solution (Ca concentration is CaCO_Three (100 ppm in terms of conversion) 0.2 g of 20% sample aqueous solution is added to 100 mL, stirred at 20 ° C. for 1 minute or 10 minutes, and then filtered through a 0.2 μm disposable filter. 10 mL of the obtained filtrate is taken, and the amount of Ca in the filtrate is measured with a photometric titrator to determine the cation exchange capacity. The amount of Ca ion exchanged per gram of zeolite per minute (CaCO_Three Cation exchange rate (CER; mgCaCO)_Three / G) and the amount of Ca ion exchanged per gram of zeolite in 10 minutes (CaCO_Three Cation exchange capacity (CEC; mgCaCO)_Three / G).
[0060]
(5) Turbidity
The turbidity (%) of the aqueous liquid (zeolite concentration: 0.013%) obtained by adding the sample to water (hardness: 4 °) and stirring for 10 minutes at room temperature (20 ° C) was measured using a turbidimeter (Murakami color). Measured using a reflection transmission meter HR-100 manufactured by Materials Research Laboratory.
[0061]
(6) Detergency
40 g of crystalline silicate (KWS-2, particle size 11 μm, manufactured by Kao), 24.8 g of nonionic surfactant (Emulgen 108, manufactured by Kao), 14.8 g of polyoxyethylene phenyl ether (manufactured by Nippon Emulsifier) and polymer Add to a mixed solution of 0.4 g type dispersant (Aqualock FC600S, manufactured by Nippon Shokubai Co., Ltd.) and stir and mix uniformly. The obtained silicate-containing mixed liquid is put into a batch type sand mill (manufactured by Imex) having a capacity of 1 L together with 500 g of zirconia beads (diameter 1 mm), and subjected to pulverization at a disc rotation speed of 1500 rpm for 60 minutes. Next, 0.3333 g of a mixed solution containing pulverized silicate (particle diameter: 2.3 μm) and 0.3333 g of a sample aqueous solution (zeolite concentration: 20%) were mixed to prepare a detergent composition, which was used. Then, in a water temperature of 20 ° C. and water (hardness: 4 °) in 1 liter, washed with a targotometer (120 rpm; manufactured by Ueshima Seisakusho Co., Ltd.) for 10 minutes, rinsed for 1 minute, dried and washed artificially contaminated cloth (5 sheets), washed Calculate the rate (%). The cleaning rate was measured by measuring the reflectance at 550 nm of the raw fabric before contamination and the artificially contaminated fabric before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation).
Cleaning rate (%)
= (Reflectance after washing-reflectance before washing) / (reflectance of raw cloth-reflectance before washing) × 100
Is obtained as an average value of five measurements.
[0062]
The artificially contaminated cloth is prepared by adhering an artificially contaminated liquid having the following composition to a cloth (cotton gold cloth 2003 cloth, manufactured by Tanigami Shoten). The artificial contamination liquid is adhered to the cloth using a gravure roll coater (cell capacity: 58 cm, coating speed: 1 m / min, drying temperature: 100 ° C., drying time: 1 minute) manufactured according to JP-A-7-270395. .
[0063]
(Artificial contamination liquid composition)
The composition of the artificial contaminated liquid was: lauric acid 0.44%, myristic acid 3.09%, pentadecanoic acid 2.31%, palmitic acid 6.18%, heptadecanoic acid 0.44%, stearic acid 1.57%, olein 7.75% acid, 13.06% trioleic acid, 2.18% n-hexadecyl palmitate, 6.53% squalene, 1.94% egg yolk lecithin liquid crystal (manufactured by Wako Pure Chemical Industries), Kanuma red soil for gardening 8.11%, carbon black (Asahi Carbon) 0.01%, and the balance is tap water.
[0064]
(7) Rinsability
Using a detergent composition obtained by mixing 22% zeolite, 11% crystalline silicate (SKS-6, particle size 26 μm, made by Clariant) and 67% nonionic surfactant (Emulgen 108, made by Kao) 2 Wash clothes with a bath-type washing machine (Toshiba “Galaxy 3.6”) with a bath ratio of 1/20, a detergent composition concentration of 20 g / 30 L, a water temperature of 20 ° C., and tap water (hardness: 4 °) for 10 minutes. Rinse at a rinse flow rate of 15 L / min for 4 minutes. After stopping the washing machine, the clothes in the washing tub are moved to the wall surface of the washing tub, and then the rinsing water is checked for transparency, and the rinsing properties are evaluated according to the following three evaluation criteria.
