JP2013163639A - Bentonite powder and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide bentonite powder which retains whiteness immediately after pulverization treatment over a relatively long period of time, so that it is made unnecessary for both producer and purchaser sides to take special measures in consideration of deterioration of whiteness over time; and a method for producing the same.SOLUTION: This bentonite powder contains only a specified quantity of a chlorine-containing inorganic salt represented by formula: M(ClO)in natural dioctahedral type smectite-based clay powder or clay powder obtained by alkali treatment of the clay, where in formula, M is a metal atom selected from the group consisting of Na, K, Mg, Ca, Ba and Al; p is a natural number of 1 to 3 showing the valence of the metal atom M; and q is 0 or a natural number of 1 to 4 showing the number of oxygen atom O constituting ionic formula of a chloride ion or a chlorate ion.

Description

  The present invention relates to a bentonite powder obtained by pulverizing natural dioctahedral smectite clay, or active bentonite obtained by alkali treatment of the clay, and a method for producing the same.

  Conventionally known is a bentonite powder obtained by pulverizing natural dioctahedral smectite clay or active bentonite obtained by alkali treatment of the clay. This kind of bentonite powder has various useful properties such as water swellability, solidification property, etc., and also has a degree of whiteness that does not impair the whiteness of the mixed product. In recent years, it has been in the limelight in applications that emphasize whiteness, such as softeners for paper and paper additives.

  There has been an attempt to improve the properties of this type of bentonite in accordance with the corresponding product (for example, see Patent Document 1).

JP 2008-290923 A

  However, it has been found that such a conventional bentonite powder exhibits a pale whiteness preferred by consumers immediately after the pulverization for pulverization, but yellowing proceeds with time. .

  FIG. 7 shows the change in color tone of such bentonite powder over time. In addition, the bentonite powder used in the example of the same figure is the conventional bentonite powder obtained by the comparative example 1 mentioned later.

In FIG. 7, the color tone is evaluated based on the Lab color model which is one of the standards used for the color tone evaluation. The Lab color model is evaluated with the following three values.
L value: Value representing brightness, transition in the range of 0 (black) to 100 (white) a value: Value representing the color component, transition in the range of -128 (green) to +127 (red) b value: Color component A value that represents, transitions from -128 (blue) to +127 (yellow)

  According to FIG. 7, it can be seen that the b value, which was 4.3 at the start of storage, increases with the passage of time to 6.5 after one month and 7.9 after two months. Thus, by increasing the b value, yellowing progresses to a level that impairs the consumer's appearance in a relatively early stage (for example, at the time when 2 to 3 months have elapsed since powdering). There is a problem that the commercial value is remarkably lowered depending on the use in which the emphasis is placed on the property.

  As a solution to such a problem, it is conceivable that the pulverization process for powdering should be performed as soon as possible, but if such measures are adopted, the shipment will be related to customer needs. In addition to the complexity of the process management leading to the process, yellowing progresses after delivery to the customer, which necessitates the recommendation of the customer to use it immediately after purchase, and this has not been the fundamental solution. .

  This invention has been made by paying attention to the above-mentioned problems in conventional bentonite powder, and its purpose is to maintain the whiteness immediately after the powdering treatment for a relatively long period of time, Accordingly, it is an object of the present invention to provide a bentonite powder and a method for manufacturing the bentonite powder that can eliminate the necessity of taking special measures in consideration of the temporal deterioration of whiteness on both the manufacturer side and the purchaser side.

  Other objects and operational effects of the present invention will be easily understood by those skilled in the art by referring to the following description.

It is considered that the above-described problems can be solved by bentonite powder having the following configuration and a manufacturing method thereof.
That is, the bentonite powder of the present invention is a dioctahedral smectite-based clay powder that is alkali-treated as necessary, and contains a predetermined amount of a chlorine-containing inorganic salt represented by the following formula.
M ^{p +} (ClO _q ⁻ ) _p (formula)
(In the formula, M is a metal atom selected from the group of Na, K, Mg, Ca, Ba, and Al, p is a natural number of 1 to 3 in terms of the valence of the metal atom M, and q is The number of oxygen atoms O constituting the ionic formula of chloride ion or chlorate ion is 0 or a natural number of 1 to 4.)

  Here, the bentonite powder referred to in the present invention is a material obtained by activating natural dioctahedral smectite clay by alkali treatment, or originally using an alkali-rich natural dioctahedral smectite clay as a raw material. Any of those produced by pulverization may be used, but it is desirable to have performance that can be an industrially useful bentonite product, that is, a swelling power of 15 ml / 2 g or more and a methylene blue adsorption amount of 30 mmol / 100 g or more.

  The chlorine-containing inorganic salt is a metal chloride or chlorate selected from the group of Na, K, Mg, Ca, Ba, and Al, and naturally includes hydrates thereof.

  And according to such bentonite powder, the whiteness immediately after the pulverization treatment is maintained for a relatively long period of time by using the chlorine-containing inorganic salt, whereby the manufacturer side and the purchaser side In both cases, it is not necessary to take special measures in consideration of deterioration of whiteness over time.

  In a preferred embodiment of the present application, a hydroxycarboxylic acid or a salt thereof may further be contained in a predetermined amount.

  According to such a configuration, in addition to the discoloration suppressing effect by the chlorine-containing inorganic salt, the discoloration suppressing effect by the hydroxycarboxylic acid is also obtained, so that the discoloration with time is further suppressed. In the following description, hydroxycarboxylic acid and hydroxycarboxylate may be simply referred to as hydroxycarboxylic acid.

  In a preferred embodiment of the present application, the water content at the time of factory shipment may be 5% by weight or less. By setting the moisture content at the time of shipment from the factory to 5% by weight or less, even when the moisture content of the bentonite powder changes after shipment, discoloration over time is further suppressed until the time when the bentonite powder is used. It becomes easy.

