JP3438076B2 - Metal-containing colored mica sheet and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-containing colored mica sheet and a method for producing the same, and more specifically to a fine-grain metal-containing fluoromica having a crystal structure in which a transition metal is intercalated between talc layers. The present invention relates to a manufactured colored mica sheet having excellent heat resistance and mechanical strength and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, as an inorganic sheet made of layered silicate, for example, a film made of sodium tetrasilicon mica is disclosed in Japanese Patent Publication No. Sho 35-6874.
No. 14242539 discloses a film made of glass and mica, JP-A No. 53-39318 discloses a film made of vermiculite, and JP-B No. 54-15043 makes a film made of synthetic fluorinated montmorillonite. Each is listed. However, such a conventional inorganic sheet has drawbacks in that bubbles are likely to enter the film at the time of manufacturing the film, and the obtained film has insufficient mechanical strength. Therefore, in order to increase the mechanical strength, it is necessary to use an organic adhesive such as a silicon adhesive as a binder.

As an inorganic film containing a metal ion, Japanese Patent Application Laid-Open No. 50-2698 discloses a metal-containing inorganic film produced by using synthetic hectorite as a starting material and ion-interchanging interlayer ions with metal ions and the like. Have been described. However, also in this case, there are drawbacks that bubbles are likely to enter the film at the time of manufacturing the film, and the obtained film has insufficient mechanical strength. Therefore, in order to increase the mechanical strength, it is necessary to use an organic adhesive such as a silicon adhesive as a binder.

Further, Japanese Patent Laid-Open No. 61-83619 discloses an inorganic film in which interlayer ions of synthetic mica are replaced with inorganic cations having an ionic index of 1.25 or more. However, the above-mentioned inorganic film uses sodium teniolite which is a limited swelling mica as a starting material, and the interlayer ion of the limited swellable mica is previously reacted with an organic cation, and then the organic cation is subjected to an ionic index. It is manufactured by a method of substituting with 1.25 or more inorganic cations. Therefore, the obtained mica sheet has
Since some organic cations such as alkylamine and aminoalcohol remained, the purity was lowered and a high-purity mica sheet could not be obtained. Further, when the temperature is raised to a high temperature, the residual organic matter is decomposed, and the heat resistance of the mica sheet is lowered, and a mica sheet having a heat resistance that can be used at a high temperature for a long time cannot be obtained. In this publication, K, as a specific example of an inorganic cation having an ionic index of 1.25 or more,
Pb, Cs, and Bi ions are described, but transition metal ions are not described.

So far, as the swellable fluoromica synthesized on an industrial scale, Na-type tetrasilicon mica (NaM
g _2.5 Si ₄ O ₁₀ F ₂ ) and Na-type teniolite (Na
Mg ₂ LiSi ₄ O ₁₀ F ₂ ). Of these, Na-type tetrasilicon mica is manufactured by a so-called melting method in which a raw material is heated to 1400 to 1500 ° C. to be melted, synthesized, cooled, and crushed, and a swelling mica obtained by this method. Is
The amount of methylene blue adsorbed (a simple method for knowing the cation exchange capacity) is as low as 10 to 30 meq / 100g, and because it has poor dispersibility in water, it undergoes an ion exchange reaction with metal ions, etc., and is a non-swelling mica sheet. It was an unsuitable material for making.

In addition, when it is produced from Na-type teniolite, since it has a limited swelling property, it is necessary to use a highly reactive organic cation in advance for the ion exchange reaction with metal ions and the like. There was a problem.

[0007]

An object of the present invention is to use a synthetic swelling fluoromica as a raw material, which has a large ion exchange capacity, and which swells in water and is cleaved to disperse into fine particles,
Fine metal-containing fluorine mica having a crystal structure in which a transition metal is intercalated with an organic cation is not synthesized in advance, and fine metal-containing fluorine is used without using a binder such as an organic adhesive. To provide a paper-like colored mica sheet excellent in heat resistance and mechanical strength, which is produced by using only mica, and a method for producing the same.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies and studies in view of the above problems, and as a result, heat-treated a powder of talc and alkali silicofluoride or a mixture of alkali fluoride without melting the talc. By using only the metal-containing fluoromica obtained by ion-exchange the interlayer ions of the synthetic swelling fluoromica obtained with transition metal ions, an excellent paper-like colored mica sheet can be obtained by drying this into a sheet. The inventors have found that they can be obtained and reached the present invention.

