CN106068079B - Antibiotic property component - Google Patents
Antibiotic property component Download PDFInfo
- Publication number
- CN106068079B CN106068079B CN201580013374.XA CN201580013374A CN106068079B CN 106068079 B CN106068079 B CN 106068079B CN 201580013374 A CN201580013374 A CN 201580013374A CN 106068079 B CN106068079 B CN 106068079B
- Authority
- CN
- China
- Prior art keywords
- antibiotic property
- overlay film
- film
- component
- property component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
- C03C17/09—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/261—Iron-group metals, i.e. Fe, Co or Ni
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/27—Mixtures of metals, alloys
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Laminated Bodies (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention relates to antibiotic property components, which is characterized in that it is formed over the transparent substrate by vapor phase method comprising forming selected from least one of Ni, Ni-P and Ni-Cr and with a thickness of the overlay film of 1nm ~ 10nm.
Description
Technical field
The present invention relates to antibiotic property components, more particularly to the component that antibiotic property and the transparency are excellent.
Background technique
In recent years, in the various uses headed by food processing industry, medical industry up to daily necessities, from health
From the perspective of aspect, for the purpose for the growth for inhibiting bacterium, mould etc., has studied use and impart antibiotic property, mildew resistance
Metal material.
But there is directly touching touch in the various occasions such as smart phone, display of computer recently and show
The chance of device, the case where going wrong in terms of leading to health because touching these displays, are also more.To previous antibiotic property metal
For material, the touch panel of the transparency can not be applied to.
In contrast, as have both the transparency and antibiotic property component, by the component for being able to report up to now enumerate as
Under.
Firstly, the known component (patent document 1) such as obtained in the organic series antibacterial agent of the internal mix of transparent resin or
Antibiotic property metallic compound (Ag) is added in glass material (organo-silicon compound) and stirs antibiotic property glass obtained from firing
Glass microballoon (patent document 2) makes antibacterial agent be scattered in component obtained from transparent resin, glass material like that.
Then, it is also reported antibiotic property polypropylene screen, is laminated at least one surface layer of substrate layer containing inorganic
Antibacterial agent (make to support with the complex compound etc. of the metal of silver representative and be obtained in zeolite, porous silica etc.) and mainly by gathering
The layer (patent document 3) that propylene is constituted.
In addition, there is also antibacterial film, for be arranged on base material film with a thickness of 0.05 ~ 3 μm and containing adhesive resin and
The antibacterial film of the antibiotic layer of antibacterial agent, which is characterized in that antibacterial agent is to make the aluminosilicate overlay film containing antibiotic property metal ion
Containing obtaining (patent document 4) in silica gel；Antibacterial glass forms on the glass surface by sol-gal process and includes
The overlay film (patent document 5) of antibiotic property metal (silver) ion.
Further, it is also known that it is following it is equal transparent resin, glass surface on form the antibacterial that photocatalyst layer obtains
Component: titanium oxide evaporation film, which is characterized in that stack gradually polymeric membrane, the metallic film on its at least 1 face or metal oxidation
Object film and thin film of titanium oxide form (patent document 6)；Photocatalyst film, to be stacked gradually on the plastic film comprising silicon
The film layer and photocatalyst layer of oxide and/or aluminum oxide form (patent document 7).
It is contemplated, however, that above-mentioned, the following problems exist respectively in the prior art.
The antibacterial component made by method described in patent document 1 and 2 is other than effect is insufficient, due to making antibacterial
Agent is scattered in component entirety, therefore the antibacterial agent for showing function is only few a part in the antibacterial agent of cooperation.
In addition, insufficient by the antibacterial effect of the antibacterial component of the production of method described in patent document 3.In addition to this,
The superficial layer for having antibacterial agent due to will form thick temporary dispersion, the ratio of the antibacterial agent functioned are small.
Antibacterial effect by the antibacterial component of the production of method described in patent document 4 and 5 is insufficient.Further, for
It is formed with the antibacterial component of photocatalyst layer disclosed in patent document 6 or 7, exists and is showed not in the case where irradiating the environment less than light
Out the problem of antibiotic property.
