CN109312193A - Antifouling cover film and antifouling nappe - Google Patents
Antifouling cover film and antifouling nappe Download PDFInfo
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- CN109312193A CN109312193A CN201780034837.XA CN201780034837A CN109312193A CN 109312193 A CN109312193 A CN 109312193A CN 201780034837 A CN201780034837 A CN 201780034837A CN 109312193 A CN109312193 A CN 109312193A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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Abstract
Antifouling cover film of the invention is formed in the surface of covering object, is at least made of nano particle, has bumps, and the radius of curvature of protrusion is in 100nm or less.After the hybrid analog-digital simulation dust for mixing organic system simulation dust and inorganic system's simulation dust adheres to and is shaken; it is shot using optical microscopy; binary conversion treatment is carried out to captured image; using the area ratio of the above-mentioned hybrid analog-digital simulation dust of the remaining calculated by above-mentioned processing as dust bond area; using the dust bond area on antifouling cover film relative to the dust bond area on the surface of not formed antifouling cover film ratio as when dust adhesive rate, the dust adhesive rate of antifouling cover film is below 15%.
Description
Technical field
The present invention relates to the antifouling cover film that can prevent or inhibit the attachment of " stemness " dirt such as dust well and surfaces
The antifouling nappe covered by the antifouling cover film.
Background technique
Even if the setting place of the various article articles used in everyday is in doors, can also adhere to time going by
Various dirts.As representative dirt, hydrophilic dirt (water-based soils) and lipophilic dirt can be enumerated
(oily dirt).These dirts are with the dirt of " moist " that water or oil etc. " liquid " are medium (solvent or dispersing agent etc.).
Therefore, it as the technology (anti-soil technology) for preventing these dirts, carries out assigning the surface of article all the time and dial
Technology that is aqueous or dialling oiliness is so that water or oil as medium are not easy to adhere to.For example, Patent Document 1 discloses one kind
Application composition, both hydrophilic dirt and lipophilic dirt in order to prevent, the application composition include have 15nm with
Under average grain diameter silica ultramicro powder and fluorinated resin particle, and they are cooperated with defined mass ratio.
But " moist " dirt not just as described above of dirt accompanying by article surface, there is also such as dirt
Not via the dirt (dry dirt) of " stemness " of the media such as water or oil as angstrom.As preventing the antifouling of this stemness dirt
Technology can typically enumerate imparting antistatic property.For example, Patent Document 2 discloses in order to make polyolefin-based resins
The duration of the antistatic property of composition is excellent, uses the rouge of the amino ethyl ethanolamine of the fatty acid with specific carbon atom number
Fat acid amide.
Existing technical literature
Patent document
Patent document 1: No. 2008/087877 pamphlet of International Publication No.
Patent document 2: Japanese Unexamined Patent Publication 2011-256293 bulletin
Summary of the invention
Technical problems to be solved by the inivention
But it is difficult to fully prevent or inhibit the stemness dirt such as dust using the above-mentioned prior art.
For example, application composition disclosed in patent document 1 to be for the purpose of preventing moist dirt, as lipophilic dirt
The tobacco tar of oil smoke or tobacco is instantiated, instantiates dust (using loam dust in the Northeast in embodiment) as hydrophilic dirt.
Dust or dust is not there is only hydrophilic stains (moist dirt), and there is also stemness dirts, in patent document 1 for preventing
Stemness dirt is not studied adequately.In addition, imparting antistatic property cited by patent document 2, all the time resin at
It is widely adopted in the field of type object etc., in the viewpoint for being better protected from or inhibiting stemness dirt, still has the leeway of discussion.
The present invention is the invention completed to solve such technical problem, and its purpose is to provide can preferably prevent
Only or inhibit stemness (dry) dirt anti-soil technology.
For solving the technical solution of technical problem
The present inventor has made intensive studies above-mentioned technical problem, as a result originally finds to do in order to prevent
Property the attachment of (dry) dirt, inhibit except electrostatic attraction except through antistatic, it is also necessary to consider the model on article surface
De Huali etc., so as to complete the present invention.
That is, in order to solve the above-mentioned technical problem, antifouling cover film of the invention is constituted as follows: it is formed in covering object
Surface, be at least made of nano particle, the antifouling cover film have bumps, and the radius of curvature of protrusion in 100nm hereinafter,
Also, after the hybrid analog-digital simulation dust for mixing organic system simulation dust and inorganic system's simulation dust adheres to and is shaken,
It is shot using optical microscopy, binary conversion treatment is carried out to captured image, by the remaining calculated by above-mentioned processing
The area ratio of above-mentioned hybrid analog-digital simulation dust as dust bond area, by the dust bond area on above-mentioned cover film relative to
When the ratio of dust bond area on the above-mentioned surface of not formed above-mentioned cover film is as dust adhesive rate, the dust adhesive rate
Below 15%.
