WO1997003018A1 - Hydrous layered silicates and detergent compositions containing the same - Google Patents

Abstract

Hydrous layered silicates represented by the following compositional formula: (M1x/n, Na1-x/n)2SiyO2y+1.zH2O (wherein M1 represents at least one metal selected among lithium, potassium and alkaline earth metals; n represents the valency of metal M1; and x, y and z are numbers, respectively, in the ranges of 0 ≤ x ≤ 0.5, 3 ≤ y ≤ 7.5 and 1 ≤ z ≤ 20) and having a spin-lattice relaxation time of 0.35 sec or less as determined by 23Na-solid nuclear magnetic resonance spectrometry. The silicates have high cation-exchange capacities and rates and suitable properties as water softeners and so forth, thus being suitable for water softeners, water treatments, detergents, and so forth.

Description

 Description Hydrated layered gayate and detergent composition containing the same

 The present invention relates to a novel hydrated layered gay acid salt, a method for producing the same, a water softener containing the same as an active ingredient, and a detergent composition containing the same. More specifically, the present invention has a high cation exchange capacity and an exchange rate-a novel crystalline hydrated layered gayate, a method for producing the same, and a water softener having excellent ion exchange properties using the same as an active ingredient. And a detergent composition containing the same. Background art

 Hardness components contained in tap water combine with surfactants contained in detergents and fatty acids contained in dirt to form water-insoluble salts when washing clothes, dishes, bathtubs, toilet bowls, etc. It has long been known that the cleaning effect is significantly reduced. To prevent this, a substance that normally traps or blocks the hardness component in tap water, that is, a water softener, is added to the detergent. For a detergent composition for clothing, tripolyphosphoric acid was used. Sodium has been used as a water softener. However, due to the problem of eutrophication of rivers, a search was made for a substitute for sodium tripolyphosphate, and A-type zeolite, a type of synthetic zeolite, was generally used as a water softener. .

On the other hand, in recent years, as household detergents have become more compact, there has been a demand for higher functionality of detergent components, and there has been a demand for highly functional water softeners that can be converted to A-type zeolites. For this purpose, the function of the water softener refers to the ability to capture calcium ions, the main hardness component in tap water, and this performance is primarily evaluated by the cation exchange capacity. If a softener is used, surfactants that coexist, fatty acids in the soil, etc. Since it is necessary to quickly capture or block the hardness component before the hardness component in the tap water and water combine, it is also important to increase the rate of capturing calcium ions (cation exchange rate).

Under such circumstances, it has been proposed to use crystalline sodium gayate or a modified product thereof such as sodium type 5 dicayate as a water softener (Japanese Patent Publication No. 1-41116) publication), the type 5 Jikei acid isocyanatomethyl Riumu, by firing at _{N a 2 0 / S i 0} 2 molar ratio to zero. 5 near the amorphous Gay acid sodium © beam of near 7 0 0 ° C temperature Although produced, it is water-soluble and, when dispersed in water, changes its crystal structure, so that calcium ion-trapping performance cannot be said to be sufficient.

 In order to overcome such drawbacks, there has been proposed an alkali metal silicate in which water solubility is suppressed by adding an element belonging to Group IIa, IIb, Ilia, IVa or VIII of the periodic table. (Japanese Unexamined Patent Publication No. 5-184496). However, since this is also produced by calcination, the obtained crystalline alkali metal gaterate is basically an anhydride regardless of the presence or absence of additives, so that the ion exchange rate is low and sufficient. It does not have a function. Further, in order to improve the ion exchange rate, there has been proposed a crystalline alkali metal silicate containing lithium and sodium (Japanese Patent Application Laid-Open No. Hei 6-128590). However, this is not only water-soluble, but also has a drawback that when it contains a large amount of potassium, it easily absorbs moisture and is difficult to handle.

