JPH07115855B2 - Surface-treated semi-synthetic mineral and its manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a surface-treated semi-synthetic mineral and a method for producing the same, and more specifically, it shows excellent emulsification performance in an oil-water system. , A surface-treated semi-synthetic mineral useful as various fillers, inorganic emulsifiers, adsorbents, etc., and a method for producing the same.

(Prior Art) Conventionally, talc has been a typical lipophilic clay mineral, and it is produced in Japan such as Matsumae district and Okayama prefecture in Hokkaido, but the production amount is small and both are impure. However, it has not been used effectively.

Further, layered magnesium fluorosilicate is known as a synthetic mineral having lipophilicity, and JP-A-61-10020 according to the proposal of the present inventors discloses that activated silicic acid obtained by acid treatment of clay mineral. Alternatively, it is described that a synthetic layered magnesium fluorosilicate having an emulsifying performance in an oil-water system is produced by hydrothermally treating an active aluminosilicate and an oxide or hydroxide of magnesium.

(Problems to be Solved by the Invention) This method requires a two-step operation of acid treatment of clay mineral and hydrothermal treatment with magnesium oxide, etc., resulting in high production cost and bulk, and as a talc substitute. Was still unsatisfactory for its use.

The present inventors, the raw material clay containing montmorillonite and cristobalite in a physically inseparable state, magnesium oxide, obtained by reacting a hydroxide or the like,
A novel semi-synthetic mineral containing dioctahedral montmorillonite and trioctahedral magnesium fluorosilicate in a physically inseparable state, a titanate system,
Surface-treated semi-synthetic mineral obtained by finely pulverizing in the presence of a silane-based or zirco-aluminate-based coupling agent to uniformly attach or bond the coupling agent to the surface of the semi-synthetic mineral particles. Has excellent properties as an inorganic emulsifier by a synergistic effect of hydrophilicity specific to dioctahedral montmorillonite, lipophilicity specific to trioctahedral magnesium fluorosilicate, and properties of the specific coupling agent. I found that.

(Means for Solving the Problems) According to the present invention, on the surface of the basic particles of a semi-synthetic mineral containing dioctahedral montmorillonite and trioctahedral magnesium fluorosilicate in a physically inseparable state, Provided is a surface-treated semisynthetic mineral having a titanate-based, silane-based, or zircoaluminate-based coupling agent attached or bonded thereto.

According to the present invention, further, a semi-synthetic mineral containing dioctahedral montmorillonite and trioctahedral magnesium fluorosilicate in a physically inseparable state, titanate-based, silane-based, or zircoaluminate-based coupling. A method for producing a surface-treated semi-synthetic mineral is provided by finely pulverizing in the presence of an agent to uniformly attach or bond the coupling agent to the surface of the semi-synthetic mineral particle.

(Operation) In the present specification, the physically inseparable state means that even if a plurality of components are attached to a physical separation means such as elutriation or elutriation,
It means a state in which a plurality of components are mixed in a state where the composition ratio of the plurality of components does not change and the components cannot be physically separated.

Naturally occurring montmorillonite group clay minerals, for example, acid clay contains various minerals such as quartz, feldspar, calcite, chlorite, zeolite and iron sulfide, and these impurities are stone sand separators, elutriates. Although it can be separated by means such as elutriation, the clay after separation contains cristobalite in addition to montmorillonite, and in many cases, montmorillonite and cristobalite are mixed in a physically inseparable state. It is considered that this is because montmorillonite and cristobalite are mixed in a crystallite state.

The present invention reacts a clay mineral containing montmorillonite and cristobalite in such a state with an oxide of magnesium in the presence of water, a hydroxide, or a compound capable of forming an oxide or a hydroxide under reaction conditions. This is based on the finding that the reaction between cristobalite and the magnesium compound occurs selectively and at least part of the cristobalite is converted to trioctahedral magnesium fluorosilicate.