The antibiotic property component excellent as antibiotic property reports the alloy film covered conduct durability of Ni-P system, antibiotic property, prevents
Component (patent document 8) obtained from the excellent surface-treated metal material of algae property is covered on metal material, although it has
Much higher than the antibacterial action of above-mentioned shown antibacterial component, but the metal as substrate and the Ni-P overlay film as surface coating are equal
For light-proofness, there are problems that the antibacterial agent of touch panel for being not used as needing the transparency etc..
In addition, also leading to the problem of the declines of antibiotic property when the film for being as thin as the level with the transparency is made.
The present invention is formed in view of such project, and it is an object of the present invention to provide having both the antibiotic property of the excellent transparency and antibiotic property
Component.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 8-199002 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2006-76854 bulletin
Patent document 3: Japanese Unexamined Patent Publication 9-248883 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2002-36447 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2001-97735 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2000-103003 bulletin
Patent document 7: Japanese Unexamined Patent Publication 2000-225663 bulletin
Patent document 8: No. 3902329 bulletins of Japanese Patent Publication No..
Summary of the invention
In order to solve aforementioned problems, further investigation is repeated in the present inventor, and discovery can solve by following compositions
State project.
That is, antibiotic property component described in one aspect of the present invention is characterized in that, by vapor phase method in transparent substrate
It is upper to be formed comprising forming selected from least one of Ni, Ni-P and Ni-Cr and with a thickness of the overlay film of 1nm ~ 10nm.
Specific embodiment
The inventors of the present invention are to solve above-mentioned the problems of the prior art and implement research from various angles.And it is conceived to logical
It is alloy film covered to be often considered the Ni system that its application is defined in metal component, discovery will by vapor phase method in specific thickness range
It is covered, it is possible thereby to maintain antibiotic property and be also maintained as the adaptation of overlay film, integrality, while ensuring the transparency,
To realize the present invention.
Antibiotic property component of the invention is obtained from covering Ni based coating on transparent substrate, but such as above-mentioned patent text
The high Ni based coating of antibiotic property shown in offering 8 is usually covered by plating, electroless plating, therefore has been generally acknowledged that it is difficult to cover
It is placed on transparent component as glass, transparent resin.In addition, vacation can cover, also think that the overlay film of Ni is opaque, from
And it is difficult to maintain the transparency.
In contrast, the inventors of the present invention have found: when forming Ni based coating, if passing through vapor phase method, particularly sputtering method
It is covered, then can be covered on the transparent component such as glass, transparent resin, and the model by making its film thickness 1nm ~ 10nm
It encloses, the transparency and antibiotic property can be taken into account.
Hereinafter, the embodiment for antibiotic property component of the present invention is specifically described, but the present invention does not limit
In these.
Antibiotic property component described in present embodiment is characterized in that, is formed over the transparent substrate by vapor phase method and includes
It is formed selected from least one of Ni, Ni-P and Ni-Cr and with a thickness of the overlay film of 1nm ~ 10nm.It is believed that according to the present invention,
The antibiotic property component for having both the excellent transparency and antibiotic property can be provided.
In present embodiment, form overlay film is to be selected from least one of Ni, Ni-P and Ni-Cr, but these Ni systems are covered
The covering method of film can be expanded using the vapor phase method to form a film under vacuum and be generated shadow in terms of showing antibiotic property
The limitation range of content for addition element contained in loud overlay film.That is, for existing illustrated by above patent document 8
Have be considered as in technology it is necessary into overlay film add P for, be added or without addition can show it is excellent
Antibiotic property.In addition, even if to for example add Cr for the purpose of carrying out unmagnetize to Ni to be easy to carry out sputtering processing
Equal elements, can also play excellent antibiotic property.
In addition, for be defined as 1 ~ 10% range in the prior art overlay film in P content do not limit, can will
Ni-P is used as antibiotic property overlay film.
Further, in the prior art, for the hydrogen content in the overlay film for being defined as 0.00001% ~ 0.005% range,
If it exceeds the range, then the toughness that there is overlay film significantly reduce and become easy crack, furthermore adaptation also reduces
Problem, therefore there are the upper limits.It but in present embodiment, can also form a film, and can show same even more than the range
Etc. more than degree antibiotic property.
That is, by being covered with vapor phase method, intentionally being added in film forming in present embodiment or not adding hydrogen,
It can show excellent antibiotic property.Its reason not yet determines, but can speculate the reason is that as the chamber to form a film
The hydrogen for including in the vapor of residual gas in room is mixed into the form of individual H or OH into overlay film.
