JPH04292426A - Production of flake-like glass - Google Patents
Production of flake-like glassInfo
- Publication number
- JPH04292426A JPH04292426A JP8077491A JP8077491A JPH04292426A JP H04292426 A JPH04292426 A JP H04292426A JP 8077491 A JP8077491 A JP 8077491A JP 8077491 A JP8077491 A JP 8077491A JP H04292426 A JPH04292426 A JP H04292426A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- film
- substrate
- flakes
- gel
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 16
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 21
- 108010025899 gelatin film Proteins 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 239000010408 film Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920000298 Cellophane Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004704 methoxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はフレーク状ガラスの製造
方法、特に、有機金属化合物を含む溶液を出発原料とし
、簡単かつ効率よくフレーク状ガラスを製造する方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing glass flakes, and more particularly to a method for producing glass flakes simply and efficiently using a solution containing an organometallic compound as a starting material.
【０００２】0002
【従来の技術】現在、フレ−ク状ガラスはプラスチック
充填材や耐食ライニングに使用されている。このような
フレ−ク状ガラスは、組成的にはソーダ石灰珪酸塩ガラ
ス系が主であり、約４μｍの厚さのものであり、熔融し
たガラスを風船の如く膨らませ、急冷、粉砕することに
より製造されている。産業の発展に伴い、より厚みの薄
いガラスフレ−クが求められているが、従来の方法では
技術的に限界がある。BACKGROUND OF THE INVENTION Currently, glass flakes are used for plastic fillers and corrosion-resistant linings. This kind of glass flake is composed mainly of soda lime silicate glass and has a thickness of about 4 μm. It is made by blowing molten glass like a balloon, rapidly cooling it, and crushing it. Manufactured. With the development of industry, there is a demand for thinner glass flakes, but conventional methods have technical limitations.
【０００３】フレ−ク状ガラス以外に工業的に利用され
ているフレ−クとしては、天然の雲母が知られている。
これは、（１）価格が高い、（２）不純物による着色が
ある、（３）耐久性に乏しい、等の問題点が指摘されて
いるものの、代替品がないため、各種の産業で使用され
ている。Natural mica is known as an industrially used flake other than glass flakes. Although problems such as (1) high price, (2) coloration due to impurities, and (3) lack of durability have been pointed out, it is still used in various industries because there are no substitutes. ing.
【０００４】有機金属化合物を含む溶液から薄いガラス
板を製造する技術は、例えば新保らによって開示された
公開特許昭５１−３４２１９号に記載されたように、加
水分解、脱水縮合を行った後の溶液を、他の液体上に浮
かべることにより、薄いガラスとする方法が知られてい
る。この公開特許によると、１μｍ以下の薄いガラス片
が得られるとされており、これを粉砕することで、フレ
ーク状ガラスを製造することが可能と推察できる。しか
し、この技術は、（１）水に浮かべたガラス片の回収が
難しい、（２）膜厚が均一になりにくい、などの欠点が
あり、この技術で工業的にフレーク状ガラスを製造する
ことは事実上困難である。[0004] A technique for producing a thin glass plate from a solution containing an organometallic compound is, for example, as described in Japanese Patent Publication No. 34219/1983 disclosed by Shinbo et al. It is known to form thin glass by floating a solution on another liquid. According to this published patent, it is said that thin glass pieces of 1 μm or less can be obtained, and it can be inferred that glass flakes can be manufactured by crushing these pieces. However, this technology has drawbacks such as (1) difficulty in recovering glass pieces floating in water, and (2) difficulty in achieving uniform film thickness, making it difficult to industrially produce glass flakes using this technology. is practically difficult.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記の従来技
術に鑑み、従来製造されることがなかった、薄いフレ−
ク状ガラスを、簡単かつ効率的に製造することのできる
方法を提供するものである。SUMMARY OF THE INVENTION In view of the above-mentioned prior art, the present invention aims to provide a thin frame that has not been manufactured in the past.
The purpose of the present invention is to provide a method that can easily and efficiently produce wedge-shaped glass.
