WO2006135049A1

WO2006135049A1 - Natural marble like crystallized glass and process for production thereof

Info

Publication number: WO2006135049A1
Application number: PCT/JP2006/312135
Authority: WO
Inventors: Yoshio Hashibe; Masahiro Sawada
Original assignee: Nippon Electric Glass Co., Ltd
Priority date: 2005-06-16
Filing date: 2006-06-16
Publication date: 2006-12-21
Also published as: CN101198558B; CN101198558A

Abstract

The invention provides a natural marble like crystallized glass which is improved in whiteness and has an unprecedented color tone and a process for the production of the same. The natural marble like crystallized glass is characterized in that the surface of the crystallized glass exhibits, in the L*a*b* color model, values of a* and b* of ±1.0 or below and a whiteness degree L* of 93.5 or above, while the process comprises packing plural small crystallizable glass pieces into a refractory vessel, heat-treating the pieces at a temperature higher than the softening point to form 20 to 50 % by mass of crystals, and thus obtaining a nature marble like crystallized glass exhibiting, in the L*a*b* color model, values of a* and b* of ±1.0 or below and a whiteness degree L* of 93.5 or above.

Description

Specification

Natural marble-like crystallized glass and method for producing the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to crystallized glass, and more particularly to natural calcite-like crystallized glass used for interior and exterior materials of buildings and a method for producing the same.

Background art

[0002] Crystallized glass with a natural marble pattern is excellent in chemical durability and mechanical strength, and initially has a beautiful appearance as a substitute for natural stone and with many options that do not exist in nature. Therefore, the interior materials of many buildings that pursue design are now used as exterior materials.

[0003] As this type of crystallized glass, Patent Documents 1 and 2 are natural large stones formed by precipitating wollastonite crystals (CaO'SiO) as main crystals by heat-treating the crystalline glass composition. A similar crystallized glass is disclosed.

[0004] In Patent Document 1, in terms of mass percentage, Si 0 50 to 75%, Al 2 O 1 to: 15%, CaO

6 ~: 16%, LiO 0. 1 ~ 5%, BO 0 ~ 1.5%, CaO + LiO + BO 10 ~: 17.5

%, ZnO 2.5 ~: 12%, BaO 0 ~: 12%, Na O + K〇 0.1 ~: 15%

Further, a natural marble-like crystallized glass obtained by precipitating / 3_wollastonite crystal as a main crystal is disclosed. This natural marble-like crystallized glass has excellent color stability for the purpose of improving productivity.

[0005] In Patent Document 2, in terms of mass percentage, Si ○ 45 to 77%, Al O 1 to 25%, CaO

2-25%, ZnO 0-: 18%, BaO 0-20%, NaO 1-: 15%, KO 0-7%, Li

O 0 to 5%, B 0 0 to: 1.5%, Ce 0. 01 to 0.5%, SO 0. 01 to 0.5% as the main crystal. A natural marble-like crystallized glass formed by depositing lastonite is disclosed. This natural marble-like crystallized glass has a whiteness equal to or higher than that of conventional products containing no AsO or SbO.

[0006] Patent Document 3 includes SiO 45 to 75%, A10 1 to 25%, CaO 1 in mass percentage.

~ 20%, MgO 0.5 ~: 17%, BaO 0 ~: 18%, Zn * 0 ~: 18%, Na * 1 ~: 15% , KO 0 to 7%, Li O 0 to 5%, B 0 0 to: 10%, P 0 0 to 10%, As O 0 to 1

%, SbO 0 to 1%, and the glass bodies, which essentially contain no nucleating agent, are accumulated in a formwork of the desired shape and then heat-treated to fuse the glass bodies together. And a method for producing natural marble-like crystallized glass obtained by precipitating diopside crystals (CaO'MgO'2SiO) is disclosed.

According to this manufacturing method, since a natural marble-like crystallized glass can be manufactured with a high yield without requiring a crystal nucleating agent such as cocoon and F, the raw material cost and the manufacturing cost can be significantly reduced. Is possible. The desired natural marble pattern can be obtained by adjusting the particle size of the glass body. Furthermore, since it can be bent by re-heat treatment, it can also be used for curved portions of wall surfaces.

Patent Document 1: JP-A-6-247744

Patent Document 2: Japanese Patent Laid-Open No. 9-295831

Patent Document 3: JP-A-3-205323

Disclosure of the invention

Problems to be solved by the invention

[0007] By the way, recently, building materials having various appearances have been developed along with the diversification of buildings, and only the building materials made of crystallized glass exhibit the natural marble pattern with the conventional color tone shown above. However, there is a demand for a high-quality appearance with high whiteness.

[0008] The present invention pays attention to the above circumstances, and natural marble-like crystallized glass having a whiteness higher than that of a conventional natural marble-like crystallized glass and exhibiting a color tone different from that of a conventional product, and the crystallized glass. It is providing the manufacturing method which enabled manufacture.

Means for solving the problem

[0009] The present inventors have found that a crystallized glass article with a whiter impression than the prototype of the conventional product has a color coordinate a * and b * in the L * a * b * color system chromaticity of the crystallized glass surface. It has been found that the L * value is in a range different from that of the conventional crystallized glass article and is higher than the whiteness of the conventional crystallized glass article.