It is formed on metal in the antibiotic property component that Ni-P overlay film obtains by the prior art, the hydrogen amount in overlay film is with quality
Meter needs for 0.005% hereinafter, pointing out in the prior art, if deviateing the range, the toughness of overlay film is reduced and cracked.
But in present embodiment in the case where covering by vapor phase method, by forming 10nm film below, to make film
Stress reduces and with distinctive overlay film tissue morphology of vapor phase method etc., therefore will not generate overlay film contains more hydrogen
The problem of crackle of overlay film.On the contrary, from the viewpoint of productivity, since the vacuum before being transferred to film forming can be loosened
Degree limitation, therefore the overlay film containing the hydrogen amount for having more than 0.005% (quality %) is more suitable for.
In present embodiment, when overlay film includes hydrogen, in order to further increase antibiotic property, preferably 0.005% or more, the upper limit
It is not particularly limited, from the viewpoint of ensuring overlay film toughness, preferably 1% or less.
As vapor phase method, sputtering method is particularly preferably used.More specifically, such as Japanese Unexamined Patent Publication 2008- can be used
Plasma CVD equipment disclosed in No. 196001 bulletins, continuous film forming disclosed in Japanese Unexamined Patent Publication 2010-265527 bulletin
Device etc. forms Ni by sputtering method and is tied to form film.
In present embodiment, overlay film is selected from least one of Ni, Ni-P and Ni-Cr, as long as these overlay films can
To play very excellent antibiotic property.These, it is preferred to use Ni-Cr forms overlay film by sputtering method, it is possible thereby to one
And obtain the very excellent transparency and antibiotic property.
When using Ni-P as overlay film, the P content in the Ni-P is not limited, it may be desirable to be usually 2% or more, preferably
It is 5% or more.This be for and meanwhile show the viewpoint of antibiotic property, mildew resistance, anti-algae property.In addition, not limited especially about the upper limit
It is fixed, it is 20% hereinafter, preferably 10% or less from the viewpoint of anti-algae property.
When using Ni-Cr as overlay film, the Cr content in the Ni-Cr is not limited, it may be desirable to be usually 1% or more, excellent
It is selected as 10% or more.This is the viewpoint of the electrochemical stability for overlay film.In addition, being not particularly limited about the upper limit, from overlay film
It is 50% hereinafter, preferably 30% or less from the perspective of toughness.
The film thickness of above-mentioned overlay film is 1nm or more and 10nm or less.If being lower than 1nm, there are the risks of antibiotic property deterioration.
On the other hand, if film thickness is more than 10nm, the tendency of transparent reduction is strong.Preferred overlay film film thickness is 1nm or more and 5nm
Hereinafter, being further 1nm or more and 3nm or less.It is believed that by adjusting to such film thickness, the available transparency with
The superior antibiotic property component of the balance of antibiotic property.
It should be noted that in the prior art, it has been described that about the hydrogen content in overlay film is limited to 0.00001% ~
0.005% range, even if the hydrogen comprising 0.005% (50ppm) or more, antibiotic property will not reduce.It is believed that in overlay film
Hydrogen amount it is more more, antibiotic property more increase, be that the hydrogen the how the more preferred instead from the viewpoint of antibiotic property.But in existing skill
In art, the hydrogen amount in overlay film is defined as 0.005% (50ppm) hereinafter, this is because the if it exceeds machine of the value then plating overlay film
Tool property (toughness) reduces.All in all it is considered that its reason is that overlay film becomes easy rupture because of hydrogen embrittlement.Another party
The thickness in face, overlay film is thinner, then hydrogen can more reduce adverse effect caused by engineering properties (toughness) deterioration aspect.It therefore can be with
Think, in the present embodiment, not will receive the drop of the overlay film toughness as caused by hydrogen as long as being 1 ~ 10nm range as long as the film thickness of overlay film
Low influence, antibiotic property further increase.
As transparent substrate used in present embodiment, can using with the transparency glass, laminar film, quartz,
Oxide crystal, transparent resins etc., without any restriction, if it is considered that actual application, then can compatibly use large size
Glass plate, strip plastic foil (laminar film) etc..
It is not particularly limited as foregoing plastics film, transparent and excellent optical characteristics poly- terephthaldehyde can be used for example
It is sour glycol ester (PET) film, polyethylene naphthalate (PEN) film, polycarbonate (PC), cyclic olefin (CO) film, heat-resisting
Excellent polystyrene (PS) film etc. of excellent polyimides (PI) film of property, barrier property.
