Glass plate having antibacterial film, method of producing the same and article having the glass plate
Abstract
It is intended to provide a glass plate having an antibacterial film which is equipped with an antibacterial film scarcely showing an interference color due to reflection. It is also intended to provide a method of producing a glass plate, which is a large-sized glass plate having an antibacterial film formed thereon and shows an improved mechanical durability of the antibacterial film, in a large amount at a low cost. This glass plate having an antibacterial film is produced by forming an antibacterial film having a film thickness of 2 nm or more but not more than 100 nm on a glass plate either directly or via an undercoat film. The antibacterial film is formed by the heat decomposition method which comprises supplying a film-forming gas onto the surface of a glass plate, which has been maintained at such a temperature as allowing the decomposition of the film-forming gas or higher, or onto the surface of a glass ribbon in the course of producing a glass plate.

Term
No projected expiry on record.
- Priority
- Filed
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- Today
24 claims: 23 independent, 1 dependent
- 1請求の範囲 [1] ガラス板上に、直接又は下地膜を介した抗菌膜を備える抗菌膜付きガラス板であつ て、前記抗菌膜の膜厚が 2nm以上 lOOnm以下である抗菌膜付きガラス板。
- 2[2] 前記抗菌膜の抗菌性能が、抗菌製品技術協議会が定める光照射フィルム密着法 に基づき 10 μ WZcm 2 の光量の紫外光を 24時間照射した後の黄色ブドウ球菌また は大腸菌の菌数を、光照射前の菌数に対して 1Z100以下に減少させる抗菌性能で ある請求項 1に記載の抗菌膜付きガラス板。
- 3[3] 前記抗菌膜の抗菌性能が、抗菌製品技術協議会が定める光照射フィルム密着法 に基づき 10 μ WZcm 2 の光量の紫外光を 8時間照射した後の黄色ブドウ球菌または 大腸菌の菌数を、光照射前の菌数に対して 1Z100以下に減少させる抗菌性能であ る請求項 1に記載の抗菌膜付きガラス板。
- 4[4] 前記抗菌膜の抗菌性能が、 lOOOLxの光量の白色蛍光灯を 24時間照射した後の 黄色ブドウ球菌または大腸菌の菌数を、光照射前の菌数に対して 1Z100以下に減 少させる抗菌性能である請求項 1に記載の抗菌膜付きガラス板。
- 5[5] 前記抗菌膜の抗菌性能が、 500Lxの光量の白色蛍光灯を 24時間照射した後の 黄色ブドウ球菌または大腸菌の菌数を、光照射前の菌数に対して 1Z100以下に減 少させる抗菌性能である請求項 1に記載の抗菌膜付きガラス板。
- 6[6] 前記抗菌膜の抗菌性能が、 250Lxの光量の白色蛍光灯を 24時間照射した後の 黄色ブドウ球菌または大腸菌の菌数を、光照射前の菌数に対して 1Z100以下に減 少させる抗菌性能である請求項 1に記載の抗菌膜付きガラス板。
- 7[7] 前記抗菌性能が、黄色ブドウ球菌又は大腸菌の菌数を、 1Z10000以下に減少さ せる抗菌性能である請求項 1に記載の抗菌膜付きガラス板。
- 8[8] 前記抗菌膜の膜厚が、 5nm以上 80nm以下である請求項 1に記載の抗菌膜付きガ ラス板。
- 9[9] 前記抗菌膜の膜厚が、 25nmを超え 70nm未満である請求項 1に記載の抗菌膜付 きガラス板。
- 10[10] 前記抗菌膜の主成分が、酸化チタン、窒素ドープ酸ィ匕チタン、酸窒化チタンおよび 窒化チタン力 なる群力 選択される 1種である請求項 1に記載の抗菌膜付きガラス 板。
- 11[11] 前記抗菌膜の主成分が、窒素ドープ酸ィ匕チタンである請求項 10に記載の抗菌膜 付きガラス板。
- 12[12] 請求項 1に記載の抗菌膜付きガラス板の製造方法であって、前記抗菌膜を熱分解 法により形成する抗菌膜付きガラス板の製造方法。
- 13[13] 前記抗菌膜を、被膜形成ガスが分解する温度以上に保持されたガラス板表面また はガラス板製造工程におけるガラスリボン表面に、被膜形成ガスを供給することによ つて形成する請求項 12記載の抗菌膜付きガラス板の製造方法。
- 14[14] 前記被膜形成ガスが、チタン含有化合物、窒素含有化合物および酸化性ガスを含 む請求項 13に記載の抗菌膜付きガラス板の製造方法。
- 15[15] 前記被膜形成ガスが、前記チタン含有ィ匕合物と前記窒素含有ィ匕合物との化学反 応を抑制する反応抑制剤をさらに含む請求項 14に記載の抗菌膜付きガラス板の製 造方法。
- 16[16] 前記窒素含有ィ匕合物が、アンモニアである請求項 14に記載の抗菌膜付きガラス板 の製造方法。
- 17[17] 前記酸ィ匕性ガスが、酸素である請求項 14に記載の抗菌膜付きガラス板の製造方 法。
- 18[18] 前記被覆形成ガス中における、窒素含有化合物に対する酸化性ガスのモル比が、 0. 05以上である請求項 14に記載の抗菌膜付きガラス板の製造方法。
- 19[19] 前記反応抑制剤が、塩ィ匕水素である請求項 15に記載の抗菌膜付きガラス板の製 造方法。
- 20[20] 前記熱分解法が、フロート法によるガラスの製造工程における、熔融状態のガラスリ ボンを板状に成形するためのバス内で行う CVD法である請求項 12に記載の抗菌膜 付きガラス板の製造方法。
- 21[21] 請求項 1に記載の抗菌膜付きガラス板を有する、建築物のガラス窓。
- 22[22] 請求項 1に記載の抗菌膜付きガラス板を有する、建築物内のガラス間仕切り。
- 23[23] 請求項 1に記載の抗菌膜付きガラス板を有する、家具。
- 24[24] 請求項 1に記載の抗菌膜付きガラス板を有する、輸送機械のガラス窓。 [25] 請求項 1に記載の抗菌膜付きガラス板を有する、情報表示用ガラスパネル。
Independent claims24
146 paragraphs in 1 section, as filed
Specification
Article which has a glass board with an antibacterial film, its manufacturing method, and its glass board Technical field
[0001] The present invention relates to a glass board with an antibacterial film, and its manufacturing method, and relates to the article which has the glass board further.