  In a preferred embodiment of the present application, the content of the chlorine-containing inorganic salt may be 0.02 parts by weight to 2 parts by weight with respect to 100 parts by weight of clay (in terms of dry matter).

  According to such a configuration, since the blending amount of the chlorine-containing inorganic salt is in an optimum range, the discoloration suppressing effect by the chlorine-containing inorganic salt can be appropriately obtained.

  In a preferred embodiment of the present application, the content of hydroxycarboxylic acid or a salt thereof may be 0.5 to 5 parts by weight with respect to 100 parts by weight of clay (in terms of dry matter).

  According to such a structure, since the compounding quantity of hydroxycarboxylic acid or its salt is the optimal range, the discoloration suppression effect by these is obtained appropriately.

  In a preferred embodiment of the present application, the chlorine-containing inorganic salt may be aluminum chloride or sodium chloride.

  According to such a configuration, the use of aluminum chloride or sodium chloride as the chlorine-containing inorganic salt makes it possible to obtain a remarkable effect of suppressing discoloration due to the chlorine-containing inorganic salt.

  In a preferred embodiment of the present application, the hydroxycarboxylic acid or salt thereof may be tartaric acid, citric acid, malic acid, or a salt thereof.

  Here, tartaric acid, citric acid, malic acid, or salts thereof are hydroxycarboxylic acids such as tartaric acid, citric acid, malic acid, or alkali metal salts thereof, and hydrates thereof are also included.

  According to such a configuration, the use of hydroxycarboxylic acid such as tartaric acid, citric acid, malic acid, or each alkali metal salt as the hydroxycarboxylic acid or salt thereof, suppresses discoloration due to hydroxycarboxylic acid or salt thereof. The effect is remarkably obtained.

  Another embodiment of the bentonite powder of the present application is a smectite-based clay powder that has been subjected to alkali treatment and is characterized by containing a predetermined amount of hydroxycarboxylic acid or a salt thereof.

  According to such a configuration, since the hydroxycarboxylic acid or a salt thereof is contained, discoloration with time is suppressed even if the chlorine-containing inorganic salt is not contained.

  In another embodiment of the bentonite powder of the present application, the volume average particle diameter d (50) may be 3 to 20 μm.

  According to such a configuration, bentonite powder having an appropriate particle size that can be easily used for various applications can be obtained.

  Moreover, as other embodiment of the bentonite powder of this application, b value may be 6 or less when 30 days passed after shipment.

  According to such a configuration, the degree of discoloration of the bentonite powder is grasped numerically, so that the discoloration state can be clearly determined.

  In another embodiment of the bentonite powder of the present application, iron may be contained in an amount of 0.5 to 5 parts by weight in terms of oxide.

  According to such a configuration, even when clay having a high iron content and easily yellowing is used as a raw material, a yellowing suppressing effect can be reliably obtained.

  Moreover, the bentonite powder of this application may be used for uses, such as a papermaking additive and a fiber softening agent.

  According to such a configuration, the excellent effect of bentonite powder can be obtained, and the whiteness of each product is not impaired, so it is suitable for applications that emphasize whiteness such as laundry softeners and papermaking additives. It is.

Next, the bentonite powder manufacturing method of the present application includes a first step of incorporating alkali ions between the basic layers of the clay by adding an alkaline compound to the dioctahedral smectite clay as a raw material and kneading. A second step of uniformly dispersing the inorganic salt in the clay by adding a predetermined amount of a chlorine-containing inorganic salt represented by the following formula to the clay having undergone the step 1 and kneading; A third step of producing the fine powder of the clay by drying and then pulverizing and classifying the clay.
M ^{p +} (ClO _q ⁻ ) _p (formula)
(In the formula, M is a metal atom selected from the group of Na, K, Mg, Ca, Ba, and Al, p is a natural number of 1 to 3 in terms of the valence of the metal atom M, and q is The number of oxygen atoms O constituting the ionic formula of chloride ion or chlorate ion is 0 or a natural number of 1 to 4.)

  Here, as the “alkaline compound”, for example, alkali hydroxide or alkali carbonate is used. The alkali species is not particularly limited, and may be any of lithium, potassium, sodium and the like, and it is of course possible to use alkali hydroxide and alkali carbonate in combination.

  And according to such a structure, since an alkali ion is taken in between the basic layers of clay in a 1st step, the swelling property of a bentonite powder can be improved. In addition, by using the chlorine-containing inorganic salt, the whiteness immediately after the pulverization treatment is maintained for a relatively long period of time, and thereby the whiteness is deteriorated with time on both the manufacturer side and the purchaser side. This makes it possible to obtain bentonite powder that does not require any special measures.

  In a preferred embodiment of the present application, the second step may further include a step of containing a predetermined amount of hydroxycarboxylic acid or a salt thereof.

  According to such a configuration, in addition to the discoloration suppressing effect by the chlorine-containing inorganic salt, the discoloration suppressing effect by the hydroxycarboxylic acid is also obtained, so that the discoloration with time is further suppressed.

  In a preferred embodiment of the present application, in the third step, the water content of the fine powder at the end of drying may be 5 parts by weight or less.

  According to such a configuration, the moisture content at the end of drying is reduced, so that even when the moisture content of the bentonite powder changes after drying, until the time when the bentonite powder is used. The water content is easily maintained within a preferable range, and the discoloration of the bentonite powder over time is more easily suppressed.

  In a preferred embodiment of the present application, in the second step, the addition amount of the chlorine-containing inorganic salt may be 0.02 to 2 parts by weight with respect to 100 parts by weight of clay (in terms of dry matter). .

  According to such a configuration, since the blending amount of the chlorine-containing inorganic salt is in an optimal range, the discoloration suppressing effect by the chlorine-containing inorganic salt can be appropriately obtained.