The suitable application of antibiotic property component as present embodiment, it is believed that have use for example as described below
On the way.
By being used as the health whens display protective film of smart phone etc., the directly display etc. of touching touch panel
The problem of aspect, is improved.
Alternatively, the antibacterial component using plastic foil as the present embodiment of substrate can be used as transparent packaging material and use
In food, pharmaceutical packing, the improvement in terms of health may be implemented.
In addition it is also preferred that being used in the field by vinyl house, glass greenhouse cultivation vegetables.Particularly, for latitude
It spends for high region (such as Europe), become problem is that plastic foil, glass because generating the bacteriums such as algae lead to transparent drop
It is low, thus light-proofness is caused to reduce, further thus causes the temperature in greenhouse to reduce, the photosynthesis of vegetables reduces to make
The productivity of vegetables reduces.And hence it is also possible to which the antibiotic property component of present embodiment is applied to such vinyl house, glass
Greenhouse.
Further, it is also possible to which the antibiotic property component of present embodiment to be applied to the inner surface of glass together.That is, by
Between insulating air layer of the clamping for the purpose of being insulated glass insulating air layer side surface on apply the antibacterial of present embodiment
Property component to endowing antibacterial, it is possible thereby to inhibit to result from because of long-time service on the insulating air layer side surface of glass
Stain (as bacterium, mould breeding caused by) generation.
This specification discloses the technology of various modes as described above, can be solved by mode as described below above-mentioned
Project.It is clear that being referred to the full content recorded in this specification the present invention is not limited to solution below.
That is, antibiotic property component described in one aspect of the present invention is characterized in that, by vapor phase method in transparent substrate
It is upper to be formed comprising forming selected from least one of Ni, Ni-P and Ni-Cr and with a thickness of the overlay film of 1nm ~ 10nm.By having this
The composition of sample can provide antibiotic property and transparent excellent component.
In above-mentioned antibiotic property component, aforementioned transparent substrate is preferably laminar film or glass plate.It is considered that it is possible thereby to mentioning
For being more suitable for the component of practical application.
In addition, aforementioned vapor phase method is preferably sputtering method in above-mentioned antibiotic property component.It is considered that it is possible thereby to more reliably
Obtain the very excellent transparency and antibiotic property.
Further, in above-mentioned antibiotic property component, aforementioned overlay film is preferably the overlay film for including Ni-Cr.It is considered that thus may be used
More reliably to obtain said effect.
In addition, Cr content is preferably 20% or more relative to aforementioned Ni-Cr overlay film in above-mentioned antibiotic property component.It is considered that
It is possible thereby to more reliably obtain said effect.
In addition, in above-mentioned antibiotic property component, in order to be showed antibiotic property effect in 10nm very thin overlay film below,
Hydrogen content in aforementioned overlay film is preferably 0.005 mass % or more.Even if constituent content is 0.005 mass % or more, according to this hair
It is bright to form a film, and the antibiotic property of equal extent or more can be shown.
Above-mentioned antibiotic property component plays excellent effect by being used as packaging material, vinyl house or display applications
Fruit.
Further illustrate the present invention by the following examples, but the scope of the present invention is not limited to these.
Embodiment
(embodiment 1)
In the Ar atmosphere of 0.3Pa, by sputtering method (device name: towards R&D in line style sputtering equipment, (strain) Kobe
Steel processed is made), using target (the overlay film raw material for carrying out spatter film forming), in pen film, (Supreme Being people's デ ュ Port Application corporation, Q65FA (are produced
The name of an article), with a thickness of 100 μm) on the covering of Ni-P (P content 5%) overlay film is carried out with the thickness of 3nm.As palladium material, using pair
Copper sheet implements the palladium material that electroless Ni-P plating obtains, and particularly, does not carry out the addition of hydrogen in overlay film.Chamber inner pressure before film forming
Power is 2 × 10-4Pa is horizontal.
It should be noted that film thickness be carry out the covering of about 200nm in advance to calculate in advance film forming speed and by by this at
Calculated value that film speed obtains is found out.Film thickness in embodiment below and comparative example is calculated by this method.
