JPS6241182B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a sintered crystallized glass molded product. Crystallized glass molded products, in which fine crystals are precipitated inside the glass molded product, are useful as building materials with a beautiful appearance that can be compared to natural marble or granite due to the internal refraction and reflection of light rays. When producing crystallized glass, two important issues are the composition of the raw material mixture that can produce crystals with the desired appearance and the heat treatment conditions for crystal formation, and these two are mutually related. be. Current manufacturing methods for crystallized glass molded products can be roughly divided into two methods: sintering methods and melting methods. The sintering method involves filling a refractory container with glass powder with a composition capable of forming a specific crystal, and heating it at a temperature between the glass's softening point and its melting temperature to form a fused sinter. Then, a crystallization heat treatment is performed to precipitate crystals inside the molded product by heating at a predetermined temperature above the softening point for one hour to complete the crystallized glass molded product. A glass raw material having a composition that can produce After obtaining a molded product through processes such as slow cooling, it is heated again for one hour at a predetermined temperature near the softening point temperature to perform crystallization heat treatment to precipitate crystals inside the molded product. This completes the glass molded product. Of these two methods, the present invention relates to a novel method using a sintering method. The types of crystals produced in crystallized glass molded products by conventional sintering methods include β-wollastonite, β-spodiumen, and β-eucryptite.
In the crystallization heat treatment process, crystals are precipitated from 850°C near the softening point, the temperature is raised to 1000°C to 1150°C to promote precipitation of crystals, and the temperature is further maintained at around 1150°C for about 60 minutes or more. Due to this, it is difficult to do so. The present invention uses fluorine mica or its isomorphic substitution.
The present invention provides a method for manufacturing a sintered crystallized glass molded product using a derivative as a crystal. In the method of the present invention, there are many varieties of fluorine mica crystals that can be produced in crystalline glass molded products, and their crystallization temperatures range from 600 to 1200°C, and the crystallization temperature can be adjusted depending on the use and form of the product. The composition of the molded product can be selected. Moreover, the manufacturing method has the characteristic that the crystallization treatment time can be kept within about 30 minutes at a predetermined temperature. The fluorine mica component has an extremely low viscosity when melted, and since it is a crystal, it has a melting point, and when it approaches the melting point, it rapidly solidifies, and it cannot be used for other methods other than cast molding, such as normal press molding or roll molding. It is impossible to use the glass molding method. The present invention enables a glass molding method by dissolving this fluorine mica component with a base glass component. That is, crystallized glass is produced by sintering in a structure in which the base material glass component and the fluorine mica component are mutually dissolved. The method for manufacturing the sintered crystallized glass molded product of the present invention will be described in detail below. The base glass component of the sintered crystallized glass molded product is borosilicate glass, such as SiO ₂ -Al ₂ O ₃ -B ₂ O ₃ -
CaO―K ₂ O―Na ₂ O, which also contains P ₂ O ₅ ,
ZnO, BaO, TiO ₂ , ZrO ₂ , PbO, etc. are added appropriately, and it can be used for plate glass, bottle glass, hollow glass, pressed glass, etc. according to the usage classification of ordinary glass products.
It is possible to use lighting glass, sealing glass, etc., crystal glass containing PbO with or without addition of B ₂ O ₃ , and sealing glass materials. The crystalline mica generated in the glass molded product has the general formula X _{0.5 ~1.0 Y2 ~3} , which will be explained in detail later.
It is represented by (Z ₄ O ₁₀ )F ₂ . The crystallized glass molded product obtained by the present invention has this crystalline fluorine mica uniformly dispersed and precipitated in the base glass component, and its content can be varied widely depending on the application. Yes, but generally 15-70%. Furthermore, there are no particular restrictions on the shape of the molded product, and it is possible to mold it into various shapes depending on the use and purpose, and it is also possible to form a crystallized glass layer on the surface of a base material such as a plate. It is possible. The molded products referred to in the present invention also include these.
The molded product can also be made into various colored glass molded products by incorporating a coloring component therein. There are two methods for blending the raw materials in the method of the present invention, one of which is to combine glass powder as the base glass component with glass powder of fluorine mica component, glass powder containing fluorine mica, or glass powder containing fluorine mica. This is a method of combining with a single crystal powder, part 2.