[0010] That is, the natural marble-like crystallized glass of the present invention is measured with a standard light D in a 10-degree field of view. L * a * b * Color coordinates in the color system chromaticity a * and b * are ± 1.0 or less and whiteness L * force S93.5 or more Is. Natural marble-like crystallized glass having such L * a * b * color system chromaticity is preferable because it has a suitable color tone as an achromatic white product. If the color coordinates a * and b * deviate from ± 1.0 or the whiteness L * is less than 93.5, coloring occurs and the color tone of the conventional product is almost unchanged. It is more preferable that the color coordinates a * and b * are ± 0.7 or less because the difference in hue from the conventional product can be clearly felt not only in color tone but also visually.

* & * 1) * Color system chromaticity is defined in 3 Z8730.

[0011] The natural marble-like crystallized glass of the present invention has an X of 0 in the XYZ color system chromaticity diagram.

3120 to 0.3130 and y-force SO. 3290 to 0.3320. Natural marble-like crystallized glass having such a color system chromaticity is a coordinate point having no hue and the lowest saturation, and is suitable as a new achromatic white product. In addition, when X is 0.3 125 to 0.3130 and y-force SO. 3300 to 0.3320, in addition to the color difference from the conventional product, the difference in hue clearly feels visually. Is more preferable. The XYZ color system chromaticity is defined in JIS Z8701.

[0012] In addition, the inventors of the present invention have found that when the Fe 2 O content in the glass is controlled to 200 ppm or less by selecting the silica raw material, the alumina raw material, the calcium raw material, and the lithium raw material, the crystallization glass

twenty three

L * a * b * color coordinate in the color system chromaticity a * and b * is in a range different from that of conventional crystallized glass articles, and is higher than the whiteness of conventional crystallized glass articles L * It was found to be a natural marble-like crystallized glass having a value.

[0013] That is, the natural marble-like crystallized glass of the present invention has a content of FeO as an impurity of 2

twenty three

It is OOppm or less, and the amount of precipitated crystals is 20 to 50% by mass.

[0014] In the present invention, a glass raw material used in preparing a glass containing the above-mentioned components is selected, and the content of FeO as an impurity is set to 200 ppm or less, whereby the glass

twenty three

A high-quality natural marble-like crystallized glass can be produced with a higher transmittance than in the past and further enhanced whiteness of the crystallized glass after heat treatment. The Fe O content is 15

twenty three

If it is Oppm or less, it is more preferable for realizing a color tone suitable as an achromatic white product. The reason for paying attention to the content of Fe 2 O is that it is more luxurious than other coloring components. This is because a certain whiteness can be obtained. In the case of natural calcite-like crystallized glass containing Fe 2 O as a colorant, crystallized glass at the base site where the colorant is not distributed is the subject of the present invention, and colorants other than Fe 2 O are used. Natural marble-like crystallized glass of varieties using different colors is also an object of the present invention. On the other hand, if the amount of precipitated crystals is less than 20% by mass, the amount of crystals becomes too small and the reflectance decreases, so that the whiteness L * becomes 93.5 or less. On the other hand, if it exceeds 50% by mass, the amount of crystals increases too much, the viscosity increases, the flow of molten glass is inhibited, and the desired surface cannot be obtained. The amount of precipitated crystals in the natural calcite-like crystallized glass of the present invention is preferably 30 to 40% by mass in terms of whiteness L * and fluidity.

[0015] Further, in the natural marble-like crystallized glass of the present invention, the crystallized glass is expressed in terms of mass percentage of SiO 45 to 75%, A1 0 1 to 25%, CaO 2 to 25%, ZnO 0 to 18%. , Ba 0 0

~ 20%, MgO 0 ~: 1.5%, Sr 0 0 ~: 1.5%, Na 0 1 ~: 15%, K 0 0 ~ 7%, LiO 0 ~ 5%, B 0 0 ~ : 1.5%, Ce 0 0-0.5%, SO 0-0.5, Sb 0 0-1

It is characterized by having β-wollastonite crystal as the main crystal and having a composition of%, AsO 0-1%.

[0016] The reason for limiting the content of each component other than FeO in the natural marble-like crystallized glass of the present invention will be described.

[0017] The content of SiO is 45 to 75%, preferably 50 to 70%. If the SiO force is higher than 75%, the melting temperature of the glass increases and the viscosity increases, resulting in poor fluidity during heat treatment.

. On the other hand, if it is less than 45%, the devitrification at the time of molding becomes strong.

[0018] The content of A10 is:! ~ 25%, preferably 3 ~: 15%. If the Al O force exceeds ¾5%, the glass solubility deteriorates and different crystals (ananosite) precipitate, resulting in poor fluidity during heat treatment. If less than 1%, devitrification increases and chemical durability increases. descend.