[0065]
〔Evaluation criteria〕
○: The rinse water is transparent and the pulse eater on the bottom of the washing tub is clearly visible
△: The pulsator is visible but the rinse water is slightly cloudy
×: The rinse water is cloudy and the outline of the pulse aerator cannot be clearly seen
[0066]
Example 1
(1) Preparation of zeolite
  2 Sodium aluminate aqueous solution (Na₂O; 21.01%, Al₂ O_Three 28.18%), 400 g of nonionic surfactant (compound name: polyoxyethylene lauryl ether; Emulgen 108, manufactured by Kao) is added while stirring with a teflon stirring blade (length: 11 cm) (400 rpm), It heated for 20 minutes at 50 degreeC using the mantle heater. No. 3 water glass (Na₂O; 9.68%, SiO₂ 29.83%, manufactured by Osaka Silica) was added dropwise over 5 minutes using a roller pump. After completion of the dropwise addition, the mixture was further stirred for 10 minutes (400 rpm), heated to 80 ° C. over 30 minutes with stirring, and further aged for 60 minutes. The obtained fine particle zeolite aqueous liquid was filtered, washed with water (until the filtrate was <pH 12), dried at 100 ° C. for 13 hours, and crushed with a cooking cutter for 1 minute. From the powder X-ray diffraction measurement of the obtained powder, it was confirmed that A-type zeolite (powder X-ray diffraction intensity ratio 46%) was generated. Moreover, the average primary particle diameter was 0.03 micrometer.
[0067]
(2) Grinding of zeolite
Zeolite aqueous solution obtained by dispersing 10 g of the obtained fine particle A-type zeolite powder in 40 g of ion-exchanged water was placed in a sealed container (capacity 250 mL, made of polystyrene) together with 300 g of 5 mm diameter zirconia balls, and ball milling (300 rpm) was performed for 24 hours. went. The Al elution concentration in the filtrate obtained by ultrafiltration (ultrafilter unit USY-1, fractional molecular weight 10000, manufactured by Advantech) of the pulverized zeolite aqueous liquid (zeolite concentration: 20%) was quantified by ICP analysis. The concentration of the total Al contained in the zeolite in the aqueous solution of 20% zeolite is 3% in the aqueous solution, the Al elution concentration obtained by ICP analysis is 900 ppm, and the ratio of the amount of Al eluted is the total Al amount. 3%. Similarly, the ratio of the amount of Al eluted from the zeolite obtained in the above (1) when not pulverized was also determined.
[0068]
In addition, according to the above method, various physical properties were measured on the zeolite before or after pulverization. In the measurement after pulverization, the filtered precipitate obtained at the time of measuring the amount of eluted Al was dried at 100 ° C. for 13 hours. The cation exchange capacity, turbidity, washing rate, and rinsing properties were evaluated using the crushed zeolite.
[0069]
Example 2
(1) Preparation of zeolite
Sodium aluminate aqueous solution (Na₂O; 21.01%, Al₂ O_Three 28.18%) To 400 g, add 137 g of polyethylene glycol (manufactured by Wako Pure Chemicals, trade name: PEG600, average molecular weight 600) while stirring with a Teflon stirring blade (length: 11 cm) and use a mantle heater. And heated at 50 ° C. for 20 minutes. No. 3 water glass (Na₂O; 9.68%, SiO₂ 29.83%, manufactured by Osaka Silica) was added dropwise over 5 minutes using a roller pump. After completion of the dropwise addition, the mixture was further stirred for 10 minutes (400 rpm), heated to 80 ° C. over 30 minutes with stirring, and then aged for another 60 minutes. The obtained fine particle zeolite aqueous liquid was filtered, washed with water (until the filtrate was <pH 12), dried at 100 ° C. for 13 hours, and crushed with a cooking cutter for 1 minute. From the powder X-ray diffraction measurement of the obtained powder, it was confirmed that A-type zeolite (powder X-ray diffraction intensity ratio 48%) was produced. Moreover, the average primary particle diameter was 0.03 micrometer.
[0070]
(2) Grinding of zeolite
Zeolite aqueous solution obtained by dispersing 16 g of the obtained fine particle A-type zeolite powder in 64 g of ion-exchanged water is placed in a crushing container (made of Teflon) together with 500 g of 0.5 mm diameter zirconia beads, and sand mill crushing (1500 rpm) is performed for 20 minutes. It was. The Al elution concentration in the filtrate obtained by ultrafiltration (ultrafilter unit USY-1, fractional molecular weight 10000, manufactured by Advantech) of the pulverized zeolite aqueous liquid (zeolite concentration: 20%) was quantified by ICP analysis. The concentration of the total Al contained in the zeolite in the 20% zeolite aqueous solution is 3% in the aqueous solution, the Al elution concentration obtained by ICP analysis is 700 ppm, and the ratio of the amount of Al eluted is the total Al amount. It was 2.3%. Further, various physical properties were measured in the same manner as in Example 1.
