JPH1160270A - Antimicrobial crystallized glass article and its production - Google Patents

Antimicrobial crystallized glass article and its production

Info

Publication number
JPH1160270A
JPH1160270A JP23329697A JP23329697A JPH1160270A JP H1160270 A JPH1160270 A JP H1160270A JP 23329697 A JP23329697 A JP 23329697A JP 23329697 A JP23329697 A JP 23329697A JP H1160270 A JPH1160270 A JP H1160270A
Authority
JP
Japan
Prior art keywords
antibacterial
glass
crystallized glass
glass article
producing
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
Application number
JP23329697A
Other languages
Japanese (ja)
Inventor
Takahiro Matano
高宏 俣野
Hiroki Yamazaki
博樹 山崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP23329697A priority Critical patent/JPH1160270A/en
Publication of JPH1160270A publication Critical patent/JPH1160270A/en
Pending legal-status Critical Current

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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
    • C03C10/0009—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 silica as main constituent
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel

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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain the subject glass article having excellent antimicrobial effect over a long period and suitable as a construction material, and to provide a method for producing the above glass article. SOLUTION: First, a number of small glass bodies having such a character that, when subjected to heat treatment at a temperature higher than the softening point, needle crystals are deposited from the surface toward the interior while softening and deforming, are prepared. Next, antimicrobial agent powder is attached to the surface of the glass bodies. Subsequently, the resulting small glass bodies are collected in a mold and heat-treated at a temperature higher than the softening point of the glass, thus obtaining the objective antimicrobial glass article where a number of the small glass bodies are integratedly fused, with needle crystals deposited therein and antimicrobial agent layers formed on the interface among the small glass bodies.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、外装材、内装材、床材
等の建築材料に用いられる抗菌性結晶化ガラス物品とそ
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial crystallized glass article used for building materials such as exterior materials, interior materials, flooring materials and the like, and a method for producing the same.

【０００２】[0002]

【従来の技術】結晶化ガラス物品は、化学耐久性、機械
的強度等の特性に優れ、美しい外観を呈するため、天然
石の代わりに外装材、内装材、床材等に広く用いられて
いるが、近年その用途が広がり、テーブルや洗面化粧台
の天板、トイレブース等にも使用されるようになってき
ている。2. Description of the Related Art Crystallized glass articles have excellent properties such as chemical durability and mechanical strength and have a beautiful appearance. Therefore, they are widely used as exterior materials, interior materials, floor materials, etc. instead of natural stones. In recent years, its use has been widened, and it has also been used as a tabletop, a vanity top plate, a toilet booth, and the like.

【０００３】この種の結晶化ガラス物品を製造する方法
として、集積法と呼ばれる方法が知られている。集積法
は、まず軟化点より高い温度で熱処理すると軟化変形し
ながら表面から内部に向かって針状の結晶が析出する性
質を有するガラス小体を多数個用意した後、ガラス小体
を型枠内に集積し、ガラスの軟化点以上の温度で熱処理
する方法であり、天然大理石様の外観を呈する結晶化ガ
ラス物品を得ることができる。[0003] As a method for producing such a crystallized glass article, a method called an integration method is known. In the integration method, first, when a heat treatment is performed at a temperature higher than the softening point, a large number of glass bodies having a property that needle-like crystals are precipitated from the surface to the inside while softening and deforming are prepared, and then the glass bodies are placed in a mold. And a heat treatment at a temperature equal to or higher than the softening point of the glass, so that a crystallized glass article having a natural marble-like appearance can be obtained.

【０００４】[0004]

【発明が解決しようとする課題】ところで、安全衛生に
関する意識の高まりから、建築材料に黴や細菌の発生を
防止する機能（いわゆる抗菌性）を付与することが求め
られており、結晶化ガラス製の建築材料についても、抗
菌性を付与することが求められている。By the way, with the increasing awareness of safety and health, it is required to provide building materials with a function of preventing the generation of mold and bacteria (so-called antibacterial properties). It is also required that antibacterial properties be imparted to building materials.

【０００５】建築材料に抗菌性を付与する方法として、
抗菌剤を樹脂や塗料と混合し、製品表面に塗布する方法
が知られているが、この方法により形成された抗菌層は
耐久性がなく、長期間の使用によって劣化、脱落して機
能が低下するという欠点がある。[0005] As a method of imparting antibacterial properties to building materials,
A method is known in which an antimicrobial agent is mixed with a resin or paint and applied to the product surface.However, the antimicrobial layer formed by this method is not durable, and deteriorates and falls off over a long period of use, resulting in reduced functionality. There is a disadvantage of doing so.