When β-wollastonite crystals are precipitated, the content of Ca 0 is 2 to 25%, preferably 8 to 18%. If CaO is more than 25%, devitrification becomes strong and molding becomes difficult, and the amount of / 3_wollastonite crystal precipitated becomes too large, making it difficult to obtain the desired surface smoothness. On the other hand, if it is less than 2% —the amount of precipitated wollastonite crystals becomes too small and the mechanical strength decreases, making it unusable as a building material. In addition, when CaO is a component of diopside, its content is 2-20%

, Preferably 3 to 18%. If CaO is less than 2%, diopside crystals will not precipitate, and if it is more than 20%, fluidity will deteriorate and β-wollastonite crystals will precipitate.

The desired characteristics cannot be obtained.

[0020] ΖηO is a component added to promote the fluidity of the glass during crystallization, and its content is 0 to 18%, preferably 2 to 15%. If ΖηΟ is more than 18%, / 3 —wollastonite crystals will be difficult to precipitate.

[0021] BaO is a component having the same effect as ΖηΟ, and its content is 0 to 20%, preferably 1 to

10%. If BaO is more than 20%, the amount of / 3-wollastonite crystals deposited decreases.

[0022] When β-wollastonite crystals are precipitated, MgO and SrO are components that promote the solubility and fluidity of the glass, but when it exceeds 1.5%, different crystals are precipitated. It is not preferable in terms of characteristics.

When MgO is a constituent component of diopside, the content thereof is 1.5 to 17%, preferably 1.5 to 12%. If MgO is less than 1.5%, diopside crystals are difficult to precipitate, and if it is more than 17%, the fluidity is poor.

[0023] The content of Na 2 O is:! ~ 15%, preferably 3 ~: 10%. If NaO is more than 15%, scientific durability deteriorates and the expansion coefficient becomes high, which is not preferable as a building material. If it is less than 1%, the viscosity of the glass increases and the solubility and fluidity deteriorate.

[0024] The content of K 2 O is 0 to 7%, preferably 0 to 5%. If K 2 O is more than 7%, chemical durability decreases.

[0025] Li 2 O has the effect of increasing the crystallization speed and the effect of promoting fluidity, and its content is 0

-5%, preferably 0.1-3%. If Li 2 O is more than 5%, the chemical durability is lowered and the viscosity is lowered too much, so that foaming tends to occur.

[0026] The content of B 0 is 0 to: 1.5%, preferably 0 to 1%. If B 2 O exceeds 1.5%, heterogeneous crystals will precipitate and the desired properties will not be obtained.

[0027] Since CeO is not preferred from the viewpoint of environmental conservation, asO or SbO as a clarifier is not preferred, the whiteness of the crystallized product is drastically reduced when its content is 0.1% or less. In this case, it is a component that suppresses the decrease in whiteness. C to suppress the decrease in whiteness The content of eO is 0.01-0.5%, preferably 0.05-0.3%. The effect is to suppress the coloration of Fe ²⁺ by Fe 2 O contained as an impurity in a glass melting environment under a reducing atmosphere. Appears in the book. When CeO is more than 0.5%, the brown coloration by Ce ⁴⁺ becomes strong, and when it is less than 0.01%, the above-mentioned effects are hardly obtained.

[0028] The SO content is 0.01 to 0.5%, preferably 0.02 to 0.4%. When SO is more than 0.5%, different crystals are precipitated, while when it is less than 0.01%, the clarifying agents AsO and Sb

When O is 0.1% or less, the solubility of the glass is lowered and the quality of the glass is deteriorated.

[0029] Further, in the natural marble-like crystallized glass of the present invention, the crystallized glass is expressed in terms of mass percentage of SiO 45 to 75%, A1 0 1 to 25%. CaO 2 to 20%, Mg 0 1.5 to : 17%, ZnO

0 ~: 18%, Ba 0 0 ~ 20%, SrO 0 ~: 1.5%, Na O 1 ~: 15%, K O 0 ~ 7%,

Li O 0 to 5%, B O 0 to: 1.5%, CeO 0 to 0.5%, S 0 0 to 0.5, Sb O 0 to

It has a composition of 1%, As 0 to 1%, and is characterized by depositing diopside crystals as main crystals.

[0030] When MgO is less than 1.5%, the main crystal diopside (CaO'MgO'2SiO) does not precipitate, and when it exceeds 17%, the amount of diopside crystal precipitated increases. The liquidus temperature becomes too high just by inhibiting the flow too much, which hinders glass forming.

[0031] Next, a method for producing the natural marble-like crystallized glass of the present invention will be described.

[0032] The method for producing a natural marble-like crystallized glass according to the present invention comprises filling a fireproof container with a plurality of crystalline glass bodies having a content of Fe 2 O as an impurity of 200 ppm or less, By heat-treating the glass body at a temperature higher than the softening point, 20 to 50% by mass of crystals are precipitated, and the whiteness L * a * b * colorimetric chromaticity of the crystallized glass surface L * is over 93.5 And a natural marble-like crystallized glass having color coordinates a * and b * of ± 1.0 or less.