In the semi-synthetic mineral produced by this method, the montmorillonite derived from the original clay mineral and the magnesium fluorosilicate produced by the reaction exist in a physically inseparable state. Montmorillonite has two AlO ₆ octahedral layers
The substrate has a three-layer structure sandwiched by tetrahedral layers of SiO ₄ , and this substrate structure has a multilayer structure in which the unit cell has the formula Al ₂ [Si ₂ O ₅ (OH)]. _Since it is ₂ , it belongs to the dioctahedral clay mineral. On the other hand, magnesium fluorosilicate is based on a three-layer structure in which an octahedral layer of MgO ₆ is sandwiched between two tetrahedral layers of SiO ₄ and has a multilayer structure in which the basic structure is somewhat randomly stacked. The unit cell has the formula Mg ₃ [Si ₂ O ₅ (O
H)] ₂ , it belongs to trioctahedral clay minerals.

The fact that these two types of layered crystal structures are present in the semi-synthetic mineral of the present invention is confirmed by an X-ray diffraction image.
FIG. 1 of the accompanying drawings is an X-ray diffraction pattern of the synthetic mineral of the basic particles of the present invention. Both dioctahedral type montmorillonite and trioctahedral type magnesium fluorosilicate have surface index [202] (d = 4.5Å) and surface index [200] (d
= 2.6Å), the diffraction peaks overlap, and the two cannot be distinguished. However, in the dioctahedral type, the diffraction peak with the surface index [060] has a surface spacing d = 1.50Å (2θ (Cu-Kα) = 62
In contrast, in the trioctahedral type, the diffraction peak with the surface index [060] has a surface spacing d = 1.54Å (2θ).
It can be confirmed that both of them are mixed in that they appear in (Cu-Kα) = 60 °.

The trioctahedral magnesium fluorosilicate in the semi-synthetic mineral of the basic particles of the present invention exhibits lipophilicity, while the dioctahedral montmorillonite exhibits hydrophilicity, and both these components exist in a physically inseparable state. Therefore, this mineral has an affinity for both oil and water, for example, when added to a system containing water and fluid paraffin in a two-layer system, both emulsions are stably formed (at a 1: 1 weight ratio). It becomes an oil-in-water emulsion).

The surface-treated semi-synthetic mineral of the present invention is one in which a titanate-based, silane-based or zirco-aluminate-based coupling agent is uniformly attached or bonded to the surface of the substrate particles of the semi-synthetic mineral having the above-mentioned characteristics. The emulsifying performance of the semi-synthetic mineral is increased, and the untreated semi-synthetic mineral alone may be used as a base particle even if a semi-synthetic mineral having a compositional structure having practically insufficient emulsifying performance is used. Excellent emulsification performance. It goes without saying that the surface-treated semi-synthetic mineral using as the base particles a semi-synthetic mineral having sufficient emulsification performance when used alone exhibits even more excellent emulsification performance.

(Preferred Embodiment of the Invention) A semi-synthetic mineral containing dioctahedral montmorillonite and trioctahedral magnesium fluorosilicate in a physically inseparable state, which is used as the base particles in the present invention, is montmorillonite and cristobalite. It can be obtained by reacting a raw material clay, which contains P in a physically inseparable state, with a magnesium oxide, a hydroxide, or a compound capable of forming an oxide or a hydroxide in the presence of water. The raw clay may be one containing montmorillonite and cristobalite, and examples thereof include montmorillonite group clay minerals such as acid clay, bentonite, subbentonite, and frass earth. FIG. 2 is an X-ray diffraction pattern of the raw clay used in Example 1, and it will be understood that it has an X-ray diffraction peak peculiar to cristobalite at 2θ (Cu-Kα) = 21.6 to 21.8 °. . The primary particles of the raw clay are extremely fine and of the order of submicron, and the clay produced can be used after being subjected to means such as stone sand separation, elutriation, and elutriation. Of course, it may be used for the reaction after performing a pretreatment such as drying and pulverization, if necessary.

The content of cristobalite in the raw clay can be varied over a wide range, but the total content of cristobalite is 5 to 50% by weight, particularly 20 to 40% by weight,
It is advantageously used for the purposes of the present invention. As the raw clay,
Hunter whiteness of 60% or more, especially 65% or more is particularly suitable.

