JP6830628B2 - Adsorbent for clay minerals, manufacturing method of clay mineral materials and clay mineral composites - Google Patents

Description

The present invention relates to an adsorbent for clay minerals capable of adsorbing clay minerals, a method for producing a clay mineral material using an adsorbent, and a clay mineral composite in which clay minerals are arranged on the surface of a mother particle by adsorption.

Clay minerals such as sericite (muscovite) are used in paints, plastics, cosmetics, pharmaceuticals, and the like. However, since naturally produced clay minerals are mixed with impure minerals such as quartz, it is necessary to remove the impure minerals. As a method for removing impure minerals from clay minerals, for example, crushed clay minerals are poured into water or precipitated, and the specific gravity is also called water ratio, which is separated by using the specific gravity difference between the clay minerals and the impure minerals. There is a sorting method. Further, as disclosed in Patent Document 1, the clay mineral raw material is primary crushed into particles having a predetermined diameter or less, the primary pulverized particles are secondary pulverized, and then the primary pulverization is performed using a Raymond mill to wet the particles. A method of wet-classifying with a classifier and classifying into coarse particles and fine particles has been proposed.

Japanese Unexamined Patent Publication No. 2013-256100

The specific gravity sorting method has a problem that it requires a lot of equipment such as having to connect sedimentation tanks in multiple stages, which is costly and also takes a long time for separation. Further, the method disclosed in Patent Document 1 requires equipment such as a wet classifier, and classifies after pulverizing many times, so that it is still costly and time consuming.

Further, when the clay mineral is used as a material for substances having an influence on the human body such as being blended in cosmetics, it is more strongly required that impurities derived from the clay mineral raw material do not remain.

That is, the present invention has been proposed in view of the above-mentioned problems related to the prior art, and has been proposed to suitably solve these problems, and is an adsorbent for clay minerals capable of adsorbing layered silicate minerals, and an adsorbent for clay minerals. It is an object of the present invention to provide a simple method for producing a clay mineral material using a clay mineral material, and a clay mineral composite containing almost no impurities.

In order to overcome the above-mentioned problems and achieve the intended purpose, the adsorbent for clay minerals according to claim 1 of the present application is used.
, A polymer compound, a clay mineral adsorbent for the organic capable of adsorbing anionic group layered silicate mineral,
The gist is that the polymer compound is a crosslinked poly (meth) acrylic acid or a crosslinked poly (meth) acrylic acid ester obtained by hydrolyzing a part of a carboxylic acid ester .
According to the invention of claim 1, since the layered silicate mineral can be adsorbed on the anionic group, the layered silicate mineral can be adsorbed and separated from the clay mineral raw material containing impurities. it can. Therefore, by using an adsorbent for clay minerals, it is possible to reduce the time, labor, cost, and the like for obtaining a layered silicate mineral with reduced or eliminated impurities. By using crosslinked poly (meth) acrylic acid or crosslinked poly (meth) acrylic acid ester as the polymer compound, layered silicate minerals can be adsorbed more efficiently.

The gist of the invention according to claim 2 is that a layered silicate mineral is adsorbed more than a clay mineral other than the layered silicate mineral in a medium having a pH in the range of 2 to 7.
According to the invention of claim 2, since layered silicate minerals are adsorbed more than clay minerals other than the layered silicate minerals in a medium in the pH range of 2 to 7, clay containing impurities. It is easier to separate layered silicate minerals from mineral raw materials.

In the invention according to claim 3, the layered silicate mineral is adsorbed up to the adsorption amount corresponding to the pH of the medium, and the adsorbed amount of the layered silicate mineral adsorbed on itself corresponds to the pH of the medium. The gist is to attach and detach the excess part.
According to the invention of claim 3, since the layered silicate mineral can be operated to be adsorbed or desorbed depending on the pH of the medium, the layered silicate mineral is adsorbed from the clay mineral raw material containing impurities. After that, the layered silicate mineral can be desorbed and easily recovered.

The gist of the invention according to claim 4 is that a layered silicate mineral is selectively adsorbed in a medium in the pH range of 6 to 7 instead of a clay mineral other than the layered silicate mineral.
According to the invention of claim 4, in a medium in the pH range of 6 to 7, layered silicate minerals are selectively adsorbed instead of clay minerals other than layered silicate minerals, so that layers with no impurities are removed. Silicate minerals can be easily obtained.

The gist of the invention according to claim 5 is that the anionic group is a sulfo group, a sulfate group, a carboxyl group, or a phosphoric acid group.
According to the invention of claim 5, the anionic group is a sulfo group, a sulfate group, a carboxyl group, or a phosphoric acid group, so that the anionic group is layered in a medium for contacting the adsorbent and the layered silicate mineral. Silicate minerals can be adsorbed more efficiently.

The gist of the invention according to claim 6 is that the content of the anionic group is in the range of 0.2 meq / g to 12 meq / g.
According to the invention of claim 6, when the content of the anionic group is in the range of 0.2 meq / g to 12 meq / g, the layered silicate mineral can be adsorbed more efficiently.

In order to overcome the above-mentioned problems and achieve the desired object, the method for producing a clay mineral material according to claim 7 of the present application is:
An adsorbent made of a polymer compound having an anionic group is brought into contact with a clay mineral raw material containing a layered silicate mineral.
The layered silicate mineral is adsorbed on the anionic group of the adsorbent, and the layered silicate mineral is separated from the clay mineral raw material to obtain a clay mineral material mainly composed of the layered silicate mineral. It is a manufacturing method of clay mineral materials.
The gist is to use crosslinked poly (meth) acrylic acid or a crosslinked poly (meth) acrylic acid ester obtained by hydrolyzing a part of a carboxylic acid ester as the polymer compound forming the adsorbent .
According to the invention of claim 7 , the layered silicate mineral is adsorbed on the adsorbent by the anionic group of the adsorbent by a simple operation of bringing the adsorbent into contact with the layered silicate mineral. , Layered silicate minerals can be separated from clay mineral raw materials containing impurities. Thereby, a clay mineral material mainly composed of a layered silicate mineral with reduced or eliminated impurities can be easily obtained. By using crosslinked poly (meth) acrylic acid or crosslinked poly (meth) acrylic acid ester as the polymer compound, the layered silicate mineral can be more efficiently adsorbed on the adsorbent. Thereby, the recovery rate of the clay mineral material can be improved.

In the invention according to claim 8 , the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 2 to 7, and the layered silicate mineral is adsorbed on the anionic group. It is a summary.
According to the invention of claim 8 , the layered silicate mineral is efficiently adsorbed on the adsorbent by a simple operation of bringing the adsorbent and the clay mineral raw material into contact with each other in a medium adjusted to the pH range of 2 to 7. be able to.

In the invention according to claim 9 , the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 2 to 7, and the layered silicate mineral is adsorbed on the anionic group.
The adsorbent on which the layered silicate mineral is adsorbed is placed in another medium adjusted to a pH higher than pH 4 and higher than the pH of the medium on which the layered silicate mineral is adsorbed, and the adsorption is performed. The gist is to desorb layered silicate minerals from the wood.
According to the invention of claim 9 , it is possible to control the adsorption of the layered silicate mineral to the adsorbent or the desorption of the layered silicate mineral from the adsorbent by a simple operation of changing the pH of the medium. it can. That is, a clay mineral material mainly composed of a layered silicate mineral can be obtained more easily.

In the invention according to claim 10 , the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 6 to 7, and only the layered silicate mineral among the clay mineral raw materials is used as the adsorbent. The gist is to selectively adsorb to clay.
According to the invention of claim 10 , by bringing the adsorbent and the clay mineral raw material into contact with each other in a medium adjusted to the pH range of 6 to 7, only the layered silicate mineral among the clay mineral raw materials is adsorbed. It can be selectively adsorbed on the material. Thereby, a clay mineral material composed of a layered silicate mineral from which impurities have been removed can be easily obtained.

The gist of the invention according to claim 11 is that the anionic group is a sulfo group, a sulfate group, a carboxyl group, or a phosphoric acid group.
According to the invention of claim 11 , when the anionic group is a sulfo group, a sulfate group, a carboxyl group, or a phosphoric acid group, it is adsorbed in a medium in which the adsorbent and the layered silicate mineral are brought into contact with each other. Layered silicate minerals can be adsorbed on the material more efficiently. Thereby, the recovery rate of the clay mineral material can be improved.

The gist of the invention according to claim 12 is that the adsorbent has an anionic group content in the range of 0.2 meq / g to 12 meq / g.
According to the invention of claim 12, when the content of the anionic group is in the range of 0.2meq / g to 12meq / g, the layered silicate mineral is more efficiently adsorbed on the adsorbent. Can be done. Thereby, the recovery rate of the clay mineral material can be improved.

In order to overcome the above-mentioned problems and achieve the intended purpose, the clay mineral composite of the invention according to claim 13 of the present application can be used.
Spherical mother particles made of a polymer compound having an anionic group and
The layered silicate mineral particles adsorbed on the anionic group of the mother particle and arranged on the surface of the mother particle are provided.
The gist is that the polymer compound is a crosslinked poly (meth) acrylic acid or a crosslinked poly (meth) acrylic acid ester obtained by hydrolyzing a part of a carboxylic acid ester .
According to the invention of claim 13 , in addition to the respective actions of the spherical mother particles made of the polymer compound and the layered silicate mineral particles arranged on the mother particles by adsorption, the synergistic action of both is achieved. can get. Moreover, since impurities other than layered silicate minerals are reduced or eliminated, it can be used in applications such as cosmetics and pharmaceuticals.