[0033] In the production method of the present invention, it is important that the content of FeO is 200 ppm or less as a raw material batch in which a glass raw material is prepared according to the composition range shown above and melted. As a glass material, feldspar with the highest content of Fe 2 O (Si 60-70%, A10 12-12

18%, K5 5-10%, Na2 2-3%) Silica sand with as little Fe O content as possible, Al O alumina or aluminum hydroxide as Al O raw material

Other raw materials such as low iron calcium carbonate as the CaO raw material and lithium carbonate as the LiO raw material are preferably selected as low as possible. And the glass batch prepared so that it may become the composition range mentioned above is melt | dissolved, and after vitrification, a desired glass body is produced through processes, such as granulation and classification. Next, when the crystalline glass bodies are accumulated in a refractory mold and heat-treated at a temperature higher than the softening point, the glass bodies are fused and integrated, and the needles from the surface of each glass body toward the inside. Β-wollastonite crystals are precipitated and the crystallization is completed. As a result, the natural marble-like crystallized glass of the present invention having a very high whiteness that does not exhibit a hue can be obtained. Fe

The content of O can be measured and confirmed by fluorescent X-ray analysis or chemical analysis.

[0034] Further, according to the method for producing a natural marble-like crystallized glass of the present invention, a plurality of crystalline glass bodies are expressed in terms of mass percentage: Si 45-75%, AlO 1-25%, CaO 2 ~twenty five%

, ZnO 0 ~: 18%, BaO 0 ~ 20%, MgO 0 ~: 1.5%, Sr〇 0 ~: 1.5%, Na〇

1 to: 15%, K O 0 to 7%, Li O 0 to 5%, B 0 0 to 1.5%, Ce 0 0 to 0.5%, S

It has a composition of O 0 to 0.5%, Sb O 0 to 1%, As O 0 to 1%, and is characterized by precipitating β-wollastonite crystals as main crystals by heat treatment.

[0035] In the production method of the present invention, a glass raw material is prepared so as to have the above composition, melted, and granulated by a process such as pulverization to produce a crystalline glass body, and a softening point. By heat treatment at a higher temperature, 20-50 mass% of β-wollastonite crystal is precipitated as the main crystal, and whiteness L * a * b * colorimetric chromaticity on the crystallized glass surface L * force S93 A natural marble-like crystallized glass having a color coordinate of a * and b * of ± 1.0 or less is 5 or more.

[0036] Further, in the method for producing a natural marble-like crystallized glass of the present invention, a plurality of crystalline glass bodies are expressed by mass percentage in terms of Si0 45 to 75%, AlO 1 to 25%, CaO. 2-20

%, MgO 1.5 ~: 17%, ZnO 0 ~: 18%, BaO 0 ~ 20%, Sr〇 0 ~: 1.5%, Na

O 1 ~: 15%, K O 0 ~ 7%,: Li O 0 ~ 5%, B O 0 ~: 1.5%, CeO 0 ~ 0.5%

S0 0 to 0.5, Sb O 0 to l%, As O 0 to 1%, and heat treatment A diopside crystal is further precipitated as a main crystal.

[0037] In the production method of the present invention, a glass raw material is prepared so as to have the above composition, melted, and granulated by a process such as pulverization to produce a crystalline glass body, and a softening point. Heat treatment at a higher temperature causes 20-50 mass% of the diopside crystal to precipitate as the main crystal, and the whiteness of the L * a * b * color system chromaticity L * force S93.5 on the crystallized glass surface A natural marble-like crystallized glass with the color coordinates a * and b * of ± 1.0 or less is produced.

[0038] The natural marble-like crystallized glass manufacturing method of the present invention has an average visible light transmittance (380 nm to 780 nm) of 89% or more when the thickness is 10 mm, and an XYZ color system chromaticity diagram. By using crystalline glass bodies with X force 0.3100 to 0.3115 and y force SO. 3160 to 0.3190 (C photogen 2 degrees), the surface of crystallized glass is expressed. is there.

[0039] The glass raw material used in the natural marble-like crystallized glass of the present invention obtained in the present invention has a high glass transmittance when the content of impure FeO is low, and crystallization after heat treatment is performed.

twenty three

The whiteness of the glass increases. However, since the glass cost is high, it is necessary to balance the quality of crystallized glass with the glass cost. In addition, by selecting a glass raw material, a crystalline glass body having X in the XYZ color system chromaticity diagram of crystalline glass having a X of 0.3100 to 0.3115 and a y force of SO 3160 to 0.3190 can be obtained. By using it, it is preferable to express the desired natural marble-like crystallized glass surface.

[0040] When handling the glass raw material and the crystalline glass body, it is preferable to give consideration to the contact surfaces of the containers and other conveying devices so that iron is not mixed in from containers and other transport devices.

The invention's effect

[0041] The natural marble-like crystallized glass according to the present invention has a color coordinate a * and b * in the L * a * b * color system chromaticity of the crystallized glass surface of ± 1.0 or less and a whiteness of L * is 93.5 or more, preferably X in the XYZ color system chromaticity diagram is 0.3120-0.3130 and y is 0.3290-0.3320. It becomes a natural marble-like crystallized glass that has a certain appearance.