【０００６】[0006]
【課題を解決するための手段】本課題を解決するため、
本発明者らは、有機金属化合物を含む溶液を基材上に塗
布し、乾燥後、基材の少なくとも表面層の相を変化させ
、ゲル状フレークまたはガラス状フレークを得る方法を
考案した。この方法によれば、従来得られなかった、非
常に薄いフレーク状ガラスの製造ができる。[Means for solving the problem] In order to solve this problem,
The present inventors have devised a method for obtaining gel-like flakes or glass-like flakes by applying a solution containing an organometallic compound onto a base material, and changing the phase of at least the surface layer of the base material after drying. According to this method, it is possible to produce extremely thin glass flakes that have not been previously available.
【０００７】原料の有機金属化合物を含む溶液を塗布す
るために本発明で使用する基材は、その上にゲル膜が形
成できる表面が平滑なものであって、物理的もしくは化
学的操作によって、少なくともその表面層が、固相から
液相または気相に変化するものであればよい。このよう
な基材に、上記有機金属化合物を含む液体を塗布し、０
．０６〜５０μｍの薄い液膜とする。The base material used in the present invention for applying the solution containing the organic metal compound as a raw material has a smooth surface on which a gel film can be formed, and is coated with a material having a smooth surface on which a gel film can be formed. It is sufficient that at least its surface layer changes from a solid phase to a liquid phase or a gas phase. A liquid containing the above-mentioned organometallic compound is applied to such a base material, and 0
．． A thin liquid film of 0.6 to 50 μm is formed.
【０００８】この基材の相の変化の原因として、熱分解
、融解、溶解、昇華等がある。これらの変化は、基材全
体で起こる必要は必ずしもなく、基材表面層で起これば
、ゲル膜を基材から分離させることができ、フレークを
得ることができる。熱分解を利用してフレークを得る場
合、基材としては、熱分解するものなら何でもよいが、
例えばセロハン等の再生セルロース、ポリ塩化ビニル、
ポリカーボネート、ポリエチレンテレフタレート等の有
機高分子が一般に使用される。[0008] Causes of this phase change of the base material include thermal decomposition, melting, dissolution, and sublimation. These changes do not necessarily need to occur in the entire substrate; if they occur in the surface layer of the substrate, the gel film can be separated from the substrate and flakes can be obtained. When obtaining flakes using pyrolysis, the base material may be anything that can be pyrolyzed, but
For example, regenerated cellulose such as cellophane, polyvinyl chloride,
Organic polymers such as polycarbonate and polyethylene terephthalate are commonly used.
【０００９】融解を利用する場合は、目的のフレークの
耐熱温度より低い融点もしくは軟化点を有する物質なら
、使用可能であるが、例えば、ポリアクリル酸系樹脂、
ポリメタクリル酸系樹脂、ポリ塩化ビニル等の熱可塑性
樹脂や氷などのように明らかに融点を持つ物質等が用い
られる。溶解を利用する場合は、ある溶媒に対する溶解
度が高いものが好ましい。例えば、ポリカーボネート等
の多くの有機ポリマーは、多くのケトン類、芳香族炭化
水素類に対する溶解度が高いので好ましい。また塩化ナ
トリウム等の結晶などは、水に対する溶解度が高いので
好ましい。[0009] When melting is used, any substance having a melting point or softening point lower than the heat resistance temperature of the target flakes can be used. For example, polyacrylic acid resin,
Thermoplastic resins such as polymethacrylic acid resins and polyvinyl chloride, and substances with clear melting points such as ice are used. When dissolution is used, it is preferable to use a material that has high solubility in a certain solvent. For example, many organic polymers such as polycarbonate are preferred because of their high solubility in many ketones and aromatic hydrocarbons. Further, crystals such as sodium chloride are preferable because they have high solubility in water.