A first problem to be solved by the present invention is to provide a novel hydrated layered gay acid salt having a high cation exchange capacity and an exchange rate and exhibiting properties suitable as a water softener. A second object is to provide a method for easily producing such a hydrated layered gate acid from easily available raw materials. A third object is to provide a high-quality water softener containing the water-containing layered gayate as an active ingredient. A fourth object is to provide a detergent composition containing the water softener as a component. Other problems will be evident from the following description of the present invention. Disclosure of the invention

 The present inventors have conducted intensive studies to develop a novel water softener suitable for use as a component of a cleaning agent. As a result, the inventors have found that some of sodium in hydrated layered sodium gateate can be converted to another aqueous solution. The hydrated layered silicate having a specific composition replaced by lithium metal or alkaline earth metal has a higher cation exchange capacity than the synthetic zeolite conventionally used as a water softener. It has been found that it is an excellent water softener and that it can be produced by simple processing using easily available minerals such as mahite as raw materials. Based on this, the present invention has been accomplished. That is, the present invention provides a composition formula

(M 'x / n. N a! -X / „) ₂ S i _y 0 ₂ y ₊ iz H ₂ 0 (I)

(Where M ¹ is at least one metal selected from lithium, lithium and alkaline earth metals, n is the valence of M ¹ , and X, y and z are in the following ranges: 0 x ≤ 0.5, 3 ≤ y ≤ 7.5, 1 ≤ z ≤ 20), and ²³ N a-spin-one-particle relaxation time measured by solid-state nuclear magnetic resonance The above-mentioned problem has been solved by providing a water-containing layered gay acid salt having a characteristic value of 0.35 seconds or less.

Previously, as a crystalline hydrated Al force Li metal Kei salt, Kanemai Doo _{(NaHSi 2 0 5 -3H 2 0} ), Makatai Doo _{(Na 2 Si 4 0 9 ·} 5Η 2 0), Ayler eye Doo (Na _{2 Si 8 0 17 '10H 2} 0), Magadiai door _{(NasSi! 4 0 29 · 10Η} 2 0), Kenya Ai door (Na ₂ Si _2O O _41', such as 10H ₂ O) are known in general, these Yes Each of them contains a layer structure composed of only silicate and an alkali metal ion which can be generally considered to be exchangeable between the layers. The hydrated layered maleate of the present invention has a composition similar to that of mashite, but has a different crystal structure. The water-containing layered gayate of the present invention can also be obtained by modifying the natural maltite produced in, for example, Kenya [“Am. Mineral. J Vol. 55, p. 358 (1970)]”. can get.

In addition, the power strength can also be obtained by synthesizing, but an example of actually synthesizing macaite has been described as S i 0 ₂ -Na ₂ 0-H ₂ 0 [Z. Kristallogr., Vol. 197, Page 1 (1991)], and those synthesized with the addition of diethanolamine [[Z. Kristallogr. J, Vol. 159, Page 203 (1982)] In any case, the ion exchange capacity of the known mahite is extremely small and cannot be put to practical use.

 The aqueous layered gayate represented by the composition formula (I) is, for example, a composition formula

M ² _{2 / m} S i _y 0 _{2y + 1z} 'H ₂ 0 (II)

(Where M ² is at least one metal selected from lithium, sodium, potassium and alkaline earth metals, m is the valence of M ² , and y and z ′ are in the following ranges: is a number. 3≤y≤ 7. 5, after 0≤ z'≤ 20) by acid treatment layered Gay salt material represented by the reduced portion of the metal M ² therein, Natoriumu compound Alternatively, it can be produced by treating with an aqueous solution containing a sodium compound and at least one metal compound selected from lithium, potassium and alkaline earth metals. BEST MODE FOR CARRYING OUT THE INVENTION

M ¹ in the water-containing layered gayate of the present invention represented by the above composition formula (I) is at least one metal selected from lithium, potassium and alkaline earth metals. Potassium is preferred because a remarkable improvement in the exchange rate is observed. n is the valence of M ^1, if M ¹ is lithium, potassium 1, in the case of alkaline earth metals is 2. X is a number in the range of 0 to 0.5, but is preferably in the range of 0 to 0.3 in consideration of the cation exchange rate. y is a number in the range of 3 to 7.5. If y is less than 3, the desired crystal structure cannot be obtained, and if y exceeds 7.5, the cation exchange capacity and cation exchange rate may decrease. From the viewpoint of crystal structure, positive ion exchange capacity, positive ion exchange rate, etc., y is preferably in the range of 3.5 to 5. On the other hand, z is a number in the range of 1 to 20, and therefore, this water-containing layered gayate always contains water in the crystal molecule. Will be. The distinction between the water contained in the crystal molecules and the water adsorbed on the crystal particle surface is that the water adsorbed on the particle surface desorbs at low temperature, but the water contained in the crystal molecules is more Since it desorbs at a high temperature, it can be quantitatively performed using this property. The amount of water contained in the crystal molecule, that is, z, is preferably in the range of 3 to 3 from the viewpoint of properties. The crystalline alkali metal gaylate of the present invention is essential to contain water of crystallization as described above, and includes a crystalline alkali metal gaylate produced by firing at a temperature of 600 ° C. or more. Are essentially different.

