JP2010018458A - Plate glass - Google Patents

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JP2010018458A
JP2010018458A JP2008178481A JP2008178481A JP2010018458A JP 2010018458 A JP2010018458 A JP 2010018458A JP 2008178481 A JP2008178481 A JP 2008178481A JP 2008178481 A JP2008178481 A JP 2008178481A JP 2010018458 A JP2010018458 A JP 2010018458A
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glass
plate
plate glass
fine particles
large number
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Hideo Nishi
英夫 西
Shigeo Yokoi
重男 横井
Takashi Masuyama
隆 増山
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GLASS CUBE KK
SANSHIBA SHOZAI KK
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GLASS CUBE KK
SANSHIBA SHOZAI KK
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Priority to JP2008178481A priority Critical patent/JP2010018458A/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide plate glass having projecting portions on the surface thereof, excellent in anti-slip properties and durability, recyclable and suitably utilizable as a building material and furniture material provided with environmental adaptability free from problems on disposal treatment. <P>SOLUTION: This plate glass is obtained by disposing a number of small clumpy portions attached on at least either surface thereof, which portions are aggregates of glass fine particles selected from borosilicate glass containing bismuth oxide component and borosilicate glass containing zinc oxide component, and the small clumpy portions are fused and fixed on the surface of the plate glass by firing to form a number of glass projecting portions. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、建築物や家具類等に使用される、優れた滑り防止性の表面を有する板ガラスに関する。特に、本発明は、建築物のガラス床、家具としてのガラステーブルのような滑り防止性が要求される箇所への利用に適する板ガラスに関する。   The present invention relates to a sheet glass having an excellent anti-slip surface used for buildings and furniture. In particular, the present invention relates to a sheet glass suitable for use in a place where anti-slip properties such as a glass floor of a building and a glass table as furniture are required.

板ガラスは、建築物の窓や、店舗内のショーケースのような透視性が求められる用途のみならず、建築物のガラス床材、ガラステーブル、建築物の非透視性採光壁等、広い分野にわたって利用されている。特に、最近では、各種商業施設、展示会場、マンションのエントランス部のような建築物の床にガラス床を構築する方式が多くなり、透視性に優れたガラス床の下部を意匠性の高い構造部としたり、非透視性のガラス床の下部に照明設備を配置して幻想的な光床を構築している例が多く見られるようになってきている。   Flat glass is used not only for applications that require transparency such as building windows and showcases in stores, but also for a wide range of fields such as glass flooring for buildings, glass tables, and non-transparent lighting walls for buildings. It's being used. In particular, recently, there are many methods of building glass floors on the floors of buildings such as various commercial facilities, exhibition halls, and condominium entrances. In many cases, a fantastic light floor is constructed by arranging lighting equipment under a non-transparent glass floor.

また、ガラステーブル用の板ガラスとしても透視性のものばかりでなく、滑り防止性の凹凸面を有する板ガラスを使用したガラステーブルが多く出回っている。   In addition, many glass tables using a plate glass having an anti-slip concavo-convex surface are on the market as glass plates for glass tables.

上記したような各種分野で利用されている板ガラスの中でも、建築物のガラス床の場合、滑り防止のために、板ガラスの表面に滑り止め用の凹凸を形成した板ガラスを使用してガラス床を形成することも行われている。また、ガラステーブルのような家具類に使用される板ガラスとしても、表面に微細な凹凸部が形成されている磨(スリ)ガラス様のガラス板を使用したものもある。   Among the glass sheets used in various fields as described above, in the case of building glass floors, to prevent slipping, glass sheets are formed using flat glass with anti-slip irregularities on the surface of the glass sheet. It has also been done. Further, as a plate glass used for furniture such as a glass table, there is a glass plate using a polished glass-like glass plate having fine irregularities formed on the surface.

上記のような各種分野で利用することができる表面に凸部を有する板ガラスとしては、板ガラスの表面に特殊加工技術によりガラス質の微粒子を強固に融着させて表面に所定パターンの均一な突起部を形成した透視性硝子板が知られている(特許文献1)。この突起部を有するガラス板は、陽光を受けると眩く反射する微粒ガラスによって適度な滑り抵抗性を有する凸部を形成しているので、意匠性に優れると共に、通常の床と同様に快適な歩行を可能とするガラス床材としての利用に適しているとされている。
特許文献1には、上記のようなガラス面に突起部を形成するための微粒子ガラスとして、「硼珪酸鉛ガラスを主成分とする低軟化点ガラス」の微粒子が使用されることが記載されている。
特許第2980536号公報
As plate glass having convex portions on the surface that can be used in various fields as described above, glassy fine particles are firmly fused on the surface of the plate glass by a special processing technique, and uniform projections with a predetermined pattern on the surface A see-through glass plate in which is formed is known (Patent Document 1). The glass plate having the protrusions is formed with convex portions having moderate slip resistance by the fine glass that reflects brightly when receiving sunlight, so that it has excellent design and is comfortable walking like a normal floor. It is said that it is suitable for use as a glass flooring that makes it possible.
Patent Document 1 describes that fine particles of “low softening point glass mainly composed of lead borosilicate glass” are used as fine particle glass for forming protrusions on the glass surface as described above. Yes.
Japanese Patent No. 2980536

本発明は、上記特許文献1記載の表面に突起部を有する硝子板と同等の滑り防止性と耐久性に優れる突起部を板ガラス面に無鉛ガラス微粒子で形成することにより、リサイクルが可能で、廃棄処理の問題がない環境適性を備えた建築材及び家具材としての利用に適している板ガラスを提供することを目的とするものである。   The present invention can be recycled by forming protrusions having excellent anti-slip properties and durability equivalent to the glass plate having protrusions on the surface described in Patent Document 1 on the surface of the plate glass with lead-free glass particles. An object of the present invention is to provide a sheet glass suitable for use as a building material and furniture material having environmental suitability without any problem of processing.

本発明者らは、板ガラス面に小突起部を形成するために使用されている従来の鉛含有ガラス微粒子に代わる無鉛ガラス微粒子の採用可能性について検討を重ねる中で、硼珪酸ガラス系に属するガラス微粒子のうち、ビスマス成分と亜鉛成分を含有する硼珪酸ガラス系のガラス微粒子が集合した小塊状部を板ガラス表面に形成した後、焼成処理により該小塊状部を融着固定して形成される多数のガラス製小凸部を表面に有する板ガラスが、ガラス床の用途において要求されるような滑り防止性、耐磨耗性及び密着性を備えた板ガラスであることを見出し、本発明を完成させたものである。   The inventors have studied the possibility of using lead-free glass fine particles instead of the conventional lead-containing glass fine particles used for forming small protrusions on the plate glass surface. Among the fine particles, a large number of fine particles are formed by forming a small lump portion on the surface of the plate glass in which borosilicate glass-based fine particles containing a bismuth component and a zinc component are gathered, and then fusing and fixing the small lump portion by a baking treatment. The sheet glass having a small glass convex portion on the surface was found to be a sheet glass having anti-slip properties, abrasion resistance and adhesion as required in glass floor applications, and the present invention was completed. Is.

本発明は、以下の記載するように、酸化ビスマスを含有する硼珪酸系ガラス及び/又は酸化亜鉛成分を含有する硼珪酸系ガラスの微粒子が集合した多数の小塊状部を板ガラスの表面に所定間隔で配置し、焼成処理により融着固定して形成されている多数のガラス製凸部を有する板ガラスに関する発明を基本発明とする。   In the present invention, as described below, a large number of small aggregates in which fine particles of borosilicate glass containing bismuth oxide and / or borosilicate glass containing a zinc oxide component are aggregated are arranged on a surface of a plate glass at a predetermined interval. The basic invention is an invention relating to a plate glass having a large number of glass convex portions that are formed by fusing and fixing by firing.

(1)板ガラスの少なくとも一方の表面に、酸化ビスマス成分を含有する硼珪酸系ガラス及び酸化亜鉛成分を含有する硼珪酸系ガラスから選ばれるガラス微粒子が集合した小塊状部を多数付着配置し、該小塊状部を焼成処理により板ガラス表面に融着固定して形成されている多数のガラス製凸部を有する板ガラス。 (1) Adhering and arranging a large number of small aggregates of glass particles selected from a borosilicate glass containing a bismuth oxide component and a borosilicate glass containing a zinc oxide component on at least one surface of a plate glass; A plate glass having a large number of glass convex portions formed by fusing and fixing a small block portion to the surface of a plate glass by a baking treatment.

(2)前記多数のガラス製凸部は、平均高さ0.3mm〜1.0mm、平均直径1.0mm〜2.0mm、及び凸部間の間隔2.0mm〜8.0mmで板ガラス表面に形成されていることを特徴とする(1)項記載の多数のガラス製凸部を有する板ガラス。 (2) The large number of glass protrusions have an average height of 0.3 mm to 1.0 mm, an average diameter of 1.0 mm to 2.0 mm, and an interval between the protrusions of 2.0 mm to 8.0 mm on the surface of the plate glass. A plate glass having a large number of glass protrusions according to item (1), which is formed.

(3)前記ガラス製凸部は、板ガラス表面に千鳥模様状又は市松模様状に配置されていることを特徴とする(1)項又は(2)項に記載の多数のガラス製凸部を有する板ガラス。 (3) The glass convex portions have a large number of glass convex portions according to (1) or (2), wherein the glass convex portions are arranged in a staggered pattern or a checkered pattern on the surface of the plate glass. Sheet glass.

(4)前記板ガラスが、普通板ガラスである(1)項〜(3)項のいずれか1項に記載の多数のガラス製凸部を有する板ガラス。 (4) The plate glass having a large number of glass protrusions according to any one of (1) to (3), wherein the plate glass is ordinary plate glass.

(5)前記(1)項〜(4)項のいずれか1項に記載の多数のガラス製凸部を有する板ガラスからなるガラス床材。 (5) A glass flooring comprising a plate glass having a large number of glass protrusions according to any one of (1) to (4).

(6)前記(1)項〜(4)項のいずれか1項に記載の多数のガラス製凸部を有する板ガラスからなるガラステーブル用天板。 (6) A glass table top plate comprising a plate glass having a large number of glass protrusions according to any one of (1) to (4).

(7)前記(1)項〜(4)項のいずれか1項に記載の多数のガラス製凸部を有する板ガラスからなる壁材。 (7) The wall material which consists of plate glass which has many glass convex parts of any one of said (1) term-(4) term.

(8)前記(1)項〜(4)項のいずれかに記載の多数のガラス製凸部を有する板ガラスを製造する方法であって、板ガラス表面に、ガラス微粒子を小塊状に付着させる付着剤を所定パターンで塗布してガラス微粒子付着部を形成し、該ガラス微粒子付着部にビスマス成分を含有する硼珪酸系ガラス及び亜鉛成分を含有する硼珪酸系ガラスから選ばれる平均粒径100μm〜500μmのガラス微粒子を付着させてガラス微粒子小塊状部を形成し、該ガラス微粒子小塊状部が形成されている板ガラスを、ガラス微粒子の軟化点以上の温度で焼成処理して該ガラス微粒子小塊状部を板ガラス表面に融着させ、次いで、該焼成処理の板ガラスを冷却処理してガラス微粒子小塊状部を板ガラス表面に固定することを特徴とする、多数のガラス製凸部を有する板ガラスの製造方法。 (8) A method for producing a plate glass having a large number of glass protrusions according to any one of (1) to (4) above, wherein the fine particles adhere to the surface of the plate glass in a small mass. Is applied in a predetermined pattern to form a glass fine particle adhering portion, and the glass fine particle adhering portion has an average particle size of 100 μm to 500 μm selected from a borosilicate glass containing a bismuth component and a borosilicate glass containing a zinc component. Glass fine particles are attached to form glass fine particles, and the glass plate with the glass fine particles formed is baked at a temperature equal to or higher than the softening point of the glass fine particles to form the glass fine particles. It has a large number of glass protrusions characterized by being fused to the surface and then cooling the plate glass of the calcination treatment to fix the glass fine particle agglomerates on the plate glass surface. Manufacturing method of that flat glass.

(9)前記焼成処理及びが冷却処理が、前記板ガラスの軟化点温度で焼成処理した後、空気の吹きつけにより板ガラスを均一に急冷する処理であることを特徴とする、(8)項記載の多数のガラス製凸部を有する板ガラスの製造方法。 (9) The method according to (8), wherein the baking treatment and the cooling treatment are treatments in which the plate glass is uniformly and rapidly cooled by blowing air after the baking treatment is performed at the softening point temperature of the plate glass. The manufacturing method of the plate glass which has many glass convex parts.

(10)前記ガラス微粒子は、平均粒径200〜400μm、好ましくは250〜350μmのガラス微粒子であることを特徴とする(8)項又は(9)項に記載の多数のガラス製凸部を有する板ガラスの製造方法。 (10) The glass fine particles are glass fine particles having an average particle size of 200 to 400 μm, preferably 250 to 350 μm, and have a large number of glass protrusions as described in (8) or (9). A manufacturing method of plate glass.