In antibiotic property component obtained in embodiment 1, the hydrogen content of overlay film is about 0.001%.For hydrogen content, in phase
The overlay film of 200nm thickness under the conditions of on the glass substrate that forms a film, using passing through atmospheric pressure ionization mass spectrograph (API-
MS, according to the document in rock field et al.: Kobe Steel's skill report/vol.47, No.1, p.24, Apr.1997 is analyzed) it obtains
Hydrogen quantitative analysis results and by the obtained hydrogen of GDOES analysis as a result, production both standard curve, further, root
According to the comparison of the GDOED analysis result of the overlay film with aftermentioned comparative example 1, thus it is speculated that be about 0.001%.Also survey in the same way
Measure the hydrogen content in embodiment below and comparative example.It should be noted that making overlay film with a thickness of 200nm in the measurement of hydrogen content
It is because of in the film thickness lower film thickness of 3nm, to can not effectively be analyzed.
(embodiment 2)
The H of 0.1Pa is added into the Ar of 0.3Pa2, in addition to this, in the same manner as in Example 1, by sputtering method,
The covering for carrying out Ni-P (P content 5%) overlay film of 3nm on pen film using palladium material, obtains antibiotic property component.
The hydrogen content of obtained overlay film is about 0.001%.Although being added to a large amount of H in atmosphere2, but know as a result,
The hydrogen amount for including in obtained overlay film does not change.
(embodiment 3)
Use the Ni-P (P content 2%) of the hydrogen comprising 0.001% as palladium material, carries out Ni-P (P content 2%) overlay film
Covering, in addition to this, obtains antibiotic property component in a manner of similarly to Example 1.
(embodiment 4)
Use Ni-Cr (20%) alloy as palladium material, carry out Ni-Cr (20%) alloy film covered covering, in addition to this, with
The same mode of embodiment 1 obtains antibiotic property component.The hydrogen content of obtained overlay film is about 0.001%.
(embodiment 5)
Use Ni as palladium material, in addition to this covering for carrying out Ni overlay film is resisted in a manner of similarly to Example 1
Bacterium property component.
(embodiment 6)
Transparent substrate is changed to glass substrate, and (Song Lang nitre subsidiary system, " MICRO SLIDE GLASS S9111 " is thick
Spend 0.8 ~ 1.0mm), in addition to this, antibiotic property component is obtained in a manner of similarly to Example 1.
(embodiment 7)
The indoor degassing process of chamber for carrying out 1 ~ 2 hour glass baseplate and device, 10-5The chamber atmosphere of Pa magnitude
Overlay film is formed under (high vacuum state), in addition to this, antibiotic property component is obtained in a manner of similarly to Example 6.It is obtained
The hydrogen content of overlay film is about 0.0005%.
(embodiment 8)
It is continuously formed a film on pen film using roll coater, in addition to this, antibacterial is obtained in a manner of similarly to Example 1
Property component.By using roll coater, film is continuously supplied into film-forming region, therefore vapor, the chamber before film forming can be brought into
Atmosphere is 10-3Pa magnitude (low vacuum state).The overlay film of 3nm is formed by adjusting the transport velocity of film.It is obtained to cover
The hydrogen content of film is about 0.007%.It is not cracked in overlay film.
(embodiment 9)
Use Ni-P (P content 2%) as palladium material, carries out the covering of Ni-P (P content 2%) overlay film, in addition to this, with
Mode similarly to Example 8 obtains antibiotic property component.
(embodiment 10)
Use Ni-Cr (20%) alloy as palladium material, carry out Ni-Cr (20%) alloy film covered covering, in addition to this, with
The same mode of embodiment 8 obtains antibiotic property component.
(embodiment 11 ~ 13)
Film formation time is adjusted, changes the thickness of overlay film as shown in Table 1 below, in addition to this, with similarly to Example 1
Mode obtains antibiotic property component.
(embodiment 14 ~ 18)
Film formation time is adjusted, changes the thickness of overlay film as shown in Table 1 below, in addition to this, with similarly to Example 4
Mode obtains antibiotic property component.
(comparative example 1)
As the benchmark of antibiotic property, the method recorded by above patent document 8 (No. 3902329 bulletins of Japanese Patent Publication No.)
Make sample.Specifically, by the plating for assigning about 3 μm of Ni-P (2%) on SUS304 stainless steel substrate, to obtain
Antibiotic property component.The hydrogen content of obtained plating overlay film is 0.001%.