【０００６】本発明の目的は、長期間にわたって優れた
抗菌性を有し、建築材料として好適な抗菌性結晶化ガラ
ス物品と、その製造方法を提供することである。An object of the present invention is to provide an antibacterial crystallized glass article having excellent antibacterial properties over a long period of time and suitable as a building material, and a method for producing the same.

【０００７】[0007]

【課題を解決するための手段】本発明の抗菌性結晶化ガ
ラス物品は、軟化点より高い温度で熱処理すると軟化変
形しながら表面から内部に向かって針状の結晶が析出す
る性質を有するガラス小体の多数個が融着一体化すると
ともに結晶が析出してなる結晶化ガラス物品であって、
ガラス小体の界面に抗菌剤からなる抗菌層が形成されて
いることを特徴とする。SUMMARY OF THE INVENTION The antibacterial crystallized glass article of the present invention is characterized in that, when heat-treated at a temperature higher than the softening point, needle-like crystals precipitate from the surface toward the inside while softening and deforming. A crystallized glass article in which a large number of bodies are fused and integrated and crystals are precipitated,
An antimicrobial layer comprising an antimicrobial agent is formed on the interface of the glass body.

【０００８】また本発明の抗菌性結晶化ガラス物品の製
造方法は、軟化点より高い温度で熱処理すると軟化変形
しながら表面から内部に向かって針状の結晶が析出する
性質を有するガラス小体を多数個用意する工程と、ガラ
ス小体を型枠内に集積する工程と、ガラスの軟化点以上
の温度で熱処理することによってガラス小体を融着一体
化させるとともに結晶化させる工程とを含む結晶化ガラ
ス物品の製造方法であって、予めガラス小体の表面に抗
菌剤粉末を付着させておくことを特徴とする。[0008] The method for producing an antibacterial crystallized glass article of the present invention is characterized in that, when heat-treated at a temperature higher than the softening point, a glass body having a property that needle-like crystals precipitate from the surface toward the inside while softening and deforming. A crystal comprising a step of preparing a large number of pieces, a step of accumulating glass bodies in a mold, and a step of fusing and integrating the glass bodies by heat treatment at a temperature equal to or higher than the softening point of the glass and crystallizing the glass bodies. What is claimed is: 1. A method for producing a glass-foamed article, characterized in that an antibacterial agent powder is previously adhered to the surface of a glass body.

【０００９】[0009]

【作用】本発明の抗菌性結晶化ガラス物品は、ガラス小
体の界面に抗菌層が存在するため、抗菌性を有する。抗
菌層は、従来公知の抗菌剤からなり、例えば金属イオン
を溶出する抗菌性粉末（Ａｇ、Ｃｕ、Ｚｎ、Ｐｂ、Ｈ
ｇ、Ｓｎ等の金属を担持したゼオライト等のセラミック
ス粉末、Ａｇ、Ｃｕ、Ｚｎ等を組成中に含むガラス粉末
等）や光触媒機能を有する抗菌性粉末（ＴｉＯ2 粉末
等）で形成される。なお抗菌剤の含有量は、結晶化ガラ
ス１００重量部に対して０．０１〜３０重量部であるこ
とが好ましい。The antibacterial crystallized glass article of the present invention has an antibacterial property because an antibacterial layer is present at the interface of the glass body. The antibacterial layer is made of a conventionally known antibacterial agent, for example, an antibacterial powder (Ag, Cu, Zn, Pb, H
It is formed of a ceramic powder such as zeolite carrying a metal such as g or Sn, a glass powder containing Ag, Cu, Zn or the like in its composition) or an antibacterial powder having a photocatalytic function (TiO 2 powder or the like). In addition, it is preferable that content of an antibacterial agent is 0.01-30 weight part with respect to 100 weight part of crystallized glass.

【００１０】また本発明のガラス物品において、使用さ
れる結晶化ガラスの析出結晶は、β−ウォラストナイト
（ＣａＯ・ＳｉＯ2 ）、ディオプサイド（ＣａＯ・Ｍｇ
Ｏ・２ＳｉＯ2 ）、デビトライト（Ｎａ2 Ｏ・３ＣａＯ
・６ＳｉＯ2 ）等の針状結晶である。これらの結晶はガ
ラス小体の形状に規制されて析出しており、その存在及
び方向の相違に基づいて現れる模様は、結晶化ガラス物
品に天然大理石模様を与える。なお針状結晶が析出する
結晶化ガラスの組成としては、例えば重量百分率でＳｉ
Ｏ2 ４０〜８０％、Ａｌ2 Ｏ3 １〜２５％、ＣａＯ
３〜２５％、ＺｎＯ ０〜１５％、ＢａＯ ０〜２０
％、ＭｇＯ ０〜２０％、Ｂ2 Ｏ3 ０〜１５％、Ｎａ
2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ ２〜２５％、ＴｉＯ2 ０〜
５％、ＺｒＯ2 ０〜５％、着色酸化物 ０〜５％を選
択することができる。In the glass article of the present invention, the precipitated crystals of the crystallized glass used are β-wollastonite (CaO.SiO 2 ), diopside (CaO.Mg).
O.2SiO 2 ), debitrite (Na 2 O.3CaO)
• Needle-like crystals such as 6SiO 2 ). These crystals are restricted by the shape of the glass body and precipitate, and the pattern that appears based on the presence and the difference in direction gives the crystallized glass article a natural marble pattern. The composition of the crystallized glass from which the acicular crystals precipitate is, for example, Si by weight percentage.
O 2 40~80%, Al 2 O 3 1~25%, CaO
3-25%, ZnO 0-15%, BaO 0-20
%, 0~20% MgO, B 2 O 3 0~15%, Na
2 O + K 2 O + Li 2 O 2 to 25%, TiO 2 0
5%, ZrO 2 0-5%, and colored oxide 0-5% can be selected.

