JPH02184542A - Crystallized black glass composition - Google Patents
Crystallized black glass compositionInfo
- Publication number
- JPH02184542A JPH02184542A JP233089A JP233089A JPH02184542A JP H02184542 A JPH02184542 A JP H02184542A JP 233089 A JP233089 A JP 233089A JP 233089 A JP233089 A JP 233089A JP H02184542 A JPH02184542 A JP H02184542A
- Authority
- JP
- Japan
- Prior art keywords
- onyx
- natural
- crystallized
- glass composition
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 239000003086 colorant Substances 0.000 claims abstract description 7
- 239000004575 stone Substances 0.000 abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野）
本発明は、天然石のメノウからつくられるオニキスと称
される黒色石の代替品となる黒色結晶化ガラス組成に関
するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a black crystallized glass composition that is a substitute for black stone called onyx, which is made from the natural stone agate.
（従来の技術）
従来から、オニキスと称される天然石のメノウからつく
られる黒色石（以下、天然石オイキスと称する）はダイ
ヤモンド、・ルビー等の天然石と同様に装飾品用の材料
として非常に需要の高いものであった。(Prior art) Black stones made from agate, a natural stone known as onyx (hereinafter referred to as natural stone oikis), have been in great demand as materials for decorative items, similar to natural stones such as diamonds and rubies. It was expensive.
ところが、天然石オニキスは天然石のメツ「りに炭素粒
（例えば、６６ナイロンの原料であるフルフラール等）
を含浸させた後、該炭素粒を３００〜４００℃で蒸し焼
きして黒色に着色するものであり、前記の炭素粒を含浸
させる染色工程に数ケ月を要し、最終の加工製品を得る
までに長期間を必要としていた。また、天然石オニキス
は耐熱性が低くかつ品質的なバラツキも多いために前記
の蒸し焼き工程で割れが生して歩留まりが非常に悪い、
あるいは耐熱性が低いために５００℃以上の焼付は処理
が不可能で全印刷等の二次加工を施すことができないと
いう欠点があった。更には、天然石のメノウ原石の大半
はブラジル等の国外より輸入するものであり、原石の輸
出形態から加工製品の輸出形態への変化に伴い原石供給
の安定性に欠けてきたという問題もあった。However, natural stone onyx contains carbon grains (such as furfural, which is the raw material for nylon 66).
After impregnating the carbon particles, the carbon particles are steam-baked at 300 to 400°C to be colored black.The dyeing process to impregnate the carbon particles takes several months, and it takes a long time to obtain the final processed product. It required a long period of time. In addition, natural onyx has low heat resistance and many variations in quality, so cracks occur during the steaming process, resulting in a very low yield.
Also, due to its low heat resistance, it cannot be baked at temperatures above 500° C., making it impossible to perform secondary processing such as full printing. Furthermore, the majority of natural agate rough stones are imported from overseas such as Brazil, and with the shift from exporting rough stones to exporting processed products, there has been a problem that the supply of rough stones has become less stable. .
（発明が解決しようとする課題）
本発明は上記のような従来の問題点を解決して、天然石
オニキス七同等の装飾用材料として使用できる黒色結晶
化ガラスであって、短期間で最終加工製品を得ることが
できるとともに品質的なバラツキが少な（、かつ耐熱性
にも優れて成形上の歩留まりが非常に高く、更には全印
刷等の二次加工も可能とすることができ、また材料の安
定供給も確保することができる天然石オニキスの代替品
きなる黒色結晶化ガラス組成を目的として完成されたも
のである。(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems and provides a black crystallized glass that can be used as a decorative material equivalent to natural stone onyx, and can be produced into a final processed product in a short period of time. It is possible to obtain high-quality materials with little variation in quality (and has excellent heat resistance, resulting in a very high molding yield; furthermore, secondary processing such as full printing is possible, and material It was completed with the aim of creating a black crystallized glass composition that would be a substitute for natural onyx and ensure a stable supply.
（課題を解決するための手段）
本発明は重量％でＳ ｉ ０２：６８．Ｏ〜７８．０％
、Ａ Ｉ ２０３： ３．０〜８．０％、Ｌ ｉ２０：
７．０〜１３．０％、Ｐ２Ｏ５：０．７〜２．５％、Ｋ
２Ｏ：０゜５〜３．５％からなる結晶化ガラス組成に、
着色剤としてＣｒ２０３：０．３〜１．５％、ＭｎＯ２
：０゜５〜３．０％、Ｃｏ Ｏ： ０ 、２〜１ 、０
９６、Ｎｉｐ：Ｏ〜１．０％を含有させてなることを特
徴とするものである。(Means for Solving the Problems) The present invention has S i 02:68. O~78.0%
, AI203: 3.0-8.0%, L i20:
7.0-13.0%, P2O5: 0.7-2.5%, K
A crystallized glass composition consisting of 2O:0°5 to 3.5%,
Cr203: 0.3-1.5%, MnO2 as coloring agent
: 0°5~3.0%, CoO: 0, 2~1, 0
96, Nip: O to 1.0%.