(comparative example 2)
Want to form overlay film on transparent pen film using method identical with comparative example 1, but can not cover well.
(comparative example 3)
Want to form overlay film on transparent glass substrate using method identical with comparative example 1, but can not cover well
Lid.
(comparative example 4)
As the benchmark of antibiotic property, the PEN substrate of the 0.1mm thickness of transparent substrate will be used as in embodiment 1 as nothing
The plastic foil of overlay film is evaluated.
(comparative example 5 ~ 7)
Film formation time is adjusted, changes the thickness of overlay film as shown in Table 1 below, in addition to this, with similarly to Example 1
Mode obtains antibiotic property component.
(comparative example 8)
Film formation time is adjusted, changes the thickness of overlay film as shown in Table 1 below, in addition to this, with similarly to Example 4
Mode obtains antibiotic property component.
[table 1]
(evaluation)
For sample obtained in above-described embodiment and comparative example, conduct the following evaluation.
(antibiotic property evaluation)
Evaluation for antibiotic property is based on JISZ2801 method, is inoculated with 1.8 ~ 2.8 × 10E5 staphylococcus aureus, right
Viable count after 24 hours is counted, and is evaluated with following benchmark.
× viable count increases；
▲ viable count is 10% ~ 100%
△ viable count is 1% ~ 10%
Zero viable count is 0.1% ~ 1%
◎ viable count is lower than 0.1%.
(transparency evaluation)
Evaluation for the transparency side by side with the transparent substrate that does not cover by the substrate covered is placed
On the blank sheet of paper paper for being printed with text, commented by the visuality with the judgement of the transparency visually carried out and background text
Valence.The benchmark of evaluation is as follows:
◎ has the transparency being not different on visually with transparent substrate.
Zero can be identified as it is transparent, but if then can be observed slightly to colour with untreated substrate side-by-side comparison.
△ observes obvious coloring, but can be with the text of visual confirmation to background.
× can not visual confirmation to background text.
(discussion)
By going out as the result is shown for table 1, the antibiotic property component of embodiment 1 ~ 18 according to the present invention is in the transparency and antibacterial
Property the two in terms of it is excellent.
In contrast, it cannot ensure the transparency or also not by being electroplated in the comparative example 1 ~ 3 that forms a film to be also observed
It can be carried out the result of covering.In addition, also being confirmed in the comparative example 5 ~ 8 for forming overlay film using vapor phase method, if the thickness of overlay film
It spends thin, is unable to get antibiotic property (comparative example 5), whereas if the thickness of overlay film is blocked up, is unable to get the transparency and (compares
Example 6 ~ 8).
In addition, according to the result of embodiment 1 ~ 3,7 and 8 it is found that in the present invention, even if unlike previous uses the conjunction of Ni system
The antibiotic property component that golden overlay film obtains intentionally controls hydrogen amount like that, can also show excellent antibiotic property.The content of hydrogen and existing
Overlay film (embodiment 1,3-7), the hydrogen content for having technology (above patent document 8) same are more equal than previous more overlay film (embodiment 8)
It shows the identical transparency and antibiotic property, but does not need prolonged vacuum row as embodiment 1,3-7 in embodiment 8
Gas, therefore, the antibiotic property component containing the hydrogen greater than 0.005% are more suitable for from the viewpoint of antibiotic property and productivity.It answers
Explanation is given, for the antibiotic property component of embodiment 8, there are overlay films in the opinion of the prior art (above patent document 8)
The opinion to become fragile, but in this test substantially without overlay film crackle the problems such as.
It should be noted that if considered from the metallic atom size (radius is about 0.3nm or so) for forming overlay film,
Reach average 1 or 2 atom or so in the film of 0.5nm or so, for the company of being formed uniformly in probabilistic film forming phenomenon
It is excessively thin for continuous film, therefore although the transparency is high a possibility that well, being unable to give full play out antibiotic property, therefore rather than the phase
It hopes.It is therefore contemplated that the thickness of overlay film needs for 1nm or more.
Based on the application is willing to 2014-050029 by Japanese patent application laid filed on March 13rd, 2014, content
It is included in the application.