【００１１】次に、本発明の抗菌性結晶化ガラス物品を
製造する方法を説明する。Next, a method for producing the antibacterial crystallized glass article of the present invention will be described.

【００１２】まず、ガラス小体と抗菌剤粉末を用意す
る。First, a glass body and an antibacterial agent powder are prepared.

【００１３】ガラス小体としては、軟化点より高い温度
で熱処理すると軟化変形しながら表面から内部に向かっ
て針状の結晶が析出する性質を有するものを使用する。
ガラス小体には、種々の結晶を析出するものが使用でき
るが、特にβ−ウォラストナイト、ディオプサイド、又
はデビトライトを主結晶として析出する性質を有するも
のが好ましい。このようなガラスとして例えば重量百分
率でＳｉＯ2 ４０〜８０％、Ａｌ2 Ｏ3 １〜２５
％、ＣａＯ ３〜２５％、ＺｎＯ ０〜１５％、ＢａＯ
０〜２０％、ＭｇＯ ０〜２０％、Ｂ2 Ｏ3 ０〜１
５％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ ２〜２５％、Ｔｉ
Ｏ2 ０〜５％、ＺｒＯ2 ０〜５％、着色酸化物 ０
〜５％の組成を有するガラスを使用することができる。
なおガラス小体には、小球状、粒状、鱗片状、破砕状、
粉状、棒状等各種の形状を有するものが使用可能であ
る。As the glass body, a glass body having such a property that, when heat-treated at a temperature higher than the softening point, needle-like crystals are precipitated from the surface toward the inside while being softened and deformed.
As the glass particles, those that precipitate various crystals can be used, but those having the property of depositing β-wollastonite, diopside, or devitrite as a main crystal are particularly preferable. As such a glass, for example, SiO 2 40 to 80% by weight percentage, Al 2 O 3 1 to 25
%, CaO 3-25%, ZnO 0-15%, BaO
0~20%, 0~20% MgO, B 2 O 3 0~1
5%, Na 2 O + K 2 O + Li 2 O 2 to 25%, Ti
O 2 0-5%, ZrO 2 0-5%, colored oxide 0
Glass having a composition of 〜5% can be used.
In addition, small glass, small spherical, granular, scale-like, crushed,
What has various shapes, such as a powder form and a stick form, can be used.

【００１４】抗菌剤粉末としては、従来公知の抗菌剤が
使用でき、例えば金属イオンを溶出する抗菌性粉末（Ａ
ｇ、Ｃｕ、Ｚｎ、Ｐｂ、Ｈｇ、Ｓｎ等の金属を担持した
ゼオライト等のセラミックス粉末、Ａｇ、Ｃｕ、Ｚｎ等
を組成中に含むガラス粉末等）や、光触媒機能を有する
抗菌性粉末（ＴｉＯ2 粉末等）が好適である。なおゼオ
ライトを使用する場合は、耐熱性に優れたものを選択す
ることが好ましい。As the antibacterial agent powder, a conventionally known antibacterial agent can be used. For example, an antibacterial powder (A
g, Cu, Zn, Pb, Hg, ceramic powder such as zeolite carrying a metal such as Sn, glass powder containing Ag, Cu, Zn, etc. in the composition), and antibacterial powder (TiO 2 ) having a photocatalytic function Powder). When zeolite is used, it is preferable to select one having excellent heat resistance.