The gist of the invention according to claim 14 is that the layered silicate mineral particles are formed so as to be difficult to separate from the mother particles in a medium having a pH lower than 7.
According to the invention of claim 14 , the layered silicate mineral particles are difficult to separate from the mother particles in a medium having a pH of less than 7, and are therefore suitable for cosmetics and pharmaceuticals adjusted in the acidic region. Can be used for.

According to the adsorbent for clay minerals according to the present invention, since layered silicate minerals are adsorbed, it can be suitably used for separating layered silicate minerals from the clay mineral raw material.
According to the method for producing a clay mineral material according to the present invention, by contacting the adsorbent with the clay mineral raw material, the layered silicate mineral can be easily separated from the clay mineral raw material by adsorbing to the adsorbent. ..
According to the clay mineral composite according to the present invention, since it contains almost no impurities other than the layered silicate mineral, it can be used for applications such as cosmetics and pharmaceuticals.

It is a schematic diagram which shows the adsorbent for clay mineral which concerns on this invention, and the clay mineral composite which adsorbed the layered silicate mineral using the adsorbent for clay mineral as a parent particle. It is a graph which shows the infrared absorption spectrum of the adsorbent of Example 2. FIG. It is a graph which shows the calibration curve of sericite about the adsorbent of Example 2 which adsorbed sericite and quartz. It is a graph which shows the calibration curve of quartz about the adsorbent of Example 2 which adsorbed sericite and quartz. It is an X-ray diffraction pattern of the adsorbent of Example 2 which adsorbed sericite and quartz, and shows the peak of sericite 45 °. It is an X-ray diffraction pattern of the adsorbent of Example 2 which adsorbed sericite and quartz, and shows the peak of quartz 60.2 °. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed sericite and quartz in a medium of pH 3 at 2500 times. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed sericite and quartz in a medium of pH 4 at 2500 times. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed sericite and quartz in a medium of pH 5 at 2500 times. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed sericite and quartz in the medium of pH 6 at 2500 times. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed only sericite in the medium of pH 3 over 1 hour, (a) is 500 times, (b) is 2500 times. .. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed only sericite in the medium of pH 3 over 3 hours, (a) is 500 times, (b) is 2500 times. .. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed only sericite in the medium of pH 3 over 5 hours, (a) is 500 times, (b) is 2500 times. .. It is a scanning electron micrograph which observed the adsorbent of Example 1 which adsorbed only sericite in the medium of pH 3, (a) is 500 times, (b) is 2500 times. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed only sericite in the medium of pH 3, (a) is 500 times, (b) is 2500 times. It is a scanning electron micrograph which observed the adsorbent of Example 3 which adsorbed only sericite in the medium of pH 3, (a) is 500 times, (b) is 2500 times. It is a scanning electron micrograph which observed the adsorbent (clay mineral composite) of Example 2 which adsorbed only sericite at 2500 times. It is a scanning electron micrograph which observed the adsorbent of Example 2 which adsorbed only quartz at 2500 times. It is a scanning electron micrograph of the adsorbent of Example 2 in which only sericite was adsorbed, in which the state in which sericite was desorbed in a medium of pH 10 was observed at 2500 times. (A) is a scanning electron micrograph of the adsorbent of Example 6 in which Amakusa porcelain was adsorbed, which was observed at 2500 times, and (b) is the adsorbent of Example 6 before adsorbing Amakusa porcelain. It is a scanning electron micrograph observed at 2500 times.

The adsorbent for clay minerals according to the present invention (hereinafter, simply referred to as an adsorbent) is made of a polymer compound and has an anionic group capable of preferentially adsorbing a layered silicate mineral among clay minerals. .. The adsorbent preferentially adsorbs layered silicate minerals from clay mineral raw materials containing layered silicate minerals in a pH-adjusted medium, and aims at impurities contained in the clay mineral raw materials. It can be used for separation from layered silicate minerals.

The clay mineral raw materials mentioned above are crushed clay minerals excavated from mines, and are not only layered silicate minerals (phyllosilicate minerals), but also quartz, square stones, bitter ash stones, feldspars, and zeolites (foiled stones). Contains impurities such as zeolite). Clay minerals other than the layered silicate minerals to be adsorbed by the adsorbent are referred to as mineral impurities in the following description. The layered silicate mineral is a sheet in which one alumina octahedral sheet is bonded between two silica tetrahedral sheets to form one aluminum silicate unit layer, and these unit layers are laminated and configured to overlap. There are cations in between, and the surface of the sheet has a negative charge. Examples of the layered silicate mineral to be adsorbed by the adsorbent according to the present invention include the following. Examples of layered silicate minerals include muscovite, sodium mica, ceradonite, glauconite, phlogopite, biotite and other mica, pyrophyllite, talc, and vermulite. In addition, smectites such as saponite, hectorite, saponite, montmorillonite, byderite, and nontronite can be mentioned. Further, serpentine, amesite, cronsteadite, verselin, greenalite, kaolin mineral, halosite, chlorite, sudow stone, cucumberite, donbacite and the like can be mentioned. Among these, sericite (sericite), which is a fine grain of muscovite, is used for things that come into contact with the human body such as cosmetics and pharmaceuticals, and can be suitably adsorbed by the adsorbent according to the present invention.

The polymer compound constituting the adsorbent may be a synthetic polymer or an organic polymer. Further, the adsorbent may be granular such as spherical or elliptical, or may have other shapes such as fibrous. By making the shape of the adsorbent granular or fibrous, it becomes easier to mix with the clay mineral raw material in the medium, and the surface on which the layered silicate mineral is adsorbed can be made relatively wide. It has the advantage of being able to efficiently adsorb silicate minerals. The size of the adsorbent may be in the range of 1 μm to 1000 μm, preferably in the range of 15 μm to 200 μm. Here, the size of the adsorbent refers to the average particle size of the particles when it is granular, and refers to the average length of the long side of the fiber when it is fibrous. If the size of the adsorbent is smaller than 1 μm, it becomes difficult to handle, and if it exceeds 1000 μm, it is not preferable in view of the adsorption efficiency.

The polymer compound forming the adsorbent is not particularly limited as long as it has an anionic group. As the synthetic polymer, for example, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polystyrene sulfonic acid, polyvinylsulfone, polyn-sulfonylalkyla (meth) crylamide, copolymers thereof and the like can be used.

When a natural polymer is used as the polymer compound forming the adsorbent, for example, the following can be used. For example, examples of polysaccharides include cellulose oxide, cellulose oxide, maleine oxide, and cellulose having a cellulonic acid residue. Alternatively, examples include cellouronic acid, alginic acid, starch oxidative starch, glutar-oxidized starch, maleine-oxidized starch, and starch having a glucuronic acid residue. Alternatively, amyuronic acid, pullulan oxalate, pullulan glutar oxide, pullulan maleine oxide, pullulan having glucuronic acid residue, glucomannan oxalate, glucomannan glutar oxide, glucomannan maleate oxide, glucuronic acid residue, or mannuronic acid, Alternatively, glucomannan having both of them can be mentioned. Alternatively, it has chitin oxalate, chitin glutar oxide, chitin maleate oxide, chitosan oxalate, chitosan glutar oxide, chitosan maleate, chitosan having a glucosamine uronic acid residue, or chitosanic acid, having an N-acetylglucosamine uronic acid residue. Examples include chitin. Alternatively, polyN-acetylglucosamine uronic acid, copper-carrageenan, iota-carrageenan, lambda-carrageenan, fucoidan, sakuran, hyaluronic acid, porphyran, sulfated cellulose, sulfated starch, sulfated chitosan, sulfated chitin and the like can be mentioned. .. Alternatively, examples of polyamino acids include polyγ-glutamic acid, poly-α-glutamic acid, poly-β-aspartic acid, and poly-α-aspartic acid.

Examples of the anionic group include a carboxyl group, a sulfo group, a sulfuric acid group, and a phosphoric acid group. Since the adsorbent has the above-mentioned anionic group, the layered silicate mineral can be more efficiently adsorbed in the medium in which the adsorbent and the layered silicate mineral are brought into contact with each other. Here, the anionic group preferably has hydrophilicity, and having a hydrophilic anionic group is advantageous when the adsorbent is brought into contact with the layered silicate mineral in the medium.

The adsorbent preferably has an anionic group content in the range of 0.2 meq / g to 12 meq / g, more preferably 0.7 meq / g to 8 meq / g. The adsorbent can more efficiently adsorb layered silicate minerals when the content of anionic groups is in the range of 0.2 meq / g to 12 meq / g. If the content of the anionic group is less than 0.2 meq / g, the alternating electrostatic interaction becomes small and the layered silicate mineral cannot be sufficiently adsorbed, which makes industrial practicality difficult. is there. Further, when the content of the anionic group exceeds 12 meq / g, the adsorption efficiency of the layered silicate mineral deteriorates due to the swelling of the polymer compound constituting the adsorbent, which makes it difficult for industrial practicality. When the content of the anionic group is in the range of 0.7meq / g to 8meq / g, the alternating electrostatic interaction and the swelling are balanced, and the layered silicate mineral can be adsorbed more efficiently.

The adsorbent preferably has a swelling degree in the range of 1wet-ml / g to 1000wet-ml / g, more preferably in the range of 1.5wet-ml / g to 500wet-ml / g. It is good to do. Since the adsorbent has an anionic group that adsorbs layered silicate minerals, the degree of swelling does not become smaller than 1 wet-ml / g. Further, when the swelling degree of the adsorbent is larger than 1000 wet-ml / g, the adsorption efficiency of the layered silicate mineral becomes high, and the physical adsorption of impurities such as quartz other than the clay mineral occurs, and the adsorbent is derived from the clay mineral raw material. The separation efficiency of the target layered silicate mineral deteriorates. The degree of swelling is an index showing the ease of containing water, and the volume (wet-ml) of the adsorbent immersed in water for 24 hours in a water bath at 30 ° C. is the weight of the adsorbent during drying (dry-). Calculated by dividing g).

The adsorbent adsorbs more layered silicate minerals than mineral impurities in a medium in the pH range of 2-7. As described above, the adsorbent has a priority of adsorbing layered silicate minerals in preference to mineral impurities depending on the pH of the medium, and when the pH of the medium is in the range of 3 to 6, the priority is given. It is preferable because it becomes stronger. The adsorbent adsorbs both layered silicate minerals and mineral impurities when the pH of the medium is less than 2, and the priority is deteriorated. When the pH of the medium is more than 7, the layered silicate mineral is adsorbed. And mineral impurities are both difficult to adsorb, especially when the pH is above 10, neither layered silicate minerals nor mineral impurities are adsorbed. The adsorbent does not adsorb mineral impurities at all in a medium adjusted to the pH range of 6 to 7, but adsorbs only layered silicate minerals. As described above, the adsorbent is used not only in the medium adjusted to the neutral region, but also in the medium adjusted to the neutral region, in addition to the priority of adsorbing the layered silicate mineral in preference to the mineral impurities. It has the selectivity to select and adsorb only layered silicate minerals.

The adsorbent is difficult to adsorb both layered silicate minerals and mineral impurities in a medium in an alkaline region whose pH is adjusted to be greater than 7, and desorbs the adsorbed layered silicate minerals and mineral impurities. To do. In particular, when the pH of the medium is higher than 10, neither the layered silicate mineral nor the mineral impurities are adsorbed, and the total amount of the adsorbed layered silicate mineral and the mineral impurities is desorbed. Therefore, the adsorbent can selectively separate the layered silicate mineral by desorbing the layered silicate mineral adsorbed in the medium in the acidic to neutral region in the medium adjusted to the alkaline region. ..

The adsorbent adsorbs layered silicate minerals in a medium adjusted to a specific pH of pH 2 to 7 until the adsorption amount corresponds to the specific pH, and the adsorption amount corresponding to the specific pH is adjusted. Does not adsorb layered silicate minerals beyond. In addition, the adsorbent desorbs a portion of the layered silicate mineral adsorbed on itself in a medium adjusted to a specific pH of pH 2 to 7, which exceeds the adsorption amount corresponding to the specific pH. Therefore, the adsorbent was placed in the medium adjusted to the second pH of pH 2 to 7 after adsorbing the layered silicate mineral in the medium adjusted to the first pH of pH 2 to 7. At that time, if the adsorption amount corresponding to the second pH is smaller than the first pH, the layered silicate mineral is desorbed. Similarly, when the adsorbent is placed in a medium adjusted to the second pH of pH 2 to 7, if the amount of adsorption corresponding to the second pH is larger than the first pH, the adsorbent is layered. Further adsorbs silicate minerals. As described above, the adsorbent can easily control the adsorption and desorption of the layered silicate mineral by adjusting the pH of the medium in contact with the layered silicate mineral.

As described above, the adsorbent adsorbs more layered silicate minerals in a medium adjusted to a specific pH of pH 2 to 7, but the minerals are adsorbed until the amount of adsorption corresponds to the specific pH. Adsorbs impurities and does not adsorb mineral impurities in excess of the adsorption amount corresponding to a specific pH. Therefore, when the adsorbent is placed in a medium adjusted to a second pH of pH 2 to 7 after adsorbing mineral impurities in a medium adjusted to a first pH of pH 2 to 7, the adsorbent is placed in a medium adjusted to a second pH of pH 2 to 7. If the amount of adsorption corresponding to the second pH is smaller than the first pH, mineral impurities are desorbed. Similarly, when the adsorbent is placed in a medium adjusted to the second pH of pH 2 to 7, if the amount of adsorption corresponding to the second pH is larger than the first pH, the adsorbent is a mineral impurity. Is further adsorbed. As described above, the adsorbent can easily control the adsorption and desorption of layered silicate minerals and mineral impurities by adjusting the pH of the medium in contact with the clay mineral raw material. Here, when the adsorbed layered silicate mineral or mineral impurities are desorbed, the adsorbent preferentially desorbs from the mineral impurities because the amount of the mineral impurities that can be adsorbed is smaller than that of the layered silicate mineral. To do.

As the adsorbent, a crosslinked polyacrylic acid ester represented by the following chemical formula 1 or a derivative of the crosslinked polymethacrylic acid ester represented by the following chemical formula 2 can be used as the polymer compound. Here, R of chemical formula 1 and chemical formula 2 is an alkyl group such as methyl, ethyl, propyl or butyl, a phenyl group, a benzyl group or the like, and is a hydrophobic functional group selected from an aliphatic or aromatic hydrocarbon group. Represents a group. In addition, polyacrylic acid ester and crosslinked polymethacrylic acid ester are collectively referred to as poly (meth) acrylic acid ester below, and when the adsorbent composed of poly (meth) acrylic acid ester is particularly distinguished, it is referred to as acrylic adsorbent. .. The acrylic adsorbent is basically composed of a crosslinked poly (meth) acrylic acid ester, and has a structure in which a part of the carboxylic acid ester in the crosslinked poly (meth) acrylic acid ester is hydrolyzed. In the acrylic adsorbent, the carboxylic acid ester on the surface of the crosslinked poly (meth) acrylic acid ester particles is hydrolyzed, and the polyacrylic acid is present on the surface portion and the carboxylic acid ester having a hydrophobic group is present on the inner portion. doing.
R in Chemical Formula 1 and Chemical Formula 2 represents a hydrophobic functional group selected from aliphatic or aromatic hydrocarbon groups. Further, n in Chemical Formula 1 and Chemical Formula 2 indicates the degree of polymerization of the monomer in parentheses.

The acrylic adsorbent has a structure in which a part or all of the carboxylic acid produced by partially hydrolyzing the crosslinked poly (meth) acrylic acid ester is metallized by an alkali metal, and is insoluble in water. is there. As the alkali metal, an alkali metal of hydroxide and an alkaline earth metal are preferably used, and in particular, sodium hydroxide, potassium hydroxide, magnesium hydroxide and the like are preferable.

Next, a method for producing the acrylic adsorbent will be described. Prepare crosslinked poly (meth) acrylic acid ester particles. In addition, a reaction solvent in which an alkaline solution and an organic solvent are mixed is separately prepared. The alkaline solution used here is a solution in which hydroxides of alkali metals and alkaline earth metals are dispersed in water. Further, as the organic solvent, one or more kinds of alcohols such as ethanol and methanol, protic solvents mixed with them, and aprotic solvents such as acetone, tetrahydrofuran and dioxane are used.

The organic solvent is mixed with the alkaline solution in the range of 8 wt% to 800 wt%, preferably in the range of 10 wt% to 350 wt%. When the concentration of the organic solvent is less than 8 wt%, the alkaline aqueous solution does not have an affinity for the crosslinked acrylic acid ester fine particles, and the hydrolysis reaction of the carboxylic acid ester does not proceed in the crosslinked polyacrylic acid ester. On the other hand, when the concentration of the organic solvent is larger than 800 wt%, the alkali is precipitated without being dissolved in the organic solvent, so that the carboxylic acid ester cannot be efficiently hydrolyzed.

The concentration of the alkaline solution is set in the range of 0.5M to 5.0M, preferably in the range of 1.0M to 3.5M. If the concentration of the alkaline solution is less than 0.5 M, the hydrolysis reaction of the carboxylic acid ester does not proceed and it cannot be industrially adopted. On the other hand, if the concentration of the alkaline solution is larger than 5.0 M, there is a disadvantage that the hydrolysis reaction of the carboxylic acid ester is difficult to control.

The crosslinked poly (meth) acrylic acid ester as a starting material is blended in the range of 5 wt% to 30 wt%, preferably 10 wt% to 20 wt% with respect to the reaction solvent. If the blending amount of the crosslinked poly (meth) acrylic acid ester is less than 5 wt%, the yield of the obtained acrylic adsorbent is poor and it cannot be industrially adopted. On the other hand, if the blending amount of the crosslinked poly (meth) acrylic acid ester particles is larger than 30 wt%, the viscosity becomes high and the reaction becomes difficult.

Then, the poly (meth) acrylic acid ester is immersed in a reaction solvent composed of an alkaline solution and an organic solvent, and the temperature condition of the reaction solvent is in the range of 15 ° C. to 90 ° C., preferably in the range of 35 to 80 ° C. (hereinafter, , The reaction temperature) to hydrolyze the carboxylic acid ester in the poly (meth) acrylic acid ester. If the reaction temperature is lower than 15 ° C, the hydrolysis reaction does not proceed, so that the poly (meth) acrylic acid ester remains hydrophobic, and if the reaction temperature is higher than 90 ° C, the reaction solvent used is limited. Not preferred. The time for immersing the poly (meth) acrylic acid ester in the reaction solvent (hereinafter referred to as reaction time) is set in the range of 1 minute to 96 hours, preferably in the range of 1 minute to 24 hours. If the reaction time is less than 1 minute, the hydrolysis reaction does not proceed, so that the poly (meth) acrylic acid ester remains hydrophobic, and if the reaction time exceeds 96 hours, the hydrolysis reaction proceeds too much. There is a disadvantage that the water absorption and hygroscopicity of the acrylic adsorbent are too high.

After the dipping treatment in the reaction solvent, the acrylic adsorbent obtained from the reaction solvent is taken out, and the acrylic adsorbent is washed with water. When recovered only by washing with water, freeze-drying is preferable if it is to be dried. When the acrylic adsorbent is recovered by solvent replacement, it is washed with water, replaced with methanol, diethyl ether or the like, and dried. Then, an acrylic adsorbent having a desired average particle size, for example, an average particle size in a wet state in the range of 1 μm to 1000 μm is isolated by a recovery method such as filtration. The method for recovering the acrylic adsorbent is not limited to filtration, and other methods such as centrifugation can also be adopted.

As shown in FIG. 1, the adsorbent can adsorb the layered silicate mineral by the alternating electrostatic interaction between the anionic group of the adsorbent and the layered silicate mineral. In FIG. 1, the adsorbent (the parent particle of the clay mineral complex described later) is designated by the reference numeral “12”, and the anionic group exemplifying the carboxyl group is designated by the reference numeral “14” to form a layered silicate mineral. The code "16" is attached to. A clay mineral composite composed of the adsorbent 12 and the layered silicate mineral 16 adsorbed on the adsorbent 12 is designated by the symbol "10". Further, in FIG. 1, reference numeral "20" indicates mineral impurities such as quartz. The "+" and "-" in the circles in FIG. 1 are images of electric charges. Since the adsorbent 12 can adsorb and separate the layered silicate mineral 16 from the clay mineral raw material containing the mineral impurity 20, the adsorbent 12 has reduced or eliminated the impurities. It is possible to reduce the time, labor and cost for obtaining the layered silicate mineral 16. Further, the clay mineral composite 10 in which the layered silicate mineral 16 is adsorbed by the anionic group 14 of the mother particle made of the adsorbent 12 and the layered silicate mineral 16 is arranged on the surface of the adsorbent (mother particle) 12. Can be obtained.

Since the adsorbent adsorbs more layered silicate minerals in a medium in the pH range of 2 to 7 in preference to mineral impurities such as quartz other than the layered silicate minerals, it adsorbs mineral impurities. It is possible to efficiently adsorb and separate layered silicate minerals. Therefore, by utilizing the property of the adsorbent that preferentially adsorbs layered silicate minerals from clay mineral raw materials containing mineral impurities, layered silicate minerals are separated with the mineral impurities further reduced. It is possible to obtain a highly pure layered silicate mineral more easily.

The adsorbent adsorbs the layered silicate mineral to an adsorption amount corresponding to the pH of the medium containing the adsorbent, and also corresponds to the pH of the medium in the layered silicate mineral adsorbed on itself. Detach the part that exceeds the adsorption amount. Further, as the adsorbent, desorption is prioritized over adsorption in a medium having a pH adjusted to be greater than 7, and all layered silicate minerals adsorbed on the adsorbent are desorbed in a medium having a pH adjusted to be greater than 10. In this way, the adsorbent can be controlled so as to adsorb or desorb layered silicate minerals depending on the pH of the medium into which the adsorbent is charged. Therefore, the adsorbent is layered from the clay mineral raw materials containing mineral impurities. After adsorbing the silicate mineral, the layered silicate mineral can be desorbed and easily recovered. Moreover, since mineral impurities are preferentially desorbed on the adsorbent over the layered silicate mineral adsorbed on itself, the mineral impurities are desorbed first, and then the layered silicate is re-desorbed in a medium different from the previous medium. By desorbing the acidate mineral, a layered silicate mineral with higher purity can be easily obtained. Furthermore, since the adsorbent selectively adsorbs only layered silicate minerals in a medium in the pH range of 6 to 7 without adsorbing mineral impurities, this selectivity was used to eliminate mineral impurities. Layered silicate minerals can be easily obtained.

By using crosslinked poly (meth) acrylic acid or crosslinked poly (meth) acrylic acid ester as the polymer compound, the adsorbent can more efficiently adsorb layered silicate minerals.

Next, a method for producing a clay mineral material mainly composed of a required layered silicate mineral using the above-mentioned adsorbent will be described below. The clay mineral raw material is obtained by crushing clay ore excavated from a mine into grains or powders, and contains layered silicate minerals and mineral impurities such as quartz as described above. First, an adsorbent made of a polymer compound having an anionic group is brought into contact with a clay mineral raw material containing a layered silicate mineral. As a result, the layered silicate mineral is adsorbed on the anionic group of the adsorbent, and the layered silicate mineral is separated from the clay mineral raw material together with the adsorbent to obtain a clay mineral material composed of the layered silicate mineral. be able to.

Specifically, the adsorbent and the clay mineral raw material are brought into contact with each other in a medium having a pH in the range of 2 to 7, more preferably pH 3 to 6, and the layered silicate mineral is adsorbed on the anionic group. .. As the medium for adsorption, an aqueous solution whose pH is adjusted with an acid such as hydrochloric acid may be used. When the adsorbent and the clay mineral raw material are brought into contact with each other in a medium whose pH is adjusted to the range of 2 to 7, more layered silicate minerals in the clay mineral raw material are adsorbed than mineral impurities in the clay mineral raw material. Adsorbed on the material. When the pH of the medium is smaller than 2, both the layered silicate mineral and the mineral impurities are adsorbed on the adsorbent, and it becomes difficult to separate the layered silicate mineral from the clay mineral raw material. Further, when the pH of the medium is higher than 7, both the layered silicate mineral and the mineral impurities are not sufficiently adsorbed on the adsorbent, so that the layered silicate mineral cannot be separated from the clay mineral raw material.

In particular, when the adsorbent and the clay mineral raw material are brought into contact with each other in a medium whose pH is adjusted to the pH range of 6 to 7, the mineral impurities in the clay mineral raw material are not adsorbed by the adsorbent at all, while the clay mineral raw material is among the clay mineral raw materials. Only the layered silicate minerals of No. 1 can be selectively adsorbed by the adsorbent. That is, by using a medium whose pH is adjusted to the pH range of 6 to 7, only the layered silicate mineral can be adsorbed on the adsorbent and taken out from the clay mineral raw materials.

When adsorbing the layered silicate mineral on the adsorbent, the temperature of the medium may be set in the range of 5 ° C. to 100 ° C., more preferably in the range of 15 ° C. to 80 ° C. If the temperature of the medium during adsorption is set lower than 5 ° C, it takes time to adsorb the layered silicate mineral to the adsorbent, and if the temperature of the medium during adsorption is set higher than 100 ° C, the boiling point of water is reached. It will reach and cost energy. Since the adsorbent adsorbs the layered silicate mineral in the pH range of 2 to 7 until the adsorption amount corresponds to a specific pH, and does not adsorb the layered silicate mineral beyond the adsorption amount corresponding to the specific pH. , The time during which the adsorption amount corresponding to a specific pH can be adsorbed may be set as the adsorption time. The operation of adsorption is not particularly limited, and examples thereof include a batch type in which the clay mineral raw material and the adsorbent are brought into contact with each other in a tank filled with a medium, and a distribution type in which the clay mineral raw material is passed through a column filled with the adsorbent. Be done.

Next, the adsorbent on which the layered silicate mineral is adsorbed is taken out from the medium by filtration using a mesh or the like. Layered silicate minerals are adsorbed on the obtained adsorbent in preference to mineral impurities, and mineral impurities remain in the medium. The operation of attachment / detachment is not particularly limited, but for example, a batch type in which the adsorbent is placed in a tank filled with a medium may be used.

Specifically, the layered silicate mineral was adsorbed in a detachable medium (another medium) adjusted to a pH higher than pH 4 and higher than the pH of the medium on which the layered silicate mineral was adsorbed. An adsorbent is added to desorb the layered silicate mineral from the adsorbent. When an adsorbent adsorbing a layered silicate mineral is placed in a medium whose pH is adjusted to be higher than 7, the layered silicate mineral is separated from the adsorbent. In particular, when an adsorbent adsorbing a layered silicate mineral is placed in a medium whose pH is adjusted to be greater than 10, all of the layered silicate mineral is separated from the adsorbent. Even if the medium at the time of desorption is in the range of pH 2 to 7, if the pH is set to be higher than 4 and higher than the pH of the medium at the time of adsorption, the amount of adsorption corresponding to the pH of the medium at the time of adsorption will be higher at the time of desorption. Since the amount of adsorption corresponding to the pH of the medium is small, the portion of the adsorbed layered silicate mineral that exceeds the amount of adsorption corresponding to the pH of the medium at the time of desorption is separated from the adsorbent. When the pH is set to be higher than 7, the medium for desorption may be an aqueous solution whose pH is adjusted with an alkali such as sodium hydroxide. Further, as the medium for desorption, when the pH is set to 7 or less, which is larger than 4, an aqueous solution whose pH is adjusted with an acid such as hydrochloric acid may be used.

When desorbing the layered silicate mineral from the adsorbent, the temperature of the medium may be set in the range of 5 ° C. to 100 ° C., more preferably in the range of 15 ° C. to 80 ° C. If the temperature of the medium at the time of desorption is set lower than 5 ° C, it takes time to desorb the layered silicate mineral from the adsorbent, and if the temperature of the medium at the time of desorption is set higher than 100 ° C, the boiling point of water is reached. It will reach and cost energy.