The chemical composition of an example of the raw clay is shown in Table 1 below.

Table 1 SiO ₂ 45 to 75 wt% Al ₂ O ₃ 7 to 25 〃 Fl ₂ O ₃ 2 to 9 〃 MgO 1 to 5 〃 CaO 0.01 to 4 〃 K ₂ O 0.05 to 0.3 〃 Na ₂ O 0.01 to 0.1 〃 Loss on ignition 5 to 12 〃 As the magnesium raw material, an oxide of magnesium, a hydroxide, or a compound capable of forming the oxide or hydroxide under the reaction conditions can be used. Examples of the latter compound include magnesium carbonate and magnesium alkoxide. Magnesium oxide and hydroxide are suitable raw materials.

The amount of the magnesium compound is, as MgO, 0.1 to 3.0 mol, particularly 0.5 to 2.0 mol, per 1 mol of SiO _{2 of} cristobalite.
It is preferable to use them in such a ratio that the molar ratio becomes. The stoichiometric ratio for converting cristobalite to magnesium fluorosilicate is SiO ₂ : MgO = 4: 3, but even if the amount of magnesium compound is higher than this ratio, the presence of free magnesium compound Is not detected by X-ray diffraction, it is presumed that the excess magnesium component is layered between the basic layers of montmorillonite. On the other hand, when the ratio is less than the stoichiometric ratio, a part of cristobalite remains in an unreacted state. Of course, even if magnesium is used in a stoichiometric ratio, unreacted cristobalite may remain due to the difference in reactivity of cristobalite.

It is important to carry out the above-mentioned reaction of both raw materials in the presence of water, and in the absence of water, conversion of cristobalite to magnesium fluorosilicate does not occur. The reaction temperature is 60
It is carried out at a temperature of not less than 0 ° C, particularly at a temperature of 80 to 160 ° C, and under normal pressure or pressure. As a reaction method, clay is slurried, magnesium oxide or magnesium hydroxide is converted, and the reaction is performed with stirring. Alternatively, the clay and the magnesium compound are sufficiently uniformly kneaded in the presence of water, and the kneaded and granulated product is steam-reacted under a non-volatile condition of water, for example, in a sealed container. Further, the slurry or the kneaded product having the above composition is charged into an autoclave and reacted under pressure. In this hydrothermal synthesis method, it is possible to use carbonate as the magnesium component. The reaction time varies depending on the system and temperature, but is 3 to 10 hours by the slurry method, 3 to 10 hours by the steaming reaction method, and 1 to 5 hours by the autoclave method.

The product after the reaction is washed with water if necessary and subjected to post-treatments such as filtration, drying and crushing depending on the reaction method to obtain a product.

The semi-synthetic mineral obtained by the above method has an improved whiteness of hunter, an improved specific surface area, an oil absorption amount, etc. as compared with the raw clay.

Semisynthetic minerals used in the present invention, dioctahedral montmorillonite and the trioctahedral magnesium Le type Fuirokei acid, X-rays diffraction peak intensity ratio of plane indices [060], i.e. R = I _D / I _T (wherein , I _D represents the peak intensity of dioctahedral type montmorillonite at the interplanar spacing of 1.49 to 1.51Å, I _T represents the peak intensity of trioctahedral magnesium fluorosilicate at the interplanar spacing of 1.53 to 1.55 Å, and R is the peak intensity ratio. It is desirable that the peak intensity ratio (R) of R.) is generally in the range of 0.5 to 5, particularly 0.7 to 3. This peak intensity ratio (R) is related to the degree of balance between hydrophilicity and lipophilicity, and as this ratio (R) increases, the degree of hydrophilicity increases,
The smaller the ratio (R), the greater the degree of lipophilicity. Semi-synthetic minerals in which R is within the above range show remarkable emulsifying performance for oil-water systems.