【００１５】次に、ガラス小体と抗菌剤粉末を混合し、
ガラス小体の表面に抗菌剤粉末を付着させる。ガラス小
体表面に抗菌剤粉末を付着させる方法としては、まずこ
れらを適当量秤量し、乾式混合する。このとき抗菌剤粉
末とともに無機顔料粉末（ピグメント）を添加してもよ
い。その後、ガラス小体１００重量部に対して水又はバ
インダーを０．１〜５重量部添加して十分に攪拌混合す
ればよい。抗菌剤粉末の添加量は、ガラス小体１００重
量部に対して０．０１〜３０重量部であることが好まし
い。なお抗菌剤粉末の添加量が０．０１重量部より少な
いと結晶化ガラス物品に十分な抗菌性を与えることが難
しくなり、３０重量部を超えると後の熱処理工程におい
てガラスの軟化流動を低下させるおそれがある。Next, the glass body and the antibacterial agent powder are mixed,
An antibacterial agent powder is attached to the surface of the glass body. As a method of attaching the antibacterial agent powder to the surface of the glass body, first, these are weighed in an appropriate amount and dry-mixed. At this time, an inorganic pigment powder (pigment) may be added together with the antibacterial agent powder. Thereafter, water or a binder may be added in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the glass body, and sufficiently stirred and mixed. The addition amount of the antibacterial agent powder is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the glass body. If the amount of the antibacterial agent powder is less than 0.01 part by weight, it becomes difficult to impart sufficient antibacterial properties to the crystallized glass article, and if it exceeds 30 parts by weight, the softening flow of the glass is reduced in the subsequent heat treatment step. There is a risk.

【００１６】続いて、抗菌剤粉末を表面に付着させたガ
ラス小体の多数個を耐火性型枠内に集積する。なお耐火
性型枠は、ガラスの熱処理温度、製品サイズ等を考慮し
て材質や大きさを決定する。型枠の材質としては、ステ
ンレス、耐熱合金等の金属類やＳｉＣ系、ムライト系、
ムライト−コーディエライト系、アルミナ系等の耐火物
が使用できる。Subsequently, a large number of small glass bodies having the antibacterial agent powder adhered to the surface are accumulated in a refractory mold. The material and size of the refractory mold are determined in consideration of the heat treatment temperature of the glass, the product size, and the like. As the material of the formwork, metals such as stainless steel and heat-resistant alloy, SiC type, mullite type,
Refractories such as mullite-cordierite and alumina can be used.

【００１７】その後、ガラスの軟化点以上の温度で熱処
理すると、各ガラス小体が軟化変形して互いに融着一体
化するとともに各ガラス小体中にβ−ウォラストナイト
等の針状結晶が析出する。またガラス小体界面に抗菌剤
からなる抗菌層が形成される。Thereafter, when heat treatment is performed at a temperature equal to or higher than the softening point of the glass, each glass body is softened and deformed and fused and integrated with each other, and needle-like crystals such as β-wollastonite are precipitated in each glass body. I do. In addition, an antibacterial layer made of an antibacterial agent is formed at the glass body interface.

【００１８】[0018]

【実施例】以下、実施例に基づいて本発明を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

【００１９】（実施例１）まずガラス小体と抗菌剤粉末
を用意した。Example 1 First, a glass body and an antibacterial agent powder were prepared.

【００２０】ガラス小体としては、重量％でＳｉＯ2
６０％、Ａｌ2 Ｏ3 ５％、ＣａＯ１７％、ＺｎＯ ６
％、ＢａＯ ６％、ＭｇＯ １％、Ｎａ2 Ｏ ３％、Ｋ
2Ｏ １．５％、Ｌｉ2 Ｏ ０．５％の組成を有する粒
径１〜５ｍｍの小球状ガラス（軟化点７５０℃）を使用
した。As the glass body, SiO 2 in weight% is used.
60%, Al 2 O 3 5%, CaO 17%, ZnO 6
%, BaO 6%, MgO 1%, Na 2 O 3%, K
2 O 1.5%, it was used a small spherical glass having a particle size of 1 to 5 mm (softening point 750 ° C.) having a composition of Li 2 O 0.5%.

【００２１】抗菌剤粉末としては、Ａｇを担持させたゼ
オライト粉末（平均粒径１０μｍ）を使用した。As the antibacterial agent powder, a zeolite powder carrying Ag (average particle size: 10 μm) was used.

【００２２】次に、ガラス小体３０ｋｇに抗菌剤粉末を
３００ｇ添加し、乾式混合した後、１０％ＰＶＡ水溶液
を３００ｇ添加して撹拌混合し、ガラス小体表面に抗菌
剤粉末を付着させた。Next, 300 g of the antibacterial agent powder was added to 30 kg of the glass body, and the mixture was dry-mixed. Then, 300 g of a 10% PVA aqueous solution was added, and the mixture was stirred and mixed, so that the antibacterial agent powder was adhered to the surface of the glass body.

【００２３】続いてこの混合物をムライト製型枠内に集
積した後、１１００℃で３時間熱処理することによっ
て、９００×６００×１５ｍｍの大きさの試料を得た。Subsequently, the mixture was accumulated in a mullite mold and heat-treated at 1100 ° C. for 3 hours to obtain a sample having a size of 900 × 600 × 15 mm.