In addition, in order to solve the above-mentioned technical problem, antifouling nappe of the invention is constituted as follows: utilizing antifouling cover film will
The surface as antifouling object for covering object covers, which is at least made of nano particle, has bumps, and
And the radius of curvature of protrusion in 100nm hereinafter, making organic system simulation dust and the inorganic hybrid guided mode that mixes of system's simulation dust
It after quasi- dust adheres to and shaken, is shot using optical microscopy, binary conversion treatment is carried out to captured image, it will
The area ratio of the above-mentioned hybrid analog-digital simulation dust of the remaining calculated by above-mentioned processing, will be relative to non-shape as dust bond area
At on the dust bond area on the above-mentioned surface of above-mentioned antifouling cover film, the covering surface that is made of above-mentioned antifouling cover film
Dust bond area ratio as dust adhesive rate when, the dust adhesive rate is below 15%.
Invention effect
In the present invention, by constituting above, performance is capable of providing (dry) dirt for being better protected from or inhibiting stemness
Anti-soil technology effect.
Detailed description of the invention
Fig. 1 is the generalized schematic for indicating to be attached with the state of dust on antifouling cover film of the invention.
Fig. 2 be examples and comparative examples of the present invention as a result, be indicate the radius of curvature of the protrusion of antifouling cover film with
The chart of the relationship of dust adhesive rate.
Specific embodiment
Antifouling cover film of the invention is constituted as follows: its surface for being formed in covering object, at least by nano particle structure
There are bumps at, the antifouling cover film, and the radius of curvature of protrusion in 100nm hereinafter, also, make organic system simulation dust and
After the hybrid analog-digital simulation dust that inorganic system's simulation dust mixes adheres to and shaken, shot using optical microscopy,
Binary conversion treatment is carried out to captured image, by the area ratio of the above-mentioned hybrid analog-digital simulation dust of the remaining calculated by above-mentioned processing
Above-mentioned table of the rate as dust bond area, by the dust bond area on above-mentioned cover film relative to not formed above-mentioned cover film
When the ratio of dust bond area on face is as dust adhesive rate, the dust adhesive rate is below 15%.
According to the above configuration, antifouling cover film is substantially made of nano particle, and the radius of curvature of protrusion be can
Reduce the Van der Waals force of dust or the value of liquid bridge power.Therefore, the dust adhesive rate of above-mentioned hybrid analog-digital simulation dust is able to suppress
15% hereinafter, thus compared with the existing general anti-soil technology for using antistatic agent, can be greatly reduced dust attachment
Rate.As a result, it is possible to realize the anti-soil technology of (dry) dirt that can be better protected from or inhibit stemness.
It in the antifouling cover film of above-mentioned composition, may be constructed are as follows: the radius of curvature of raised part is in 5nm or more.
In the antifouling cover film of above-mentioned composition, may be constructed are as follows: by the height of raised part relative to adjacent
When the ratio between mutual interval in the vertex of raised part is set as aspect ratio, the aspect ratio is below 1.0.
In addition, may be constructed in the antifouling cover film of above-mentioned composition are as follows: above-mentioned nano particle is selected from metal nano
Grain, inorganic oxide nanoparticles, inorganic nitride nano particle, inorganic chalcogenide nano particle, (methyl) acrylic acid series
It is at least one kind of in resin nano particle, fluororesin nano particle.
Antifouling nappe of the invention is constituted as follows: using antifouling cover film by cover object as antifouling object
Surface covering, which is at least made of nano particle, has a bumps, and the radius of curvature of protrusion 100nm with
Under, after the hybrid analog-digital simulation dust for mixing organic system simulation dust and inorganic system's simulation dust adheres to and is shaken, benefit
It is shot with optical microscopy, binary conversion treatment is carried out to captured image, by the upper of the remaining calculated by above-mentioned processing
The area ratio of hybrid analog-digital simulation dust is stated as dust bond area, by the above-mentioned table relative to not formed above-mentioned antifouling cover film
The ratio conduct of dust bond area on dust bond area on face, the covering surface that is made of above-mentioned antifouling cover film
When dust adhesive rate, the dust adhesive rate is below 15%.
According to the above configuration, the antifouling cover film constituted as follows, the antifouling cover film are equipped on the surface of antifouling nappe
Substantially it is made of nano particle, the radius of curvature of protrusion is controlled as reducing the Van der Waals force of dust or the value of liquid bridge power, and
And the dust adhesive rate of above-mentioned hybrid analog-digital simulation dust is controlled in 15% or less.As a result, with use the existing of antistatic agent
General anti-soil technology is compared, and dust adhesive rate can be greatly reduced.As a result, may be implemented to be better protected from or press down
The anti-soil technology of (dry) dirt of stemness processed.
It in the antifouling nappe of above-mentioned composition, may be constructed are as follows: the above-mentioned radius of curvature of above-mentioned antifouling cover film exists
30nm hereinafter, the above-mentioned dust adhesive rate on above-mentioned covering surface below 10%.
It in the antifouling nappe of above-mentioned composition, may be constructed are as follows: the curvature of the raised part of above-mentioned antifouling cover film half
Diameter is in 5nm or more.