[0071]
Example 3
(1) Preparation of zeolite
Sodium aluminate powder (400 rpm) with stirring with Teflon stirring blade (length 11 cm) to 147 g of 40% acrylic acid polymer aqueous solution (oligomer D, weight average molecular weight 10,000, manufactured by Kao) in a 2 L stainless steel container Na₂O; 40.1%, Al₂ O_Three 200 g of 53.8%, NAP-120, manufactured by Sumitomo Chemical Co., Ltd.) was added and heated at 50 ° C. for 20 minutes using a mantle heater. No. 3 water glass (Na₂O; 9.68%, SiO₂ 29.83%, manufactured by Osaka Silica) was added dropwise over 5 minutes using a roller pump. After completion of the dropwise addition, the mixture was further stirred for 10 minutes (400 rpm), heated to 80 ° C. over 30 minutes with stirring, and then aged for another 60 minutes. The obtained fine particle zeolite aqueous liquid was filtered, washed with water (until the filtrate was <pH 12), dried at 100 ° C. for 13 hours, and crushed with a cooking cutter for 1 minute. From the powder X-ray diffraction measurement of the obtained powder, it was confirmed that A-type zeolite (powder X-ray diffraction intensity ratio 49%) was produced. Moreover, the average primary particle diameter was 0.03 micrometer.
[0072]
(2) Grinding of zeolite
Zeolite aqueous solution obtained by dispersing 10 g of the obtained fine particle A-type zeolite powder in 40 g of ion-exchanged water was placed in a sealed container (capacity 250 mL, made of polystyrene) together with 300 g of 5 mm diameter zirconia balls, and ball milling (300 rpm) was performed for 24 hours. went. The Al elution concentration in the filtrate obtained by ultrafiltration (ultrafilter unit USY-1, fractional molecular weight 10000, manufactured by Advantech) of the pulverized zeolite aqueous liquid (zeolite concentration: 20%) was quantified by ICP analysis. The concentration of the total Al contained in the zeolite in the 20% zeolite aqueous solution is 3% in the aqueous solution, the Al elution concentration obtained by ICP analysis is 700 ppm, and the ratio of the amount of Al eluted is the total Al amount. It was 2.3%. Further, various physical properties were measured in the same manner as in Example 1.
[0073]
Comparative Example 1
(1) Preparation of zeolite
Sodium aluminate aqueous solution (Na₂O; 21.01%, Al₂ O_Three 28.18%) To 400 g, with stirring with a Teflon stirring blade (length 11 cm) (400 rpm), 211 g of an aqueous caustic soda solution (48% NaOH aqueous solution) was added and heated at 50 ° C. for 20 minutes using a mantle heater. . No. 3 water glass (Na₂O; 9.68%, SiO₂ ; 29.83%, Osaka Silica) 445g and calcium chloride aqueous solution (1% CaCl₂(Aqueous solution) 236 g of the mixed solution was added dropwise over 5 minutes using a roller pump. After completion of the dropwise addition, the mixture was further stirred for 10 minutes (400 rpm), and the temperature was raised to 80 ° C. over 30 minutes while stirring, followed by further aging for 5 minutes. The obtained aqueous zeolite solution was filtered, washed with water (until the filtrate was <pH 12), dried at 100 ° C. for 13 hours, and crushed with a cooking cutter for 1 minute. From the powder X-ray diffraction measurement of the obtained powder, it was confirmed that A-type zeolite (powder X-ray diffraction intensity ratio 62%) was generated. The average primary particle size was 0.2 μm.
[0074]
(2) Grinding of zeolite
The zeolite was pulverized in the same manner as in Example 1, and the Al elution concentration was measured by ICP analysis. The concentration of the total Al contained in the zeolite in the 20% zeolite aqueous solution is 3% in the aqueous solution, the Al elution concentration obtained by ICP analysis is 1300 ppm, and the ratio of the amount of Al eluted is 4% of the total Al amount. 3%. Further, various physical properties were measured in the same manner as in Example 1.
[0075]
Comparative Example 2
Various physical properties were measured in the same manner as in Example 1 using commercially available A-type zeolite (Toyo Builder, manufactured by Tosoh Corporation). However, in this comparative example, the zeolite was not pulverized.
[0076]
Comparative Example 3
Various physical properties were measured in the same manner as in Example 1 using commercially available 4A zeolite (Toyo Builder, manufactured by Tosoh Corporation). The concentration of total Al contained in the zeolite in the 20% zeolite aqueous solution is 3% in the aqueous solution, and the Al elution concentration obtained by ICP analysis after pulverization is 1200 ppm. Was 4% of the total amount of Al.