【００２４】このようにして得られた試料の表面は、平
滑で光沢がある白色の天然大理石模様を呈していた。析
出結晶をＸ線回折により確認したところ、β−ウォラス
トナイトが析出していた。表面をＥＰＭＡ分析により観
察したところ、ガラス小体の界面に、ゼオライトに担持
されているＡｇが存在しており、抗菌層が形成されてい
ることが確認された。The surface of the sample thus obtained exhibited a smooth and glossy white natural marble pattern. When the precipitated crystal was confirmed by X-ray diffraction, β-wollastonite was precipitated. When the surface was observed by EPMA analysis, it was confirmed that Ag supported on zeolite was present at the interface of the glass bodies, and that an antibacterial layer was formed.

【００２５】次に抗菌性について評価した。まず試料を
５０×５０ｍｍに切り出して試験片を得た。次に菌種と
して大腸菌、黄色ブドウ球菌の２種類を準備し、これら
の菌濃度がそれぞれ２×１０3 ／ｃｍ2 となるように調
整したゼラチンをシート状に加工し、滅菌処理後の試験
片に各々貼り付けた。その後３５℃で４８時間培養した
後、菌数を測定し、生菌が１０個未満であったものを
良、１０個以上であったものを不良とした。この結果、
大腸菌、黄色ブドウ球菌ともに生菌が１０個未満であ
り、良好な抗菌性を有していることがわかった。Next, the antibacterial properties were evaluated. First, a sample was cut out to 50 × 50 mm to obtain a test piece. Next, two types of bacteria, Escherichia coli and Staphylococcus aureus, were prepared, and gelatin adjusted to a concentration of 2 × 10 3 / cm 2 was processed into a sheet, and the test pieces after the sterilization were processed. Respectively. After culturing at 35 ° C. for 48 hours, the number of bacteria was measured, and those with less than 10 viable bacteria were regarded as good, and those with 10 or more viable bacteria were regarded as defective. As a result,
Both Escherichia coli and Staphylococcus aureus had less than 10 viable bacteria, indicating that they had good antibacterial properties.

【００２６】さらに機械的強度及び明度（Ｌ値）を測定
したところ、機械的強度が３９０ｋｇ／ｃｍ2 、明度が
９３であった。なお機械的強度は、５０×２５０×１５
ｍｍの大きさに加工した試料を用い、４点荷重法により
測定した。明度は色差計により測定した。Further, when the mechanical strength and the lightness (L value) were measured, the mechanical strength was 390 kg / cm 2 and the lightness was 93. The mechanical strength is 50 × 250 × 15
It measured using the sample processed to the size of mm by the four-point load method. The lightness was measured with a color difference meter.

【００２７】なお比較のために、抗菌剤を含まず、他は
実施例と同様にして作製した試料は、機械的強度が４０
０ｋｇ／ｃｍ2 、明度が９４と良好であったが、抗菌性
を評価したところ、大腸菌、黄色ブドウ球菌ともに菌数
の減少は認められなかった。For comparison, a sample prepared in the same manner as in the example except that no antibacterial agent was contained had a mechanical strength of 40%.
Although 0 kg / cm 2 and lightness were as good as 94, antibacterial properties were evaluated, and no decrease in the number of E. coli and Staphylococcus aureus was observed.

【００２８】（実施例２）まずガラス小体と抗菌剤粉末
と無機顔料粉末を用意した。Example 2 First, a glass body, an antibacterial agent powder and an inorganic pigment powder were prepared.

【００２９】ガラス小体としては、重量％でＳｉＯ2
６０％、Ａｌ2 Ｏ3 ９％、ＣａＯ１０％、ＺｎＯ ４
％、ＢａＯ ４％、ＭｇＯ ５％、Ｎａ2 Ｏ ４％、Ｋ
2Ｏ ２．５％、Ｌｉ2 Ｏ １．５％の組成を有する粒
径０．２５〜１ｍｍの小球状ガラス（軟化点７００℃）
を使用した。As the glass body, SiO 2 by weight% is used.
60%, Al 2 O 3 9%, CaO 10%, ZnO 4
%, BaO 4%, MgO 5%, Na 2 O 4%, K
2 O 2.5%, a small spherical glass particle size 0.25~1mm having a composition of Li 2 O 1.5% (softening point 700 ° C.)
It was used.

【００３０】抗菌剤粉末としては、重量％でＺｎＯ ４
０％、Ｂ2 Ｏ3 ４０％、Ｎａ2 Ｏ１５％、ＳｉＯ2
４％、Ａｌ2 Ｏ3 １％の組成を有するガラス粉末（最
大粒径１０００μｍ）を使用した。As an antibacterial agent powder, ZnO 4
0%, B 2 O 3 40 %, Na 2 O15%, SiO 2
A glass powder having a composition of 4% and Al 2 O 3 1% (maximum particle size 1000 μm) was used.