This is a method in which a glass melt is prepared in advance from a base glass component or its raw material and a fluorine mica component or its raw material, and a powder obtained by pulverizing this is used. After molding, these are subjected to fusion sintering and crystallization heat treatment to obtain a crystallized glass molded product.
Each case will be explained below. The fluorine mica crystals produced in the molded product of the present invention have the general formula X _{0.5 to 1.0} Y _{2 to 3} as described above.
(Z ₄ O ₁₀ )F ₂ . In the general formula, X is coordination number 1
Z is a cation with a coordination number of 4 and is usually based on a silicate tetrahedron (SiO ₄ regular tetrahedron), and Y
constitutes an octahedral layer of cations with a coordination number of 6. The crystal structure of mica is a hexagonal network of silicate tetrahedrons, with two plates on the top and bottom, between which ions with octahedral coordination are bonded.This is called a tablet, and these tablets form a layer. The tablets are stacked, with alkali metal or alkaline earth metal ions bound between the tablets, which are called interlayer ions. In the general formula, X is
Na ⁺ , K ⁺ , Ca ²⁺ , Ba ²⁺ , Rb ⁺ , Sr ²⁺ , and Y
are Mg ²⁺ , Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Li ⁺
and Z is (Al ³⁺ , Si ⁴⁺ )Si ⁴⁺ , Ge ⁴⁺ , Al ³⁺ ,
Indicates Fe ³⁺ , B ³⁺ . There are many fluorine mica produced by such isomorphic substitution, but for the purpose of introducing them into the present invention, they can be classified for ease of understanding: (1) Fluorine phologopite [KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ] Y is Mg based on
trisilicon mica group, (2) Y based on fluorine muscovite [KAl ₂ (AlSi ₃ O ₁₀ ) F ₂ ] is
trisilicon mica group which is Al, (3) tetrasilicon mica group based on fluorine tetrasilicon mica [ _{KMg 2.5} (Si ₄ O ₁₀ ) F ₂ ], (4) crystallization is performed by solid-state reaction Swelling trisilicon mica group, (5)
X, Y, and Z are Fe ²⁺ , ³⁺ , Co ³⁺ , Ni ²⁺ , ³⁺ , Cu ²⁺ ,
Colored mica group with Mn ²⁺ , ³⁺ , Ti ³⁺ , ⁴⁺ 〓〓〓〓〓
Can be divided. (1) The standard composition of the fluorine phologopite group is KMg ₃ (AlSi ₃ O ₁₀ )F ₂ , and K ₂ O.
It is produced by melting a mixture batch with a molar ratio of 2MgO・1.1MgF ₂・0.5Al ₂ O ₃・3SiO ₂ at a temperature of about 1400°C or higher. Even if the fluorine phologopite melt is allowed to cool naturally in the atmosphere, more than 80% of the crystals are formed, and the remainder is glass with the same composition. A synthetic lump is obtained, which is pulverized to provide the raw material (fluorine mica-containing glass powder) of the present invention. Melting point of fluorine phologopite crystal alone is 1375
℃, it has a strong affinity with borosilicate and is compatible with borosilicate at high temperatures of 800℃ or higher, so it is well fused with the base glass component powder in the sintering process of the present invention. For example, for lead borosilicate glass and fluorine fluorogopite, it is possible to
Crystal formation is possible down to a low temperature range of ~800℃. In high temperature areas, glass becomes molten,
Fluorine phologopite dissolves in it, but
When this is cooled, phologopite precipitates again as crystals. In this case, there is an advantage that crystals can be formed even if the cooling rate is fast. 600~
In the method of sintering at a low temperature such as 800℃, a pre-crystallized fluorine mica component or a fluorine mica glass composite is blended with a base glass component, filled in a container, and heated. The sintered body is fused in its original state, and a sintered body with a homogeneous distribution of crystals is obtained with a random structure in the crystal direction. By combining it with a type of mica that can be crystallized by a solid-state reaction, which will be described later, a crystallized glass molded product can be obtained by sintering and crystallizing in a low temperature range. (2) The standard composition of the fluorine muscovite group is [KAl ₂ (AlSi ₃ O ₁₀ ) F ₂ ], and the amount of crystallization by the melting method is small, but solid-solid reactions, that is, at temperatures before the particles are in a molten state, The atoms of the blended particles enter the radius of action of the atoms on the surface of other particles due to thermal vibration, and the two bond to form a dense sintered structure. It also occurs in glasses that are compatible with the components and fluorine muscovite compositions. The raw material composition of fluorine muscovite is 1/6K ₂ O・1/3K ₂ SiF ₆・
The standard is 3/2Al ₂ O ₃ and 32/3SiO ₂ , but the typical ones are KAl ₂ (AlSi ₃ O ₁₀ )F ₂ and Na ₂ Al _{2
( AlSi3O10} ) _F2 . There are two methods for producing the crystallized glass of the present invention using a fluorine muscobide group as a crystallization component. (a) The glass powder of the molten composition obtained by melting the mixture of the base glass component and the fluorine muscovite composition is molded to a powder size of 700 to 950.