Further, hydrated layered Gay salts of the present invention, ²³ N a- solid-state nuclear magnetic resonance spectroscopy ⁽²³ N a- solid NMR) measured spin one-lattice relaxation time of preferably less 35 seconds 0. 0. 25 seconds or less It is necessary to be. Those with spin-lattice relaxation times longer than 0.35 seconds do not exhibit high cation exchange capacity. For example, any of the known force titers described above exhibit a spin-lattice relaxation time of 0.4 seconds or more. The spin-lattice relaxation time indicates the environment of the sodium ions contained between the layers of the hydrated layered gaterate, and such a difference clearly indicates a structural difference. The lower limit of the spin-lattice relaxation time of the water-containing layered gayate of the present invention is not particularly limited, and it has been confirmed that a high cation exchange capacity is exhibited even if it is as small as 10 to ³ seconds.

The spin-lattice relaxation time is a value obtained by the following method. In other words, ²³ Na-solid state NMR was measured by the following method under an angle spinning method using a single pulse of ²³ Na under magic angle spinning under the following conditions. Then, the least-squares fitting using the exponential function was performed, and the ²³ Na spin-single lattice relaxation time was analyzed. When the analysis result is considered as a sum of the plurality of components, it is necessary ^{to 23} N a spin one-lattice relaxation time of at least one component is in the above range. [ ²³ N a—Solid state NMR measurement conditions]

Equipment JEOL Ltd. Satsu GX-270 Measurement core ²³ Na

 Observation frequency 71. 464MHz

 Observation width 15015.OH z

 Data points 8192

Pulse width ²³ N a 180 ° pulse = 0.4 5.4 m Repeated integration 3 sec

 Waiting time 0.01-: 0 points in the range of 10,000 msec Sample rotation speed 4.0 kHz

 Number of accumulation 16 times

 Window treatment B F = 20 Hz, T 3 = 20%, T 4 = 50% Measurement temperature

 Chemical shift standard 1 mo 1 ZL sodium chloride aqueous solution

(External standard; 0.0 ppm) The water-containing layered gayate of the present invention has a X-ray diffraction diagram of a known mahite titer (a number JCPDS23 indicated by the Joint Committee on Powder Diffraction Standards). -703 diffraction data), no clear peak may be observed at all, and there are halos that are recognized as amorphous on X-ray diffraction. When diffraction lines are observed, they often include those that show 0.989 to 0.97 nm, 0.49 to 0.53 nm, and 0.366 to 0.376 nm. It is not particularly necessary in the invention. The chemical shift measured by ²⁹ Si-solid state nuclear magnetic resonance spectroscopy of this hydrated layered silicate shows that each silicate unit in the crystal is bonded to the other three silicate units. The chemical shift shown is observed. This indicates that it has a layered structure.

Hydrated layered Gay salts of the present invention having the above composition and crystal structure, 250 C a COsmgZg more often 300 C a CO ₃ mgZg than It shows a high cation exchange capacity as above.

Next, an example of the method for producing a water-containing layered gayate of the present invention will be described. As this production method, for example, a method which applies the method described in the aforementioned “Z. Kristallogr.”, Vol. 197, page 1, (1991) can be mentioned. That is, according to this method, (A) S in ^{_{i 0 2 / M 3 2 0}} ( provided that M ³ represents lithium, one metal at least selected from among Natoriumu and force Riumu) molar ratio of 1 to 20, H ₂ O Roh M ³ ₂ O ( However, M ³ is an aqueous solution of Al force Li metal Gay acid salt molar ratio 5-40 of having) the and the same meaning, (B) compositional formula

M ³ ₂ S i _y 0 _{2y + 1} z'H ₂ 0 (III)

(Where Μ ³ , y, z 'have the same meaning as above)

Is added as a seed crystal, and a hydrothermal reaction is performed to produce a layered gaylate raw material represented by the above composition formula (II). The addition amount of the seed crystal is suitably in the range of 0.1 to 50% by weight based on Sio _{2 of the} component (A). As the seed crystal, it is preferable to use a product obtained in the previous manufacturing process, but a natural product or a product obtained by another method may be used.