  According to the bentonite powder of the present invention, by using the chlorine-containing inorganic salt, the whiteness immediately after the pulverization treatment is maintained for a relatively long period of time, whereby both the manufacturer side and the purchaser side can be maintained. Therefore, it is not necessary to take special measures in consideration of deterioration of whiteness over time.

  Further, according to the method for producing bentonite powder of the present invention, sodium ions are taken in between the basic layers of clay in the first step, so that the swelling property of the bentonite powder can be improved. In addition, by using the chlorine-containing inorganic salt, the whiteness immediately after the pulverization treatment is maintained for a relatively long period of time, and thereby the whiteness is deteriorated with time on both the manufacturer side and the purchaser side. This makes it possible to obtain bentonite powder that does not require any special measures.

It is a graph which shows the yellowing change inhibitory effect by each physical property of the bentonite powder obtained by the Example and the comparative example, and a chlorine containing inorganic salt. It is a graph which shows the yellowing change inhibitory effect by the difference in the addition amount of the chlorine containing inorganic salt of the bentonite powder obtained in the Example and the comparative example. It is a graph which shows the yellowing suppression effect by the difference in the moisture content of the bentonite powder which added NaCl. It is a graph which shows the yellowing change inhibitory effect by each physical property and hydroxycarboxylic acid of the bentonite powder obtained by the Example and the comparative example. It is a table | surface which shows each physical property and the yellowing change inhibitory effect of a bentonite powder at the time of not performing an alkali activation process. It is a graph which shows the chemical composition of the bentonite powder obtained in the Example and the comparative example. It is a figure which shows the time-dependent change of b value of the bentonite powder by the comparative example 1. 4 is a diagram showing an X-ray diffraction pattern of bentonite powder according to Comparative Example 1. FIG.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following descriptions.

<Dioctahedral smectite clay>
As described above, the bentonite powder of the present invention is obtained by adding a predetermined amount of a chlorine-containing inorganic salt to dioctahedral smectite clay. In addition, the bentonite referred to here is one obtained by activating natural dioctahedral smectite clay by alkali treatment, or by drying and pulverizing the original alkali-rich natural dioctahedral smectite clay as it is. Any of them may be used, but it is desirable to have an industrially useful bentonite product, that is, a swelling power of 15 ml / 2 g or more and a methylene blue adsorption amount of 30 mmol / 100 g or more.

Dioctahedral smectite in the present invention is a natural dioctahedral smectite main component clay mineral clay used as a raw material consists SiO ₄ tetrahedral layers -AlO ₆ octahedral layer -SiO ₄ tetrahedra layer, and these tetrahedral The basic structure (unit layer) is a three-layer structure in which the layer and the octahedral layer are partially replaced with the same type of metal from different types. Between the laminated layers (= basic layers) having such a three-layer structure, there are cations such as Ca, Mg, K, Na, hydrogen ions, and water molecules coordinated with them. In addition, a part of Al in the octahedral layer of the basic trilayer structure is replaced with Mg or Fe ^(II) , and a part of Si in the tetrahedral layer is replaced with Al, so the crystal lattice is negative. The negative charge is neutralized by metal cations and hydrogen ions existing between the basic layers.

  This type of smectite clay includes bentonite, subbentonite, fuller's earth, acid clay, etc., and exhibits different characteristics depending on the type and amount of metal cations present between the basic layers, the amount of hydrogen ions, and the like.

  For example, in bentonite, the amount of Na ions existing between the basic layers is large, and therefore, the pH of the dispersion suspended and dispersed in water is high (generally 9.5 or more), and the swelling is high in water. In addition, it exhibits a property of gelling and solidifying. That is, when water enters between the laminated layers of the above unit layers and spreads the layers so as to surround Na ions, so-called swelling occurs, and when more water is supplied, the unit layers eventually become disjointed colloidal shapes. Disperses and becomes fluidized. If this is left as it is, a card-house structure is formed by suction repulsion between the unit layers, and it becomes a gelled gel (lump).

  On the other hand, in sub-bentonite, fuller's earth, and acid clay, the amount of Na ions existing between the basic layers is small, and Ca ions, Mg ions, and hydrogen ions are larger, so the pH when dispersed in water is Lower than bentonite (generally 4.5 to 9.5). Moreover, although high water absorption is shown, swellability is very low and it does not lead to solidification by gelation.

  In the present invention, the dioctahedral smectite clay used as a raw material may be a raw material for bentonite as long as it is a so-called Na-bentonite rich in Na ions present between the basic layers at the time of natural production.

  On the other hand, even if so-called subbentonite, fuller's earth, or acid clay with a small amount of Na ions existing between the basic layers and a large amount of Ca ions, Mg ions, and even hydrogen ions, treatment with alkali hydroxide or alkali carbonate is performed. It can be used as a raw material for bentonite by introducing an alkali prior to the addition of the chlorine-containing inorganic salt. In other words, sub-bentonite, fuller's earth, and acid clay are less swellable with respect to water than bentonite, but by introducing alkali between the layers, they exhibit properties specific to bentonite. It can also be used as a starting material.

  In general, natural dioctahedral smectite clay used as a raw material varies in the content of impurities such as opal, cristobalite, quartz, feldspar, etc. depending on the production area, etc. The composition in terms of physical properties is as follows.

Composition of raw material dioctahedral smectite clay SiO ₂ : 60-80% by weight
Al ₂ O ₃ : 10 to 30% by weight
Fe ₂ O ₃ : 1.0 to 10.0% by weight
Na ₂ O: 0.1 to 4.0% by weight
K ₂ O: 0.1 to 3.0% by weight
MgO: 1.0 to 8.0% by weight
CaO: 0.5 to 5.0% by weight
Loss on ignition (1000 ° C.): 3 to 12% by weight

  In addition, since the dioctahedral smectite clay used as a raw material in the present invention has the property of absorbing water between the basic layers described above and spreading the basic layers, the relative humidity is 75% after drying at 150 ° C. for 2 hours, for example. When X-ray diffraction measurement (Cu-kα) is carried out after holding for 48 hours, a [001] plane diffraction peak is shown in the region of 2θ = 5.0 to 7.5 degrees. In general, bentonite has a large amount of Na, easily absorbs water, and easily obtains an extended interlayer with a certain interval. The peak area showing a diffraction peak on the [001] plane is large, and small in acid clay.

  As an example, an X-ray diffraction pattern by a conventional bentonite powder is shown in FIG. In the figure, the horizontal axis represents the diffraction angle (2θ), and the vertical axis represents the X-ray intensity. It is also clear from this figure that the bentonite powder has a large peak area showing a diffraction peak on the [001] plane. In addition, the bentonite powder used for the measurement of FIG. 8 is the bentonite powder which has the conventional structure obtained by the comparative example 1 mentioned later.

  In the present application, the alkali species of alkali hydroxide or alkali carbonate used for the alkali activation treatment is not particularly limited, and may be any of lithium, potassium, sodium, etc., but from the viewpoint of cost and the like, sodium is usually used and is preferable. For this, an aqueous sodium hydroxide solution or solid sodium carbonate is used. Of course, it is also possible to use alkali hydroxide and alkali carbonate in combination. Here, when sodium is used as the alkali species, the swellability of bentonite is improved, and as a result, a bentonite powder having high dispersibility is obtained. For this reason, when applying to uses that require high dispersibility such as a laundry softener, it is preferable to use an alkali hydroxide or alkali carbonate containing sodium such as sodium hydroxide or sodium carbonate.

  In addition, when the product containing the bentonite powder of the present application is used in combination with a product containing a surfactant such as a detergent, the alkali species used for the alkali activation treatment is a monovalent that does not inhibit the function of the surfactant. It is desirable to use an alkali hydroxide or an alkali carbonate containing the above alkali species.

  In addition, the alkali activation treatment in the present invention comprises a raw material dioctahedral smectite clay and alkali hydroxide or alkali carbonate, a uniaxial or biaxial extrusion kneader, a roll kneader, a Banbury mixer, a clay kneader, It can be carried out by kneading using a concrete mixer, a disk pelleter or the like. Here, when alkali treatment is performed using solid sodium carbonate, an appropriate amount of moisture is supplied, and kneading is performed by appropriately absorbing the raw material clay in order to quickly introduce alkali between the layers. Preferably, in order to perform the alkali treatment uniformly, it is preferable that the raw material dioctahedral smectite clay is finely divided.

  After the alkali activation treatment as described above, a chlorine-containing inorganic salt is added, kneaded, dried and pulverized, and classified as necessary to obtain the target bentonite powder of the present invention.

<About manufacturing process of bentonite powder>
Next, an example of a manufacturing process for bentonite powder according to the present application will be described. As described above, the bentonite powder of the present application is made from natural bentonite, acid clay, or the like.

  First, these raw earth blocks (blocks) mined are crushed using a flat roll crusher, etc., and after adjusting the water content to 30-40% as appropriate, the screw extruder is used to obtain 8-12 mmφ granular materials and Eggplant.

  Next, a predetermined amount of alkali hydroxide or alkali carbonate is added as necessary, and the mixture is thoroughly kneaded through a screw-type kneading extruder and subjected to alkali activation treatment to obtain 3 to 7 mmφ columnar granules. By performing the alkali activation treatment, the swelling property of the dioctahedral smectite clay is increased, and a more excellent effect as bentonite can be obtained.

  Following the alkali activation treatment, a kneading treatment is performed by adding a chlorine-containing inorganic salt and / or hydroxycarboxylic acid as a yellowing inhibitor. At this time, these yellowing inhibitors may be added in the form of a solid such as a powder, or may be added as an aqueous solution dispersed or dissolved in water. However, if the amount of water added is too large, there is a risk that granulation or molding becomes difficult. Therefore, when the inhibitor is added as an aqueous solution, the amount of water used is dioctahedral smectite clay 100. It is desirable to be within 5 parts by weight with respect to parts by weight.

  After kneading and granulating, the process proceeds to a drying process. The drying process is performed, for example, in a co-current rotary drying furnace (rotary kiln) so that the outlet exhaust temperature is 100 to 200 ° C., and the dried granular material is finished to have a desired moisture content.

  After the drying process, the powder is pulverized and classified as necessary, and the powder having an average particle size of about 3 to 20 μm is packaged and shipped after quality inspection. If the moisture content is 5% or less at the time of shipment, the change with time of the b value is further suppressed, and if it is about 1 to 3%, it is more desirable.

  The following examples illustrate the invention in detail. In addition, the measurement of the physical-property value in each Example and a comparative example was performed with the following method.

(1) Hue Measurement Using a color meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd., a powder sample is filled about half in a 35 mm glass cell, tapped 20 times, and then the L value in the Lab color system, a Value and b value are measured. The L value, a value, and b value in the Lab color system indicate the following values, respectively.
L value: Value representing brightness, transition in the range of 0 (black) to 100 (white) a value: Value representing the color component, transition in the range of -128 (green) to +127 (red) b value: Color component In this example, particular attention was paid to the yellow change among the hue changes, and the b value was used as the yellow change degree that is a measure of the yellow change.

(2) Measurement of chemical composition The content of each component was measured using a fluorescent X-ray diffractometer ZSX-Primus-II manufactured by Rigaku Corporation. All metal atoms were converted to oxides and expressed as the content (%) of each component when the total composition was 100%.

(3) Measurement of powder X-ray diffraction Using an X-ray diffractometer (manufactured by Rigaku Corporation, MultiFlex, Cu-Kα), measurement was performed under the following conditions.
Tube voltage: 40 kV, tube current: 30 mA, divergence slit: 0.15 mm,
Scattering slit: 1 °, light receiving slit: 0.3 mm

(4) Measurement of degree of swelling (ACC method) Add 2 g of the sample to a 100 ml graduated cylinder with 100 ml of ion-exchange water so that it hardly adheres to the inner wall. The sample was added in about 10 times. After the addition of the sample, the measuring cylinder was capped and allowed to stand for 24 hours, and the apparent volume of the sample deposited in the container was read. The unit of swelling is expressed as (ml / 2g).

(5) Measurement of adsorption amount of methylene blue (MB) It was measured according to “(3) Adsorption amount of methylene blue” described in P456 of Clay Handbook (3rd edition, edited by Japan Clay Society). Specifically, it is as follows.
The bentonite powder is dried to a constant weight at 105 ° C. and allowed to cool in a desiccator. Weigh 0.500 g of dry bentonite and add to a conical beaker (200 ml) containing 50 ml of 2% sodium pyrophosphate solution. The bentonite is dispersed by treatment with an ultrasonic disperser (frequency: 20 to 30 kHz, output: 100 to 150 W) for 10 minutes. If there is no ultrasonic disperser, cover with a watch glass and boil gently for 10 minutes to disperse, then cool to room temperature. Next, titrate with a 0.01M methylene blue solution (3.74 g of reagent-grade methylene blue trihydrate is dissolved in water to 1 L).
Add about 80% of the expected consumption of methylene blue solution and stir for 30 seconds using a stirrer. One drop is dropped on a filter paper (Qualitative No. 2 or No. 131) using a comagome pipette. If no blue halo from the methylene blue solution appears on the outside of the bentonite dyed dark blue with methylene blue, add another 1 ml of methylene blue solution and stir for 30 seconds, take one drop of the solution and place it on the filter paper. Repeat this operation until a light blue halo appears. If a light blue halo appears after stirring for 30 seconds, stir for an additional 2 minutes and again take a drop of liquid and place on the filter paper. If the blue halo disappears, add 1 ml of methylene blue solution and repeat the same procedure. If a halo with a width of 1.5 to 2.0 mm that does not disappear even after stirring for 2 minutes appears, it is the end point of the titration. If the consumption amount of 0.01 M methylene blue solution (ml / 0.5 g) is doubled, the methylene blue adsorption amount (mmol / 100 g) is obtained.

(6) Measurement of average particle diameter Using a master sizer 2000 manufactured by Malvern, a powder sample was dispersed in pure water, the average particle diameter was measured, and the 50% volume average diameter (μm) was determined to obtain the average particle diameter. It was.

(7) Measurement of pH Based on JIS K5101-17-2: 04, the sample was suspended in pure water at a concentration of 2% and measured.

(8) Measurement of moisture About 1 g of a sample was weighed in a weighing bottle with a diameter of 40 mm, dried in an oven set at 110 ° C. for 2 hours, then transferred to a desiccator, allowed to cool, and again weighed. Moisture (%) was determined from the change in weight before and after drying.

<Verification of chlorine-containing inorganic salts>
The inventors of the present application verified the chlorine-containing inorganic salt used in the present application by Examples 1 to 7 and Comparative Example 1 using seven types of chlorine-containing inorganic salts.

[Examples 1-7]
<First step>
As the dioctahedral smectite clay, 20 kg of raw clay (hydrous material) from the Koto N-1 district, Shibata City, Niigata Prefecture was used, and this dioctahedral smectite clay was fitted with a granulating plate having a 10 mm wide corrugated hole. after extrusion by screw single screw extruder, sprinkle Na ₂ CO ₃ (Wako pure Chemical) powder as Na ₂ CO ₃ minutes is 3.0% of the total conversion 0.99 ° C. drying was mixed with a spoon The mixture was extruded twice with a screw type single screw extruder (5 mmφ circular hole-granulation plate mounted), kneaded and granulated to prepare an intermediate raw material (A-1) before adding a yellowing inhibitor.

<Second step>
In a 100 ml beaker, weigh 0.5 g of each chlorine-containing inorganic salt (anhydrous equivalent) as a yellowing inhibitor, add pure water to 30 g, and stir with a magnetic stirrer to completely remove the chlorine-containing inorganic salt. Each chlorine-containing inorganic salt aqueous solution was prepared. In addition, the chlorine containing inorganic salt used in Examples 1-7 is as follows, respectively.
Example 1: CaCl ₂ (Wako Pure Chemicals reagent special grade)
Example 2: MgCl ₂ (special grade reagent manufactured by Wako Pure Chemical Industries)
Example 3: NaCl (special grade reagent manufactured by Wako Pure Chemical Industries)
Example 4: KCl (special grade reagent manufactured by Wako Pure Chemical Industries)
Example 5: BaCl ₂ (special grade reagent manufactured by Wako Pure Chemical Industries)
Example 6: AlCl ₃ (special grade reagent manufactured by Wako Pure Chemical Industries)
Example 7: NaClO ₄ (special grade reagent manufactured by Wako Pure Chemical Industries)
The intermediate raw material (A-1) obtained in the first step is weighed to 1 kg in terms of 150 ° C. dry matter, spread into a stainless steel container to a thickness of about 2 cm, and separately prepared. Sprinkle the entire amount of each chlorine-containing inorganic salt aqueous solution and mix well with a spoon, then extrude three times with a screw type single screw extruder (5mmφ circular hole-equipped with granulation plate), knead and granulate, I got a thing.

<Third step>
After drying the water-containing granular material obtained in the second step in an oven at 170 ° C. for 2 hours, about 50 g of the dried granular material (X-1) is pulverized with a table mill (IKA pulverizer Allbasic), The bentonite powder of the present invention was obtained by passing through a 200-mesh sieve. The powders obtained in Examples 1 to 7 were stored in a polyethylene bag with a chuck made of polyethylene (PE) (powder storage).

[Comparative Example 1]
For the intermediate raw material (A-1), a bentonite powder according to the prior art was obtained by performing the same operation as in the third step without adding a chlorine-containing inorganic salt as a yellowing inhibitor. The obtained powder was stored in a polyethylene bag with a chuck made of polyethylene (PE).

  For the powder samples obtained in Examples 1 to 7 and Comparative Example 1 described above, the hue after starting (0 day), 15 days, 30 days, and 60 days was measured, and the b value was shown as the degree of yellowing change. It was shown in 1. Further, as other general properties, the water content, pH, average particle size, MB adsorption amount, and swelling degree are also shown in FIG.

  Further, the dried granular material (X-1) obtained in the third step was stored as an unpulverized granular material in a polyethylene bag with a polyethylene (PE) zipper (preservation of granular material). Also about this granular material preservation | save sample, it grind | pulverizes and sieving on the same conditions as the above after 15th, 30th, 45th, and 60th, and a hue is measured like a powder preservation sample about the obtained powder sample, The b value is shown in FIG. 1 as the yellowing degree.

As is clear from the results in FIG. 1, in Examples 1 to 6 except Example 7 to which sodium perchlorate (NaClO ₄ ) was added, the sample was stored in either powder storage or granular storage. Even when compared with Comparative Example 1 in which the chlorine-containing inorganic salt was not added, both the value at the start of storage and the value over time for the following two months had a low b value, which depended on time. It can be seen that there is little yellowing.

  In addition, it can be seen that the powder storage sample and the granular material storage sample to which the same chlorine-containing inorganic salt is added have a smaller increase in b value over time in the granular material storage sample.

The sample of Example 7 to which sodium perchlorate (NaClO ₄ ) was added had a slightly larger b value than the sample of Comparative Example 1 to which no chlorine-containing inorganic salt was added at the start of storage. However, the increase in b value over time for the subsequent two months is slight, and it is clear that yellowing can be effectively suppressed as compared with the increase in b value in Comparative Example 1.

  As described above, with the addition of chlorine-containing inorganic salt, there is a slight difference depending on the type of the chlorine-containing inorganic salt, but in any case, the effect of suppressing yellowing during the storage period of bentonite powder is recognized. It was. In particular, in the bentonite powder of Comparative Example 1 to which no chlorine-containing inorganic salt is added, the degree of yellowing varies depending on the storage form, and powder storage tends to cause yellowing more easily in powder storage and granular storage. Was recognized.

  In the chlorine-containing inorganic salts used in Examples 1 to 7, it is clear that aluminum chloride (Example 6) has the most excellent yellowing-inhibiting effect when attention is paid to the effect of inhibiting yellowing. In the case of use in fields where high swelling and cation exchange properties are expected (for example, softening agents for clothing, etc.), 2- to 3-valent polyvalent metal ions (magnesium, calcium, barium) , Each ion of aluminum), especially aluminum ions in large amounts may deteriorate their properties, so it is preferable to add only a small amount or use sodium chloride or sodium chlorate.

  Next, the yellowing change effect due to the difference in the amount of chlorine-containing inorganic salt added is verified in Examples 8 to 10 and Comparative Example 2.

[Examples 8 to 10]
<First step>
As the dioctahedral smectite clay, yellowing suppressant is carried out in the same manner as in the first step of Examples 1 to 7 except that 20 kg of raw clay (hydrated material) from Odo N-2 district, Shibata City, Niigata Prefecture is used. The intermediate raw material (A-2) before addition was prepared.

<Second step>
As shown in FIG. 2, the same procedure as in the second step of Examples 1 to 7 was performed except that sodium hypochlorite was used as a yellowing inhibitor and the amount of sodium hypochlorite added was changed. Thus, a water-containing granular material was obtained. In addition, the addition amount of sodium hypochlorite used in Examples 8 to 10 is as follows.
Example 8: 0.05 part by weight of sodium hypochlorite Example 9: 0.1 part by weight of sodium hypochlorite Example 10: 0.2 part by weight of sodium hypochlorite

<Third step>
It implemented similarly to the 3rd step of the said Examples 1-7, and obtained the bentonite powder of this invention.

[Comparative Example 2]
The intermediate raw material (A-2) is bentonite powder according to the prior art by performing the same operation as the third step without adding a chlorine-containing inorganic salt (sodium hypochlorite) as a yellowing inhibitor. Got.

  Half of each bentonite powder obtained in Examples 8 to 10 and Comparative Example 2 was stored in a polyethylene bag with polyethylene (PE) and a sealed glass container. About these powder samples, the hue after the start (0 day), 30 days, and 60 days passed was measured, and the b value is shown in FIG.

  As is clear from the results of FIG. 2, the powder samples obtained in Examples 8 to 10 contain the sample at the start of storage regardless of whether the storage form is plastic bag storage or glass container storage. The b value is about the same or slightly larger than that of Comparative Example 2 in which no chlorine inorganic salt was added. However, the increase in the b value of the samples obtained in Examples 8 to 10 over the subsequent two months was negligible, and after 60 days, any sample was obtained in Comparative Example 2. The b value is smaller than the obtained sample.

  In addition, the addition amount was changed between three stages of addition of 0.05 parts by weight (Example 8), 0.1 parts by weight (Example 9), and 0.2 parts by weight (Example 10). The sample with a smaller amount can effectively suppress yellowing. Regarding the difference in the degree of yellowing change depending on the storage form, it was found that the plastic bag storage and the glass container storage tended to cause yellowing more easily in the plastic bag storage.

<Verification of water content>
Next, a change in hue due to a difference in moisture content is verified in Reference Examples 1 and 2.

[Reference Experiment] Reference Examples 1-2
In the third step of Example 3, the water-containing granular material before drying obtained in the second step is divided into two containers and placed in a 60 ° C. constant temperature dryer, and the water content is about 7% (Reference Example 1). ) And about 2% (Experimental Example 2), and thereafter, the same procedure as in Example 3 was performed to obtain bentonite powder.

  Regarding the hue change of these two samples over time, the L value, a value, and b value in the Lab color system were measured and are shown in FIG. In the figure, with respect to bentonite powder in which sodium chloride (NaCl) was added to suppress yellowing, Reference Example 1 in which the moisture after drying was adjusted to about 7% and Reference Example adjusted to about 2% 2 shows the hue change during the storage period of the two types of powder samples. From the results of FIG. 3, it can be seen that Reference Example 1 having a higher water content has a larger b value at the start of storage, and further, the increase in the b value with the passage of time for the next two months is also large.

  As described above, the difference in yellowing due to the difference in storage form (powder storage, granular storage) in Examples 1 to 10 and Comparative Examples 1 and 2, and the difference in yellowing due to the moisture content in Reference Examples 1 and 2 From this, it is inferred that yellowing is likely to occur when the surface of the bentonite powder or particles is more easily contacted with the atmosphere, in other words, more easily affected by oxygen and moisture in the air. Components contained in naturally-occurring bentonite that may turn yellow due to long-term contact with air include divalent iron (Fe) atoms in the smectite structure and impurities. Phenolic substances such as humic acid derived from humus are considered. A part of the divalent Fe atom is oxidized by oxygen to a trivalent Fe atom having a yellow to reddish brown color, and a phenolic substance is also a substance having a phenoxide or quinoid structure in which a part of the same is also yellow to reddish brown. It is oxidized to. It is speculated that oxidation is promoted particularly in the presence of a certain amount of moisture, but the correct mechanism is not clear. In addition, it has been found that the yellowing suppression effect according to the present invention appears more prominently when a clay containing 0.5 to 5 parts by weight of iron in terms of oxide is used as a raw material.

<Verification of hydroxycarboxylic acid or its salt>
Subsequently, about the discoloration inhibitory effect by hydroxycarboxylic acid, Example 11-13 and the comparative example 3 verify.

[Examples 11 to 13]
<First step>
Suppressing yellowing by carrying out in the same manner as in the first step of Examples 1 to 7, except that 20 kg of raw clay (hydrated material) from Odo N-3, Shibata City, Niigata Prefecture was used as the dioctahedral smectite clay. An intermediate raw material (A-3) before the addition of the agent was prepared.

<Second step>
As shown in FIG. 4, except that hydroxycarboxylic acid (tartaric acid, citric acid, malic acid) is used as a yellowing change inhibitor and the amount of addition is changed, the second step of Examples 1 to 7 is performed. A water-containing granular material was obtained. In addition, the hydroxycarboxylic acid used in Examples 11-13 and its addition amount are as follows, respectively.
Example 11: 2 parts by weight of tartaric acid Example 12: 2 parts by weight of citric acid Example 13: 2 parts by weight of malic acid

<Third step>
It implemented similarly to the 3rd step of the said Examples 1-7, and obtained the bentonite powder of this invention.

[Comparative Example 3]
About the said intermediate raw material (A-3), the bentonite powder by a prior art was obtained by performing operation similar to the said 3rd step, without adding the hydroxycarboxylic acid as a yellowing change inhibitor.

  For the bentonite powders obtained in Examples 11 to 13 and Comparative Example 3, the same preservation as that in Examples 1 to 7 was performed, and the measurement results for the same items as described above are shown in FIG. Yes.

  As is clear from FIG. 4, in all of Examples 11 to 13, the b value at the start of storage is smaller than that of the sample obtained in Comparative Example 3, and further, the b value over time for the following two months. The increase in was also small. From these results, it is clear that the change in b value with time can be suppressed by adding hydroxycarboxylic acid.

  Further, the addition of hydroxycarboxylic acid means that the alkali salt of hydroxycarboxylic acid neutralized by excess alkali adhering to the surface of the dioctahedral smectite clay particles alkali-treated as necessary is substantially It can be regarded as the addition effect of hydroxycarboxylic acid or a salt thereof according to the amount ratio of the hydroxycarboxylic acid and the amount of excess alkali.

  Next, with respect to aluminum chloride which showed the most excellent yellowing effect in Examples 1 to 7 and sodium chloride which is preferable in terms of swellability and the like, chlorine-containing inorganic salt is added to bentonite powder which has not been subjected to alkali activation treatment. Were added in Examples 14 to 16 and Comparative Example 4.

[Examples 14 to 16]
<First step>
As a dioctahedral smectite clay, 20 kg of raw clay (hydrous material) from Odo T-1 area, Shibata City, Niigata Prefecture was extruded with a screw type single screw extruder equipped with a granulated plate having a 10 mm wide corrugated hole, Without adding Na ₂ CO ₃ , kneaded and granulated twice with a screw type single screw extruder (5 mmφ circular hole-granulated plate mounted), and added the intermediate raw material (B-1) before adding the yellowing inhibitor. Prepared.

<Second step>
As shown in Table 6, sodium chloride (Example 14: 0.5 part added, Example 15: 1.0 part added) and aluminum chloride (Example 16: 0) as chlorine-containing inorganic salts as yellowing inhibitors. .5 parts addition) was carried out in the same manner as in the second step of Examples 1 to 7 to obtain water-containing granular materials.

<Third step>
It implemented similarly to the 3rd step of the said Examples 1-7, and obtained the bentonite powder of this invention.

[Comparative Example 4]
About the said intermediate raw material (B-1), the bentonite powder by a prior art was obtained by performing operation similar to the said 3rd step, without adding the chlorine containing inorganic salt as a yellowing change inhibitor. The powders obtained in Examples 14 to 16 and Comparative Example 4 were stored in the same manner as in Examples 1 to 7, measured for the same items as described above, and the results are shown in FIG.

  The b value of the sample to which sodium chloride obtained in Examples 14 and 15 was added was the case of Example 3 in which sodium chloride was used as a chlorine-containing inorganic salt in the same manner as in Examples 14 and 15 after alkali activation treatment. The value was comparable. On the other hand, the b value of the sample added with aluminum chloride obtained in Example 16 is inferior to that in Example 6 in which aluminum chloride is used as a chlorine-containing inorganic salt in the same manner as in Example 16 after performing alkali activation treatment. As a result.

  The sample to which sodium chloride was added showed the same b value regardless of the presence or absence of the alkali activation treatment, whereas the sample to which aluminum chloride was added had a b value when the alkali activation treatment was not performed. The reason for the tendency to increase is unknown, but it is presumed that the difference between sodium and aluminum as alkali species leads to the difference in results.

  Moreover, the chemical composition of the powder sample obtained by Example 3, 10, 14 and the comparative example 1 is shown by FIG.

  According to the bentonite powder of the present invention, by using the chlorine-containing inorganic salt, the whiteness immediately after the pulverization treatment is maintained for a relatively long period of time, whereby both the manufacturer side and the purchaser side can be maintained. Therefore, it is not necessary to take special measures in consideration of deterioration of whiteness over time.

  Further, according to the method for producing bentonite powder of the present invention, sodium ions are taken in between the basic layers of clay in the first step, so that the swelling property of the bentonite powder can be improved. In addition, by using the chlorine-containing inorganic salt, the whiteness immediately after the pulverization treatment is maintained for a relatively long period of time, and thereby the whiteness is deteriorated with time on both the manufacturer side and the purchaser side. This makes it possible to obtain bentonite powder that does not require any special measures.

Claims (20)

A bentonite powder comprising a natural dioctahedral smectite clay powder or a clay powder obtained by subjecting the clay to an alkali treatment, and containing a predetermined amount of a chlorine-containing inorganic salt represented by the following formula.
M ^{p +} (ClO _q ⁻ ) _p (formula)
(In the formula, M is a metal atom selected from the group of Na, K, Mg, Ca, Ba, and Al, p is a natural number of 1 to 3 in terms of the valence of the metal atom M, and q is The number of oxygen atoms O constituting the ionic formula of chloride ion or chlorate ion is 0 or a natural number of 1 to 4.)   The bentonite powder according to claim 1, further comprising a predetermined amount of hydroxycarboxylic acid or a salt thereof.   The bentonite powder according to claim 1 or 2, wherein the moisture content at the time of shipment from the factory is 5 wt% or less on a dry basis.   2. The bentonite powder according to claim 1, wherein the content of the chlorine-containing inorganic salt is 0.02 to 2 parts by weight with respect to 100 parts by weight of clay (in terms of dry matter).   2. The bentonite powder according to claim 1, wherein the content of the hydroxycarboxylic acid or a salt thereof is 0.2 to 2 parts by weight with respect to 100 parts by weight of clay (in terms of dry matter).   The bentonite powder according to claim 1, wherein the chlorine-containing inorganic salt is aluminum chloride or sodium chloride.   The bentonite powder according to claim 2, wherein the hydroxycarboxylic acid or a salt thereof is at least one selected from the group consisting of tartaric acid, citric acid, malic acid, and salts thereof.   A bentonite powder comprising a natural dioctahedral smectite clay powder or a clay powder obtained by subjecting the clay to an alkali treatment, and containing a predetermined amount of hydroxycarboxylic acid or a salt thereof.   The bentonite powder according to claim 8, wherein the moisture content at the time of shipment from the factory is 5 wt% or less on a dry basis.   The bentonite powder according to claim 8, wherein the content of the hydroxycarboxylic acid or a salt thereof is 0.5 to 5 parts by weight with respect to 100 parts by weight of clay (in terms of dry matter).   The bentonite powder according to claim 8, wherein the hydroxycarboxylic acid or a salt thereof is at least one selected from the group consisting of tartaric acid, citric acid, malic acid, and salts thereof. A first step of incorporating alkali ions between the basic structural layers of the clay by adding an alkaline compound to the dioctahedral smectite clay as a raw material and kneading;
A second step of uniformly dispersing the chlorate in the clay by adding and kneading a predetermined amount of a chlorate represented by the following formula in the clay having undergone the first step; ,
M ^{p +} (ClO _q ⁻ ) _p (formula)
(In the formula, M is a metal atom selected from the group of Na, K, Mg, Ca, Ba, and Al, p is a natural number of 1 to 3 in terms of the valence of the metal atom M, and q is The number of oxygen atoms O constituting the ionic formula of chloride ion or chlorate ion is 0 or a natural number of 1 to 4.)
And a third step of producing the fine powder of the clay by drying and then pulverizing and classifying the clay that has undergone the second step.   The method for producing bentonite powder according to claim 12, wherein the second step further comprises a step of containing a predetermined amount of hydroxycarboxylic acid or a salt thereof.   The method for producing bentonite powder according to claim 12, wherein in the third step, the water content of the fine powder at the end of drying is 5 parts by weight or less.   The said 2nd step WHEREIN: The addition amount of the said chlorine-containing inorganic salt is 0.02 to 2 weight part with respect to 100 weight part (in dry matter conversion) of clay content, The Claim 12 characterized by the above-mentioned. A method for producing bentonite powder.   The bentonite powder according to claim 1, wherein the volume average particle diameter d (50) is 3 to 20 µm.   The bentonite powder according to claim 1, wherein the b value is 6 or less when 30 days have passed after shipment.   The bentonite powder according to claim 1, wherein iron is contained in an amount of 0.5 to 5 parts by weight in terms of oxide.   The bentonite powder according to claim 1, wherein the bentonite powder contains at least a paper additive and a fabric softener.   The method for producing bentonite powder according to claim 12, wherein the pulverization in the third step is performed within 15 days before shipment.

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