本発明の多数のガラス製凸部を有する板ガラスは、前記板ガラス表面にガラス微粒子が付着して形成されている小塊状部における個々のガラス微粒子が、ガラス微粒子の軟化点以上の温度で焼成処理されることによって相互に融着し合った状態で板ガラス表面に融着し、その後の冷却処理により強固な固化体として板ガラス表面に固定されているので、該固化体からなる凸部は、優れた耐摩耗性及び耐剥離性を備えており、また、凸部自体もガラス製であって光透過性を有することから、各種商業施設、展示会場、マンションのエントランス部に意匠性に優れた透光性の床を構築するためのノンスリップガラス床材として極めて有用である。   In the glass sheet having a large number of glass convex portions according to the present invention, the individual glass fine particles in the small block portion formed by adhering glass fine particles to the surface of the flat glass are fired at a temperature equal to or higher than the softening point of the glass fine particles. Are fused to each other in a state where they are fused together, and are fixed to the surface of the plate glass as a solidified body by a subsequent cooling process. It has wear and peel resistance, and the convex part itself is made of glass and has light transmissivity. Therefore, it has excellent translucency in various commercial facilities, exhibition halls, and condominium entrances. It is extremely useful as a non-slip glass flooring material for constructing a floor.

また、該表面凸部が存在することにより貼紙等が貼付された場合の粘着剤層面とガラス面との接触面積が小さくなるため、不法な貼紙等を簡単に剥離することができるので、易清掃性が求められる公共建築物等の窓ガラス等への使用に適しているし、手の平が該ガラス面に接触しても手跡や指紋が目立たないという利点もある。
さらに、環境汚染原因となる成分を含まないことから、埋め立て等による廃棄処理が可能であるし、ガラス原料として再利用することも可能である。
Moreover, since the contact area between the pressure-sensitive adhesive layer surface and the glass surface when a paper sticker is affixed due to the presence of the surface convex portion, the illegal paper sticker etc. can be easily peeled off, so that it is easy to clean. It is suitable for use on window glass and the like of public buildings and so forth, and there is an advantage that hand prints and fingerprints are not noticeable even when the palm touches the glass surface.
Furthermore, since it does not contain components that cause environmental pollution, it can be disposed of by landfill or reused as a glass raw material.

本発明の多数のガラス製凸部を有する板ガラスは、酸化ビスマス成分を含有する硼珪酸系ガラスの微粒子及び/又は酸化亜鉛成分を含有する硼珪酸系ガラスの微粒子が集合した多数の小塊状部を基板となる板ガラスの表面に任意の間隔で配置し、焼成処理により該小塊状部を板ガラス面に融着させ、次いで冷却固化して板ガラス表面に固定されている多数のガラス製凸部を有する板ガラスである。   The plate glass having a large number of glass protrusions according to the present invention comprises a large number of small aggregates in which fine particles of borosilicate glass containing a bismuth oxide component and / or fine particles of borosilicate glass containing a zinc oxide component are aggregated. Plate glass having a large number of glass protrusions arranged on the surface of a plate glass to be a substrate at an arbitrary interval, fused to the plate glass surface by firing treatment, then cooled and solidified to be fixed to the surface of the plate glass It is.

基板となる板ガラスとしては、建築物や交通車両等に通常使用される普通板ガラスが使用できる。
基板としての板ガラスの厚さには特に制限はなく、建築物や交通車両等に通常使用される厚さの板ガラスが使用できる。
As the plate glass used as the substrate, ordinary plate glass usually used for buildings, transportation vehicles, and the like can be used.
There is no restriction | limiting in particular in the thickness of the plate glass as a board | substrate, The plate glass of the thickness normally used for a building, a traffic vehicle, etc. can be used.

板ガラス表面に形成されるガラス製凸部を形成するガラス微粒子としては、酸化ビスマス成分を含有する硼珪酸系ガラスの微粒子と酸化亜鉛成分を含有する硼珪酸系ガラスの微粒子から選ばれる少なくとも1種が使用される。
ガラス微粒子の大きさは、焼成処理によって基板の板ガラス表面に融着させる温度で微粒子が完全に溶融してしまう程度の小粒径ではなく、また、微粒子同士の融着面積が小さくなって最終的に形成される凸部が脆いものとなるほどの大粒径でない範囲で適宜選択されるが、一般的には、平均粒径が100〜500μm、好ましくは200〜400μm、より好ましくは250〜350μmのガラス微粒子が使用される。
The glass fine particles forming the glass protrusions formed on the surface of the plate glass include at least one selected from fine particles of borosilicate glass containing a bismuth oxide component and fine particles of borosilicate glass containing a zinc oxide component. used.
The size of the glass microparticles is not a small particle size such that the microparticles are completely melted at the temperature at which they are fused to the glass plate surface of the substrate by the firing process. Is appropriately selected within a range that does not have such a large particle size that the ridges formed are brittle, but generally the average particle size is 100 to 500 μm, preferably 200 to 400 μm, more preferably 250 to 350 μm. Glass particulates are used.

上記のような組成を有する酸化ビスマス成分を含有する硼珪酸系ガラスの微粒子は、酸化ビスマス含有率が50〜60質量%のものが使用される。
また、酸化亜鉛成分を含有する硼珪酸系ガラスの微粒子としては、酸化亜鉛含有率が20〜30質量%のものが使用される。
As the fine particles of the borosilicate glass containing the bismuth oxide component having the above composition, those having a bismuth oxide content of 50 to 60% by mass are used.
Further, as the fine particles of the borosilicate glass containing the zinc oxide component, those having a zinc oxide content of 20 to 30% by mass are used.

基板となる板ガラスの表面に形成されるガラス微粒子の小塊状部は、平均粒径が100〜500μmのガラス微粒子を小塊状にガラス基板面に付着させることができる付着剤によりガラス基板面に形成された付着部にガラス微粒子を任意の手法で小塊状に付着させることによって形成される。一例としては、基板ガラス面に付着剤を所定パターンで塗布して付着剤塗布部を形成し、次いで、ガラス微粒子を該付着剤塗布部に振り掛け又は吹き付けにより供給してガラス微粒子を小塊状に付着させ、該付着剤塗布部以外の基板ガラス面上に存在するガラス微粒子を振るい落とす方法、空気吹き付けにより吹き飛ばす方法等によって取り除いて形成する方法を挙げることができる。   The small part of the glass fine particles formed on the surface of the plate glass to be the substrate is formed on the glass substrate surface by an adhesive capable of adhering the glass fine particles having an average particle size of 100 to 500 μm to the glass substrate surface in a small shape. It is formed by adhering glass fine particles to the adhering portion in a small lump shape by an arbitrary method. As an example, an adhesive is applied to a substrate glass surface in a predetermined pattern to form an adhesive application portion, and then glass fine particles are sprinkled or sprayed onto the adhesive application portion to adhere the glass fine particles in a small lump shape. And a method of removing and forming glass fine particles existing on the surface of the substrate glass other than the adhesive application part, a method of blowing off by air blowing, and the like.

ガラス基板面に形成する上記付着部の形状に特に制限はなく、真円形、楕円形、矩形、多角形等から任意に選択することができる。
また、個々の付着部の大きさ(面積)や配置間隔は、形成される多数のガラス製凸部を有する板ガラスの用途に適応するように任意に選択することができる。
付着剤の塗布量は、ガラス微粒子が小塊状に一体化した集合体が塗布部に形成される程度の塗布量の範囲で適宜設定される。
There is no restriction | limiting in particular in the shape of the said adhesion part formed in a glass substrate surface, It can select arbitrarily from a perfect circle, an ellipse, a rectangle, a polygon, etc.
Further, the size (area) and the arrangement interval of the individual adhering portions can be arbitrarily selected so as to adapt to the use of the plate glass having a large number of glass convex portions to be formed.
The application amount of the adhesive is appropriately set within a range of application amount such that an aggregate in which glass fine particles are integrated into a small lump is formed on the application part.

付着剤としては、無機インクやセラミックインクと称される無機性の付着剤やガラス微粒子の小塊状部を焼成処理して板ガラス面に融着させる時に分解消滅するか蒸発乃至気化して消滅して基板ガラス面に残存しないスクリーンオイルと称される有機系付着剤が使用される。無機インクの例としては、商品名「GLASS COLOR KPY−ホワイト」(奥野製薬工業社製)等が挙げられ、スクリーンオイルの例としては、希釈オイルと接着剤とを組み合わせたもの等が挙げられる。   Adhesives include inorganic adhesives called inorganic inks and ceramic inks, and are decomposed or extinguished when the small particles of glass fine particles are fired and fused to the plate glass surface, or disappeared by evaporation or vaporization. An organic adhesive called screen oil that does not remain on the substrate glass surface is used. Examples of the inorganic ink include trade name “GLASS COLOR KPY-White” (Okuno Pharmaceutical Co., Ltd.) and the like, and examples of the screen oil include a combination of diluted oil and an adhesive.

ガラス基板面に形成された上記付着部にガラス微粒子の小塊状部を形成するためのガラス微粒子の付着量は、多数のガラス製凸部を有する板ガラスの用途に適応する凸部を形成できる範囲で適宜設定される。一般的には、付着量が少なくなるにしたがって、形成される凸部の高さが低くなる傾向があるし、付着量が多くなるにしたがって凸部が高くなる。
通常、上記ガラス微粒子の付着量は、後記するようなサイズの凸部が形成できる量の範囲で設定される。
The amount of adhesion of the glass fine particles for forming the glass fine particles in the adhering portion formed on the glass substrate surface is within a range in which the convex portion adapted to the use of the plate glass having a large number of glass convex portions can be formed. Set as appropriate. Generally, as the amount of adhesion decreases, the height of the formed convex portion tends to decrease, and as the amount of adhesion increases, the convex portion increases.
Usually, the adhesion amount of the glass fine particles is set within a range of an amount capable of forming a convex portion having a size as described later.

付着剤塗布部に付着されたガラス微粒子小塊状部を融着させるための焼成温度及び焼成時間は、基板板ガラスの溶融温度以下で、ガラス微粒子が軟化するか表面部分が溶融状態となる温度及び時間の範囲内で設定される。ガラス微粒子が完全に溶融する焼成条件では、形成される凸部の表面がなだらかで平滑な状態となり、滑り止め効果が小さい凸部となるので好ましくない。一般的な焼成温度は、基板が板ガラスの場合、650〜800℃の範囲で、好ましくは基板板ガラスの軟化点の温度であり、焼成時間は5分間〜9分間の範囲内で設定される。基板となる板ガラス面への前記凸部の形成を板ガラスの軟化点の温度で行い、次いで、常温の空気流を大量に吹き付けて板ガラス全体を急冷することにより、基板の板ガラスの強化処理を同時に行うことが好ましい。   The firing temperature and firing time for fusing the glass fine particle agglomerates attached to the adhesive application part are equal to or lower than the melting temperature of the substrate plate glass, and the temperature and time at which the glass fines are softened or the surface part is in a molten state. It is set within the range. The firing conditions in which the glass fine particles are completely melted are not preferable because the surface of the convex portion to be formed becomes a smooth and smooth state and the convex portion has a small anti-slip effect. When a board | substrate is plate glass, a general baking temperature is the temperature of 650-800 degreeC, Preferably it is the temperature of the softening point of board | substrate plate glass, and baking time is set within the range of 5 minutes-9 minutes. The above-mentioned convex portions are formed on the surface of the plate glass to be the substrate at the temperature of the softening point of the plate glass, and then the entire plate glass is rapidly cooled by blowing a large amount of room temperature air flow to simultaneously perform the strengthening processing of the plate glass of the substrate. It is preferable.

表面にガラス製凸部を有するガ板ラスにおける前記多数の凸部は、一般的には、平均高さ0.3mm〜1.0mm、平均直径1.0mm〜3.0mm、及び凸部間の間隔2.0mm〜8.0mmとなるように形成されるが、用途に応じて凸部のサイズや間隔は上記数値範囲外とすることも可能である。
一般的に、上記凸部の高さが0.3mmより低くなるに従って凸部表面の滑り止め機能が低くなる傾向があるし、粘着シート等に対する剥離性も悪くなる。また、1.0mmより高くなると、滑り止め性は良くなるが、凸部の強度が不足し、耐摩耗性が不十分となる場合がある。
In general, the large number of convex portions in the glass lath having glass convex portions on the surface has an average height of 0.3 mm to 1.0 mm, an average diameter of 1.0 mm to 3.0 mm, and between the convex portions. Although it is formed so that the interval is 2.0 mm to 8.0 mm, the size and interval of the convex portions can be outside the above numerical range depending on the application.
Generally, as the height of the convex portion becomes lower than 0.3 mm, the anti-slip function on the convex portion surface tends to be lowered, and the peelability from the pressure-sensitive adhesive sheet and the like also deteriorates. On the other hand, when it is higher than 1.0 mm, the anti-slip property is improved, but the strength of the convex portion is insufficient, and the wear resistance may be insufficient.