[0042] Further, the natural marble-like crystallized glass of the present invention has a Fe 2 O content of 200 ppm or less. In addition, the amount of precipitated crystals is 20-50% by mass, so that the mechanical strength and chemical durability are not impaired, and the whiteness is very high. These interior materials are suitable as exterior materials.

[0043] Further, the natural marble-like crystallized glass of the present invention is represented by SiO 45-7 in mass percentage.

5%, A1 0 l to 25%, Ca 0 2 to 25%, Zn 0 to 18%, Ba 0 0 to 20%, Mg 0

0 to 1.5%, Sr 0 to 1.5%, Na 1 to 15%, K 0 to 7%, Li 0 to 5%, B

○ 0 to 1.5%, CeO 0 to 0.5%, SO 0 to 0.5, Sb ○ 0 to 1%, As ○ 0 to 1

%, Preferably Fe 2 O content of 200 ppm or less,

-Since wollastonite crystals are precipitated, the needle-like crystals stretch and immediately scatter light effectively, creating a natural marble-like pattern with a high-grade appearance with high whiteness as described above. It will be easy to get.

[0044] In addition, the natural marble-like crystallized glass of the present invention is expressed in terms of mass percentage.

%, A10 l-25%, CaO 2-20%, MgO 1.5-17%, Zn0 0-18%, BaO

0 to 20%, Sr 0 0 to 1.5%, Na 0 1 to 15%, K 0 0 to 7%, Li 0 0 to 5%, B

O 0 to 1.5%, CeO 0 to 0.5%, SO 0 to 0.5, SbO 0 to 1%, As 0 0 to 1

% Composition, preferably Fe O content of 200 ppm or less, and formed by depositing a dipside crystal as the main crystal. The chemical durability is excellent as long as a natural marble-like pattern with an appearance is obtained.

[0045] In the method for producing a natural marble-like crystallized glass of the present invention, a plurality of crystalline glass bodies having a content of Fe 2 O as an impurity of 200 ppm or less are filled in a refractory container, and the crystallinity is obtained. By heat-treating the glass body at a temperature higher than the softening point, 20 to 50% by mass of crystals are precipitated, and the whiteness L * in the L * a * b * color system chromaticity of the crystallized glass surface is 9 Since natural marble-like crystallized glass with a color coordinate a * and b * of ± 1.0 or less is manufactured at least 3.5, feldspar with a high content of FeO, which is an impurity, is used as a glass raw material. Without using a substitute glass raw material, and also for other glass raw materials, by selecting and using low iron products with low Fe 2 O content, the amount of precipitated crystals can be controlled to have translucency. Even so, it is preferable because it suppresses greenish coloring by FeO in the glass phase. Natural marble-like crystallized glass with an appearance. Even when coloring is performed using a colorant, the colorant vibrates vividly and becomes a natural marble-like crystallized glass with a high-class feeling.

[0046] Further, in the method for producing a natural marble-like crystallized glass according to the present invention, the plurality of crystalline glass bodies have an FeO content of 200 ppm or less, and expressed in mass percentage, SiO 45-7

5%, A1 0 1-25%, CaO 2-25%, Zn 0 0: 18%, BaO 0-20%, MgO

0 to: 1.5%, Sr 0 0 to: 1.5%, Na 1 to 15%, K 0 to 7%, Li 0 0 to 5%, B

O 0 to: 1.5%, CeO 0 to 0.5%, SO 0 to 0.5%, SbO 0 to l%, As 0

J3 _ wollastonite crystal is precipitated as the main crystal by heat treatment of the crystalline glass body with a composition of ˜1%. However, it is possible to obtain natural marble-like crystallized glass with a characteristic and natural marble-like pattern that has a high-quality and high-quality appearance.

[0047] Further, in the method for producing a natural marble-like crystallized glass according to the present invention, the plurality of crystalline glass bodies have an FeO content of 200 ppm or less, and are expressed in terms of mass percentage.

75%, Al 0 1-25%, CaO 2-20%, MgO 1.5-5: 17%, ZnO 0-: 18%, Ba 0 0-20%, Sr 0 0-: 1.5%, Na O 1 ~: 15%, K ○ 0 ~ 7%,: Li Ο 0 ~ 5%

, B 0 ~: 1.5%, Ce 0 0-0.5%, SO 0-0.5, SbO 0 ~: 1%, As O 0

A diopside crystal is precipitated as a main crystal having a composition of ˜1% and a crystal precipitation amount of 20-50% by mass by heat-treating the crystalline glass body. Natural marble-like crystallized glass with excellent chemical durability as well as natural marble-like patterns with needle-like crystals with a high-grade appearance can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

[0048] Hereinafter, the present invention will be described based on examples and comparative examples.

Example

[0049] Table 1 shows examples of the present invention:! To 6 and shows a glass composition that does not use feldspar as a glass raw material so that the content of Fe 2 O as an impurity is 200 ppm or less. Example 1 in the table shows that SiO raw material is converted into normal A silica sand, CaO raw material into normal calcium carbonate, and LiO raw material into When normal spojumen is used, Fe O content in glass batch is 200p

twenty three

pm. In Example 2, SiO raw material is normal A silica sand, CaO raw material is normal calcium carbonate

2

This is the case where lithium carbonate with low Fe 2 O content is used as the Li 2 O raw material.

2 2 3

The content of FeO in the bush will be 150ppm. In Example 3, the SiO raw material contains Fe 2 O

2 3 2 2 3 Low in B Silica sand, CaO raw material with low FeO content and low iron calcium carbonate,

twenty three

This is the case when ordinary spodumene is used as the Li O raw material, and the Fe O content in the glass batch is

2 2 3 Content is lOOppm. In Example 4, SiO raw material is low in FeO content B silica sand, CaO

2 2 3

Low iron calcium carbonate with low Fe O content in raw material, Fe O content in LiO raw material

2 3 2 2 3 This is the case when lithium carbonate is used, and Example 5 is the same as Example 2. However, it is a case where Sb 2 O, which is a clarifier and a harmful substance, is not used. It was. Ma

twenty three

Example 6 uses the same raw materials as in Example 2 and MgO raw material, and Fe O in the glass batch.

The content of 2 3 is 150 ppm, and the composition has a composition for precipitating diopside crystals.

[0050] Each sample was prepared as follows. First, mix silica sand, aluminum oxide or aluminum hydroxide, calcium carbonate, zinc white, barium carbonate, soda ash, potassium carbonate, spodumene or lithium carbonate, sodium nitrate, antimony oxide so that the composition shown in Table 1 is obtained. Melted at C temperature for 12 hours. Next, the molten glass was formed into a predetermined shape, and after annealing, it was used as a measurement sample for visible light transmittance and x and y values. Further, the molten glass was crushed with water, dried and classified to obtain a crystalline glass body having a particle size of 1 to 5 mm. Subsequently, this glass body is accumulated in a fire-resistant mold with the inner wall coated with alumina powder, placed in an electric furnace, heated at a rate of 2 ° C / min, and at 1050-1100. By maintaining for 1 hour, each glass body was fused and crystallized, and then the appearance was evaluated by color tone (L *, a *, b *). The results are shown in Table 1.

[0051] [Table 1] Ingredient (wt ¾) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6

S i 0 ₂ 61. 0 6 1. 0 61. 0 61. 0 61.

AI ₂ 0 ₃ 6. ο 6. 0 6. 0 6. 0 6. Ο 7.0

Ca O 1 5. 5 1 5. 5 1 5. 5 1 5. 5 1 5. 5 7. 0

Ms O One--3. Ο

L i ₂ 0 0. 5 O. 5 0. 5 Ο. 5 0. 5 0. 5

B ₂ 0 ₃ 0. 3 0. 3 0. 3 0. 3 Ο. 3 0. 5

Z n O Θ. Ο 6. 0 6. 0 6. 0 6. Ο Q. 0

4. 7 4. 4. 7 4. 7 4. 7 9.

N β _a O 3.5 5 3. 5 3. 5 3. 5 3. 5 3. 3 eO 2. 0 2. 0 2. 0 2. 0 2. 0 2. 2

C e O a-― ― Ο. 2-

SO ₃ ---― 0. 3-

S b ₂ 0 ₃ 0. 5 0. 5 0. 5 0. 5-0.5

F ea O 0. 020 0. 01 5 0. 01 O 0. Ο 05 Ο. 01 5 0. 1 5 sio ₂ Raw materials A quartz sand A quartz sand B quartz sand Β quartz sand Α quartz sand Α quartz sand

C s O raw material Normal carbonate; W Normal calcium carbonate Low iron gallium carbonate Low iron carbonate Carbon normal carbonate; W 'Normal calcium carbonate

L i ₂₀ Raw material Spodium Lithium carbonate Spodumene Lithium carbonate Lithium carbonate lithium carbonate

Average permeability 89-5 90. 0 90. 3 90. 6 90. 0 89. 5 Crystalline glass

O. 31 1 3 0. 3 1 1 0 0. 3 1 0 8 Ο. 31 05 0. 3 1 1 0 0. 3 1 1 3 y 0. 3 1 85 0. 3 1 80 O. 3 1 7 8 3 1 7 2 O. 3 1 80 O. 3 1 8 6 Crystallized glass

0. 31 30 0. 3 1 2 7 0, 3 1 2 5 Ο, 31 22 O. 3 1 2 7 0. 3 1 30 y 0. 331 5 0. 331 0 O. 3300 Ο. 3295 O. 3 31 O O. 3 31 5 Color tone

93. 5 93. 8 9 4. 2 94. 6 93. 8 93. 5 a * ■ 1 .0-O. 9 — 0. 7 1 0. 3-0. 9-1. 0 b * 1. 0. 8 0. 6 0. 4 0. 8 1. 0 Precipitated crystals β—Wollastonite β One Wollastonite β—Wollastonite ^ 3 One Wollastonite β—Wollastonite 'Y ί Pasite F of each glass raw material containing e ₂ 0 ₃