Background art
[0002] the needs for a comfortable life space -- very -- high Extremely hot -- the bottom of humid environment -- bacteria -- fine -- Breeding of a living thing etc. becomes active. such bacteria, a microorganism, etc. have a bad influence in a human body In order to check breeding of many These effectively, use is possible as members forming of a life space. The manufacturing method of a Noh tabular antibacterial member and the member concerned which can be mass-produced [ that it is cheap and ] asks. , -- Being done .
[0003] For example, provisional publication of a patent 2001 -- The coat by * fat constituent which contains acid Y titanium etc. in No. 72438 gazette as antibacterial medicine is formed, and the antibacterial processing board glass material which can demonstrate an antibacterial effect is indicated. ing. It is at the antibacterial Completion of work board glass material concerned, carrying out and carrying out power, Roll coating, dip A coating, spray coating, electrostatic coating, electrodeposition coating, a wire coat, a flow coat, Doc Since a coat is formed by one selected from Turquoises etc. of methods, Coat Thickness becomes 10*50 / zeta piiota, and a micron unit, and is Formation uniformly about a film still thinner than these. A film was not able to be carried out. In order to give antibacterial properties to a member in this specification The film formed in the member surface is called "an antibacterial film." As an antibacterial film, they are silver, zinc, copper, etc. The charge of a metallic material and photocatalyst materials, such as titanium oxide, are used.
[0004] Since photocatalyst activity is excellent in high Tooth chemical stability, titanium oxide is widely used as a photocatalyst material. If titanium oxide is irradiated with ultraviolet rays, an electron and an electron hole will generate.
A photoinduced degradation reaction and an optical induction hydrophilic reaction come to be shown. these reactions were used -- anti- -- The bacillus tile etc. are already commercialized.
[0005] The art in which International Publication 94ZNo. 11092 pamphlet was made to sinter powdered acid Y titanium on a glass board is indicated. This which will obtain a tabular antibacterial member if the art concerned is used Although it can do, when coating particle-like acid Y titanium on a glass board, it is acid End. Tongue particles condense and the particle diameter of acid Y titanium becomes large unescapable. Particle diameter of acid Y titanium Intermediary Cause in which the film thickness of the antibacterial film containing acid Y titanium is large if it becomes large. as a result -- anti- -- The reflectance of the bacillus film became high and there was a problem that a reflective interference color comes to be conspicuous.
[0006] moreover -- since an antibacterial film is formed in the method of International Publication 94ZNo. 11092 pamphlet using powdered titanium oxide -- the mechanical endurance of an antibacterial film -- low -- There are and a Ivy problem. It is necessary to perform it being not only difficult for the glass substrate of a large area to form an antibacterial film uniformly but calcination processing, and coating processing, there are many manufacturing processes, and they are a Noodle result and manufacture Co. The problem which becomes high also had a strike and it was unsuitable for continuation mass production of the glass board of a large area.
[0007] A manufacturing method of the nitrogen dope acid Y titanium membrane furthermore indicated by International Publication 01/No. 10552 pamphlet, Invention about the manufacturing method of the glass board which formed the antibacterial film on the surface Atmosphere which contains ammonia and nitrogen after being and forming a TiO film by the sputtering method
2
It is the method of coming out and carrying out calcination processing. while carrying out and carrying out power -- International Publication 01ZNo. 10552 pamphlet In a method, the large-scale vacuum device of what can obtain a tabular antibacterial member is required. it is -- as for a power or To case, a film deposition system has much immense expense. The necessity of performing calcination processing There and a manufacturing process increased and there was a problem to which a manufacturing cost becomes high. Thus, the manufacturing method of the nitrogen dope acid Y titanium membrane indicated by International Publication 01/No. 10552 pamphlet is large. It was unsuitable for continuation mass production of the glass board of area.
The indication of an invention
[0008] The present invention is completed paying attention to the above problems. If it is the object It is in providing the glass board with an antibacterial film which a reflective interference color arises and is provided with a Hata antibacterial-properties film at the time. it is the glass board of a large area with which the antibacterial film was formed, and an antibacterial film is mechanical -- -proof -- providing the method of manufacturing cheaply the glass board with which Kumi was improved in large quantities -- the object and To do.
[0009] the glass board with an antibacterial film of the present invention is a glass board with an antibacterial film provided with the antibacterial film which passed the direct or ground film on the glass board -- the film thickness of the above-mentioned antibacterial film -- below 2-nm or more lOOnm it is .
[0010] The antibacterial performance of the above-mentioned antibacterial film of good Up , embodiment Well , and The is Society of Industrial Technology for Antimicrobial Articles. It is based on light irradiation film contact printing to define, and is 10 mu WZcm.<sup>2</sup>It is 24-hour Looking about the purple outdoor daylight of Light intensity. It is the antibacterial performance which decreases the number of microorganism of the Staphylococcus aureus after putting, or coliform bacillus to zero or less lZio to the number of microorganism in front of light irradiation.