In order to show the present invention, the present invention is adequately and sufficiently illustrated by previous embodiment, but should
It recognizes, as long as those skilled in the art, then easily can change and/or improve to aforementioned embodiments.Therefore,
As long as change mode or mode of ameliorating that those skilled in the art implement are not depart from the claim recorded in claims
Interest field level, then the right to be interpreted that the claims are included in for the change mode or the mode of ameliorating
In range.
Industrial applicibility
The present invention has extensive industrial applicibility in the technical field of antibiotic property component.
Claims (7)
1. antibiotic property component, be covered with the overlay film formed over the transparent substrate by vapor phase method, the overlay film include selected from Ni,
At least one of Ni-P and Ni-Cr and with a thickness of 1nm ~ 5nm, the vapor phase method is sputtering method.
2. antibiotic property component, be covered with the overlay film formed over the transparent substrate by vapor phase method, the overlay film include selected from Ni,
At least one of Ni-P and Ni-Cr and with a thickness of 1nm ~ 5nm, the hydrogen atom content in the overlay film be 0.005 mass % with
On, the vapor phase method is sputtering method.
3. antibiotic property component as claimed in claim 1 or 2, wherein the transparent substrate is laminar film or glass plate.
4. antibiotic property component as claimed in claim 1 or 2, wherein the overlay film is the overlay film comprising Ni-Cr.
5. antibiotic property component as claimed in claim 4, wherein Cr content is 20 mass % relative to the Ni-Cr overlay film total amount
More than.
6. antibiotic property component as claimed in claim 1 or 2, wherein the overlay film with a thickness of 1nm ~ 2nm.
7. antibiotic property component as claimed in claim 1 or 2, is used for packaging material, vinyl house or display.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014050029A JP6336789B2 (en) | 2014-03-13 | 2014-03-13 | Antibacterial material |
| JP2014-050029 | 2014-03-13 | ||
| PCT/JP2015/051474 WO2015136986A1 (en) | 2014-03-13 | 2015-01-21 | Antibacterial member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106068079A CN106068079A (en) | 2016-11-02 |
| CN106068079B true CN106068079B (en) | 2019-11-29 |
Family
ID=54071440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580013374.XA Active CN106068079B (en) | 2014-03-13 | 2015-01-21 | Antibiotic property component |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6336789B2 (en) |
| KR (1) | KR102006528B1 (en) |
| CN (1) | CN106068079B (en) |
| WO (1) | WO2015136986A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112462B (en) * | 2018-09-30 | 2020-08-25 | 中国科学院宁波材料技术与工程研究所 | Electrothermal antibacterial coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000198709A (en) * | 1998-11-06 | 2000-07-18 | Kobe Steel Ltd | Antimicrobial member |
| EP1420084A1 (en) * | 2001-08-21 | 2004-05-19 | Kabushiki Kaisha Kobe Seiko Sho | MEMBER EXCELLENT IN ANTIBACTERIAL AND/OR ANTIALGAE EFFECTS AND PROCESS FOR PRODUCING THE SAME |
| WO2007147842A2 (en) * | 2006-06-21 | 2007-12-27 | Agc Flat Glass Europe Sa | Substrate with antimicrobial properties and process for the production of an antimicrobial substrate |
| EP2018960A1 (en) * | 2006-05-17 | 2009-01-28 | Ishida Co., Ltd. | Antibacterial laminate |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08199002A (en) | 1995-01-30 | 1996-08-06 | Unitika Ltd | Antibacterial resin composition |
| JPH09248883A (en) | 1996-03-14 | 1997-09-22 | Toray Ind Inc | Antibacterial polypropylene film |
| JP3902329B2 (en) * | 1998-05-29 | 2007-04-04 | 株式会社神戸製鋼所 | Surface-treated metal material with durability, antibacterial properties, algae-proofing properties and anti-fouling properties |
| JPH11349422A (en) * | 1998-06-08 | 1999-12-21 | Toto Ltd | Member having antibacterial agent layer and its production |
| JP2000103003A (en) | 1998-09-30 | 2000-04-11 | Oji Paper Co Ltd | Titanium oxide deposited film |
| JP3695965B2 (en) * | 1998-11-06 | 2005-09-14 | 株式会社神戸製鋼所 | Antibacterial powder and antibacterial member for surface treatment |