本発明のガラス組成においてＳｉＯ２を６８．０〜７８
．０％七したのは、この範囲を外れると溶融性が悪くな
るためであり、Ａｌ２Ｏ３を３．０〜８．０％としたの
は３．０％未満では失透傾向が大きくなり、８，０％を
越えると主結晶がベータースポジューメン系となって所
望する黒色が得られなくなるためである。Ｌｉ２Ｏを７
．０〜１３．０％、Ｐ２Ｏ５を０．７〜２．５％とした
のば、これらはガラスの結晶化のための核形成剤、結晶
成分として作用するものであって上記範囲を外れると十
分な結晶化ができないためである。尚、ガラスの結晶化
工程は後の実施例で示すとおりであるが、これらの核形
成剤を用いることによりリチウムダイシリケート（Ｌｉ
２０・２Ｓｉ０２）の結晶を析出させ強度及び硬度を確
保することができる。Ｋ２Ｏを０．５〜３．５％とした
のは、０．５％未満では溶融温度が高（なり、３．５％
を越えると結晶化の熱処理工程中にガラスの変形を生ず
るおそれがあるためである。In the glass composition of the present invention, SiO2 is 68.0 to 78
．． The reason why the Al2O3 content was set at 0%7 is because the meltability deteriorates when it is out of this range, and the reason why the Al2O3 content was set at 3.0% to 8.0% is because if it is less than 3.0%, the tendency to devitrify increases. This is because if it exceeds 0%, the main crystals become beta-spodumene-based, making it impossible to obtain the desired black color. Li2O 7
．． If P2O5 is set to 0 to 13.0% and P2O5 is set to 0.7 to 2.5%, these will act as nucleating agents and crystal components for glass crystallization, and if it is outside the above range, it will not be sufficient. This is because crystallization cannot be achieved. Incidentally, the glass crystallization process is as shown in a later example, but by using these nucleating agents, lithium disilicate (Li
20.2Si02) can be precipitated to ensure strength and hardness. The reason for setting K2O to 0.5 to 3.5% is that if it is less than 0.5%, the melting temperature will be high (3.5%
This is because if it exceeds this amount, there is a risk that the glass will be deformed during the heat treatment process of crystallization.
前記のベースとなる結晶化ガラス組成に加え、着色剤と
してＣｒ２０３：０．３〜１．５％、Ｍｎ０ｚ＝０．５
〜３．０％、Ｃｏｏ：０．２〜１．０％、ＮｉＯ二〇〜
１．０％を含有させることによって４００〜７５０ｎｍ
の可視光線域を遮断して、天然石オニキスと同等の色調
を有する黒色結晶化ガラスを得ることができる。また、
その他の着色剤として微量のＦｅ２Ｏ３、■２０５等を
適宜加えることも可能である。In addition to the above-mentioned base crystallized glass composition, as a colorant Cr203: 0.3 to 1.5%, Mn0z = 0.5
~3.0%, Coo: 0.2~1.0%, NiO20~
400-750nm by containing 1.0%
It is possible to obtain black crystallized glass having a color tone equivalent to that of natural onyx by blocking the visible light range. Also,
It is also possible to appropriately add a small amount of Fe2O3, 205, etc. as other colorants.
尚、以上に説明した主要成分の他にＡｓ２Ｏ：＋、５ｂ
２０３等の副成分を微量添加することにより清澄性の改
善を図ることもできる。In addition to the main components explained above, As2O:+, 5b
Clarity can also be improved by adding a small amount of subcomponents such as 203.
このような組成の結晶化ガラスは原料を調合した後、約
１４００℃で溶融し、成形・徐冷工程を経て結晶化のた
めの熱処理を施すことによって安定した結晶を得ること
ができる
（実施例）
次に本発明の好ましい実施例を示す。After preparing the raw materials, crystallized glass with such a composition is melted at about 1400°C, and stable crystals can be obtained by heat treatment for crystallization after forming and slow cooling steps (Example) ) Next, preferred embodiments of the present invention will be shown.
珪砂、アルミナ、炭酸リチウム、リン酸−カリウム、硝
酸カリウムよりなるガラス原料に対して着色剤として重
クロム酸カリウム、二酸化マンガン、酸化コバルト、酸
化ニッケルを添加し、更に清澄剤として亜砒酸を加えて
調合した原料をるつぼで１４００℃で溶融した。溶融し
たガラスを板状に成形し、これを５００℃で２０分間徐
冷した。その後、前記板ガラスを電気式加熱炉において
５５０℃で１時間、更に８００℃で２時間熱処理を行い
ガラスの結晶化をさせた。It was prepared by adding potassium dichromate, manganese dioxide, cobalt oxide, and nickel oxide as coloring agents to glass raw materials consisting of silica sand, alumina, lithium carbonate, potassium phosphate, and potassium nitrate, and further adding arsenic acid as a clarifying agent. The raw materials were melted in a crucible at 1400°C. The molten glass was formed into a plate shape, and this was slowly cooled at 500°C for 20 minutes. Thereafter, the plate glass was heat-treated in an electric heating furnace at 550° C. for 1 hour and then at 800° C. for 2 hours to crystallize the glass.
原料の調合比を変えて得られた３種類の結晶化ガラスの
組成、及び諸特性を第１表に示す。′また比較例として
天然石オニキスの組成、及び諸特性を第１表右欄に示し
である。Table 1 shows the compositions and properties of three types of crystallized glass obtained by changing the mixing ratio of raw materials. 'As a comparative example, the composition and various properties of natural onyx are shown in the right column of Table 1.
本発明の黒色結晶化ガラスは天然石オニキスと色調は遜
色なく、天然石オニキスの代替品として十分に使用でき
るものであった。また、第１表からも明らかなように強
度、硬度においても天然石オニキスよりも優れたもので
あり、更には耐熱性においても８００〜９００℃と高（
全印刷等の二次加工を施しても熱衝撃で割れることはな
く、十分に熱的に耐え得るものであった。The black crystallized glass of the present invention had a color tone comparable to that of natural onyx, and could be fully used as a substitute for natural onyx. In addition, as is clear from Table 1, it is superior to natural stone onyx in terms of strength and hardness, and it also has a high heat resistance of 800-900℃ (
Even when subjected to secondary processing such as full printing, it did not crack due to thermal shock and was able to withstand heat sufficiently.
第
表
る黒色結晶化ガラスであって、天然石オニキスの場合の
ように染色工程を全（必要とせず、短期間で最終加工製
品を得ることができるとともに品質的なバラツキが少な
く、かつ耐熱性にも優れていて加工上の歩留まりが非常
に高い材料を提供できるものである。更には、従来の天
然石オニキスでは耐熱性の問題からできなかった全印刷
等の二次加工も可能とすることができ、また天然原料と
違い材料の安定供給も確保することができるという利点
も備えたものである。よって本発明は、天然石オニキス
の代替品となる新規な材料を提供するものとして業界に
寄与するところは極めて大きいものである。It is a black crystallized glass that does not require a complete dyeing process as is the case with natural onyx, making it possible to obtain the final processed product in a short period of time, with little variation in quality, and with excellent heat resistance. It is possible to provide a material with excellent properties and a very high processing yield.Furthermore, it is also possible to perform secondary processing such as full printing, which was not possible with conventional natural onyx due to heat resistance issues. Moreover, unlike natural raw materials, it also has the advantage of being able to secure a stable supply of the material.Therefore, the present invention contributes to the industry by providing a new material that can be a substitute for natural stone onyx. is extremely large.
特許出顯人 石塚硝子株式会社 （発明の効果）Patent issuer Ishizuka Glass Co., Ltd. (Effect of the invention)
Claims (1)
ｌ＿２Ｏ＿３：３．０〜８．０％、Ｌｉ＿２Ｏ：７．０
〜１３．０％、Ｐ＿２Ｏ＿５：０．７〜２．５％、Ｋ＿
２Ｏ：０．５〜３．５％からなる結晶化ガラス組成に、
着色剤としてＣｒ＿２Ｏ＿３：０．３〜１．５％、Ｍｎ
Ｏ＿２：０．５〜３．０％、ＣｏＯ：０．２〜１．０％
、ＮｉＯ：０〜１．０％を含有させてなることを特徴と
する黒色結晶化ガラス組成。(1) SiO_2: 68.0-78.0% by weight, A
l_2O_3: 3.0 to 8.0%, Li_2O: 7.0
~13.0%, P_2O_5:0.7-2.5%, K_
2O: A crystallized glass composition consisting of 0.5 to 3.5%,
Cr_2O_3: 0.3-1.5%, Mn as a coloring agent
O_2: 0.5-3.0%, CoO: 0.2-1.0%
A black crystallized glass composition characterized by containing 0 to 1.0% of NiO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP233089A JPH07115885B2 (en) | 1989-01-09 | 1989-01-09 | Black crystallized glass composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP233089A JPH07115885B2 (en) | 1989-01-09 | 1989-01-09 | Black crystallized glass composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02184542A true JPH02184542A (en) | 1990-07-19 |
| JPH07115885B2 JPH07115885B2 (en) | 1995-12-13 |
Family
ID=11526304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP233089A Expired - Lifetime JPH07115885B2 (en) | 1989-01-09 | 1989-01-09 | Black crystallized glass composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07115885B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754277A (en) * | 2021-10-29 | 2021-12-07 | 成都光明光电股份有限公司 | Glass material |
-
1989
- 1989-01-09 JP JP233089A patent/JPH07115885B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754277A (en) * | 2021-10-29 | 2021-12-07 | 成都光明光电股份有限公司 | Glass material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07115885B2 (en) | 1995-12-13 |
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