【００１０】昇華を利用する場合は、ショウノウやドラ
イアイスなどが利用可能である。これら物質をそのまま
利用してもよいし、耐熱性、耐溶媒性等を有する下地基
板の上に、これら物質を層状に形成させてこれを、有機
金属化合物を含む溶液を塗布すべき基材として使用して
もよい。下地基板としては、安定であれば何でも使用可
能であるが、一般には、ステンレス、板ガラスなど表面
平滑性に優れた板状体が用いられる。特に、１０００℃
付近まで温度を上げる必要がある場合には、モリブデン
、タングステン、シリカガラス等が使用される。[0010] When using sublimation, camphor, dry ice, etc. can be used. These substances may be used as they are, or they may be formed in a layer on a heat-resistant, solvent-resistant, etc. base substrate and used as a base material to which a solution containing an organometallic compound is applied. May be used. As the base substrate, any stable material can be used, but generally a plate-like material with excellent surface smoothness, such as stainless steel or plate glass, is used. In particular, 1000℃
If it is necessary to raise the temperature to a certain level, molybdenum, tungsten, silica glass, etc. are used.
【００１１】上記基板にゲル膜を形成する技術は、公知
の技術を用いればよく、例えば、上記有機金属化合物を
含む溶液に基板を浸漬した後引き上げる方法や、基板上
に上記溶液を滴下し、基板を高速で回転させる方法など
が用いられる。この塗布膜の厚みは例えば上記溶液の粘
性を制御することにより調節できる。[0011] The technique for forming the gel film on the substrate may be any known technique, such as a method of immersing the substrate in a solution containing the organometallic compound and then pulling it up, or a method of dropping the solution on the substrate, A method such as rotating the substrate at high speed is used. The thickness of this coating film can be adjusted, for example, by controlling the viscosity of the solution.
【００１２】本発明に用いる原料としての有機金属化合
物は、加水分解、脱水縮合を行なうものであれば基本的
にはどんな化合物でもよいが、アルコキシル基を有する
金属アルコキシドが好ましい。更に具体的には、シリコ
ン、チタン、アルミニウム、ジルコニウム、リン、ホウ
素等のメトキシド、エトキシド、プロポキシド、ブトキ
シド等が、単体あるいは混合体として用いられる。従っ
て、本発明によって得られるフレーク状ガラスの組成は
、例えば純粋なシリカ、珪酸塩系、チタン酸塩系、アル
ミン酸系、ジルコニウム酸塩系、リン酸塩系、ホウ酸塩
系の非晶質または結晶質のものである。The organometallic compound used as a raw material in the present invention may basically be any compound as long as it undergoes hydrolysis and dehydration condensation, but metal alkoxides having an alkoxyl group are preferred. More specifically, methoxides, ethoxides, propoxides, butoxides of silicon, titanium, aluminum, zirconium, phosphorus, boron, etc. are used singly or as a mixture. Therefore, the composition of the flaky glass obtained by the present invention is, for example, pure silica, silicate-based, titanate-based, aluminate-based, zirconate-based, phosphate-based, borate-based amorphous. or crystalline.
【００１３】上記有機金属化合物を含む原料溶液の溶媒
は、実質的に上記有機金属化合物を溶解すれば基本的に
何でもよいが、メタノ−ル、エタノ−ル、プロパノ−ル
、ブタノ−ル等のアルコ−ル類が最も好ましい。この溶
媒の使用量は有機金属化合物と溶媒との合計量に対して
容積比で０．１〜０．９９５、好ましくは０．２〜０．
９、更に好ましくは０．３〜０．８５である。The solvent for the raw material solution containing the organometallic compound may be basically any solvent as long as it dissolves the organometallic compound, but methanol, ethanol, propanol, butanol, etc. may be used. Alcohols are most preferred. The amount of this solvent to be used is 0.1 to 0.995, preferably 0.2 to 0.995, by volume relative to the total amount of the organometallic compound and solvent.
9, more preferably 0.3 to 0.85.
【００１４】上記原料の有機金属化合物の加水分解には
水分が必要である。これは中性、酸性、塩基性の何れで
もよいが、加水分解を促進するためには、塩酸、硝酸、
硫酸等で酸性にした水を用いるのが好ましい。その使用
量は、有機金属化合物１モルに対して水１モル〜１００
モルの範囲が好ましい。そして酸の使用量は有機金属化
合物に対してモル比で０．０１〜２、好ましくは０．０
５〜１．５である。[0014] Moisture is required for hydrolysis of the organometallic compound as the raw material. This can be neutral, acidic, or basic, but in order to promote hydrolysis, hydrochloric acid, nitric acid,
It is preferable to use water acidified with sulfuric acid or the like. The amount used is 1 mol to 100 mol of water per 1 mol of organometallic compound.