According to the first aspect of the present invention, talc and alkali silicofluoride or a mixed powder of alkali fluoride are used.
Of the intercalation ions of synthetic swelling fluoromica obtained by heat treatment of talc without melting, 5 of exchangeable ions
A metal-containing colored mica sheet comprising a metal-containing fluoromica represented by the following formula (1) obtained by ion-exchange of 0 to 95 equivalent% by a transition metal ion. αMF · βLF · γ (aMgF ₂ · bMgO) · σSiO ₂ (1) (In the formula, M is an interlayer ion and represents a transition metal ion,
L is an interlayer ion and represents Na ⁺ and / or Li ⁺ , α is 0.05 to 1.8, β is 0.005-1, and α + β is 0.1 to 2, and γ is 2 to 3.5, σ represents 3 to 4, and a and b represent 0 to 1 respectively.
And a + b = 1)

The invention of claim 2 of the present invention is characterized in that the transition metal is at least one selected from zinc, copper, iron, titanium, tin, nickel and cobalt.
It is the described metal-containing colored mica sheet.

According to a third aspect of the present invention, talc is a mixed powder of sodium silicofluoride or lithium silicofluoride and talc, or a mixed powder of sodium silicofluoride or lithium silicofluoride and sodium fluoride or lithium fluoride and talc. A synthetic swellable fluoromica represented by the following formula (2) obtained by heat treatment at 700 ° C. or higher without melting, and a water-soluble transition metal salt aqueous solution,
Among the interlayer ions by stirring, 50 to 95 of exchangeable ions
A method for producing a metal-containing colored mica sheet, which comprises producing the metal-containing fluoromica represented by the formula (1) according to claim 1 in which an equivalent% is exchanged with a transition metal ion, and drying the metal-containing fluoromica. Is. α′LF · γ (aMgF ₂ · bMgO) · σSiO ₂ (2) (In the formula, L is an interlayer ion, and Na ⁺ and / or Li
Represents ⁺ , α ′ represents 0.1 to 2, γ represents 2 to 3.5, σ represents 3 to 4, and a and b each represent 0 to 1
And a + b = 1)

The invention according to claim 4 of the present invention is characterized in that the transition metal is at least one selected from zinc, copper, iron, titanium, tin, nickel and cobalt.
It is a method for producing the described metal-containing colored mica sheet. Hereinafter, the present invention will be described in detail.

The method for producing the synthetic swelling fluoromica represented by the above formula (2) used in the present invention is not particularly limited,
For example, it can be produced by the method described in JP-A-2-149415. That is, a mixed powder of sodium silicate fluoride (Na ₂ SiF ₆ ) or lithium silicate fluoride (Li ₂ SiF ₆ ) and talc, or sodium silicate fluoride or lithium silicate fluoride and sodium fluoride (NaF) or lithium fluoride (Li
It is obtained by heating the mixed powder of F) and talc at 700 to 1000 ° C. without melting the mixed powder.

This method is called an intercalation method and is a manufacturing method in which Na ⁺ or Li ⁺ is coordinated between the layers of talc, and at the same time, OH ⁺ and F ⁺ are replaced.
The synthetic swelling fluoromica produced by these production methods has an excellent swelling function as compared with the fused synthetic swelling mica obtained by the conventional melting method, and has a thickness of 0.1 μm or less in water,
As for the size in the plane direction, since flaky fine particles having a side of several μm to several tens of μm are dispersed, the sheet forming property is excellent and the sheet can be easily formed into a sheet.

The interlayer ions are composed of exchangeable cations and non-exchangeable cations, and the synthetic swelling fluoromica has a high proportion of exchangeable cations and is 50 to 110 meq / 100.
Since it exhibits a high adsorption amount of methylene blue of g (a simple method for measuring the cation exchange capacity), it is possible to easily and intercalate a large amount of cations of transition metals such as copper, iron, titanium, tin and nickel. is there.

The method for preparing a mica sheet using only the metal-containing fluoromica used in the present invention without using a binder such as an organic adhesive such as a silicone adhesive is not particularly limited. As a specific manufacturing method, for example, the following method can be mentioned. First, it is necessary to make the metal-containing fluoromica thin, but the metal-containing fluoromica is one in which exchangeable ions are ion-exchanged with transition metal ions among the interlayer ions of the synthetic swelling mica as described above. Therefore, it has a non-swelling property and precipitates in water to form a gel layer of extremely thin flaky fine particles. Mica can be aggregated to produce a metal-containing colored mica sheet.

At this time, the exchange rate of the exchangeable ions substituting the transition metal ions is preferably 50 to 95 equivalent%. When the exchange rate is 50 equivalent% or less, the sol of the metal-containing colored mica still has a strong swelling property, so that it is difficult to form a sheet, and the obtained metal-containing colored mica sheet also has a transition metal ion added. Since the amount is small, coloring is insufficient, and when the exchange rate is 95 equivalent% or more, the strength of the sheet tends to decrease probably because the aggregation of the metal-containing colored mica becomes too large. As described above, the metal-containing colored mica sheet of the present invention has a unique color obtained by ion-exchanging Na ⁺ or Li ^+, which is an interlayer ion of the synthetic swelling fluoromica represented by the formula (2), with a transition metal ion. It can be manufactured by drying the metal-containing fluoromica shown in a sheet form.

Examples of the transition metal used in the present invention include zinc, copper, iron, titanium, tin, nickel and cobalt. Interlayer ions Na ⁺ or Li,
As a method of ion-exchange with a transition metal ion, for example, the concentration of synthetic swelling fluoromica is 0.1 to 10% by weight.
The method can be performed by mixing the aqueous solution prepared as above with the aqueous solution containing transition metal ions and then stirring. Aqueous solution containing transition metal ions, chloride of transition metal, sulfate,
What dissolved various salts, such as nitrate, in water can be used.

As the stirring method, a usual stirrer can be used, but among them, a high-speed rotating machine such as a mixer is preferably used because the reaction time can be shortened. Further, the liquid temperature during stirring may be increased to promote the ion exchange reaction.

When two or more kinds of transition metal ions are ion-exchanged, two or more kinds of transition metal ions may be simultaneously ion-exchanged, or a specific transition metal ion may be ion-exchanged, and then another ion is exchanged. It may be ion-exchanged with the transition metal ion. In addition, when sufficient ion exchange cannot be performed by one-time ion exchange, the same transition metal ion is used, and by repeatedly performing ion exchange,
It is possible to increase the interlayer ion concentration.

The metal-containing fluoromica obtained by the ion exchange in this manner can produce the metal-containing colored mica sheet of the present invention even if it is directly dried into a sheet, but the metal-containing fluoromica is excessive. Since it contains the salt of, it is preferable to wash, and more preferably, after washing, synthetic fluorine mica uniformly dispersed in water using a known dispersing machine such as a strong shearing machine, an ultrasonic disperser, and a homogenizer. It is preferable to prepare a sol and dry the sol.

As a method of cleaning the metal-containing fluoromica,
For example, a water washing method such as a filtration method, a centrifugation method, or a gradient method can be used. Further, two or more of these methods may be combined in order to enhance the cleaning efficiency.

As a method for drying the metal-containing fluoromica thus obtained into a sheet, the sol concentration is 1
What is adjusted to 20% by weight is cast on a substrate having releasability, or blown and spread to obtain 25
A method of peeling from the substrate after drying at ˜250 ° C. is preferable.

For drying the sol, an infrared heater or the like may be used to shorten the drying time, or an excess solvent may be removed by a centrifugal separation method or a reduced pressure drying method, and then dried. In addition, in order to continuously produce mica sheets,
A rotating drum or an endless belt can be used as the substrate. Also, by pressing with an elastic roll,
It is also possible to increase the tensile strength of the mica sheet.

The metal-containing colored mica sheet of the present invention has a unique color because the transition metal is contained between the layers of synthetic mica. When describing these colors together with the types of transition metal elements, zinc (white), copper (light blue), iron (light brown), titanium (light yellow), tin (white yellow), nickel (yellow green), cobalt ( Light pink).

[0026]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but without departing from the gist of the present invention,
The invention is in no way limited by these examples. (Example 1) Synthetic swelling fluoromica produced according to the method described in JP-A-2-149415 [trade name: ME, manufactured by Corp Chemical Co., Ltd .: MB adsorption amount 102
meq / 100 g] 20.0 g was added to 980 ml of pure water, stirred sufficiently, and allowed to stand overnight to obtain 1000 ml of a synthetic swellable fluoromica 2% dispersion liquid. 5 in this dispersion
% ZnSO ₄ aqueous solution (250 ml) was added, and the mixture was stirred at room temperature for 3 hours using a stirrer to obtain an ion exchange product in which most of the Na ⁺ of interlayer ions were replaced with Zn ²⁺ . This ion-exchanged product was washed with 5000 ml of distilled water by a filtration method to form a cake, which was dispersed in water to prepare a 5% metal-containing fluoromica-containing sol. Next, this metal-containing fluoromica sol was applied on a stainless steel plate (SUS304) to a thickness of 10
2 mm at 120 ° C using a dryer
After drying for an hour, a white metal-containing mica sheet A having a thickness of 0.4 mm was obtained. The component analysis results and ion exchange rate of the obtained mica sheet A were measured, and the results are shown in Table 1. The mechanical tensile strength, bending strength and hygroscopicity were measured by the following measuring methods, and the results are shown in Table 1.
Next, regarding the obtained metal-containing colored mica sheet A,
Weight change was measured using a differential thermal analyzer. As a result, no change in weight was observed up to 850 ° C.

(Measurement Method): (Mechanical Tensile Strength) (kg / mm ² ) In accordance with the method specified in JIS-Z-1702, using an Instron type tensile tester at room temperature (25 ° C.)
The tensile strength of the mica sheet was measured by. (Bending strength test) A metal-containing mica sheet having a thickness of 0.4 mm is cut into a rectangle having a width of 3 cm and a length of 18 cm, lightly bent by hand into a U-shape, and further bent until both ends come into contact with each other. The change in shape, presence of cracks, etc. were observed. There is no change in the shape of the metal-containing mica sheet, etc.- ○ The metal-containing mica sheet was cracked ...- △ The metal-containing mica sheet was broken into two pieces ...

(Hygroscopicity) (%) A dried mica sheet was placed in a closed container having a humidity of 80%.
The sample was left for a period of time and the amount of moisture absorption was measured.

Example 2 To 1000 ml of a synthetic swellable fluoromica 2% dispersion liquid obtained in the same manner as in Example 1, 5
% Ti ₂ (SO ₄ ) ₃ aqueous solution and 300 ml of dilute sulfuric acid were added, and the same treatment as in Example 1 was carried out to obtain a 5% metal-containing fluoromica-containing sol. The metal-containing fluoromica sol was treated in the same manner as in Example 1, washed, filtered, cast and dried to obtain a light yellow metal-containing colored mica sheet B having a thickness of 0.4 mm. The component analysis results and ion exchange rate of the obtained mica sheet B are also shown in Table 1. Also, in the same manner as in Example 1, the mechanical tensile strength,
Bending strength and hygroscopicity were measured. The results are also shown in Table 1. The heat resistance of the obtained metal-containing colored mica sheet B was evaluated in the same manner as in Example 1. As a result, no change in weight was observed up to 850 ° C.

Example 3 To 1000 ml of a synthetic swelling fluoromica 2% dispersion liquid obtained in the same manner as in Example 1, 5
% SnCl ₂ aqueous solution (300 ml) was added and the same treatment as in Example 1 was performed to obtain a 5% metal-containing fluoromica-containing sol.
This metal-containing fluoromica sol was washed, filtered, cast and dried in the same manner as in Example 1 to give a thickness of 0.4 mm.
Then, a white-yellow colored metal-containing colored mica sheet C
Got Table 1 shows the component analysis results and the ion exchange rate of the obtained mica sheet C. Further, in the same manner as in Example 1, the mechanical tensile strength, bending strength and hygroscopicity were measured. The results are shown together in Table 1. The heat resistance of the obtained metal-containing colored mica sheet C was evaluated in the same manner as in Example 1. As a result, no change in weight was observed up to 850 ° C.

(Example 4) 1 ml was added to 1000 ml of a synthetic swellable fluoromica 2% dispersion obtained in the same manner as in Example 1.
300 ml of 0% CuSO ₄ aqueous solution was added and the same treatment as in Example 1 was carried out to obtain a 5% metal-containing fluoromica-containing sol. This metal-containing fluoromica sol was washed, filtered, cast and dried in the same manner as in Example 1 to give a thickness of 0.4 mm.
Thus, a light blue metal-containing colored mica sheet D was obtained. Table 1 shows the component analysis results and the ion exchange rate of the obtained mica sheet D. Further, in the same manner as in Example 1, the mechanical tensile strength, bending strength and hygroscopicity were measured. The results are also shown in Table 1. The heat resistance of the obtained metal-containing colored mica sheet D was evaluated in the same manner as in Example 1. As a result, no change in weight was observed up to 850 ° C.

(Example 5) 5 ml was added to 1000 ml of a synthetic swellable fluoromica 2% dispersion obtained in the same manner as in Example 1.
% Fe ₂ (SO ₄ ) ₃ aqueous solution was added and the same treatment as in Example 1 was carried out to obtain a 5% metal-containing fluoromica-containing sol. This metal-containing fluoromica sol was washed, filtered, cast and dried in the same manner as in Example 1 to give a thickness of 0.4 m.
m, a light brown metal-containing colored mica sheet E
Got The component analysis results and ion exchange rate of the obtained mica sheet E are also shown in Table 1. Further, in the same manner as in Example 1, measurement tests of mechanical tensile strength, bending strength and hygroscopicity were conducted. The results are also shown in Table 1. The heat resistance of the obtained metal-containing colored mica sheet E was evaluated in the same manner as in Example 1. As a result, no change in weight was observed up to 850 ° C.

Example 6 To 1000 ml of a 2% synthetic swellable fluoromica dispersion obtained in the same manner as in Example 1, 2
300 ml of a 0% NiCl ₂ aqueous solution was added, and the same treatment as in Example 1 was carried out to obtain a 5% metal-containing fluoromica-containing sol.
This metal-containing fluoromica sol was washed, filtered, cast and dried in the same manner as in Example 1 to give a thickness of 0.4 mm.
Then, the yellow-green metal-containing colored mica sheet F
Got The component analysis results and ion exchange rate of the obtained mica sheet F are also shown in Table 1. Further, in the same manner as in Example 1, the mechanical tensile strength, bending strength and hygroscopicity were measured. The results are also shown in Table 1. The heat resistance of the obtained metal-containing colored mica sheet F was evaluated in the same manner as in Example 1. As a result, no change in weight was observed up to 850 ° C.

(Example 7) 1 ml was added to 1000 ml of a synthetic swellable fluoromica 2% dispersion obtained in the same manner as in Example 1.
300 ml of 0% CoSO ₄ aqueous solution was added, and the same treatment as in Example 1 was performed to obtain a sol containing 5% metal-containing fluoromica.
This metal-containing fluoromica sol was washed, filtered, cast and dried in the same manner as in Example 1 to give a thickness of 0.4 mm.
Thus, a light pink metal-containing colored mica sheet G was obtained. The component analysis result and ion exchange rate of the obtained mica sheet G are also shown in Table 1. Further, in the same manner as in Example 1, the mechanical tensile strength, bending strength and hygroscopicity were measured. The results are also shown in Table 1. The heat resistance of the obtained metal-containing colored mica sheet G was evaluated in the same manner as in Example 1. As a result, no change in weight was observed up to 850 ° C.

(Comparative Example 1) 57 parts by weight of anhydrous silicate, 29 parts by weight of magnesium oxide, 7 parts by weight of magnesium fluoride and 7 parts by weight of sodium silicofluoride were mixed to obtain 1400.
After melting at ℃ for 5 hours, at a speed of 2 ℃ / min 90
The mixture was gradually cooled to 0 ° C., and the crystallized product was pulverized to obtain a synthetic swellable fluoromica by the melt pulverization method (hereinafter referred to as “melt swellable fluoromica”). M of the obtained melt-swelling synthetic mica
The B adsorption amount was 18 meq / 100 g. Using 20.0 g of this melt-swellable fluoromica, a 2% dispersion of melt-swellable fluoromica obtained in the same manner as in Example 1
250 ml of a 5% ZnSO ₄ aqueous solution was added to 0 ml to obtain a metal-containing fluoromica sol in which a part of Na ⁺ of interlayer ions was replaced with Zn ²⁺ . This metal-containing fluoromica sol was washed, filtered, cast and dried in the same manner as in Example 1 to obtain a white comparative metal-containing colored mica sheet H having a thickness of 0.4 mm. The results of component analysis and the ion exchange rate of the obtained metal-containing colored mica sheet H are also shown in Table 1. Further, in the same manner as in Example 1, the mechanical tensile strength, bending strength and hygroscopicity were measured. The results are also shown in Table 1. The heat resistance of the obtained metal-containing colored mica sheet H was evaluated in the same manner as in Example 1. As a result, no change in weight was observed up to 850 ° C.

[0036]

[Table 1]

[0037]

The present invention provides a metal-containing colored mica sheet and a method for producing the same, which is obtained by heat-treating talc and alkali silicofluoride or a mixed powder of alkali fluoride without melting talc. The synthetic swelling fluoromica swells when it is placed in water, disperses into fine particles by cleavage, and its interlayer ions can be easily and abundantly exchanged with transition metal ions.
It can be easily made into a sol, and since the sol has an extremely large sheet-forming ability and can be easily formed into a sheet, it is possible to use an organic substance such as an adhesive or a binder in the sheet manufacturing process. Sufficient mechanical strength, bending strength,
A metal-containing colored mica sheet having heat resistance can be manufactured. The metal-containing colored mica sheet of the present invention contains a metal element between the layers of synthetic mica, and thus exhibits a unique color.

Continuation of the front page (56) Reference JP-A-63-248713 (JP, A) JP-A-61-201616 (JP, A) JP-A-57-82114 (JP, A) JP-A-2-149415 (JP , A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) D21H 13/44 C01B 33/20-33/46

Claims (4)

(57) [Claims] 1. A methylene blue adsorption amount of 50 to 110 m.
Of interlayer ions of the synthetic swellable fluorinated mica is eq / 100 g, characterized in that it consists resulting Rukin genus containing fluorine mica by ion exchange 50-95 equivalent percent of the ion-exchangeable cations in the transition metal ion A metal-containing colored mica sheet to be used. 2. The transition metal is zinc, copper, iron, titanium, tin,
The metal-containing colored mica sheet according to claim 1, which is at least one selected from nickel and cobalt. 3. A mixed powder of sodium silicofluoride or lithium silicofluoride and talc, or a mixed powder of sodium silicofluoride or lithium silicofluoride and sodium fluoride or lithium fluoride and talc is melted at 700 ° C. or higher without melting the talc. in the heat treatment to the obtained equation (2): α'LF · γ ( aMgF 2 · bMgO) · σSiO 2 (2) ( wherein, L is an interlayer ion, the Na ⁺ and / or Li ⁺
Α ′ represents 0.1 to 2 and γ represents 2 to 3.5.
, Σ represents 3 to 4, and a and b represent 0 to 1 respectively.
And a synthetic swelling fluoromica represented by a + b = 1) and a water-soluble transition metal salt aqueous solution are mixed and stirred to obtain 50 to 50 ion-exchangeable cations among the interlayer ions.
The following formula (1) in which 95 equivalent% was exchanged for transition metal ions : αMF · βLF · γ (aMgF ₂ · bMgO) · σSiO ₂ (1) (wherein M is an interlayer ion and represents a transition metal ion). ,
L is an interlayer ion and represents Na ⁺ and / or Li ⁺ , and α
Is 0.05 to 1.8, β is 0.005 to 1, and
α + β is 0.1 to 2, γ is 2 to 3.5, and σ is
Represents 3 to 4, and a and b represent 0-1 respectively.
A + b = 1) , and a method for producing a metal-containing colored mica sheet, which comprises drying the metal-containing fluoromica mica shown in FIG. 4. The transition metal is zinc, copper, iron, titanium, tin,
It is at least 1 selected from nickel and cobalt, The manufacturing method of the metal containing colored mica sheet of Claim 3 characterized by the above-mentioned.