Next, by recovering the layered silicate mineral from the medium at the time of desorption by filtration using a mesh or the like, a clay mineral material mainly composed of the layered silicate mineral with reduced mineral impurities can be obtained. In particular, by desorbing the layered silicate mineral from the adsorbent to which the layered silicate mineral is adsorbed by setting the pH of the medium at the time of adsorption to 6 to 7, the layered silicate mineral containing no mineral impurities A clay mineral material consisting of only adsorbent can be obtained. The method for recovering the adsorbent after adsorption and the layered silicate mineral desorbed from the adsorbent is not limited to filtration, and other methods such as centrifugation can also be adopted.

According to the above-mentioned production method according to the present invention, the layered silicate mineral is adsorbed on the adsorbent by the anionic group of the adsorbent by a simple operation of bringing the adsorbent into contact with the layered silicate mineral. Therefore, the layered silicate mineral can be easily separated from the clay mineral raw material containing mineral impurities. Thereby, it is possible to easily obtain a clay mineral material mainly composed of a layered silicate mineral in which mineral impurities are reduced or eliminated without using a special chemical or performing a special or complicated operation. Further, by adsorbing the layered silicate mineral on an adsorbent having a particle size larger than that of the layered silicate mineral, separation from the medium becomes easy. Further, the above-mentioned manufacturing method includes equipment for bringing the adsorbent and the clay mineral raw material into contact with each other in the medium, equipment for separating the adsorbent from the medium by filtering with a mesh or the like, and layered silicate mineral from the adsorbent. Simple equipment with the equipment to separate is sufficient, and no special or complicated equipment is required. Moreover, as described above, the adsorption step of adsorbing the layered silicate mineral on the adsorbent and the desorption step of desorbing the layered silicate mineral from the adsorbent differ only in the pH of the medium, so the same equipment is used. Can be used. Therefore, according to the above-mentioned production method, the time, labor, and cost for producing a clay mineral material mainly composed of a layered silicate mineral can be significantly reduced. Moreover, the adsorbent can be used repeatedly.

According to the above-mentioned production method, the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 2 to 7, and a large amount of layered silicate mineral is adsorbed in preference to mineral impurities. It can be adsorbed on the material. That is, by simply controlling the pH of the medium, the amount of layered silicate minerals adsorbed on the adsorbent can be increased to suppress the adsorption of mineral impurities, and the layered silicates adsorbed and separated by the adsorbent can be suppressed. The recovery efficiency of minerals can be improved. In addition, since the obtained clay mineral material contains less mineral impurities adsorbed on the adsorbent, the mineral impurities can be reduced or eliminated as a result, and the layered silicate can be used for cosmetics and pharmaceuticals. The purity of minerals can be improved.

In the above-mentioned production method, the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 2 to 7, and an adsorption step of adsorbing the layered silicate mineral on the adsorbent is performed. Next, the adsorbent on which the layered silicate mineral was adsorbed was placed in a removable medium adjusted to a pH higher than pH 4 and higher than the pH of the adsorbing medium on which the layered silicate mineral was adsorbed. Then, a desorption step of desorbing the layered silicate mineral from the adsorbent is performed. In the desorption step, even if the medium is in the acidic to neutral region, the layered silicate mineral can be desorbed from the adsorbent to some extent by adjusting the pH to be larger than 4, and the pH of the medium is alkaline greater than 7. By forming the region, the layered silicate mineral can be desorbed from the adsorbent. In particular, by setting the pH of the medium to an alkaline region greater than 10, all the layered silicate minerals can be desorbed from the adsorbent. As described above, according to the above-mentioned production method, the adsorbent is adsorbed on the adsorbent or the layered silicate mineral is adsorbed by a simple operation of changing the pH of the medium in which the adsorbent is brought into contact with the clay mineral raw material. It is possible to control the desorption of minerals from the adsorbent. That is, a clay mineral material mainly composed of a layered silicate mineral can be more easily obtained only by controlling the pH of the medium.

In the above-mentioned production method, the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 6 to 7, so that only the layered silicate mineral among the clay mineral raw materials is selectively used as the adsorbent. Can be adsorbed. In other words, when the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 6 to 7, the mineral impurities in the clay mineral raw material are not adsorbed by the adsorbent at all, so that the layered silicate mineral It is possible to obtain an adsorbent in which only minerals are adsorbed. By recovering this adsorbent and separating / recovering the adsorbent into the adsorbent, a clay mineral material composed of a layered silicate mineral from which mineral impurities have been removed can be easily obtained. As described above, according to the above-mentioned production method, a clay mineral material having a very high purity that can be suitably used for cosmetics, pharmaceuticals, etc. by a simple operation of performing an adsorption step with a medium adjusted to a pH in a specific range. Can be obtained.

Next, the clay mineral composite according to the present invention using the above-mentioned adsorbent as a base particle will be described below. The clay mineral composite according to the present invention is adsorbed on a spherical mother particle using the above-mentioned adsorbent made of a polymer compound having an anionic group and an anionic group of the mother particle on the surface of the mother particle. It is equipped with arranged layered silicate mineral particles. As the mother particle, a spherical shape of the above-mentioned adsorbent may be used. Further, the layered silicate mineral particles are layered silicate minerals to be adsorbed by the above-mentioned adsorbent, and sericite suitable for cosmetics and pharmaceutical applications may be used, for example.

The particle size of the layered silicate mineral particles is preferably in the range of 0.2 μm to 20 μm, more preferably 1 μm to 15 μm, and smaller than the mother particles. When the particle size of the layered silicate mineral particles is larger than 20 μm, a squeaky feeling is likely to occur when used in products used for skin such as cosmetics. Further, if the particle size of the layered silicate mineral particles is smaller than 0.2 μm, it becomes difficult to wash them off when used in products used for skin such as cosmetics, and if it is too small, epidermal absorption occurs. There is a possibility that the function as cosmetics etc. may be impaired. The particle size of the layered silicate mineral particles can be obtained by using a size measurement by a dynamic light scattering method, a laser diffraction type particle size distribution measuring device, a flow particle image analyzer, or the like.

The clay mineral composite preferably has an average particle diameter (hereinafter referred to as an average particle size) in a wet state in the range of 1 μm to 1000 μm, and more preferably has a spherical shape in the range of 3 μm to 300 μm. When the average particle size of the clay mineral complex is larger than 1000 μm, a squeaky feeling is likely to occur when used in products used for skin such as cosmetics. Further, if the average particle size of the clay mineral composite is smaller than 1 μm, it becomes difficult to wash it off when used in products used for skin such as cosmetics, and if it is too small, epidermal absorption may occur. , There is a possibility of impairing the function as cosmetics. The clay mineral composite having an average particle size in the range of 3 μm to 200 μm shows a suitable spherical shape and can be easily produced. The average particle size of the clay mineral complex is a value measured by dispersing the clay mineral complex in a large excess of water exceeding the water absorption amount, and is a volume average particle size measured by an image processing device from an image obtained by a microscope. Is calculated. A clay mineral complex having a size of 1 μm or less is measured by a light scattering method. Since the particle size of the clay mineral composite is derived from the particle size of the mother particles, the average particle size in a wet state is in the range of 1 μm to 1000 μm, preferably a spherical mother particle in the range of 3 μm to 200 μm. Used.

The clay mineral complex preferably has a cation exchange capacity in the range of 0.15 meq / g to 10 meq / g, and more preferably in the range of 0.2 meq / g to 6.5 meq / g. Here, when the cation exchange capacity of the clay mineral complex is larger than 10 meq / g, the spherical shape is impaired, and when it is smaller than 0.15 meq / g, it exhibits hydrophobicity and the moisturizing function is deteriorated. The clay mineral composite having a cation exchange capacity in the range of 0.15 meq / g to 6.5 meq / g shows a suitable spherical shape and can be easily produced.

The clay mineral composite is preferably set so that the saturated water absorption amount is in the range of 10 g / g to 80 g / g, and more preferably in the range of 20 g / g to 70 g / g. Saturated water absorption is a value calculated by subtracting the weight of the clay mineral complex during drying from the weight of the clay mineral complex after immersion in water and dividing it by the weight of the clay mineral complex during drying. is there.
・ Saturated water absorption = (“Weight of clay mineral complex after water absorption”-“Weight of clay mineral complex during drying”) / “Weight of clay mineral complex during drying”
Here, the drying conditions of the clay mineral complex are as follows: water contained in the clay mineral complex is replaced with methanol, methanol is replaced with ether, and then the clay mineral complex is dried under reduced pressure for 24 hours. The weight of the clay mineral complex after water absorption is measured by immersing the clay mineral complex dried under the above conditions in water for 3 hours to absorb water. When the saturated water absorption of the clay mineral complex is less than 10 g / g, the clay mineral complex becomes more hydrophobic and becomes difficult to be compatible with water. On the other hand, when the saturated water absorption of the clay mineral complex is larger than 80 g / g, the shape of the clay mineral complex is easily crushed, and the clay mineral complex feels on the skin when it is blended into a product used for the skin. There is an inconvenience that the improvement effect is reduced.