The semi-synthetic minerals used in the present invention are generally 65% or more, especially
It has a Hunter whiteness of 70% or more, and the specific surface area is generally 70 m ² / g or more, particularly in the range of 100 to 200 m ² / g, and the oil absorption is 40 ml / 100 g or more, particularly 60 to 150 ml / 100 g. Within range.

As the coupling agent in the present invention, all titanate coupling agents, silane coupling agents and zircoaluminate coupling agents can be used. Examples of the titanate coupling agent include isopropyl stearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate. , Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, Isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate Isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenylalanine titanate, isopropyl Lil tri (N- aminoethyl-aminoethyl) titanate, and the like diisostearoyl ethylene titanate. Examples of the silane coupling agent include vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-
Aminopropyltriethoxysilane, N-phenyl-3
-Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and the like can be mentioned. Furthermore, examples of the zircoaluminate-based coupling agent include 3-aminopropoxyl zircoaluminate, 5-carboxypentoxyl zircoaluminate, tetradecanoxyl zircoaluminate, and 3-mercaptopropoxyl zircoaluminate. You can

In the surface-treated semi-synthetic mineral of the present invention, the coupling agent is 0.001 to 0.1 g per 1 g of the semi-synthetic mineral base particles,
In particular, it is preferable that they are uniformly attached or bonded at a rate of 0.002 to 0.05 g.

The base particles of the semi-synthetic mineral and the coupling agent adhere to each other with a strong force even in the case of adhesion due to their functionalities, in the form of adsorption or a form close to adsorption. Are connected. Therefore, when the surface-treated semi-synthetic mineral is used, the semi-synthetic mineral particles and the coupling agent are hardly desorbed.

The method of attaching or coupling the above-mentioned coupling agent to the base particles of the semi-synthetic mineral is as follows: when the semi-synthetic mineral obtained as described above is finely pulverized, the coupling agent is added. A method of finely pulverizing a semi-synthetic mineral in the coexistence of is adopted. Although various methods can be adopted as means for finely pulverizing, pulverization by an ordinary ball mill is preferable. The average particle size of surface-treated semi-synthetic minerals varies depending on the application, but generally it is 1 to 20 μm.
Is preferred, and the semi-synthetic mineral is finely pulverized until the average particle size is about that. In the case of fine pulverization in the presence of a coupling agent, if the pulverization work is too small, the coupling agent does not adhere or bond evenly over the entire base particles of semi-synthetic minerals, and the pulverization process becomes excessive. If it is too much, the emulsification performance and adsorption performance of the surface-treated semi-synthetic mineral will rather deteriorate. Therefore, the coupling agent can be added to the semi-synthetic mineral before the pulverization treatment, or can be added according to the amount of pulverization energy during the pulverization treatment of the semi-synthetic mineral. The surface-treated semi-synthetic mineral of the present invention is useful not only as a filler for internal filling or external filling for paper, but also as a filler for various plastics and as an inorganic emulsifier, Further, it is also useful as an adsorbent for adsorbing an oily substance in an aqueous phase system and, conversely, as an adsorbent for adsorbing a hydrophilic substance in an oil phase system. For example, cosmetics,
It is used as an additive for detergents and as an adsorbent for treating industrial wastewater and domestic wastewater.

Test Method The test method for each item in this specification was as follows.

1. X-ray Diffraction In this example, an X-ray diffractometer (X-ray generator 4036A1, goniometer-2125D1, counter 5071) manufactured by Rigaku Denki Co., Ltd. was used. The diffraction conditions are as follows.

Target Cu Filter Ni Detector SC Voltage 35KVP Current 15mA Count Full Scale 8000c / s Time Constant 1sec Scanning Speed 2 ° / min Chart Speed 2cm / min Radiation Angle 1 ° Slit Width 0.3mm Illumination Angle 6 ° 2. Area Index Measurement method of intensity ratio (R) of X-ray diffraction peak of [060] a X-ray diffraction condition Target Cu filter Ni detector SC voltage 40KVP current 20mA count full scale 8000c / s time constant 1sec scanning speed 1 ° / min Chart speed 1 cm / min Radiation angle 2 ° Slit width 0.3 mm Illumination angle 6 ° Measurement diffraction angle range 58 ° to 62 ° (2θ) In the present embodiment, the conditions are not limited to the above, but from the baseline. The conditions such as voltage and current may be set so that the peak height of 1 is in the range of 1 to 5 cm.

b. Calculation method of intensity ratio (R) X based on the surface index [060] obtained under the above X-ray diffraction conditions
Line diffraction spectrum of trioctahedral magnesium fluorosilicate starting point (2θ = 58 °) and dioctahedral type montmorillonite ending point (2θ =
63.5 °) is used as the base line and the surface index [06
The height of the dioctahedral type montmorillonite of [0] to the apex of the diffraction peak is I _D, and the height of the trioctahedral type magnesium fluorosilicate of surface index [060] to the apex of the diffraction peak is I _T.

The intensity ratio (R) is calculated by the following formula.

R = _ID / _IT 3. Average particle size Micron Fort Sizer based on the principle of centrifugal sedimentation
It was measured with SKN-1000 type (Seishin Enterprise). The sample was dispersed for 5 minutes using SK-DISPERSER (ultrasonic disperser) manufactured by Seishin Enterprise. The median particle diameter (50% cumulative) was determined from the obtained particle size distribution.

4. Hunter Whiteness In this example, an automatic reflectometer TR-600 type manufactured by Tokyo Denshoku Co., Ltd. was used.

5. BET specific surface area [SA] The specific surface area of each powder is so-called BET due to adsorption of nitrogen gas.
It measured according to the method. For details, refer to the following documents.

S.Brunauer, PHEmmett, E.Teller, J.Am.Chem.Soc, Vol.6
0, 309 (1938) Note that the measurement of the specific surface area in this specification is 15
What was dried to 0 ° C was placed in a weighing bottle of 0.5 to 0.6 g, dried in a thermostatic oven at 150 ° C for 1 hour, and the weight was immediately weighed precisely. Put this sample in an adsorption sample tube and heat it to 200 ° C, degas until the vacuum level in the adsorption sample tube reaches 10 ^-4 mmHg, and after cooling, put the adsorption sample tube in liquid nitrogen at about -196 ° C. , PN ₂ / p ₀ = 0.05 to 0.30 (pN ₂ : nitrogen gas pressure, p ₀ = atmospheric pressure at the time of measurement), the adsorbed amount of N ₂ gas is measured at 4 to 5 points. Then, the adsorption amount of N ₂ gas from which the dead volume is subtracted is converted into the adsorption amount at 0 ° C. and 1 atm and substituted into the BET formula to obtain Vm [cc / g] (necessary to form a monolayer on the sample surface. The amount of nitrogen gas adsorbed was shown). Specific surface area SA = 4.35 × Vm [m ² / g] 6. Oil absorption amount Measured by the JIS K-5101 pigment test method. The test sample was 1 g.

7. Powder oil-water phase dispersion state Take 20 g of pure water and 20 g of liquid paraffin (first-grade reagent) in a 50 ml glass tablet bottle, add 1 g of the sample to it, and use a paint shaker (Red Devil) to Disperse for minutes. After the dispersion is left at room temperature for 24 hours, the dispersed state of the sample is observed.

Example 1 Acid white clay (water content 35%, cristobalite content 30%) from Kushibiki Town, Yamagata Prefecture, crushed to about 1 cm or less 770 g and magnesium hydroxide (for reagent chemistry, MgO content 68.7%) 146 g, ion-exchanged water 160 g was mixed well and kneaded 5 times with an extrusion type granulator (PELLETER EXD-60 manufactured by Fuji Paudal) to obtain a clay / magnesium hydroxide kneaded granulated product having a thickness of about 5 mm. This granulated product was placed in a closed stainless steel container and placed in a thermostat kept at 98 ° C. for 7 hours while being sealed to carry out a reaction. The reaction product was taken out and dried at a temperature of 130 ° C. to obtain 650 g of a dried product. 650g of this dried product is put into a pot mill of 7 and the diameter is about
It was pulverized for 2 hours together with a 2.5 cm magnetic ball to obtain a white powder. (First Step) When this product was analyzed by X-ray diffraction, it was a semi-synthetic mineral containing montmorillonite and layered magnesium fluorosilicate.

Put 100g of the powder obtained in the first step in the pot mill of 2,
Isopropyltriisostearoyl titanate (Ajinomoto Co., Inc., Planeact TTS) (0.2 g) was added, and the mixture was ground with a Korean ball having a diameter of about 1 cm for 2 hours to obtain a white fine powder having a good emulsifying property in an oil-water system.

The X-ray diffraction peak area ratio R of the surface index [060] of this product, Hunter whiteness, specific surface area, oil absorption, and oil layer-water layer dispersion state are shown in Table 2.

Example 2 100 g of the powder obtained in the first step of Example 1 was placed in a pot mill of 2, and 2 g of hexamethyldisilazane (HMDS-1 of Shin-Etsu Chemical Co., Ltd.) was added, and 2 with a Korean ball having a diameter of about 1 cm was added. It was pulverized for a period of time to obtain a white fine powder having a good emulsifying property in an oil-water system.

The X-ray diffraction peak area ratio R of the surface index [060] of this product, Hunter whiteness, specific surface area, oil absorption, and oil layer-water layer dispersion state are shown in Table 2.

Example 3 100 g of the powder obtained in the first step of Example 1 was placed in a pot mill of 2, and 5 g of tetradecanoxyl zircoaluminate (Cabucomodo F, Cavedon Chemical, USA) was added,
It was crushed for 2 hours together with a Korean ball having a diameter of about 1 cm to obtain a white fine powder having a good emulsifying property in an oil-water system.

The X-ray diffraction peak area ratio R of the surface index [060] of this product, Hunter whiteness, specific surface area, oil absorption, and oil layer-water layer dispersion state are shown in Table 2.

Example 4 Acid white clay (35% water, cristobalite content 30%) from Kushibiki, Yamagata Prefecture, crushed to about 1 cm or less 770 g and magnesium hydroxide (for reagent chemistry, MgO content 68.7%) 146 g, ion-exchanged water 160g was mixed well and kneaded 5 times with an extrusion type granulator (PELLETER EXD-60 made by Fuji Paudal), thickness about 5mm
To obtain a clay / magnesium hydroxide kneading granulation product. This granulated product was placed in an autoclave and reacted at a temperature of 165 ° C. for 4 hours. The reaction product was taken out and dried at a temperature of 130 ° C. to obtain 640 g of a dried product. 640g of this dried product is put into a pot mill of 7 and 2 together with a magnetic ball of about 2.5cm in diameter.
It was crushed for hours to obtain a white powder. (First Step) When this product was analyzed by X-ray diffraction, it was a semi-synthetic mineral containing montmorillonite and layered magnesium fluorosilicate.

Put 100g of the powder obtained in the first step in the pot mill of 2,
Isopropyltriisostearoyl titanate (Ajinomoto Co., Inc., Planeact TTS) (0.2 g) was added, and the mixture was ground with a Korean ball having a diameter of about 1 cm for 2 hours to obtain a white fine powder having a good emulsifying property in an oil-water system.

The X-ray diffraction peak area ratio R of the surface index [060] of this product, Hunter whiteness, specific surface area, oil absorption, and oil layer-water layer dispersion state are shown in Table 2.

Comparative Example 1 Acid white clay (water content 35%, cristobalite content 30%) from Kushibiki Town, Yamagata Prefecture was crushed to a size of about 1 cm or less and dried at a temperature of 130 ° C. 650 g of this dried product was put in a pot mill 7 and pulverized for 2 hours together with a magnetic ball mill having a diameter of about 2.5 cm to obtain an off-white powder. (First step) 100 g of the powder obtained in the first step is placed in a pot mill of 2,
1 g of isopropyl triisostearoyl titanate (Ajinomoto Co., Inc., Planeact TTS) was added, and the mixture was ground with a Korean ball having a diameter of about 1 cm for 2 hours to obtain an off-white fine powder.