A quartz sand 1 30 D p m

B quartz sand 1 G p 1 m

Normal calcium carbonate 400 p m

Low iron calcium carbonate 1 50 pm

Lithium carbonate 50 p m

Spodumene 800 pm Table 2 shows comparative examples:! These have a glass composition using feldspar usually used as a glass raw material. The feldspar used contains about 1200 ppm of Fe 2 O. In Comparative Example 1, SiO raw material is normal A silica sand, CaO raw material is normal calcium carbonate,

This is the case when spodumene is used as the Li O raw material, and the FeO content in the glass batch is 550 ppm. In Comparative Example 2, SiO raw material is low in FeO content B silica sand, CaO raw material is low iron calcium carbonate in low FeO content, LiO raw material is low in FeO content in lithium carbonate In this case, the FeO content in the glass batch is 450 ppm. Since Comparative Example 1 4 uses feldspar as the glass raw material, The content of FeO is 450ppm or more. Moreover, Comparative Example 3 was the same as Comparative Example 1 and did not use SbO, which is a strength clarifying agent and harmful, and the results were also the same. Furthermore, Comparative Example 4 uses the same raw material and MgO raw material as Comparative Example 1 to

N

Crystals are precipitated. Each sample was adjusted in the same manner as in the example. Table o

Shown in 2.

[Table 2] Ingredients ( _w t%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4

S i 0 ₂ 61. 0 61.

AI ₂ 0 ₃ 6. 0 6 .Ο 6-ο 7-ο

C a O 1 5. 5 1 5. 5 1 5. 5 7. Ο

MgO 1 1 1 3-0

L i ₂ 0 0. 5 0. 5 0. 5 Ο-5

B ₂ 0 ₃ O. 3 0. 3 0-3 0 .5

6. 0 6. 0 6-0 6. 0

B a O 4. 7 4. 7 4-7 9-ο

N a ₂ 0 3. 5 3. 5 3, 5 3-3

K _a O 2. 0 2. 0 2. 0 2-2

C e 0 ₂ ―-0 .2 One so ₃ ― ― 0. 3-

S b ₂ ○ ₃ O. 5 Ο. 5-Ο-5

F e ₂ 0 ₃ O. 055 Ο. 045 Ο. 055 0. 055

S i 0 ₂ Raw materials Λ¾sand Β¾sand Α¾sand ΑSilica feldspar Raw materials Use Use Use

C a O Raw material Normal carbon dioxide Low iron calcium carbonate Normal carbonate Λ room Normal carbonate

L i ₂₀ Raw material Suhojumen Lithium carbonate Spodumene Lithium carbonate Crystalline glass

Average transmittance (%) 88. 5 88. 8 88. 5 88. 5

Crystalline glass

0. 31 1 8 0. 31 15 Ο. 31 1 8 0. 31 1 8 y 0. 3208 0- 3200 0. 3208 Ο. 3208 Crystallized glass

45. 31 45 Ο. 3140 0. 31 45 0. 3150 y Ο. 334 Ο 0- 3335 0. 3340 0. 3345 Color IS

*: 92. Ο 92. 3 92. Ο 91 -F a *-1. 5 1 1. 1 1 5 1 1-8 b * 2. 4 2, 1 2. 4 2-8 Analysis lL ίπ West Knight / 3 Liwa Stone-West Knight Teite F Site feldspar Fe 0 ₃ Content: 1200 ppm [0054] As is apparent from Table 1, each of the examples:! To 6 shows an average visible light transmittance of 89.5% or more when the thickness of the crystalline glass before heat treatment is 10 mm. In the XYZ color system chromaticity diagram, X represents 0.3105 to 0.3113, y represents 0.3172 to 0.3185, and as a result, after heat treatment in L * a * b * color system chromaticity L * of 93.5 or more, and a * and b * showed a value of ± 1.0 or less. Examples:! To 5 are X force 0.3120 to 3130 and y force 0.3290 to 0.3320 in the XYZ color system chromaticity diagram after crystallization, and each sample has surface smoothness. It was a natural marble-like crystallized glass with a high natural marble pattern and a very bright, high whiteness. The main crystals of Examples 1 to 5 were / 3_wollastonite crystals, and the main crystals of Example 6 were diopside crystals.

[0055] Thus, the content of FeO as an impurity as a glass raw material is large, without using feldspar,

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Select and use calcium carbonate and lithium carbonate with low Fe O content

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More natural marble-like crystallized glass of Example was obtained.

[0056] On the other hand, as is clear from Table 2, the transmittance of the crystalline glass before the heat treatment of each sample of the comparative example is less than 89.0%, and that of the comparative example 1 is reduced to 88.5% or less. The straight of x and y have an X force S0.3115 to 0.3118 and a y force SO.3200 to 0.3208, respectively, and the color of the glass is green. As a result, the whiteness L * after heat treatment was less than 93.5, a * and b * showed a hue with a value exceeding ± 1.0, and X in the XYZ color system chromaticity diagram after crystallization The force SO. 3140 to 0.3145 and the y force SO. 3335 to 0.3340. In particular, comparative column 1 was a natural marble-like crystallized glass showing a darker appearance than the greenish examples. In Comparative Example 2, although the whiteness was improved, the degree of improvement in whiteness was insufficient, as the difference from the conventional product was not clear. In Comparative Example 4, the whiteness L * was further decreased as compared with Comparative Examples 1 and 3. This indicates that diopside crystals are susceptible to Fe 2 O.

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It is. These crystallized glasses were natural marble-like crystallized glasses in which one wollastonite crystal and diopside crystal were precipitated as the main crystals as in the examples.

[0057] The average transmittance was measured as follows. First, molten glass was formed to obtain a glass plate having a thickness of 1 :! to 12 mm, and was gradually cooled at around 650 ° C. Next, the glass plate was mirror-polished so as to have a thickness of 10 mm ± 0.1 mm, and then obtained by a spectrophotometer. At the same time XYZ table In the color system chromaticity diagram, x and straight were obtained.

[0058] Further, the whiteness L * and a * b * of the crystallized glass after the heat treatment were obtained with a colorimeter. The main crystal was determined by an X-ray diffractometer.

Industrial applicability

[0059] According to the present invention, it is possible to provide a natural calcite-like crystallized glass with improved whiteness and unprecedented color tone, and a method for producing the same.

Claims

The scope of the claims

Natural marble-like, characterized in that the color coordinates a * and b * in the color system chromaticity of the crystallized glass surface are * 1.0 or less and the whiteness L * is 93.5 or more Crystallized glass.

The natural marble-like crystallized glass according to claim 1, which has X force SO. 3120 to 0.3130 and y force 0.3290 to 0.3320 in the XYZ color system chromaticity diagram.

The content of FeO as an impurity is 200 ppm or less, and the amount of precipitated crystals is 20-50.

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3. The natural marble-like crystallized glass according to claim 1, wherein the natural marble-like crystallized glass is in an amount of%.

In terms of mass percentage, SiO 45 to 75%, A1 0:! To 25%, Ca 0 to 25%, ZnO 0

2 2 3

~ 18%, BaO 0 ~ 20%, MgO 0 ~: 1.5%, SrO 0 ~: 1.5%, NaO 1 ~: 15%,

2

K 0-7%, Li 0-5%, B O 0-: 1.5%, CeO 0-0.5%, SO 0-0.

2 2 2 3 2 3

5, SbO 0-1%, AsO 0-1% composition, j3-wollastonite as the main crystal

2 3 2 3

The natural marble-like crystallized glass according to any one of claims 1 to 3, wherein the crystal is precipitated.

In terms of mass percentage, SiO 45-75%, A1 0 1-25%, CaO 2-20%, Mg ○

2 2 3

1. 5 ~: 17%, ZnO 0 ~: 18%, Ba 0 0 ~ 20%, Sr 0 0 ~: 1.5%, Na 0 1 ~: 15

2

%, K O 0-7% ,: Li O 0-5%, B 0 0 :: 1.5%, Ce 0 0-0.5%, S 0 0

2 2 2 3 2 3

~ 0.5, SbO 0 ~: 1%, As O 0 ~: 1%

2 3 2 3

The natural marble-like crystallized glass according to any one of claims 1 to 3, wherein a crystal is precipitated.

A plurality of crystalline glass bodies whose content of FeO as impurities is 200 ppm or less

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In a refractory container and heat-treating the crystalline glass body at a temperature higher than the soft point, thereby precipitating 20 to 50% by mass of crystals, so that L * a * b * Color system A method for producing natural marble-like crystallized glass, wherein the whiteness L * in chromaticity is 93.5 or more and the color coordinates a * and b * are ± 1.0 or less.

A plurality of crystalline glass bodies are expressed by mass percentage, SiO 45-75%, Al O 1

2 2 3

-25%, CaO 2-25%, Zn 0-18%, Ba 0-20%, MgO 0-1.5%, S r〇 0〜: 1.5%, Na O 1〜： 15%, K〇 0〜7% ,： Li〇 0〜5%, BO 0〜： 1.5

2 2 2 2 3

%, CeO 0-0.5%, SO 0-0.5%, SbO 0-:!%, As O 0-: 1%

2 3 2 3 2 3

7. The method for producing a natural marble-like crystallized glass according to claim 6, wherein; 3-wollastonite crystal is precipitated as a main crystal by heat treatment.

Multiple crystalline glass corporal forces, expressed as mass percentage, SiO 45-75%, Al O 1

2 2 3

-25%, Ca 0-20%, Mg 0 1.5-17%, Zn 0-18%, Ba 0-20%, Sr 0-0-1.5%, Na 0-15%, K 0-7% i 0 0-5%, B 0 0-1.5

2 2 2 2 3

%, CeO 0-0.5%, SO 0-0.5, Sb 0-1%, As 0 0-1%

2 3 2 3 2 3

7. The method for producing a natural marble-like crystallized glass according to claim 6, wherein diopside crystals are precipitated as main crystals by heat treatment.

When the thickness is 10 mm, the average transmittance of visible light is 89% or more, and the crystal strength is X force SO. 3100 to 0.3115 and y force SO. 3160 to 0.3190 in the XYZ color system chromaticity diagram. 9. The method for producing a natural marble-like crystallized glass according to any one of claims 6 to 8, wherein the crystallized glass surface is expressed by using raw glass / J powder.