[0011] In a desirable embodiment, the antibacterial performance of the above-mentioned antibacterial film is Society of Industrial Technology for Antimicrobial Articles. It is based on light irradiation film contact printing to define, and is 10 mu WZcm.<sup>2</sup>It is 8-hour Looking about the purple outdoor daylight of Light intensity. It is the number of microorganism of the Staphylococcus aureus after putting, or coliform bacillus to the number of microorganism in front of light irradiation 1Z10 It is the antibacterial performance which decreases zero or less.
[0012] Good Up , embodiment Well , and The, The antibacterial performance of the above-mentioned antibacterial film is Society of Industrial Technology for Antimicrobial Articles. It is based on light irradiation film contact printing to define, and is 24-hour Looking about the white fluorescent light of the light volume of lOOOLx. It is the number of microorganism of the Staphylococcus aureus after putting, or coliform bacillus to the number of microorganism in front of light irradiation 1Z10 It is the antibacterial performance which decreases zero or less.
[0013] Good Up , embodiment Well , and The, The antibacterial performance of the above-mentioned antibacterial film is Society of Industrial Technology for Antimicrobial Articles. It irradiates with the white fluorescent light of the light volume of 500Lx for 24 hours based on light irradiation film contact printing to define. It is the number of microorganism of the Staphylococcus aureus after carrying out, or coliform bacillus to the number of microorganism in front of light irradiation 1Z100 It is the antibacterial performance decreased below.
[0014] Good Up , embodiment Well , and The, The antibacterial performance of the above-mentioned antibacterial film is Society of Industrial Technology for Antimicrobial Articles. It irradiates with the white fluorescent light of the light volume of 250Lx for 24 hours based on light irradiation film contact printing to define. It is the number of microorganism of the Staphylococcus aureus after carrying out, or coliform bacillus to the number of microorganism in front of light irradiation 1Z100 It is the antibacterial performance decreased below.
[0015] In a desirable embodiment, the above-mentioned antibacterial performance is the antibacterial performance which decreases the number of microorganism of Staphylococcus aureus or coliform bacillus or less to 1Z10000.
[0016] In a desirable embodiment, the film thickness of the above-mentioned antibacterial film is 5 nm or more and 80 nm or less, the film thickness of the above-mentioned antibacterial film exceeds 25 nm in and a still more desirable embodiment, and it is a 70-nm sheep. It is Full.
[0017] In a desirable embodiment, the main ingredients of the above-mentioned antibacterial film are titanium oxide, nitrogen dope titanium oxide, a titanium oxynitride, and titanium nitride power. Group force It is one sort chosen.
[0018] In a desirable embodiment, the main ingredients of the above-mentioned antibacterial film are nitrogen dope titanium oxide.
[0019] According to another aspect of affairs of the present invention, the manufacturing method of a glass board with an antibacterial film is provided. !Go forms the above-mentioned antibacterial film in this manufacturing method by a thermal decomposition method.
[0020] the glass board surface where good Up and embodiment Please were held more than the temperature into which tunic formation gas disassembles the above-mentioned antibacterial film, or the glass ribbon surface in a glass board manufacturing process -- -ed -- It forms by supplying film formation gas.
[0021] In a desirable embodiment, the above-mentioned tunic formation gas contains a titanium content compound, a nitrogen content compound, and a oxidizing gas.
[0022] Good Up and embodiment Please further contain the reaction inhibitor in which the above-mentioned tunic formation gas inhibits the chemical reaction of the above-mentioned titanium content compound and the above-mentioned nitrogen content compound.
[0023] In a desirable embodiment, the above-mentioned nitrogen content compound is ammonia.
[0024] The above-mentioned acid Integrity gas of good Up , embodiment Well , and The is oxygen.
[0025] good -- better -- 0.05 or more molar ratio power of acid Integrity gas, such as the above-mentioned oxygen to nitrogen content Composite item, such as the above-mentioned [ , embodiment Well , and The ] ammonia in the above-mentioned covering formation gas It is.
[0026] The above-mentioned reaction inhibitor of good Up , embodiment Well , and The is salt Hydrogen.
[0027] A for the describing [ above ] thermal decomposition method to fabricate the glass ribbon of a fusion state which can be set like manufacture A of the glass by a float process tabular in a desirable embodiment It carries out within A. CVD method it is .
[0028] According to another aspect of affairs of the present invention, the glass window of a building is provided. They have a glass board with the above-mentioned antibacterial-properties film. For example, the glass window in habitation space or medical facilities, indoor glass, etc. are provided.
[0029] According to another aspect of affairs of the present invention, the glass partition in a building is provided. They have a glass board with the above-mentioned antibacterial-properties film.
[0030] According to another aspect of affairs of the present invention, furniture is provided. They have a glass board with the above-mentioned antibacterial-properties film. For example, a glass table, a glass shelf, a glass showcase, or a glass foodstuffs case is provided.
[0031] According to another aspect of affairs of the present invention, the glass window of transportation machinery is provided. They have a glass board with the above-mentioned antibacterial-properties film. For example, the glass window of a car, a vessel, or an airplane, etc. are Offer. It is offered. [0032] According to another aspect of affairs of the present invention, the glass panel for an information display is provided. Them It has a glass board with the above-mentioned antibacterial-properties film. for example, a display panel -- touch panel When is provided.
[0033] According to the above-mentioned present invention, set the thickness of an antibacterial film as a range called below 2-nm or more lOOnm. Since it carries out, even if it uses the titanium compound which has quantity ! and a refractive index comparatively, it is generating of a reflective interference color. The controlled glass board with an antibacterial film provided with an antibacterial film is provided.
[0034] According to the present invention, it is Glass ribo of , The, and a fusion state to the manufacturing process of a float glass. A thermal decomposition method is performed in the bus for fabricating A tabular, How to manufacture cheaply the glass board with an antibacterial film with which it is a large area and the mechanical endurance of the antibacterial film was improved in large quantities It is provided.
[0035] According to the present invention, the article which has glass with an antibacterial film is provided.
Brief explanation of the drawings
[0036] [-- figure 1] -- it is a sectional view showing an example of the glass board with an antibacterial film of the present invention -- a figure -- 1 (a) -- antibacterial film the example currently directly formed on the glass board -- a figure -- 1 (b) shows the example to which the ground film intervenes between a glass board and an antibacterial film.
[figure 2] On-line It is a schematic illustration of the device used for a CVD method.
The best form for inventing
[0037] Hereinafter, power of explaining while referring to drawings for the desirable embodiment of the present invention The present invention is not limited to these embodiments.
[0038] The term "antibacterial properties" controls the multiplication of bacteria or a microorganism adhering to an object, and means that the viable cell count of bacteria or a microorganism decreases with progress of time. [ as used herein ] The term "main ingredients" means the ingredient which occupies 50 % of the weight or more. it was determined as the term "light irradiation film contact printing which an antibacterial product technology conference defines" by Society of Industrial Technology for Antimicrobial Articles the case where mean light irradiation film contact printing (version in the 2003 fiscal year), and it does not annotate in particular -- being concerned -- dense Antibacterial performance is evaluated based on the conditions provided in the arrival method. This measuring method is this appearance. It is JIS R1702 after application of the basic application of A request. : It was one of the most general measuring methods for evaluating and the antibacterial characteristic of a product for the person skilled in the art until 2006 was published.
[0039] a figure -- 1 is a cross section explaining two forms of glass board 4 with an antibacterial film by the present invention. the glass board by the present invention -- as the first form -- a figure -- 1 it is shown in (a) -- as -- glass board 1 top Antibacterial film 2 is formed.
[0040] moreover -- as the second form -- a figure -- 1 It is preferred to constitute so that ground film 3 of one or more layers may be inserted between glass board 1 and antibacterial film 2 as shown in (b). This ground film is an alkali barrier. It is desirable when it has roles, such as a function. With the glass board with which glass board 1 contains an alkali component If an alkali component moves to antibacterial film 2 into the membrane formation process of antibacterial film 2, for example in a certain case, the crystallinity of an antibacterial film will worsen and antibacterial performance will deteriorate. In that case, it is a style so that a ground film may be inserted. If it accomplishes, the bad influence by an alkali component moving can be prevented.
[0041] If the film thickness of a [range] antibacterial-properties film with preferred film thickness is large, a reflective interference color will be shown and appearance quality will be reduced remarkably. On the other hand, if film thickness is too small, the antibacterial performance of that by which a reflective interference color is controlled will fall. This a sake -- as the film thickness of an antibacterial film -- the range below 2 or more nm lOOnm -- Desire -- better -- Tooth and also more than 5 nm, and the range of 80 nm or less are preferred. It exceeds 20 nm and the range below 70 nm is most. It is desirable.
[0042] [Antibacterial performance]
Philharmonic light irradiation whom Society of Industrial Technology for Antimicrobial Articles sets as antibacterial performance of the antibacterial film of the present invention They are , The, and 10 mu WZcm to Beam contact printing (version in the 2003 fiscal year).<sup>2</sup>irradiating with the purple outdoor daylight of Light intensity for 24 hours receiving the number of microorganism in front of light irradiation in the number of microorganism of the Staphylococcus aureus after It was, or coliform bacillus -- 1Z100 -- with -- The antibacterial performance decreased downward is preferred. More preferably they are 10/zWZcm.<sup>2</sup>Purple outdoor daylight of Light intensity About the number of microorganism of the Staphylococcus aureus after glaring for 8 hours, or coliform bacillus, it is a pair to the number of microorganism in front of light irradiation. It is the antibacterial performance which carries out and decreases 1Z100 or less. it sets to light irradiation film contact printing (version in the 2003 fiscal year) which Society of Industrial Technology for Antimicrobial Articles defines -- the number of microorganism of the Staphylococcus aureus after irradiating with the white fluorescent light of the light volume of lOOOLx for 24 hours, or coliform bacillus -- the number of microorganism in front of light irradiation -- an opposite -- The antibacterial performance which carries out and decreases 1Z100 or less is preferred. it is more desirable -- light volume of 500Lx the number of microorganism of the Staphylococcus aureus after irradiating with a white fluorescent light for 24 hours, or coliform bacillus -- Mitsuteru It is the antibacterial performance which shoots and decreases 1Z100 or less to front number of microorganism. The Staphylococcus aureus after irradiating with the white fluorescent light of the light volume of 25 OLx more preferably for 24 hours, or bacillus of coliform bacillus It is the antibacterial performance which decreases a number below to * zeta*omicron omicron to the number of microorganism in front of light irradiation. Antibacterial properties It compares with other physical-properties evaluations from it being the examination which uses a microorganism, and ability evaluation is an evaluation trial. Experimental error becomes large. If the number of microorganism after light irradiation is 1Z100 or less (99% or more of rate of disinfection), in an error span, it can be said that there is an advantageous effect dropping off concerning antibacterial performance clearly. Association method It is [ in / on man-day book building-materials and a housing equipment industrial association and / an antibacterial quality assessment ] bacterial survival. If a rate is 1% or less (number of microorganism decreases or less to 1Z100), it is a phase of an antibacterial treatment article and a raw article. It is supposed that Different can judge intentionally. As a more desirable range, the number of microorganism after light irradiation is below 1 Ziooo. As a desirable range, the number of microorganism after light irradiation is 1Z10000 or less. It is.
[0043] The intensity of purple outdoor daylight and the illumination of a white fluorescent light with which it irradiates in an antibacterial quality assessment are Use. It is necessary to set up according to the situation by which for is carried out. The intensity of purple outdoor daylight, and illumination of a white fluorescent light It is represented at the following use places.
Purple outdoor daylight WZcm<sup>2</sup>- Separate about 1.5 m from the window containing sunlight in the interior of a room of -' daytime. Place.
Place of the height about [ the indoor floor which only the fluorescent light lOOOLx - - - fluorescent light turned on to ] lm Place. The intensity of the purple outdoor daylight in fluorescent light lOOOLx is 4/z WZcm.<sup>2</sup>Grade.
The indoor floor which only the fluorescent light 500Lx - - - fluorescent light turned on. The intensity of the purple outdoor daylight in fluorescent light 1000 Lx is 2/z WZcm.<sup>2</sup>Grade.
[0044] Although there is no restriction in particular about the bacillus decreased by the present invention, the present invention can be used to the following fungi. for example, the bacteria of gram positive bacteria (Staphylococcus aureus, a bacillus bacillus, etc.) or gram negative bacteria (coliform bacillus, a salmonella, etc.) -- or it molds and there are the eumycetes, such as a mushroom and yeast, other viruses, a protist, etc.
[0045] [Ingredient of an antibacterial film]
As the main ingredients of the antibacterial film of the present invention, they are titanium oxide, nitrogen dope acid Y titanium, and oxynitriding Chi. A tongue and titanium nitride power Group force It is good Up that it is one sort chosen. Main in these It is because the antibacterial performance is excellent in high Tooth chemical stability if it is an antibacterial film used as an ingredient, and is Ah. To.
[0046] It is good Up especially that the main ingredients are nitrogen dope acid Y titanium. since especially nitrogen dope titanium oxide is a photocatalyst material which answers visible Mitsushiro's light -- sunlight and a fluorescent light -- many -- It is desirable at the point that the light of a Containing rare To visible light range can be used.
[0047] [Materials]
(Materials of an antibacterial film)
It is required for the materials of the antibacterial film of the present invention to include at least one or more sorts of titanium content Composite item, at least one or more sorts of nitrogen content Figi, and at least one or more sorts of acid Hie gas.
[0048] As a titanium content compound, they are a titanium chloride and titanium Alkoxide titanium Chely Chew. Compound etc. are preferred. being [ these titanium content compounds / gas or a fluid ]-at normal temperature power a child -- better -- when it is a fluid at To and normal temperature, the one where the boiling point is lower is preferred. These desirable titanium content compounds can be evaporated only by heating as it is or a few, and can be used as the ingredient of material gas. The titanium content compound sublimated even if it is a solid at normal temperature and A Titanium content Composite item which can be dissolved in organic solvents, such as a record and toluene, can also be used. To.
[0049] As such titanium content Composite item, they are 4 salt Y titanium (TiCl) and Titanium ethoxy, for example.
4
Do (Ti (OCH)), titanium iso pro Xide (Ti (OCH)), titanium Normal butoxide (Ti)
2 5 4 3 7 4
(OC H) -- Titanium Acetate Acetonato (C HO) (Ti (CHO)) etc. can be illustrated
4 9 4 3 7 2 2 5 7 2 2
To. In particular, they are 4 salt Y titanium (TiCl) and titanium iso pro Xide (Ti (OC H)) or Chita.
4 3 7 4
Number butoxide (Ti (OCH)) , is used suitably.
4 9 4
[0050] As nitrogen content Composite item, they are ammonia (NH), amine, and hydrazine derivative I like it..
3
It can be illustrated that it is Suitable. since liquid Y is carried out easily and it is gas in normal temperature normal pressure, when ammonia compresses also in this -- the point that the introduction to material gas is easy -- good -- better -- Tooth -- cheap It is desirable at especially the point that can be obtained in large quantities. A Amin hydrazine derivative has high reactivity. It accumulates and the point that a quality film can be manufactured easily is excellent. a point expensive on the other hand -- short -- It is a place.
[0051] using oxygen (O) as acid Integrity gas -- good -- better -- Carbon dioxide (CO) and -- acid
2 Two Compounds containing oxygen, such as-izing carbon (CO) and vapor (H O), can be used. Water (H)
2 2
The equipment for evaporating fluid materials, when fluid materials, such as O) and ester, are used is Must. It is an important point and the amount of evaporation becomes unstable further easily. Gas materials with easy control of the amount of supply Using is preferred. Especially the thing for which oxygen is used is [ among these ] preferred. Air It can also use. When air is used as acid Integrity gas, the nitrogen (N) contained in the air can be made to act as a reaction diluent.
2
[0052] It is Ammonium, when ammonia is used as nitrogen content Composite item and oxygen is used as acid Integrity gas. It is preferred to make the molar ratio (O ZNH ratio) of oxygen to Ure or more into 0.05. Ammonium
2 3
By making the molar ratio of oxygen to Ure or more into 0.05, it is because membranous crystallinity can be raised. Generated re-combination of an electron and an electron hole is as happening by the defective part of a crystal. It thinks. Therefore, This which raises crystallinity, namely, reduces the defective part of a crystal The rate of an electron and a success re-combined can decrease and it can improve antibacterial properties.