There are no particular restrictions on the raw materials used in this reaction, and various ones can be used. However, in view of production costs, water glass, alkali metal hydroxides and carbonates, which are generally easily available, are used. A combination of an aqueous solution and powdered silica is suitable. Further, in some cases, a part or all of Na in the reaction composition may be replaced with another aluminum metal to cause a hydrothermal reaction. After the raw materials are thoroughly mixed to prepare a reaction mixture, crystallization is carried out at a temperature usually in the range of 80 to 250 ° C, preferably 90 to 200 ° C. After the reaction (after completion of crystallization), the reaction mixture is washed with water, separated into a solid and a liquid, and dried to obtain a strong titer. Although any method may be used for solid-liquid separation, it is important that drying is performed at a temperature of 120 ° C or less. If the drying is performed at a higher temperature, the crystal structure is changed, and it becomes difficult to obtain a strong titer. At this time, organic salts and inorganic salts are not added to the reaction system. It is advantageous to add H ₂ O ₂ to the reaction system because the molar ratio of H ₂ O ZNa ₂₀ can be made higher than the above range and the crystallization time can be greatly reduced. Various organic and inorganic salts can be used, and in particular, citric acid, tartaric acid, acetic acid, sulfuric acid, hydrochloric acid, hydrogen bromide, hydrogen peroxide, thiocyanic acid, nitric acid, chloric acid, etc. Alkali metal salts are preferred. These organic salts and inorganic salts may be used alone or in combination of two or more, but the addition amount is 0.1 to 300% by weight based on the solid content of the reaction system. Is preferred.

 In order to produce a water-containing layered gayate represented by the composition formula (I) of the present invention from the layered gayate raw material represented by the composition formula (II) thus obtained, first, the layered gayate is prepared by Once the salt raw material is acid-treated to form a layered gayate or layered gay acid with a reduced amount of alkali metal or alkaline earth metal, sodium compound or sodium compound and lithium, potassium and aluminum The treatment is performed using a compound of at least one metal selected from the alkaline earth metals, for example, a salt or hydroxide thereof. Here, as the acid, those having an pH of 7 or less, preferably 4 or less when converted to an aqueous solution are advantageous. This acid may be used alone or in combination of two or more. As the acid, mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid are preferable from the viewpoint that they require a small amount of use and are inexpensive. After the acid treatment in this manner, 50% or more, and preferably almost all, of the metal ions between layers originally contained in the layered gayate raw material are replaced (ion-exchanged) by hydrogen ions, and the layered gayate material is substantially layered. The power of being acid ^ This method is an important point. This acid treatment is preferably carried out by dispersing the layered gateate raw material in an aqueous solution in which an acid is dissolved or added. This condition achieves the above-mentioned degree of ion exchange by hydrogen ions and the desired maintenance of the layered structure. Is selected within the range.

Next, the treatment is carried out using a salt or hydroxide of sodium-containing alkali metal, which is usually selected from a sodium compound or a sodium compound and lithium, potassium or alkaline earth metal. With less Also, an aqueous solution containing at least pH 7.5, preferably at least 9 containing a compound of one kind of metal, for example, a salt or hydroxide thereof, and a layered silicate or a layered gay acid treated with the above-mentioned acid. Is performed by mixing. Suitable salts of these metals include water-soluble chlorides, sulfates, nitrates and carbonates. In this treatment, these alkali metal or alkaline earth metal compounds, for example, their salts and hydroxides may be used alone or in combination of two or more. The treatment conditions are appropriately set within a range in which the layered gayate or the layered gay acid can be converted into the hydrated layered gayate of the present invention. If the pH of the aqueous solution is lower than the above range, it is difficult to convert the layered gayate or layered gay acid into the water-containing layered gayate of the present invention. In addition, the concentration of the aqueous solution of the sodium compound or the other alkali metal or alkaline earth metal salt or hydroxide is not particularly limited, but the amount is not less than the equivalent of the layered gayate or the layered gay acid. Is at least necessary, and preferably at least 2 equivalents. If it is less than this, conversion to the desired hydrous layered gayate will not be sufficiently performed. The layered gayate raw material is dispersed in an aqueous acid solution to form a layered gayate or layered gay acid having a reduced interlayer ion content, and then the above-mentioned sodium compound or lithium, lithium, aluminum, or aluminum lye is added to the dispersion. It can also be carried out by adding a compound of at least one metal selected from earth metals, for example, a salt or a hydroxide. After this treatment, ordinary solid-liquid separation and drying are carried out to obtain the hydrous layered gayate of the present invention. The drying at this time is desirably performed at 120 ° C. or less so as not to deteriorate the crystal structure. The hydrating agent of the present invention contains the water-containing layered silicate of the present invention thus obtained, has a high cation exchange capacity and an exchange rate, and is suitably used as, for example, a component of a detergent. Can be

 Since the water-containing layered gay salt of the present invention has excellent properties as a water softener, it is used in combination as at least one detergent component selected from an anionic surfactant and a nonionic surfactant. This gives an excellent cleaning composition.

