JPH08175830A - Production of patterned, colored and crystallized glass article - Google Patents

Abstract

PURPOSE: To obtain the subject glass article having a smooth and beautiful surface by respectively preparing prescribed small crystallizable glass pieces, a prescribed glass powder, prescribed small crystallized glass pieces and an inorganic pigment powder, mixing the glass powder with the inorganic pigment powder, further mixing the resultant mixed powder with the small crystallizable and crystallized glass pieces and heat-treating the mixture under specified conditions. CONSTITUTION: This glass article is obtained by preparing many small crystallizable glass pieces capable of depositing needlelike crystals from the surface toward the interior while softening and deforming by heat treatment at a higher temperature than the softening point, small crystallized glass pieces, a glass powder having a difference between the small crystallizable and crystallized glass pieces at the fixing temperature in the thermal expansion coefficient within the range of 5×10<-7> / deg.C and an inorganic pigment powder, then mixing the glass powder with the inorganic pigment powder, providing a mixed powder, mixing the resultant mixed powder with the small crystallizable and crystallized glass pieces, affording a mixture in which the mixed powder sticks to the surfaces of the small crystallizable and crystallized glass pieces, subsequently accumulating the mixture and heat-treating the accumulated mixture at a higher temperature than the softening point of the crystallizable glass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a patterned colored crystallized glass article used as a decorative material such as an exterior material and an interior material of a building.

[0002]

2. Description of the Related Art Various crystallized glass articles have been proposed for use as decorative materials such as exterior and interior materials for buildings.

For example, Japanese Examined Patent Publication No. 55-29018 discloses a method for producing a natural marble-like crystallized glass article in which a large number of crystalline glass particles are accumulated and heat-treated to crystallize them. Further, as a method for producing a colored crystallized glass article, a method of accumulating a mixture of crystalline glass particles and an inorganic pigment powder and heat-treating is disclosed in JP-B-5-43651.

[0004]

By the way, with the diversification of buildings in recent years, diversification of decorative materials is required. One of the diversifications is the diversification of appearance such as color tone and pattern, and it is desired that the decorative material made of crystallized glass also has a new appearance.

Under these circumstances, a method for producing a crystallized glass article having a novel appearance by accumulating and crystallizing a mixture of crystalline glass particles, crystallized glass granules and inorganic pigment powder is developed. Has been done.

However, in the above method, if the particle size difference between the crystalline glass particles or the crushed crystallized glass and the inorganic pigment powder is too large, the inorganic pigment powder separates and floats up during the heat treatment, and the surface hardly flows. However, there is a problem that unevenness and voids remain on the surface.

The object of the present invention is to produce a patterned colored crystallized glass article having a smooth and beautiful surface even if a crystalline glass particle or a crystallized glass granule having a large particle size difference from the inorganic pigment powder is used. It is to provide a possible method.

[0008]

Means for Solving the Problems As a result of various researches by the present inventors, a glass powder having almost no difference in expansion from crystalline glass particles or crystallized glass particles at the fixing temperature was designated as an inorganic pigment powder. The inventors have found that the above object can be achieved by mixing the mixed powders to prepare mixed powders, and propose the present invention.

That is, the method for producing a patterned crystallized glass article of the present invention is a crystalline glass having the property of acicular crystals precipitating from the surface toward the inside while being softened and deformed by heat treatment at a temperature higher than the softening point. A plurality of small bodies, a crystallized glass body, a glass powder having a difference in thermal expansion coefficient between the crystalline glass body and the crystallized glass body at a fixing temperature of 5 × 10 ⁻⁷ / ° C. or less, and an inorganic substance A step of preparing each of the pigment powder, a step of mixing the glass powder and the inorganic pigment powder to obtain a mixed powder, and a step of mixing the crystalline glass small particles, the crystallized glass small particles and the mixed powder with each other. The method is characterized by including a step of obtaining a mixture in which the mixed powder is adhered to the surfaces of the body and the crystallized glass small bodies, and a step of accumulating the mixture and heat-treating at a temperature equal to or higher than the softening point of the crystalline glass.

The crystalline glass particles used in the present invention have the property of acicular crystals precipitating from the surface toward the inside while softening and deforming when heat-treated at a temperature higher than the softening point, and are required as a cosmetic material. Any composition system can be used as long as it satisfies the various properties (mechanical strength, weather resistance, etc.). For example, β as the main crystal
- wollastonite _{(β-CaO · SiO 2)} , diopside (CaO · MgO · 2SiO ₂₎ glass to precipitate crystals can be used, such as, in particular weight%, SiO ₂ 4
0-80%, Al ₂ O ₃ 2-15%, CaO 3-25
%, ZnO 0 to 15%, BaO 0 to 20%, B ₂ O
_{3 0~10%, Na 2 O +} K 2 O + Li 2 O 2~20
%, Crystalline glass that precipitates β-wollastonite as a main crystal, SiO ₂ 45 to 80%, Al
₂ O ₃ 1 to 25%, CaO 1 to 20%, MgO 0.
5-20%, CaO + MgO 1.5-18%, BaO
0-18%, ZnO 0-18%, Na ₂ O 1-1
_{5%, K 2 O 0~7%} , Li 2 O 0~5%, B 2 O
₃ 0-10%, has a composition of P ₂ O ₅ 0-10%, it is preferable to use a glass to deposit diopside as the main crystal.

The crystallized glass particles in the present invention include, for example, a large number of glass particles having the property of acicular crystals precipitating from the surface toward the inside while being softened and deformed by heat treatment at a temperature higher than the softening point. However, it is possible to use crystallized glass that is softened and fused and crystallized. Such a crystallized glass body is manufactured as follows. First, a large number of glass small bodies having the property of precipitating needle-like crystals from the surface toward the inside while softening and deforming when heat-treated at a temperature higher than the softening point are prepared. At this time, an inorganic pigment powder described later may be attached to the surface of the glass body. Then collect these in the formwork,
It is manufactured by heat treatment to fuse and integrate and crystallize. The crystallized glass thus obtained may be used as it is as a crystallized glass small body, but it is better to use it after further processing such as cutting and crushing to obtain a desired shape. . It is preferable to use glass having substantially the same composition as the above-mentioned crystalline glass body as the glass body used when producing the crystallized glass body.

The glass powder used in the present invention has a difference in thermal expansion coefficient between the crystalline glass particles and the crystallized glass particles at a fixing temperature of 5 × 10 ⁻⁷ / ° C. or less.
In general, when two or more kinds of glass are fixed, when there is a difference in the viscosity characteristics of each glass, the fixing starts at a temperature near the transition point of the glass having the lowest viscosity. Refers to the temperature at which Further, the reason why the range of the difference in thermal expansion coefficient is limited in this way is that if the difference in thermal expansion coefficient becomes larger than the above range, cracks due to the difference in expansion occur. As such a glass powder, those having various compositions can be used, and either crystalline glass or amorphous glass can be used, but in particular, a glass powder having substantially the same composition as a crystalline glass body. Is preferred.

The inorganic pigment powder used in the present invention is not particularly limited as long as it has excellent heat resistance and does not fade. Examples of the inorganic pigment include NiO and MnO.
_2, CoO, coloring oxides of a single such _{Fe 2 O 3, Cr 2 O} 3 and, Zn-Cr-Ni-Al spinel, Sn-Si
-Ca-Cr-Zn sphene, Zr-Si-Pr zircon, Zr-Si-V-Pr zircon, Zr-Si-V
Zircon, Zr-V zirconia, Al-Co-Cr-Z
n spinel, Al-Zn-Fe-Cr spinel, Fe-
Cr-Zn-Al spinel, Fe-Cr-Zn spinel, Fe-Cr-Ni-Mn spinel, Ni-Fe-C
Colored oxides such as o spinel can be used.

Next, the method for producing the patterned colored crystallized glass article of the present invention will be described in detail.

First, when a heat treatment is performed at a temperature higher than the softening point, a large number of crystalline glass bodies having a property of acicular crystals precipitating from the surface toward the inside while softening and deforming are prepared. The glass particles have a grain size of 0.5 to 1 in order to reveal the pattern.
It is preferable to use one having a diameter of about 0 mm. Note that the glass small particles referred to in the present invention are water granulated products, granules, small spheres,
Includes various shapes such as small pieces and rods. Further, the crystalline glass particles used are not necessarily limited to only one kind, and two or more kinds of glass particles having different compositions may be mixed and used.

Further, a crystallized glass body is prepared. Since the shape of the crystallized glass body is maintained by the subsequent heat treatment, it is possible to make the crystallized glass article have a desired shape by selecting an appropriate shape. Become. For example, the use of coarsely crushed crystallized glass particles can give the appearance of natural minerals such as granite. A large number of crystallized glass bodies may be prepared, but it is possible to use only one crystallized glass body.

The difference in thermal expansion coefficient between the crystalline glass particles and the crystallized glass particles at the fixing temperature is 5 × 10 ^-7 / ° C.
Prepare the glass powder that is within. It is preferable to use glass powder having a maximum particle size of 150 μm or less so that the particle size difference with the inorganic pigment powder does not become large.

Further, an inorganic pigment powder having a desired color tone is prepared. The inorganic pigment powder may be used alone, or two or more kinds may be mixed and used.

Next, the glass powder and the inorganic pigment powder are stirred and mixed by a vibration mixer, an alumina ball mill, a mixer or the like to prepare a mixed powder. Here, the mixing ratio of both is preferably in the range of 45:55 to 95: 5 of glass powder: inorganic pigment powder. The reason for limiting the ratio of the both is as described above. When the ratio of the glass powder is less than the above range, the effect is reduced and the softening flow of the crystalline glass bodies is hindered, and it becomes difficult to obtain a smooth surface. Further, when the proportion of the glass powder is too large, the amount of the inorganic pigment powder becomes relatively small, so that it is necessary to use a large amount of the mixed powder for effective coloring, which is not economical.

Subsequently, the crystalline glass particles, the crystallized glass particles and the mixed powder are mixed by a mixer or the like to obtain a mixture in which the mixed powder is adhered to the surface of each glass particle. The mixing ratio of these mixtures is 60 to 90 parts by weight of crystalline glass particles, 40 to 10 parts by weight of crystallized glass particles, and mixed powder 2
A range of up to 20 parts by weight is suitable. The reason for limiting the mixing ratio in this way is that when the amount of the crystalline glass particles exceeds 90 parts by weight, the pattern due to the crystallized glass particles becomes difficult to appear, and when the amount is less than 60 parts by weight, the flow becomes difficult. When the amount of the crystallized glass particles is more than 40 parts by weight, the amount of the crystallized glass particles is small and it is difficult to flow, and when it is less than 10 parts by weight, the pattern of the crystallized glass particles is difficult to appear. If the amount of the mixed powder is more than 20 parts by weight, the softening flow of the crystallizable glass particles is hindered, and it tends to be difficult to obtain a smooth surface. On the other hand, if the mixed powder is less than 2 parts by weight, it is difficult to obtain sufficient color development.

As a method for mixing each glass body and the mixed powder, after weighing these in an appropriate amount and dry-mixing, 0.1 to 5 parts of water or a water-soluble binder is added to 100 parts by weight of the glass body. It suffices to add parts by weight and sufficiently stir and mix. By adding water or a water-soluble binder, the mixed powder easily adheres to the surface of the glass body, and the mixed powder remaining without adhering easily aggregates to form a colored portion. The amount of water or water-soluble organic binder added was adjusted to 0.
The amount of 1 to 5 parts by weight makes it difficult to perform the mixing sufficiently when the amount is less than 0.1 parts by weight, because the particle size of the mixed powder and the glass small particles are greatly different. Furthermore, it is difficult for the mixed powder to adhere to the surface of the glass bodies, and the resulting crystallized glass article tends to have severe color unevenness. On the other hand, if the amount exceeds 5 parts by weight, the agglomeration of the mixed powder becomes remarkable and the color unevenness is apt to become severe similarly to the above.

Then, the obtained mixture is accumulated in a mold made of refractory and heat-treated at a temperature higher than the softening point of the crystalline glass, so that the crystalline glass bodies are softened and deformed to melt the glass bodies. While being adhered and integrated, needle-like crystals are deposited from the surface of the crystalline glass body toward the inside. Also,
A colored layer of inorganic pigment powder is formed at the interface of each glass body. On the other hand, the mixed powder not adhering to the surface of the glass bodies flows into the spaces between the glass bodies or into the cracks in the glass bodies due to the softening flow of the glass powder to form colored portions.

A patterned colored crystallized glass article can be obtained in this manner.

In the method of the present invention, the step of mixing the glass powder and the inorganic pigment powder and the step of mixing the glass particles and the mixed powder are preferably carried out independently of each other. The glass powder and the inorganic pigment powder may be supplied and mixed, and then the crystalline glass particles and the crystallized glass particles may be further supplied and mixed to form a continuous series of steps.

[0025]

In general, the inorganic pigment powder has a very small average particle size of 10 μm or less. For this reason, when the glass particles having a large particle size are attached to the surface of the glass particles, when the glass particles start to flow due to the heat treatment, the particle size difference between the glass particles becomes large, so that separation occurs and the inorganic pigment powder floats on the surface.

In the method for producing a patterned colored crystallized glass article of the present invention, since the difference in particle size between the glass powder and the inorganic pigment powder in the mixed powder is small, separation between the two does not occur. Therefore, before the mixed powder adhering to the surface of the glass body separates from the glass body, the glass powder in the mixed powder softens and adheres to the glass body with the inorganic pigment powder, coloring the glass body interface. Form the layers. In the mixed powder that is not attached to the surface of the glass bodies, the glass powder softens and flows together with the inorganic pigment powder, and flows into fine cracks between the glass bodies or into minute cracks in the glass bodies to form colored portions. .

[0027]

EXAMPLES Hereinafter, a method for producing a patterned colored crystallized glass of the present invention will be described based on Examples and Comparative Examples.

(Example) First, SiO ₂ 6 was used as a weight percentage.
3.0%, Al ₂ O ₃ 6.5%, CaO 15.0%,
ZnO 4.3%, BaO 5.0%, B ₂ O ₃ 0.8
%, Na ₂ O 2.8%, K ₂ O 1.0%, Li ₂ O
14 glass raw materials prepared to have a composition of 1.6%
It melted at 00 to 1500 ° C. for 12 hours. Next, this glass was dropped into water to be granulated, dried and classified to obtain a crystallized glass granule having a particle size of 0.5 to 5 mm. This glass granulation product has a transition point of 591 ° C., a softening point of 800 ° C. and a thermal expansion coefficient of 66.4 × 10 ⁻⁷ / ° C. at the transition point, and when crystallized, β-wollastonite is used as a main crystal. It was composed of crystalline glass which was deposited and became white crystallized glass.

Further, a large number of crystallized glass coarsely crushed products having the same composition as the above crystallized glass crushed product and exhibiting a blackish brown color tone were prepared. This crystallized glass crushed product was produced as follows. First, the above-mentioned crystalline glass granules were crushed and classified to obtain a glass crushed product having a maximum particle size of 2 mm. Next, this crushed glass and Fe—Cr—Ni—Mn spinel pigment (average particle size 10 μm, blackish brown) were weighed so as to have a weight ratio of 99: 1 and dry-mixed in a mixer.
2 parts by weight of 5% polyvinyl alcohol (PVA) aqueous solution was added and further mixed with stirring. Subsequently, these mixtures were accumulated in a mullite mold and heat-treated at 1100 ° C. for 2 hours to obtain a crystallized glass plate having a blackish brown color tone due to the presence of the inorganic pigment. Then, it was crushed by a crusher to obtain a crystallized glass crushed product having a maximum length of 20 mm or less. Note that this crystallized glass coarse crushed product had 67.1 × 10 ^{−7 at} the transition point (591 ° C.) of the crystalline glass crushed product.
It had a coefficient of thermal expansion of / ° C.

Further, the above-mentioned crystallized glass granules were crushed for 24 hours using alumina balls and then passed through a 100-mesh sieve to obtain a glass powder having a maximum particle size of 150 μm.

Further, Sn-Si-Ca-Cr-Zn sphene pigment (average particle size 10 μm, red) and Fe-Cr
-Ni-Mn spinel pigment was prepared.

Next, glass powder and Sn-Si-Ca-Cr were used.
-Zn-based sphene pigment and Fe-Cr-Ni-Mn-based spinel pigment were weighed in a weight ratio of 70:15:15 and dry-mixed for 10 minutes in a vibration mixer to prepare a uniform mixed powder. did.

Subsequently, the crystallized glass granules, the crystallized glass granules and the mixed powder were weighed in a weight ratio of 70: 25: 5, dry-mixed in a mixer, and then 2 parts by weight of 5%. A polyvinyl alcohol (PVA) aqueous solution was added and further mixed with stirring.

Thereafter, these mixtures were collected in a mullite mold and heat-treated at 1100 ° C. for 2 hours to obtain a crystallized glass plate.

The crystallized glass plate thus obtained has a smooth and crack-free surface, and a discontinuous brown colored layer is formed in the matrix portion where the white portion and the brown portion are mixed. It had a beautiful appearance with scattered black-brown parts of the roughly crushed material.

When the surface was observed in detail, a brown colored layer was formed at the interface of the white glass bodies in the matrix portion, and a relatively large brown colored portion was observed between the glass bodies. In addition, it was confirmed that streaky brown colored parts had penetrated into the glass bodies. On the other hand, the coarsely crushed material had a black-brown color tone as a whole, but detailed observation revealed that it consisted of very fine white glass particles and a black-brown colored layer present at the interface.

(Comparative Example) The crystallized glass granules, crystallized glass granules and inorganic pigment powder used in Example 1 were weighed in a weight ratio of 73.5: 25: 1.5. After dry-mixing in a mixer, 2 parts by weight of 5% polyvinyl alcohol (PVA) aqueous solution was added and mixed by stirring with a mixer. Then, it heat-processed similarly to Example 1 and the crystallized glass plate was obtained.

Observation of the obtained crystallized glass plate revealed that the inorganic pigment powder floated on the surface and aggregated,
Due to insufficient flow, there were many irregularities due to small glass bodies.

In order to eliminate the insufficient fluidity, the heat treatment temperature was raised to 1150 ° C. and a crystallized glass plate was produced in the same manner as above. The surface condition was almost the same as that described above, and the inorganic pigment was decolorized. Was happening.

[0040]

According to the method of the present invention, a crystallized glass article having a smooth surface can be produced even if a crystalline glass particle or a crystallized glass particle having a large particle size difference from the inorganic pigment powder is used. can do. For this reason, it becomes possible to manufacture a patterned colored crystallized glass article having a different taste from conventional products, and it is possible to satisfy the demand for diversification of decorative materials.

Claims (1)

[Claims] 1. A large number of crystalline glass bodies having a property of acicular crystals precipitating from the surface toward the inside while being softened and deformed by heat treatment at a temperature higher than the softening point, and a crystallized glass body, A step of preparing a glass powder having a thermal expansion coefficient difference of 5 × 10 ⁻⁷ / ° C. or less between the crystalline glass particles and the crystallized glass particles at the fixing temperature, and an inorganic pigment powder, and the glass powder and the inorganic material. The step of mixing the pigment powders to obtain the mixed powder, and mixing the crystalline glass particles, the crystallized glass particles and the mixed powder to attach the mixed powder to the surfaces of the crystalline glass particles and the crystallized glass particles. A method for producing a patterned colored crystallized glass article, comprising: a step of obtaining the mixed mixture; and a step of accumulating the mixture and heat-treating the crystalline glass at a temperature equal to or higher than the softening point of the crystalline glass.