In addition, the antifouling nappe of above-mentioned composition may be constructed are as follows: above-mentioned hybrid analog-digital simulation dust as inorganic system by simulating
The silica sand of dust and as organic system simulation dust velveteen and cornstarch these three constitute and will be above-mentioned in advance
Covering surface adheres to above-mentioned hybrid analog-digital simulation dust after destaticing.
In addition, may be constructed in the antifouling nappe of above-mentioned composition are as follows: above-mentioned covering object be family's electrical article or its
Component.
Representative configuration example of the invention is specifically described below.
[antifouling cover film]
Antifouling cover film of the invention is at least made of nano particle, has indent and convex film.Constitute antifouling cover film
Nano particle be not particularly limited, can typically enumerate metal nanoparticle, inorganic oxide nanoparticles, inorganic nitrogen
Compound nano particle, inorganic chalcogenide nano particle (not including inorganic oxide nanoparticles), (methyl) acrylic acid series tree
Rouge nano particle, fluororesin nano particle etc..
It can specifically enumerate for example: as the gold (Au) of metal nanoparticle, silver-colored (Ag), copper (Cu), iron platinum (FePt) etc.
The 11st race's element of the periodic table of elements or its alloy；The element week of nickel (Ni, the 10th race's element), tin (Sn, the 14th race's element) etc.
Plating metallic element etc. other than 11 race's element of phase Biao.In addition, dioxy can be enumerated as inorganic oxide nanoparticles
SiClx (silica, SiO2), yttrium oxide (Y2O3), barium titanate (BaTiO3), tin oxide (ATO), the titanium oxide (TiO of antimony dopant2)、
Indium oxide (In2O3) etc..As inorganic nitride nano particle, gallium nitride (GaN) etc. can be enumerated.As inorganic chalcogenide
Nano particle can enumerate cadmium selenide (CdSe) etc..As (methyl) acrylic resin nano particle, poly- methyl can be enumerated
Methyl acrylate (PMMA) etc..As fluororesin nano particle, polytetrafluoroethylene (PTFE) (PTFE) etc. can be enumerated.
These nano particles substantially only constitute antifouling cover film by a kind, but multiple combinations can also be constituted antifouling
Cover film.Wherein, consider from versatility, cost, easy modulability of aftermentioned radius of curvature etc., particularly preferably use titanium dioxide
Nano silicon particles.In addition, antifouling cover film is substantially only made of nano particle, but as long as antifouling cover film is not interfered to be brought
Anti-pollution, the ingredient other than nano particle can also be contained.Such as antifouling cover film can be gone back other than nano particle
Contain antistatic agent.
The partial size of nano particle is not particularly limited, in the present embodiment, can be in the range of several nm~hundreds of nm.
The measuring method of the partial size of nano particle is not particularly limited, be suitble to using well known method (diffusion method, inertia method, sedimentation,
Microscopic method, light Scattering and diffracting method etc.).About the measured value of present embodiment, the partial size measured by well known method is in and receives
Meter level.
Antifouling cover film can also include fine bumps, and the specific configuration is not particularly limited in addition to this.For example, anti-
The film thickness of dirty cover film is not particularly limited, usually can be in the range of 10nm~10 μm (10,000nm), in order to obtain
In the case where the transparency, preferably in the range of 10~200nm.Wherein, the measuring method of film thickness is not particularly limited, in this reality
It applies in mode, as illustrating in embodiment as be described hereinafter, covers section using electron microscope observation, calculate and schemed by multiple observations
As the average value of the film thickness measured.
The specific forming method (manufacturing method) of antifouling cover film is not particularly limited, if can due to nano particle shape
At fine bumps, so that it may use well known various methods.As representative forming method, sol-gel can be enumerated
Method, uses the transfer of anodic oxidation mold, sandblasting, self-organization of ceramics etc. at nano impression.
Fine concaveconvex shape possessed by antifouling cover film, the radius of curvature of protrusion can in 100nm hereinafter, it is preferred that
In 30nm or less." radius of curvature of protrusion " mentioned here is the average value of the radius of curvature of multiple protrusions.The curvature of protrusion
When radius is more than 100nm, good anti-pollution can not be played by sometimes resulting in antifouling cover film.
In addition, the upper limit of the radius of curvature of the protrusion of antifouling cover film about lower limit as described above in 100nm hereinafter, do not have
It is particularly limited to.As preferred lower limit, 5nm or more can be enumerated.When the radius of curvature of protrusion is lower than 5nm, although also depending on
Each conditions such as the specific composition of antifouling cover film, the type of covering object, the surface state of covering object, but surface
Protrusion becomes too small, and good anti-pollution can not be played by sometimes resulting in.
Wherein, the measuring method of the radius of curvature of protrusion is not particularly limited, in the present embodiment, embodiment as be described hereinafter
As middle explanation, measured by observing section using microscope etc..Wherein, it is made of in antifouling cover film spherical particle
In the case of, using the radius of the spherical particle as the radius of curvature of protrusion.