In this case, as the anionic surfactant, olefin sulfonic acid salt and aniline surfactant are used. Alkyl benzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, sulfo fatty acid ester salts, higher fatty acid salts, ie, soaps, are used. Examples of nonionic surfactants include alcohol ethoxylate in which ethylene oxide is added to alcohol, nonylphenol ethoxylate, adduct in which propylene oxide and ethylene oxide are added to alcohol, fatty acid alcohol amide, Sucrose fatty acid esters, alkylamine oxides and the like are used. The detergent composition of the present invention contains at least one selected from these anionic surfactants and nonionic surfactants, and the concentration is preferably 0.5 to 80% by weight. The concentration of the hydrous layered gayate is preferably from 0.1 to 60% by weight.

 The detergent composition of the present invention may further comprise, if necessary, other surfactants such as an amphoteric surfactant and a cationic surfactant, an alkali builder, a calcium ion trapping builder, and the like, in addition to the above essential components. Builders, enzymes, bleaches, and other additives can also be included.

 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

 In addition, each physical property was calculated | required as follows.

 (1) Identification of crystal structure

 Using the powder X-ray diffraction method, the matric titer was identified by comparison with the diffraction diagram of JCPDS 23-703, and the others were identified from the three with the highest diffraction intensity. Was. The presence of amorphous was determined by the presence or absence of halo derived from amorphous.

 (2) Composition analysis

 Surface adsorbed water was determined from the weight loss when dried at 105 ° C for 72 hours, and crystallization water was determined by subtracting the surface adsorbed water from the loss on ignition at 800 ° C for 1 hour. . X-ray fluorescence analysis was used for Si and Alkyri metal.

 (3) Cation exchange capacity

 It was evaluated by the ability to exchange Ca.

0.5 g (solid content) of the sample was ultrasonically dispersed in 200 ml of ion-exchanged water. Separately, a calcium chloride aqueous solution of 6000 ppm in C a 0 conversion

Includes 25 ml and 3 ml of ammoniacal ammonium chloride pH 10 buffer

A 300 ml aqueous solution was prepared, added to the sample dispersion, and ion-exchanged at 25 ° C for 10 minutes. Then, the solution was filtered, and the calcium ion concentration of the filtrate was quantified using EDTA, and determined by the following equation.

Cation exchange capacity (C a C0 ₃ mgZg) =

[[Ca amount tested (mo 1)-Ca amount in filtrate (mo 1)] Z sample amount (solid content: g)] X 10 ⁵

 (4) Cation exchange rate

 Estimated by short term cation exchange capacity. That is, in the method for measuring the cation exchange capacity, the sample dispersion was mixed with an aqueous solution containing calcium ion, and then filtered after a lapse of 1 minute. Hereinafter, the same operation was performed.

However, the unit is C a C 0 ₃ mg / g. Min.

 (5) Spin-lattice relaxation time

According to the method described in the specification text, ²³ Na-solid state NMR was measured and determined.

 (6) Detergency evaluation method

 (i) Preparation of artificial soil

 Clay, which is mainly composed of crystalline minerals such as Riki Orinite and Vermiculite, was dried at 200 ° C for 30 hours and used as inorganic soil.

After dissolving 3.5 g of gelatin in 950 ml of water at about 40 ° C, 0.25 g of carbon black was dispersed in water using a powerful emulsifying and dispersing machine, Polytron (manufactured by KINEMATICA, Switzerland). Next, 14.9 g of inorganic soil was added and emulsified with polytron, and 31.35 g of organic soil was further added and emulsified and dispersed with polytron to prepare a stable soil bath. After soaking a predetermined 10 cm x 20 cm cleaning cloth (Cotton cloth No. 60 designated by the Japan Oil Chemistry Association) in the dirt bath, water was removed with two rubber rolls to equalize the amount of dirt deposited. . After drying the cloth at 105 ° C for 30 minutes, both sides of the cloth were rubbed left and right 25 times. This is cut to 5 cm x 5 cm and the reflectance is Two

Table 1 shows the soil composition of the artificial soil cloth obtained by subjecting the cloth in the range of 42 ± 2% to the soil cloth.

(ii) Cleaning method

 The washing machine used was a two-tub washing machine (Mitsubishi Electric Corporation "Chikuma" CW-660W type). For the item to be washed, 10 pieces of the above-mentioned artificial soiling cloth are sewn to the worn skin shirt to make the total weight 1 kg. Pour 30 liters of tap water at 25 ° C into a washing machine, and put in a specified amount of detergent composition and the object to be washed to a 0.05% detergent concentration, and wash for 10 minutes. After washing, dehydrate for 1 minute, then rinse for 3 minutes. After 1 minute of dehydration, rinse for 3 minutes, measure the reflectance of the soiled cloth, and calculate the detergency by the following formula.

 (KZS of dirty cloth-KZS of cleaning cloth)

 Detergency (%) = ■ X 100

 (K / S of dirty cloth-KZS of unsoiled cloth)

However

 R 2 R

 K / S = [1—] [Kubelka Munk formula]

100 100 And R is the reflectivity (%) measured by Carl Zeiss ELREPHO reflectometer. The evaluation of detergency was determined by the average value of 10 test artificial soil cloths.

Example 1

S i 0 ₂ ZN a ₂ 0 molar ratio of 3.07, solids 37.6 wt% commercial gay sodium solution (No. 3 water glass) was moisture adjusted _{120 ° C, Η 2 ΟΖΝ a} 2 The molar ratio of 0 was set to 7. This mixture was placed in a stainless steel sealed container and crystallized at a temperature of 120 ° C. for 30 days. Thereafter, the mixture was discharged from the container, washed with water, separated into a solid and a liquid, and dried at 50 ° C. Resulting et powder the composition that was found to be _{N a 2 S i 4.!} 0 9. 2 · 4. Ma force Thailand preparative together with the results of powder X-ray diffraction at 9H ₂ 0.

Next, 20 parts by weight (in terms of solid content) of the unmodified mahite was dispersed in 1000 parts by weight of 1N hydrochloric acid. After stirring was continued for 1 hour, filtration and washing with ion exchanged water were performed. Composition analysis of the obtained powder at having conducted were _{N a 2 0/4 S i 0 2} = 0. 01.

 Further, 20 parts by weight of the acid-treated macatite was added to 1000 parts by weight of a 0.5 N NaOH aqueous solution, and the mixture was stirred for 1 hour, filtered, washed with ion-exchanged water, separated into a solid and a liquid. Drying was performed at ° C. The composition is

_{N a 2 S i 4. O0} 9 · 5. 2 H 2 0

Met. The properties are shown in Tables 2 to 4.

 The water content of the above composition indicates the sum of water of crystallization (z) and attached water. The same applies hereinafter.

Example 2

 After forming the mashite in the same manner as in Example 1, the unmodified mashite was subjected to an acid treatment.

Next, 20 parts by weight of acid-treated mahite was added to 1000 parts by weight of a mixed aqueous solution of 0.5 N NaOH and KOH (Na: K = 1: 1 molar ratio) and stirred for 1 hour. After that, filtration, washing with ion-exchanged water, solid-liquid separation, and then drying at 60 ° C were performed. The composition of the obtained powder is (Ko.! · N a o . 9) 2 S i 4. i0 9 .2 · 5. 5 H 2 0

 Met. The properties are shown in Tables 2 to 4.

Example 3

While the powder silica gel and S i 0 ₂ / N a ₂ molar ratio 3.1 Gay aqueous sodium 1 00 parts by weight of 0, prepared using a hydroxide Natoriumu was撹拌, sodium chloride 1 7.5 part by weight 77.5 parts by weight of an aqueous solution in which (47% by weight based on the solid content of aqueous sodium gayate solution) was added. Then, the mixture was adjusted to a water content of 120 ° C. so that the total amount was 77.5 parts by weight. At this time H ₂ 0 Bruno N a ₂ 0 (N a gay acid sodium © anhydrous solution derived) the molar ratio of was 7. This mixture was placed in a stainless steel sealed container and crystallized at a temperature of 120 ° C for 48 hours. Thereafter, the mixture was discharged from the container, washed with water, solid-liquid separated, and dried at 60 ° C. The resulting powder composition has been found to be _{N a 2 S i 3. 9 0} 8. 8 · 4. Ma force Thailand preparative together with the results of powder X-ray diffraction at 7 H ₂ 0.

Next, this unmodified macatite was treated with an acidic substance in the same manner as in Example 1. When a composition analysis of the obtained powder was performed, it was found that Na ₂ OZ 4 S i O ₂ = 0.004.

 Further, 20 parts by weight of the acid-treated mahite is added to 1 000 parts by weight of a mixed aqueous solution of 0.5 N NaOH and KOH [Na: K = 1: 2 (molar ratio)], and the mixture is left for 1 hour. After stirring, the mixture was filtered, washed with ion-exchanged water, separated into solid and liquid, and then dried at 60 ° C. The composition of the obtained powder is

(Ko. ₁₉ N a o. Si) ₂ S i 4. o0 ₈ · 5.6 H ₂₀ . The properties are shown in Tables 2 to 4.

Example 4

 After forming the mashite in the same manner as in Example 3, the unmodified mashite was subjected to an acid treatment.

Next, 20 parts by weight of the obtained acid-treated mahite is added to 1,000 parts by weight of a mixed aqueous solution of 0.5N NaH and KOH [Na: K = 1: 8 (molar ratio)]. After stirring for 1 hour, filtration, washing with ion exchanged water, solid-liquid fraction Then, drying was performed at 60 ° C. The composition of the obtained powder is

(Ko. ₄ N a o.6) ₂ S i 4. o0 ₈ · 5.2 H ₂₀ . The properties are shown in Tables 2 to 4.

Example 5

 After forming macatites in the same manner as in Example 1, the unmodified malachite was subjected to an acid treatment.

Next, the acid treatment Ma force Thailand preparative 20 parts by weight of 0.5 N N a OH and C a mixed aqueous solution of _{C l 2 (N a: C} a = l: 0. 05 molar ratio) projecting enter City 1000 parts by weight After stirring for 1 hour, the mixture was filtered, washed with ion-exchanged water, separated into solid and liquid, and then dried at 60 ° C. The composition of the obtained powder is

Was _{(C a 0. 07 N a 0.} 85) 2 S i 4. 0 O 9 · 4. 9 H 2 0. The properties are shown in Tables 2 to 4.

Example 6

The water content of the commercially available aqueous sodium gayate solution (No. 3 water glass) used in Example 1 was adjusted at 120 ° C. so that the molar ratio of H ₂₀ / Na ₂₀ became 18. The mixture was placed in a stainless steel container, and in so that Do and 2 wt% with respect to S i 0 ₂ gay acid Natoriumu in aqueous solution Ma Katai bets prepared in Example 1, with stirring, after addition It was sealed and crystallized at 120 ° C for 20 hours. After that, it was discharged from the container, washed with water and dried at 105 ° C. The resulting powder composition _{N a 2. T S i 4} .. It 0 ₉ - 5. the results in conjunction with Ma force Thai preparative powder X-ray diffraction by IH ₂ 0 were observed.

 Thereafter, an acid treatment and a NaOH aqueous solution treatment were performed in the same manner as in Example 1. Tables 2 to 4 show the properties.

Comparative Example 1

 Tables 2 to 4 show the properties of the maizeite before the acid treatment in Example 1. Comparative Example 2

Tables 2 to 4 show the properties of the maize tile before the acid treatment in Example 3. 6 Table 2 Composition

 M X y Water content

 Crystallized water (Z) Attached water port = +

 ο \ Example 1 0 4.0 0 5.0 0 25.2 Example 2 K 0.10 4.1 15.2 0.3 5.5 Example 3 K 0 .1 9 4.05 30.3.5.6 Example 4 K 0.40 4.0.4.9 0.3.5.2 Example 5 Ca 0.1.4 4.0.0 4.80.14.9 Example 6 0 4.1 5.1 0. 2 5.3 Comparative example 1 0 4. 1 4. 8 0. 1 4.9 Comparative example 2 0 3. 9 4. 6 0. 1 4.7

Spin size Diffraction peak by powder X-ray diffraction Relaxation time (3 peaks from strongest peak) Non-HHA (sec) Lattice spacing (nm) Noro Example 1 0. 20 6 0. 93 5 0. 5 2 1 0.375 Yes Example 2 0.222 0.93 0 0.5 2 0 0.37 Yes Example 3 0.18 9 0.9 2 7 0.5.2 0 0.37 Yes Yes Example 4 0.220 Clear peaks were not observed.Example 5 0.12 20 Clear peaks were not observed.Example 6 0.188 0.93 30.5 0.52 1 0.375 Comparative Example 1 0.4.18 Matches JCPDS 2 3—7 0 3 None Comparative Example 2 0.432 JC PD S 2 3— Matches 7 0 3 None Table 4

Examples 7 and 8, Comparative Examples 3 and 4

 A detergent slurry having a solid content of 45% was prepared using each component other than the nonionic surfactant, the enzyme and the flavor in the composition shown in Table 5. The detergent slurry was dried using an AC spray drying tower at a hot air temperature of 380 ° C. to a water content of 5% to obtain a spray-dried product.

 Next, a nonionic surfactant and water were introduced into the above-mentioned dried product into a continuous kneader (KRC Kneader # 2, manufactured by Kurimoto Tetsusho Co., Ltd.) to obtain a dense and uniform kneaded product. This kneaded product was made into a cylindrical pellet by passing through a perforated plate provided at the outlet of the cylinder.

 The pellets are introduced into a crusher [Speed Mill ND-10 Type Okada Seie Co., Ltd.] together with the cooling air and pulverized. Thus, a detergent composition having the composition shown in Table 5 was obtained.

Table 5 also shows the results of examining the detergency of these detergent compositions. 8 Table 5

Examples 9 and 10, Comparative Examples 5 and 6

A cleaning composition having the composition shown in Table 6 was prepared in the same manner as in Example 7. Table 6 shows the detergency of these detergent compositions. 9 Table 6

なお、 表 5 , 表 6のゼオライ トとしては、 N a— A型ゼォライ トを用 いた。 産業上の利用可能性

As the zeolite in Tables 5 and 6, Na-A type zeolite was used. Industrial applicability

The water-containing layered gay acid salt of the present invention has a high cation exchange capacity and an exchange rate, and has favorable properties as a water softener. Therefore, it can be suitably used as a water softener, a water treatment agent, a cleaning agent, and the like. Also this The detergent composition containing the compound shows superior detergency than the composition containing the conventional calcium ion trapping builder.

Claims

The scope of the claims 1. Composition formula (IVPx _{Ha, N a ix / ") 2} S i y 0 2y + i · z H 2 0 (Where M ¹ is at least one metal selected from lithium, potassium and alkaline earth metals, n is the valency of M ¹ , and X, y and z are numbers in the following range: 0 ≤ x ≤ 0.5, S ≤ y ≤ l. 5, 1 ≤ z ≤ 20), and ²³ Na-spin-grating relaxation time measured by solid-state nuclear magnetic resonance is 0 A water-containing layered gayate having a duration of 35 seconds or less. 2. The water-containing layered gayate according to claim ¹ , wherein M ¹ in the composition formula is at least one metal selected from lithium, potassium, magnesium, and calcium.  3. Composition formula M ² _{2 / m} S i _y 〇 _{2y + 1z} 'H ₂ 0 (Where M ² is at least one metal selected from lithium, sodium, potassium and alkaline earth metals, m is the valence of M ² , and y and z ′ are in the following ranges: is a number. 3≤y≤ 7. 5, 0≤ z ' ≤ 20) by acid treatment layered Gay salt material represented by, after reducing the portion of the metal M ² therein, Natoriumu compound Alternatively, the composition is characterized by being treated with an aqueous solution containing a sodium compound and at least one compound selected from the group consisting of lithium, lithium and alkaline earth metals. (M ¹ _{x /} „. N a! -X / n) ₂ S i y0 _{2y +} 1z H ₂ 0 (Wherein M ¹ is at least one metal selected from lithium, lithium and alkaline earth metals, n is the valence of M ¹ , and y has the same meaning as above. , X, z are numbers in the range: 0≤x≤0.5, 1≤ z≤20) And a spin-layer relaxation time measured by ²³ N-solid-state nuclear magnetic resonance of 0.35 seconds or less. 4. Claim 3 wherein the acid treatment is performed using an aqueous acid solution having a pH of 6 or less. The method for producing a water-containing layered gay acid salt of the above. 5. method of producing a layer Gay salt water layered Gay salt ranging third claim of claims content of M ² in the feed to the acid treatment to less than half.  6. A water softener comprising the water-containing layered gayate according to claim 1. 7. A cleaning composition comprising the water softener according to claim 6.