| JP2000225663A (en) | 1999-02-08 | 2000-08-15 | Toyo Ink Mfg Co Ltd | Photocatalyst film |
| JP2001097735A (en) | 1999-10-01 | 2001-04-10 | Nippon Electric Glass Co Ltd | Antibacterial glass and its production method |
| JP2002036447A (en) | 2000-07-24 | 2002-02-05 | Oike Ind Co Ltd | Antibacterial film and antibacterial yarn |
| JP2006076854A (en) | 2004-09-10 | 2006-03-23 | Nippon Electric Glass Co Ltd | Antibacterial glass fine sphere and manufacturing method therefor |
-
2014
- 2014-03-13 JP JP2014050029A patent/JP6336789B2/en active Active
-
2015
- 2015-01-21 CN CN201580013374.XA patent/CN106068079B/en active Active
- 2015-01-21 WO PCT/JP2015/051474 patent/WO2015136986A1/en active Application Filing
- 2015-01-21 KR KR1020167018355A patent/KR102006528B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000198709A (en) * | 1998-11-06 | 2000-07-18 | Kobe Steel Ltd | Antimicrobial member |
| EP1420084A1 (en) * | 2001-08-21 | 2004-05-19 | Kabushiki Kaisha Kobe Seiko Sho | MEMBER EXCELLENT IN ANTIBACTERIAL AND/OR ANTIALGAE EFFECTS AND PROCESS FOR PRODUCING THE SAME |
| EP2018960A1 (en) * | 2006-05-17 | 2009-01-28 | Ishida Co., Ltd. | Antibacterial laminate |
| WO2007147842A2 (en) * | 2006-06-21 | 2007-12-27 | Agc Flat Glass Europe Sa | Substrate with antimicrobial properties and process for the production of an antimicrobial substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6336789B2 (en) | 2018-06-06 |
| WO2015136986A1 (en) | 2015-09-17 |
| KR20160096166A (en) | 2016-08-12 |
| KR102006528B1 (en) | 2019-08-01 |
| JP2015174827A (en) | 2015-10-05 |
| CN106068079A (en) | 2016-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10155691B2 (en) | Antimicrobial glass articles and methods of making and using same | |
| EP3010866B1 (en) | Antimicrobial glass articles with improved strength and methods of making same | |
| Shemesh et al. | Antibacterial and antifungal LDPE films for active packaging | |
| GB2472968A (en) | Antimicrobial coatings | |
| TW200802423A (en) | Crystalline transparent conductive thin film, method of producing the same, transparent conductive film, and touch panel | |
| CN103909699A (en) | Coated member and making method thereof | |
| MX2014008572A (en) | Substrate provided with a stack having thermal properties and comprising four functional metal films. | |
| EP2584074A3 (en) | Large area deposition and doping of graphene, and products including the same | |
| WO2012135294A3 (en) | Antimicrobial action of cu, cuo and cu2o nanoparticles on glass surfaces and durable coatings | |
| MX2011008989A (en) | Coated article with sputter-deposited transparent conductive coating capable of surviving harsh environments, and method of making the same. | |
| US20160086683A1 (en) | Conductive film and electronic device having conductive film | |
| JP2017518949A (en) | Surface nitrided alkali-free glass | |
| CN106068079B (en) | Antibiotic property component | |
| JP2018513920A (en) | Water-repellent nano-coating agent for vacuum deposition having antibacterial activity and coating method using the same | |
| PL2074239T3 (en) | Low temperature method of making a zinc oxide coated article | |
| Aissani et al. | Magnetron sputtering of transition metal nitride thin films for environmental remediation | |
| Yao et al. | Antibacterial and tribological performance of carbonitride coatings doped with W, Ti, Zr, or Cr deposited on AISI 316L stainless steel | |
| MX2021007953A (en) | Polyethylene compositions and articles with good barrier properties. | |
| Iconaru et al. | Preparations of silver/montmorillonite biocomposite multilayers and their antifungal activity | |
| WO2018117759A3 (en) | Zinc-based plated steel material having excellent sealer adhesion and composition for forming post-treatment film | |
| MX359624B (en) | Method of making coated article having anti-bacterial and/or anti-fungal coating and resulting product. | |
| KR101487309B1 (en) | A glass with the antibacterial function and its manufacturing method | |
| JP5776260B2 (en) | Water vapor barrier film | |
| JP3163574U (en) | Surface protection film for touch panel | |
| Youssef et al. | A novel approach to prepare Poly (vinyl acetate)/Ag nanocomposite for effective antimicrobial coating applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |