Antibacterial substratum and process for producing the same
Abstract
An antibacterial substratum comprising a substratum and, provided on a surface thereof, multiple antibacterial metal islands. The multiple antibacterial metal islands are in contact with ambient atmosphere. The average value of contact angles exhibited by the substratum and the multiple antibacterial metal islands, as determined on the basis of surface observation results by scanning electron micrograph, is 90 degrees or less.

Term
No projected expiry on record.
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17 claims: 15 independent, 2 dependent
- 1請求の範囲 [I] 基材と、 前記基材の表面に形成された複数の抗菌金属アイランドとを備え、 前記複数の抗菌金属アイランドが外部雰囲気に接し、 走査型電子顕微鏡による表面観察の結果に基づいて測定される前記基材と前記 複数の抗菌金属アイランドとの接触角の平均値が 90度以下である、抗菌性基材。
- 2[2] 前記複数の抗菌金属アイランドの直径の平均値が 5〜500nmの範囲にある、請求 項 1に記載の抗菌性基材。
- 3[3] 前記複数の抗菌金属アイランドの直径の平均値が 5〜50nmの範囲にある、請求 項 1に記載の抗菌性基材。
- 4[4] 前記基材の表面における 1 X I μ mの広さの任意の領域中に、少なくとも 1つの前 記抗菌金属アイランドが存在する、請求項 1に記載の抗菌性基材。
- 5[5] 前記基材が透光性を有し、 前記抗菌性基材の可視光透過率と、前記抗菌性基材から前記抗菌金属アイランド を除去した前記基材の可視光透過率との差異 Δ Τが 15%以下である、請求項 1に記 載の抗菌性基材。
- 6[6] 前記基材が透光性を有し、 可視光透過率が 30%以上である、請求項 1に記載の抗菌性基材。
- 7[7] 前記抗菌金属アイランドの最大高さが 50nm以下である、請求項 1に記載の抗菌性 基材。
- 8[8] 前記抗菌金属アイランドは、銀、銅および亜鉛からなる群より選ばれる!/、ずれか 1種 を主成分金属として含む、請求項 1に記載の抗菌性基材。
- 9[9] 前記抗菌金属アイランドが、主成分金属と添加金属とを含む、請求項 1に記載の抗 菌性基材。
- 10[10] 前記主成分金属が銀であり、前記添加金属がパラジウムである、請求項 9に記載の 抗菌性基材。 [I I] 前記基材が、酸化チタンを含む光触媒層を有し、前記光触媒層によって前記基材 の表面が形成されて!/、る、請求項 1に記載の抗菌性基材。 [12] 前記基材が、前記光触媒層の下地層として、単斜晶型の結晶構造を含む多結晶 酸化ジルコニウムを含む膜をさらに有し、 前記光触媒層が、アナターゼ型の結晶構造を含む多結晶酸化チタンを含む、請求 項 11に記載の抗菌性基材。
- 11[13] 前記基材が、基材本体と、前記基材本体に接するように形成された下地層とを有す る、請求項 1に記載の抗菌性基材。
- 12[14] 前記下地層が、酸化珪素、窒化珪素、酸化錫および亜鉛と錫との複合酸化物から なる群より選ばれる少なくとも 1つを含む、請求項 13に記載の抗菌性基材。
- 13[15] 前記基材が、ガラス板、プラスチック板および樹脂フィルムからなる群より選ばれる 1 種または 2種以上の素材によって構成されている、請求項 1に記載の抗菌性基材。
- 14[16] 前記基材が、強化または半強化された型板ガラスによって構成されている、請求項 1に記載の抗菌性基材。
- 15[17] 前記基材が鏡によって構成されている、請求項 1に記載の抗菌性基材。
- 16[18] 前記抗菌金属アイランドが、スパッタリング法により形成されている、請求項 1に記載 の抗菌性基材。
- 17[19] 不活性ガスを主成分としたガス雰囲気下で行われ、ターゲットを構成する抗菌金属 の目安膜厚を 0. Inm以上 3nm以下とするスパッタリング法により、基材の表面に前 記抗菌金属をアイランド状に堆積させる工程を含む、抗菌性基材の製造方法。
Independent claims17
225 paragraphs in 2 sections, as filed
Specification
An antibacterial substrate and a manufacturing method for the same
Technical field
[0001] The present invention relates to an antibacterial substrate and a manufacturing method for the same.
Background art
[0002] Antibacterial medicine of the inorganic system which was excellent in respect of safety or endurance in recent years as compared with the antibacterial medicine of an organic system It is observed. the antibacterial effect mainly concerned with silver, copper, and zinc as antibacterial medicine of an inorganic system -- an owner -- Antibacterial medicine using the photocatalyst mainly concerned with the antibacterial medicine using an antibacterial metal to carry out, or titanium oxide It is mentioned.
[0003] By a displacement reaction with a cell membrane and a cytoplasmic organization substance, antibacterial metal, such as silver, copper, and zinc, deactivates a bacillus, and demonstrates an antibacterial effect. Photocatalysts, such as titanium oxide, are irradiation of ultraviolet rays. The reactive oxygen species which carry out Occurred are attacking the cell wall of a bacillus, and a cell membrane, and it demonstrates an antibacterial effect. It carries out.
[0004] moreover -- using a photocatalyst and an antibacterial metal together and destroying cell walls, such as bacteria, with a photocatalyst -- furthermore -- Promoting the antibacterial function by an antibacterial metal is also known.
[0005] Provisional publication of a patent 2004 -- "The foil or film which has an antibacterial function providing tunic layers which consist of an antibacterial metal on the surface of a base, such as a metal skin or a metal thin film layer," is shown in No. 183030 gazette, and it is also shown in it that the above-mentioned antibacterial metal is silver.
[0006] Provisional Publication No. 9 -- No. 111380 gazette "Ag: 20*60 atoms<sup>0</sup>Hmm Cu : 20*60 atoms<sup>0</sup>Hmm Zn :
Ag excellent in antibacterial and Safety Behavior nature with composition of 20* 60-atom % -- Cu -- Zn alloy" is shown. ing. Alloy covering is formed by the sputtering method as the target in this alloy.
[0007] Provisional publication of a patent 2006 -- "Ag which contains Cu as an essential ingredient -- the Cu alloy antibacterial-properties thin film" is shown in No. 152353 gazette. Ag -- Cu alloy is targeted and it is Ag by the sputtering method. -- Forming Cu alloy antibacterial-properties thin film is also shown.
[0008] Provisional publication of a patent 2000 -- In No. 246115 gazette, Depart about "the light catalytic function member which laminated at least the material containing the substance which shows a photocatalyst operation to the exposure surface of a substrate, or the substance on the discontinuous film state so that it might distribute uniformly substantially and less than Partition mosquito Slmm between average molecules might become" Ming is shown. Semiconductor which has a photocatalyst operation as a substance in which a photocatalyst operation is shown It is shown that It was uses a particulate semiconductor! /, To.
[0009] In international publication 2006/No. 064059 pamphlet, To the manufacturing method of the substrate which has antibacterial properties It is Including about the inorganic antibacterial medicine which set and was obtained from the precursor of metal, colloid, chelate, or ion. The method of forming a Mu metal non-gel layer, heat-treating this, and diffusing antibacterial medicine is indicated. It is.
[0010] However, don't contribute substantially an antibacterial metal diffused inside the substrate to an antibacterial effect. Therefore, the substrate indicated in international publication 2006/No. 064059 pamphlet is Existence of an antibacterial metal. An antibacterial effect cannot be efficiently demonstrated to the amount of In, but economical futility is large. Antibacterial properties Metal tends to invite appearance change of discoloration of a substrate, etc. Therefore, a substrate is made to deposit. The quantity of an antibacterial metal should be controlled highly.
[0011] Methods of making a little antibacterial metal adhering to a substrate include the method of spraying the dispersion liquid containing the antibacterial metal particles of a nanometer order to a substrate face. However, by this method, the antibacterial metal particles adhering to a substrate have near shape spherically, and adhesion nature with a substrate It is bad. Therefore, peeling omission and antibacterial properties do not continue simply [ antibacterial metal particles ] from a substrate. There is a problem to say.
The indication of an invention
[0012] The present invention was made paying attention to the above-mentioned conventional subject, sufficient antibacterial properties continue, and are demonstrated and the object is to provide the antibacterial substrate which is excellent also in economical efficiency.
[0013] Namely, the present invention,
Substrate,
It has a plurality of antibacterial metal islands formed on the surface of the substrate,
A plurality of antibacterial metal islands touch external atmosphere,
the substrate measured based on the result of the surface observation by a scanning electron microscope, and plurality -- anti- -- The average value of an angle of contact with a bacillus metal island provides the antibacterial substrate which is 90 degrees or less.
[0014] In other sides, it is the present invention,
antibacterial metal which is performed under the gas atmosphere which made inactive gas the main ingredients, and constitutes a target the sputtering method which sets standard film thickness to more than 0. lnm and 3 nm or less -- the surface of a substrate -- anti- -- The manufacturing method of an antibacterial substrate including the process on which bacillus metal is made to deposit in the shape of an island is provided.
[0015] The thin film formation by the sputtering method passes through the process that nucleation happens first, and continuation film formation progresses continuously. However, in the present invention, sputtering is suspended in the stage before continuation film formation dares to start. Thereby, it is an audit observation in a scanning electron microscope. It is antibacterial gold to the surface of a substrate so that the average value of the angle of contact measured by being based may be 90 degrees or less. A Genus island is formed.
[0016] Since a proper quantity of antibacterial metal existed in the surface of the substrate, the antibacterial substrate of the present invention was excellent. An antibacterial effect is demonstrated. moreover -- the angle of contact of a substrate and an antibacterial metal island is on an average -- 90 degrees -- with -- since it is as small as the bottom, the adhesion nature of a substrate and an antibacterial metal island is also good -- an antibacterial effect -- long -- It continues over a term. The amount of deposition of an antibacterial metal to a substrate is controlled highly. By that, when a substrate has light transmission nature, the light transmission nature is not checked but it excels also in economical efficiency.
[0017] The discrete state where it is dotted in addition with the island where "the shape of an island" is small in this specification It means. That is, "a plurality of antibacterial metal islands formed on the surface of the substrate" means the group of the antibacterial metal object (antibacterial island) deposited on the state where it was dotted, on the surface of the substrate.
[0018] A "angle of contact" means the angle which the tangent in the contact portion of a substrate and an antibacterial metal island and the surface of a substrate make. It shall assume that the surface of a substrate is a plane and shall measure the angle of contact of the appearance of an antibacterial metal island as an actual angle of contact. Ten antibacterial metal selected as arbitrarily [ plurality and when it should measure strictly ] as "the average value of an angle of contact is less than 9 0 degree" It means that the value which equalized the angle of contact of the island is 90 degrees or less. An angle of contact is measured based on the result of surface observation of the antibacterial substrate by a Running * type electron microscope.
[0019] As for an antibacterial metal, since it oxidizes with progress of time, a metal oxide is contained in an antibacterial metal island in many cases, but with this specification, the oxide of an antibacterial metal is also Included to an antibacterial metal. Suppose that division * Li does not carry out as that of To write.
Brief explanation of the drawings
[0020] [-- figure 1] -- the sectional view [figure showing an example of the typical composition of the antibacterial substrate of the present invention -- the sectional view showing other examples of the typical composition of the antibacterial substrate of 2] present invention
[figure 3] The sectional view showing the example of further others of the typical composition of the antibacterial substrate of the present invention
[figure 4] The sectional view showing the example of further others of the typical composition of the antibacterial substrate of the present invention
[figure 5] The key map showing how to form an antibacterial metal island on the surface of a substrate
[figure 6] The section SEM image of the antibacterial substrate of Example 1
[figure 7] The reflective electronic image of the surface of the antibacterial substrate of Example 14
[figure 8] The section SEM image of comparative example 9
[figure 9] The surface of comparative example 9 Secondary electron image
[figure 10] The section SEM image of the antibacterial substrate of Example 20
[figure 11] The reflective electronic image of the surface of the antibacterial substrate of Example 20
[figure 12] The section SEM image of the antibacterial substrate of Example 22
[figure 13] The reflective electronic image of the surface of the antibacterial substrate of Example 22
[figure 14] The section SEM image of comparative example 16
[figure 15] The surface of comparative example 16 Secondary electron image
The best form for inventing
[0021] Hereinafter, describe the embodiment of the antibacterial substrate of the present invention.
[0022] Explain first the antibacterial metal island formed on the surface of a substrate. Antibacterial metal Ireland can be formed so that the average value of a diameter may serve as a range which is 5*500 nm. According to this feature, specific surface area of an antibacterial metal island can be enlarged, and it is Depart about an antibacterial effect effectively. The antibacterial substrate which can carry out Vienna can be provided.
[0023] It may be in the average value of the diameter of an antibacterial metal island, and the range of 5*50 nm. According to this feature, the antibacterial substrate excellent in abrasion resistance can be provided.
[0024] In addition, the average value of the diameter of an antibacterial metal island means the average value of the diameter of the circle in the contact surface of an antibacterial metal island and a substrate. When a contact surface is not circular, area It is You even if it adopts the average value of the diameter of an equal circle.
[0025] An antibacterial metal island is good to exist all over [ at least one ] the arbitrary fields of the width of 1 X 1 m in the surface of a substrate. this feature -- the inside of a field -- uniform -- an antibacterial effect -- Power to express S -- last . [0026] B and economical efficiency which the amount of deposition of an antibacterial metal to a substrate becomes about appearance change of a substrate -- improvement -- , from a To viewpoint, it should be controlled highly. Difference with the visible optical transmittance of the substrate which removed the antibacterial metal island from the visible optical transmittance of an antibacterial substrate, and an antibacterial substrate, for example when a substrate had light transmission nature It is good in deltatau being 15% or less.
[0027] Difference between the visible optical transmittance of an antibacterial substrate, and the visible optical transmittance of the substrate which removed the antibacterial metal island from the antibacterial substrate Removal of the antibacterial metal island in the case of measuring deltatau Removal method is explained. Etching with an antibacterial suitable metal deposited on the surface of a substrate It is Research about the method of carrying out selective etching of the antibacterial metal concerned using A liquid, and the surface of an antibacterial substrate. It is removable by the method of carrying out Polishing. The layer part of a substrate is slightly in an antibacterial metal. Xiao IJ To be possibility is also a certain power. The influence on visible optical transmittance is minor, and can be disregarded.