[0053] It is preferred that the reaction inhibitor which inhibits the chemical reaction of a titanium content compound and a nitrogen content compound is further included in the materials of the antibacterial film of the present invention.
[0054] As an reaction inhibitor, it is good Up to use salt Hydrogen.
[0055] When titanium tetrachloride is used for a titanium content compound and ammonia is used for nitrogen content Composite item, gaseous phase reaction may advance by the attainment to the glass board of material gas. Advance of this gaseous phase reaction will produce a solid reaction product in material gas piping. This reaction generation Piping may blockade with a thing. This reaction product is a flow of material gas. To the glass board surface, it is conveyed, is taken into the film formed and is a pinhole etc. It becomes a cause of a fault. In order to prevent this gaseous phase reaction, hydrogen chloride is used as reaction control. To is preferred.
[0056] [Manufacturing method of a glass board with an antibacterial film]
Heat which drops off in that to which especially the manufacturing method of the above-mentioned antibacterial film is limited A CVD method or A The fine powder of the above-mentioned antibacterial film is adhered to a glass surface besides the thermal decomposition method the playing method etc. are publicly known. It carries out and the method of heating the whole glass after that and making the above-mentioned fine powder condense, etc. are illustrated. Up Use condensed fine powder as a core by a thermal decomposition method after making It was and this fine powder condense, and they are antibacterial properties. Crystal growth of the film may be carried out. Also in these, they are a thermal decomposition method, especially heat. According to the CVD method, it is an opportunity. High of Machine endurance and a film can be formed easily.
[0057] Membrane formation by a heat CVD method can be performed by heating the glass board of a predetermined size and spraying gas-like materials on the surface of the heated glass board, for example, using a glass board as a substrate.
[0058] Specifically, it can carry out as follows. A glass board is put on a mesh belt. Transport is carried out and the inside of a tunnel-like heating furnace is passed. A glass board is conveyed in a heating furnace and heated to the temperature which tunic formation gas decomposes (it abbreviates to "tunic formation gas decomposition temperature" hereafter.). When the glass board is heated by tunic formation gas decomposition temperature, it is inside of a heating furnace about material gas. It supplies. Material gas reacts with the heat of the surface of a glass board, and is an antibacterial action on a glass board. The antibacterial film which it has is formed.
[0059] As for tunic formation gas decomposition temperature, it is preferred that it is more than 500"[ from a viewpoint that high crystallinity is acquired and high membrane formation speed is obtained ] C. That is, it is preferred to form an antibacterial film in the surface of the glass board more than 500 degreeC. In the case of less than 500 degreeC, they are TiNCl, TiCl, etanueta, etc.
4 It is because the low-temperature output of 3 becomes easy to be made.
[0060] Heat It is preferred to use that a glass board is high temperature at the process from which , The, and glass Melt are fabricated in a CVD method by the glass board at the manufacturing process of a glass board, or the slow cooling process after being fabricated by the glass board. It is because a using- and special heating equipment Without thin film can be formed if material gas is supplied on a hot glass board. It is To in this way. A thin film can be formed in Leave and the glass board of a big area at high speed, and they are a building, vehicles, and A dice. The glass board with a thin film of the use which needs large areas, such as a play panel, can be manufactured. To. As mentioned above, the method of forming membranes to the hot glass board in the middle of a manufacturing process is Online. Inn It is called a CVD method.
[0061] ( CVD method in a bus)
In the glass board manufacturing process by a float process, the process fabricated by the glass Melt solution ゝ glass board mentioned above is performed in a fusion tin tub (it is called a float bus). Glass Melt dissolved at the fusion furnace (it is called A [ Flo - ] kiln) flows into a float bus. The glass Melt It is extended by the beltlike long board, without breaking off, and is called a glass ribbon.
[0062] On-line The method of performing a CVD method in a float bus is inside of a bus. It is called a CVD method. Inside of Noss There are the following strong points other than the advantage mentioned above in a CVD method. First, the inside of a float bus is having atmosphere controlled so that the atmosphere does not invade. Therefore, pinhole etc. Control of a fault is possible. The temperature of the glass ribbon in a float bus is very. It is high temperature. Power in which the temperature is dependent on Thread formation of a glass ribbon The usual soda rye Musily In the case of Kate glass, it is the range of 650*1150 degreeC, for example.
[0063] If it is such a temperature range, the crystallinity of the thin film which has antibacterial performance can be raised, and antibacterial performance can be improved. Since reactivity with sufficient material gas is shown, even if it does not reduce the bearer rate of a glass ribbon, it has the antibacterial performance of thickness sufficient on the glass ribbon. A thin film can be easily formed now. As a result, since improvement in productivity can be expected, they are antibacterial properties. It becomes possible to manufacture a glass board with a film cheaply in large quantities.
[0064] in a float process -- a glass ribbon top -- inside of a bus one form of the device for forming membranes with a CVD method -- a figure -- it is shown in 2. Figure As shown in 2, with this device, it is float kiln 11 to float bus 1. It flows out in two, the surface power of glass ribbon 10 which moves beltlike in fusion tin 15 top also separates prescribed distance, and coater 16 of the number of appointed numbers is arranged in the float bus. a figure -- 2 -- three coaters 16a, 16b, Power by which 16c is shown The number of coaters is the design of film composition etc. It can design appropriately. Materials of the antibacterial film which has an antibacterial action from such coaters, and a ground film It is supplied in the state of gas, and each thin film is continuously formed on glass ribbon 10. If and a plurality of coaters are used, a thin film can be laminated on glass ribbon 10. Ga Arrange the temperature of Las ribbon in a float bus so that it may become prescribed temperature just before coater 16. It is adjusted by the heater and Kuula (illustration abbreviation) as whom it acted. Glass ribo in which the thin film was formed A 10 can be pulled up with roller 17 -- rare (slow cooling kiln) -- it is sent into 13. Les the general-purpose cutting device with which the glass board by which slow cooling was carried out by A 13 omits illustration -- a predetermined size -- coming It is cut to the glass board of To.
[0065] ( CVD method in rare)
It is on-line as mentioned above. A CVD method can also be performed at the slow cooling process (called Raa) after being fabricated by the glass board. In this case, introduction of material gas is rare (slow cooling kiln). It is carried out inside an entrance and Z, or rare. Hereinafter, it is inside of rare about this method. CVD method It calls. The glass ribbon a rare entrance or near [ in rare ] the rare entrance is compared in a bus. Although it is Low temperature, it has sufficient high temperature for a membrane formation reaction. Inside of rare With a CVD method, they are and A. Inside of A Unlike a CVD method, there are the following features. First, inside of a bus Field unsuitable for a CVD method Charge, for example, materials that reaction velocity is too quick at the glass ribbon temperature of the CVD method in a bus, Even if it is materials which have the concern which has the influence which is not preferred on a float bus, it adopts. It can carry out. Applying to a glass board manufacturing process without a float bus It can do. applying to the glass board manufacturing process for example, by the roll-out method -- an antibacterial action -- an owner -- Template glass, the wired sheet glass, and the glass containing a line in which the antibacterial film to carry out was formed can be manufactured. To.
EXAMPLE
[0066] Hereinafter, the present invention is not restricted by the following examples although an example explains the present invention still in detail.
[0067] (Example 1*12, a comparative example)
the nonalkali glass board of 0.7 mm thickness is cut so that one side may become a square which is 10 cm -- it was made to dry after washing To one surface of this glass board, it is conveyance of a normal pressure heat CVD device. A furnace is used and it is normal pressure heat. Nitrogen dope acid Y titanium membrane was formed with the CVD method. Are concrete.
It is as follows.
[0068] which put the above-mentioned glass board on the mesh belt, conveyed the inside of the above-mentioned furnace, and heated the glass board. In the field in the furnace at which the temperature of a glass board reaches 850 degrees of abbreviation C, nitrogen dope acid Y titanium membrane was formed by supplying material gas to the surface of a glass board. In this material gas, it is hydrogen chloride as titanium tetrachloride (TiCl), oxygen (O), ammonia (NH), and an reaction inhibitor.
4 2 3
(HC1) was adopted and the gas diluted with nitrogen gas to predetermined concentration was used. the concentration of material gas -- By calling and adjusting a bearer rate, nitrogen dope acid Y titanium membrane was formed.
[0069] (Example 13*14)
The device shown in Drawing 2 is used and it is inside of a bus. A thin film is formed in the glass ribbon surface with a CVD method. It was. Specifically, it is as follows.
[0070] Fuse by float kiln and it is temperature 1150* : About glass Melt controlled to L 100"C, it is a float bus. It was made to flow. In a float bus, glass Melt is fabricated to a glass ribbon, being cooled. It was carried out. The glass ribbon was fabricated so that thickness might be set to 4. Omm. On the glass ribbon, as a ground film, with the coater (inside 16a of Drawing 2) of The 1, the SiO film was formed so that it might become the thickness of 50 nm.
2
. Then, from the coater (inside 16b of Drawing 2) of The 2, material gas was sprayed and the thin film was formed. [0071] In Example 13, they are 4 salt Y titanium (TiCl) and acetic acid Ethyl (C HO) in material gas.
4 4 8
It adopted and used the gas diluted with nitrogen gas to predetermined concentration. the concentration of material gas -- and
2
The titanium oxide film was formed by adjusting a bearer rate.
[0072] In Example 14, the nitrogen dope titanium oxide film was formed using the same material gas as Example 1*12 and a comparative example.
[0073] (Film thickness of an antibacterial film)
The section of the glass board in which the thin film was formed is observed with a scanning electron microscope (SEM). It measured.
[0074] (Interference color)
The existence of the interference color was judged by visual observation.
[0075] (Antibacterial performance)
To light irradiation film contact printing as which Society of Industrial Technology for Antimicrobial Articles determines the antibacterial characteristic of the obtained film It evaluated.
[0076] (Antibacterial system performance testing 1)
It is based on light irradiation film contact printing which the above and Society of Industrial Technology for Antimicrobial Articles define, Black rye The ultraviolet-rays intensity measured with the ultraviolet-rays intensity plan (UVR made from TOPCON -- 2, light sensing portion UD -- 36) is 10 WZcm using a A fluorescence lamp (Toshiba Lighting & Technology FL20S'BLB'JET 20W).<sup>2</sup>When -- To -- it adjusted like and made it irradiate with ultraviolet rays under conditions with a humidity [ 95% of ], and a temperature [ C ] of 25 degrees for 24 hours the evaluation which used yellow grape Bacterial species (Staphylococcus aureus NBRC12732) for the test organism -- real -- It gave. About Examples 3 and 5 and 8*14, evaluation which used coliform bacillus (Escherichiacoli N BRC3972) for the test organism was also carried out.
[0077] Also about which thin film of Example 1*14 and a comparative example, it is 24 hours after an ultraviolet exposure. It is decreasing to the number of Staphylococcus aurei, and 1Z100 or less, and has good antibacterial properties. In Examples 3 and 5 and the thin film of 8*14, it is the number of the coliform bacillus 24 hours after an ultraviolet exposure. It was decreasing or less to 1Z100, and had good antibacterial properties.
[0078] (Antibacterial system performance testing 2)
They are 10/z WZcm about ultraviolet-rays intensity about Examples 3 and 5 and 8*14.<sup>2</sup>purple [ it adjusts so that it may become, and ] except for having made irradiation time of outside line into 8 hours -- the above (antibacterial system performance testing 1) -- the same -- an examination -- real -- It gave. Yellow grape Bacterial species (Staphylococcus aureus NBRC12732) was used for the test organism. It evaluated.
[0079] Also about Examples 3 and 5 and which thin film of 8*14, the number of bacteria 8 hours after an ultraviolet exposure was decreasing or less to 1Z100, and had good antibacterial properties.
[0080] (Antibacterial system performance testing 3)
Philharmonic light irradiation whom the above and Society of Industrial Technology for Antimicrobial Articles set about Examples 3 and 5 and 8*14 It is based on Beam contact printing, Using a white fluorescent light, it adjusts so that illumination may serve as lOOOLx, and it is a white firefly. It is an examination like the above (antibacterial system performance testing 1) except having made irradiation time of Lighting lamp into 24 hours. It carried out. a test organism -- yellow grape Bacterial species (Staphylococcus aureus NBRC12732) -- and -- Evaluation using coliform bacillus (Escherichia coli NBRC3972) was carried out.
[0081] Also about Examples 3 and 5 and which thin film of 8*14, it was decreasing to the number of bacteria 24 hours after an ultraviolet exposure, and 1Z100 or less, and had good antibacterial properties.
[0082] (Antibacterial system performance testing 4)
Philharmonic light irradiation whom the above and Society of Industrial Technology for Antimicrobial Articles set about Examples 3 and 5 and 9*14 It is based on Beam contact printing, Using a white fluorescent light, it adjusts so that illumination may serve as 500Lx, and it is a white firefly. It is an examination like the above (antibacterial system performance testing 1) except having made irradiation time of Lighting lamp into 24 hours. It carried out. In a test organism, it is business about yellow grape Bacterial species (Staphylococcus aureus NBRC12732). Required evaluation was carried out.
[0083] Also about Examples 3 and 5 and which thin film of 9*14, it was decreasing to the number of bacteria 24 hours after an ultraviolet exposure, and 1Z100 or less, and had good antibacterial properties.
[0084] (Antibacterial system performance testing 5)
Light irradiation Phi whom the above and Society of Industrial Technology for Antimicrobial Articles set about Examples 4 and 9 and 12*13 It is based on Lum contact printing, White [ using a white fluorescent light, it adjusts so that illumination may serve as 250Lx, and ] It examines like the above (antibacterial system performance testing 1) except having made irradiation time of the fluorescent light into 24 hours. It carried out. In a test organism, it is business about yellow grape Bacterial species (Staphylococcus aureus NBRC12732). Required evaluation was carried out.
[0085] Also about Examples 4 and 9 and which thin film of 12*13, it was decreasing to the number of bacteria 24 hours after an ultraviolet exposure, and 1Z100 or less, and had good antibacterial properties. [0086] The above result is shown in a table.
[0087] [-- table 1]
<img file="WO2007108514A1_D0001.tif" />
<img file="WO2007108514A1_D0002.tif" />
[0088] As shown in a table, since film thickness is in the range which is 5*80 nm, the thin film of Example 1*14 is Dry. Negligence has arisen and is It is a force. On the other hand, in film thickness, an interference color to the thin film of the comparative example which is 150 nm It had produced.
Industrial applicability
[0089] The glass board with an antibacterial film of the present invention, Unlike the former, a reflective interference color arises in fields, such as a glass window of a building, a glass window of transportation machinery, and a glass panel for an information display, and it is a Follow machine. Big use value at the point that the glass board with an antibacterial film with which Machine endurance was improved can be provided It has a value.
4 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4
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| WO2022090708A1 | Cited by | World Intellectual Property Organization (WIPO) | – | Applicant |
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| DE102014013528B4 | Cited by | Germany | – | Applicant |
| WO2021260370A1 | Cited by | World Intellectual Property Organization (WIPO) | – | Applicant |
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| JPH08187604A | Cites | Japan | Y | International search |
2 members in 2 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 2006078818 | Japan | A | |
| 2006078818 | Japan | A | |
| 2006078818 | – | – | – |
| JP20060078818 | – | – | – |
Members2
| Document | Office | Kind | |
|---|---|---|---|
| WO2007108514A1This record | World Intellectual Property Organization (WIPO) | A1 | |
| JP2007254192A | Japan | A |
3 legal events, as 2 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Ep: pct application non-entry in european phase122 | 122 | WO | |
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Numbers
- Publication
- 2007/108514
- Publication, DOCDB
- 2007108514
- Publication, EPODOC
- WO2007108514
- Application
- 55915
- Application, DOCDB
- 2007055915
- Application, EPODOC
- WO2007JP55915
Titles2
- English
- GLASS PLATE HAVING ANTIBACTERIAL FILM, METHOD OF PRODUCING THE SAME AND ARTICLE HAVING THE GLASS PLATE
- French
- plaque de verre MUNIE D'un film antibactérien, procédé de fabrication d'une telle plaque et article COMPORTant la plaque de verre
Classification
- CPC, 10
- C23C16/0272
- C03C17/225
- C03C17/2456
- C03C17/3417
- C03C17/3435
- C03C2204/02
- C03C2217/212
- C03C2217/71
- C23C16/34
- C23C16/405
- IPC, 5
- C03C17 245
- B01J35 00
- B60J1 00
- C23C16 34
- C23C16 40
Designated states4
- Regional, 4
- Zimbabwe
- Turkmenistan
- Türkiye
- Togo