The upper limit of the radius of curvature of protrusion is based on the main of the attachment of the dust (stemness dust) of stemness dirt
Factor and export.Under normal conditions, shown in the principal element of the attachment of stemness dust such as following formula (1), liquid bridge power FL, Van der Waals
Power FVWith electrostatic attraction FEThe sum of be greater than gravity.
FL+FV+FE> gravity ... (1)
In the prior art, the principal element as the attachment of stemness dust, electrostatic attraction FEIn critical role, substantially
Liquid bridge power F is not accounted forLOr Van der Waals force FV.Thus, for example illustrated by patent document 2 like that, studying raising and being assigned to article
The antistatic property given.But the present inventor has made intensive studies, and as a result originally finds in fine stemness dust
In, liquid bridge power FLWith Van der Waals force FVWith very important influence.
Van der Waals force FVIt is the principal element for phenomena such as branch fits over attachment or sorption that the surface of solids occurs, such as following formula
(2) shown in, the relative radius R of stemness dust can be usedsIt indicates.Wherein, the A in formula (2) is Ha Meike (Hamaker) normal
Number, is the constant for determining the Van der Waals force acted between different solids, and d is different the distance between solid.Exist in stemness dust
In the state of the surface attachment (contact) of article, d is truncation (cut off) distance (0.15nm).
Liquid bridge power FLIt is that there are generations when liquid in the extremely narrow space in contact site between solid
Power, as shown in following formula (3), with Van der Waals force FVEqually, using the relative radius R of stemness dustsIt indicates.Wherein, formula (3)
In γLIt is the surface tension of liquid, θ1And θ2It is contact angle.
FL=2 π RsγL(cosθ1+cosθ2)…(3)
Here, in the prior art, about relative radius Rs, stemness dust and flat face contact in the case where be regarded as with
The radius R of stemness dust1Equal (Rs=R1), in the case where stemness dust is in contact with each other, with the radius of 2 stemness dust it
Product (R1R2) divided by the sum of the radius of 2 stemness dust (R1+R2) obtained value (Rs=R1R2/(R1+R2)) calculate.Relative to
This, the present inventor originally has found, in the case where constituting antifouling cover film by nano particle, relative radius RsPrevented
A possibility that radius of curvature of the protrusion of dirty cover film dominates is high.
About this point, it is illustrated referring to Fig.1.In Fig. 1, in this example it is schematically indicated that stemness dust 10 and antifouling covering
Body 20.Antifouling nappe 20 is that the surface of covering object 22 is formed with the composition of antifouling cover film 21, antifouling 21 shape of cover film
At there is multiple protrusions 23.The attachment of stemness dust 10 is able to suppress using multiple protrusion 23.
Here, stemness dust 10 is considered as radius R1Ball, and antifouling cover film 21 bumps by with radius of curvature r
Ideal protrusion 23 formed when, relative radius RsWith the radius R of stemness dust 101With the product (R of radius of curvature r1R) divided by dry
The radius R of property dust 101With the sum of radius of curvature r (R1+ r) obtained value (Rs=R1r/(R1+ r)) it calculates.As a result, if adjusted
Section radius of curvature r makes the radius R relative to stemness dust 101, reduce relative radius Rs, then stemness dust can be greatly reduced
10 adhesion.
It is appropriate by the way that the aspect ratio for constituting the nano particle of protrusion 23 to be limited to also, in antifouling cover film 21
In range, the adhesion of stemness dust 10 can be further decreased.In the present embodiment, as shown in Figure 1, by adjacent convex
The vertex in portion 23 it is mutual interval be set as W, by the height of protrusion 23 (from the bottom surface of recess portion between the vertex of protrusion 23
Every) be considered as H when, aspect ratio is defined as the ratio between the mutual interval W in vertex of the height H of protrusion 23 relative to protrusion 23 (aspect ratio
=H/W).Wherein, the T in Fig. 1 is the film thickness of antifouling cover film 21, and the height H of protrusion 23 is less than the value of film thickness T.
Aspect ratio is below 1.0, preferably below 0.5.When aspect ratio is more than 1.0, the radius of curvature of protrusion 23 can
It can exceed that 100nm, may cause antifouling cover film 21 can not play good anti-pollution.In addition, the height H of protrusion 23 and convex
The measuring method of the mutual interval W in portion 23 is not particularly limited, can be same as film thickness T, is covered using electron microscope observation
Section calculates the average value of the height H and interval W that are measured by multiple observation images.
In addition, surface roughness is not particularly limited in antifouling cover film 21, preferably in the range of 2.5~100nm
It is interior, more preferably in the range of 5~50nm.Surface roughness in the range when, antifouling cover film 21 can play good
Anti-pollution.Wherein, measurement (evaluation) method of surface roughness is not particularly limited, can be used for example laser microscope or
Atomic force microscope (AFM) measures (evaluation) arithmetic mean roughness Ra, is calculated based on JIS B0601.