A molar range is preferred. The amount of acid used is 0.01 to 2, preferably 0.0 in molar ratio to the organometallic compound.
5 to 1.5.
【００１５】その他、上記原料溶液の特性を変化させる
ために、例えば基板に塗布する溶液の厚みを調節するた
めに、有機増粘剤等を上記溶液に添加してもよい。しか
し、この添加量が多いと最終段階の加熱により薄膜上に
炭化物として残ることがあるので、１０重量％以下にし
ておくべきである。In addition, an organic thickener or the like may be added to the solution in order to change the characteristics of the raw material solution, for example to adjust the thickness of the solution applied to the substrate. However, if the amount added is too large, it may remain as a carbide on the thin film due to heating in the final stage, so it should be kept at 10% by weight or less.
【００１６】本発明によって製造されるフレーク状ガラ
スの厚さは、通常０．０３μｍ〜５μｍである。５μｍ
より厚いと、自由表面の膜部分と基材付近の膜部分との
乾燥速度の差が大きくなりすぎ、得られるフレーク状ゲ
ルに、基板に水平な方向の膜間剥離が発生するようにな
る。このような膜間剥離が発生すると、得られるフレー
ク状ガラスの膜厚の分布が 広くなり製品としての 品
質が悪くなる。逆に０．０３μｍより薄いと、もはやフ
レーク状とはならず、粉末に近くなる。また本発明によ
って製造されるフレーク状ガラスの直径は通常１０μｍ
〜数ｍｍであり、そのアスペクト比は少なくとも５、好
ましくは少なくとも１０である。The thickness of the glass flakes produced according to the present invention is usually 0.03 μm to 5 μm. 5μm
If it is thicker, the difference in drying rate between the film portion on the free surface and the film portion near the substrate becomes too large, and the resultant flaky gel will experience delamination in the direction horizontal to the substrate. When such interlayer peeling occurs, the film thickness distribution of the resulting glass flakes widens, resulting in poor quality as a product. On the other hand, if it is thinner than 0.03 μm, it will no longer be flaky and will be close to powder. Furthermore, the diameter of the glass flakes produced by the present invention is usually 10 μm.
~ several mm, and its aspect ratio is at least 5, preferably at least 10.
【００１７】基材の相の変化によって基材から分離して
得られたフレークが、ゲル状である場合は、熱処理によ
って、ガラスにすることができる。この焼結に関しては
、その方法に特に制限はない。焼結温度および時間は、
ゲルからガラスへの転移を確実にするような条件以上に
加熱することが望ましく、通常は３００℃〜１２００℃
で１０分〜２時間加熱する。[0017] If the flakes obtained by separation from the substrate due to a change in the phase of the substrate are in the form of a gel, they can be made into glass by heat treatment. Regarding this sintering, there are no particular limitations on the method. The sintering temperature and time are
It is desirable to heat above the conditions that ensure the transition from gel to glass, usually 300°C to 1200°C.
Heat for 10 minutes to 2 hours.
【００１８】[0018]
【実施例】以下に実施例を示す。
実施例−１
市販のシリコンテトラエトキシド、 エタノ−ル、およ
び水を、体積比で１：２：１の割合で混合し、室温で約
３時間攪拌を行なって溶液を準備した。また、厚さ２０
μｍのセロハンフィルムを、１０ｃｍ角の大きさに切断
して、基材として用意した。先に調製した溶液に、この
基材を浸漬し、毎分３０ｃｍの一定速度で鉛直方向に引
き上げてセロハンフィルム基材の表面に薄膜を形成した
。これを大気中に放置して約５分間乾燥し、次にこれを
１０００℃で３時間熱処理することによって、セロハン
フィルムを焼失させ、同時にゲル膜をガラス化した。[Example] Examples are shown below. Example 1 Commercially available silicone tetraethoxide, ethanol, and water were mixed at a volume ratio of 1:2:1 and stirred at room temperature for about 3 hours to prepare a solution. Also, the thickness is 20
A μm cellophane film was cut into 10 cm square pieces and prepared as a base material. This base material was immersed in the solution prepared previously and pulled up in the vertical direction at a constant speed of 30 cm per minute to form a thin film on the surface of the cellophane film base material. This was left in the air to dry for about 5 minutes, and then heat treated at 1000° C. for 3 hours to burn out the cellophane film and vitrify the gel film at the same time.