【００３１】無機顔料粉末として、Ｃｏ−Ｚｎ−Ａｌ系
スピネル（平均粒径１μｍ、青色）を使用した。As the inorganic pigment powder, a Co-Zn-Al-based spinel (average particle size: 1 μm, blue) was used.

【００３２】次に、ガラス小体５０ｋｇに対し、抗菌剤
粉末を１ｋｇ及び無機顔料粉末を５００ｇ添加し、乾式
混合した後、１０％ＰＶＡ水溶液を５００ｇ添加して撹
拌混合し、ガラス小体表面に抗菌剤粉末と無機顔料粉末
を付着させた。Next, 1 kg of the antibacterial agent powder and 500 g of the inorganic pigment powder were added to 50 kg of the glass body and dry-mixed, and then 500 g of a 10% PVA aqueous solution was added and stirred and mixed. The antibacterial agent powder and the inorganic pigment powder were adhered.

【００３３】続いてこの混合物をムライト製型枠内に集
積した後、１１００℃で３時間熱処理することによって
９００×９００×１７ｍｍの大きさの試料を得た。Subsequently, the mixture was accumulated in a mullite mold and heat-treated at 1100 ° C. for 3 hours to obtain a sample having a size of 900 × 900 × 17 mm.

【００３４】このようにして得られた試料の表面は、平
滑で光沢があり、ガラス小体の界面に存在する無機顔料
によって青色に着色された美しい天然大理石様の外観を
呈していた。析出結晶をＸ線回折により確認したとこ
ろ、ディオプサイドが析出していた。また表面をＥＰＭ
Ａ分析したところ、ガラス小体の界面にガラス粉末の主
成分であるＺｎＯが存在しており、抗菌層が存在してい
ることが確認された。さらに実施例１と同様にして抗菌
性を評価したところ、良好な抗菌性を有していることが
わかった。The surface of the sample thus obtained was smooth and glossy, and exhibited a beautiful natural marble-like appearance colored blue by an inorganic pigment present at the interface of the glass bodies. When the precipitated crystals were confirmed by X-ray diffraction, diopside was deposited. The surface is EPM
As a result of the A analysis, it was confirmed that ZnO, which is a main component of the glass powder, was present at the interface of the glass body, and that the antibacterial layer was present. Further, when the antibacterial property was evaluated in the same manner as in Example 1, it was found that the composition had good antibacterial property.

【００３５】[0035]

【発明の効果】本発明の抗菌性結晶化ガラス物品は、機
械的強度や化学耐久性等の特性に優れ、美しい外観を呈
する。しかも長期間に亘って優れた抗菌性を発揮するた
め、黴や細菌の発生を防止することができる。それゆえ
特にテーブルや洗面化粧台の天板、トイレブース、或い
は病院の内装材等、衛生面での配慮が要求される用途に
使用される建築材料として好適である。The antibacterial crystallized glass article of the present invention has excellent properties such as mechanical strength and chemical durability and exhibits a beautiful appearance. Moreover, since it exhibits excellent antibacterial properties over a long period of time, it is possible to prevent the occurrence of molds and bacteria. Therefore, it is particularly suitable as a building material used in applications requiring consideration for hygiene, such as tabletops, vanity tops, toilet booths, and hospital interior materials.

【００３６】さらに本発明の結晶化ガラス物品は、物品
内部にも抗菌剤が存在しているため、研磨や切断等の後
加工を行っても、加工面が抗菌性を有しており、新たに
抗菌処理をする必要がない。Further, since the crystallized glass article of the present invention has an antibacterial agent also inside the article, the processed surface has antibacterial properties even if post-processing such as polishing or cutting is performed. No need for antibacterial treatment.

【００３７】また本発明の方法によれば、上記した抗菌
性結晶化ガラス物品を、結晶化ガラスの持つ優れた特性
を損ねることなく、安価に、しかも従来の工程を大幅に
変更することなく容易に製造することが可能である。Further, according to the method of the present invention, the above-mentioned antibacterial crystallized glass article can be easily produced at a low cost without deteriorating the excellent properties of the crystallized glass and without greatly changing the conventional process. It is possible to manufacture.

Claims (12)

【特許請求の範囲】[Claims] 【請求項１】 軟化点より高い温度で熱処理すると軟化
変形しながら表面から内部に向かって針状の結晶が析出
する性質を有するガラス小体の多数個が融着一体化する
とともに結晶が析出してなる結晶化ガラス物品であっ
て、ガラス小体の界面に抗菌剤からなる抗菌層が形成さ
れていることを特徴とする抗菌性結晶化ガラス物品。When a heat treatment is performed at a temperature higher than the softening point, a large number of glass bodies having a property that needle-like crystals are precipitated from the surface toward the inside while being softened and deformed are fused and integrated, and crystals are precipitated. An antibacterial crystallized glass article, characterized in that an antibacterial layer made of an antibacterial agent is formed at the interface between the glass bodies. 【請求項２】 抗菌剤が、Ａｇ、Ｃｕ、Ｚｎ、Ｐｂ、Ｈ
ｇ、Ｓｎから選ばれる１種以上の金属を担持したセラミ
ックスからなることを特徴とする請求項１の抗菌性結晶
化ガラス物品。2. An antimicrobial agent comprising Ag, Cu, Zn, Pb, H
The antibacterial crystallized glass article according to claim 1, wherein the article is made of a ceramic supporting at least one metal selected from g and Sn. 【請求項３】 抗菌剤が、Ａｇ、Ｃｕ、Ｚｎから選ばれ
る１種以上を組成中に含むガラスからなることを特徴と
する請求項１の抗菌性結晶化ガラス物品。3. The antibacterial crystallized glass article according to claim 1, wherein the antibacterial agent comprises a glass containing at least one selected from Ag, Cu and Zn in the composition. 【請求項４】 抗菌剤の含有量が、結晶化ガラス１００
重量部に対して０．０１〜３０重量部であることを特徴
とする請求項１の抗菌性結晶化ガラス物品。4. An antibacterial agent having a content of the crystallized glass 100
The antibacterial crystallized glass article according to claim 1, wherein the amount is 0.01 to 30 parts by weight based on part by weight. 【請求項５】 針状結晶が、β−ウォラストナイト、デ
ィオプサイド、デビトライトから選ばれる１種以上であ
ることを特徴とする請求項１の抗菌性結晶化ガラス物
品。5. The antibacterial crystallized glass article according to claim 1, wherein the needle-like crystals are at least one selected from β-wollastonite, diopside, and devitrite. 【請求項６】 結晶化ガラスが、重量百分率でＳｉＯ2
４０〜８０％、Ａｌ2 Ｏ3 １〜２５％、ＣａＯ ３
〜２５％、ＺｎＯ ０〜１５％、ＢａＯ ０〜２０％、
ＭｇＯ ０〜２０％、Ｂ2 Ｏ3 ０〜１５％、Ｎａ2 Ｏ
＋Ｋ2 Ｏ＋Ｌｉ2 Ｏ ２〜２５％、ＴｉＯ2 ０〜５
％、ＺｒＯ2 ０〜５％、着色酸化物０〜５％の組成を
有することを特徴とする請求項５の抗菌性結晶化ガラス
物品。6. The crystallized glass is composed of SiO 2 in weight percentage.
40~80%, Al 2 O 3 1~25 %, CaO 3
-25%, ZnO 0-15%, BaO 0-20%,
0~20% MgO, B 2 O 3 0~15%, Na 2 O
+ K 2 O + Li 2 O 2 to 25%, TiO 2 0 to 5
%, The antibacterial crystallized glass article according to claim 5, characterized in that it comprises ZrO 2 0-5%, the coloring oxides 0-5% composition. 【請求項７】 軟化点より高い温度で熱処理すると軟化
変形しながら表面から内部に向かって針状の結晶が析出
する性質を有するガラス小体を多数個用意する工程と、
ガラス小体を型枠内に集積する工程と、ガラスの軟化点
以上の温度で熱処理することによってガラス小体を融着
一体化させるとともに結晶化させる工程とを含む結晶化
ガラス物品の製造方法であって、予めガラス小体の表面
に抗菌剤粉末を付着させておくことを特徴とする抗菌性
結晶化ガラス物品の製造方法。7. A step of preparing a large number of glass bodies having a property that needle-like crystals are precipitated from the surface toward the inside while being softened and deformed by heat treatment at a temperature higher than the softening point;
A method for producing a crystallized glass article, comprising the steps of: accumulating glass bodies in a mold; and heat-treating the glass bodies by heat treatment at a temperature equal to or higher than the softening point of the glass to fuse and integrate the glass bodies and crystallize the glass bodies. A method for producing an antibacterial crystallized glass article, wherein an antibacterial agent powder is previously adhered to the surface of a glass body. 【請求項８】 抗菌剤粉末として、Ａｇ、Ｃｕ、Ｚｎ、
Ｐｂ、Ｈｇ、Ｓｎから選ばれる１種以上の金属を担持し
たセラミックス粉末を使用することを特徴とする請求項
７の抗菌性結晶化ガラス物品の製造方法。8. Antibacterial agent powders of Ag, Cu, Zn,
The method for producing an antibacterial crystallized glass article according to claim 7, wherein a ceramic powder supporting at least one metal selected from Pb, Hg, and Sn is used. 【請求項９】 抗菌剤粉末として、Ａｇ、Ｃｕ、Ｚｎか
ら選ばれる１種以上を組成中に含むガラス粉末を使用す
ることを特徴とする請求項７の抗菌性結晶化ガラス物品
の製造方法。9. The method for producing an antibacterial crystallized glass article according to claim 7, wherein a glass powder containing at least one selected from Ag, Cu, and Zn in the composition is used as the antibacterial agent powder. 【請求項１０】 抗菌剤粉末の添加量が、ガラス小体１
００重量部に対して０．０１〜３０重量部であることを
特徴とする請求項７の抗菌性結晶化ガラス物品の製造方
法。10. The amount of the antimicrobial agent powder added to the glass body 1
The method for producing an antibacterial crystallized glass article according to claim 7, wherein the amount is 0.01 to 30 parts by weight based on 00 parts by weight. 【請求項１１】 β−ウォラストナイト、ディオプサイ
ド、デビトライトから選ばれる１種以上の針状結晶を析
出する性質を有するガラス小体を使用することを特徴と
する請求項７の抗菌性結晶化ガラス物品の製造方法。11. The antibacterial crystal according to claim 7, wherein a glass body having a property of precipitating at least one needle-like crystal selected from β-wollastonite, diopside, and devitrite is used. A method for producing a fossilized glass article. 【請求項１２】 重量百分率でＳｉＯ2 ４０〜８０
％、Ａｌ2 Ｏ3 １〜２５％、ＣａＯ ３〜２５％、Ｚ
ｎＯ ０〜１５％、ＢａＯ ０〜２０％、ＭｇＯ ０〜
２０％、Ｂ2 Ｏ3 ０〜１５％、Ｎａ2 Ｏ＋Ｋ2 Ｏ＋Ｌ
ｉ2 Ｏ ２〜２５％、ＴｉＯ2 ０〜５％、ＺｒＯ2
０〜５％、着色酸化物 ０〜５％の組成を有するガラス
小体を使用することを特徴とする請求項１１の抗菌性結
晶化ガラス物品の製造方法。12. SiO 2 40-80 by weight percentage.
%, Al 2 O 3 1~25% , CaO 3~25%, Z
nO 0-15%, BaO 0-20%, MgO 0
20%, B 2 O 3 0~15 %, Na 2 O + K 2 O + L
i 2 O 2~25%, TiO 2 0~5%, ZrO 2
The method for producing an antibacterial crystallized glass article according to claim 11, wherein a glass body having a composition of 0 to 5% and a colored oxide of 0 to 5% is used.
JP23329697A 1997-08-13 1997-08-13 Antimicrobial crystallized glass article and its production Pending JPH1160270A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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Publications (1)