[the dust adhesive rate of antifouling cover film]
The dust adhesive rate of the antifouling cover film of above-mentioned composition is below 15%.Here, dust adhesive rate of the invention with
It is formed with the simulation dust on the surface (the covering surface being made of antifouling cover film) of the covering object of antifouling cover film
Attachment of the adhesion amount relative to the simulation dust on the surface (covering front surface) of the covering object of not formed antifouling cover film
Amount calculates.
About the simulation dust for calculating dust adhesive rate, in the present invention it is preferable to use by organic system simulation dust and
The hybrid analog-digital simulation dust that inorganic system's simulation dust mixes.Organic system simulates the specific type of dust and inorganic system's simulation dust
It is not particularly limited, is suitble to the test powder of various prescribed by standard etc. using JIS (Japanese Industrial Standards) etc..In addition,
It can be a kind that organic system, which simulates dust and inorganic system simulation dust, but preferably two or more is applied in combination.
In the present invention, shown in embodiment as be described hereinafter, 2 kinds of silica sands, and conduct are used as inorganic system simulation dust
Organic system simulates dust and uses velveteen and cornstarch.As specific silica sand, a kind of 8901 defined of JIS Z is used
(class1) silica sand and 3 kinds of (class3) silica sands both.As velveteen, assisted using by the air cleaning of Japan of public good civic organization
The product that meeting (JACA) is sold as a kind of test with powder.Cornstarch is commercially available product.Silica sand is for evaluating inorganic system's dust
Attachment, velveteen are used to evaluate the attachment of the fiber system dust in organic system dust, and cornstarch is for evaluating in organic system dust
Powder system dust (dust, grain system dust) attachment.
In the embodiment and comparative example of patent document 1, as simulation dust, use individually Northeast loam dust or
Carbon black evaluates the adhesion (anti-pollution) of dust.But dust present in living space is usually mixed there are many more
Therefore the substance of sample as described herein, in terms of the anti-pollution of evaluation stemness dirt, uses the dirt of single kind respectively
Angstrom when evaluating adhesion (anti-pollution), satisfactory evaluation result cannot be obtained.Wherein, loam dust in the Northeast is for commenting
The hydrophilic dirt of valence, carbon black is for evaluating lipophilic dirt.
In contrast, in the present invention, making living space without using single simulation dust as the dirt of stemness
Present in actual dust model, use and organic system simulated into dust and the inorganic hybrid guided mode that mixes of system's simulation dust
Quasi- dust.Therefore, the anti-pollution of stemness dirt can be evaluated well.In addition, in the powder system dust as stemness dirt
Also including being in hydrophilic dust as the loam dust of the Northeast in although, in hybrid analog-digital simulation dust of the invention, as
Organic system simulates dust, the hydrophily other than used as the velveteen of fiber system dust, also used as powder system dust
Cornstarch.Cornstarch shows the behavior as stemness dirt in the dry state, but there are when moisture, just will do it
It absorbs water and shows the behavior as hydrophilic dirt.By using the cornstarch with this characteristic as powder system dirt
Angstrom, the anti-pollution for actual dust can be evaluated well.
As described above, dust adhesive rate is defined as on the covering surface being made of antifouling cover film in covering object
Ratio of the adhesion amount of hybrid analog-digital simulation dust relative to the adhesion amount of the hybrid analog-digital simulation dust in the covering front surface of antifouling cover film
Rate.In the present invention, it covers front surface or covers the adhesion amount of the hybrid analog-digital simulation dust on surface by aobvious using optics
The image of micro mirror shooting carries out binary conversion treatment and calculates, the area ratio of remaining hybrid analog-digital simulation dust calculates.Wherein, will
The area ratio is as dust bond area.The dust bond area covered in front surface is set as A0, will covering surface on
Dust bond area is set as A1When, dust adhesive rate ARIt can be calculated by following formula (4).
The dust adhesive rate of antifouling cover film below 15%, preferably 10% hereinafter, more preferably 5% hereinafter,
Particularly preferably below 2%.When dust adhesive rate is below 15%, by range estimation, the attachment of dust is unobvious, thus judges energy
Enough obtain sufficient anti-pollution.
When calculating dust adhesive rate, as covering object, the part of various materials can be used, in the covering object
The surface of object forms antifouling cover film, and the evaluation sample for evaluating dust adhesive rate is thus made.In evaluation sample,
Using the surface for being formed with antifouling cover film as when " covering surface ", hybrid analog-digital simulation dust adheres on the covering surface, but preferably
Before adhering to hybrid analog-digital simulation dust, evaluation is destaticed with sample.
In addition, hybrid analog-digital simulation dust is made to be attached to the method for evaluation sample and shake the hybrid analog-digital simulation dust of attachment
The method fallen also is not particularly limited, and can be suitble to use various methods.Such as in the later-described embodiments, make hybrid analog-digital simulation dirt
Angstrom covering surface accumulation specified amount after, fall it with sample vertical tilt evaluation, thus by hybrid analog-digital simulation dust
Shake is fallen.In addition, being also not particularly limited, about the image using optical microscopy shooting covering surface mixing can be observed
The multiplying power for simulating dust shoots multiple images.The binary conversion treatment of image about shooting, is also not particularly limited, can be with
Use well known image processing software etc..
[antifouling nappe]
Antifouling nappe of the invention can use above-mentioned antifouling cover film will cover object surface covering and structure
At.As described above, the radius of curvature of the protrusion of antifouling cover film is in 100nm or less, preferably in 30nm or less and preferred protrusion
Radius of curvature in 5nm or more, dust adhesive rate is suppressed in 15% or less, it is thus possible to play excellent anti-pollution.
About antifouling nappe of the invention specific type or it is specific constitute, be not particularly limited, can need to
The article of anti-pollution is assigned as covering object, covers above-mentioned antifouling cover film.As representative covering object
Object can enumerate an electrical article or its component.Antifouling cover film is formed by being on electrical article or its component, family's electrical article is not
The easily dirt of attachment stemness, can reduce the frequency of cleaning.In addition, if it is family's electrical article that specified position is arranged in, at this
The dust of the floating as stemness dirt is accumulated in the upper surface of family's electrical article sometimes, but if forming the present invention in the upper surface
Antifouling cover film, then the dust of accumulation can easily be removed and the cleaning for the degree gently wiped away.
It as specific family's electrical article, such as can enumerate: air-conditioning (air regulator), electric fan, dust catcher, air cleaning
Device, ventilation fan, drying machine etc. generate family's electrical article of wind when in use；Television set, refrigerator, micro-wave oven etc. are arranged in predetermined bits
Set the family's electrical article etc. used.
Generate wind family's electrical article in the case where, dust be easy wind generation mechanism accumulation and it is attached as stemness dirt
, thus by forming antifouling cover film of the invention, the dirt in the generation mechanism attachment stemness of wind can be effectively inhibited.
Such as in air-conditioning, dust is easy to accumulate in heat exchanger, air grille, cross flow fan etc., but by being formed on these parts
Antifouling cover film can be effectively prevented the attachment of stemness dirt.In other words, antifouling nappe of the invention not only includes air-conditioning etc.
Complete family electrical article also includes the component of families' electrical articles such as heat exchanger, air grille, the cross flow fan for constituting air-conditioning.In addition,
It is different because of the type of family's electrical article and construction etc. as the component of antifouling nappe, it is not limited to the heat exchange of air-conditioning
Device etc..
As described above, according to the present invention, antifouling cover film is substantially made of nano particle, and the radius of curvature of protrusion
For the Van der Waals force of dust or the value of liquid bridge power can be reduced.Therefore, the dust adhesive rate of hybrid analog-digital simulation dust is suppressed in
15% hereinafter, can be greatly reduced dust adhesive rate thus compared with the existing general anti-soil technology for using antistatic agent.
As a result, the anti-soil technology of (dry) dirt that can be better protected from or inhibit stemness may be implemented.
Embodiment
Based on embodiment, comparative example and reference example to present invention progress more specific description, but the present invention is not limited to
This.Those skilled in the art can make various changes without departing from the scope of the invention, modifications and variations.Wherein,
Embodiment below, comparative example and the measurement of radius of curvature of the protrusion in reference example, the measurement of film thickness, dust adhesive rate are commented
Valence carries out as described below.
(measuring method of the radius of curvature of film thickness and protrusion)
Using electron microscope (Hitachi Ltd., product name: S-5500) with observe multiplying power 10,000~
With 0.2~60 μm in the range of 200,000 times2Range observation covering section, shooting 5 at the covering section image.About
Film thickness measures the film thickness size of obtained 5 images respectively, uses its average value.In addition, about radius of curvature, by these
The size of the radius of curvature of the protrusion in determining image section uses its average value.
(evaluation method of dust adhesive rate)
The electrification for using sample is measured and evaluated using static measuring device (SIMCO JAPAN corporation, trade name FMX-004)
Current potential, and the evaluation is used using electro-dissociator (ionizer) (Shimadzu Scisakusho Ltd's system, trade name STABLO-EX)
Sample is destaticed, and electric potential is adjusted in the range of 0 ± 0.1kV.Then, make hybrid analog-digital simulation dust in evaluation examination
Accumulate about 0.3g/cm in the covering surface of sample2Amount.Then, it tilts evaluation with sample, is erect with plumbness, this is maintained to hang down
Straight state falls on it on table from the height of 1cm, and the hybrid analog-digital simulation dust shake of attachment is fallen.Using the whereabouts of plumbness into
Capable shake is fallen to be repeated 3 times.
Later, using optical microscopy (Olympus Co., Ltd's system, product name: SZX7) in 10~20 times of multiplying power of observation
In the range of with 1~4cm2In the range of observation covering surface, shooting 5 at the covering surface image.It is soft using image procossing
Part (product name ImageJ " increasing income (open source), the freeware of public sphere " or trade name Adobe Photoshop
[Adobe Systems Incorporated system]) by obtained 5 image binaryzations.Thus the dust on covering surface is calculated
Bond area A1。
It is also the same for the surface (covering front surface) of the evaluation sample of not formed antifouling cover film to calculate dust attachment
Area A0, according to these dust bond areas A0And A1Dust adhesive rate A is calculated using above-mentioned formula (4)R。
(embodiment 1)
As hybrid analog-digital simulation dust, using as described above by 3 kinds of (class3) silica sands, a kind of (class1) silica sand, velveteen and
Cornstarch is respectively with dust made of mixed in equal amounts.
As covering object (substrate), glass slide (production of Song Langxiaozi Industrial Co., Ltd, product name: Bai Yuan are used
Grind (Shirofuchimigaki) No.1), it is formed on the surface of the glass slide by silica nanometer using sol-gal process
The antifouling cover film that grain is constituted makes the evaluation sample of embodiment 1.The protrusion of antifouling cover film in the evaluation sample
Radius of curvature is 21nm, film thickness 130nm, dust adhesive rate ARIt is 1.3%.In addition, as shown in Fig. 2, by the dust of calculating
Adhesive rate ARValue in the radius of curvature that horizontal axis is protrusion, chart that the longitudinal axis is dust adhesive rate (radius of curvature-dust attachment
Rate chart) in the marked of bullet.
(reference example)
Using the plate of the ABS resin added with well known antistatic agent as with reference to evaluation sample.This is used with reference to evaluation
The not formed substantial bumps in the surface of sample, are flat.Prepare the plate for being not added with the ABS resin of antistatic agent, with reality
It applies the equally operation of example 1 and calculates dust bond area A0, and calculate the dust bond area A with reference to evaluation sample1, by above-mentioned
Formula (4) calculates dust adhesive rate AR.As a result 89%.In addition, as shown in Fig. 2, by the dust adhesive rate A of calculatingRValue in song
With the marked of triangle in rate radius-dust adhesive rate chart.
(comparative example 1)
(the Daikin Industries strain formula meeting of commercially available fluororesin film is formed on the surface of the glass slide as covering object (substrate)
Society's production, product name: Optool DSX), the evaluation sample of comparison example 1.Fluororesin film in the evaluation sample is not
Substantial bumps are formed, are flat.The dust adhesive rate A of the evaluation sampleRIt is 17%.In addition, as shown in Fig. 2, will
The dust adhesive rate A of calculatingRValue in radius of curvature-dust adhesive rate chart with the marked of diamond shape.
(comparative example 2)
Commercially available pendent lamp (ceiling light) (production of Co., Ltd. of Panasonic, product name LGBZ1142) is used
Antifouling cover film, similarly to Example 1 measure protrusion radius of curvature, evaluate dust adhesive rate AR.It cuts and is formed with work
Evaluation sample for a part of the cover of the pendent lamp of the silica dioxide granule film of antifouling cover film, as comparative example 2.It should
Evaluation is 200nm, dust adhesive rate A with the radius of curvature of the protrusion of the silica dioxide granule film in sampleRIt is 17%.In addition,
As shown in Fig. 2, by the dust adhesive rate A of calculatingRValue in radius of curvature-dust adhesive rate chart with the mark of open circles
Label.
(comparative example 3)
For commercially available air duct with ventilation fan (multi blade fan, Mitsubishi's electrode Co. Ltd. system, VD-15ZLX9-IN)
Used antifouling cover film measures the radius of curvature of protrusion similarly to Example 1, evaluates dust adhesive rate AR.It cuts to be formed
There are a part of the flabellum part of the ventilation fan of the silica dioxide granule film as antifouling cover film, the evaluation as comparative example 3
Use sample.The evaluation is 300nm, dust adhesive rate A with the radius of curvature of the protrusion of the silica dioxide granule film in sampleRFor
17%.In addition, as shown in Fig. 2, by the dust adhesive rate A of calculatingRValue in radius of curvature-dust adhesive rate chart with sky
The marked of heart circle.
(comparative example 4)
For commercially available air duct with ventilation fan (multi blade fan, Mitsubishi's electrode Co. Ltd. system, VD-15ZLX10-IN)
Used antifouling cover film measures the radius of curvature of protrusion similarly to Example 1, evaluates dust adhesive rate AR.It cuts to be formed
There are a part of the flabellum part of the ventilation fan of the silica dioxide granule film as antifouling cover film, the evaluation as comparative example 4
Use sample.The evaluation is 500nm, dust adhesive rate A with the radius of curvature of the protrusion of the silica dioxide granule film in sampleRFor
28%.In addition, as shown in Fig. 2, by the dust adhesive rate A of calculatingRValue in radius of curvature-dust adhesive rate chart with sky
The marked of heart circle.
(comparison of embodiment, reference example and comparative example)
As shown in Fig. 2, the radius of curvature of protrusion is in 100nm or less (21nm), dirt in the evaluation sample of embodiment 1
Angstrom adhesive rate is 1.3%, and covers the evaluation sample of the comparative example 1 of existing fluororesin and cover existing two
The evaluation sample of the comparative example 2~4 of silicon oxide particle film, dust adhesive rate is 17% or more.
In addition, in reference example, instead of forming antifouling cover film, for the composition for imparting antistatic property, but in the reference
Dust adhesive rate is very high in example.According to these results it is found that antifouling cover film of the invention and existing antifouling cover film phase
Than that can be effectively prevented or inhibit the attachment of stemness dirt, and dust cannot be effectively reduced when assigning antistatic property
Adhesive rate.
Also, in Fig. 2, according to embodiment 1, the result of reference example, comparative example 1~3 comparison it is found that protrusion curvature
Radius is in 100nm or less, it is known that range more preferably, such as can be in the range of 5nm or more 30nm or less.
Wherein, the present invention is not limited to the records of above embodiment, are able to carry out in the range of being claimed each
Kind of change, will distinguish in different embodiment or multiple variations disclosed technical characteristic it is appropriately combined obtained from embodiment party
Formula is also included in the technical scope of the present invention.
Industrial availability
The present invention is suitble to be widely used in the field for preventing or inhibiting the attachment of stemness dirt.
Symbol description
10 stemness dust
20 antifouling nappes
21 antifouling cover films
22 covering objects
23 protrusions
Claims (9)
1. a kind of antifouling cover film, it is characterised in that:
The antifouling cover film is formed in the surface of covering object, is at least made of nano particle, which has recessed
It is convex, and the radius of curvature of protrusion in 100nm hereinafter,
Also, the hybrid analog-digital simulation dust for mixing organic system simulation dust and inorganic system's simulation dust adheres to and is shaken
Afterwards, it is shot using optical microscopy, binary conversion treatment is carried out to captured image, the remaining that will be calculated by the processing
The hybrid analog-digital simulation dust area ratio as dust bond area,
By the dust bond area on the cover film relative to the dust attachment on the surface of the not formed cover film
When the ratio of area is as dust adhesive rate,
The dust adhesive rate is below 15%.
2. antifouling cover film as described in claim 1, it is characterised in that:
The radius of curvature of the protrusion is in 5nm or more.
3. antifouling cover film as claimed in claim 1 or 2, it is characterised in that:
It, should when the ratio between the mutual interval in vertex by the height of the protrusion relative to the adjacent protrusion is set as aspect ratio
Aspect ratio is below 1.0.
4. antifouling cover film according to any one of claims 1 to 3, it is characterised in that:
The nano particle is selected from metal nanoparticle, inorganic oxide nanoparticles, inorganic nitride nano particle, inorganic
It is chalcogenide nano particle, (methyl) acrylic resin nano particle, at least one kind of in fluororesin nano particle.
5. a kind of antifouling nappe, it is characterised in that:
Covering as the surface of antifouling object for object will be covered using antifouling cover film, the antifouling cover film is at least by nanometer
Particle constitute, have bumps, and the radius of curvature of protrusion in 100nm hereinafter,
It is right after the hybrid analog-digital simulation dust for mixing organic system simulation dust and inorganic system's simulation dust adheres to and shaken
Binary conversion treatment is carried out using the image of optical microscopy shooting, by the hybrid analog-digital simulation dirt of the remaining calculated by the processing
Angstrom area ratio as dust bond area,
By relative to the dust bond area on the surface of the not formed antifouling cover film, by the antifouling cover film
When the ratio of dust bond area on the covering surface of composition is as dust adhesive rate,
The dust adhesive rate is below 15%.
6. antifouling nappe as claimed in claim 5, it is characterised in that:
The radius of curvature of the antifouling cover film in 30nm hereinafter,
The dust adhesive rate on the covering surface is below 10%.
7. such as antifouling nappe described in claim 5 or 6, it is characterised in that:
The radius of curvature of the protrusion of the antifouling cover film is in 5nm or more.
8. the antifouling nappe as described in any one of claim 5~7, it is characterised in that:
The hybrid analog-digital simulation dust by as it is inorganic system simulation dust silica sand and as organic system simulation dust velveteen and
Three kinds of cornstarch compositions,
After destaticing in advance to the covering surface, adhere to the hybrid analog-digital simulation dust.
9. the antifouling nappe as described in any one of claim 5~8, it is characterised in that:
The covering object is family's electrical article or its component.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016115329 | 2016-06-09 | ||
| JP2016-115329 | 2016-06-09 | ||
| PCT/JP2017/020868 WO2017213097A1 (en) | 2016-06-09 | 2017-06-05 | Antifouling coating film and antifouling coated object |
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| CN109312193A true CN109312193A (en) | 2019-02-05 |
| CN109312193B CN109312193B (en) | 2021-02-02 |
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| JP (1) | JPWO2017213097A1 (en) |
| CN (1) | CN109312193B (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011204A (en) * | 2019-05-29 | 2020-12-01 | 华为技术有限公司 | Fingerprint-resistant coating, terminal and preparation method |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2017213097A1 (en) | 2017-12-14 |
| JPWO2017213097A1 (en) | 2019-04-04 |
| CN109312193B (en) | 2021-02-02 |
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