The clay mineral composite is preferably set so that the moisture absorption amount is in the range of 1.15 g / g to 2.5 g / g, more preferably in the range of 1.22 g / g to 2.2 g / g. Will be done. The amount of moisture absorbed is a value calculated by dividing the weight of the clay mineral composite after being left in a specific humidity environment for a predetermined time by the weight of the clay mineral composite at the time of drying.
・ Moisture absorption = "Weight of clay mineral complex after moisture absorption" / "Weight of clay mineral complex when dried"
Here, the drying conditions of the clay mineral complex are as follows: water contained in the clay mineral complex is replaced with methanol, methanol is replaced with ether, and then the clay mineral complex is dried under reduced pressure for 24 hours. The weight of the clay mineral composite after moisture absorption is such that the clay mineral composite dried under the above conditions is left in an empty sample bottle set at a temperature of 40 ° C. and a humidity of 90% for 60 hours to absorb moisture. The weight after the clay is measured. When the moisture absorption amount of the clay mineral complex is less than 1.15 g / g, the clay mineral complex becomes more hydrophobic and becomes difficult to be compatible with water. On the other hand, when the moisture absorption amount of the clay mineral complex is larger than 2.5 g / g, the clay mineral complex is too soft and the shape of the clay mineral complex is easily crushed, and when the clay mineral complex is blended into a product used for skin. There is a disadvantage that the effect of improving the feel on the skin is reduced.

It is desirable that the clay mineral complex has a circularity in the range of 0.95 to 1.0 in an aqueous dispersion state. Here, the circularity is a value obtained by dividing the peripheral length calculated from the diameter of a perfect circle having the same projected area as the peripheral length of the image obtained by imaging the clay mineral complex by the peripheral length of the image obtained by imaging the clay mineral complex. is there. The circularity is "1" for a perfect circle, and the more complicated the shape, the smaller the value. If the roundness of the clay mineral composite is less than 0.95, for example, when it is used as a cosmetic product, it will not roll well on the surface of the skin, so that it will be difficult to obtain the desired stretch and feel of the cosmetic product.
Circularity = "peripheral length calculated from the diameter of a perfect circle with the same projected area as the peripheral length of the image of the clay mineral complex" / "peripheral length of the image of the clay mineral complex"
In the clay mineral composite, most of the properties of cation exchange capacity, saturated water absorption, moisture absorption and roundness are derived from the mother particles.

When a particle corresponding to the above-mentioned acrylic adsorbent is used as the mother particle, the crosslinked polyacrylic acid ester used as a starting material may be, for example, particles obtained by cross-linking an acrylic acid ester monomer with a cross-linking agent into fine spherical shapes. Just do it. The method for producing spherical crosslinked polyacrylic acid ester particles is as follows, as a crosslinking agent, alcandiacrylate, phenyldiacrylate, alcantriacrylate, alcantetraacrylate, or alcandimethacrylate, alcantrimethacrylate, alcantetramethacrylate, phenyldimethacrylate. , Emulsion copolymerization of acrylic acid ester using a bifunctional or higher functional cross-linking agent such as divinylbenzene, suspension copolymerization method and the like.

The molar concentration of the cross-linking agent used in the production of the cross-linked polyacrylic acid ester particles forming the mother particles is set to be blended in the range of 10 mol% to 100 mol% with respect to all the monomers in the case of polyfunctional acrylate. To. In this case, if the molar concentration of the cross-linking agent is less than 10 mol%, the cross-linking agent immediately hydrolyzes during the hydrolysis reaction when producing the mother particles, so that the spherical shape cannot be maintained. is there. When divinylbenzene, which is stable to acids and alkalis, or polyfunctional methacrylate, acrylamide, or divinylbenzene is used as the cross-linking agent, it should be blended in the range of 10 mol% to 50 mol% with respect to all the monomers. preferable. In this case, when the molar concentration of the cross-linking agent is larger than 50 mol%, the cross-linking agent is hydrophobic, so that the cross-linking agent inhibits the hydrophilicity of polyacrylic acid even if a hydrolysis reaction occurs during the production of the mother particles. As a result, the clay-mineral complex as a whole exhibits hydrophobicity, and the moisturizing effect required when blended in products used for skin such as cosmetics cannot be obtained. The method for producing the spherically crosslinked polymethacrylic acid ester particles is the same as that for the crosslinked polyacrylic acid alkyl ester particles. The acrylic resin includes a methacrylic acid ester and an acrylic acid ester, and the starting material may be either an acrylic acid ester or a methacrylic acid ester.

According to the clay mineral complex described above, in addition to the respective actions of the spherical mother particles composed of the polymer compound and the layered silicate mineral particles arranged by adsorption on the mother particles, the synergistic action of both is achieved. can get. That is, the clay mineral composite has properties such as elasticity and rolling property due to spherical mother particles made of a polymer compound, and properties such as glossiness and slipperiness (smooth feel) due to layered silicate minerals. It is suitable for applications such as cosmetics and pharmaceuticals that require these properties. In addition, since the clay mineral complex has reduced or eliminated mineral impurities other than layered silicate minerals, it can be suitably used for applications such as cosmetics and pharmaceuticals that come into contact with the human body. The clay mineral composite is not limited to applications such as cosmetics and pharmaceuticals that come into contact with the human body, but can also be used as a filler such as paper, paint or resin, or as a coating material such as filler or porcelain.

Since the mother particles have the same properties as the adsorbent described above, when the clay mineral composite is blended in a medium having a pH lower than 7, the layered silicate mineral particles are unlikely to separate from the mother particles. More specifically, if the layered silicate mineral particles are adsorbed on the mother particles so that the amount of the clay mineral composite is less than or equal to the adsorption amount corresponding to the pH of the compounded medium, the clay mineral complex is layered in the compounded medium. Silicate minerals do not desorb. Therefore, the clay mineral complex can be suitably used for cosmetics, pharmaceuticals, etc., which are prepared in the acidic region.

In the clay mineral composite according to the present invention, the acrylic adsorbent described above can be used as the mother particles. The clay mineral composite (hereinafter referred to as acrylic composite) using an acrylic adsorbent as a mother particle has a structure in which a part of the carboxylic acid ester in the crosslinked (meth) acrylic acid ester of the mother particle is hydrolyzed. Therefore, it has hygroscopicity and water absorption due to the hydrophilicity exhibited by the carboxyl group produced by hydrolysis. Further, the acrylic composite has a carboxyl group and an ester having a hydrophobic functional group (hydrophobic group) in the mother particle, and although it absorbs moisture and water due to the hydrophilicity shown by the carboxyl group, the ester having a hydrophobic group shows. Due to its hydrophobicity, there is a hydrophobic part that does not blend with water and does not swell, so only a part of it swells, so it does not absorb excessive water. That is, the acrylic composite can suppress the sticky feeling and improve the moist feeling when blended in a product used for the skin such as cosmetics. Furthermore, the acrylic composite retains the strength and properties derived from the spherical (meth) acrylic acid ester particles, although some of the mother particles are moistened, so that when incorporated into a product used for the skin, the acrylic composite retains its strength and properties. Goods on the skin and feels good on the skin. As described above, the acrylic composite can achieve both a moist feeling and a silky feeling when used in a product used for the skin. Further, since the acrylic composite has a spherical shape, it is possible to improve the elongation of the product when it is used in a product used for skin such as cosmetics. Further, since the acrylic composite causes charge repulsion due to the formation of carbanion, the dispersion stability of the composition constituting the product can be improved.

Moreover, since the acrylic composite has a carboxyl group on the surface of the mother particle and an ester having a hydrophobic group inside the mother particle, it absorbs water from the surface and absorbs water, but does not swell inside without being compatible with water. Due to the hydrophobic portion, the surface swells, but the inside retains the strength and properties of the spherical (meth) acrylic acid ester particles. Therefore, when the acrylic composite is blended into a product used for the skin such as cosmetics, a moist feeling due to the hydrophilicity of the surface is preferably expressed, and the characteristics of the spherical (meth) acrylic acid ester particles make it possible to obtain a moist feeling. It feels good on the skin and feels good on the skin.

The acrylic composite has a structure in which a part or all of the carboxylic acid produced by partially hydrolyzing the crosslinked poly (meth) acrylic acid ester particles forming the mother particles is metallized by an alkali metal. Moreover, it is insoluble in water. As described above, since the acrylic composite has a structure in which the mother particles are metal-chlorinated, it is easy to adjust the pH, and it is easy to commercialize it as a product used for the skin such as cosmetics.

The clay mineral composite can be produced under the same procedure and conditions as the above-mentioned adsorption step of clay mineral material. That is, by a simple operation of controlling the pH of the medium, the number of layered silicate mineral particles adsorbed on the mother particles can be increased, and the adsorption of mineral impurities on the mother particles can be suppressed, resulting in high-purity layered silicate. A clay mineral complex in which the mother particles are coated with a mineral can be obtained. In particular, by bringing the mother particles and the layered silicate mineral particles into contact with each other in a medium adjusted to a pH range of 6 to 7, only the layered silicate minerals can be selectively adsorbed on the mother particles. By bringing the mother particles and the clay mineral raw material containing mineral impurities into contact with each other in a medium adjusted to a pH range of 6 to 7, the mineral impurities in the clay mineral raw material are not adsorbed by the adsorbent at all. A clay mineral complex in which only salt mineral particles are adsorbed on the mother particles can be obtained. When producing a clay mineral composite, a clay mineral composite in which a layered silicate mineral having a very high purity is supported on a mother particle is prepared without separately preparing a layered silicate mineral particle from which mineral impurities have been eliminated. It can be obtained directly from clay mineral raw materials. As described above, a clay mineral composite that can be suitably used for cosmetics, pharmaceuticals, and the like can be obtained by a simple operation of performing an adsorption step with a medium adjusted to a pH in a specific range.

Next, the adsorbent, the method for producing a clay mineral material, and the clay mineral composite according to the present invention will be described below with reference to suitable examples.

Spherical crosslinked polyacrylic acid ester particles (manufactured by Sekisui Kasei Kogyo Co., Ltd .: trade name ARX-30, average particle size 30 μm) are mixed with a reaction solvent (acetone) consisting of 3 M potassium hydroxide (KOH) aqueous solution and acetone. The mixture was dispersed in (concentration: 20.8 wt%), the reaction temperature was set to 60 ° C., and the hydrolysis treatment was carried out while stirring for a predetermined time shown in Table 1. After a lapse of a predetermined time, the product was collected by filtration from the reaction solvent, washed with water, methanol and diethyl ether and dried to partially hydrolyze the carboxylic acid alkyl ester of the crosslinked polyacrylic acid ester particles. The adsorbent according to Examples 1 to 5 having the above was obtained. Further, as an adsorbent of the comparative example, crosslinked butyl polyacrylate particles (manufactured by Sekisui Plastics Co., Ltd .: trade name ARX-30, average particle size 30 μm) which had not been hydrolyzed were prepared.

When the infrared absorption spectrum of the adsorbent of Example 2 was measured by a Fourier transform infrared spectroscope, as shown in FIG. 2, it was compared with the unhydrolyzed crosslinked polyacrylate butyl particles (Comparative Example). A sharp absorption derived from the carboanion appeared near 1560 cm- ¹ , and it is clear that the adsorbent of Example 2 was hydrolyzed by the crosslinked butyl polyacrylate particles. As the infrared spectroscope, the product name FT / IR-700 manufactured by JASCO Corporation was used. In some cases, the crosslinked butyl polyacrylate particles that have not been hydrolyzed are referred to as "PBA", and those in which a carboxyl group is introduced into PBA are referred to as "PBA-PAA" (for example, FIG. 2).

The content of anionic groups was examined for the adsorbents of Examples 1 to 5. The adsorbents of Examples 1 to 5 are titrated by conductivity titration, and as shown in Table 1, it can be seen that the content of carboxyl groups increases as the reaction time increases. As described above, it can be seen that as the reaction time becomes longer, the hydrolysis reaction of the ester bond proceeds and more carboxyl groups are generated. Specifically, the content of anionic groups (the amount of carboxyl groups) was calculated as follows by measuring the conductivity. 0.2 g of the freeze-dried adsorbent of Examples 1 to 5 was collected, and 137 ml of water was added. To this, 0.1 M hydrochloric acid (HCl) was added to adjust the pH to 2.5. Next, 200 ml of a 0.1 M aqueous solution of sodium hydroxide (NaOH) was added, the conductivity and pH were observed, and the mixture was added dropwise until the pH reached about 11. The neutralization step of the strong acid is carried out with hydrochloric acid (HCl) and sodium hydroxide (NaOH), and the neutralization step of the weak acid is carried out with the carboxylic acid (R-COOH) and sodium hydroxide (NaOH). Termination was done with sodium hydroxide (NaOH). In the neutralization step of the weak acid, the consumed sodium hydroxide was read by the conductivity curve and the pH curve, and the amount of carboxyl groups was determined from this value by the following formula.
・ Amount of carboxyl group = (0.1 mol / L × amount of NaOH dropped in the neutralization stage of weak acid (mL)) / amount of adsorbent (g)
The sodium hydroxide (NaOH) consumed in the neutralization step of the weak acid was (a) pH 2 to 2.5, (b) 5.0 to 6.0, and (c) 10.0 to 10.5. A tangent line is drawn for the conductivity curve in each region of (a), and 0.1 mol / mol dropped between the intersection of the tangents of (a) and (b) and the intersection of the tangents of (b) and (c). It is defined as the amount of L sodium hydroxide (NaOH) aqueous solution.

Next, the adsorption of the adsorbents of Examples and Comparative Examples with the layered silicate mineral was investigated. 2.25 g of the adsorbents of Examples and Comparative Examples were added to 90 ml of water, and a dispersion liquid dispersed in water while stirring was prepared for each of Examples and Comparative Examples. To the dispersion liquid, 0.45 g of serisite and quartz were added so as to have a weight ratio of 1: 1 and a 10 wt% hydrochloric acid (HCl) aqueous solution was added dropwise to the dispersion liquid in a 300 ml beaker to disperse the mixture. The liquid (medium for adsorption) was adjusted to have the predetermined pH conditions shown in Table 2. Then, the pH-adjusted dispersion was administered to a 300 ml eggplant flask and stirred at 40 ° C. for 3 hours. For sericite, the trade name "Serisite FSE" (average particle size 1 μm to 18 μm) manufactured by Sanshin Mining Co., Ltd. is used, and for quartz, single crystal silica (average particle size 0.35 μm to 3.5 μm) is used. Is used.

Next, in order to calculate the content and recovery rate of minerals (serisite, quartz) adsorbed on the adsorbents of Examples and Comparative Examples, calibration curves were prepared as shown in FIGS. 3 and 4. The calibration curve of sericite was prepared from 45 °, and the calibration curve of quartz was prepared from 60.2 °. The calibration curve of sericite is calculated by the integrated area of the 45 ° X-ray diffraction peak peculiar to sericite at a ratio of 1: 9, 3: 7, 5: 5, 7: 3 between the adsorbent and sericite. did. In addition, the calibration curve of quartz shows that the adsorbent and quartz have a ratio of 99: 1, 95: 5, 90:10, 70:30, 50:50, 30:70, which is 60.2 ° peculiar to quartz. It was calculated by the integrated area of the X-ray diffraction peak. Further, the contents and recovery rates of minerals (serisite, quartz) adsorbed on the adsorbents of Examples and Comparative Examples calculated from these calibration curves are shown in Table 2 for each pH condition of the adsorbing medium. The content rate is the ratio of minerals to the adsorbent to which minerals (serisite, quartz) are adsorbed, and the recovery rate is the amount of minerals (serisite, quartz) mixed with the adsorbent adsorbed to the adsorbent. Shown. In FIG. 5, using the adsorbent of Example 2, as described above, the mixture of sericite: quartz = 1: 1 and the adsorbent are brought into contact with each other for 3 hours at a temperature of 40 ° C., and the mixture is brought into contact with the adsorbent. It is an X-ray diffraction pattern of the complex adsorbed on, and shows the peak of sericite 45 °. Further, in FIG. 6, using the adsorbent of Example 2, as described above, the mixture of sericite: quartz = 1: 1 and the adsorbent were brought into contact with each other for 3 hours at a temperature of 40 ° C. to bring the mixture together. It is an X-ray diffraction pattern of the composite adsorbed on the adsorbent, and shows the peak of quartz 60.2 °.

As shown in FIGS. 7 to 10, it was confirmed that sericite was adsorbed on the adsorbent by bringing the mineral (serisite, quartz) into contact with the adsorbent in the medium of pH3, pH4, pH5 and pH6. it can.

In the examples shown in FIGS. 11 to 13 and 17, 2.25 g of the adsorbent of Example 2 was added to 90 ml of water to prepare a dispersion liquid dispersed in water while stirring, and the dispersion liquid was added to the dispersion liquid. 0.45 g of sericite was added, and a 10 wt% hydrochloric acid (HCl) aqueous solution was added dropwise to the dispersion in a 300 ml beaker, and the dispersion (adsorption medium) was adjusted to pH 3 and adsorbed. It is a thing. Further, in the example shown in FIG. 18, 2.25 g of the adsorbent of Example 2 was added to 90 ml of water to prepare a dispersion liquid dispersed in water while stirring, and hydrochloric acid was added to the dispersion liquid. 45 g was added, and a 10 wt% hydrochloric acid (HCl) aqueous solution was added dropwise to the dispersion in a 300 ml beaker, and the dispersion (adsorption medium) was adjusted to pH 3 and adsorbed. For sericite, the trade name "Serisite FSE" (average particle size 1 μm to 18 μm) manufactured by Sanshin Mining Co., Ltd. is used, and for quartz, single crystal silica (average particle size 0.35 μm to 3.5 μm) is used. Is used.

Conventionally, it has been said that layered silicate minerals such as sericite do not electrostatically adsorb to polymer compounds having anionic groups because they have a negative charge. However, as shown in FIGS. 7 to 17, it was confirmed that sericite was adsorbed on the adsorbent according to the example composed of the polymer compound having an anionic group, which was the anionic group of the adsorbent. It is considered that sericite is adsorbed by alternating electrostatic interaction with sericite. Further, as shown in FIG. 18, it can be seen that quartz is more difficult to adsorb to the adsorbent even under the same adsorption conditions as sericite. As can be seen from FIGS. 5, 6 and 2, the adsorbent of the example was found to adsorb sericite in a medium of pH 3 to 7, and under pH conditions of pH 3 to 7, sericite was more absent than quartz. It was confirmed that a large amount of adsorbent was adsorbed, and that the adsorbent had the property of preferentially adsorbing sericite. It can also be confirmed that the adsorbent of the example has a selectivity of adsorbing sericite in a medium having a pH of 6 to 7 but not quartz at all.

As shown in FIGS. 11 to 13, the time (adsorption time) for contacting the mineral (serisite, quartz) with the adsorbent in the medium was 1 hour (FIG. 11), 3 hours (FIG. 12), and 5 hours (FIG. 12). It was confirmed that the amount of sericite adsorbed did not change much even if it was changed as shown in FIG. 13). It is considered that this is because the amount of sericite adsorbed on the adsorbent depends on the pH of the medium.

In the examples shown in FIGS. 14 to 16, 2.25 g of each of the adsorbents of Example 1, Example 2 and Example 3 was added to 90 ml of water to prepare a dispersion liquid dispersed in water while stirring. Then, 0.45 g of sericite is added to this dispersion, and a 10 wt% hydrochloric acid (HCl) aqueous solution is added dropwise to the dispersion in a 300 ml beaker so that the dispersion (adsorption medium) has a pH of 3. It was adjusted to and adsorbed. As described above, it can be seen that the adsorbents of Examples 1 to 3 adsorb all sericite.

Further, as shown in FIGS. 7 to 17, it is also possible to obtain a clay mineral composite in which the surface of the adsorbent of the example is used as a mother particle and the surface of the mother particle is coated with sericite adsorbed on the mother particle. You can check it.

Next, the desorption of sericite from the adsorbents of Examples 2 and 3 in which sericite was adsorbed as described above was investigated. 2.25 g of the adsorbent of Examples 2 and 3 having already adsorbed sericite was added to 90 ml of water, and a dispersion liquid dispersed in water while stirring was prepared for each of Examples 2 and 3. A 10 wt% sodium hydroxide (NaOH) aqueous solution was added dropwise to the dispersion in a 300 ml beaker, and the dispersion (detachable medium) was adjusted to have the predetermined pH conditions shown in Table 3. The pH-adjusted dispersion was administered to a 300 ml eggplant flask and stirred at 40 ° C. for 3 hours.

Next, a calibration curve was prepared to calculate the desorption rate of minerals (serisite, quartz) desorbed from the adsorbents of Examples 2 and 3. The calibration curves of sericite and quartz are prepared in the same manner as described above. The desorption rates of minerals (serisite, quartz) desorbed from the adsorbents of Examples 2 and 3 calculated from the calibration curve are shown in Table 3 for each pH condition of the desorption medium. The desorption rate was measured by the weight change between the adsorbent before desorption and the adsorbent after desorption. For sericite, the trade name "Serisite FSE" (average particle size 1 μm to 18 μm) manufactured by Sanshin Mining Co., Ltd. is used, and for quartz, single crystal silica (average particle size 0.35 μm to 3.5 μm) is used. Is used.

FIG. 19 shows a state in which sericite is desorbed from the adsorbent of Example 2 in which sericite is adsorbed using a desorption medium having a pH of 10. As shown in Table 3, it was confirmed that sericite adsorbed on the adsorbent was desorbed in the medium having a pH higher than 7, and it was found that the higher the pH, the higher the desorption rate. It can also be confirmed that when the pH of the medium becomes 10 or more, all of the sericite adsorbed on the adsorbent is desorbed. Therefore, it can be seen that a clay mineral material mainly composed of sericite can be obtained by preferentially or selectively adsorbing and separating sericite from the clay mineral raw material by the adsorbent and desorbing sericite from the adsorbent. ..

In Examples 1 to 5, PBA-PAA particles in which a carboxyl group was introduced into crosslinked butyl acrylate particles by hydrolysis were used as an adsorbent, but an adsorbent made of a water-absorbent resin such as acrylic acid particles having a carboxylic acid. It may be. An adsorbent made of such a water-absorbent resin is considered to have the same action as the acrylic adsorbent described above. The adsorbent of the modified example composed of acrylic acid particles having a carboxylic acid can be produced, for example, by polymerizing a water-soluble ethylenically unsaturated monomer by a reverse phase suspension polymerization method or the like. The water-absorbent resin present in the polymerization reaction of the water-soluble ethylenically unsaturated monomer is not particularly limited, and any commercially available water-absorbent resin can be used. For example, water addition of a starch-acrylonitrile graft copolymer. Decompositions, neutralized starch-acrylic acid graft copolymers, saponified vinyl acetate-acrylic acid ester copolymers, partially neutralized polyacrylic acid, maleic anhydride-isobutylene copolymers and water-soluble ethylenic Examples thereof include polymers of unsaturated monomers. In addition, a water-soluble monomer is blended in an appropriate amount ratio of a polyfunctional polymerizable monomer, added to a hydrophobic solvent such as an aliphatic or aromatic carbide containing a surfactant, and a radical polymerization initiator is added. Then, the suspended polymer particles may be used.

As an example of the method for producing the adsorbent of the modified example, 600 ml of n-alkane was added to a 1 L four-necked cylindrical round-bottom flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube. To this, 0.97 g of sorbitan monolaurate (surfactant: Nonion LP-20R manufactured by Nippon Oil & Fats Co., Ltd.) having an HLB of 8.6 was added and dispersed, and the temperature was raised to 50 ° C. to add the surfactant. After melting, it was cooled to 30 ° C. On the other hand, a 500 ml Erlenmeyer flask was prepared separately, and 92 g of an aqueous acrylic acid solution was added thereto. To this, 152.6 g of an aqueous sodium hydroxide solution was added dropwise from the outside while cooling with ice to neutralize 75 mol%, and then 0.10 g of potassium persulfate was further added to dissolve the adsorbent of the modified example. Obtainable.

Next, the adsorbent of Example 6 corresponding to the adsorbent of the modified example will be described. 160 ml of water was added to 0.5 g of polyacrylic acid particles (manufactured by Sumitomo Seika Chemical Co., Ltd., trade name: Aquakeep 10SHNF) as an adsorbent of Example 6, and dispersed while stirring. 0.45 g of Amakusa pottery stone was added, and the pH was adjusted to a predetermined pH condition while dropping with a 10 wt% aqueous solution of HCl in a 300 ml beaker. It was administered to a 300 ml eggplant flask and stirred at 40 ° C. for 3 hours. The Amakusa pottery stone contains 34% sericite and 44% quartz on average, and is obtained by sieving with a 32 μm pass.

As shown in FIG. 20, it can be seen that even the adsorbent of Example 6 adsorbs sericite (Amakusa pottery stone). That is, it can be confirmed that the adsorbent is not limited to PBA-PAA particles, but may be acrylic acid particles having a carboxylic acid.

10 clay mineral composite, 12 mother particles (adsorbent), 14 anionic groups,
16 layered silicate minerals, 20 quartz (mineral impurities)

Claims (14)

, A polymer compound, a clay mineral adsorbent for the organic capable of adsorbing anionic group layered silicate mineral,
The polymer compound is an adsorbent for clay minerals , which is a crosslinked poly (meth) acrylic acid or a crosslinked poly (meth) acrylic acid ester obtained by hydrolyzing a part of a carboxylic acid ester . The adsorbent for clay minerals according to claim 1, which adsorbs more layered silicate minerals than clay minerals other than the layered silicate minerals in a medium having a pH in the range of 2 to 7. Claim 1 that adsorbs a layered silicate mineral up to an adsorption amount corresponding to the pH of the medium and desorbs a portion of the layered silicate mineral adsorbed on itself that exceeds the adsorption amount corresponding to the pH of the medium. Alternatively, the adsorbent for clay minerals according to 2. The adsorption for clay minerals according to any one of claims 1 to 3, which selectively adsorbs layered silicate minerals instead of clay minerals other than layered silicate minerals in a medium having a pH in the range of 6 to 7. Material. The adsorbent for clay minerals according to any one of claims 1 to 4, wherein the anionic group is a sulfo group, a sulfate group, a carboxyl group, or a phosphoric acid group. The adsorbent for clay minerals according to any one of claims 1 to 5, wherein the content of the anionic group is in the range of 0.2 meq / g to 12 meq / g. An adsorbent made of a polymer compound having an anionic group is brought into contact with a clay mineral raw material containing a layered silicate mineral.
The layered silicate mineral is adsorbed on the anionic group of the adsorbent, and the layered silicate mineral is separated from the clay mineral raw material to obtain a clay mineral material mainly composed of the layered silicate mineral. It is a manufacturing method of clay mineral materials.
A clay mineral characterized by using crosslinked poly (meth) acrylic acid or a crosslinked poly (meth) acrylic acid ester obtained by hydrolyzing a part of a carboxylic acid ester as the polymer compound forming the adsorbent. Method of manufacturing the material. The production of the clay mineral material according to claim 7, wherein the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 2 to 7 to adsorb the layered silicate mineral on the anionic group. Method. The adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 2 to 7, and the layered silicate mineral is adsorbed on the anionic group.
The adsorbent on which the layered silicate mineral was adsorbed was placed in another medium adjusted to a pH higher than pH 4 and higher than the pH of the medium on which the layered silicate mineral was adsorbed, and the adsorption was performed. The method for producing a clay mineral material according to claim 7 or 8 , wherein the layered silicate mineral is desorbed from the material. The claim that the adsorbent and the clay mineral raw material are brought into contact with each other in a medium adjusted to a pH range of 6 to 7, and only the layered silicate mineral among the clay mineral raw materials is selectively adsorbed on the adsorbent. The method for producing a clay mineral material according to any one of 7 to 9 . The method for producing a clay mineral material according to any one of claims 7 to 10 , wherein the anionic group is a sulfo group, a sulfate group, a carboxyl group, or a phosphoric acid group. The method for producing a clay mineral material according to any one of claims 7 to 11 , wherein the adsorbent has an anionic group content in the range of 0.2 meq / g to 12 meq / g. Spherical mother particles made of a polymer compound having an anionic group and
The layered silicate mineral particles adsorbed on the anionic group of the mother particle and arranged on the surface of the mother particle are provided.
The polymer compound is a crosslinked poly (meth) acrylic acid or a crosslinked poly (meth) acrylic acid ester obtained by hydrolyzing a part of a carboxylic acid ester . The clay mineral composite according to claim 13, wherein the layered silicate mineral particles are formed so as to be difficult to separate from the mother particles in a medium having a pH lower than 7.