【００１９】このようにして、厚さ０．２１μｍのシリ
カガラスフレークを得た。これをＸ線回折法で調べたと
ころ、シャ−プなピ−クを示さず、ガラス状態であった
。また、表面に薄膜を形成し上記のセロハンフィルム基
材は折り紙のように自由に折り曲げることができ、所定
の形状に折り曲げた薄膜付きセロハンフィルム基材を乾
燥、加熱処理することにより、基材の両表面の膜は一体
となり、かつ折り曲げた形状をそのまま保持したシリカ
ガラスフィルム体が得られた。In this way, silica glass flakes with a thickness of 0.21 μm were obtained. When this was examined by X-ray diffraction, it did not show any sharp peaks and was found to be in a glassy state. In addition, the above-mentioned cellophane film base material with a thin film formed on its surface can be bent freely like origami. A silica glass film body was obtained in which the films on both surfaces were integrated and the bent shape was maintained as it was.
【００２０】実施例−２
基材として、２μｍ厚のポリ塩化ビニリデンで表面にコ
ーティングを施した厚みが２ｍｍのモリブデン板を使用
した以外は、実施例−１と同じ条件で、ガラスフレーク
を作製したところ、厚さ０．２３μｍのシリカガラスフ
レークを得た。Example 2 Glass flakes were produced under the same conditions as Example 1, except that a 2 mm thick molybdenum plate whose surface was coated with 2 μm thick polyvinylidene chloride was used as the base material. As a result, silica glass flakes with a thickness of 0.23 μm were obtained.
【００２１】実施例−３
０．５μｍ厚のポリエチレンテレフタレートコーティン
グを施したモリブデン板を基材として用い、実施例−１
と同じ方法で、基材上にゲル膜を形成した。これを、２
６０℃、窒素気流中で加熱し、ポリエチレンテレフタレ
ートを融解させ、これをフレークと共に回収した。この
フレークとポリエチレンテレフタレートの混合物を、酸
素雰囲気下１０００℃で熱処理し、厚さ０．２２μｍの
シリカガラスフレークを得た。Example 3 Using a molybdenum plate coated with 0.5 μm thick polyethylene terephthalate as a base material, Example 1
A gel film was formed on the substrate using the same method as described above. This, 2
It was heated at 60° C. in a nitrogen stream to melt the polyethylene terephthalate, which was recovered together with the flakes. A mixture of these flakes and polyethylene terephthalate was heat-treated at 1000° C. in an oxygen atmosphere to obtain silica glass flakes with a thickness of 0.22 μm.
【００２２】実施例−４
シリコンテトラエトキシド、エタノール、０．１規定塩
酸を、体積比で１０：２０：１で混合し、４０℃で２時
間攪拌反応させた。次に、チタンイソプロポキシドを、
焼結後の酸化物として１０重量％含有されるように添加
し、攪拌を継続した。更に反応を完全にするために、等
量の純水で希釈した。この溶液を４０℃で２０時間反応
させて、塗布溶液とした。Example 4 Silicon tetraethoxide, ethanol, and 0.1N hydrochloric acid were mixed in a volume ratio of 10:20:1, and reacted with stirring at 40°C for 2 hours. Next, titanium isopropoxide,
It was added so that it contained 10% by weight as an oxide after sintering, and stirring was continued. Furthermore, in order to complete the reaction, it was diluted with an equal amount of pure water. This solution was reacted at 40° C. for 20 hours to obtain a coating solution.