(b) sintering at 600-700°C for 20-30 minutes to crystallize the sintered body, and (b) heating only the base glass component and the fluorine muscovite composition in advance. Fluorine muscovite powder is blended into a predetermined blending ratio, molded, and sintered at 700 to 950℃.
This method crystallizes the sintered body by holding it at 600 to 700°C for 20 to 30 minutes, and since this method involves sintering in a low temperature range, it can be used not only for the molded body itself but also for ceramic molded products such as silicon. calcium acid, asbestos, cement, mullite fibers, refractories,
Molded products can be made by forming a layer of crystallized glass structure on the surface of a substrate made of ceramic or the like. (3) The standard composition of the fluorine tetrasilicon mica group is fluorine tetrasilicon mica (KMg _2.5 Si ₄ O ₁₀ F ₂ ), with a molar ratio of K ₂ O・MgF ₂・1.5MgO・4SiO ₂ Even if the azalea is melted at about 1400℃ or higher and allowed to cool naturally in the atmosphere, the amount of crystal formation will be at least 60%.
% or more, a synthetic lump of glass with the same composition as the rest is obtained, which is crushed and used as the raw material of the present invention. Fluorine tetrasilicon mica has a melting point of 1176°C and, like fluorine phologopite, has an affinity for silicate. Like fluorine phologopite, fluorine tetrasilicon mica or a glass containing it can also be used alone or in combination with other fluorine mica-containing glasses or mixtures thereof to form a sintering compound in addition to the base glass component. Prepare and mold
It is sintered at 700 to 900°C and held at that temperature for about 30 minutes to crystallize, resulting in a crystallized glass molded product. (4) The trisilicon mica group, which forms crystals through solid-state reactions, crystallizes through solid-state reactions when the raw material mixture batch is heated to a certain temperature, similar to fluorine muscovite. When this trisilicon mica group is used in the present invention, the mica components in this section are
A method of heating and melting a composition in combination with a base material glass component, sintering the resulting powder by pulverizing it, and crystallizing it by holding it in a predetermined temperature range during the process; There is a method in which crystallization is carried out by sintering a blend of a powder and a powder previously prepared from a melt having a fluorine mica composition. This fluorine mica group is a group of trisilicon mica in which Mg is coordinated at the Y position in the general formula of fluorine mica _.
(AlSi ₃ O ₁₀ )F ₂ ]. To give specific examples of typical compositions (substituted elements) and crystallization temperatures (Ct) due to solid-state reactions, K
In the case where the position of is replaced, (Rb, 1330℃),
(Cs, 1330℃), (Ba _0.5 , 1380℃), (Pb _0.5 ,
1000℃), but in the case where the Mg position is substituted,
(Mg ₂ Ni, 1000℃), (MgNi ₂ , 1000℃), (Ni ₃ ,
1000℃), (Mg _2.5 Co _0.5 , 1000℃),
(Mg ₂ Co, 1000℃), (Mg _1.5 Co _1.5 , 1000
℃), (MgCo ₂ , 1000℃), (Mg _0.5 Co _2.5 ,
1000℃), (Co ₃ , 1000℃), (Mg ₂ Fe, 950℃),
(Mg _1.5 Fe _1.5 , 900℃), (Mg Fe ₂ , 900℃),
(Fe ₃ , 800℃), (Mg _1.5 Mn _1.5 , 1100℃)
(Mg _2.5 Ti ²⁺ _{0.5 1000} ℃), (Mg ₂ Ti ²⁺ , 1000℃)
(Mg _2.25 Ti ³⁺ _0.5 , 1100℃), ₍ Mg _2.5 Zn, 1200
℃) (Mg _2.5 Cu _0.5 , 1000℃), and in the case where the Al position is substituted (B, 1000℃),
(Mn, 1000℃), (V, 900℃) are K(=X)
and the one in which the position of Al (=Z) is substituted (X=Tl, Z=B, 950°C), but the one in which the position of Mg (=Y) and Al (=Z) is substituted (Y=Ni ₃ , Z=B, 900℃), (Y=Fe ₃ , Z=
B, 550℃), (Y=Fe ₃ , Z=Fe, 650℃), (Y
=Mg _2.5 Mn, Z=B, 700℃), (Y=
Mg _2.5 Ti ²⁺ ₀ . ₅ , Z=B, 900℃), etc. From among those with such a wide range of crystal formation temperatures, by selecting appropriate fluorine mica components according to the various uses described below, it is possible to
Crystallized glass molded products can be obtained at a sintering temperature range of 1000°C, a sintering temperature range of 1000°C to 800°C, and a sintering temperature range of 800°C to 600°C. (5) The colored mica group is a type of mica with a mica crystal structure, X,
Fe ²⁺ , Fe ³⁺ , Co ³⁺ , Ni ²⁺ at Y and Z positions,
It has a mica composition coordinated with metal ions such ^as Ni ³⁺ , Cu ²⁺ , Mn ²⁺ , Mn 3+ , Ti ⁴⁺ , Ti ³⁺ , etc., and has a variety of colors. In other words, by using a composition of base glass components and colored mica, crystallized glass molded products can be made with varying shading,
They come to have an aesthetic appearance that suits their environment, such as sesame or striped patterns. To give a typical example of colored mica, in the series of isomorphic substitution products of fluorine fluorogopite,
Pink color KMg _2.8~2.9 C ^o _0.2~0.1
(AlSi ₃ O ₁₀ ) F ₂ , brownish-brown
KMg _2.65~2.80 Cu _{0.35~0.2 ( AlSi3O10} )
F ₂ , green-yellow KMg _2.8 Ni _0.2 (AlSi ₃ O ₁₀ ) F ₂ , brown KMg _2.7 Fe ²⁺ _0.12 Fe ³⁺ _0.28 (AlSi ₃ O ₁₀ )
F ₂ , brown KMg _2.67 Mn _0.33 Fe _0.01
(AlSi ₃ O ₁₀ )F _2, etc., and in the series of isomorphic substitution products of fluorine muscovite, beige color KAlTi ³⁺
(AlSi ₃ O ₁₀ ) F ₂ , black-gray KAlFe ³⁺ (AlSi ₃ O ₁₀ )
_F2 , the coordination position of the metal ion mentioned above,
Various colors and tones can be adjusted by adjusting the amount added and temperature treatment. In producing the above-mentioned sintered crystallized glass molded product of the present invention, even if the sintering temperature is below 600°C or the crystallization temperature is below 550°C, the crystallization rate is low and a good product cannot be obtained. As described above, the present invention focuses on the compatibility between the various fluorine mica components and the base glass component, the formation of fluorine mica crystals in an integrated glass core, and the powder obtained from the fluorine mica component melt. It is easy to fuse with the powder of the base glass component and recrystallize the sintered molded product, and a crystallized glass molded product can be obtained by heat treatment at a low temperature. When this molded product is finally polished to a mirror-like finish using conventional methods, it has a gorgeous, solid feel and an appearance similar to marble or anointing due to the striae. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Base material glass component A Glass frit with the following component ratio by weight:
_SiO2 50%, _{Al2O3 5} %, _{B2O3 15} %, CaO10%,
K ₂ O 5%, Na ₂ O 15%, frit fineness 0.10.2 mm,
The softening point is 610°C, the viscosity is 10 ² poise at 1350-1400°C, and 10 ⁴ poise at 1100°C. Fluorine mica component B 〓〓〓〓〓
B-1 A composition aimed at producing fluorine phologopite crystals, with the following blending ratio by weight:
Powder obtained by melting at 1450℃, leaving it in the air to cool naturally, and then crushing it (fluorine mica-containing glass powder). The amount of fluorine phologopite crystals produced was 85% by X-ray diffraction measurement of powder by CuKα irradiation.
It was estimated that about %. Blend ratio (weight ratio)
_{K2SiF6 25.1} %, MgO32.7%, _{Al2O3 11.5} %,
_SiO2 30.7%, fineness 60-80 mesh. B-2 Commercially available fluorine fluorogopite obtained by slow cooling method, powder size 80-120 mesh. (Fluorine mica crystal single powder) Melted composition of base glass component and fluorine mica component C C-1 A (base glass component frit) and fluorine mica component raw materials having the same composition as B-1 at a weight ratio of 30 :70,
Mixed at a ratio of 50:50 and 70:30, each approximately 1450
Melt by heating for 20 minutes at °C, cooling rate approximately 100 °C per minute
℃ to 600℃. A powder with a particle size of 0.1 to 1.0 mm is obtained by crushing this molten agglomerate. C-2 Fluorine phologopite of A and B-2 in weight ratio
Powder with a particle size of 0.1 to 1.0 mm prepared by the same method as C-1 was used at a ratio of 60:40. (1) Formulation

[Table] (2) Molding 100 parts by weight of the above compound and 1 part CMC as a binder.
After adding parts by weight and stirring well, the moisture content is 1 to 2%.
The mixture was homogeneously filled into an iron mold and molded under pressure using a hydraulic molding machine at 100 kg/cm ² to obtain a molded product measuring 30 cm x 30 cm x 10 cm and having a porosity of 45%. (3) Sintering and crystallization The molded product was placed on a mullite plate from which talcum had been removed as a mold release agent, and heated at 950°C from room temperature in a Matsufuru electric furnace.
Heat at a heating rate of 50-60 °C per minute to
After crystallizing by heating at 950 to 1000°C for 30 minutes, the mixture was cooled to about 200°C for 20 minutes to obtain a crystallized glass molded product. These molded products are mirror-polished and have a splendid marble-like appearance with no porosity. Next, the physical properties are shown.

[Table] Example 2 Base material glass component 2A Glass frit having the following component ratio by weight was used. _SiO2 58%, _{Al2O3 3} %, _{B2O3 15} %, PbO12
%, Na ₂ O 5%, K ₂ O 7%, fineness particle size 0.1-1 mm,
Softening point 620℃. 〓〓〓〓〓
Fluorine mica component 2B 2B-1 Fluorine muscovite [KAl ₂ (AlSi ₃ O ₁₀ ) F ₂ ] Compounding ratio by weight for the purpose of crystal formation:
_SiO2 44.8%, _K2CO3 12.3 _% , _{K2SiF6 27.4} %,
A blended batch containing 15.5% Al ₂ O ₃ was stirred and mixed to obtain an unmelted blend (fluorine mica component raw material). 2B-2 The blend of 2B-1 above was melted at 1350°C, and then allowed to cool in the atmosphere to obtain a glassy lump, which was crushed to obtain a powder (glass powder containing fluorine mica component). This powder was heated in an electric furnace at 600 to 700° C. for 30 minutes, and a glass powder was used in which 50% or more of fluorine muscovite crystals were thought to be formed as measured by X-ray diffraction. Molten composition of base glass component and fluorine mica component
2C 2C-1 2A (base material glass component) and 2B-1 (mica component batch) are mixed in a weight ratio of 30:70, 50:50, 70:30, heated and melted at 1200℃ for 30 minutes, and exposed to the atmosphere. The powder was left to cool naturally in a vacuum chamber, then pulverized, and the resulting powder was held at 650°C for 30 minutes. Manufacture of crystallized glass molded products

[Table] (2) Molding, sintering and crystallization (A) 100 parts by weight of the above compound was mixed into a mold with internal dimensions of 30 cm x 30
It has a rectangular plate shape with a depth of 5 cm and a wall thickness of approximately 2 cm with colloidal graphite coated as a mold release agent on the surface.
The cordierite refractory container was filled homogeneously to a height of 20 mm, and heated from room temperature to no.
Blends No. 1 to No. 7 are heated to 800°C, Blends No. 8 and No. 9 are heated to 700°C, respectively, at a heating rate of 50 to 60°C per minute, and then heated to approximately After heating for 30 minutes to crystallize, the temperature is approximately 100℃.
Cool in 25 minutes until the wall thickness is approximately 12 to 15 mm.
A thick plate-shaped crystallized glass molded product was obtained. All of these molded products that were mirror-polished had a pore-free marble-like appearance. Next, the physical properties are shown.

[Table] (B) The above formulations No. 4 and No. 8 in parts by weight
A calcium silicate plate surrounding a slurry of 80 parts of purified montmorillonite and 20 parts of thixotropic liquid containing 3% of purified montmorillonite and 1% of sodium alkinate, with the remainder being water, in a metal frame with a height of 10 mm. (50cm x 50cm x 0.7cm) and stir rapidly.
The mixture was fluidized and spread to form a coating layer with a thickness of 5 mm. After removing moisture by drying for 12 hours at a temperature between room temperature and 50°C, the board was heated in a Matsufuru electric furnace for 650°C.
Heat at a heating rate of 50 °C per minute to 650 °C.
After crystallization at ~600°C, cooling to approximately 100°C in 20 minutes resulted in the formation of a crystallized glass layer fused to the calcium silicate plate. Example 3 Base glass component The same composition A as in Example 1 was used. Fluorine mica component D Fluorine tetrasilicon mica with a composition intended to produce crystals, with the following blending ratio melted at approximately 1400°C, left to cool in the atmosphere, and the resulting mass crushed to powder. And so. The amount of fluorine tetrasilicon mica crystals formed was estimated to be over 80% by measurement using powder X-ray diffraction using CuKα irradiation. Blending ratio: K ₂ O 11.3%, MgO 14.4%, MgF ₂ 17
%, _SiO2 57.3%, fineness 60-80 mesh. Manufacture of crystallized glass molded product The steps up to charging into the furnace for sintering are the same as in Example 1. The manufacturing conditions and physical properties of the molded product obtained are as follows.

【table】 Heating rate: 50-60℃/min to 1000℃

[Table] Each molded product was polished to a mirror-polished state by a conventional polishing method, and all had a pore-free marble-like appearance. Example 4 Base glass component Glass powder (0.1 to 1.0 mm diameter) having the following component ratio was used to obtain a base glass frit. A-3: _SiO2 56%, _{B2O3 7} %, _{Al2O3 16} %, CaO8
%, MgO7%, BaO6%, softening point 905℃, expansion coefficient 50×10 ^-7 A-4: SiO ₂ 63%, CaO 0.9%, Al ₂ O ₃ 3%,
PbO20%, _Na2O6 %, _K2O7.1 %, softening point 625
°C, expansion coefficient 88×10 ^-7 Fluorine mica component E Solid-state reaction type classified by crystallization temperature. K ₂ O, MgO, Al ₂ O ₃ , SiO ₂ , respectively
ZnO _{, MnO2 ,} PbO, NiO, _Fe2O3 , CoO, _B2O3
etc. was used. E-1 Crystallization temperature 1200℃ KMg _2.5 Zn
(AlSi ₃ O ₁₀ ) F ₂ E-2 〃 1100℃ KMg _1.5 Mn _1.5
(AlSi ₃ O ₁₀ ) F ₂ E-3 〃 1000℃ PbMg ₃ (AlSi ₃ O ₁₀ )
F ₂ E-4 〃 900℃ KNi ₃ (AlSi ₃ O ₁₀ ) F ₂ E-5 〃 800℃ KFe ₃ (AlSi ₃ O ₁₀ ) F ₂ E-6 〃 700℃ KCo ₃ (BSi ₃ O ₁₀ ) F ₂ E-7 〃 600℃ KFe ₃ (FeSi ₃ O ₁₀ ) F ₂ E-8 〃 550℃ KFe ₃ (BSi ₃ O ₁₀ ) F ₂ Manufacturing composition of crystallized glass molded product (wt%) Base material glass component A- E-1, E-2 for 3,
Blend E-3, E-4, and E-5, E-6, E-7, and E-8 in a ratio of 60:40, 50:50, and 40:60 to the base glass component A-4, respectively. Then, the mold was filled to a depth of 15 mm into a Gordierite refractory container (30 cm x 30 cm x 5 cm depth) using the same method as in Example 2, and heated at a heating rate of 20 to 30 °C per minute to the respective sintering temperature. After crystallizing by heating at each of the above temperatures for about 30 minutes, cool to about 100℃ at a cooling rate of 20℃ per minute to form a plate-shaped crystallized glass molded product with a wall thickness of about 8 to 10 mm. Obtained. All of these molded products finished by a conventional polishing method had a pore-free marble-like appearance. Among these, those containing E-5, E-7, and E-8 are
Due to crystallization, the color was blackish gray, E-2 was thiokolate brown, E-4 was purple, and E-6 was green. Example 5 Base Glass Components The following composition ratios by weight were used as a blend to obtain a base glass frit. _SiO2 72.6%, _{Al2O3 1.8} %, MgO1.0%, CaO5.2
%, Na ₂ O 17.2%, K ₂ O 2.2% Fluorine mica component The following component ratio is used as a compound for crystal formation of fluorine mica composition [K Mg ₃ (BSi ₃ O ₁₀ ) F ₂ ]. Raw material batches were used. _SiO2 38.5%, _{B2O3 8} %, MgO13.0%, _MgF2 20.2
%, K ₂ O2 0.3% Preparation of glass/mica molten composition After blending the mother glass component raw material batch and the fluorine mica component raw material batch at a weight ratio of 60:40 and mixing them homogeneously, they were placed in a silicon carbide crucible. After heating in an electric furnace at around 1350℃ and continuing heating until the filling material melts and the molten material becomes a clear melt,
Pour it onto a refractory plate made of fused zircon and let it cool naturally to obtain a glassy molten mass. This is crushed and the particle size is 0.1~0.3mm35%, 0.3~0.5mm35%, 0.5~0.
Prepare one with a particle size distribution of 1.0mm30%, and
30cm x 30cm x 10cm, porosity by the same molding method as (2)
A molded product of 32% was obtained. (Sintering and crystallization) The molded product is placed on a mullite plate sprinkled with carbonized cork powder as a mold release agent, and heated at a heating rate of 30°C per minute from room temperature to 750°C in a Matsufuru electric furnace. Then, the mixture was heated to 900°C at a temperature increase rate of 15°C per minute, held at 900°C for 30 minutes to effect crystallization, and then cooled to obtain a pore-free crystallized glass molded product. Those finished with a mirror polish had a splendid marble-like appearance. Physical properties of molded product: Specific gravity 2.58 Cutting strength 612Kg/
cm ² Shore hardness: 91 Softening temperature: 750℃ Crystal formation rate (X-ray diffraction and chemical analysis): 30% According to this method, the volume of the blended raw materials in the melting furnace is relatively large, and the melting time is relatively long. However, it is suitable for small-scale production, and the quality of the product obtained remains the same. 〓〓〓〓〓

Claims (1)

[Scope of Claims] 1. After blending at least one selected from fluorine mica component glass powder, fluorine mica-containing glass powder, and fluorine mica single crystal powder into the base glass component raw material and molding. A method for producing a sintered crystallized glass molded product containing fluorine mica crystals, characterized by sintering at a temperature of 600°C or higher, and then crystallizing heat treatment at a temperature of 550°C or higher. 2. After melting and integrating the base glass component or its raw material and the fluorine mica component or its raw material, it is cooled and crushed to form a powder, the powder is molded, and sintered at a temperature of 600°C or higher, A method for producing a sintered crystallized glass molded product containing fluorine mica, which is then subjected to crystallization heat treatment at a temperature of 550°C or higher.