[0028] When a substrate has light transmission nature, be at the visible optical transmittance of an antibacterial substrate, and 30% or more. It is good to be.
[0029] They may be the maximum height of an antibacterial metal island, and 50 nm or less. this feature -- objects, such as a dustcloth, -- an antibacterial metal island -- Catching force and Ri -- << -- it becomes. As a result, an antibacterial substrate with high abrasion resistance can be provided. Lower limit of the maximum height of an antibacterial metal island Especially as for the antibacterial metal island of a size where !/, [ have ] to limit can demonstrate quantity ! and an antibacterial effect, it has the height more than lnm, for example.
[0030] An antibacterial metal island is chosen from the group which consists of silver, copper, and zinc! Main in /, a gap, or one sort It is good to contain as an ingredient metal. The antibacterial substrate with which the antibacterial effect which was excellent in silver, copper, and zinc was added by this feature can be provided. In this specification, the "main ingredients" means the ingredient most contained with mass %. The antibacterial metal island may consist of main-ingredients metal substantially. "substantial" -- Impurities mixed unescapable what is eliminated -- it Les and obtains with Lech [ Then. ] and is the meaning.
[0031] The antibacterial metal island may contain main-ingredients metal and the addition metal of a quantity (with mass %) smaller than main-ingredients metal. According to this feature, the antibacterial substrate which has an antibacterial metal island where endurance is high can be provided.
[0032] For example, when using silver as a main-ingredients metal of an antibacterial metal island, Noradium can be conveniently used as an addition metal. According to this feature, the antibacterial substrate excellent in corrosion resistance and abrasion resistance can be provided. At least one sort chosen from the group which replaces with palladium or consists of platinum, gold, iron, zinc, tin, and neodymium with palladium may be used as a Attach Callot metal.
[0033] There is surface resistance of an antibacterial substrate as a fact which, in addition, shows that an antibacterial metal has accumulated in the shape of an island in addition to a SEM image. When a substrate is insulation, it is Surface resistance of an antibacterial substrate. Anti is 10.<sup>7</sup>it is formation about a film with an antibacterial perfect metal that it is omega / more than a mouth (ohm per square) Do not carry out but deposit in the shape of an island! power S Les(ing) and obtaining with /and To -- things -- it can do.
[0034] next, a substrate -- One! /-- it Explanation. the substrate gave antibacterial properties! if it is /and a substrate -- especially -- It is not limited. It is desirable when the substrate has light transmission nature. Concretely, a substrate can be constituted using one sort or two sorts or more of materials chosen from the group which consists of a glass board, a plastic sheet, and a resin film. The substrate may be constituted by the mirror. These materials may be used as a substrate as they are, and the thing in which the ground film and the photocatalyst film were formed on these materials may be used for them as a substrate so that it may explain below.
[0035] The substrate may further have a photocatalyst layer containing titanium oxide. In this case, the surface of a substrate may be formed of a photocatalyst layer.
[0036] The substrate may have a film containing the multi-crystal zirconium dioxide which includes a monoclinic crystal structure as a foundation layer of a photocatalyst layer. In this case, a photocatalyst layer is a Anatase type. It is good in it being a thing containing multi-crystal titanium oxide including a crystal structure. Monoclinic oxidization Zirco The grating constant of 2 Um is close to the grating constant of Anatase type titanium oxide. Therefore, single slant By providing as a Crystal type zirconium dioxide foundation layer, it passes through a titanium oxide film and is Telopita. Quicar growth can be carried out. Thereby, it is To form about the high photocatalyst layer of a photocatalyst effect. Ability to S It can do. As for the above-mentioned form, a part of photocatalyst layer is zirconium oxide membrane. Composed of is carried out and it can also be realized as The.
[0037] Form the above photocatalyst layers on a substrate in advance of formation of an antibacterial metal island with publicly known methods for film deposition, such as a chemical vapor deposition method, the sputtering method, and a liquid phase method. Power can be carried out. The sputtering method especially since a uniform film can be easily formed by a large area It is recommended. It is To form by the sputtering method about a photocatalyst layer and an antibacterial metal island. A To case is a spa about the sputtering process and the antibacterial metal island for forming a photocatalyst layer. It is expectation about improvement in productivity since a Buttering process can be carried out by the same production line. It cuts.
[0038] It is Use as a body part (main part of a substrate) of a substrate about the glass board manufactured by a float process. Heat which used the heat at the time of glass formulation when for was carried out The photocatalyst layer which contains titanium oxide with a CVD method may be formed. Heat using the heat at the time of float glass formation Generally a CVD method is on-line. It is called a CVD method (or CVD method in a bus). On-line According to the CVD method, a photocatalyst layer is formed on the forming line of the glass by a float process (for example, inside of a float bus). The CVD device for carrying out is installed. It is based on a CVD method with fabrication of the glass by a float process. Since formation of a photocatalyst layer can be performed continuously, it excels in economical efficiency.
[0039] In addition, to a photocatalyst layer, metal may be added to such an extent that disorder of a crystal structure is not produced. Addition of a little metal promotes generating of a career, and improves photocatalyst activity. Suitable [ in a photocatalyst ] are . As a metal content, it is 0. 001 mass %*; It is 1. 0 mass %. The amount of addition is fewer than this. When There and an effect may not show up and it is too large, he is disorder and the recombination center student of the crystal structure of a photocatalyst. It may become a cause of Formation and photocatalyst activity may fall.
[0040] The substrate may contain the main part of a substrate, and the foundation layer formed so that the main part of a substrate might be touched. A foundation layer has the function to prevent diffusion of the alkali component contained in a glass board (main part of a substrate), for example.
[0041] A foundation layer is good to include at least one chosen from the group which consists of a compound oxide of oxidization silicon, silicon nitride, tin oxide, and zinc and tin. The thickness of a foundation layer is 5*; !. Sufficient effect with Onm is acquired. A foundation layer is point Stand to formation of a photocatalyst layer or an antibacterial island. It is a basis by publicly known methods for film deposition, such as an intermediary, a chemical vapor deposition method, the sputtering method, and a liquid phase method. It can form on a material main part.
[0042] Next, some typical composition of an antibacterial substrate is shown in a drawing.
[0043] a figure -- 1 is a sectional view showing an example of the typical composition of the antibacterial substrate of the present invention. the surface of soda lime glass board 11 as a substrate which has light transmission nature in this example -- plurality -- anti- -- Bacillus metal island 10 (island group) is formed. Antibacterial metal island 10 is outside. It is in contact with part atmosphere. By making an antibacterial metal deposit in the shape of an island, the original color tone and light transmittance state of glass board 11 can be kept good. [0044] Antibacterial metal island 10 and glass board 1 Angle of contact of 1 theta is 90 degrees or less on an average. Contact Antenna Since theta is comparatively small, the adhesion nature of antibacterial metal island 10 and glass board 11 is good. it is . Angle of contact theta is measured based on the result of the surface observation by a scanning electron microscope (SEM : Scanning Electron Microscop e). The magnifying power of SEM, and 50,000*200,000 It is good to be set as about twice. With such magnification, they are antibacterial metal island 10 and Ga. Angle of contact with the Russ board 11 theta is easily and exactly computable.
[0045] a figure -- it is shown in 2 -- as -- the surface of soda lime glass board 11 (main part of a substrate) -- as a foundation layer -- acid -izing silicon film 20 may be formed and antibacterial metal island 10 may be formed in the surface of oxidization silicon film 20.
[0046] further -- a figure -- as shown in 3, Anatase type titanium oxide film 22 may be formed as a photocatalyst layer on oxidization silicon film 20, and antibacterial metal island 10 may be formed in the surface of titanium oxide film 22. by making an antibacterial metal deposit in the shape of an island, the photooxidative degradation nature of titanium oxide film 22 prevents -- having -- << -- it becomes.
[0047] further -- a figure -- it is shown in 4 -- as -- between oxidization silicon film 20 and titanium oxide films 22 -- acid of a monoclinic system -izing zirconium membrane 21 is formed! /and The -- OK,
[0048] Next, explain the manufacturing method of an antibacterial substrate.
[0049] The antibacterial substrate of the present invention can be manufactured by forming an antibacterial metal island by the sputtering method on the surface of a substrate. The quantity of an antibacterial metal made to deposit by the sputtering method can be controlled highly.
[0050] the bottom of the gas atmosphere which made the main ingredients inactive gas [ like argon ] whose sputtering method is -- real -- It is as good as To to give. In order to make an antibacterial metal deposit in the shape of an island, it is based on the sputtering method. It is good to set standard film thickness as more than 0. lnm and 3 nm or less. Here, standard film thickness converted that the whole quantity of the metal which constitutes an antibacterial metal island constituted the continuation film with uniform film thickness. The actual height of the antibacterial metal island which said the film thickness of the continuation film in the case, and was formed itself It is not shown.
[0051] This standard film thickness can be defined as follows, for example. First, antibacterial metal Membrane formation conditions (a film deposition system, membrane formation atmosphere gas, a degree of vacuum, substrate temperature, membrane formation power, etc.) are defined. forming membranes over comparatively long time on the membrane formation conditions -- a substrate top -- an antibacterial metal -- from A Continuous film is formed. Only membrane formation time is changed, membranes are formed several times, and film thickness differs. A plurality of continuation films are obtained. The film thickness of the obtained continuation film is measured and it is the relation between film thickness and membrane formation time. It asks. The film thickness of a continuation film can be measured by the sensing pin type level difference film thickness meter or an ellipsometer. To. This which calculates the predicted value of film thickness and the film thickness to membrane formation time predetermined from the relation of membrane formation time It can do and can use this predicted value as standard film thickness. Namely, predetermined standard film The membrane formation time equivalent to thickness is computed beforehand, and it is to this computed membrane formation time at the membrane formation time of an antibacterial metal. Between is set up. It is that it is possible to make an antibacterial metal deposit in the shape of an island with such a procedure. It becomes.
[0052] With the reason that in addition the method of controlling the amount of deposition of an antibacterial metal highly is limited to a described method It is Picking up without problems if it is the method that an antibacterial metal dropping off can be made to deposit in the shape of an island. for can be carried out.
[0053] a figure -- 5 is a key map showing how to form an antibacterial metal island on the surface of a substrate. Figure
As shown in 5, a plurality of substrates 31 are arranged in career 42. Career 42 moves in the direction of an arrow in target 32 top.
[0054] Between career 42 and target 30, two shield plates 30 are arranged in parallel. To. adjusting the width of the opening slot formed by shield plate 30 -- membrane formation rate it controls -- thing power can be carried out. The width of an opening slot is lmm*, for example; It adjusts in about 150 mm. It is good to carry out. It replaces with adjusting the width of an opening slot, or substrate 31 conveys with this. A membrane formation rate may be controlled by making speed quick or stopping injection power low. moreover -- considering membrane formation standard film thickness and membrane formation efficiency, when sputtering conditions are changed -- an opening slot -- extensive -- To may be adjusted.
[0055] Perform sputtering, passing argon gas from outlet 40 of argon which is inactive gas in the direction of the upper part of a straight line arrow, i.e., the direction of target 32. The antibacterial metal atom emitted by sputtering is a connoisseur about the opening slot formed by shield plate 30. It deposits on an intermediary and substrate 31.
[0056] Target 32 uses silver, copper, or an antibacterial metal like zinc as main-ingredients metal. It is good. Target 32 may contain a proper quantity of addition metal other than main-ingredients metal. For example, when using silver as a main-ingredients metal, they are platinum, gold, and A. At least one sort chosen from the group which consists of radium, iron, zinc, tin, and neodymium may be contained in target 32 as an addition metal. Antibacterial island where addition of a little metal contains silver as the main ingredients Corrosion-resistant improvement and silver condensation are controlled. A especially Radium is an effect of condensation control. It excels and is recommended by that of Les and To.
[0057] It is even if at least one sort chosen from the group which consists of tin, iron, Zirkoyuum, and chromium as an addition metal when using copper as a main-ingredients metal is contained in target 32. It is good. Thereby, a corrosion-resistant improvement of the antibacterial metal island which contains copper as the main ingredients is expectable.
EXAMPLE
[0058] In order to explain the present invention still in detail, an example and a comparative example are shown. Sun which explained to The 1 the sample which has not provided the photocatalyst layer, and provided the photocatalyst layer in it at The 2 Pull is explained and the sample which used template glass for The 3 is explained.
O
[0059] Toughness example;! * 19, comparative example;! * 9>>
the details of an example and a comparative example -- a table -- 1 1* table -- 2 -- It is shown in 4. Table 2 -- ; !. * 2 -- 4 is carried out. Composition of each class of example 1*;19, the shape of an antibacterial metal island, surface resistance, and visible optical transmittance -- anti- -- Visible optical transmittance change (difference in the visible optical transmittance in the case where and an antibacterial metal island do not exist when an antibacterial metal island exists) by bacillus metal island formation, * it can set to a place -- anti- -- A bacillus active value and the antibacterial active value in * place after dustcloth Wiping are summarized. Table 1 1 and 1--2 are summarized like an example about comparative example 1*9.
[0060] In addition, comparative example 8 is an antibacterial tile of marketing which contained an antibacterial metal inside glaze. Comparative example 9 is marketing to the surface of a substrate. Ag particulate alcoholic dispersion liquid are sprayed and it is at normal temperature. It is made to dry.
[0061] [Front 1-1] 0062
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And the long and slender crevice which extends in the conveyance direction and the direction which intersects perpendicularly was made. The width of a crevice is 5 mm. It carried out. Heating of a substrate was not given at the time of membrane formation.
[0068] The detailed conditions of sputtering in which the antibacterial metal island was formed are as follows.
. Target: Ag, Cu, Zn, and Ag+Pd (Pd : l .0 mass %),
Ag+Pd (Pd : 15. 0 mass)<sup>0</sup>/<sub>0</sub>,
Or 8<sub>8</sub>+ ? (1+ Tooth 11 (? (Cu : 1 : 0. 9 mass %, 0. 6 mass)))<sup>0</sup>/<sub>0</sub>)
* Dregs J ground: 1 OmTorr
* Inactive gas kind: Ar 100%
* 0.3 kW (0.62 W/cm) injection power DC: <sup>2</sup>)
* Bearer rate 1000 mm/min (it follows on the membrane formation rate of a target, and is very-small-quantity adjustment)
[0069] the outlet of argon gas -- a figure -- being formed with a shield plate and a target, as shown in 5 It installed so that gas might be emitted to the inside of Space.
[0070] Membrane formation of the oxidization silicon film as a foundation layer in comparative example 2, Example 4, Example 5, and Example 9 and in-line type sputter device MLH by ULVAC -- It is business about 6215! /Go spa It carried out by the Buttering method. In order to beX[ 5 ] 15 inches in size and to specifically take out conductivity The silicon target which doped Lynn is used and it is a reactant spa under oxygen gas atmosphere. The oxidization silicon film was formed by the Buttering method. Heating of a substrate was not given at the time of membrane formation. Basis Distance of material and a target was made into 60 mm of abbreviation. Sputtering conditions of other oxidization silicon films It is as follows for details.
[0071] The sputtering conditions at the time of oxidization silicon (SiO) membrane formation
. Target: Si (P dope)
* Gas pressure: dmTorr
* Gas ratio : oxygen (0) 80%+ Argon (Ar) 20%
* Injection power DC pulse 2 and OkW: (power density: 4 and 13W/cm)<sup>2</sup>)
[0072] the section SEM image Of Example 1 which did in this way and formed the antibacterial metal island -- a figure -- it is shown in 6. Hitachi electric field radiation type scanning electron microscope [ image / section SEM ] S -- 4700 is used. Taken with was carried out. They are 5 kV and magnifying power about accelerating voltage. It is considered as 100,000 times and is Taking by ten inclinations from a section. The shadow was carried out. It is based on a section SEM image and they are an angle of contact of an antibacterial metal island and a substrate, and an antibacterial metal eye. The height of a land and the height of the antibacterial metal island were measured. An angle of contact is 90 degrees or less on an average, and is Ah. Ivy. The average diameters of an antibacterial metal island are 25 nm of abbreviation, and it distributes them uniformly in a field comparatively. Had been.
[0073] In the antibacterial substrate of the present invention, 60 averages or less may be sufficient as the angle of contact of an antibacterial metal island and a substrate so that the result of an example may show. For example, in order to make an angle of contact into 60 degrees or less on an average, it is good to make an antibacterial metal deposit by making into a lnm grade standard film thickness mentioned above. contact the time of an object contacting an antibacterial metal island, when the angle became small -- Catching force and Ri -- << -- since abrasion resistance improves, it is desirable.
[0074] next, the reflective electronic image of the surface Of Example 1 -- a figure -- it is shown in 7. The portion reflected to punctate is an antibacterial metal island. The density of an antibacterial metal island is measured based on a reflective electronic image. It was. The density of an antibacterial metal island is abbreviation 80 piece/.<sup>2</sup>It came out. an antibacterial metal -- deposition -- To do it! / -- !. /and the reflective electronic image of the surface of a substrate -- the spot of Ming * -- nothing! /and a thing were also checked.
[0075] the same -- the section SEM image of comparative example 9 -- a figure -- it is shown in 8. Hitachi Electric field emission [ image / SEM ] Projection scanning electron microscope S -- A photograph was taken using 4000. They are 15 kV and expansion twice about accelerating voltage. Rate It was considered as 50,000 times and a photograph was taken by ten inclinations from the section. Contact with antibacterial metal particles and a substrate The angle was [ on the average ] larger than 90 degrees. it originates in this and Ag particulate dispersion liquid the Ag particulate (antibacterial metal particles) was made to adhere -- it is a sake. The average diameters of antibacterial metal particles are 60 nm of abbreviation, and are Ah. Ivy. In Ag particulate dispersion liquid, particle diameter is too small. It is stabilized and an Ag particulate is dispersed. It is difficult. the surface of comparative example 9 photoed by 15 kV of accelerating voltage a secondary electron image -- a figure -- it is shown in 9. The densities of antibacterial metal particles are three abbreviation / m.<sup>2</sup>It came out.
[0076] In addition, the average angle of contact of the antibacterial metal island was computed as follows. Section SEM Image force also chose ten antibacterial metal islands, measured the angle of contact of each antibacterial metal island, and used the average value as the average angle of contact.
[0077] The average diameter of the antibacterial metal island was computed as follows. Ten antibacterial metal islands were chosen from the section SEM image, the diameter of each antibacterial metal island was measured, and the average value was made into the average diameter.
[0078] The density of the antibacterial metal island measured and computed the number of the antibacterial metal island in the range of 500nm X from surface reflective electronic image 500nm. [0079] The following procedures estimated the antibacterial properties of each sample.
Staphylococcus aureus (Staphylococcus aureus) was used for the test organism. First, it is Culture about a test organism. It cultivates with a background (Nutrient Agar made from Difco) for 37 degreeC 18 hours, a growth colony is suspended to a culture medium (product made from Nutrition research usually bouillon culture medium), and it is abbreviation 10.<sup>6</sup>Test organism suspension was adjusted so that it might become CFU/mL. Next Test organism suspension 0. lmL was dropped at the sample measured in the size ofX[ 5 ] 5 cm. Next, inside of the petri dish which put the polypropylene film of 4 X 4cm size on and a sample, and was moisturized It dedicated and acted on temperature 25 ± 5degreeC and the conditions of 95% of humidity in * place for 24 hours. 24-hour operation Samples are behind collected into a stomacher use sterilization bag, and it is a culture medium (SCDLP bouillon made from Daigo). In addition, it was probed. Culture media were collected from the sterilization bag and this was made into the sample undiluted solution. a sample undiluted solution and the 10 time dilution sequence (the 10 time diluted solution by a physiological salt solution, a 100 time diluted solution, and 1000 time diluted solution --) of a sample undiluted solution -- respectively -- every [ lmL ] -- putting into a petri dish and adding a culture medium (Nutrient Agar) -- bacillus It cultivated. The number of generating colonies after 48-hour cultivation was measured by 37 degreeC. From the number of generating colonies to the following The antibacterial active value was computed by the formula.
A Log= [log (A/B)]
delta Log: Antibacterial active value (the amount of change of a viable cell count)
A: Average value of the viable cell count immediately after inoculation of an unprocessed specimen (piece)
B: Average value of the residual viable cell count after the 24-hour operation of an antibacterial treatment specimen (piece)
[0080] It is an antibacterial active value of each sample so that it may be easy to compare. Ranking attachment was performed for the value of delta Log to four steps as follows, and the superiority or inferiority of the antibacterial effect were attached.
X : A Log< 0
LEVEL1 : 0* A Log< 2
LEVEL2 : 2* A Log< 4
LEVEL3 : 4* delta Log (99. 99% or more extinction)
[0081] The ultraviolet illuminance of * place in evaluation of this antibacterial evaluation and the below-mentioned antifungus in addition is 0.001 mW/cm.<sup>2</sup>It points out that it is the following.
[0082] The following procedures estimated the antibacterial properties after dustcloth Wiping.
The dustcloth (new article) of the toweling used well is often soaked in an ordinary home with pure water, and it is the dustcloth. It used and rubbed the sample surface in the direction 250 times. Then, running water washing is carried out with pure water, and it is * place. Lower antibacterial properties were evaluated.
[0083] The penetration color tone (a*, b*) of each sample, It measures by Lambda20 made from PERKIN ELMER. Japanese Industrial Standards JIS from the transmission spectrum carried out -- Z -- It computed according to 8729 "the method of presentation of a color -- a L*a table color system and a L*uV color system." In measurement of a transmission spectrum, it is standard Illumina. Tent D was used.
[0084] Visible optical transmittance of each sample, It measured by Lambda20 made from PERKIN ELMER. Japanese Industrial Standards JIS from a transmission spectrum -- R -- Transmissivity and reflectance - It computed according to test method " of a radiant heat' insolation heat acquisition rate. [ of 3106"sheet glass ] However, a transmission spectrum is The. The light which entered and penetrated beam light to A simple was installed in 60-mm distance from the sample. It condensed and obtained with the convex lens.
[0085] Sheet resistance (surface resistance) of each sample, 4 probe probe was pressed and measured to the center position of the sample of lOOmm X 10 Omm immediately after antibacterial metal island formation using resistivity meter Loresta IP MCP--T250 by Mitsubishi Petrochemical Co., Ltd. (appearing : Mitsubishi Chemical). Surface resistance Other test methods can also be used for measurement of Anti, for example, a hole measuring device is used, and it is Measurement. Surface resistance may be computed from the constant specific resistance carried out.
[0086] the above -- a table -- 1 1* table -- 2 -- The following things became Brightness from the evaluation result shown in 4.
[0087] The antibacterial effect which was excellent in each example in * place was checked. This shows that the antibacterial effect by an antibacterial metal island is demonstrated. He is antibacterial metal Ira to it. An antibacterial effect was not demonstrated in comparative example 1 which does not form The, and 2. Inside of glaze The antibacterial properties of comparative example 8 which an antibacterial metal is distributing in the part were weak.
[0088] Each example whose average angle of contact of an antibacterial metal island is 90 degrees or less was maintaining high antibacterial properties after dustcloth Wiping. That is, antibacterial money of quantity even with after [ sufficient ] dustcloth Wiping The Genus island remained. The average angle of contact of an antibacterial metal island is 90 degrees to it. Large comparative example 9 did not have the antibacterial properties after dustcloth Wiping. that is, dustcloth Wiping -- anti- -- The bacillus metal island was removed.
[0089] Although each example is making silver and copper with high conductivity deposit on the surface, surface resistance is 9.1chi10.<sup>7</sup>High Conductivity was very lower than omega/mouth. This is an antibacterial metal eye. A land is discontinuously formed on a substrate! /and To are suggested! /, To. [0090] each example -- visible optical transmittance difference before and behind formation of an antibacterial metal island deltatau15% or less it was . comparative example 3*7 on which an antibacterial metal of sufficient quantity to form a film was made to deposit to it -- visible optical transmittance difference before and behind membrane formation deltatau is 15% or more -- intermediary There was with a large change of a* and b*, and and appearance quite bad [ change ].
[0091] next, a table -- the antifungus in Example 1, 11, 14, and * place of 17 (that whose main ingredients of an antibacterial metal island of all are silver ), and comparative example 1 is shown in 3.
[0092] [-- table 3]
[] 0093
<img file="WO2008047810A1_D0009.tif" />
<img file="WO2008047810A1_D0010.tif" />
Photo (Penicillium foniculosum) was used for the test organism. First, a test organism is cultivated for 25 degrees C two weeks by a culture medium (Potato Dextrose Agar made from Difc o), a growth colony is suspended to a culture medium (0 and 005% Ey mouth sol), and it is abbreviation 10.<sup>5</sup>Test organism suspension was adjusted so that it might become CFU/mL. Next, trial Test bacteria suspension 0. lmL was dropped at the sample measured toX[ 5 ] 5 cm. Next, the polypropylene film of 4 X 4cm size is put on a sample, and it dedicates in the moisturized petri dish, and is * place. It acted on Temperature25 ± 5degreeC and the conditions of 95% of humidity for 24 hours. It is a sample after a 24-hour operation. It collected into a stomacher use sterilization bag, and added and probed the culture medium (0.005% Ey mouth sol). Culture media were collected from the sterilization bag and this was made into the sample undiluted solution. 10 times [ of a sample undiluted solution and a sample undiluted solution ] rarer Interpretation (the 10 time diluted solution by a physiological salt solution, a 100 time diluted solution, and 1000 time diluted solution -- -) -- it -- every [ Re lmL ] -- it put into the petri dish, the culture medium (Potato Dextrose Agar) was added, and the bacillus was cultivated. 2 The number of generating colonies after one-week cultivation was measured by 5"C. The number power of generating colonies It is an anti-mosquito by the following formulas. Viability 10 student Straight was computed.
<img file="WO2008047810A1_D0011.tif" />
delta Log: Anti-mold active value (the amount of change of the number of raw mold)
A: Average value of the number of raw power Bi immediately after inoculation of a Not installed specimen (piece)
B: Average value of the number of residual student mold after the 24-hour operation of an antibacterial treatment specimen (piece)
[0094] It is an anti-mold active value of each sample so that it may be easy to compare. They are a value of delta Log four steps as follows. Ranking attachment was performed and the superiority or inferiority of the antibacterial effect were attached.
X : A Log< l
LEVEL1 : 1* A Log< 2
LEVEL2 : 2* A Log< 3
LEVEL3 : 3* delta Log (99. 9% or more extinction)
[0095] a table -- as shown in 3, there was no antifungus at comparative example 1 in which the antibacterial metal island is not formed. On the other hand, each of Example 1 in which the antibacterial metal island was formed, 11, 14, and 17 should have high Les and antifungus! /, It was.
[0096] Toughness example 20*39, comparative example 10*; 16>>
Next, the example and comparative example which provided the photocatalyst layer are explained. example and ratio the details of the example of Comparison -- a table -- 4 1* table -- 5 -- It is shown in 4. an antibacterial metal island -- shadow of a photocatalyst layer in order to receive sound strongly, even if the formation conditions by the sputtering method are the same -- photocatalyst layer the existence of a kind or a photocatalyst layer -- the form (shape, a number, a size) of an antibacterial metal island -- a large -- The thing which it hears and to change is refused. The same photocatalyst layer was also formed by the sputtering method. A photocatalyst layer and heat It is with the photocatalyst layer formed with the CVD method, and the form of an antibacterial metal island is Change. To come.
[table 4-1]
<img file="WO2008047810A1_D0012.tif" />
[][^" 00995
<img file="WO2008047810A1_D0013.tif" />
<img file="WO2008047810A1_D0014.tif" />
<img file="WO2008047810A1_D0015.tif" />
[] D**00051 -
<img file="WO2008047810A1_D0016.tif" />
<img file="WO2008047810A1_D0017.tif" />
[
<img file="WO2008047810A1_D0018.tif" />
[0103] The formation conditions of an antibacterial metal island and an oxidization silicon film by the sputtering method are as having explained previously.
[0104] Membrane formation of the photocatalyst layer of Example 20, 21, 23*36 and comparative example 11, 12, 14, and 18 is UL.
In-line type sputter device MLH by a VAC company -- It is business about 6215! It is a line by /and the The sputtering method. Ivy. 5 Use the metallic target of X 15 inch size, and it is the reactivity under oxygen gas atmosphere. The photocatalyst layer was formed by the sputtering method. Heating of a substrate is Do not do it at the time of membrane formation. Ivy. Distance of a substrate and a target was made into 60 mm of abbreviation. Sputtering of other photocatalyst layers The details of conditions are as follows.
[0105] The sputtering conditions at the time of (TiO) titanium oxide membrane formation
* Target : titanium
* Gas pressure: 20mTorr
* Gas ratio : oxygen (O) 100%
* Injection power DC3. OkW: (power density: 6 and 40W/cm)<sup>2</sup>)
[0106] The sputtering conditions at the time of zirconium dioxide (ZrO) membrane formation
. Target : zirconium (Zr)
* Dregs J ground: 1 OmTorr
* Gas ratio : oxygen (O) 100%
* 2.6 kW (power density: 5 and 54W/cm) injection power DC: <sup>2</sup>)
[0107] The photocatalyst layer of Example 22, 37*39, and comparative example 13 is inside of a bus. By a CVD method, it is a substrate book. The glass ribbon was adopted as the body and the titanium oxide thin film was formed in this surface. Concrete membrane formation The method is as follows.
[0108] Fuse by float kiln and it is temperature 1150*; About glass Melt controlled to 1100"C, it is a float bus. It was made to flow. Glass Melt is fabricated by the glass ribbon in a float bus, being cooled. It was. The glass ribbon was fabricated so that thickness might be set to 4 and Omm. On this glass ribbon, it is a ground. As a layer, the oxidization silicon film was formed so that it might become a thickness of 20 nm. In the float bus, after that, material gas was sprayed and the titanium oxide thin film was formed. In material gas, it is a Chi tetrachloride. Gas which adopted a tongue (TiCl) and acetic acid Ethyl (C H O), and was diluted with nitrogen gas to predetermined concentration
4 4 8 2
Was used. By adjusting the concentration and the bearer rate of material gas, the titanium oxide film was formed so that it might become a thickness of 30 nm.
[0109] Comparative examples 16 are zirconium oxide membrane and titanium oxide membrane force at the sputtering conditions same on the surface of a glass board as Example 20 and 23*26. After forming a photocatalyst layer, light It is marketing to the surface of a catalyst bed. spraying Ag particulate alcoholic dispersion liquid -- normal temperature -- dryness -- It is a Did thing.
[0110] the section SEM image Of Example 20 which did in this way and formed the antibacterial metal island -- a figure -- it is shown in 10. Hitachi electric field radiation type scanning electron microscope [ image / section SEM ] S -- It is Use about 4700. for carried out and it took a photograph. They are 5 kV and magnifying power about accelerating voltage. It is considered as 100,000 times and they are ten inclinations from a section. A photograph was taken. The angle of contact of an antibacterial metal island and a substrate was 90 degrees or less on the average. anti- -- The average diameters of the bacillus metal island were 20 nm of abbreviation.
[0111] the reflective electronic image of the surface Of Example 20 photoed by accelerating voltage lkV -- a figure -- it is shown in 11. Figure
In 11, the portion reflected to punctate is an antibacterial metal island. In a reflective electronic image It was based and the density of the antibacterial metal island was measured. The densities of an antibacterial metal island are 850 abbreviation / H m.<sup>2</sup>It came out.
[0112] the section SEM image Of Example 22 photoed on the same conditions as Example 20 -- a figure -- 12 -- a reflective electronic image -- a figure -- it is shown in 13, respectively. The angle of contact of an antibacterial metal island and a substrate is 90 degrees or less on an average. It was. The average diameter of the antibacterial metal island was abbreviation 11 Onm.
[0113] the same -- the section SEM image of comparative example 16 -- a figure -- it is shown in 14. Hitachi electric field [ image / SEM ] Emanated type scanning electron microscope S -- A photograph was taken using 4000. Accelerating voltage is expanded by 15 kV. Magnification It was considered as 50,000 times and a photograph was taken by ten inclinations from the section. Contact of antibacterial metal particles and a substrate The average diameters of the antenna of size Listen antibacterial-properties metal particles were 50 nm of abbreviation from 90 degrees on the average. the surface of comparative example 16 photoed by and 15 kV of accelerating voltage a secondary electron image -- a figure -- it is shown in 15. The densities of the antibacterial metal particles of comparative example 16 are about four pieces / H m.<sup>2</sup>It came out.
[0114] The following procedures estimated photooxidative degradation activity.
It is ultraviolet illuminance 1. OmW/cm to a sample.<sup>2</sup>It comes out, irradiates with ultraviolet rays for 1 hour, and is among a tedlar bag. After putting in a sample, it cuts using a polypropylene adhesion tape (made by 3M), and it is Included. Body was pasted up. Then, lvol% Asset after pouring in synthetic air 1L into a tedlar bag Aldehyde gas is poured in by 95mL gastight Syringe, and it is Assert Alde in a tedlar bag. Hyd dilution gas (90*100 ppm) was prepared. After the above-mentioned Asset aldehyde insufflation, Tedler It waited to intercept the light which enters into nog for 60 minutes, and for adsorption to reach an equilibrium situation. It That. Initial Asset aldehyde concentration is measured 60 minutes after The, and it is ultraviolet illuminance 1. OmW/cm.<sup>2</sup>Besides [ it comes out and purple ] Irradiation of the line was started. It is Assert aldehyde after 30 minutes, 60 minutes, 120 minutes, and 300-minute progress henceforth. Gas concentration was measured and photooxidative degradation activity was evaluated from the rate of change in the Asset aldehyde gas concentration in the range in which Asset aldehyde gas concentration carries out alignment reduction.
[0115] In addition, it is a valuation method of antibacterial properties, the antibacterial properties after dustcloth Wiping, a penetration color tone, and visible optical transmittance. It is as having explained previously.
[0116] the above -- a table -- 4 1* table -- 5 -- The following things became Brightness from the evaluation result indicated to 4.
[0117] Each example is ultraviolet illuminance 0. OlmW/cm.<sup>2</sup>Twins under the ultraviolet exposure which comes out, and * place Way To and the Outstanding antibacterial-properties effect were checked. Antibacterial effect according [ this ] to an antibacterial metal island It is shown that Result is demonstrated. as opposed to it -- comparative example 10 -- the bottom of an ultraviolet exposure, and * -- an antibacterial function is not exhibited under a place -- comparative example 11*; setting under * place in 13 -- anti- -- The power which a bacillus function reveals, and Ivy.
[0118] Each example whose average angle of contact of an antibacterial metal island is 90 degrees or less was maintaining high antibacterial properties after dustcloth Wiping. That is, antibacterial money of quantity even with after [ sufficient ] dustcloth Wiping The Genus island remained. as opposed to it -- the average angle of contact of an antibacterial metal island -- 90 degrees large comparative example 16 -- the antibacterial properties after dustcloth Wiping -- power and Ivy. That is, dustcloth Wiping The antibacterial metal island was removed.
[0119] Even after each example formed the antibacterial metal island, photooxidative degradation nature was maintained. It has suggested that the titanium oxide side is exposed and this can demonstrate a photocatalyst effect since the antibacterial metal island is formed discontinuously. A photocatalyst layer is formed to it. Power [ carry out ], the power [ have ] in which photooxidative degradation nature demonstrates Ivy comparative example 10, Ivy. Comparative example 14 and 15 There is too much antibacterial metal, and it is not formed in the shape of an island, but covers a photocatalyst layer nearly completely. Power [ have ] which photooxidative degradation nature demonstrates since it kept It was.
[0120] Although each example is making silver and copper with high conductivity deposit on the surface, surface resistance is 9.1chi10.<sup>7</sup>High Conductivity are low power and Ivy very much from omega/mouth. This is an antibacterial metal eye. A land is discontinuously formed on a titanium oxide film! /and To are suggested! /, To. [0121] each example -- visible optical transmittance difference before and behind formation of an antibacterial metal island deltatau15% or less it was . visible optical transmittance difference deltatau before and behind membrane formation of comparative example 14 on which an antibacterial metal of sufficient quantity to form a film was made to deposit to it is 15% or more -- change of a* and b* -- size Listen Intermediary in which appearance is quite bad! /and It was.
[0122] next, a table -- 6--1 and 6 -- which shows the antifungus in Example 20, 22*25 and (that whose main ingredients of an antibacterial metal island of all are silver) comparative example 10, 11, and * place of 13 to 2. An antifungal valuation method is as having explained previously.
[0123] [Front 6-1]
<img file="WO2008047810A1_D0019.tif" />
[table 6-2]
<img file="WO2008047810A1_D0020.tif" />
[0124] a table -- 6 -- 1 and 6 -- Comparative example 1 in which the antibacterial metal island is not formed as shown in 2 0 and 1 1 13 did not have antifungus. On the other hand, Example 20 in which the antibacterial metal island was formed and 22 25 is * place and Ultra spring 0. lmW/cm.<sup>2</sup>Also in any under irradiation, it is high. It had antifungus.
[0125] To <example 40 43 and comparative example 17 20>>
Next, the example and comparative example using template glass are explained. an example -- and -- As for the template glass used by the comparative example, the side on which an antibacterial metal is made to deposit is unevenness to the principal surface of the side opposite to. It is the glass board which was formed and was made opaque, and is general as a structural glass board. Further -- Example 42, 43 and comparative example 19, and the template glass used by 20 are heat treatment -- strong -- It turns. It is strength about being concrete and the template glass heated for 3 minutes with the heating furnace of 700"C. System air cooling was carried out. The tin oxide film was adopted as a ground film.
[0126] Membrane formation of a tin oxide film, and Iin Lin type sputter device^11by 111^8 Tooth Co.^ -- It carried out by the sputtering method using 6215. 5 The tin oxide film was formed by the reactive sputtering method under oxygen gas atmosphere using the metal tin target of X 15 inch size. Heating of a substrate is Applied power and Ivy at the time of membrane formation. Distance of a substrate and a target was made into 60 mm of abbreviation. In addition to this The details of the sputtering conditions of a tin oxide film are as follows.
[0127] The sputtering conditions at the time of tin oxide (SnO) membrane formation
* Target: sn
* Dregs J ground: 1 OmTorr
* Gas ratio : oxygen (O) 100%
* Injection power DC2. OkW: (power density: 4 and 13W/cm)<sup>2</sup>)
[0128] the details of an example and a comparative example, and the evaluation result of the various characteristics -- a table -- 7 and a table -- it is shown in 8.
In the case of template glass, it is Measurement condition even if it is the same sample by the influence of light scattering. The visible optical transmittance and the penetration color tone in this specification although transmissivity changes with affairs It is considered as the value acquired by the measuring method explained previously. Conditions of heat treatment for strengthening It may be the conditions of the usual strengthening and they may be the so-called conditions of a little more than[ half a ]-izing.
[0129] [-- table 7]
[] -- [
<img file="WO2008047810A1_D0021.tif" />
<img file="WO2008047810A1_D0022.tif" />
[0131] As shown in comparative example 17, the visible optical transmittance of template glass was as low as 43% of abbreviation. In Example 40*43, the maintainable antibacterial properties which decline in visible optical transmittance also divides few Without 10 are obtained. It was. Power [ have ] which most change of a color tone looks at, Ivy.
[0132] It is Depart about the antibacterial effect which was excellent in according to the present invention forming a detailed antibacterial metal island on a substrate, and controlling the quantity as explained above without spoiling transparency. The antibacterial substrate which carries out Vienna can be provided.
Industrial applicability
[0133] On all the articles in which, as for the antibacterial substrate of the present invention, microorganisms, such as fungi, such as bacteria and mold, and a virus, may touch, and a concrete target, The windowpane for construction, for partitions Glass, door glass, and glass for cars, Transparent [ the glass for a display a mirror, and for DNA analysis ] A substrate, a solar cell, an information portable device, health, medical science, electronic equipment, an optical component, for a biochemistry experiment Applicable to glassware, the inspection chip for medical science, and optical fiber 1 for a medical endoscope' operation To. The antibacterial substrate of the present invention using strengthening or the template glass formed into a little more than [ half ] is a bathroom door. It is suitable for especially a bathroom window.
[0134] Reduction of a problem the health which made bacteria and mold the cause since breeding of the Bacteria mold in a hospital, a nursing home, a residence, etc. was controlled when using the antibacterial substrate of the present invention, and sanitary is a term. Wait is carried out.
Contents2
29 sheets
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| JPH08109043A | Cites | Japan | Y | International search |
| JPH09111380A | Cites | Japan | Y | International search |
| JPH1097940A | Cites | Japan | Y | International search |
5 members in 4 offices
Priority claims8
| Document | Office | Kind | Date |
|---|---|---|---|
| 2006280850 | Japan | A | |
| 2006280850 | Japan | A | |
| 2006280865 | Japan | A | |
| 2006280865 | Japan | A | |
| 2006280850 | – | – | – |
| 2006280865 | – | – | – |
| JP20060280850 | – | – | – |
| JP20060280865 | – | – | – |
Members5
| Document | Office | Kind | |
|---|---|---|---|
| WO2008047810A1This record | World Intellectual Property Organization (WIPO) | A1 | |
| EP2088131A1 | European Patent Office (EPO) | A1 | |
| US2010015193A1 | United States of America | A1 | |
| JPWO2008047810A1 | Japan | A1 | |
| EP2088131A4 | European Patent Office (EPO) | A4 |
5 legal events, as 2 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Non-entry into the national phaseNENP | NENP | DE | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Ep: the epo has been informed by wipo that ep was designated in this application121 | 121 | WO |
Numbers
- Publication
- 2008/047810
- Publication, DOCDB
- 2008047810
- Publication, EPODOC
- WO2008047810
- Application
- 70202
- Application, DOCDB
- 2007070202
- Application, EPODOC
- WO2007JP70202
Titles2
- English
- ANTIBACTERIAL SUBSTRATUM AND PROCESS FOR PRODUCING THE SAME
- French
- Substrat antibactérien et son procédé de production
Classification
- CPC, 12
- C23C14/22
- A01N25/34
- C03C17/09
- C03C17/36
- C03C17/3607
- C03C17/3663
- C03C2204/02
- C03C2217/40
- C03C2217/71
- C23C14/185
- C23C14/228
- B01J35/39
- IPC, 10
- C03C17 09
- A01N25 08
- A01N59 16
- A01N59 20
- A01P3 00
- B01J35 00
- B32B15 04
- B32B17 06
- C03C17 36
- C23C14 34
Designated states4
- Regional, 4
- Zimbabwe
- Turkmenistan
- Türkiye
- Togo