前記凸部の直径が上記数値範囲より小さくなっても、上記範囲より大きくなっても滑り止め効果が低下する傾向がある。
また、前記凸部の間隔が2.0mmに満たないような狭い配置間隔で凸部が形成されていると、凸部が連なった状態に近くなって滑り止め性が十分に発揮されない場合があるし、逆に8.0mmを越えて間隔が拡がるにしたがって凸部による滑り止め効果は低下していく。
Even if the diameter of the convex portion is smaller than the above numerical range or larger than the above range, the anti-slip effect tends to be lowered.
In addition, when the convex portions are formed at a narrow arrangement interval such that the interval between the convex portions is less than 2.0 mm, the anti-skid property may not be sufficiently exhibited because the convex portions are close to each other. On the other hand, as the distance increases beyond 8.0 mm, the anti-slip effect by the convex portion decreases.

基板となる板ガラスの表面の凸部は、基板ガラス表面に間隔を置いて所定パターンで付着剤が塗布された付着部にガラスの微粒子を小塊状に付着させ、焼成処理により該小塊状のガラス微粒子群を基板ガラス面に融着させ、冷却固化して固定することによって形成される。
基板となる板ガラス表面は、任意の方法で予め清浄化された状態で付着剤によるガラス微粒子の付着部が形成される。
付着剤による付着部の形成は、例えば、スクリーン印刷法等により所定量の付着剤を所定パターン、例えば、千鳥模様、市松模様の配置となるように板ガラス面に塗布することによって行うことができる。
The convex portions on the surface of the plate glass serving as the substrate are formed by attaching glass particles in small lumps to the adhering portion to which the adhesive is applied in a predetermined pattern at intervals on the surface of the substrate glass, and the small glass tiny particles by baking treatment. It is formed by fusing the group to the substrate glass surface, cooling and solidifying it.
On the surface of the plate glass serving as the substrate, the adhering portion of the glass fine particles by the adhering agent is formed in a state of being previously cleaned by an arbitrary method.
Formation of the adhesion part by an adhesive agent can be performed by apply | coating a predetermined amount of adhesive agents to a plate glass surface by the screen printing method etc. so that it may become arrangement | positioning of a predetermined pattern, for example, a zigzag pattern, a checkered pattern.

付着剤の付着部にガラス微粒子からなる小塊状部を付着形成する方法に特に制限はなく、付着剤の各付着部にガラス微粒子を均一に付着させることができる方法であればいずれも採用することができる。例えば、付着部を有する板ガラス面全体にガラス微粒子を十分に吹きつけるか、振りかけて所定量のガラス微粒子群を付着部に均一に付着させ、該付着部以外の板ガラス面上のガラス微粒子を振動処理、空気吹き付け処理により除去する方法等を採用することができる。   There is no particular limitation on the method for adhering and forming small clumps made of glass fine particles on the adhering part of the adhering agent, and any method can be used as long as the glass fine particles can uniformly adhere to each adhering part of the adhering agent. Can do. For example, sufficiently spray glass particles on the entire surface of the plate glass having the adhering portion or sprinkle it to uniformly adhere a predetermined amount of glass particles to the adhering portion, and vibrate the glass particles on the plate glass surface other than the adhering portion. A method of removing by air blowing treatment can be employed.

板ガラス面に付着されたガラス微粒子の小塊状部は、次いで、焼成処理により板ガラス面に融着される。
焼成処理は、ガラス微粒子の小塊状部が所定パターンで形成されている板ガラス全体を焼成炉に入れて所定時間焼成することによって行われる。
焼成処理は、前記したように、ガラス微粒子の小塊状部が軟化乃至部分溶融して板ガラス面に融着される焼成条件で行われる。
焼成処理後、ガラス微粒子の小塊状部が融着している板ガラス面に冷却用の空気が吹き付けられることによって、融着されている小塊状部が冷却固化し、板ガラス面に強固に固定される。
The small particle portion of the glass fine particles attached to the plate glass surface is then fused to the plate glass surface by a firing process.
The baking process is performed by putting the whole plate glass in which the small-part portions of the glass fine particles are formed in a predetermined pattern into a baking furnace and baking it for a predetermined time.
As described above, the baking treatment is performed under the baking conditions in which the small lump portion of the glass fine particles is softened or partially melted and fused to the plate glass surface.
After the firing treatment, cooling air is blown onto the plate glass surface to which the glass particles are fused, so that the fused pieces are cooled and solidified and firmly fixed to the plate glass surface. .

基板が普通板ガラスである場合は、ガラス微粒子の小塊状部を軟化乃至部分溶融させてガラス面に融着させる温度として、基板の普通板ガラスが軟化する温度を選択し、焼成処理後の板ガラス全体を大量の冷却用空気の吹き付けにより急速冷却して普通板ガラス部分を強化させる処理を同時に行うことも可能である。   When the substrate is ordinary glass, the temperature at which the ordinary glass sheet of the substrate is softened is selected as the temperature at which the glass particles are softened or partially melted and fused to the glass surface. It is also possible to simultaneously perform a process of strengthening the ordinary glass plate part by rapid cooling by blowing a large amount of cooling air.

以下、具体的な製造例及び試験例により本発明を具体的に説明するが、本発明は以下の実施例等によって限定されるものではない。なお、各製造例における「部」や「%」は特に断らない限り「質量部」及び「質量%」を意味する。   Hereinafter, the present invention will be specifically described with specific production examples and test examples, but the present invention is not limited to the following examples. “Parts” and “%” in each production example mean “parts by mass” and “% by mass” unless otherwise specified.

試験体1〜8
<基板板ガラスの調製>
厚さ8mmの普通板ガラスの表面を洗剤で洗浄した後、水洗し、乾燥した後、縦100mm×横100mmに切断した基板板ガラス30枚、300mm×200mmに切断した基板板ガラス20枚を調製し、前者のサイズのものを試験体No.1〜6に、後者のサイズのものを試験体No.7、試験体No.8の各基板板ガラスとして使用した。
Specimens 1-8
<Preparation of substrate plate glass>
After washing the surface of the normal plate glass having a thickness of 8 mm with a detergent, washing with water and drying, 30 substrate plate glasses cut into 100 mm length × 100 mm width and 20 substrate plate glasses cut into 300 mm × 200 mm were prepared. No. Specimen No. 1 to 6, the latter size specimens No. 7. Specimen No. It used as each 8 board | substrate plate glass.

<ガラス微粒子付着部の形成>
上記2種類のサイズの基板板ガラス面に、表1に示す付着剤をスクリーン印刷により塗布して、直径1.3mmの付着部を3.5mm間隔で千鳥模様状に配置した。
次いで、表1に示す2種類の付着剤のいずれかによる付着部を有する各基板板ガラス面に、表1に示す3種類のガラス微粒子を振りかけて全面に均一に堆積させた後、ガラス微粒子堆積面を下向きにして付着部以外に堆積しているガラス微粒子をふるい落として除去し、平均高さ1.0mmのガラス微粒子小塊状部を形成した。
<Formation of glass fine particle adhesion part>
Adhesives shown in Table 1 were applied to the two types of substrate glass plate surfaces by screen printing, and adhering portions having a diameter of 1.3 mm were arranged in a staggered pattern at intervals of 3.5 mm.
Next, after the three types of glass fine particles shown in Table 1 are sprinkled and uniformly deposited on the entire surface of each substrate plate glass surface having an adhering portion by one of the two types of adhesives shown in Table 1, the glass fine particle deposition surface The glass fine particles deposited on the portions other than the adhering portion were removed by sieving downward to form glass fine particles having an average height of 1.0 mm.

使用した3種のガラス微粒子と2種の付着剤は以下とおりである。
<ガラス微粒子>
ガラス微粒子A:SiO−ZnO−B系ガラス粉末(ZnO20%含有、平均粒径300μm、奥野製薬工業社製)
ガラス微粒子B:SiO−Bi−B系ガラス粉末(Bi50%含有、平均粒径300μm、奥野製薬工業社製)
ガラス微粒子C:SiO−B−PbO−CdO系ガラス粉末(商品名「CR−5S」、平均粒径300μm、奥野製薬工業社製)
The three types of glass fine particles and the two types of adhesives used are as follows.
<Glass fine particles>
Glass fine particles A: SiO 2 —ZnO—B 2 O 3 glass powder (containing 20% ZnO, average particle size 300 μm, manufactured by Okuno Pharmaceutical Co., Ltd.)
Glass fine particle B: SiO 2 —Bi 2 O 3 —B 2 O 3 glass powder (containing 50% Bi 2 O 3 , average particle size 300 μm, manufactured by Okuno Pharmaceutical Co., Ltd.)
Glass fine particle C: SiO 2 —B 2 O 3 —PbO—CdO glass powder (trade name “CR-5S”, average particle size 300 μm, manufactured by Okuno Pharmaceutical Co., Ltd.)

<付着剤>
付着剤A:スクリーンオイル〔希釈オイル(商品名「9701D」、奥野製薬工業社製)7部に対して、スクリーンプリントインク(商品名「EPOXY 1000 800メジューム」、セイコーアドバンス社製)3部の割合で混合した混合物〕
付着剤B:白色セラミックインク(無機インク、商品名「GLASS COLOR KPT−ホワイト70618」、奥野製薬工業社製)
<Adhesive>
Adhesive A: Ratio of 3 parts of screen print ink (trade name “EPOXY 1000 800 medium”, Seiko Advance) to 7 parts of screen oil (diluted oil (trade name “9701D”, manufactured by Okuno Pharmaceutical Co., Ltd.)) Mixture mixed with
Adhesive B: white ceramic ink (inorganic ink, trade name “GLASS COLOR KPT-White 70618”, manufactured by Okuno Pharmaceutical Co., Ltd.)

<焼成・固定処理>
前記縦100mm×横100mmのサイズの基板板ガラス面上の付着剤Aの塗布部に、上記ガラス微粒子Aによる小塊状部を形成した試験体1、ガラス微粒子Bによる小塊状部を形成した試験体3、ガラス微粒子Cによる小塊状部を形成した試験体5と、付着剤Bの塗布部に、上記ガラス微粒子Aによる小塊状部を形成した試験体2、ガラス微粒子Bによる小塊状部を形成した試験体4、ガラス微粒子Cによる小塊状部を形成した試験体6と、
前記縦300mm×横200mmのサイズの基板板ガラス面上の付着剤Bの塗布部に、上記ガラス微粒子Bによる小塊状部を形成した試験体7と、ガラス微粒子Cによる小塊状部を形成した試験体8のそれぞれを、熱処理炉(同昌機械股有限公司製)に入れ、温度680℃で320秒間焼成処理してガラス微粒子小塊状部を各基板板ガラス上に融着させた。
次いで、該焼成処理後の板ガラスを大量の常温空気を240秒間吹き付けて急速冷却して、表面にガラス製凸部が多数固定されている試験体1〜試験体6のそれぞれを5枚ずつ作製し、試験体7及び試験体8のそれぞれを10枚ずつ作製した。
<Baking / fixing treatment>
Specimen 1 in which a small lump portion formed of the glass fine particles A is formed on an application part of the adhesive A on the substrate plate glass surface having a size of 100 mm in length and 100 mm in width, and a test piece 3 in which a small lump portion with the glass fine particles B is formed. , Test body 5 in which a small lump portion formed of glass fine particles C was formed; test body 2 in which a small lump portion formed of glass fine particles A was formed on the application part of adhesive B; A test body 6 having a body 4 and a small lump formed of glass fine particles C;
A test body 7 in which a small lump portion formed of the glass fine particles B is formed on a coating portion of the adhesive B on the surface of the substrate plate glass having a size of 300 mm in length and 200 mm in width, and a test body in which a small lump portion formed of the glass fine particles C is formed. Each of No. 8 was put in a heat treatment furnace (manufactured by Dochang Chang Machinery Co., Ltd.), and baked at a temperature of 680 ° C. for 320 seconds to fuse the glass fine particle agglomerates on each substrate plate glass.
Next, the plate glass after the baking treatment is rapidly cooled by blowing a large amount of room temperature air for 240 seconds to prepare five each of the test bodies 1 to 6 each having a large number of glass convex portions fixed on the surface. 10 pieces of each of the test body 7 and the test body 8 were produced.

<試験方法>
1.耐磨耗性試験
上記のように作製した試験体1〜試験体6の各5枚から無作為に各3枚ずつを取出し、各試験体を試験機に取り付け、磨耗輪を試験体上に設置して試験体を回転させ、2000回転後に試験体を取り外して、試験前の試験体と試験後の試験体の質量を測定し、試験前後の質量差を算出した。
試験機として、テーバー社の磨耗試験機を使用し、磨耗輪「CS−17」を使用して、荷重500g(250g×2個)で試験した。試験前と試験後の6種類の試験体の質量の平均値及び試験前後の各試験体の質量差の平均値を表1に示す。
<Test method>
1. Abrasion resistance test Three of each of the five specimens 1 to 6 produced as described above are randomly taken out, each specimen is attached to a testing machine, and a wear ring is placed on the specimen. Then, the test body was rotated, the test body was removed after 2000 rotations, the mass of the test body before the test and the test body after the test was measured, and the mass difference before and after the test was calculated.
As a tester, an abrasion tester manufactured by Taber was used, and a wear wheel “CS-17” was used and tested under a load of 500 g (250 g × 2 pieces). Table 1 shows the average value of the masses of the six test specimens before and after the test and the average value of the mass difference between the test specimens before and after the test.

2.耐滑り性試験(C.S.R.値)
「JIS A 1509−12:2008」の「陶磁器質タイル試験方法−第12部:耐滑り性試験方法」に準じて、各10枚の試験体7及び試験体8から無作為に各5枚ずつを取り出し、耐滑り性試験を行って平均値を算出した。なお、滑り試験機「OY−PSM」は東京工業大学で開発された試験機で、人間の歩行感覚に対応した評価方法とされている。結果を表2に示す。
滑り試験機:「OY−PSM:O−Y PULL SLIP METERT」
滑り片の材質:EVAC独立気泡発泡体シート(硬度:A45〜55、厚さ:8〜11mm、密度:0.30〜0.40g/cm
試料表面に散布する介在物:JIS試験用粉体1の7種を質量比約4倍の水道水と混合した混濁液
介在物散布量:400g/cm
測定環境温度:21℃
2. Slip resistance test (CSR value)
According to “JIS A 1509-12: 2008” “Ceramic Ceramic Tile Test Method-Part 12: Slip Resistance Test Method”, each of 5 samples randomly from 10 test bodies 7 and 8 each. Was taken out and subjected to a slip resistance test to calculate an average value. The slip test machine “OY-PSM” is a test machine developed at Tokyo Institute of Technology, and is an evaluation method corresponding to human walking sensation. The results are shown in Table 2.
Slip tester: “OY-PSM: OY PULL SLIP METER”
Material of sliding piece: EVAC closed cell foam sheet (hardness: A45-55, thickness: 8-11 mm, density: 0.30-0.40 g / cm 2 )
Inclusions to be sprayed on the surface of the sample: A turbid liquid obtained by mixing seven kinds of powder 1 for JIS testing with tap water having a mass ratio of about 4 times Inclusion scattering amount: 400 g / cm 2
Measurement ambient temperature: 21 ° C

表1の結果から、板ガラス表面に融着固定して形成されている多数のガラス製凸部の耐摩耗性は、同じ付着剤Aを使用して作製されている試験体1(酸化亜鉛成分含有)、試験体3(酸化ビスマス成分含有)は試験体5(酸化鉛成分含有の既存品)に比べて耐磨耗性は若干劣るし、同じく、付着剤Bを使用して作製されている試験体2(酸化亜鉛成分含有)、試験体4(酸化ビスマス成分含有)は試験体6(酸化鉛成分含有の既存品)に比べて耐磨耗性は若干劣る結果となっているが、いずれもガラス床用途において求められる耐摩耗性の基準は充分に満たしているものである。
また、表2に示されているように、試験体7(酸化ビスマス成分含有)に対する「EVAC独立気泡発泡体」からなる滑り片を使用した耐滑り性試験結果は、試験体7(本発明品)が試験体8(酸化鉛成分含有)に匹敵する極めて優れた耐滑り性(C.S.R.値)を示すこと、すなわち、実際の人間の歩行時に感じる優れた滑り防止性を有することを示している。
なお、床材としての用途においては、耐滑り性のC.S.R.値は、0.45C.S.R.以上が望ましいとされている。
From the results shown in Table 1, the abrasion resistance of a large number of glass protrusions formed by fusing and fixing to the surface of a plate glass indicates that the specimen 1 (containing a zinc oxide component) is prepared using the same adhesive A. ), Specimen 3 (containing bismuth oxide component) is slightly inferior in abrasion resistance to Specimen 5 (existing product containing lead oxide component), and is also produced using Adhesive B The body 2 (containing zinc oxide component) and the test body 4 (containing bismuth oxide component) are slightly inferior to the test body 6 (existing product containing lead oxide component), but both The standards of abrasion resistance required in glass floor applications are sufficiently satisfied.
Further, as shown in Table 2, the result of the slip resistance test using the sliding piece made of “EVAC closed cell foam” with respect to the specimen 7 (containing bismuth oxide component) is the specimen 7 (the product of the present invention). ) Exhibits extremely excellent slip resistance (CSR value) comparable to that of test body 8 (containing lead oxide component), that is, it has excellent slip resistance that is felt during actual human walking. Is shown.
For use as a flooring material, the slip resistant C.I. S. R. The value is 0.45 C.I. S. R. The above is considered desirable.

本発明の多数のガラス製凸部を有する板ガラスは、表面に耐摩耗性に優れた多数のガラス製凸部により人間の歩行感覚で優れた滑り防止性を感じることができるので、各種商業施設、展示会場、マンションのエントランス部に意匠性に優れた透光性の床を構築するためのノンスリップガラス床材として極めて有用である。
さらに、環境汚染原因となる成分を含まないことから、埋め立て等による廃棄処理が可能であるし、ガラス原料として再利用することも可能である。
Since the plate glass having a large number of glass convex portions of the present invention can feel excellent anti-slip properties in human walking sensation due to the large number of glass convex portions having excellent wear resistance on the surface, various commercial facilities, It is extremely useful as a non-slip glass flooring for building a translucent floor with excellent design at the exhibition hall and apartment entrance.
Furthermore, since it does not contain components that cause environmental pollution, it can be disposed of by landfill or reused as a glass raw material.

Claims (8)

板ガラスの少なくとも一方の表面に、酸化ビスマス成分を含有する硼珪酸系ガラス及び酸化亜鉛成分を含有する硼珪酸系ガラスから選ばれるガラス微粒子が集合した小塊状部を多数付着配置し、該小塊状部を焼成処理により板ガラス表面に融着固定して形成されている多数のガラス製凸部を有する板ガラス。   A large number of small lump portions in which glass fine particles selected from a borosilicate glass containing a bismuth oxide component and a borosilicate glass containing a zinc oxide component are gathered are arranged and attached to at least one surface of the plate glass. A plate glass having a large number of glass protrusions formed by fusing and fixing the material to the surface of the plate glass by baking. 前記多数のガラス製凸部は、平均高さ0.3mm〜1.0mm、平均直径1.0mm〜2.0mm、及び凸部間の間隔2.0mm〜8.0mmで板ガラス表面に形成されていることを特徴とする請求項1記載の多数のガラス製凸部を有する板ガラス。   The plurality of glass convex portions are formed on the surface of the plate glass with an average height of 0.3 mm to 1.0 mm, an average diameter of 1.0 mm to 2.0 mm, and a distance between the convex portions of 2.0 mm to 8.0 mm. The plate glass having a large number of glass protrusions according to claim 1. 前記ガラス製凸部は、板ガラス表面に千鳥模様状又は市松模様状に配置されていることを特徴とする請求項1又は2に記載の多数のガラス製凸部を有する板ガラス。   The said glass convex part is arrange | positioned on the plate glass surface in zigzag pattern shape or checkered pattern shape, The plate glass which has many glass convex parts of Claim 1 or 2 characterized by the above-mentioned. 前記板ガラスが、普通板ガラスである請求項1〜3のいずれか1項に記載の多数のガラス製凸部を有する板ガラス。   The said plate glass is a normal plate glass, The plate glass which has many glass convex parts of any one of Claims 1-3. 前記請求項1〜4のいずれか1項に記載の多数のガラス製凸部を有する板ガラスからなるガラス床材。   The glass flooring which consists of plate glass which has many glass convex parts of any one of the said Claims 1-4. 前記請求項1〜4のいずれかに記載の多数のガラス製凸部を有する板ガラスを製造する方法であって、板ガラス表面に、ガラス微粒子を小塊状に付着させる付着剤を所定パターンで塗布してガラス微粒子付着部を形成し、該ガラス微粒子付着部にビスマス成分を含有する硼珪酸系ガラス及び亜鉛成分を含有する硼珪酸系ガラスから選ばれる平均粒径100μm〜500μmのガラス微粒子を付着させてガラス微粒子小塊状部を形成し、該ガラス微粒子小塊状部が形成されている板ガラスを、ガラス微粒子の軟化点以上の温度で焼成処理して該ガラス微粒子小塊状部を板ガラス表面に融着させ、次いで、該焼成処理した板ガラスを冷却処理してガラス微粒子小塊状部を板ガラス表面に固定することを特徴とする、多数のガラス製凸部を有する板ガラスの製造方法。   A method for producing a plate glass having a large number of glass protrusions according to any one of claims 1 to 4, wherein an adhesive for adhering glass fine particles in a small lump shape is applied to the plate glass surface in a predetermined pattern. A glass fine particle adhering portion is formed, and glass fine particles having an average particle size of 100 μm to 500 μm selected from a borosilicate glass containing a bismuth component and a borosilicate glass containing a zinc component are adhered to the glass fine particle adhering portion. Forming the fine particle agglomerated portion, firing the plate glass on which the glass fine particle agglomerated portion is formed at a temperature equal to or higher than the softening point of the glass fine particles, and fusing the glass fine particle agglomerated portion to the surface of the plate glass, A plate gas having a large number of glass projections, characterized in that the fired plate glass is cooled to fix the glass fine particles to the surface of the plate glass. A manufacturing method for laths. 前記焼成処理及びが冷却処理が、前記板ガラスの軟化点温度で焼成処理した後、空気の吹きつけにより板ガラスを均一に急冷する処理であることを特徴とする、請求項6記載の多数のガラス製凸部を有する板ガラスの製造方法。   The said baking process and a cooling process are the processes which carry out the baking process by the softening point temperature of the said sheet glass, and rapidly quench the sheet glass by air blowing, The many glass products of Claim 6 characterized by the above-mentioned. The manufacturing method of the plate glass which has a convex part. 前記ガラス微粒子は、平均粒径250〜350μmのガラス微粒子であることを特徴とする請求項6又は7に記載の多数のガラス製凸部を有する板ガラスの製造方法。   The method for producing a plate glass having a large number of glass convex portions according to claim 6 or 7, wherein the glass fine particles are glass fine particles having an average particle diameter of 250 to 350 µm.
JP2008178481A 2008-07-08 2008-07-08 Plate glass Pending JP2010018458A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012084820A (en) * 2010-10-08 2012-04-26 Hino Jushi:Kk Structure of solar cell panel with decorative display for advertisement
CN106836717A (en) * 2017-02-23 2017-06-13 上海博历机械科技有限公司 The environmentally friendly glass floor that a kind of discarded glass is made
WO2023238831A1 (en) * 2022-06-09 2023-12-14 Agc株式会社 Paving photovoltaic module, solar photovoltaic power generation paving block, method for manufacturing paving photovoltaic module, glass plate, and laminated glass for glass floor

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JPH06271335A (en) * 1993-03-18 1994-09-27 Okuno Chem Ind Co Ltd Decorative plate glass for building
JPH08253347A (en) * 1995-03-14 1996-10-01 Nippon Parkerizing Co Ltd Plate glass having projected material and its production
JPH11343141A (en) * 1998-04-27 1999-12-14 Cerdec Ag Keramische Farben Low melting lead-free glass-and enamel composition having high bismuth content
JP2009042499A (en) * 2007-08-09 2009-02-26 Central Glass Co Ltd Light diffusive thin film formed on translucent substrate, and method of manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06271335A (en) * 1993-03-18 1994-09-27 Okuno Chem Ind Co Ltd Decorative plate glass for building
JPH08253347A (en) * 1995-03-14 1996-10-01 Nippon Parkerizing Co Ltd Plate glass having projected material and its production
JPH11343141A (en) * 1998-04-27 1999-12-14 Cerdec Ag Keramische Farben Low melting lead-free glass-and enamel composition having high bismuth content
JP2009042499A (en) * 2007-08-09 2009-02-26 Central Glass Co Ltd Light diffusive thin film formed on translucent substrate, and method of manufacturing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012084820A (en) * 2010-10-08 2012-04-26 Hino Jushi:Kk Structure of solar cell panel with decorative display for advertisement
CN106836717A (en) * 2017-02-23 2017-06-13 上海博历机械科技有限公司 The environmentally friendly glass floor that a kind of discarded glass is made
CN106836717B (en) * 2017-02-23 2019-01-15 南通向阳光学元件有限公司 Environmental protection glass floor made of a kind of post-consumer glass
WO2023238831A1 (en) * 2022-06-09 2023-12-14 Agc株式会社 Paving photovoltaic module, solar photovoltaic power generation paving block, method for manufacturing paving photovoltaic module, glass plate, and laminated glass for glass floor

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