Publication Number Publication Date
JPH1160270A true JPH1160270A (en) 1999-03-02

Family

ID=16952889

Family Applications (1)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009073726A (en) * 2007-08-28 2009-04-09 Nippon Electric Glass Co Ltd Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and its manufacturing method
WO2010024283A1 (en) * 2008-08-27 2010-03-04 日本板硝子株式会社 Scale-like glass and coated scale-like glass
KR101174402B1 (en) 2012-05-30 2012-08-16 주식회사 휴코텍 Method for manufacturing antimicrobial glass and antimicrobial glass manufactured by the same
US9840438B2 (en) 2014-04-25 2017-12-12 Corning Incorporated Antimicrobial article with functional coating and methods for making the antimicrobial article
US10131574B2 (en) 2013-06-17 2018-11-20 Corning Incorporated Antimicrobial glass articles and methods of making and using same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009073726A (en) * 2007-08-28 2009-04-09 Nippon Electric Glass Co Ltd Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and its manufacturing method
WO2010024283A1 (en) * 2008-08-27 2010-03-04 日本板硝子株式会社 Scale-like glass and coated scale-like glass
US9237994B2 (en) 2008-08-27 2016-01-19 Nippon Sheet Glass Company, Limited Glass flake and coated glass flake
KR101174402B1 (en) 2012-05-30 2012-08-16 주식회사 휴코텍 Method for manufacturing antimicrobial glass and antimicrobial glass manufactured by the same
US10131574B2 (en) 2013-06-17 2018-11-20 Corning Incorporated Antimicrobial glass articles and methods of making and using same
US10676394B2 (en) 2013-06-17 2020-06-09 Corning Incorporated Antimicrobial glass articles and methods of making and using same
US9840438B2 (en) 2014-04-25 2017-12-12 Corning Incorporated Antimicrobial article with functional coating and methods for making the antimicrobial article

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