【００２３】厚み３ｍｍの１０ｃｍ角ポリ塩化ビニル板
をこの溶液に浸漬し、毎分３０ｃｍの一定速度で引き上
げて、この基板上に薄膜を形成した。８０℃で５分間乾
燥後、基材ごとテトラヒドロフランの浴に浸漬したとこ
ろ、亀裂の入った薄膜の間からテトラヒドロフランが浸
入して基材表面が溶解して、ゲル膜が剥離したところで
基材を引き上げた。同一のテトラヒドロフランの浴を用
いて、この操作を５０回繰り返して得たゲルフレーク分
散液から、濾過、洗浄、乾燥によりゲル状フレークを得
た。A 10 cm square polyvinyl chloride plate with a thickness of 3 mm was immersed in this solution and pulled up at a constant speed of 30 cm per minute to form a thin film on the substrate. After drying at 80°C for 5 minutes, the base material was immersed in a tetrahydrofuran bath. Tetrahydrofuran penetrated through the cracked thin film, dissolved the base material surface, and when the gel film peeled off, the base material was pulled up. Ta. Using the same tetrahydrofuran bath, this operation was repeated 50 times to obtain gel flakes from a gel flake dispersion obtained by filtration, washing, and drying.
【００２４】このゲルフレークを９５０℃で約３時間熱
処理して、粒径が１〜５ｍｍのシリカ−チタニアのフレ
ーク状物が得られた。分析の結果、チタニアの含有量は
９．６ｗｔ％であった。Ｘ線回折法で調べたところ、ガ
ラス状態であった。電子顕微鏡でこれを観察したところ
、膜厚が０．１７μｍのガラスフレ−クであった。なお
、このフレーク状ガラスを更に高温で焼結したところ、
１１００℃で、ルチル結晶の析出が認められた。[0024] The gel flakes were heat-treated at 950°C for about 3 hours to obtain silica-titania flakes having a particle size of 1 to 5 mm. As a result of analysis, the titania content was 9.6 wt%. When examined by X-ray diffraction, it was found to be in a glassy state. When this was observed using an electron microscope, it was found to be glass flakes with a film thickness of 0.17 μm. Furthermore, when this glass flake was sintered at an even higher temperature,
At 1100°C, precipitation of rutile crystals was observed.
【００２５】[0025]
【発明の効果】本発明によれば、有機金属化合物を含む
溶液の基板上の塗布厚みは溶液の粘性を調節することに
より制御でき、従って従来製造が困難であった厚みが１
μｍ以下の非常に薄いフレーク状ガラス、例えば厚みが
０．５μｍ未満のフレーク状ガラスが、簡単かつ効率的
に製造できる。According to the present invention, the coating thickness of a solution containing an organometallic compound on a substrate can be controlled by adjusting the viscosity of the solution.
Very thin glass flakes of μm or less, for example glass flakes with a thickness of less than 0.5 μm, can be easily and efficiently produced.
Claims (2)
塗布し、これを乾燥してゲル状膜を形成させた後、基材
の少なくともゲル状膜が付着した表面層の相を変化させ
ることにより、ゲル状膜を基材から分離してフレーク状
物とし、これを必要に応じて熱処理することを特徴とす
るフレーク状ガラスの製造方法。Claim 1: After applying a solution containing an organometallic compound onto a substrate and drying it to form a gel-like film, the phase of at least the surface layer of the substrate to which the gel-like film is attached is changed. A method for producing glass flakes, which comprises separating the gel film from the base material to obtain flakes, and subjecting the flakes to heat treatment as required.
気相への変化である特許請求の範囲第１項記載のフレー
ク状ガラスの製造方法。2. The method for producing glass flakes according to claim 1, wherein the phase change is from a solid phase to a gas phase due to thermal decomposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8077491A JPH04292426A (en) | 1991-03-19 | 1991-03-19 | Production of flake-like glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8077491A JPH04292426A (en) | 1991-03-19 | 1991-03-19 | Production of flake-like glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04292426A true JPH04292426A (en) | 1992-10-16 |
Family
ID=13727777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8077491A Pending JPH04292426A (en) | 1991-03-19 | 1991-03-19 | Production of flake-like glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04292426A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017128743A (en) * | 2001-07-12 | 2017-07-27 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Multilayer pigment based on glass flake |
-
1991
- 1991-03-19 JP JP8077491A patent/JPH04292426A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017128743A (en) * | 2001-07-12 | 2017-07-27 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Multilayer pigment based on glass flake |
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