The Hunter whiteness, specific surface area, oil absorption, and oil layer-water layer dispersion state of this product are shown in Table 2.

[Brief description of drawings]

FIG. 1 shows the final white fine powder Cu-Kα obtained in Example 1.
It is an X-ray diffraction spectrum by a line. FIG. 2 is an X-ray diffraction spectrum by Cu-Kα ray of the raw clay used in Example 1. FIG. 3 shows d = 1. In the X-ray diffraction spectrum of FIG.
It is the diagram which expanded the diffraction peak between 50 Å and 1.59 Å, and illustrates how to obtain the intensity ratio (R).

Claims (10)

[Claims] 1. A titanate-based, silane-based or zircoaluminate-based cup is formed on the surface of a semi-synthetic mineral substrate particle containing dioctahedral montmorillonite and trioctahedral magnesium fluorosilicate in a physically inseparable state. A surface-treated semi-synthetic mineral with a ring agent attached or bonded. 2. The surface-treated semi-synthetic material according to claim 1, wherein the semi-synthetic mineral has X-ray diffraction peaks at interplanar spacings of 1.49 to 1.51Å and interplanar spacings of 1.53 to 1.55Å. mineral. 3. A dioctahedral montmorillonite and a trioctahedral magnesium fluorosilicate are represented by the following formula R = I _D / I _T (where I _D is the peak intensity of the dioctahedral montmorillonite at a surface spacing of 1.49 to 1.51Å). Where I _T is the peak intensity of trioctahedral magnesium fluorosilicate at a surface spacing of 1.53 to 1.55 Å, and R is the peak intensity ratio.) X-ray diffraction peak intensity of surface index [060] Ratio R
The surface-treated semi-synthetic mineral according to claim 1, characterized in that the content is 0.5 to 5. 4. The semi-synthetic mineral comprises a starting clay containing montmorillonite and cristobalite in a physically inseparable state, magnesium oxide, hydroxide or an oxide or hydroxide under reaction conditions. The surface-treated semi-synthetic mineral according to claim 1, which is a semi-synthetic mineral obtained by reacting with a compound capable of forming in the presence of water. 5. Coexistence of a titanate-based, silane-based, or zircoaluminate-based coupling agent with a semisynthetic mineral containing dioctahedral montmorillonite and trioctahedral magnesium fluorosilicate in a physically inseparable state. A method for producing a surface-treated semi-synthetic mineral, which comprises finely pulverizing the particles to uniformly attach or bond the coupling agent to the surfaces of the semi-synthetic mineral particles. 6. The method according to claim 5, wherein the semi-synthetic mineral contains 90% or more of particles having a size of 325 mesh or less on Tyler standard sieve. 7. The method according to claim 5, wherein the semi-synthetic mineral is pulverized into fine particles having an average particle size of 1 to 20 microns. 8. The method according to claim 5, wherein the semi-synthetic mineral has an X-ray diffraction peak at a face spacing of 1.49 to 1.51Å and a face spacing of 1.53 to 1.55Å. 9. A dioctahedral montmorillonite and a trioctahedral magnesium fluorosilicate are represented by the following formula R = I _D / I _T (where I _D is the peak intensity of the dioctahedral montmorillonite at a surface spacing of 1.49 to 1.51Å). Where I _T is the peak intensity of trioctahedral magnesium fluorosilicate at a surface spacing of 1.53 to 1.55 Å, and R is the peak intensity ratio.) X-ray diffraction peak intensity of surface index [060] Ratio R
The manufacturing method according to claim 5, wherein the content is 0.5 to 5. 10. The semi-synthetic mineral comprises a starting clay containing montmorillonite and cristobalite in a physically inseparable state, magnesium oxide, hydroxide, or an oxide or hydroxide under reaction conditions. The production method according to claim 5, which is a semi-synthetic mineral obtained by reacting a compound capable of forming with water in the presence of water.