[0077]
Comparative Example 4
Sodium aluminate aqueous solution (Na₂O; 21.01%, Al₂O_Three28.18%) To 400 g, 155 g of propylene glycol (molecular weight 76, manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring with a Teflon stirring blade (length 11 cm) (400 rpm) at 50 ° C. using a mantle heater. Heated for 20 minutes. No. 3 water glass (Na₂O; 9.68%, SiO₂ 29.83%, manufactured by Osaka Silica) was added dropwise over 5 minutes using a roller pump. After completion of the dropwise addition, the mixture was further stirred for 10 minutes (400 rpm), heated to 80 ° C. over 30 minutes with stirring, and then aged for another 60 minutes. The obtained fine particle zeolite aqueous liquid was filtered, washed with water (until the filtrate was <pH 12), dried at 100 ° C. for 13 hours, and crushed with a cooking cutter for 1 minute. From the powder X-ray diffraction measurement of the obtained powder, it was confirmed that A-type zeolite (powder X-ray diffraction intensity ratio 61%) was generated. The average primary particle size was 0.2 μm. Zeolite was pulverized and evaluated in the same manner as in Example 1. The total Al concentration in the 20% aqueous zeolite solution was 3%, the Al elution concentration obtained by ICP analysis was 1300 ppm, and the proportion of the Al amount eluted was 4.3% of the total Al amount. Further, various physical properties were measured in the same manner as in Example 1.
[0078]
The charged composition of zeolite is summarized in Table 1, and the above results are summarized in Table 2.
[0079]
[Table 1]

[0080]
[Table 2]

[0081]
From Examples 1 to 3, a fine particle A-type zeolite having an average primary particle size of 0.1 μm or less is obtained by performing a zeolite synthesis reaction in the presence of a crystal growth inhibiting compound according to the method for producing a fine particle zeolite of the present invention. I understand that. In Comparative Example 4, the synthesis reaction of zeolite is performed in the presence of propylene glycol, which is an organic compound having a functional group containing an oxygen atom. The molecular weight of the compound is 76, and the average primary particle size is 0.1 μm. The following fine particle zeolite has not been obtained.
[0082]
In addition, the average agglomerated particle diameters of the zeolites of Examples and Comparative Examples can be made 0.4 μm or less by appropriately pulverizing, but Comparative Examples 1, 3, and 4 in which the average primary particle diameter before pulverization exceeds 0.1 μm. In this zeolite, the deterioration of crystallinity has progressed after pulverization, and the average primary particle size distribution is also deteriorated, the amount of eluted Al is increased, and the cleaning rate of the detergent composition obtained using such zeolite and It can be seen that / or rinsing properties are reduced. On the other hand, in Examples 1 to 3, even when pulverization is performed, the progress of the crystallinity deterioration is suppressed (for example, the crystallinity deterioration rate), and there is no substantial change in the average primary particle size distribution, It can be seen that a fine particle zeolite having a desired average agglomerated particle size and excellent in cation exchange ability is obtained, and the cleaning rate and rinsing property of the detergent composition obtained using the zeolite are high.
[0083]
【The invention's effect】
According to the present invention, there is provided a fine particle zeolite having an average primary particle size of 0.1 μm or less, excellent cation exchange ability, a small amount of Al eluted in water in an aqueous liquid, and a low turbidity of water in the aqueous liquid. can get. In addition, a cleaning composition comprising the fine particle zeolite and having excellent cleaning properties and rinsing properties can be obtained.

Claims (7)

The average primary particle size is 0.08 μm or less (coefficient of variation 90% or less), and the ratio of the peak area above the background to the total peak area in the range of 2θ = 20 to 40 ° of the powder X-ray diffraction spectrum is Fine particle type A zeolite that is 30% or more. The fine particle A-type zeolite according to claim 1, having an average agglomerated particle size of 0.4 µm or less. The fine particle A-type zeolite according to claim 1 or 2, wherein the proportion of the amount of Al eluted in water in the aqueous liquid is less than 4% by weight of the total amount of Al contained. The fine particle A-type zeolite according to any one of claims 1 to 3, which has a cation exchange rate of 180 mgCaCO ₃ / g or more. In producing zeolite by reacting a silica source and an aluminum source , a molar ratio of a compound containing an alkali metal and a charged composition of water in the reaction system (M ₂ O / H ₂ O: M represents an alkali metal) The method for producing a fine particle A-type zeolite according to any one of claims 1 to 4, wherein the reaction is carried out in the presence of an organic compound having a molecular weight of 100 or more and having a functional group containing an oxygen atom. The functional group containing an oxygen atom is an OR group and / or a COOR group (R is at least one selected from a saturated or unsaturated organic group having 1 to 22 carbon atoms, a hydrogen atom, and an alkali metal atom) Item 6. A method for producing a particulate A-type zeolite according to Item 5. A detergent composition comprising a surfactant and the fine particle A-type zeolite according to any one of claims 1 to 4.